TW202109185A

TW202109185A - Active-light-sensitive or radiation-sensitive resin composition, resist film, pattern formation method, method for manufacturing electronic device, and composition-accommodating body

Info

Publication number: TW202109185A
Application number: TW109114960A
Authority: TW
Inventors: 丸茂和博
Original assignee: 日商富士軟片股份有限公司
Priority date: 2019-06-28
Filing date: 2020-05-06
Publication date: 2021-03-01
Also published as: JPWO2020261753A1; JP7495404B2; WO2020261753A1

Abstract

Provided is an active-light-sensitive or radiation-sensitive resin composition with which it is possible to form a pattern in which defects are suppressed even after being stored for a prescribed period. Also provided are a resist film in which the active-light-sensitive or radiation-sensitive resin composition is used, a pattern formation method, and a method for manufacturing an electronic device in which the pattern formation method is used. Also provided is a composition-accommodating body that includes the active-light-sensitive or radiation-sensitive resin composition. The active-light-sensitive or radiation-sensitive resin composition includes: a resin that dissolves due to the effect of acid, increasing polarity; a compound that generates acid due to being irradiated with active light or radiation; and a solvent, the compound that generates acid due to being irradiated with active light or radiation including a compound having a specified structure including a multivalent salt structure in each molecule, and the water content being 1.00 mass% or less in relation to the total mass of the composition.

Description

感光化射線性或感放射線性樹脂組成物、抗蝕劑膜、圖案形成方法、電子元件的製造方法、組成物收容體Sensitizing radiation-sensitive or radiation-sensitive resin composition, resist film, pattern formation method, manufacturing method of electronic component, composition container

本發明是有關於一種感光化射線性或感放射線性樹脂組成物、抗蝕劑膜、圖案形成方法、電子元件的製造方法、組成物收容體。The present invention relates to an sensitizing radiation-sensitive or radiation-sensitive resin composition, a resist film, a pattern forming method, a manufacturing method of an electronic component, and a composition container.

KrF準分子雷射（248 nm）用抗蝕劑以後，為了彌補由光吸收引起的感度降低，而使用利用化學增幅的圖案形成方法。例如，正型的化學增幅法中，首先，曝光部中所含的光酸產生劑藉由光照射而分解並產生酸。而且，於曝光後的烘烤（PEB：Post Exposure Bake）過程等中，因所產生的酸的觸媒作用而使感光化射線性或感放射線性樹脂組成物中所含的樹脂所具有的鹼不溶性的基變化為鹼可溶性的基等，從而使相對於顯影液的溶解性發生變化。然後，例如使用鹼性水溶液來進行顯影。藉此，將曝光部去除而獲得所期望的圖案。為了半導體組件的微細化，曝光光源的短波長化及投影透鏡的高開口數（高數值孔徑（Numerical Aperture，NA））化正在發展，目前已開發出將具有193 nm的波長的ArF準分子雷射作為光源的曝光機。基於所述現狀，作為感光化射線性或感放射線性樹脂組成物（抗蝕劑組成物），提出了各種構成。After the resist for KrF excimer laser (248 nm), in order to compensate for the decrease in sensitivity caused by light absorption, a patterning method using chemical amplification is used. For example, in the positive chemical amplification method, first, the photoacid generator contained in the exposure part is decomposed by light irradiation to generate acid. In addition, in the post-exposure baking (PEB: Post Exposure Bake) process, etc., the alkali in the resin contained in the sensitized radiation or radiation-sensitive resin composition is caused by the catalytic action of the acid generated The insoluble group is changed to an alkali-soluble group or the like, thereby changing the solubility with respect to the developer. Then, for example, an alkaline aqueous solution is used for development. Thereby, the exposure part is removed, and a desired pattern is obtained. For the miniaturization of semiconductor components, the short wavelength of the exposure light source and the high number of apertures (high numerical aperture (NA)) of the projection lens are being developed. At present, an ArF excimer mine with a wavelength of 193 nm has been developed. Exposure machine that shoots as a light source. Based on the above-mentioned current situation, various constitutions have been proposed as actinic radiation-sensitive or radiation-sensitive resin compositions (resist compositions).

例如，在專利文獻1中，作為抗蝕劑組成物中使用的成分，揭示了含有下述式（I）所表示的鹽的酸產生劑。For example, in Patent Document 1, as a component used in the resist composition, an acid generator containing a salt represented by the following formula (I) is disclosed.

[化1]

[現有技術文獻] [專利文獻][化1]

[Prior Art Document] [Patent Document]

[專利文獻1]日本專利特開2015-024989號[Patent Document 1] Japanese Patent Laid-Open No. 2015-024989

[發明所欲解決之課題] 本發明者等人對專利文獻1中記載的抗蝕劑組成物進行了研究，結果發現於使用保管規定期間後的所述抗蝕劑組成物來形成圖案時，圖案會產生許多缺陷。即，對於所述抗蝕劑組成物而言明確的是需要進一步的改善，以使得即使於保管規定期間後供於圖案形成的情況下，所得的圖案亦不會產生缺陷。[The problem to be solved by the invention] The inventors of the present invention conducted studies on the resist composition described in Patent Document 1, and found that when the resist composition after a predetermined period of storage is used to form a pattern, many defects are generated in the pattern. That is, it is clear that the resist composition requires further improvement so that even when it is used for pattern formation after a predetermined period of storage, the resulting pattern does not cause defects.

因此，本發明的課題在於提供一種感光化射線性或感放射線性樹脂組成物，即使於保管規定期間後，亦可形成缺陷得到抑制的圖案。另外，本發明的課題在於提供一種使用了所述感光化射線性或感放射線性樹脂組成物的抗蝕劑膜及圖案形成方法、以及使用了所述圖案形成方法的電子元件的製造方法。另外，本發明的課題在於提供一種包含所述感光化射線性或感放射線性樹脂組成物的組成物收容體。 [解決課題之手段]Therefore, the subject of the present invention is to provide an actinic radiation-sensitive or radiation-sensitive resin composition that can form a pattern with suppressed defects even after storage for a predetermined period of time. In addition, the subject of the present invention is to provide a resist film and a pattern forming method using the sensitizing radiation-sensitive or radiation-sensitive resin composition, and a manufacturing method of an electronic component using the pattern forming method. In addition, the subject of the present invention is to provide a composition container containing the above-mentioned actinic ray-sensitive or radiation-sensitive resin composition. [Means to solve the problem]

本發明者等人為了解決所述課題而進行了潛心研究，結果發現，藉由以下構成可解決所述課題。The inventors of the present invention conducted painstaking studies to solve the above-mentioned problem, and as a result, found that the above-mentioned problem can be solved by the following configuration.

[1]一種感光化射線性或感放射線性樹脂組成物，包含：因酸的作用分解而極性增大的樹脂；藉由光化射線或放射線的照射而產生酸的化合物；以及溶劑，所述藉由光化射線或放射線的照射而產生酸的化合物包含選自由後述的化合物（I）～化合物（III）所組成的群組中的一種以上，相對於組成物的總質量，含水率為1.00質量%以下。 [2]如[1]所述的感光化射線性或感放射線性樹脂組成物，其中相對於組成物的總質量，所述含水率為0.50質量%以下。 [3]如[1]或[2]所述的感光化射線性或感放射線性樹脂組成物，其中相對於組成物的總質量，所述含水率為0.30質量%以下。 [4]如[1]～[3]中任一項所述的感光化射線性或感放射線性樹脂組成物，其中相對於組成物的總質量，所述含水率為0.03質量%～0.30質量%。 [5]如[1]～[4]中任一項所述的感光化射線性或感放射線性樹脂組成物，其中下述式（1X）所表示的量比T為4.0～500.0；式（1X）：量比T=選自由所述化合物（I）～所述化合物（III）所組成的群組中的化合物相對於組成物中的固體成分量的含有率（質量%）/相對於組成物的總質量的含水率（質量%）。 [6]一種抗蝕劑膜，是使用如[1]～[5]中任一項所述的感光化射線性或感放射線性樹脂組成物而形成。 [7]一種圖案形成方法，包括：使用如[1]～[5]中任一項所述的感光化射線性或感放射線性樹脂組成物於支持體上形成抗蝕劑膜的步驟；對所述抗蝕劑膜進行曝光的步驟；以及使用顯影液對所述經曝光的抗蝕劑膜進行顯影的步驟。 [8]一種電子元件的製造方法，包括如[7]所述的圖案形成方法。 [9]一種組成物收容體，包括：收容容器；以及收容在所述收容容器內的如[1]～[5]中任一項所述的感光化射線性或感放射線性樹脂組成物。 [10]如[9]所述的組成物收容體，其中所述收容容器內的與所述感光化射線性或感放射線性樹脂組成物接觸的區域的材料為樹脂。 [11]如[9]或[10]所述的組成物收容體，其中所述收容容器內的與所述感光化射線性或感放射線性樹脂組成物接觸的區域的材料為選自由聚烯烴樹脂及含氟原子的聚烯烴樹脂所組成的群組中的一種以上。 [發明的效果][1] A sensitized ray-sensitive or radiation-sensitive resin composition, comprising: a resin whose polarity is increased due to decomposition by an acid; a compound that generates an acid by irradiation with actinic rays or radiation; and a solvent, The compound that generates acid by irradiation with actinic rays or radiation includes one or more selected from the group consisting of compounds (I) to (III) described later, The moisture content is 1.00% by mass or less with respect to the total mass of the composition. [2] The actinic radiation-sensitive or radiation-sensitive resin composition according to [1], wherein the water content is 0.50% by mass or less with respect to the total mass of the composition. [3] The sensitizing radiation-sensitive or radiation-sensitive resin composition according to [1] or [2], wherein the moisture content is 0.30% by mass or less with respect to the total mass of the composition. [4] The sensitized radiation-sensitive or radiation-sensitive resin composition according to any one of [1] to [3], wherein the moisture content is 0.03% by mass to 0.30% by mass relative to the total mass of the composition %. [5] The sensitizing radiation-sensitive or radiation-sensitive resin composition according to any one of [1] to [4], wherein the amount ratio T represented by the following formula (1X) is 4.0 to 500.0; Formula (1X): Amount ratio T=The content (mass%) of a compound selected from the group consisting of the compound (I) to the compound (III) with respect to the solid content in the composition (mass %)/relative The moisture content (mass%) of the total mass of the composition. [6] A resist film formed using the sensitizing radiation-sensitive or radiation-sensitive resin composition according to any one of [1] to [5]. [7] A pattern forming method, including: A step of forming a resist film on a support using the sensitized radiation-sensitive or radiation-sensitive resin composition according to any one of [1] to [5]; A step of exposing the resist film; and A step of developing the exposed resist film using a developing solution. [8] A method of manufacturing an electronic component, including the pattern forming method as described in [7]. [9] A composition container, comprising: a container; and the photosensitive radiation or radiation-sensitive resin composition according to any one of [1] to [5] contained in the container. [10] The composition container according to [9], wherein the material of the area in contact with the actinic radiation-sensitive or radiation-sensitive resin composition in the storage container is a resin. [11] The composition container according to [9] or [10], wherein the material of the region in contact with the photosensitive ray-sensitive or radiation-sensitive resin composition in the container is selected from polyolefins One or more types of resins and polyolefin resins containing fluorine atoms. [Effects of the invention]

根據本發明，可提供一種感光化射線性或感放射線性樹脂組成物，即使於保管規定期間後，亦可形成缺陷得到抑制的圖案。另外，根據本發明，可提供一種使用了所述感光化射線性或感放射線性樹脂組成物的抗蝕劑膜及圖案形成方法、以及使用了所述圖案形成方法的電子元件的製造方法。另外，根據本發明，可提供一種包含所述感光化射線性或感放射線性樹脂組成物的組成物收容體。According to the present invention, it is possible to provide an actinic radiation-sensitive or radiation-sensitive resin composition that can form a pattern with suppressed defects even after storage for a predetermined period of time. In addition, according to the present invention, it is possible to provide a resist film and a pattern forming method using the sensitizing radiation-sensitive or radiation-sensitive resin composition, and a manufacturing method of an electronic component using the pattern forming method. In addition, according to the present invention, it is possible to provide a composition container including the above-mentioned actinic radiation-sensitive or radiation-sensitive resin composition.

以下，對本發明進行詳細說明。以下記載的構成要件的說明有時基於本發明的具代表性的實施形態而成，但本發明並不限定於所述實施形態。關於本說明書中的基（原子團）的表述，只要不違反本發明的主旨，則未記載經取代及未經取代的表述亦包含不具有取代基的基與具有取代基的基。例如，所謂「烷基」不僅包含不具有取代基的烷基（未經取代的烷基），亦包含具有取代基的烷基（經取代的烷基）。另外，所謂本說明書中的「有機基」，是指包含至少一個碳原子的基。只要無特別說明，取代基較佳為一價取代基。所謂本說明書中的「光化射線」或「放射線」，例如是指水銀燈的明線光譜、以準分子雷射為代表的遠紫外線、極紫外線（EUV光：Extreme Ultraviolet）、X射線及電子束（EB：Electron Beam）等。所謂本說明書中的「光」，是指光化射線或放射線。所謂本說明書中的「曝光」，並無特別限定，不僅是指利用水銀燈的明線光譜、以準分子雷射為代表的遠紫外線、極紫外線、X射線及EUV光等進行的曝光，亦包含利用電子束及離子束等粒子束進行的描繪。本說明書中，所謂「～」是以包含其前後所記載的數值作為下限值及上限值的含義使用。本說明書中表述的二價基的鍵結方向只要無特別說明，則並不受限制。例如，於「X-Y-Z」形成的通式所表示的化合物中的Y為-COO-的情況下，Y可為-CO-O-，亦可為-O-CO-。另外，所述化合物可為「X-CO-O-Z」，亦可為「X-O-CO-Z」。Hereinafter, the present invention will be described in detail. The description of the constituent elements described below may be based on the representative embodiments of the present invention, but the present invention is not limited to the above-mentioned embodiments. Regarding the expression of the group (atomic group) in this specification, as long as it does not violate the gist of the present invention, the expression that does not describe substituted and unsubstituted also includes a group having no substituent and a group having a substituent. For example, the term "alkyl" includes not only an unsubstituted alkyl group (unsubstituted alkyl group) but also a substituted alkyl group (substituted alkyl group). In addition, the "organic group" in this specification refers to a group containing at least one carbon atom. Unless otherwise specified, the substituent is preferably a monovalent substituent. The "actinic rays" or "radiation rays" in this manual refer to, for example, the bright-ray spectrum of mercury lamps, extreme ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV light: Extreme Ultraviolet), X-rays, and electron beams. (EB: Electron Beam) and so on. The "light" in this specification refers to actinic rays or radiation. The "exposure" in this manual is not particularly limited. It not only refers to exposure using the bright line spectrum of a mercury lamp, extreme ultraviolet, extreme ultraviolet, X-ray, and EUV light represented by excimer lasers, but also includes Drawing using particle beams such as electron beams and ion beams. In this specification, the term "to" is used to include the numerical values described before and after it as the lower limit and the upper limit. The bonding direction of the divalent group described in this specification is not limited unless otherwise specified. For example, when Y in the compound represented by the general formula formed by "X-Y-Z" is -COO-, Y may be -CO-O- or -O-CO-. In addition, the compound may be "X-CO-O-Z" or "X-O-CO-Z".

本說明書中，(甲基)丙烯酸酯表示丙烯酸酯及甲基丙烯酸酯，(甲基)丙烯酸表示丙烯酸及甲基丙烯酸。本說明書中，樹脂的重量平均分子量（Mw）、數量平均分子量（Mn）及分散度（亦稱為分子量分佈）（Mw/Mn）定義為藉由利用凝膠滲透層析（Gel Permeation Chromatography，GPC）裝置（東曹（Tosoh）公司製造的HLC-8120GPC）進行的GPC測定（溶媒：四氫呋喃、流量（樣品注入量）：10 μL、管柱：東曹（Tosoh）公司製造的TSK gel Multipore HXL-M、管柱溫度：40℃、流速：1.0 mL/分鐘、檢測器：示差折射率檢測器（Refractive Index Detector））所得的聚苯乙烯換算值。In this specification, (meth)acrylate means acrylate and methacrylate, and (meth)acrylic means acrylic and methacrylic acid. In this specification, the weight average molecular weight (Mw), number average molecular weight (Mn) and dispersion (also called molecular weight distribution) (Mw/Mn) of the resin are defined as by using gel permeation chromatography (Gel Permeation Chromatography, GPC) ) GPC measurement (solvent: tetrahydrofuran, flow rate (sample injection volume): 10 μL, column: TSK gel Multipore HXL- manufactured by Tosoh) by the device (HLC-8120GPC manufactured by Tosoh) M. Column temperature: 40°C, flow rate: 1.0 mL/min, detector: Refractive Index Detector (Refractive Index Detector) obtained by polystyrene conversion value.

本說明書中，所謂酸解離常數（pKa）表示水溶液中的pKa，具體而言是使用下述軟體包1，藉由計算求出基於哈米特（Hammett）的取代基常數及公知文獻值的資料庫的值而得的值。本說明書中記載的pKa的值全部表示使用所述軟體包並藉由計算而求出的值。In this specification, the so-called acid dissociation constant (pKa) means the pKa in an aqueous solution. Specifically, the following software package 1 is used to obtain data based on Hammett's substituent constant and publicly known literature values. Value derived from the value of the library. The values of pKa described in this specification all indicate values obtained by calculation using the software package.

軟體包1：用於Solaris的高級化學開發（Advanced Chemistry Development（ACD/Labs）軟體（software）V8.14 for Solaris（1994-2007 ACD/Labs））。Software package 1: Advanced Chemistry Development (ACD/Labs) software V8.14 for Solaris (1994-2007 ACD/Labs) for Solaris.

另一方面，pKa亦藉由分子軌道計算法求出。作為該具體的方法，可列舉藉由基於熱力學循環計算水溶液中的H⁺ 解離自由能量而算出的方法。關於H⁺ 解離自由能量的計算方法，例如可藉由密度泛函法（Density Functional Theory，DFT）進行計算，除此以外亦在文獻等中報告了其他各種方法，並不限制於此。再者，存在多個可實施DFT的軟體，例如可列舉高斯（Gaussian）16。On the other hand, pKa is also obtained by the molecular orbital calculation method. As this specific method, a method of calculating the free energy ^{of H +} dissociation in an aqueous solution based on a thermodynamic cycle can be mentioned. Regarding the calculation method of H ⁺ dissociation free energy, for example, it can be calculated by density functional theory (Density Functional Theory, DFT). In addition to this, various other methods have been reported in the literature and are not limited to this. Furthermore, there are many software that can implement DFT, for example, Gaussian 16 can be cited.

所謂本說明書中的pKa如上所述是指使用軟體包1，藉由計算求出基於哈米特的取代基常數及公知文獻值的資料庫的值而得的值，於無法藉由該方法計算出pKa的情況下，採用基於DFT（密度泛函法）並藉由高斯（Gaussian）16而所得的值。另外，本說明書中的pKa如上所述是指「水溶液中的pKa」，於無法算出水溶液中的pKa的情況下，採用「二甲基亞碸（dimethylsulfoxide，DMSO）溶液中的pKa」。The so-called pKa in this specification refers to the value obtained by calculating the value of the database based on Hammett’s substituent constants and well-known literature values by using software package 1, as described above. Therefore, it cannot be calculated by this method. In the case of pKa, the value obtained by Gaussian 16 based on DFT (Density Functional Method) is used. In addition, the pKa in this specification refers to the "pKa in an aqueous solution" as described above, and when the pKa in an aqueous solution cannot be calculated, the "pKa in a dimethylsulfoxide (DMSO) solution" is used.

本說明書中，作為鹵素原子，例如可列舉：氟原子、氯原子、溴原子及碘原子。In this specification, as a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned, for example.

[感光化射線性或感放射線性樹脂組成物] 作為本發明的感光化射線性或感放射線性樹脂組成物（以下亦稱為「抗蝕劑組成物」）的特徵點，可列舉：包含選自由後述的化合物（I）～化合物（III）所組成的群組中的一種以上（以下，亦稱為「光酸產生劑B」）作為藉由光化射線或放射線的照射而產生酸的化合物（以下，亦簡稱為「光酸產生劑」）的方面；以及相對於組成物的總質量，抗蝕劑組成物的含水率為1.00質量%以下的方面。[Sensitizing radiation-sensitive or radiation-sensitive resin composition] As the characteristic points of the actinic radiation-sensitive or radiation-sensitive resin composition of the present invention (hereinafter also referred to as "resist composition"), include: One or more of the group consisting of (hereinafter, also referred to as "photoacid generator B") as a compound that generates acid by irradiation with actinic rays or radiation (hereinafter, also referred to as "photoacid generator") With respect to the total mass of the composition, the moisture content of the resist composition is 1.00% by mass or less.

親水性高的光酸產生劑由於親水性高，因此存在凝聚性強的傾向。如專利文獻1中使用的所述通式（I）所表示的光酸產生劑及所述光酸產生劑B般，於分子內含有多價（例如2價）鹽結構的光酸產生劑由於其鹽結構引起的親水性高，因此凝聚性強，若調配於抗蝕劑組成物中，則推測容易以抗蝕劑組成物中微量含有的水分為核而形成聚集體。因此，於將含有所述光酸產生劑且含水率高的抗蝕劑組成物保管規定期間的情況下，於抗蝕劑組成物內產生許多光酸產生劑的凝聚體，其結果，認為使用所述抗蝕劑組成物形成的圖案產生許多缺陷。根據本發明者等人的此次研究明確了，在包含於分子內含有多價鹽結構的光酸產生劑的抗蝕劑組成物中，於相對於組成物的總質量，將抗蝕劑組成物中的含水率設為1.00質量%以下的情況下，可顯著抑制光酸產生劑的凝聚體的形成。即，明確了根據所述抗蝕劑組成物，可形成缺陷抑制能力優異的圖案。A photoacid generator with high hydrophilicity tends to have strong cohesion due to its high hydrophilicity. Like the photoacid generator represented by the general formula (I) and the photoacid generator B used in Patent Document 1, a photoacid generator containing a multivalent (for example, divalent) salt structure in the molecule is due to Its salt structure has high hydrophilicity and therefore strong cohesiveness. If it is blended into a resist composition, it is estimated that a trace amount of moisture contained in the resist composition is likely to be used as a nucleus to form aggregates. Therefore, when a resist composition containing the photoacid generator and having a high water content is stored for a predetermined period of time, many agglomerates of the photoacid generator are generated in the resist composition. As a result, it is considered to be used The pattern formed by the resist composition has many defects. According to the present study by the inventors, it is clear that in a resist composition containing a photoacid generator containing a polyvalent salt structure in the molecule, the resist is composed of a resist composition relative to the total mass of the composition. When the water content in the product is 1.00% by mass or less, the formation of aggregates of the photoacid generator can be significantly suppressed. That is, it was clarified that according to the resist composition, a pattern excellent in defect suppression ability can be formed.

另外，如後所述，關於本發明的抗蝕劑組成物，就可進一步抑制所得的圖案的缺陷的方面而言，相對於組成物的總質量，含水率較佳為0.03質量%以上。如上所述，於分子內含有多價鹽結構的光酸產生劑由於其鹽結構引起的親水性高，因此凝聚性強，有時光酸產生劑彼此亦會凝聚（即、自凝聚）。若相對於組成物的總質量，抗蝕劑組成物的含水率為0.03質量%以上，則亦可抑制光酸產生劑彼此的凝聚，可形成缺陷得到進一步抑制的圖案。尤其是於相對於組成物的總質量，本發明的抗蝕劑組成物的含水率為0.03質量%～0.30質量%的情況下，所形成的圖案的缺陷抑制能力顯著優異。In addition, as described later, the resist composition of the present invention preferably has a moisture content of 0.03% by mass or more with respect to the total mass of the composition in terms of further suppressing defects in the obtained pattern. As described above, the photoacid generator containing a multivalent salt structure in the molecule has high hydrophilicity due to its salt structure, and therefore has strong cohesion. Sometimes the photoacid generators may also aggregate with each other (ie, self-agglomerate). If the moisture content of the resist composition is 0.03% by mass or more with respect to the total mass of the composition, the aggregation of photoacid generators can also be suppressed, and a pattern in which defects can be further suppressed can be formed. In particular, when the moisture content of the resist composition of the present invention is 0.03% by mass to 0.30% by mass relative to the total mass of the composition, the defect suppression ability of the formed pattern is remarkably excellent.

另外，如後所述，作為用於保管本發明的抗蝕劑組成物的收容容器，較佳為與所述抗蝕劑組成物接觸的區域（例如，所述收容容器內的收容抗蝕劑組成物的收容部的內壁及/或抗蝕劑組成物的流路）的材料為樹脂。例如，於收容容器的與抗蝕劑組成物接觸的區域的材料為玻璃的情況下，由於玻璃的親水性高，因此抗蝕劑組成物中含有的水分容易附著在玻璃的表面。於分子內含有多價鹽結構的光酸產生劑由於其鹽結構引起的親水性高，因此凝聚性強，容易以附著在玻璃表面的水分為核而形成凝聚體。相對於此，於收容容器的與抗蝕劑組成物接觸的區域的材料為樹脂（較佳為選自由聚烯烴樹脂及含氟原子的聚烯烴樹脂所組成的群組中的一種以上的樹脂）的情況下，水分在所述區域中的附著得到抑制，光酸產生劑難以形成凝聚體，可形成缺陷得到進一步抑制的圖案。In addition, as will be described later, as a storage container for storing the resist composition of the present invention, an area in contact with the resist composition (for example, the storage resist in the storage container The material of the inner wall of the accommodating part of the composition and/or the flow path of the resist composition) is resin. For example, when the material of the region in contact with the resist composition of the storage container is glass, since the glass is highly hydrophilic, the moisture contained in the resist composition tends to adhere to the surface of the glass. A photoacid generator containing a polyvalent salt structure in its molecule has high hydrophilicity due to its salt structure, and therefore has strong cohesion, and is likely to form agglomerates with water attached to the glass surface as a nucleus. On the other hand, the material in the area in contact with the resist composition of the storage container is a resin (preferably one or more resins selected from the group consisting of polyolefin resins and polyolefin resins containing fluorine atoms) In the case of, the adhesion of moisture in the region is suppressed, the photoacid generator is unlikely to form agglomerates, and it is possible to form a pattern in which defects are further suppressed.

以下，對本發明的抗蝕劑組成物進行詳細說明。本發明的抗蝕劑組成物為正型的抗蝕劑組成物，亦可為負型的抗蝕劑組成物。另外，可為鹼顯影用抗蝕劑組成物，亦可為有機溶劑顯影用抗蝕劑組成物。本發明的抗蝕劑組成物典型而言為化學增幅型抗蝕劑組成物。Hereinafter, the resist composition of the present invention will be described in detail. The resist composition of the present invention is a positive type resist composition, and may also be a negative type resist composition. In addition, it may be a resist composition for alkali development or a resist composition for organic solvent development. The resist composition of the present invention is typically a chemically amplified resist composition.

[含水率] 相對於組成物的總質量，本發明的抗蝕劑組成物的含水率為1.00質量%以下，較佳為0.50質量%以下，更佳為0.30質量%以下。例如相對於組成物的總質量，下限值為0.00質量%以上，就所形成的圖案的缺陷得到進一步抑制的方面而言，較佳為0.01質量%以上，更佳為0.03質量%以上。再者，含水率可藉由卡爾費歇爾水分計（例如京都電子工業股份有限公司製造的MKC-510N）測定。[Water content] With respect to the total mass of the composition, the moisture content of the resist composition of the present invention is 1.00 mass% or less, preferably 0.50 mass% or less, and more preferably 0.30 mass% or less. For example, with respect to the total mass of the composition, the lower limit is 0.00% by mass or more. In terms of further suppressing defects in the formed pattern, it is preferably 0.01% by mass or more, and more preferably 0.03% by mass or more. Furthermore, the moisture content can be measured with a Karl Fischer moisture meter (for example, MKC-510N manufactured by Kyoto Electronics Industry Co., Ltd.).

進而，就所形成的圖案的缺陷得到進一步抑制的方面而言，本發明的抗蝕劑組成物較佳為下述式（1X）所表示的量比T為1.0～1600.0，更佳為2.0～1000.0，進而佳為4.0～500.0。式（1X）：量比T=選自由化合物（I）～化合物（III）所組成的群組中的化合物（光酸產生劑B）相對於組成物中的固體成分量的含有率（質量%）/相對於組成物的總質量的含水率（質量%）Furthermore, in terms of further suppressing the defects of the formed pattern, the resist composition of the present invention preferably has an amount ratio T represented by the following formula (1X) of 1.0 to 1600.0, more preferably 2.0 to 1000.0, more preferably 4.0-500.0. Formula (1X): Amount ratio T=The content (mass%) of a compound (photoacid generator B) selected from the group consisting of compound (I) to compound (III) with respect to the solid content in the composition )/Water content relative to the total mass of the composition (mass%)

以下，對本發明的抗蝕劑組成物的各種成分進行詳述。 [光酸產生劑] 以下，首先對藉由光化射線或放射線的照射而產生酸的化合物（光酸產生劑）進行說明。本發明的抗蝕劑組成物中，相對於組成物的總固體成分，光酸產生劑的含量（於含有多種時為其合計含量）較佳為0.1質量%～45.0質量%，更佳為2.0質量%～40.0質量%，進而佳為4.0質量%～30.0質量%。再者，所謂「固體成分」是指形成抗蝕劑膜的成分，不含溶劑。另外，只要是形成抗蝕劑膜的成分，即使其性狀為液體狀，亦視為固體成分。Hereinafter, various components of the resist composition of the present invention will be described in detail. [Photo Acid Generator] Hereinafter, first, a compound (photoacid generator) that generates an acid by irradiation with actinic rays or radiation will be described. In the resist composition of the present invention, relative to the total solid content of the composition, the content of the photoacid generator (the total content when containing multiple types) is preferably 0.1% by mass to 45.0% by mass, more preferably 2.0 Mass% to 40.0% by mass, more preferably 4.0% to 30.0% by mass. In addition, the term "solid content" refers to a component that forms a resist film, and does not contain a solvent. In addition, as long as it is a component that forms a resist film, even if its properties are liquid, it is regarded as a solid component.

所述光酸產生劑含有一種以上選自由後述的化合物（I）～（III）所組成的群組中的化合物（光酸產生劑B）。相對於組成物的總固體成分，所述光酸產生劑B的含量較佳為0.1質量%～45.0質量%，更佳為2.0質量%～40.0質量%，進而佳為4.0質量%～30.0質量%。所述光酸產生劑B可單獨使用一種，亦可使用兩種以上。於使用兩種以上的情況下，其合計含量較佳為在所述較佳含量的範圍內。The photoacid generator contains one or more compounds (photoacid generator B) selected from the group consisting of compounds (I) to (III) described later. Relative to the total solid content of the composition, the content of the photo acid generator B is preferably 0.1% by mass to 45.0% by mass, more preferably 2.0% by mass to 40.0% by mass, and still more preferably 4.0% by mass to 30.0% by mass . The photoacid generator B may be used singly, or two or more may be used. When two or more types are used, the total content is preferably within the range of the preferred content.

另外，本發明的抗蝕劑組成物亦可包含所述光酸產生劑B以外的其他光酸產生劑（以下，亦稱為「光酸產生劑C」）。作為所述光酸產生劑C，並無特別限制，就所形成的圖案的線寬粗糙度（Line Width Roughness，LWR）性能更優異的方面而言，較佳為選自由後述的通式（1）所表示的化合物及後述的通式（2）所表示的化合物所組成的群組中的化合物。相對於組成物的總固體成分，所述光酸產生劑C的含量較佳為0.1質量%～20.0質量%，更佳為0.1質量%～15.0質量%，進而佳為0.1質量%～12.0質量%，尤佳為0.1質量%～8.0質量%。所述光酸產生劑C可單獨使用一種，亦可使用兩種以上。於使用兩種以上的情況下，其合計含量較佳為在所述較佳含量的範圍內。In addition, the resist composition of the present invention may include other photoacid generators other than the photoacid generator B (hereinafter also referred to as "photoacid generator C"). The photoacid generator C is not particularly limited. In terms of the line width roughness (Line Width Roughness, LWR) performance of the formed pattern, it is preferably selected from the general formula (1 A compound in the group consisting of the compound represented by and the compound represented by the general formula (2) described later. Relative to the total solid content of the composition, the content of the photoacid generator C is preferably 0.1% by mass to 20.0% by mass, more preferably 0.1% by mass to 15.0% by mass, and still more preferably 0.1% by mass to 12.0% by mass , Particularly preferably 0.1% by mass to 8.0% by mass. The photoacid generator C may be used singly, or two or more may be used. When two or more types are used, the total content is preferably within the range of the preferred content.

以下，對光酸產生劑B及光酸產生劑C分別進行說明。Hereinafter, the photoacid generator B and the photoacid generator C are respectively demonstrated.

＜光酸產生劑B＞光酸產生劑B是選自由下述化合物（I）～（III）所組成的群組中的化合物。＜Photoacid generator B＞ The photoacid generator B is a compound selected from the group consisting of the following compounds (I) to (III).

由包含光酸產生劑B的抗蝕劑組成物形成的圖案的LWR性能優異。所述光酸產生劑B於一分子中包含具有相當於光酸產生劑的功能的結構部位X、以及具有相當於酸擴散控制劑的功能的結構部位（結構部位Y或結構部位Z）此兩者，因此於抗蝕劑膜中可使所述結構部位的各自的存在比率固定。其結果，於抗蝕劑膜中可使光酸產生劑與酸擴散控制劑的濃度分佈均勻，因此曝光時酸的量及擴散容易變得均勻，顯影後所得的圖案的寬度容易穩定。即，所形成的圖案的LWR性能優異。以下，對化合物（I）～（III）分別進行說明。The pattern formed from the resist composition containing the photoacid generator B has excellent LWR performance. The photoacid generator B includes a structural part X having a function equivalent to a photoacid generator and a structural part (structural part Y or structural part Z) having a function equivalent to an acid diffusion control agent in one molecule. Therefore, the respective abundance ratios of the structural parts can be fixed in the resist film. As a result, the concentration distribution of the photoacid generator and the acid diffusion control agent can be made uniform in the resist film. Therefore, the amount and diffusion of the acid during exposure are easily uniform, and the width of the pattern obtained after development is easily stabilized. That is, the LWR performance of the formed pattern is excellent. Hereinafter, the compounds (I) to (III) will be described respectively.

（化合物（I））以下，對化合物（I）進行說明。化合物（I）：分別具有一個下述結構部位X與下述結構部位Y且藉由光化射線或放射線的照射而產生酸的化合物，所述酸包含源自下述結構部位X的下述第一酸性部位與源自下述結構部位Y的下述第二酸性部位結構部位X：包含陰離子部位A₁ ^- 與陽離子部位M₁ ⁺ 且藉由光化射線或放射線的照射而形成HA₁ 所表示的第一酸性部位的結構部位結構部位Y：包含陰離子部位A₂ ^- 與陽離子部位M₂ ⁺ 且藉由光化射線或放射線的照射而形成與所述結構部位X中形成的所述第一酸性部位的結構不同的HA₂ 所表示的第二酸性部位的結構部位其中，化合物（I）滿足下述條件I。條件I：所述化合物（I）中，將所述結構部位X中的所述陽離子部位M₁ ⁺ 及所述結構部位Y中的所述陽離子部位M₂ ⁺ 取代為H⁺ 而成的化合物PI具有源自將所述結構部位X中的所述陽離子部位M₁ ⁺ 取代為H⁺ 而成的HA₁ 所表示的酸性部位的酸解離常數a1、以及源自將所述結構部位Y中的所述陽離子部位M₂ ⁺ 取代為H⁺ 而成的HA₂ 所表示的酸性部位的酸解離常數a2，且所述酸解離常數a2大於所述酸解離常數a1。再者，酸解離常數a1及酸解離常數a2可藉由所述方法求出。若更具體地說明，則化合物PI的酸解離常數a1及酸解離常數a2是於求出化合物PI的酸解離常數的情況下，化合物PI（化合物PI相當於「具有HA₁ 與HA₂ 的化合物」）為「具有A₁ ^- 與HA₂ 的化合物」時的pKa是酸解離常數a1，所述「具有A₁ ^- 與HA₂ 的化合物」為「具有A₁ ^- 與A₂ ^- 的化合物」時的pKa是酸解離常數a2。另外，所述化合物PI相當於藉由對化合物（I）照射光化射線或放射線而產生的酸。(Compound (I)) Hereinafter, the compound (I) will be described. Compound (I): A compound having one of the following structural site X and the following structural site Y, respectively, and generating an acid by irradiation of actinic rays or radiation, the acid including the following first derived from the following structural site X An acidic site and the following second acidic site derived from the following structural site Y. The structural site X includes an anion site A ₁ ^- and a cation site M ₁ ^+, and is represented _{by the formation of HA 1} by irradiation with actinic rays or radiation The structural part of the first acidic part of the structural part Y: includes the anion part A ₂ ^- and the cationic part M ₂ ⁺ and is formed by the irradiation of actinic rays or radiation to form the first acidic acid formed in the structural part X Among the structural sites of the second acidic site represented by HA _{2 with} different site structures, the compound (I) satisfies the following condition I. Condition I: The compound (I) in the cationic portion of the cation site in the structural site X and M ₁ ⁺ Y in the structural site M ₂ ⁺ H ⁺ PI-substituted compound obtained by It has an acid dissociation constant a1 derived from the acidic site represented by _{HA 1} formed by _{substituting the cationic site M 1} ⁺ with H ^{+ in} the structural site X, and the acid dissociation constant a1 derived from the structural site Y. The acid dissociation constant a2 of the acidic site represented by HA ₂ formed by replacing the cationic site M ₂ ⁺ ^{with H +} , and the acid dissociation constant a2 is greater than the acid dissociation constant a1. Furthermore, the acid dissociation constant a1 and the acid dissociation constant a2 can be obtained by the method described above. To be more specific, the acid dissociation constant a1 and the acid dissociation constant a2 of the compound PI are obtained when the acid dissociation constant of the compound PI is calculated, and the compound PI (compound PI is equivalent to "a compound having HA ₁ and HA ₂ " ) Is the " _{compound with A 1} ^- and HA ₂ " when the pKa is the acid dissociation constant a1, and the " _{compound with A 1} ^- and HA ₂ " is "compound with A ₁ ^- and A ₂ ^- " pKa is the acid dissociation constant a2. In addition, the compound PI corresponds to an acid generated by irradiating the compound (I) with actinic rays or radiation.

就所形成的圖案的LWR性能更優異的方面而言，所述化合物PI中，酸解離常數a1與所述酸解離常數a2的差較佳為2.0以上，更佳為3.0以上。再者，酸解離常數a1與所述酸解離常數a2的差的上限值並無特別限制，例如為15.0以下。As far as the LWR performance of the formed pattern is more excellent, in the compound PI, the difference between the acid dissociation constant a1 and the acid dissociation constant a2 is preferably 2.0 or more, more preferably 3.0 or more. In addition, the upper limit of the difference between the acid dissociation constant a1 and the acid dissociation constant a2 is not particularly limited, and is, for example, 15.0 or less.

另外，所述化合物PI中，酸解離常數a2例如為6.5以下，就抗蝕劑組成物內的化合物（I）的陽離子部位的穩定性更優異的方面而言，較佳為2.0以下，更佳為1.0以下。再者，作為酸解離常數a2的下限值，例如為-3.5以上，較佳為-2.0以上。In addition, in the compound PI, the acid dissociation constant a2 is, for example, 6.5 or less, and in terms of more excellent stability of the cation site of the compound (I) in the resist composition, it is preferably 2.0 or less, more preferably It is 1.0 or less. In addition, the lower limit of the acid dissociation constant a2 is, for example, -3.5 or more, and preferably -2.0 or more.

另外，就所形成的圖案的LWR性能更優異的方面而言，所述化合物PI中，酸解離常數a1較佳為2.0以下，更佳為0.5以下，進而佳為-0.1以下。再者，作為酸解離常數a1的下限值，較佳為-15.0以上。In addition, in terms of more excellent LWR performance of the formed pattern, in the compound PI, the acid dissociation constant a1 is preferably 2.0 or less, more preferably 0.5 or less, and even more preferably -0.1 or less. Furthermore, the lower limit of the acid dissociation constant a1 is preferably -15.0 or more.

作為化合物（I），並無特別限制，例如可列舉下述通式（Ia）所表示的化合物。 M₁₁ ⁺ A₁₁ ^- -L₁ -A₁₂ ^- M₁₂ ⁺ （Ia）The compound (I) is not particularly limited, and examples thereof include compounds represented by the following general formula (Ia). M ₁₁ ⁺ A ₁₁ ^-- L ₁ -A ₁₂ ^- M ₁₂ ⁺ (Ia)

通式（Ia）中，「M₁₁ ⁺ A₁₁ ^- 」及「A₁₂ ^- M₁₂ ⁺ 」分別相當於結構部位X及結構部位Y。化合物（Ia）藉由光化射線或放射線的照射而產生HA₁₁ -L₁ -A₂₁ H所表示的酸。即，「M₁₁ ⁺ A₁₁ ^- 」形成HA₁₁ 所表示的第一酸性部位，「A₁₂ ^- M₁₂ ⁺ 」形成與所述第一酸性部位的結構不同的HA₁₂ 所表示的第二酸性部位。In the general formula (Ia), "M _₁₁ ⁺ A ₁₁ ^-" and "A _₁₂ ^- M ₁₂ ^+" correspond to the structure and the structural site site X Y. The compound (Ia) generates an acid represented by _{HA 11} -L ₁ -A _{21 H by irradiation with actinic rays or radiation.} That is, "M _₁₁ ⁺ A ₁₁ ^-" HA ₁₁ is formed a first acid sites represented by "A _₁₂ ^- M ₁₂ ^+" acid sites forming a second structure of the first portion of the acidic HA ₁₂ different expressed .

通式（Ia）中，M₁₁ ⁺ 及M₁₂ ⁺ 分別獨立地表示有機陽離子。 A₁₁ ^- 及A₁₂ ^- 分別獨立地表示陰離子性官能基。其中，A₁₂ ^- 表示與A₁₁ ^- 所表示的陰離子性官能基不同的結構。 L₁ 表示二價連結基。其中，所述通式（Ia）中，於將M₁₁ ⁺ 及M₁₂ ⁺ 所表示的有機陽離子取代為H⁺ 而成的化合物PIa（HA₁₁ -L₁ -A₁₂ H）中，源自A₁₂ H所表示的酸性部位的酸解離常數a2大於源自HA₁₁ 所表示的酸性部位的酸解離常數a1。再者，酸解離常數a1與酸解離常數a2的較佳值如上所述。In the general formula (Ia), M ₁₁ ⁺ and M ₁₂ ⁺ each independently represent an organic cation. A ₁₁ ^- and A ₁₂ ^- each independently represent an anionic functional group. Here, A ₁₂ ^- represents a structure different from the anionic functional group represented by _{A 11} ^-. L ₁ represents a divalent linking group. Wherein, in the general formula (Ia), in the compound PIa (HA ₁₁ -L ₁ -A ₁₂ H) obtained by substituting organic cations represented by _{M 11} ⁺ and M ₁₂ ⁺ ^{with H +} , it is derived from A The acid dissociation constant a2 of the acidic site represented by ₁₂ H is greater than the acid dissociation constant a1 derived from the acidic site represented by _{HA 11.} Furthermore, the preferable values of the acid dissociation constant a1 and the acid dissociation constant a2 are as described above.

通式（Ia）中，M₁₁ ⁺ 及M₁₂ ⁺ 所表示的有機陽離子如後所述。In the general formula (Ia), the organic cations represented by _{M 11} ⁺ and M ₁₂ ^{+ are as described later.}

作為A₁₁ ^- 及A₁₂ ^- 所表示的陰離子性官能基，例如可列舉下述通式（B-1）～通式（B-13）所表示的基。Examples of the anionic functional group represented by A ₁₁ ^- and A ₁₂ ^- include groups represented by the following general formulas (B-1) to (B-13).

[化2]

[化2]

通式（B-1）、（B-2）、（B-4）、（B-5）及（B-12）中，R^X1 表示取代基。作為R^X1 ，較佳為直鏈狀、支鏈狀或環狀的烷基。所述烷基的碳數較佳為1～15，更佳為1～10。所述烷基亦可具有取代基。作為取代基，較佳為氟原子或氰基。於所述烷基具有氟原子作為取代基的情況下，亦可為全氟烷基。另外，所述烷基的碳原子亦可經羰基取代。In the general formulas (B-1), (B-2), (B-4), (B-5), and (B-12), R ^X1 represents a substituent. R ^{X1 is} preferably a linear, branched or cyclic alkyl group. The carbon number of the alkyl group is preferably 1-15, more preferably 1-10. The alkyl group may have a substituent. As the substituent, a fluorine atom or a cyano group is preferred. When the alkyl group has a fluorine atom as a substituent, it may be a perfluoroalkyl group. In addition, the carbon atoms of the alkyl group may be substituted with a carbonyl group.

通式（B-3）中，R^X4 表示取代基。作為R^X4 ，較佳為直鏈狀、支鏈狀或環狀的烷基。所述烷基的碳數較佳為1～15，更佳為1～10。所述烷基亦可具有取代基。作為取代基，較佳為氟原子或氰基。再者，於R^X4 為具有氟原子作為取代基的烷基的情況下，較佳為並非為全氟烷基。另外，所述烷基的碳原子亦可經羰基取代。In the general formula (B-3), R ^X4 represents a substituent. R ^{X4 is} preferably a linear, branched or cyclic alkyl group. The carbon number of the alkyl group is preferably 1-15, more preferably 1-10. The alkyl group may have a substituent. As the substituent, a fluorine atom or a cyano group is preferred. Furthermore, when R ^X4 is an alkyl group having a fluorine atom as a substituent, it is preferably not a perfluoroalkyl group. In addition, the carbon atoms of the alkyl group may be substituted with a carbonyl group.

通式（B-7）及（B-11）中，R^X2 表示氫原子、或氟原子及全氟烷基以外的取代基。作為R^X2 所表示的氟原子及全氟烷基以外的取代基，較佳為直鏈狀、支鏈狀或環狀的烷基。所述烷基的碳數較佳為1～15，更佳為1～10。所述烷基亦可具有氟原子以外的取代基。In the general formulas (B-7) and (B-11), R ^X2 represents a substituent other than a hydrogen atom, or a fluorine atom and a perfluoroalkyl group. The substituents other than the fluorine atom and perfluoroalkyl group represented by R ^{X2 are preferably a linear, branched or cyclic alkyl group.} The carbon number of the alkyl group is preferably 1-15, more preferably 1-10. The alkyl group may have a substituent other than a fluorine atom.

通式（B-8）中，R^XF1 表示氫原子、氟原子或全氟烷基。其中，多個R^XF1 中的至少一個表示氟原子或全氟烷基。 R^XF1 所表示的全氟烷基的碳數較佳為1～15，更佳為1～10，進而佳為1～6。In the general formula (B-8), R ^XF1 represents a hydrogen atom, a fluorine atom, or a perfluoroalkyl group. Here, at least one of the plurality of R ^XF1 represents a fluorine atom or a perfluoroalkyl group. The carbon number of the perfluoroalkyl group represented by R ^XF1 is preferably 1-15, more preferably 1-10, and still more preferably 1-6.

通式（B-10）中，R^XF2 表示氟原子或全氟烷基。 R^XF2 所表示的全氟烷基的碳數較佳為1～15，更佳為1～10，進而佳為1～6。In the general formula (B-10), R ^XF2 represents a fluorine atom or a perfluoroalkyl group. The carbon number of the perfluoroalkyl group represented by R ^XF2 is preferably 1-15, more preferably 1-10, and still more preferably 1-6.

通式（B-9）中，n表示0～4的整數。In general formula (B-9), n represents an integer of 0-4.

作為A₁₁ ^- 及A₁₂ ^- 所表示的陰離子性官能基的組合，並無特別限制，例如於A₁₁ ^- 為通式（B-8）或（B-10）所表示的基的情況下，作為A₁₂ ^- 所表示的陰離子性官能基，可列舉通式（B-1）～（B-7）、（B-9）或（B-11）～（B-13）所表示的基，於A₁₁ ^- 為通式（B-7）所表示的基的情況下，作為A₁₂ ^- 所表示的陰離子性官能基，可列舉通式（B-6）所表示的基。The combination of anionic functional groups represented by A ₁₁ ^- and A ₁₂ ^- is not particularly limited. For example, when A ₁₁ ^- is a group represented by general formula (B-8) or (B-10), Examples of the anionic functional group represented by A ₁₂ ^- include groups represented by general formulas (B-1) to (B-7), (B-9), or (B-11) to (B-13), When A ₁₁ ^- is a group represented by general formula (B-7), _{the anionic functional group represented by A 12} ^- includes a group represented by general formula (B-6).

通式（Ia）中，作為L₁ 所表示的二價連結基，並無特別限制，可列舉-CO-、-NR-、-CO-、-O-、伸烷基（較佳為碳數1～6。可為直鏈狀亦可為支鏈狀）、伸環烷基（較佳為碳數3～15）、伸烯基（較佳為碳數2～6）、二價脂肪族雜環基（較佳為於環結構內具有至少一個N原子、O原子、S原子或Se原子的5員環～10員環，更佳為5員環～7員環，進而佳為5員環～6員環）、以及將該些的多個組合而成的二價連結基等。所述R可列舉氫原子或一價取代基。作為一價取代基，並無特別限制，例如較佳為烷基（較佳為碳數1～6）。該些二價連結基亦可進而包含選自由-S-、-SO-及-SO₂ -所組成的群組中的基。另外，所述伸烷基、所述伸環烷基、所述伸烯基及所述二價脂肪族雜環基亦可經取代基取代。作為取代基，例如可列舉鹵素原子（較佳為氟原子）。In the general formula (Ia), the _{divalent linking group represented by L 1} is not particularly limited, and examples include -CO-, -NR-, -CO-, -O-, alkylene groups (preferably carbon number 1 to 6. It can be linear or branched), cycloalkylene (preferably carbon number 3-15), alkenylene group (preferably carbon number 2-6), divalent aliphatic Heterocyclic group (preferably a 5-membered ring to 10-membered ring having at least one N atom, O atom, S atom or Se atom in the ring structure, more preferably 5-membered ring to 7-membered ring, and more preferably 5-membered ring Ring to 6-membered ring), and a divalent linking group formed by combining a plurality of these. The R can be a hydrogen atom or a monovalent substituent. The monovalent substituent is not particularly limited, and for example, an alkyl group (preferably carbon number 1 to 6) is preferred. These divalent linking groups may further include groups selected from the group consisting of -S-, -SO-, and -SO ₂ -. In addition, the alkylene group, the cycloalkylene group, the alkenylene group, and the divalent aliphatic heterocyclic group may be substituted with a substituent. Examples of the substituent include a halogen atom (preferably a fluorine atom).

通式（Ia）中，對M₁₁ ⁺ 及M₁₂ ⁺ 所表示的有機陽離子的較佳的形態進行詳述。 M₁₁ ⁺ 及M₁₂ ⁺ 所表示的有機陽離子分別獨立地較佳為通式（ZaI）所表示的有機陽離子（陽離子（ZaI））或通式（ZaII）所表示的有機陽離子（陽離子（ZaII））。In the general formula (Ia), preferred forms of organic cations represented by _{M 11} ⁺ and M ₁₂ ^{+ will be described in detail.} The organic cations represented by M ₁₁ ⁺ and M ₁₂ ⁺ are each independently preferably an organic cation represented by the general formula (ZaI) (cation (ZaI)) or an organic cation represented by the general formula (ZaII) (cation (ZaII)) ).

[化3]

[化3]

所述通式（ZaI）中， R²⁰¹ 、R²⁰² 及R²⁰³ 分別獨立地表示有機基。作為R²⁰¹ 、R²⁰² 及R²⁰³ 的有機基的碳數通常為1～30，較佳為1～20。另外，R²⁰¹ ～R²⁰³ 中的兩個可鍵結而形成環結構，環內可含有氧原子、硫原子、酯基、醯胺基或羰基。作為R²⁰¹ ～R²⁰³ 中的兩個鍵結而形成的基，例如可列舉伸烷基（例如伸丁基及伸戊基）及-CH₂ -CH₂ -O-CH₂ -CH₂ -。In the general formula (ZaI), R ²⁰¹ , R ²⁰² and R ²⁰³ each independently represent an organic group. The carbon number of the organic group as R ²⁰¹ , R ²⁰² and R ^{203 is usually 1-30, preferably 1-20.} In addition, two of R ²⁰¹ to R ²⁰³ may be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester group, an amido group, or a carbonyl group. Examples of the group formed by bonding two of R ²⁰¹ to R ²⁰³ include an alkylene group (for example, a butylene group and a pentylene group) and -CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -.

作為通式（ZaI）中的有機陽離子的較佳的形態，可列舉後述的陽離子（ZaI-1）、陽離子（ZaI-2）、通式（ZaI-3b）所表示的有機陽離子（陽離子（ZaI-3b））、以及通式（ZaI-4b）所表示的有機陽離子（陽離子（ZaI-4b））。As a preferable form of the organic cation in the general formula (ZaI), the cation (ZaI-1), the cation (ZaI-2), and the organic cation represented by the general formula (ZaI-3b) (the cation (ZaI) -3b)), and an organic cation (cation (ZaI-4b)) represented by the general formula (ZaI-4b).

首先，對陽離子（ZaI-1）進行說明。陽離子（ZaI-1）是所述通式（ZaI）的R²⁰¹ ～R²⁰³ 中的至少一個為芳基的芳基鋶陽離子。芳基鋶陽離子可為R²⁰¹ ～R²⁰³ 全部為芳基，亦可為R²⁰¹ ～R²⁰³ 的一部分為芳基，剩餘為烷基或環烷基。另外，R²⁰¹ ～R²⁰³ 中的一個為芳基，R²⁰¹ ～R²⁰³ 中的剩餘兩個可鍵結而形成環結構，環內亦可含有氧原子、硫原子、酯基、醯胺基或羰基。作為R²⁰¹ ～R²⁰³ 中的兩個鍵結而形成的基，例如可列舉一個以上的亞甲基可經氧原子、硫原子、酯基、醯胺基及/或羰基取代而成的伸烷基（例如伸丁基、伸戊基或-CH₂ -CH₂ -O-CH₂ -CH₂ -）。作為芳基鋶陽離子，例如可列舉：三芳基鋶陽離子、二芳基烷基鋶陽離子、芳基二烷基鋶陽離子、二芳基環烷基鋶陽離子及芳基二環烷基鋶陽離子。First, the cation (ZaI-1) will be described. The cation (ZaI-1) is an aryl cation in which at least one ^{of R 201} to R ^{203 of the general formula (ZaI) is an aryl group.} The aryl sulfonium cation may be that all of R ²⁰¹ to R ²⁰³ are aryl groups, or part of R ²⁰¹ to R ²⁰³ may be aryl groups, and the remainder may be alkyl groups or cycloalkyl groups. In addition, one of R ²⁰¹ to R ²⁰³ is an aryl group, ^{and the remaining two of R 201} to R ²⁰³ may be bonded to form a ring structure. The ring may also contain oxygen atoms, sulfur atoms, ester groups, amide groups or Carbonyl. Examples of groups formed by bonding two of R ²⁰¹ to R ²⁰³ include alkylene groups in which one or more methylene groups may be substituted with oxygen atoms, sulfur atoms, ester groups, amide groups, and/or carbonyl groups. Group (for example, butylene, pentylene or -CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -). Examples of the aryl sulfonium cation include triaryl sulfonium cation, diaryl alkyl sulfonium cation, aryl dialkyl sulfonium cation, diaryl cycloalkyl sulfonium cation, and aryl dicycloalkyl sulfonium cation.

作為芳基鋶陽離子中所含的芳基，較佳為苯基或萘基，更佳為苯基。芳基可為含有具有氧原子、氮原子或硫原子等的雜環結構的芳基。作為雜環結構，可列舉吡咯殘基、呋喃殘基、噻吩殘基、吲哚殘基、苯並呋喃殘基及苯並噻吩殘基等。於芳基鋶陽離子具有兩個以上的芳基的情況下，具有的兩個以上的芳基可相同亦可不同。芳基鋶陽離子視需要具有的烷基或環烷基較佳為碳數1～15的直鏈狀烷基、碳數3～15的支鏈狀烷基或碳數3～15的環烷基，例如可列舉甲基、乙基、丙基、正丁基、第二丁基、第三丁基、環丙基、環丁基及環己基等。The aryl group contained in the aryl alumium cation is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. The aryl group may be an aryl group containing a heterocyclic structure having an oxygen atom, a nitrogen atom, a sulfur atom, or the like. Examples of the heterocyclic structure include pyrrole residues, furan residues, thiophene residues, indole residues, benzofuran residues, and benzothiophene residues. When the aryl alumium cation has two or more aryl groups, the two or more aryl groups it has may be the same or different. The alkyl group or cycloalkyl group that the aryl cation has as necessary is preferably a linear alkyl group having 1 to 15 carbon atoms, a branched chain alkyl group having 3 to 15 carbon atoms, or a cycloalkyl group having 3 to 15 carbon atoms For example, methyl, ethyl, propyl, n-butyl, second butyl, tertiary butyl, cyclopropyl, cyclobutyl, cyclohexyl, etc. can be mentioned.

作為R²⁰¹ ～R²⁰³ 的芳基、烷基及環烷基可具有的取代基，可分別獨立地列舉：烷基（例如碳數1～15）、環烷基（例如碳數3～15）、芳基（例如碳數6～14）、烷氧基（例如碳數1～15）、環烷基烷氧基（例如碳數1～15）、鹵素原子、羥基及苯硫基。所述取代基可在可能的情況下進而具有取代基，例如，所述烷基可具有鹵素原子作為取代基，成為三氟甲基等鹵化烷基。As ^{substituents that the aryl group, alkyl group, and cycloalkyl group of R 201} to R ²⁰³ may have, each independently includes an alkyl group (for example, carbon number of 1-15) and cycloalkyl group (for example, carbon number of 3-15) , Aryl (for example, carbon number 6-14), alkoxy (for example, carbon number 1-15), cycloalkylalkoxy (for example, carbon number 1-15), halogen atom, hydroxyl group and thiophenyl group. The substituent may further have a substituent when possible. For example, the alkyl group may have a halogen atom as a substituent to become a halogenated alkyl group such as a trifluoromethyl group.

其次，對陽離子（ZaI-2）進行說明。陽離子（ZaI-2）是式（ZaI）中的R²⁰¹ ～R²⁰³ 分別獨立地表示不具有芳香環的有機基的陽離子。此處，所謂芳香環，亦包含含有雜原子的芳香族環。作為R²⁰¹ ～R²⁰³ 的不具有芳香環的有機基通常為碳數1～30，較佳為碳數1～20。 R²⁰¹ ～R²⁰³ 分別獨立地較佳為烷基、環烷基、烯丙基或乙烯基（vinyl group），更佳為直鏈狀或支鏈狀的2-氧代烷基、2-氧代環烷基或烷氧基羰基甲基，進而佳為直鏈狀或支鏈狀的2-氧代烷基。Next, the cation (ZaI-2) will be described. The cation (ZaI-2) is a cation in which R ²⁰¹ to R ²⁰³ in the formula (ZaI) each independently represent an organic group without an aromatic ring. Here, the term "aromatic ring" also includes aromatic rings containing heteroatoms. The organic group having no aromatic ring as R ²⁰¹ to R ²⁰³ usually has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms. R ²⁰¹ to R ²⁰³ are each independently preferably an alkyl group, a cycloalkyl group, an allyl group, or a vinyl group, and more preferably a linear or branched 2-oxoalkyl group and a 2-oxygen group. Substituted cycloalkyl or alkoxycarbonylmethyl is more preferably linear or branched 2-oxoalkyl.

作為R²⁰¹ ～R²⁰³ 的烷基及環烷基，例如可列舉碳數1～10的直鏈狀烷基或碳數3～10的支鏈狀烷基（例如甲基、乙基、丙基、丁基及戊基）、以及碳數3～10的環烷基（例如環戊基、環己基及降冰片基）。 R²⁰¹ ～R²⁰³ 亦可經鹵素原子、烷氧基（例如碳數1～5）、羥基、氰基或硝基進一步進行取代。Examples of the alkyl group and cycloalkyl group of R ²⁰¹ to R ²⁰³ include a linear alkyl group having 1 to 10 carbon atoms or a branched chain alkyl group having 3 to 10 carbon atoms (e.g., methyl, ethyl, propyl , Butyl and pentyl), and cycloalkyl groups with 3 to 10 carbon atoms (such as cyclopentyl, cyclohexyl and norbornyl). R ²⁰¹ to R ²⁰³ may be further substituted with a halogen atom, an alkoxy group (for example, a carbon number of 1 to 5), a hydroxyl group, a cyano group, or a nitro group.

其次，對陽離子（ZaI-3b）進行說明。陽離子（ZaI-3b）是下述通式（ZaI-3b）所表示的陽離子。Next, the cation (ZaI-3b) will be described. The cation (ZaI-3b) is a cation represented by the following general formula (ZaI-3b).

[化4]

[化4]

通式（ZaI-3b）中， R_1c ～R_5c 分別獨立地表示氫原子、烷基、環烷基、芳基、烷氧基、芳氧基、烷氧基羰基、烷基羰氧基、環烷基羰氧基、鹵素原子、羥基、硝基、烷硫基或芳硫基。 R_6c 及R_7c 分別獨立地表示氫原子、烷基（第三丁基等）、環烷基、鹵素原子、氰基或芳基。 R_x 及R_y 分別獨立地表示烷基、環烷基、2-氧代烷基、2-氧代環烷基、烷氧基羰基烷基、烯丙基或乙烯基。In the general formula (ZaI-3b), R _1c to R _5c each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group, Cycloalkylcarbonyloxy group, halogen atom, hydroxyl group, nitro group, alkylthio group or arylthio group. R _6c and R _7c each independently represent a hydrogen atom, an alkyl group (tertiary butyl group, etc.), a cycloalkyl group, a halogen atom, a cyano group, or an aryl group. R _x and R _y each independently represent an alkyl group, a cycloalkyl group, a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonylalkyl group, an allyl group, or a vinyl group.

R_1c ～R_5c 中的任意兩個以上、R_5c 與R_6c 、R_6c 與R_7c 、R_5c 與R_x 以及R_x 與R_y 可分別鍵結而形成環，該環亦可分別獨立地包含氧原子、硫原子、酮基、酯鍵或醯胺鍵。作為所述環，可列舉芳香族或非芳香族的烴環、芳香族或非芳香族的雜環、以及將該些環組合兩個以上而成的多環稠環。作為環，可列舉3員環～10員環，較佳為4員環～8員環，更佳為5員環或6員環。Any two or more of R _1c to R _5c _{, R 5c} and R _6c , R _6c and R _7c , R _5c and R _x, and R _x and R _y may be bonded respectively to form a ring, and the ring may also be independently Contains oxygen atom, sulfur atom, ketone group, ester bond or amide bond. Examples of the ring include an aromatic or non-aromatic hydrocarbon ring, an aromatic or non-aromatic heterocyclic ring, and a polycyclic condensed ring formed by combining two or more of these rings. Examples of the ring include a 3-membered ring to a 10-membered ring, preferably a 4-membered ring to an 8-membered ring, and more preferably a 5-membered ring or a 6-membered ring.

作為R_1c ～R_5c 中的任意兩個以上、R_6c 與R_7c 、以及R_x 與R_y 鍵結而形成的基，可列舉伸丁基及伸戊基等伸烷基。所述伸烷基中的亞甲基可經氧原子等雜原子取代。作為R_5c 與R_6c 、以及R_5c 與R_x 鍵結而形成的基，較佳為單鍵或伸烷基。作為伸烷基，可列舉亞甲基及伸乙基等。Examples of groups formed by bonding any two or more of R _1c to R _5c _{, R 6c} and R _7c , and R _x and R _y include alkylene groups such as butylene and pentylene. The methylene group in the alkylene group may be substituted with heteroatoms such as oxygen atoms. The group formed by bonding R _5c and R _6c and R _5c and R _{x is} preferably a single bond or an alkylene group. As an alkylene group, a methylene group, an ethylene group, etc. are mentioned.

其次，對陽離子（ZaI-4b）進行說明。陽離子（ZaI-4b）是下述通式（ZaI-4b）所表示的陽離子。Next, the cation (ZaI-4b) will be described. The cation (ZaI-4b) is a cation represented by the following general formula (ZaI-4b).

[化5]

[化5]

通式（ZaI-4b）中， l表示0～2的整數。 r表示0～8的整數。 R₁₃ 表示氫原子、氟原子、羥基、烷基、烷氧基、烷氧基羰基或具有環烷基的基（可為環烷基本身，亦可為一部分含有環烷基的基）。該些基亦可具有取代基。 R₁₄ 表示羥基、烷基、烷氧基、烷氧基羰基、烷基羰基、烷基磺醯基、環烷基磺醯基或具有環烷基的基（可為環烷基本身，亦可為一部分含有環烷基的基）。該些基亦可具有取代基。R₁₄ 於存在多個的情況下分別獨立地表示羥基等所述基。 R₁₅ 分別獨立地表示烷基、環烷基或萘基。該些基亦可具有取代基。兩個R₁₅ 可彼此鍵結而形成環。於兩個R₁₅ 彼此鍵結而形成環時，於環骨架中亦可包含氧原子或氮原子等雜原子。於一形態中，兩個R₁₅ 為伸烷基，彼此鍵結而形成環結構。In the general formula (ZaI-4b), l represents an integer of 0-2. r represents an integer of 0-8. R ₁₃ represents a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, an alkoxy group, an alkoxycarbonyl group, or a group having a cycloalkyl group (the cycloalkyl group itself may be used, or a part of the cycloalkyl group-containing group may be used). These groups may have a substituent. R ₁₄ represents a hydroxy group, an alkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, a cycloalkylsulfonyl group, or a group having a cycloalkyl group (the cycloalkyl group itself may be Is a part of the group containing a cycloalkyl group). These groups may have a substituent. When _{a plurality of R 14} are present, each independently represents the aforementioned groups such as a hydroxyl group. R ₁₅ each independently represents an alkyl group, a cycloalkyl group, or a naphthyl group. These groups may have a substituent. Two R ₁₅ may be bonded to each other to form a ring. When two R ₁₅ are bonded to each other to form a ring, a hetero atom such as an oxygen atom or a nitrogen atom may be included in the ring skeleton. In one aspect, two R ₁₅ are alkylene groups, which are bonded to each other to form a ring structure.

通式（ZaI-4b）中，R₁₃ 、R₁₄ 及R₁₅ 的烷基為直鏈狀或支鏈狀。烷基的碳數較佳為1～10。作為烷基，更佳為甲基、乙基、正丁基或第三丁基等。In the general formula (ZaI-4b), _{the alkyl groups of R 13} , R ₁₄ and R ₁₅ are linear or branched. The number of carbon atoms in the alkyl group is preferably 1-10. As the alkyl group, a methyl group, an ethyl group, a n-butyl group or a tertiary butyl group is more preferable.

其次，對通式（ZaII）進行說明。通式（ZaII）中，R²⁰⁴ 及R²⁰⁵ 分別獨立地表示芳基、烷基或環烷基。作為R²⁰⁴ 及R²⁰⁵ 的芳基，較佳為苯基或萘基，更佳為苯基。R²⁰⁴ 及R²⁰⁵ 的芳基亦可為含有具有氧原子、氮原子或硫原子等的雜環的芳基。作為具有雜環的芳基的骨架，例如可列舉吡咯、呋喃、噻吩、吲哚、苯並呋喃及苯並噻吩等。作為R²⁰⁴ 及R²⁰⁵ 的烷基及環烷基，較佳為碳數1～10的直鏈狀烷基或碳數3～10的支鏈狀烷基（例如甲基、乙基、丙基、丁基或戊基）、或碳數3～10的環烷基（例如環戊基、環己基或降冰片基）。Next, the general formula (ZaII) will be explained. In the general formula (ZaII), R ²⁰⁴ and R ²⁰⁵ each independently represent an aryl group, an alkyl group, or a cycloalkyl group. The aryl group of R ²⁰⁴ and R ²⁰⁵ is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. The aryl group of R ²⁰⁴ and R ²⁰⁵ may be an aryl group containing a heterocyclic ring having an oxygen atom, a nitrogen atom, a sulfur atom, or the like. Examples of the skeleton of the aryl group having a heterocyclic ring include pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene. The alkyl group and cycloalkyl group of R ²⁰⁴ and R ²⁰⁵ are preferably a linear alkyl group having 1 to 10 carbon atoms or a branched chain alkyl group having 3 to 10 carbon atoms (e.g., methyl, ethyl, propyl , Butyl or pentyl), or a cycloalkyl group with 3 to 10 carbons (for example, cyclopentyl, cyclohexyl or norbornyl).

R²⁰⁴ 及R²⁰⁵ 的芳基、烷基及環烷基可分別獨立地具有取代基。作為R²⁰⁴ 及R²⁰⁵ 的芳基、烷基及環烷基可具有的取代基，例如可列舉：烷基（例如碳數1～15）、環烷基（例如碳數3～15）、芳基（例如碳數6～15）、烷氧基（例如碳數1～15）、鹵素原子、羥基及苯硫基等。The aryl group, alkyl group, and cycloalkyl group of R ²⁰⁴ and R ^{205 may each independently have a substituent.} Examples of substituents that the aryl group, alkyl group, and cycloalkyl group of R ²⁰⁴ and R ²⁰⁵ may have include alkyl groups (for example, carbon numbers 1 to 15), cycloalkyl groups (for example, carbon numbers 3 to 15), and aromatic groups. Group (for example, carbon number 6-15), alkoxy (for example, carbon number 1-15), halogen atom, hydroxyl group, thiophenyl group, etc.

（化合物（II））其次，對化合物（II）進行說明。化合物（II）：具有兩個以上所述結構部位X、與所述結構部位Y且藉由光化射線或放射線的照射而產生酸的化合物，所述酸包含兩個以上源自所述結構部位X的所述第一酸性部位、與源自所述結構部位Y的所述第二酸性部位其中，化合物（II）滿足下述條件II。條件II：所述化合物（II）中，將所述結構部位X中的所述陽離子部位M₁ ⁺ 及所述結構部位Y中的陽離子部位M₂ ⁺ 取代為H⁺ 而成的化合物PII具有源自將所述結構部位X中的所述陽離子部位M₁ ⁺ 取代為H⁺ 而成的HA₁ 所表示的酸性部位的酸解離常數a1、以及源自將所述結構部位Y中的所述陽離子部位M₂ ⁺ 取代為H⁺ 而成的HA₂ 所表示的酸性部位的酸解離常數a2，且所述酸解離常數a2大於所述酸解離常數a1。酸解離常數a1及酸解離常數a2藉由所述方法求出。此處，對化合物PII的酸解離常數a1及酸解離常數a2進行更具體的說明。於化合物（II）例如為產生酸的化合物的情況下，化合物PII相當於「具有兩個HA₁ 與HA₂ 的化合物」，所述酸具有兩個源自所述結構部位X的所述第一酸性部位、與一個源自所述結構部位Y的所述第二酸性部位。於求出所述化合物PII的酸解離常數的情況下，化合物PII為「具有一個A₁ ^- 以及一個HA₁ 與HA₂ 的化合物」時的pKa是酸解離常數a1，「具有兩個A₁ ^- 與HA₂ 的化合物」為「具有兩個A₁ ^- 與A₂ ^- 的化合物」時的pKa是酸解離常數a2。即，於化合物PII具有多個源自將所述結構部位X中的所述陽離子部位M₁ ⁺ 取代為H⁺ 而成的HA₁ 所表示的酸性部位的酸解離常數的情況下，將其最小值視為酸解離常數a1。(Compound (II)) Next, the compound (II) will be described. Compound (II): a compound having two or more of the structural part X and the structural part Y, and generating an acid by irradiation with actinic rays or radiation, the acid including two or more derived from the structural part Among the first acidic site of X and the second acidic site derived from the structural site Y, the compound (II) satisfies the following condition II. Condition II: In the compound (II), the compound PII obtained by substituting _{the cation site M 1} ^{+ in} the structural site X and the cation site M ₂ ⁺ ^{in the structural site Y with H + has a source} _{The acid dissociation constant a1 of the acidic site represented by HA 1} which is formed by substituting _{the cation site M 1} ⁺ in the structural site X with ^{H +} , and the acid dissociation constant a1 derived from the cation in the structural site Y The acid dissociation constant a2 of the acidic site represented by HA _{2 in} which the site M ₂ ^{+ is} substituted with H ⁺ , and the acid dissociation constant a2 is greater than the acid dissociation constant a1. The acid dissociation constant a1 and the acid dissociation constant a2 are obtained by the method described above. Here, the acid dissociation constant a1 and the acid dissociation constant a2 of the compound PII will be described in more detail. In the case where compound (II) is, for example, an acid-generating compound, compound PII is equivalent to "a compound having two HA ₁ and HA ₂ ", and the acid has two first components derived from the structural site X. An acidic site, and a second acidic site derived from the structural site Y. Acid hydrolysis to obtain the compound PII case where the dissociation constant of the compound for the PII "having a A ₁ ^- and HA ₂ with a compound HA _1" when the pKa of the acid dissociation constant a1, "having two A ₁ ^- When the _{"compound with HA 2} " is "a compound having two A ₁ ^- and A ₂ ^- ", the pKa is the acid dissociation constant a2. That is, in the case where the compound PII has a plurality of acid dissociation constants derived from the acidic site represented by _{HA 1} formed by substituting _{the cation site M 1} ⁺ ^{in the structural site X with H +, it is minimized} The value is regarded as the acid dissociation constant a1.

另外，所述化合物PII相當於藉由對化合物（II）照射光化射線或放射線而產生的酸。再者，化合物（II）亦可具有多個所述結構部位Y。In addition, the compound PII corresponds to an acid generated by irradiating the compound (II) with actinic rays or radiation. Furthermore, the compound (II) may also have a plurality of the structural parts Y.

就所形成的圖案的LWR性能更優異的方面而言，所述化合物PII中，酸解離常數a1與所述酸解離常數a2的差較佳為2.0以上，更佳為3.0以上。再者，酸解離常數a1與所述酸解離常數a2的差的上限值並無特別限制，例如為15.0以下。As far as the LWR performance of the formed pattern is more excellent, in the compound PII, the difference between the acid dissociation constant a1 and the acid dissociation constant a2 is preferably 2.0 or more, more preferably 3.0 or more. In addition, the upper limit of the difference between the acid dissociation constant a1 and the acid dissociation constant a2 is not particularly limited, and is, for example, 15.0 or less.

另外，所述化合物PII中，酸解離常數a2例如為6.5以下，就抗蝕劑組成物內的化合物（I）的陽離子部位的穩定性更優異的方面而言，較佳為2.0以下，更佳為1.0以下。再者，作為酸解離常數a2的下限值，例如為-3.5以上，較佳為-2.0以上。In addition, in the compound PII, the acid dissociation constant a2 is, for example, 6.5 or less, and in terms of more excellent stability of the cation site of the compound (I) in the resist composition, it is preferably 2.0 or less, more preferably It is 1.0 or less. In addition, the lower limit of the acid dissociation constant a2 is, for example, -3.5 or more, and preferably -2.0 or more.

另外，就所形成的圖案的LWR性能更優異的方面而言，所述化合物PII中，酸解離常數a1較佳為2.0以下，更佳為0.5以下，進而佳為-0.1以下。再者，作為酸解離常數a1的下限值，較佳為-15.0以上。In addition, in terms of more excellent LWR performance of the formed pattern, in the compound PII, the acid dissociation constant a1 is preferably 2.0 or less, more preferably 0.5 or less, and even more preferably -0.1 or less. Furthermore, the lower limit of the acid dissociation constant a1 is preferably -15.0 or more.

作為化合物（II），並無特別限制，例如可列舉下述通式（IIa）所表示的化合物。There is no restriction|limiting in particular as a compound (II), For example, the compound represented by the following general formula (IIa) is mentioned.

[化6]

[化6]

通式（Ia）中，「M₂₁ ⁺ A₂₁ ^- 」及「A₂₂ ^- M₂₂ ⁺ 」分別相當於結構部位X及結構部位Y。化合物（IIa）藉由光化射線或放射線的照射而產生下述通式（IIa-1）所表示的酸。即，「M₂₁ ⁺ A₂₁ ^- 」形成HA₂₁ 所表示的第一酸性部位，「A₂₂ ^- M₂₂ ⁺ 」形成與所述第一酸性部位的結構不同的HA₂₂ 所表示的第二酸性部位。In the general formula (Ia), "M _₂₁ ⁺ A ₂₁ ^-" and "A _₂₂ ^- M ₂₂ ^+" correspond to the structure and the structural site site X Y. The compound (IIa) generates an acid represented by the following general formula (IIa-1) by irradiation with actinic rays or radiation. That is, "M _₂₁ ⁺ A ₂₁ ^-" form a first acid sites represented by the HA _21, "A _₂₂ ^- M ₂₂ ^+" acid sites are formed with a second structure of the first portion of the acidic HA ₂₂ different expressed .

[化7]

[化7]

通式（IIa）中，M₂₁ ⁺ 及M₂₂ ⁺ 分別獨立地表示有機陽離子。 A₂₁ ^- 及A₂₂ ^- 分別獨立地表示陰離子性官能基。其中，A₂₂ ^- 表示與A₂₁ ^- 所表示的陰離子性官能基不同的結構。 L₂ 表示（n1+n2）價有機基。 n₁ 表示2以上的整數。 n₂ 表示1以上的整數。其中，所述通式（IIa）中，於將M₂₁ ⁺ 及M₂₂ ⁺ 所表示的有機陽離子取代為H⁺ 而成的化合物PIIa（相當於所述通式（IIa-1）所表示的化合物）中，源自A₂₂ H所表示的酸性部位的酸解離常數a2大於源自HA₂₁ 所表示的酸性部位的酸解離常數a1。再者，酸解離常數a1與酸解離常數a2的較佳值如上所述。In the general formula (IIa), M ₂₁ ⁺ and M ₂₂ ⁺ each independently represent an organic cation. A ₂₁ ^- and A ₂₂ ^- each independently represent an anionic functional group. Here, A ₂₂ ^- represents a structure different from the anionic functional group represented by _{A 21} ^-. L ₂ represents a (n1+n2) valent organic group. n ₁ represents an integer of 2 or more. n ₂ represents an integer of 1 or more. Wherein, in the general formula (IIa), in the compound PIIa (corresponding to the compound represented by the general formula (IIa-1), the organic cations represented by _{M 21} ⁺ and M ₂₂ ⁺ ^{are replaced with H +} In ), the acid dissociation constant a2 derived from the acidic site represented by _{A 22} H is greater than the acid dissociation constant a1 derived from the acidic site represented by _{HA 21.} Furthermore, the preferable values of the acid dissociation constant a1 and the acid dissociation constant a2 are as described above.

所述通式（IIa）中，M₂₁ ⁺ 、M₂₂ ⁺ 、A₂₁ ^- 及A₂₂ ^- 分別與所述通式（Ia）中的M₁₁ ⁺ 、M₁₂ ⁺ 、A₁₁ ^- 及A₁₂ ^- 為相同含義，較佳的形態亦相同。所述通式（IIa）中，n1個M₂₁ ⁺ 彼此、n1個A₂₁ ⁺ 彼此分別表示相互相同的基。In the general formula (IIa), M ₂₁ ⁺ , M ₂₂ ⁺ , A ₂₁ ^- and A ₂₂ ^- _{correspond to M 11} ⁺ , M ₁₂ ⁺ , A ₁₁ ^- and A ₁₂ ^-in the general formula (Ia), respectively It has the same meaning, and the preferred form is also the same. In the general formula (IIa), n1 M ₂₁ ⁺ and n1 A ₂₁ ⁺ each represent the same group as each other.

所述通式（IIa）中，L₂ 所表示的（n1+n2）價有機基並無特別限制，例如可列舉下述（A1）及下述（A2）所表示的基等。再者，於下述（A1）及（A2）中，*中的至少兩個表示與A₂₁ ^- 的鍵結位置，*中的至少一個表示與A₂₂ ^- 的鍵結位置。In the general formula (IIa), _{the (n1+n2)-valent organic group represented by L 2} is not particularly limited, and examples thereof include groups represented by (A1) and (A2) below. Furthermore, in the following (A1) and (A2), at least two of * indicate _{the bonding position with A 21} ^- , and at least one of * indicates the bonding position _{with A 22} ^-.

[化8]

[化8]

所述（A1）及（A2）中，T¹ 表示三價烴環基或三價雜環基，T² 表示碳原子、四價烴環基或四價雜環基。In the above (A1) and (A2), T ¹ represents a trivalent hydrocarbon ring group or a trivalent heterocyclic group, and T ² represents a carbon atom, a tetravalent hydrocarbon ring group or a tetravalent heterocyclic group.

所述烴環基可為芳香族烴環基，亦可為脂肪族烴環基。所述烴環基中所含的碳數較佳為6～18，更佳為6～14。所述雜環基可為芳香族雜環基，亦可為脂肪族雜環基。所述雜環較佳為於環結構內具有至少一個N原子、O原子、S原子或Se原子的5員環～10員環，更佳為5員環～7員環，進而佳為5員環～6員環。The hydrocarbon ring group may be an aromatic hydrocarbon ring group or an aliphatic hydrocarbon ring group. The number of carbons contained in the hydrocarbon ring group is preferably 6-18, more preferably 6-14. The heterocyclic group may be an aromatic heterocyclic group or an aliphatic heterocyclic group. The heterocyclic ring is preferably a 5-membered ring to 10-membered ring having at least one N atom, O atom, S atom or Se atom in the ring structure, more preferably 5-membered ring to 7-membered ring, and more preferably 5-membered ring Ring ~ 6-member ring.

另外，所述（A1）及（A2）中，L²¹ 及L²² 分別獨立地表示單鍵或二價連結基。 L²¹ 及L²² 所表示的二價連結基與所述通式（Ia）中的L₁ 所表示的二價連結基為相同含義，較佳的形態亦相同。 n1表示2以上的整數。上限並無特別限制，例如為6以下，較佳為4以下，更佳為3以下。 n2表示1以上的整數。上限並無特別限制，例如為3以下，較佳為2以下。In addition, in the above (A1) and (A2), L ²¹ and L ²² each independently represent a single bond or a divalent linking group. The ^{divalent linking group represented by L 21} and L ²² has the same meaning as the divalent linking group represented by _{L 1} in the general formula (Ia), and the preferred aspect is also the same. n1 represents an integer of 2 or more. The upper limit is not particularly limited. For example, it is 6 or less, preferably 4 or less, and more preferably 3 or less. n2 represents an integer of 1 or more. The upper limit is not particularly limited, and is, for example, 3 or less, preferably 2 or less.

（化合物（III））其次，對化合物（III）進行說明。化合物（III）：具有兩個以上所述結構部位X、與下述結構部位Z且藉由光化射線或放射線的照射而產生酸的化合物，所述酸包含兩個以上源自所述結構部位X的所述第一酸性部位、與所述結構部位Z 結構部位Z：可中和酸的非離子性的有機部位(Compound (III)) Next, the compound (III) will be described. Compound (III): A compound having two or more of the above-mentioned structural parts X and the following structural part Z and generating an acid by irradiation with actinic rays or radiation, the acid including two or more derived from the structural parts The first acidic site of X and the structural site Z Structural part Z: Non-ionic organic part that can neutralize acid

作為結構部位Z中的可中和酸的非離子性的有機部位，並無特別限制，例如較佳為包含具有可與質子發生靜電相互作用的基或電子的官能基的有機部位。作為具有可與質子發生靜電相互作用的基或電子的官能基，可列舉具有環狀聚醚等大環結構的官能基、或含有具有無助於π共軛的非共有電子對的氮原子的官能基。所謂具有無助於π共軛的非共有電子對的氮原子，例如是指具有下述式所示的部分結構的氮原子。The nonionic organic moiety capable of neutralizing an acid in the structural site Z is not particularly limited. For example, it is preferably an organic moiety containing a functional group capable of electrostatically interacting with a proton or an electron. Examples of functional groups having groups or electrons capable of electrostatically interacting with protons include functional groups having macrocyclic structures such as cyclic polyethers, or nitrogen atoms having non-shared electron pairs that do not contribute to π-conjugation. Functional group. The nitrogen atom having a non-shared electron pair that does not contribute to π-conjugation means, for example, a nitrogen atom having a partial structure represented by the following formula.

[化9]

[化9]

作為具有可與質子發生靜電相互作用的基或電子的官能基的部分結構，例如可列舉：冠醚結構、氮雜冠醚結構、一級胺結構～三級胺結構、吡啶結構、咪唑結構及吡嗪結構等，其中，較佳為一級胺結構～三級胺結構。Examples of partial structures having functional groups capable of electrostatically interacting with protons or electrons include: crown ether structure, aza crown ether structure, primary to tertiary amine structure, pyridine structure, imidazole structure, and pyridine Among them, a primary amine structure to a tertiary amine structure are preferable.

於所述化合物（III）中將所述結構部位X中的所述陽離子部位M₁ ⁺ 取代為H⁺ 而成的化合物PIII中，就所形成的圖案的LWR性能更優異的方面而言，源自將所述結構部位X中的所述陽離子部位M₁ ⁺ 取代為H⁺ 而成的HA₁ 所表示的酸性部位的酸解離常數a1較佳為2.0以下，更佳為0.5以下，進而佳為-0.1以下。再者，作為酸解離常數a1的下限值，較佳為-15.0以上。再者，於化合物PIII具有多個源自將所述結構部位X中的所述陽離子部位M₁ ⁺ 取代為H⁺ 而成的HA₁ 所表示的酸性部位的酸解離常數的情況下，將其最小值視為酸解離常數a1。即，於化合物（III）例如為產生酸的化合物的情況下，化合物PIII相當於「具有兩個HA₁ 的化合物」，所述酸具有兩個源自所述結構部位X的所述第一酸性部位、與所述結構部位Z。於求出所述化合物PIII的酸解離常數的情況下，化合物PIII為「具有一個A₁ ^- 與一個HA₁ 的化合物」時的pKa是酸解離常數a1。即，於化合物PIII具有多個源自將所述結構部位X中的所述陽離子部位M₁ ⁺ 取代為H⁺ 而成的HA₁ 所表示的酸性部位的酸解離常數的情況下，將其最小值視為酸解離常數a1。再者，所謂於所述化合物（III）中將所述結構部位X中的所述陽離子部位M₁ ⁺ 取代為H⁺ 而成的化合物PIII，例如於化合物（III）為後述的化合物（IIIa）所表示的化合物的情況下，相當於HA₃₁ -L₃ -N(R^2X )-L₄ -A₃₁ H。In the compound (III), the cation site M ₁ ⁺ in the structural site X is substituted with H ⁺ in the compound PIII. In terms of the LWR performance of the formed pattern, the source _{The acid dissociation constant a1 of the acidic site represented by HA 1} formed by _{substituting the cation site M 1} ⁺ with H ^{+ in} the structural site X is preferably 2.0 or less, more preferably 0.5 or less, and still more preferably -0.1 or less. Furthermore, the lower limit of the acid dissociation constant a1 is preferably -15.0 or more. Furthermore, when the compound PIII has a plurality of acid dissociation constants derived from the acidic site represented by _{HA 1} formed by substituting _{the cation site M 1} ⁺ ^{in the structural site X with H +, the} The minimum value is regarded as the acid dissociation constant a1. That is, in the case where the compound (III) is, for example, an acid-generating compound, the compound PIII corresponds to "a compound having two HA ₁ ", and the acid has two first acidic acids derived from the structural site X Location, and the structural location Z. In the case of calculating the acid dissociation constant of the compound PIII _{, the pKa when the compound PIII is "a compound having one A 1} ^- and one HA ₁ " is the acid dissociation constant a1. That is, when the compound PIII has a plurality of acid dissociation constants derived from the acidic site represented by _{HA 1} _{in which the cation site M 1} ⁺ in the structural site X is replaced by H ^{+, it is minimized} The value is regarded as the acid dissociation constant a1. Furthermore, the so-called _{compound PIII in which the cation site M 1} ⁺ in the structural site X is substituted with H ⁺ in the compound (III), for example, the compound (III) is the compound (IIIa) described later In the case of the compound shown, it corresponds to HA ₃₁ -L ₃ -N(R ^2X )-L ₄ -A ₃₁ H.

作為化合物（III），並無特別限制，例如可列舉下述通式（IIIa）所表示的化合物。The compound (III) is not particularly limited, and examples thereof include compounds represented by the following general formula (IIIa).

[化10]

[化10]

通式（IIIa）中，「M₃₁ ⁺ A₃₁ ^- 」相當於結構部位X。化合物（IIIa）藉由光化射線或放射線的照射而產生HA₃₁ -L₃ -N(R^2X )-L₄ -A₃₁ H所表示的酸。即，「M₃₁ ⁺ A₃₁ ^- 」形成HA₃₁ 所表示的第一酸性部位。In the general formula (IIIa), "M _₃₁ ⁺ A ₃₁ ^-" corresponds to the structural part X. The compound (IIIa) generates an acid represented by _{HA 31} -L ₃ -N(R ^2X )-L ₄ -A _{31 H by irradiation with actinic rays or radiation.} That is, "M _₃₁ ⁺ A ₃₁ ^-" HA ₃₁ is formed a first acid sites indicated.

通式（IIIa）中，M₃₁ ⁺ 表示有機陽離子。 A₃₁ ^- 表示陰離子性官能基。 L₃ 及L₄ 分別獨立地表示二價連結基。 R^2X 表示一價取代基。In the general formula (IIIa), M ₃₁ ⁺ represents an organic cation. A ₃₁ ^- represents an anionic functional group. L ₃ and L ₄ each independently represent a divalent linking group. R ^2X represents a monovalent substituent.

所述通式（IIIa）中，M₃₁ ⁺ 及A₃₁ ^- 分別與所述通式（Ia）中的M₁₁ ⁺ 及A₁₁ ^- 為相同含義，較佳的形態亦相同。所述通式（IIIa）中，L₃ 及L₄ 分別與所述通式（Ia）中的L₁ 為相同含義，較佳的形態亦相同。所述通式（IIIa）中，兩個M₃₁ ⁺ 彼此及兩個A₃₁ ^- 彼此分別表示相互相同的基。In the general formula (IIIa), M ₃₁ ⁺ and A ₃₁ ^- _{respectively have the same meaning as the M 11} ⁺ and A ₁₁ ^- in the general formula (Ia), and preferred forms are also the same. In the general formula (IIIa), L ₃ and L ₄ _{respectively have the same meaning as L 1} in the general formula (Ia), and preferred forms are also the same. In the general formula (IIIa), two M ₃₁ ⁺ and two A ₃₁ ^- each represent the same group as each other.

通式（IIIa）中，作為R^2X 所表示的一價取代基，並無特別限制，例如可列舉：-CH₂ -可經選自由-CO-、-NH-、-O-、-S-、-SO-及-SO₂ -所組成的群組中的一種或兩種以上的組合取代的烷基（較佳為碳數1～10。可為直鏈狀亦可為支鏈狀）、環烷基（較佳為碳數3～15）或烯基（較佳為碳數2～6）等。另外，所述伸烷基、所述伸環烷基及所述伸烯基可經取代基取代。In the general formula (IIIa), the ^{monovalent substituent represented by R 2X} is not particularly limited. For example, -CH ₂ -can be selected from -CO-, -NH-, -O-, -S- , -SO- and -SO ₂ -group consisting of one or a combination of two or more substituted alkyl groups (preferably carbon number 1-10. It may be linear or branched), Cycloalkyl (preferably with 3 to 15 carbons) or alkenyl (preferably with 2 to 6 carbons), etc. In addition, the alkylene group, the cycloalkylene group, and the alkenylene group may be substituted with a substituent.

所述化合物（I）～（III）所表示的化合物的分子量較佳為300～3000，更佳為500～2000，進而佳為700～1500。The molecular weight of the compounds represented by the compounds (I) to (III) is preferably 300-3000, more preferably 500-2000, and still more preferably 700-1500.

以下示出所述化合物（I）～（III）所表示的化合物的較佳例。Preferred examples of the compounds represented by the aforementioned compounds (I) to (III) are shown below.

[化11]

[化11]

[化12]

[化12]

＜光酸產生劑C＞所述抗蝕劑組成物亦可包含除此以外的其他光酸產生劑（光酸產生劑C）。＜Photoacid generator C＞ The resist composition may also include other photoacid generators (photoacid generator C).

作為光酸產生劑C，可將藉由光化射線或放射線的照射而產生酸的公知的化合物單獨或者作為該些的混合物適宜選擇使用。例如，可較佳地使用美國專利申請公開2016/0070167A1號說明書的段落[0125]～[0319]、美國專利申請公開2015/0004544A1號說明書的段落[0086]～[0094]、美國專利申請公開2016/0237190A1號說明書的段落[0323]～[0402]以及日本專利特開2018-155788號說明書的段落[0074]～[0122]及[0137]～[0146]中揭示的公知的化合物作為光酸產生劑C。As the photoacid generator C, a known compound that generates an acid by irradiation with actinic rays or radiation can be appropriately selected and used alone or as a mixture of these. For example, paragraphs [0125] ~ [0319] of US Patent Application Publication No. 2016/0070167A1, paragraphs [0086] ~ [0094] of US Patent Application Publication No. 2015/0004544A1, and US Patent Application Publication 2016 The well-known compounds disclosed in paragraphs [0323] to [0402] of the specification of /0237190A1 and paragraphs [0074] to [0122] and [0137] to [0146] of the specification of Japanese Patent Laid-Open No. 2018-155788 are produced as photoacids剂 C.

另外，作為光酸產生劑C，例如亦較佳為選自由下述通式（1）所表示的化合物及下述通式（2）所表示的化合物所組成的群組中的化合物。以下，對通式（1）所表示的化合物及下述通式（2）所表示的化合物分別進行說明。In addition, as the photoacid generator C, for example, a compound selected from the group consisting of a compound represented by the following general formula (1) and a compound represented by the following general formula (2) is also preferable. Hereinafter, the compound represented by the general formula (1) and the compound represented by the following general formula (2) will be described respectively.

（通式（1）所表示的化合物）(Compound represented by general formula (1))

[化13]

通式（1）中，M₃ ⁺ 表示有機陽離子。A₃ ^- 表示陰離子性官能基。 R_a 表示氫原子或一價有機基。L_a 表示單鍵或二價連結基。[化13]

In the general formula (1), M ₃ ⁺ represents an organic cation. A ₃ ^- represents an anionic functional group. R _a represents a hydrogen atom or a monovalent organic group. L _a represents a single bond or a divalent linking group.

M₃ ⁺ 所表示的有機陽離子與化合物（Ia）中的M₁₁ ⁺ 為相同含義，較佳的形態亦相同。作為A₃ ^- 所表示的陰離子性官能基，並無特別限制，例如表示下述通式（C-1）～（C-7）所表示的基。The organic cation represented by M ₃ ⁺ _{has the same meaning as M 11} ⁺ in the compound (Ia), and the preferred form is also the same. The anionic functional group represented by A ₃ ^- is not particularly limited, and, for example, it represents a group represented by the following general formulas (C-1) to (C-7).

[化14]

[化14]

通式（C-1）中，R^X1 表示取代基。作為R^X1 ，較佳為直鏈狀、支鏈狀或環狀的烷基。所述烷基的碳數較佳為1～15，更佳為1～10。所述烷基可具有取代基。取代基較佳為氟原子或氰基。於所述烷基具有氟原子作為取代基的情況下，亦可為全氟烷基。In the general formula (C-1), R ^X1 represents a substituent. R ^{X1 is} preferably a linear, branched or cyclic alkyl group. The carbon number of the alkyl group is preferably 1-15, more preferably 1-10. The alkyl group may have a substituent. The substituent is preferably a fluorine atom or a cyano group. When the alkyl group has a fluorine atom as a substituent, it may be a perfluoroalkyl group.

通式（C-2）及（C-3）中，R^X2 表示氫原子、或氟原子及全氟烷基以外的取代基。作為R^X2 所表示的氟原子及全氟烷基以外的取代基，較佳為直鏈狀、支鏈狀或環狀的烷基。所述烷基的碳數較佳為1～15，更佳為1～10。所述烷基亦可具有氟原子以外的取代基。In the general formulas (C-2) and (C-3), R ^X2 represents a substituent other than a hydrogen atom, or a fluorine atom and a perfluoroalkyl group. The substituents other than the fluorine atom and perfluoroalkyl group represented by R ^{X2 are preferably a linear, branched or cyclic alkyl group.} The carbon number of the alkyl group is preferably 1-15, more preferably 1-10. The alkyl group may have a substituent other than a fluorine atom.

通式（C-3）中，R^XF1 表示氟原子或全氟烷基。 R^XF1 所表示的全氟烷基的碳數較佳為1～15，更佳為1～10，進而佳為1～6。In the general formula (C-3), R ^XF1 represents a fluorine atom or a perfluoroalkyl group. The carbon number of the perfluoroalkyl group represented by R ^XF1 is preferably 1-15, more preferably 1-10, and still more preferably 1-6.

通式（C-5）中，R^X3 表示氟原子以外的取代基。作為R^X2 所表示的氟原子以外的取代基，較佳為直鏈狀、支鏈狀或環狀的烷基。所述烷基的碳數較佳為1～15，更佳為1～10。In the general formula (C-5), R ^X3 represents a substituent other than a fluorine atom. The substituent other than the fluorine atom represented by R ^X2 is preferably a linear, branched or cyclic alkyl group. The carbon number of the alkyl group is preferably 1-15, more preferably 1-10.

通式（C-5）及（C-6）中，n表示0～4的整數。作為n，更佳為1～4的整數。In general formulas (C-5) and (C-6), n represents an integer of 0-4. As n, it is more preferable that it is an integer of 1-4.

通式（C-7）中，L_c 表示直鏈狀、支鏈狀或環狀的伸烷基。所述伸烷基的碳數較佳為1～15，更佳為1～10。所述伸烷基可經取代基（例如氟原子等）取代。In the general formula (C-7), L _c represents a linear, branched or cyclic alkylene group. The carbon number of the alkylene group is preferably 1-15, more preferably 1-10. The alkylene group may be substituted with a substituent (for example, a fluorine atom, etc.).

作為L_a 所表示的二價連結基，並無特別限制，例如可列舉將選自由-CO-、-NH-、-O-、-S-、-SO-、-SO₂ -及伸烷基（較佳為碳數1～10。可為直鏈狀亦可為支鏈狀）所組成的群組中的一種以上或兩種以上組合而成的基。另外，所述伸烷基亦可經取代基（例如氟原子等）取代。As the divalent linking group represented by L _a, it is not particularly limited, for example, selected from the group consisting of the -CO -, - NH -, - O -, - S -, - SO -, - SO 2 - and an alkylene group (Preferably carbon number 1-10. It may be linear or branched) A group composed of one or more or a combination of two or more of the group. In addition, the alkylene group may be substituted with a substituent (for example, a fluorine atom, etc.).

作為R_a 所表示的一價有機基，並無特別限制，例如可列舉氟烷基（較佳為碳數1～10，更佳為碳數1～6）以及包含環狀結構的有機基，其中，較佳為環狀有機基。作為環狀有機基，例如可列舉脂環基、芳基及雜環基。脂環基可為單環式，亦可為多環式。作為單環式的脂環基，例如可列舉環戊基、環己基及環辛基等單環的環烷基。作為多環式的脂環基，例如可列舉降冰片基、三環癸基、四環癸基、四環十二烷基及金剛烷基等多環的環烷基。其中，較佳為降冰片基、三環癸基、四環癸基、四環十二烷基及金剛烷基等具有碳數7以上的體積大的結構的脂環基。再者，所述脂環基的碳原子亦可經羰基取代。The _{monovalent organic group represented by Ra} is not particularly limited, and examples thereof include a fluoroalkyl group (preferably with a carbon number of 1 to 10, more preferably a carbon number of 1 to 6) and an organic group containing a cyclic structure, Among them, a cyclic organic group is preferred. Examples of the cyclic organic group include an alicyclic group, an aryl group, and a heterocyclic group. The alicyclic group may be monocyclic or polycyclic. Examples of the monocyclic alicyclic group include monocyclic cycloalkyl groups such as cyclopentyl, cyclohexyl, and cyclooctyl. Examples of the polycyclic alicyclic group include polycyclic cycloalkyl groups such as norbornyl, tricyclodecyl, tetracyclodecyl, tetracyclododecyl, and adamantyl. Among them, preferred are alicyclic groups having a bulky structure with 7 or more carbon atoms, such as norbornyl, tricyclodecyl, tetracyclodecyl, tetracyclododecyl, and adamantyl. Furthermore, the carbon atom of the alicyclic group may be substituted by a carbonyl group.

芳基可為單環式，亦可為多環式。作為所述芳基，例如可列舉苯基、萘基、菲基及蒽基。雜環基可為單環式，亦可為多環式。多環式更能進一步抑制酸的擴散。另外，雜環基可具有芳香族性，亦可不具有芳香族性。作為具有芳香族性的雜環，例如可列舉呋喃環、噻吩環、苯並呋喃環、苯並噻吩環、二苯並呋喃環、二苯並噻吩環及吡啶環。作為不具有芳香族性的雜環，例如可列舉四氫吡喃環、內酯環、磺內酯環及十氫異喹啉環。作為內酯環及磺內酯環的例子，可列舉後述的樹脂中例示的內酯結構及磺內酯結構。作為雜環基中的雜環，尤佳為呋喃環、噻吩環、吡啶環或十氫異喹啉環。The aryl group may be monocyclic or polycyclic. Examples of the aryl group include phenyl, naphthyl, phenanthryl, and anthracenyl. The heterocyclic group may be monocyclic or polycyclic. The polycyclic type can further inhibit the diffusion of acid. In addition, the heterocyclic group may be aromatic or not. Examples of the aromatic heterocyclic ring include a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, and a pyridine ring. Examples of the heterocyclic ring having no aromaticity include a tetrahydropyran ring, a lactone ring, a sultone ring, and a decahydroisoquinoline ring. As examples of the lactone ring and the sultone ring, the lactone structure and the sultone structure exemplified in the resin described later can be cited. The heterocyclic ring in the heterocyclic group is particularly preferably a furan ring, a thiophene ring, a pyridine ring or a decahydroisoquinoline ring.

所述環狀有機基亦可具有取代基。作為所述取代基，例如可列舉烷基（可為直鏈狀及支鏈狀中的任一種，較佳為碳數1～12）、環烷基（可為單環、多環及螺環中的任一種，較佳為碳數3～20）、芳基（較佳為碳數6～14）、羥基、烷氧基、酯基、醯胺基、胺基甲酸酯基、脲基、硫醚基、磺醯胺基及磺酸酯基。再者，構成環狀有機基的碳（有助於環形成的碳）亦可為羰基碳。The cyclic organic group may also have a substituent. Examples of the substituent include an alkyl group (which may be linear or branched, and preferably has 1 to 12 carbon atoms), cycloalkyl (which may be monocyclic, polycyclic, or spirocyclic). Any of them, preferably 3-20 carbons), aryl (preferably 6-14 carbons), hydroxyl, alkoxy, ester, amide, urethane, ureido , Thioether group, sulfonamide group and sulfonate group. Furthermore, the carbon (carbon that contributes to ring formation) constituting the cyclic organic group may be a carbonyl carbon.

就所形成的圖案的LWR性能更優異的方面而言，於將所述通式（1）中的M₃ ⁺ 取代為H⁺ 而成的HA₃ -La-Ra所表示的化合物Q中，HA₃ 所表示的酸性部位的酸解離常數為-2.0以上，較佳為-1.0以上，更佳為0以上。再者，所述酸解離常數的上限值並無特別限制，例如為6.0以下，較佳為2.0以下。In terms of the LWR performance of the formed pattern more excellent, in the compound Q represented by _{HA 3} -La-Ra formed by substituting _{M 3} ⁺ ^{in the general formula (1) with H +, HA} _{The acid dissociation constant of the acidic site represented by 3} is -2.0 or more, preferably -1.0 or more, and more preferably 0 or more. Furthermore, the upper limit of the acid dissociation constant is not particularly limited, for example, it is 6.0 or less, preferably 2.0 or less.

（通式（2）所表示的化合物）(Compound represented by general formula (2))

[化15]

[化15]

所述通式（2）中，M₄ ⁺ 表示硫離子或碘離子。 m表示1或2，於M₄ ⁺ 為硫離子的情況下，m為2，於M₄ ⁺ 為碘原子的情況下，m為1。 R_b 分別獨立地表示可含有雜原子的烷基或烯基、芳基或雜芳基。再者，於m為2的情況下，兩個R_b 可彼此鍵結而形成環。 L_b 表示二價連結基。 A₄ ^- 表示陰離子性官能基。In the general formula (2), M ₄ ⁺ represents sulfide ion or iodide ion. m represents 1 or 2. When M ₄ ⁺ is a sulfide ion, m is 2, and when M ₄ ⁺ is an iodine atom, m is 1. R _b each independently represents an alkyl group or an alkenyl group, an aryl group, or a heteroaryl group which may contain a hetero atom. Furthermore, when m is 2, two R _b may be bonded to each other to form a ring. L _b represents a divalent linking group. A ₄ ^- represents an anionic functional group.

作為R_b 所表示的可含有雜原子的烷基或烯基，並無特別限制，例如可列舉：-CH₂ -可經雜原子取代的碳數1～20的烷基（較佳為碳數1～10）及-CH₂ -可經雜原子取代的碳數1～20的烯基（較佳為碳數2～10）等。作為雜原子，例如可列舉氧原子、氮原子及硫原子等。再者，R_b 所表示的可含有雜原子的烷基或烯基亦可為直鏈狀、支鏈狀及環狀中的任一種。另外，R_b 所表示的可含有雜原子的烷基或烯基亦可具有取代基。作為所述取代基，例如可列舉芳基（較佳為碳數6～14）、羥基、烷氧基、酯基、醯胺基、胺基甲酸酯基、脲基、硫醚基、磺醯胺基及磺酸酯基。The alkyl group or alkenyl group that may contain a hetero atom represented by R _b _{is not particularly limited, and examples include: -CH 2} -an alkyl group having 1 to 20 carbons (preferably a carbon number) which may be substituted with a hetero atom 1 to 10) and -CH ₂ -Alkenyl groups having 1 to 20 carbons (preferably 2 to 10 carbons) which may be substituted with heteroatoms, and the like. As a hetero atom, an oxygen atom, a nitrogen atom, a sulfur atom, etc. are mentioned, for example. In addition, the alkyl group or alkenyl group which may contain a hetero atom represented by _{R b may be any of linear, branched, and cyclic.} In addition, the alkyl group or alkenyl group which may contain a hetero atom represented by _{R b may have a substituent.} Examples of the substituent include aryl groups (preferably carbon numbers 6 to 14), hydroxyl groups, alkoxy groups, ester groups, amide groups, urethane groups, ureido groups, thioether groups, and sulfonyl groups. Amido and sulfonate groups.

R_b 所表示的芳基可為單環式，亦可為多環式。作為所述芳基，例如可列舉苯基、萘基、菲基及蒽基。 R_b 所表示的雜芳基可為單環式，亦可為多環式。多環式更可抑制酸的擴散。作為構成所述雜芳基的芳香族雜環，例如可列舉呋喃環、噻吩環、苯並呋喃環、苯並噻吩環、二苯並呋喃環、二苯並噻吩環及吡啶環。The aryl group represented by R _b may be monocyclic or polycyclic. Examples of the aryl group include phenyl, naphthyl, phenanthryl, and anthracenyl. The heteroaryl group represented by R _b may be monocyclic or polycyclic. The polycyclic type can inhibit the diffusion of acid. Examples of the aromatic heterocyclic ring constituting the heteroaryl group include a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, and a pyridine ring.

R_b 所表示的芳基及雜芳基亦可具有取代基。作為所述取代基，例如可列舉烷基（可為直鏈狀及支鏈狀中的任一種，較佳為碳數1～12）、環烷基（可為單環、多環及螺環中的任一種，較佳為碳數3～20）、芳基（較佳為碳數6～14）、羥基、烷氧基、酯基、醯胺基、胺基甲酸酯基、脲基、硫醚基、磺醯胺基及磺酸酯基。The aryl group and heteroaryl group represented by R _{b may have a substituent.} Examples of the substituent include an alkyl group (which may be linear or branched, and preferably has 1 to 12 carbon atoms), cycloalkyl (which may be monocyclic, polycyclic, or spirocyclic). Any of them, preferably 3-20 carbons), aryl (preferably 6-14 carbons), hydroxyl, alkoxy, ester, amide, urethane, ureido , Thioether group, sulfonamide group and sulfonate group.

作為L_b 所表示的二價連結基，並無特別限制，例如可列舉將選自由-CO-、-NH-、-O-、-S-、-SO-、-SO₂ -、伸烷基（較佳為碳數1～10。可為直鏈狀亦可為支鏈狀）及伸芳基（較佳為碳數6～10）所組成的群組中的一種以上或兩種以上組合而成的基。另外，所述伸烷基及伸芳基亦可經取代基（例如氟原子等）取代。The _{divalent linking group represented by L b} is not particularly limited. For example, it can be selected from -CO-, -NH-, -O-, -S-, -SO-, -SO ₂ -, alkylene (Preferably carbon number 1-10. It may be linear or branched) and arylene group (preferably carbon number 6-10) consisting of one or more or a combination of two or more Formed base. In addition, the alkylene and arylalkylene groups may also be substituted with substituents (for example, fluorine atoms, etc.).

作為A₄ ^- 所表示的陰離子性官能基，與所述A₃ ^- 所表示的陰離子性官能基為相同含義，較佳的形態亦相同。The anionic functional group represented by A ₄ ^- _{has the same meaning as the anionic functional group represented by A 3} ^- described above, and the preferred form is also the same.

就所形成的圖案的LWR性能更優異的方面而言，於將所述通式（2）中的A₄ ^- 取代為HA₄ 而成的HA₄ -L_b -M₄ ⁺ -(R_b )_m 所表示的化合物R中，HA₄ 所表示的酸性部位的酸解離常數為-2.0以上，較佳為-1.0以上，更佳為0以上。再者，所述酸解離常數的上限值並無特別限制，例如為6.0以下，較佳為2.0以下。In terms of more excellent LWR performance aspects of the formed pattern, in the A (2) in the formula ₄ ^- substituted HA HA ₄ is formed by _{_{_{^{4 -L b -M 4 + - (}}}} R b) _In the compound R represented by _{m, the acid dissociation constant of the acidic site represented by HA 4} is -2.0 or more, preferably -1.0 or more, and more preferably 0 or more. Furthermore, the upper limit of the acid dissociation constant is not particularly limited, for example, it is 6.0 or less, preferably 2.0 or less.

所述通式（1）所表示的化合物及所述通式（2）所表示的化合物的分子量較佳為300～3000，更佳為500～2000，進而佳為700～1500。The molecular weight of the compound represented by the general formula (1) and the compound represented by the general formula (2) is preferably 300-3000, more preferably 500-2000, and still more preferably 700-1500.

以下示出所述通式（1）及（2）所表示的化合物的較佳例。Preferred examples of the compounds represented by the general formulas (1) and (2) are shown below.

[化16]

[化16]

[化17]

[化17]

[酸分解性樹脂（樹脂（A））] 本發明的抗蝕劑組成物含有因酸的作用分解而極性增大的樹脂（以下，亦稱為「酸分解性樹脂」或「樹脂（A）」）。即，本發明的圖案形成方法中，典型而言，於採用鹼性顯影液作為顯影液的情況下，可較佳地形成正型的圖案，於採用有機系顯影液作為顯影液的情況下，可較佳地形成負型的圖案。樹脂（A）通常含有因酸的作用分解而極性增大的基（以下，亦稱為「酸分解性基」），較佳為含有具有酸分解性基的重複單元。[Acid decomposable resin (resin (A))] The resist composition of the present invention contains a resin (hereinafter, also referred to as "acid-decomposable resin" or "resin (A)") that is decomposed by the action of an acid to increase its polarity. That is, in the pattern forming method of the present invention, typically, when an alkaline developer is used as the developer, a positive pattern can be preferably formed, and when an organic developer is used as the developer, It is preferable to form a negative pattern. The resin (A) usually contains a group whose polarity increases due to decomposition by an acid (hereinafter also referred to as an "acid-decomposable group"), and preferably contains a repeating unit having an acid-decomposable group.

＜具有酸分解性基的重複單元＞所謂酸分解性基是指因酸的作用分解而生成極性基的基。酸分解性基較佳為具有極性基經因酸的作用而脫離的脫離基保護的結構。即，樹脂（A）具有重複單元，該重複單元具有因酸的作用分解而生成極性基的基。具有該重複單元的樹脂因酸的作用而極性增大且相對於鹼性顯影液的溶解度增大，相對於有機溶劑的溶解度減少。作為極性基，較佳為鹼可溶性基，例如可列舉：羧基、酚性羥基、氟化醇基、磺酸基、磷酸基、磺醯胺基、磺醯亞胺基、(烷基磺醯基)(烷基羰基)亞甲基、(烷基磺醯基)(烷基羰基)醯亞胺基、雙(烷基羰基)亞甲基、雙(烷基羰基)醯亞胺基、雙(烷基磺醯基)亞甲基、雙(烷基磺醯基)醯亞胺基、三(烷基羰基)亞甲基及三(烷基磺醯基)亞甲基等酸性基、以及醇性羥基等。其中，作為極性基，較佳為羧基、酚性羥基、氟化醇基（較佳為六氟異丙醇基）或磺酸基。＜Repeating unit with acid-decomposable group＞ The acid-decomposable group refers to a group that is decomposed by the action of an acid to generate a polar group. The acid-decomposable group preferably has a structure in which a polar group is protected by a leaving group that is released by the action of an acid. That is, the resin (A) has a repeating unit, and the repeating unit has a group that decomposes by the action of an acid to generate a polar group. A resin having this repeating unit increases in polarity due to the action of an acid, and has an increase in solubility with respect to an alkaline developer, and a decrease in solubility with respect to an organic solvent. The polar group is preferably an alkali-soluble group, for example, a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group, a sulfonic acid group, a phosphoric acid group, a sulfonamide group, a sulfonylimide group, (alkylsulfonyl group) )(Alkylcarbonyl)methylene, (alkylsulfonyl)(alkylcarbonyl)imino, bis(alkylcarbonyl)methylene, bis(alkylcarbonyl)imino, bis( Acidic groups such as alkylsulfonyl)methylene, bis(alkylsulfonyl)imino, tris(alkylcarbonyl)methylene and tris(alkylsulfonyl)methylene, and alcohols Hydroxy and so on. Among them, the polar group is preferably a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), or a sulfonic acid group.

作為因酸的作用而脫離的脫離基，例如可列舉式（Y1）～（Y4）所表示的基。式（Y1）：-C(Rx₁ )(Rx₂ )(Rx₃ ) 式（Y2）：-C(=O)OC(Rx₁ )(Rx₂ )(Rx₃ ) 式（Y3）：-C(R₃₆ )(R₃₇ )(OR₃₈ ) 式（Y4）：-C(Rn)(H)(Ar)Examples of the leaving group to be released by the action of the acid include groups represented by formulas (Y1) to (Y4). Formula (Y1): -C(Rx ₁ )(Rx ₂ )(Rx ₃ ) Formula (Y2): -C(=O)OC(Rx ₁ )(Rx ₂ )(Rx ₃ ) Formula (Y3): -C (R ₃₆ )(R ₃₇ )(OR ₃₈ ) Formula (Y4): -C(Rn)(H)(Ar)

式（Y1）及式（Y2）中，Rx₁ ～Rx₃ 分別獨立地表示烷基（直鏈狀或支鏈狀）或環烷基（單環或多環）、烯基（直鏈狀或支鏈狀）、或芳基（單環或多環）。再者，於Rx₁ ～Rx₃ 全部為烷基（直鏈狀或支鏈狀）的情況下，較佳為Rx₁ ～Rx₃ 中的至少兩個為甲基。其中，Rx₁ ～Rx₃ 較佳為分別獨立地表示直鏈狀或支鏈狀的烷基，Rx₁ ～Rx₃ 更佳為分別獨立地表示直鏈狀的烷基。 Rx₁ ～Rx₃ 的兩個可鍵結而形成單環或多環。作為Rx₁ ～Rx₃ 的烷基，較佳為甲基、乙基、正丙基、異丙基、正丁基、異丁基及第三丁基等碳數1～5的烷基。作為Rx₁ ～Rx₃ 的環烷基，較佳為環戊基及環己基等單環的環烷基、以及降冰片基、四環癸基、四環十二烷基及金剛烷基等多環的環烷基。作為Rx₁ ～Rx₃ 的芳基，較佳為碳數6～10的芳基，例如可列舉苯基、萘基及蒽基等。作為Rx₁ ～Rx₃ 的烯基，較佳為乙烯基。作為Rx₁ ～Rx₃ 的兩個鍵結而形成的環，較佳為環烷基。作為Rx₁ ～Rx₃ 的兩個鍵結而形成的環烷基，較佳為環戊基或環己基等單環的環烷基、或者降冰片基、四環癸基、四環十二烷基或金剛烷基等多環的環烷基，更佳為碳數5～6的單環的環烷基。 Rx₁ ～Rx₃ 的兩個鍵結而形成的環烷基中，例如構成環的亞甲基的一個可經氧原子等雜原子、羰基等具有雜原子的基、或亞乙烯基取代。另外，該些環烷基中構成環烷烴環的伸乙基的一個以上可經伸乙烯基取代。可經取代。式（Y1）或式（Y2）所表示的基較佳為例如Rx₁ 為甲基或乙基、Rx₂ 與Rx₃ 鍵結而形成所述環烷基的形態。In formula (Y1) and formula (Y2), Rx ₁ to Rx ₃ each independently represent an alkyl group (linear or branched) or cycloalkyl (monocyclic or polycyclic), alkenyl (linear or Branched), or aryl (monocyclic or polycyclic). Furthermore, when all of Rx ₁ to Rx ₃ are alkyl groups (linear or branched), it is preferable that at least two of _{Rx 1} to Rx _{3 are methyl groups.} Among them, Rx ₁ to Rx ₃ preferably each independently represent a linear or branched alkyl group, and Rx ₁ to Rx _{3 more} preferably each independently represent a linear alkyl group. Two of Rx ₁ to Rx ₃ may be bonded to form a monocyclic ring or a polycyclic ring. The alkyl group of Rx ₁ to Rx ₃ is preferably an alkyl group having 1 to 5 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and tertiary butyl. As _{the cycloalkyl group of Rx 1} to Rx ₃ , monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl, norbornyl, tetracyclodecyl, tetracyclododecyl, and adamantyl are preferred. Cycloalkyl of the ring. The aryl group of Rx ₁ to Rx ₃ is preferably an aryl group having 6 to 10 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, and an anthryl group. The alkenyl group of Rx ₁ to Rx ₃ is preferably a vinyl group. The ring formed by two bonding of Rx ₁ to Rx _{3 is preferably a cycloalkyl group.} The cycloalkyl formed by the two bonds of Rx ₁ to Rx ₃ is preferably a monocyclic cycloalkyl such as cyclopentyl or cyclohexyl, or norbornyl, tetracyclodecyl, or tetracyclododecane A polycyclic cycloalkyl group such as an adamantyl group or an adamantyl group is more preferably a monocyclic cycloalkyl group having 5 to 6 carbon atoms. In _{the cycloalkyl group formed by two bonding of Rx 1} to Rx ₃ , for example, one of the methylene groups constituting the ring may be substituted with a hetero atom such as an oxygen atom, a group having a hetero atom such as a carbonyl group, or a vinylene group. In addition, one or more of the ethylene groups constituting the cycloalkane ring in these cycloalkyl groups may be substituted with ethylene groups. Can be replaced. The group represented by the formula (Y1) or the formula (Y2) is preferably a form in which, for example, Rx ₁ is a methyl group or an ethyl group, and Rx ₂ and Rx _{3 are} bonded to form the cycloalkyl group.

式（Y3）中，R₃₆ ～R₃₈ 分別獨立地表示氫原子或一價有機基。R₃₇ 與R₃₈ 可彼此鍵結而形成環。作為一價有機基，可列舉烷基、環烷基、芳基、芳烷基及烯基等。R₃₆ 亦較佳為氫原子。再者，所述烷基、環烷基、芳基及芳烷基中可含有氧原子等雜原子及/或羰基等具有雜原子的基。例如，所述烷基、環烷基、芳基及芳烷基中，例如亞甲基的一個以上可經氧原子等雜原子及/或羰基等具有雜原子的基取代。另外，R₃₈ 亦可與重複單元的主鏈所具有的其他取代基彼此鍵結而形成環。R₃₈ 與重複單元的主鏈所具有的其他取代基彼此鍵結而形成的基較佳為亞甲基等伸烷基。In formula (Y3), R ₃₆ to R ₃₈ each independently represent a hydrogen atom or a monovalent organic group. R ₃₇ and R ₃₈ may be bonded to each other to form a ring. As a monovalent organic group, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, etc. are mentioned. R _{36 is} also preferably a hydrogen atom. In addition, the alkyl group, cycloalkyl group, aryl group, and aralkyl group may contain heteroatoms such as oxygen atoms and/or groups having heteroatoms such as carbonyl groups. For example, in the alkyl group, cycloalkyl group, aryl group, and aralkyl group, one or more of, for example, a methylene group may be substituted with a heteroatom such as an oxygen atom and/or a group having a heteroatom such as a carbonyl group. In addition, R ₃₈ and other substituents of the main chain of the repeating unit may be bonded to each other to form a ring. The group formed by bonding R ₃₈ and other substituents of the main chain of the repeating unit to each other is preferably a methylene etc. alkylene group.

作為式（Y3），較佳為下述式（Y3-1）所表示的基。The formula (Y3) is preferably a group represented by the following formula (Y3-1).

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此處，L₁ 及L₂ 分別獨立地表示氫原子、烷基、環烷基、芳基、或者將該些組合而成的基（例如將烷基與芳基組合而成的基）。 M表示單鍵或二價連結基。 Q表示可含有雜原子的烷基、可含有雜原子的環烷基、可含有雜原子的芳基、胺基、銨基、巰基、氰基、醛基、或者將該些組合而成的基（例如將烷基與環烷基組合而成的基）。烷基及環烷基中，例如亞甲基的一個可經氧原子等雜原子或羰基等具有雜原子的基取代。再者，較佳為L₁ 及L₂ 中的其中一者為氫原子，另一者為烷基、環烷基、芳基或者將伸烷基與芳基組合而成的基。 Q、M及L₁ 中的至少兩個可鍵結而形成環（較佳為5員環或6員環）。就圖案的微細化的方面而言，L₂ 較佳為二級烷基或三級烷基，更佳為三級烷基。作為二級烷基，可列舉異丙基、環己基或降冰片基，作為三級烷基，可列舉第三丁基或金剛烷基。該些形態中，由於Tg（玻璃轉移溫度）及活性化能量變高，因此除了確保膜強度以外，亦可抑制灰霧。Here, L ₁ and L ₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a group formed by combining these (for example, a group formed by combining an alkyl group and an aryl group). M represents a single bond or a divalent linking group. Q represents an alkyl group that may contain a hetero atom, a cycloalkyl group that may contain a hetero atom, an aryl group that may contain a hetero atom, an amino group, an ammonium group, a mercapto group, a cyano group, an aldehyde group, or a combination of these (For example, a group formed by combining an alkyl group and a cycloalkyl group). In the alkyl group and the cycloalkyl group, for example, one methylene group may be substituted with a hetero atom such as an oxygen atom or a group having a hetero atom such as a carbonyl group. Furthermore, it is preferable that one of L ₁ and L ₂ is a hydrogen atom, and the other is an alkyl group, a cycloalkyl group, an aryl group, or a group formed by combining an alkylene group and an aryl group. At least two of Q, M and L ₁ may be bonded to form a ring (preferably a 5-membered ring or a 6-membered ring). In terms of the refinement of the pattern, L _{2 is} preferably a secondary alkyl group or a tertiary alkyl group, and more preferably a tertiary alkyl group. Examples of the secondary alkyl group include isopropyl, cyclohexyl, or norbornyl, and examples of the tertiary alkyl group include tertiary butyl or adamantyl. In these forms, since Tg (glass transition temperature) and activation energy become high, in addition to ensuring film strength, fog can also be suppressed.

式（Y4）中，Ar表示芳香環基。Rn表示烷基、環烷基或芳基。Rn與Ar可彼此鍵結而形成非芳香族環。Ar更佳為芳基。In formula (Y4), Ar represents an aromatic ring group. Rn represents an alkyl group, a cycloalkyl group or an aryl group. Rn and Ar may bond with each other to form a non-aromatic ring. Ar is more preferably an aryl group.

就重複單元的酸分解性優異的方面而言，於保護極性基的脫離基中，於非芳香族環與極性基（或其殘基）直接鍵結的情況下，所述非芳香族環中的、和與所述極性基（或其殘基）直接鍵結的環員原子鄰接的環員原子亦較佳為不具有氟原子等鹵素原子作為取代基。In terms of the excellent acid decomposability of the repeating unit, in the leaving group for protecting the polar group, when the non-aromatic ring is directly bonded to the polar group (or a residue thereof), the non-aromatic ring It is also preferable that the ring member atoms adjacent to the ring member atoms directly bonded to the polar group (or a residue thereof) do not have a halogen atom such as a fluorine atom as a substituent.

因酸的作用而脫離的脫離基除此以外亦可為3-甲基-2-環戊烯基之類的具有取代基（烷基等）的2-環戊烯基、以及1,1,4,4-四甲基環己基之類的具有取代基（烷基等）的環己基。The leaving group that is released by the action of the acid may also be 2-cyclopentenyl with substituents (alkyl etc.) such as 3-methyl-2-cyclopentenyl, and 1,1, Cyclohexyl having substituents (alkyl etc.) such as 4,4-tetramethylcyclohexyl.

作為具有酸分解性基的重複單元，亦較佳為式（A）所表示的重複單元。The repeating unit having an acid-decomposable group is also preferably a repeating unit represented by formula (A).

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L₁ 表示可具有氟原子或碘原子的二價連結基，R₁ 表示氫原子、氟原子、碘原子、可具有氟原子或碘原子的烷基、或者可具有氟原子或碘原子的芳基，R₂ 表示因酸的作用而脫離、且可具有氟原子或碘原子的脫離基。其中，L₁ 、R₁ 及R₂ 中的至少一個具有氟原子或碘原子。 L₁ 表示可具有氟原子或碘原子的二價連結基。作為可具有氟原子或碘原子的二價連結基，可列舉-CO-、-O-、-S、-SO-、-SO₂ -、可具有氟原子或碘原子的烴基（例如伸烷基、伸環烷基、伸烯基、伸芳基等）、以及該些的多個連結而成的連結基等。其中，作為L₁ ，較佳為-CO-、或-伸芳基-具有氟原子或碘原子的伸烷基-。伸芳基較佳為伸苯基。伸烷基可為直鏈狀，亦可為支鏈狀。伸烷基的碳數並無特別限制，較佳為1～10，更佳為1～3。具有氟原子或碘原子的伸烷基中所含的氟原子及碘原子的合計數並無特別限制，較佳為2以上，更佳為2～10，進而佳為3～6。L ₁ represents a divalent linking group which may have a fluorine atom or an iodine atom, and R ₁ represents a hydrogen atom, a fluorine atom, an iodine atom, an alkyl group which may have a fluorine atom or an iodine atom, or an aryl group which may have a fluorine atom or an iodine atom , R ₂ represents a leaving group which is released by the action of an acid and may have a fluorine atom or an iodine atom. Among them, _{at least one of L 1} , R ₁ and R ₂ has a fluorine atom or an iodine atom. L ₁ represents a divalent linking group which may have a fluorine atom or an iodine atom. Examples of the divalent linking group that may have a fluorine atom or an iodine atom include -CO-, -O-, -S, -SO-, -SO ₂ -, and a hydrocarbon group that may have a fluorine atom or an iodine atom (for example, alkylene , Cycloalkylene, alkenylene, arylalkylene, etc.), and a linking group formed by linking a plurality of these. Among them, as L ₁ , -CO- or -arylene-alkylene having a fluorine atom or an iodine atom is preferable. The arylene group is preferably a phenylene group. The alkylene group may be linear or branched. The carbon number of the alkylene group is not particularly limited, but is preferably 1-10, more preferably 1-3. The total number of fluorine atoms and iodine atoms contained in the alkylene group having a fluorine atom or an iodine atom is not particularly limited, but is preferably 2 or more, more preferably 2-10, and still more preferably 3-6.

R₁ 表示氫原子、氟原子、碘原子、可具有氟原子或碘原子的烷基、或者可具有氟原子或碘原子的芳基。烷基可為直鏈狀，亦可為支鏈狀。烷基的碳數並無特別限制，較佳為1～10，更佳為1～3。具有氟原子或碘原子的烷基中所含的氟原子及碘原子的合計數並無特別限制，較佳為1以上，更佳為1～5，進而佳為1～3。所述烷基亦可含有鹵素原子以外的氧原子等雜原子。R ₁ represents a hydrogen atom, a fluorine atom, an iodine atom, an alkyl group which may have a fluorine atom or an iodine atom, or an aryl group which may have a fluorine atom or an iodine atom. The alkyl group may be linear or branched. The carbon number of the alkyl group is not particularly limited, but is preferably 1-10, more preferably 1-3. The total number of fluorine atoms and iodine atoms contained in the alkyl group having a fluorine atom or an iodine atom is not particularly limited, but is preferably 1 or more, more preferably 1 to 5, and still more preferably 1 to 3. The alkyl group may contain heteroatoms such as oxygen atoms other than halogen atoms.

R₂ 表示因酸的作用而脫離、且可具有氟原子或碘原子的脫離基。其中，作為脫離基，可列舉式（Z1）～（Z4）所表示的基。式（Z1）：-C(Rx₁₁ )(Rx₁₂ )(Rx₁₃ ) 式（Z2）：-C(=O)OC(Rx₁₁ )(Rx₁₂ )(Rx₁₃ ) 式（Z3）：-C(R₁₃₆ )(R₁₃₇ )(OR₁₃₈ ) 式（Z4）：-C(Rn₁ )(H)(Ar₁ )R ₂ represents a leaving group which is released by the action of an acid and may have a fluorine atom or an iodine atom. Among them, examples of the leaving group include groups represented by formulas (Z1) to (Z4). Formula (Z1): -C(Rx ₁₁ )(Rx ₁₂ )(Rx ₁₃ ) Formula (Z2): -C(=O)OC(Rx ₁₁ )(Rx ₁₂ )(Rx ₁₃ ) Formula (Z3): -C (R ₁₃₆ )(R ₁₃₇ )(OR ₁₃₈ ) Formula (Z4): -C(Rn ₁ )(H)(Ar ₁ )

式（Z1）、（Z2）中，Rx₁₁ ～Rx₁₃ 分別獨立地表示可具有氟原子或碘原子的烷基（直鏈狀或支鏈狀）、可具有氟原子或碘原子的環烷基（單環或多環）、可具有氟原子或碘原子的烯基（直鏈狀或支鏈狀）、或者可具有氟原子或碘原子的芳基（單環或多環）。再者，於Rx₁₁ ～Rx₁₃ 全部為烷基（直鏈狀或支鏈狀）的情況下，較佳為Rx₁₁ ～Rx₁₃ 中的至少兩個為甲基。 Rx₁₁ ～Rx₁₃ 除了可具有氟原子或碘原子的方面以外，與所述（Y1）、（Y2）中的Rx₁ ～Rx₃ 相同，與烷基、環烷基、烯基及芳基的定義及較佳範圍相同。In the formulas (Z1) and (Z2), Rx ₁₁ to Rx ₁₃ each independently represent an alkyl group (linear or branched) that may have a fluorine atom or an iodine atom, and a cycloalkyl group that may have a fluorine atom or an iodine atom (Monocyclic or polycyclic), an alkenyl group (linear or branched) which may have a fluorine atom or an iodine atom, or an aryl group (monocyclic or polycyclic) which may have a fluorine atom or an iodine atom. Furthermore, when all of Rx ₁₁ to Rx ₁₃ are alkyl groups (linear or branched), it is preferable that at least two of _{Rx 11} to Rx _{13 are methyl groups.} Rx ₁₁ to Rx ₁₃ _{are the same as Rx 1} to Rx _{3 in} (Y1) and (Y2) except that they may have a fluorine atom or an iodine atom, and are the same as those of an alkyl group, a cycloalkyl group, an alkenyl group, and an aryl group. The definition and preferred range are the same.

式（Z3）中，R₁₃₆ ～R₁₃₈ 分別獨立地表示氫原子、或者可具有氟原子或碘原子的一價有機基。R₁₃₇ 與R₁₃₈ 可彼此鍵結而形成環。作為可具有氟原子或碘原子的一價有機基，可列舉：可具有氟原子或碘原子的烷基、可具有氟原子或碘原子的環烷基、可具有氟原子或碘原子的芳基、可具有氟原子或碘原子的芳烷基、以及將該些組合而成的基（例如將烷基與環烷基組合而成的基）。再者，所述烷基、環烷基、芳基及芳烷基中，除了氟原子及碘原子以外，亦可含有氧原子等雜原子。即，所述烷基、環烷基、芳基及芳烷基中，例如亞甲基的一個可經氧原子等雜原子、或羰基等具有雜原子的基取代。另外，R₁₃₈ 亦可與重複單元的主鏈所具有的其他取代基彼此鍵結而形成環。該情況下，R₁₃₈ 與重複單元的主鏈所具有的其他取代基彼此鍵結而形成的基較佳為亞甲基等伸烷基。In formula (Z3), R ₁₃₆ to R ₁₃₈ each independently represent a hydrogen atom or a monovalent organic group which may have a fluorine atom or an iodine atom. R ₁₃₇ and R ₁₃₈ may be bonded to each other to form a ring. Examples of the monovalent organic group which may have a fluorine atom or an iodine atom include an alkyl group which may have a fluorine atom or an iodine atom, a cycloalkyl group which may have a fluorine atom or an iodine atom, and an aryl group which may have a fluorine atom or an iodine atom. , Aralkyl groups that may have a fluorine atom or an iodine atom, and a group formed by combining these (for example, a group formed by combining an alkyl group and a cycloalkyl group). In addition, the alkyl group, cycloalkyl group, aryl group, and aralkyl group may contain heteroatoms such as oxygen atoms in addition to fluorine atoms and iodine atoms. That is, in the alkyl group, cycloalkyl group, aryl group, and aralkyl group, for example, one methylene group may be substituted with a heteroatom such as an oxygen atom, or a group having a heteroatom such as a carbonyl group. In addition, R ₁₃₈ and other substituents of the main chain of the repeating unit may be bonded to each other to form a ring. In this case, _{the group formed by bonding R 138} and other substituents of the main chain of the repeating unit to each other is preferably a methylene isotene group.

作為式（Z3），較佳為下述式（Z3-1）所表示的基。The formula (Z3) is preferably a group represented by the following formula (Z3-1).

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此處，L₁₁ 及L₁₂ 分別獨立地表示氫原子；可具有選自由氟原子、碘原子及氧原子所組成的群組中的雜原子的烷基；可具有選自由氟原子、碘原子及氧原子所組成的群組中的雜原子的環烷基；可具有選自由氟原子、碘原子及氧原子所組成的群組中的雜原子的芳基；或者將該些組合而成的基（例如，可具有選自由氟原子、碘原子及氧原子所組成的群組中的雜原子的、烷基與環烷基組合而成的基）。 M₁ 表示單鍵或二價連結基。 Q₁ 表示可具有選自由氟原子、碘原子及氧原子所組成的群組中的雜原子的烷基；可具有選自由氟原子、碘原子及氧原子所組成的群組中的雜原子的環烷基；選自由氟原子、碘原子及氧原子所組成的群組中的芳基；胺基；銨基；巰基；氰基；醛基；或者將該些組合而成的基（例如，可具有選自由氟原子、碘原子及氧原子所組成的群組中的雜原子的、烷基與環烷基組合而成的基）。Here, L ₁₁ and L ₁₂ each independently represent a hydrogen atom; an alkyl group that may have a hetero atom selected from the group consisting of a fluorine atom, an iodine atom, and an oxygen atom; may have an alkyl group selected from a fluorine atom, an iodine atom, and Cycloalkyl groups with hetero atoms in the group consisting of oxygen atoms; aryl groups with hetero atoms selected from the group consisting of fluorine atoms, iodine atoms and oxygen atoms; or groups formed by combining these (For example, it may have a heteroatom selected from the group consisting of a fluorine atom, an iodine atom, and an oxygen atom, and a group formed by a combination of an alkyl group and a cycloalkyl group). M ₁ represents a single bond or a divalent linking group. Q ₁ represents an alkyl group which may have a hetero atom selected from the group consisting of fluorine atom, iodine atom and oxygen atom; it may have a hetero atom selected from the group consisting of fluorine atom, iodine atom and oxygen atom Cycloalkyl groups; aryl groups selected from the group consisting of fluorine atoms, iodine atoms and oxygen atoms; amino groups; ammonium groups; mercapto groups; cyano groups; aldehyde groups; or groups formed by combining these (for example, It may have a heteroatom selected from the group consisting of a fluorine atom, an iodine atom, and an oxygen atom, and a group formed by a combination of an alkyl group and a cycloalkyl group).

式（Z4）中，Ar₁ 表示可具有氟原子或碘原子的芳香環基。Rn₁ 表示可具有氟原子或碘原子的烷基、可具有氟原子或碘原子的環烷基、或者可具有氟原子或碘原子的芳基。Rn₁ 與Ar₁ 可彼此鍵結而形成非芳香族環。In the formula (Z4), Ar ₁ represents an aromatic ring group which may have a fluorine atom or an iodine atom. Rn ₁ represents an alkyl group which may have a fluorine atom or an iodine atom, a cycloalkyl group which may have a fluorine atom or an iodine atom, or an aryl group which may have a fluorine atom or an iodine atom. Rn ₁ and Ar ₁ may be bonded to each other to form a non-aromatic ring.

作為具有酸分解性基的重複單元，亦較佳為通式（AI）所表示的重複單元。The repeating unit having an acid-decomposable group is also preferably a repeating unit represented by general formula (AI).

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通式（AI）中， Xa₁ 表示氫原子或者可具有取代基的烷基。 T表示單鍵或二價連結基。 Rx₁ ～Rx₃ 分別獨立地表示烷基（直鏈狀或支鏈狀）、環烷基（單環或多環）、烯基（直鏈狀或支鏈狀）、或芳基（單環或多環）。其中，於Rx₁ ～Rx₃ 全部為烷基（直鏈狀或支鏈狀）的情況下，較佳為Rx₁ ～Rx₃ 中的至少兩個為甲基。 Rx₁ ～Rx₃ 的兩個可鍵結而形成單環或多環（單環或多環的環烷基等）。In the general formula (AI), Xa ₁ represents a hydrogen atom or an alkyl group which may have a substituent. T represents a single bond or a divalent linking group. Rx ₁ to Rx ₃ each independently represent an alkyl group (linear or branched), cycloalkyl (monocyclic or polycyclic), alkenyl (linear or branched), or aryl (monocyclic) Or multiple loops). Among them, when all of Rx ₁ to Rx ₃ are alkyl groups (linear or branched), it is preferable that at least two of _{Rx 1} to Rx _{3 are methyl groups.} Two of Rx ₁ to Rx ₃ may be bonded to form a monocyclic or polycyclic ring (monocyclic or polycyclic cycloalkyl group, etc.).

作為Xa₁ 所表示的可具有取代基的烷基，例如可列舉甲基或-CH₂ -R₁₁ 所表示的基。R₁₁ 表示鹵素原子（氟原子等）、羥基或一價有機基，例如可列舉鹵素原子可取代的碳數5以下的烷基、鹵素原子可取代的碳數5以下的醯基、以及鹵素原子可取代的碳數5以下的烷氧基，較佳為碳數3以下的烷基，更佳為甲基。作為Xa₁ ，較佳為氫原子、甲基、三氟甲基或羥基甲基。Examples of the optionally substituted alkyl group represented by Xa ₁ include a methyl group or a group represented by _{-CH 2} -R _11. R ₁₁ represents a halogen atom (fluorine atom, etc.), a hydroxyl group, or a monovalent organic group. Examples include an alkyl group with 5 or less carbon atoms that can be substituted by a halogen atom, an acyl group with 5 or less carbon atoms that can be substituted by a halogen atom, and a halogen atom The substitutable alkoxy group having 5 or less carbon atoms is preferably an alkyl group having 3 or less carbon atoms, and more preferably a methyl group. Xa _{1 is} preferably a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.

作為T的二價連結基，可列舉伸烷基、芳香環基、-COO-Rt-基及-O-Rt-基等。式中，Rt表示伸烷基或伸環烷基。 T較佳為單鍵或-COO-Rt-。於T表示-COO-Rt-基的情況下，Rt較佳為碳數1～5的伸烷基，更佳為-CH₂ -基、-(CH₂ )₂ -基或-(CH₂ )₃ -基。As the divalent linking group of T, an alkylene group, an aromatic ring group, a -COO-Rt- group, an -O-Rt- group, and the like can be mentioned. In the formula, Rt represents an alkylene group or a cycloalkylene group. T is preferably a single bond or -COO-Rt-. When T represents a -COO-Rt- group, Rt is preferably an alkylene having 1 to 5 carbon atoms, more preferably -CH ₂ -group, -(CH ₂ ) ₂ -group or -(CH ₂ ) ₃ -base.

作為Rx₁ ～Rx₃ 的烷基，較佳為甲基、乙基、正丙基、異丙基、正丁基、異丁基及第三丁基等碳數1～4的烷基。作為Rx₁ ～Rx₃ 的環烷基，較佳為環戊基及環己基等單環的環烷基、或者降冰片基、四環癸基、四環十二烷基及金剛烷基等多環的環烷基。作為Rx₁ ～Rx₃ 的芳基，較佳為碳數6～10的芳基，例如可列舉苯基、萘基及蒽基等。作為Rx₁ ～Rx₃ 的烯基，較佳為乙烯基。作為Rx₁ ～Rx₃ 的兩個鍵結而形成的環烷基，較佳為環戊基及環己基等單環的環烷基，除此以外亦較佳為降冰片基、四環癸基、四環十二烷基及金剛烷基等多環的環烷基。其中，較佳為碳數5～6的單環的環烷基。 Rx₁ ～Rx₃ 的兩個鍵結而形成的環烷基中，例如構成環的亞甲基的一個可經氧原子等雜原子、羰基等具有雜原子的基、或亞乙烯基取代。另外，該些環烷基中構成環烷烴環的伸乙基的一個以上可經伸乙烯基取代。通式（AI）所表示的重複單元較佳為例如Rx₁ 為甲基或乙基、Rx₂ 與Rx₃ 鍵結而形成所述環烷基的形態。The alkyl group of Rx ₁ to Rx ₃ is preferably an alkyl group having 1 to 4 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and tertiary butyl. The cycloalkyl group of Rx ₁ to Rx ₃ is preferably a monocyclic cycloalkyl group such as cyclopentyl and cyclohexyl, or many others such as norbornyl, tetracyclodecyl, tetracyclododecyl, and adamantyl. Cycloalkyl of the ring. The aryl group of Rx ₁ to Rx ₃ is preferably an aryl group having 6 to 10 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, and an anthryl group. The alkenyl group of Rx ₁ to Rx ₃ is preferably a vinyl group. As _{the cycloalkyl formed by the two bonds of Rx 1} to Rx ₃ , monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl are preferred. In addition, norbornyl and tetracyclodecyl are also preferred. , Polycyclic cycloalkyl such as tetracyclododecyl and adamantyl. Among them, a monocyclic cycloalkyl group having 5 to 6 carbon atoms is preferred. In _{the cycloalkyl group formed by two bonding of Rx 1} to Rx ₃ , for example, one of the methylene groups constituting the ring may be substituted with a hetero atom such as an oxygen atom, a group having a hetero atom such as a carbonyl group, or a vinylene group. In addition, one or more of the ethylene groups constituting the cycloalkane ring in these cycloalkyl groups may be substituted with ethylene groups. The repeating unit represented by the general formula (AI) is preferably a form in which, for example, Rx ₁ is a methyl group or an ethyl group, and Rx ₂ and Rx _{3 are} bonded to form the cycloalkyl group.

於所述各基具有取代基的情況下，作為取代基，例如可列舉烷基（碳數1～4）、鹵素原子、羥基、烷氧基（碳數1～4）、羧基及烷氧基羰基（碳數2～6）等。取代基中的碳數較佳為8以下。When each group has a substituent, examples of the substituent include an alkyl group (carbon number 1 to 4), a halogen atom, a hydroxyl group, an alkoxy group (carbon number 1 to 4), a carboxyl group, and an alkoxy group. Carbonyl (carbon number 2-6) and so on. The number of carbon atoms in the substituent is preferably 8 or less.

作為通式（AI）所表示的重複單元，較佳為酸分解性(甲基)丙烯酸三級烷基酯系重複單元（Xa₁ 表示氫原子或甲基且T表示單鍵的重複單元）。The repeating unit represented by the general formula (AI) is preferably an acid-decomposable tertiary alkyl (meth)acrylate repeating unit (Xa ₁ represents a hydrogen atom or a methyl group, and T represents a single bond).

相對於樹脂（A）中的全部重複單元，具有酸分解性基的重複單元的含量較佳為15莫耳%以上，更佳為20莫耳%以上，進而佳為30莫耳%以上。另外，作為其上限值，較佳為80莫耳%以下，更佳為70莫耳%以下，尤佳為60莫耳%以下。The content of the repeating unit having an acid-decomposable group relative to all repeating units in the resin (A) is preferably 15 mol% or more, more preferably 20 mol% or more, and still more preferably 30 mol% or more. In addition, the upper limit is preferably 80 mol% or less, more preferably 70 mol% or less, and particularly preferably 60 mol% or less.

以下示出具有酸分解性基的重複單元的具體例，但本發明並不限定於此。再者，式中，Xa₁ 表示H、CH₃ 、CF₃ 及CH₂ OH中的任一者，Rxa及Rxb分別表示碳數1～5的直鏈狀或支鏈狀的烷基。Although the specific example of the repeating unit which has an acid-decomposable group is shown below, this invention is not limited to this. In addition, in the formula, Xa ₁ represents any of H, CH ₃ , CF ₃ and CH ₂ OH, and Rxa and Rxb each represent a linear or branched alkyl group having 1 to 5 carbon atoms.

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樹脂（A）亦可包含所述重複單元以外的重複單元。例如，樹脂（A）亦可包含選自由以下的A群組所組成的群組中的至少一種重複單元及/或選自由以下的B群組所組成的群組中的至少一種重複單元。 A群組：由以下的（20）～（29）的重複單元所組成的群組。（20）後述的具有酸基的重複單元（21）後述的具有氟原子或碘原子的重複單元（22）後述的具有內酯基、磺內酯基或碳酸酯基的重複單元（23）後述的具有光酸產生劑的重複單元（24）後述的通式（V-1）或下述通式（V-2）所表示的重複單元（25）後述的式（A）所表示的重複單元（26）後述的式（B）所表示的重複單元（27）後述的式（C）所表示的重複單元（28）後述的式（D）所表示的重複單元（29）後述的式（E）所表示的重複單元 B群組：由以下的（30）～（32）的重複單元所組成的群組。（30）後述的具有選自內酯基、磺內酯基、碳酸酯基、羥基、氰基及鹼可溶性基中的至少一種基的重複單元（31）後述的具有脂環烴結構、不顯示酸分解性的重複單元（32）後述的不具有羥基及氰基的任一者的、通式（III）所表示的重複單元Resin (A) may contain repeating units other than the said repeating unit. For example, the resin (A) may also include at least one repeating unit selected from the group consisting of the following A group and/or at least one repeating unit selected from the group consisting of the following B group. Group A: A group consisting of the following repeating units (20) to (29). (20) Repeating unit with acid group mentioned later (21) Repeating unit having fluorine atom or iodine atom mentioned later (22) Repeating units having a lactone group, a sultone group, or a carbonate group described later (23) Repeating unit with photoacid generator described later (24) The repeating unit represented by the following general formula (V-1) or the following general formula (V-2) (25) Repeating unit represented by formula (A) described later (26) Repeating unit represented by formula (B) described later (27) Repeating unit represented by formula (C) described later (28) Repeating unit represented by formula (D) described later (29) Repeating unit represented by formula (E) described later Group B: A group consisting of the following repeating units (30) to (32). (30) A repeating unit having at least one group selected from a lactone group, a sultone group, a carbonate group, a hydroxyl group, a cyano group, and an alkali-soluble group described later (31) The repeating unit that has an alicyclic hydrocarbon structure and does not show acid decomposability as described later (32) The repeating unit represented by the general formula (III) that does not have any of a hydroxyl group and a cyano group described later

於本發明的抗蝕劑組成物用作EUV用感光化射線性或感放射線性樹脂組成物的情況下，樹脂（A）較佳為具有選自由所述A群組所組成的群組中的至少一種重複單元。另外，於本發明的抗蝕劑組成物用作EUV用感光化射線性或感放射線性樹脂組成物的情況下，樹脂（A）較佳為含有氟原子及碘原子中的至少一者。於樹脂（A）含有氟原子及碘原子兩者的情況下，樹脂（A）可具有含有氟原子及碘原子兩者的一個重複單元，樹脂（A）亦可含有具有氟原子的重複單元與含有碘原子的重複單元此兩種。另外，於本發明的抗蝕劑組成物用作EUV用感光化射線性或感放射線性樹脂組成物的情況下，樹脂（A）較佳為含有具有芳香族基的重複單元。於本發明的抗蝕劑組成物用作ArF用感光化射線性或感放射線性樹脂組成物的情況下，樹脂（A）較佳為具有選自由所述B群組所組成的群組中的至少一種重複單元。再者，於本發明的抗蝕劑組成物用作ArF用感光化射線性或感放射線性樹脂組成物的情況下，樹脂（A）較佳為不包含氟原子及矽原子中的任一者。另外，於本發明的抗蝕劑組成物用作ArF用感光化射線性或感放射線性樹脂組成物的情況下，樹脂（A）較佳為不具有芳香族基。When the resist composition of the present invention is used as a sensitizing or radiation-sensitive resin composition for EUV, the resin (A) is preferably selected from the group consisting of the A group At least one repeating unit. In addition, when the resist composition of the present invention is used as a sensitizing or radiation-sensitive resin composition for EUV, the resin (A) preferably contains at least one of a fluorine atom and an iodine atom. When the resin (A) contains both fluorine atoms and iodine atoms, the resin (A) may have a repeating unit containing both fluorine atoms and iodine atoms, and the resin (A) may also contain a repeating unit containing fluorine atoms and These two repeating units containing iodine atoms. In addition, when the resist composition of the present invention is used as a sensitizing or radiation-sensitive resin composition for EUV, the resin (A) preferably contains a repeating unit having an aromatic group. When the resist composition of the present invention is used as a sensitizing or radiation-sensitive resin composition for ArF, the resin (A) is preferably selected from the group consisting of the B group At least one repeating unit. Furthermore, when the resist composition of the present invention is used as a sensitizing radiation or radiation-sensitive resin composition for ArF, the resin (A) preferably does not contain any of fluorine atoms and silicon atoms . In addition, when the resist composition of the present invention is used as a sensitizing radiation-sensitive or radiation-sensitive resin composition for ArF, the resin (A) preferably does not have an aromatic group.

＜具有酸基的重複單元＞樹脂（A）亦可含有具有酸基的重複單元。作為酸基，較佳為pKa為13以下的酸基。作為酸基，例如較佳為羧基、酚性羥基、氟化醇基（較佳為六氟異丙醇基）、磺酸基、磺醯胺基或異丙醇基等。另外，所述六氟異丙醇基中，氟原子的一個以上（較佳為1個～2個）可經氟原子以外的基（烷氧基羰基等）取代。如此形成的-C(CF₃ )(OH)-CF₂ -作為酸基亦較佳。另外，氟原子的一個以上亦可被取代為氟原子以外的基而形成包含-C(CF₃ )(OH)-CF₂ -的環。具有酸基的重複單元較佳為具有極性基經藉由所述酸的作用脫離的脫離基保護的結構的重複單元、以及與後述的具有內酯基、磺內酯基或碳酸酯基的重複單元不同的重複單元。<Repeating unit having an acid group> The resin (A) may contain a repeating unit having an acid group. The acid group is preferably an acid group having a pKa of 13 or less. As the acid group, for example, a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), a sulfonic acid group, a sulfonamide group, or an isopropanol group are preferable. In addition, in the hexafluoroisopropanol group, one or more fluorine atoms (preferably 1 to 2) may be substituted with groups other than fluorine atoms (alkoxycarbonyl groups, etc.). The thus formed -C(CF ₃ )(OH)-CF ₂ -is also preferable as the acid group. In addition, one or more fluorine atoms may be substituted with groups other than fluorine atoms to form a ring _{containing -C(CF 3} )(OH)-CF _{2 -.} The repeating unit having an acid group is preferably a repeating unit having a structure in which a polar group is protected by a leaving group detached by the action of the acid, and a repeating unit having a lactone group, a sultone group, or a carbonate group described later Repeating units with different units.

具有酸基的重複單元亦可具有氟原子或碘原子。The repeating unit having an acid group may also have a fluorine atom or an iodine atom.

作為具有酸基的重複單元，較佳為式（B）所表示的重複單元。The repeating unit having an acid group is preferably a repeating unit represented by formula (B).

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R₃ 表示氫原子、或者可具有氟原子或碘原子的一價有機基。作為可具有氟原子或碘原子的一價有機基，較佳為-L₄ -R₈ 所表示的基。L₄ 表示單鍵或酯基。R₈ 可列舉可具有氟原子或碘原子的烷基、可具有氟原子或碘原子的環烷基、可具有氟原子或碘原子的芳基、或者將該些組合而成的基。R ₃ represents a hydrogen atom or a monovalent organic group which may have a fluorine atom or an iodine atom. The monovalent organic group which may have a fluorine atom or an iodine atom is preferably a group represented by _{-L 4} -R _8. L ₄ represents a single bond or an ester group. Examples of R ₈ include an alkyl group which may have a fluorine atom or an iodine atom, a cycloalkyl group which may have a fluorine atom or an iodine atom, an aryl group which may have a fluorine atom or an iodine atom, or a group formed by combining these.

R₄ 及R₅ 分別獨立地表示氫原子、氟原子、碘原子、或者可具有氟原子或碘原子的烷基。R ₄ and R ₅ each independently represent a hydrogen atom, a fluorine atom, an iodine atom, or an alkyl group which may have a fluorine atom or an iodine atom.

L₂ 表示單鍵或酯基。 L₃ 表示（n+m+1）價芳香族烴環基、或（n+m+1）價脂環式烴環基。作為芳香族烴環基，可列舉苯環基及萘環基。作為脂環式烴環基，可為單環，亦可為多環，例如可列舉環烷環基。 R₆ 表示羥基或氟化醇基（較佳為六氟異丙醇基）。再者，於R₆ 為羥基的情況下，L₃ 較佳為（n+m+1）價芳香族烴環基。 R₇ 表示鹵素原子。作為鹵素原子，可列舉：氟原子、氯原子、溴原子或碘原子。 m表示1以上的整數。m較佳為1～3的整數，更佳為1～2的整數。 n表示0或1以上的整數。n較佳為1～4的整數。再者，（n+m+1）較佳為1～5的整數。L ₂ represents a single bond or an ester group. L ₃ represents an (n+m+1)-valent aromatic hydrocarbon ring group or an (n+m+1)-valent alicyclic hydrocarbon ring group. Examples of the aromatic hydrocarbon ring group include a benzene ring group and a naphthalene ring group. The alicyclic hydrocarbon ring group may be a monocyclic ring or a polycyclic ring, and examples thereof include a cycloalkane ring group. R ₆ represents a hydroxyl group or a fluorinated alcohol group (preferably a hexafluoroisopropanol group). Furthermore, when R ₆ is a hydroxyl group, L _{3 is} preferably an (n+m+1)-valent aromatic hydrocarbon ring group. R ₇ represents a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. m represents an integer of 1 or more. m is preferably an integer of 1-3, more preferably an integer of 1-2. n represents an integer of 0 or more. n is preferably an integer of 1-4. Furthermore, (n+m+1) is preferably an integer of 1-5.

作為具有酸基的重複單元，亦較佳為下述通式（I）所表示的重複單元。The repeating unit having an acid group is also preferably a repeating unit represented by the following general formula (I).

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通式（I）中， R₄₁ 、R₄₂ 及R₄₃ 分別獨立地表示氫原子、烷基、環烷基、鹵素原子、氰基或烷氧基羰基。其中，R₄₂ 可與Ar₄ 鍵結而形成環，該情況下的R₄₂ 表示單鍵或伸烷基。 X₄ 表示單鍵、-COO-或-CONR₆₄ -，R₆₄ 表示氫原子或烷基。 L₄ 表示單鍵或伸烷基。 Ar₄ 表示（n+1）價芳香環基，於與R₄₂ 鍵結而形成環的情況下，表示（n+2）價芳香環基。 n表示1～5的整數。In the general formula (I), R ₄₁ , R ₄₂ and R ₄₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. Among them, R ₄₂ may be _{bonded to Ar 4} to form a ring. In this case, R ₄₂ represents a single bond or an alkylene group. X ₄ represents a single bond, -COO- or -CONR ₆₄ -, and R ₆₄ represents a hydrogen atom or an alkyl group. L ₄ represents a single bond or an alkylene group. Ar ₄ represents an (n+1)-valent aromatic ring group, and when it _{bonds with R 42} to form a ring, it represents an (n+2)-valent aromatic ring group. n represents an integer of 1-5.

作為通式（I）中的R₄₁ 、R₄₂ 及R₄₃ 的烷基，較佳為甲基、乙基、丙基、異丙基、正丁基、第二丁基、己基、2-乙基己基、辛基及十二烷基等碳數20以下的烷基，更佳為碳數8以下的烷基，進而佳為碳數3以下的烷基。 _{As the alkyl group of R 41} , R ₄₂ and R ₄₃ in the general formula (I), methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, hexyl, 2-ethyl are preferred The alkyl group having 20 or less carbon atoms, such as hexyl, octyl, and dodecyl group, is more preferably an alkyl group having 8 or less carbon atoms, and still more preferably an alkyl group having 3 or less carbon atoms.

作為通式（I）中的R₄₁ 、R₄₂ 及R₄₃ 的環烷基，可為單環型，亦可為多環型。其中，較佳為環丙基、環戊基及環己基等碳數為3個～8個的單環型的環烷基。作為通式（I）中的R₄₁ 、R₄₂ 及R₄₃ 的鹵素原子，可列舉：氟原子、氯原子、溴原子及碘原子，較佳為氟原子。作為通式（I）中的R₄₁ 、R₄₂ 及R₄₃ 的烷氧基羰基中所含的烷基，較佳為與所述R₄₁ 、R₄₂ 、R₄₃ 中的烷基相同的烷基。 _{The cycloalkyl group of R 41} , R ₄₂ and R ₄₃ in the general formula (I) may be a monocyclic type or a polycyclic type. Among them, preferred are monocyclic cycloalkyl groups having 3 to 8 carbon atoms, such as cyclopropyl, cyclopentyl, and cyclohexyl. _{Examples of the halogen atom of R 41} , R ₄₂ and R ₄₃ in the general formula (I) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferred. The alkyl group contained in the alkoxycarbonyl group _{of R 41} , R ₄₂ and R ₄₃ in the general formula (I) is preferably the same alkyl group as the alkyl group of _{R 41} , R ₄₂ , and R ₄₃ .

作為所述各基中的較佳的取代基，例如可列舉烷基、環烷基、芳基、胺基、醯胺基、脲基、胺基甲酸酯基、羥基、羧基、鹵素原子、烷氧基、硫醚基、醯基、醯氧基、烷氧基羰基、氰基及硝基。取代基的碳數較佳為8以下。As preferred substituents in each of the above groups, for example, alkyl groups, cycloalkyl groups, aryl groups, amino groups, amide groups, ureido groups, urethane groups, hydroxyl groups, carboxyl groups, halogen atoms, Alkoxy, thioether, acyl, alkoxy, alkoxycarbonyl, cyano and nitro groups. The carbon number of the substituent is preferably 8 or less.

Ar₄ 表示（n+1）價芳香環基。n為1時的二價芳香環基例如較佳為伸苯基、甲伸苯基、伸萘基及伸蒽基等碳數6～18的伸芳基或含有噻吩環、呋喃環、吡咯環、苯並噻吩環、苯並呋喃環、苯並吡咯環、三嗪環、咪唑環、苯並咪唑環、***環、噻二唑環及噻唑環等雜環的二價芳香環基。再者，所述芳香環基亦可具有取代基。Ar ₄ represents an (n+1)-valent aromatic ring group. When n is 1, the divalent aromatic ring group is preferably, for example, phenylene, phenylene, naphthylene, and anthracenyl, and other arylene groups having 6 to 18 carbon atoms or containing a thiophene ring, a furan ring, or a pyrrole ring. , Benzothiophene ring, benzofuran ring, benzopyrrole ring, triazine ring, imidazole ring, benzimidazole ring, triazole ring, thiadiazole ring and thiazole ring and other heterocyclic divalent aromatic ring groups. Furthermore, the aromatic ring group may have a substituent.

作為n為2以上的整數時的（n+1）價芳香環基的具體例，可列舉自二價芳香環基的所述具體例中去除（n-1）個任意的氫原子而成的基。（n+1）價芳香環基亦可進而具有取代基。As a specific example of the (n+1)-valent aromatic ring group when n is an integer of 2 or more, there can be exemplified those obtained by removing (n-1) arbitrary hydrogen atoms from the specific example of the divalent aromatic ring group. base. The (n+1)-valent aromatic ring group may further have a substituent.

作為所述烷基、環烷基、烷氧基羰基、伸烷基及（n+1）價芳香環基可具有的取代基，例如可列舉於通式（I）中的R₄₁ 、R₄₂ 及R₄₃ 中列舉的烷基、甲氧基、乙氧基、羥基乙氧基、丙氧基、羥基丙氧基及丁氧基等烷氧基；苯基等芳基等。作為由X₄ 所表示的-CONR₆₄ -（R₆₄ 表示氫原子或烷基）中的R₆₄ 的烷基，可列舉甲基、乙基、丙基、異丙基、正丁基、第二丁基、己基、2-乙基己基、辛基及十二烷基等碳數20以下的烷基，較佳為碳數8以下的烷基。作為X₄ ，較佳為單鍵、-COO-或-CONH-，更佳為單鍵或-COO-。Examples of the substituents that the alkyl group, cycloalkyl group, alkoxycarbonyl group, alkylene group, and (n+1)-valent aromatic ring group may have include R ₄₁ and R _{42 in the general formula (I)} And alkoxy groups such as alkyl, methoxy, ethoxy, hydroxyethoxy, propoxy, hydroxypropoxy, and butoxy, exemplified in _{R 43; aryl groups such as phenyl and the like.} _{Examples of the alkyl group of R 64} in -CONR _64- (R ₆₄ represents a hydrogen atom or an alkyl group) represented by X ₄ include methyl, ethyl, propyl, isopropyl, n-butyl, and second Alkyl groups with 20 or less carbon atoms, such as butyl, hexyl, 2-ethylhexyl, octyl, and dodecyl, are preferably alkyl groups with 8 or less carbon atoms. X _{4 is} preferably a single bond, -COO- or -CONH-, and more preferably a single bond or -COO-.

作為L₄ 中的伸烷基，較佳為亞甲基、伸乙基、伸丙基、伸丁基、伸己基及伸辛基等碳數1～8的伸烷基。作為Ar₄ ，較佳為碳數6～18的芳香環基，更佳為苯環基、萘環基及伸聯苯環基。通式（I）所表示的重複單元較佳為具備羥基苯乙烯結構。即，Ar₄ 較佳為苯環基。The _{alkylene group in L 4} is preferably an alkylene group having 1 to 8 carbon atoms such as a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, and an octylene group. Ar _{4 is} preferably an aromatic ring group having 6 to 18 carbon atoms, more preferably a benzene ring group, a naphthalene ring group, and a biphenyl ring group. The repeating unit represented by general formula (I) preferably has a hydroxystyrene structure. That is, Ar _{4 is} preferably a benzene ring group.

作為通式（I）所表示的重複單元，較佳為下述通式（1）所表示的重複單元。The repeating unit represented by the general formula (I) is preferably a repeating unit represented by the following general formula (1).

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通式（1）中， A表示氫原子、烷基、環烷基、鹵素原子或氰基。 R表示鹵素原子、烷基、環烷基、芳基、烯基、芳烷基、烷氧基、烷基羰氧基、烷基磺醯氧基、烷氧基羰基或芳氧基羰基，於具有多個的情況下可相同亦可不同。於具有多個R的情況下，可彼此共同而形成環。作為R，較佳為氫原子。 a表示1～3的整數。 b表示0～（5-a）的整數。In the general formula (1), A represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom or a cyano group. R represents a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, an aralkyl group, an alkoxy group, an alkylcarbonyloxy group, an alkylsulfonyloxy group, an alkoxycarbonyl group or an aryloxycarbonyl group, in When there are a plurality of them, they may be the same or different. In the case of having a plurality of Rs, they may form a ring together with each other. As R, a hydrogen atom is preferred. a represents an integer of 1-3. b represents an integer from 0 to (5-a).

以下例示具有酸基的重複單元。式中，a表示1或2。The repeating unit having an acid group is exemplified below. In the formula, a represents 1 or 2.

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再者，在所述重複單元中，較佳為以下具體記載的重複單元。式中，R表示氫原子或甲基，a表示2或3。Furthermore, among the repeating units, the repeating units specifically described below are preferred. In the formula, R represents a hydrogen atom or a methyl group, and a represents 2 or 3.

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相對於樹脂（A）中的全部重複單元，具有酸基的重複單元的含量較佳為10莫耳%以上，更佳為15莫耳%以上。另外，作為其上限值，較佳為70莫耳%以下，更佳為65莫耳%以下，進而佳為60莫耳%以下。The content of the repeating unit having an acid group relative to all repeating units in the resin (A) is preferably 10 mol% or more, and more preferably 15 mol% or more. In addition, the upper limit is preferably 70 mol% or less, more preferably 65 mol% or less, and still more preferably 60 mol% or less.

＜具有氟原子或碘原子的重複單元＞樹脂（A）除了所述＜具有酸分解性基的重複單元＞及＜具有酸基的重複單元＞以外，亦可含有具有氟原子或碘原子的重複單元。另外，此處所述的＜具有氟原子或碘原子的重複單元＞較佳為與後述的＜具有內酯基、磺內酯基或碳酸酯基的重複單元＞及＜具有光酸產生基的重複單元＞等屬於A群組的其他種類的重複單元不同。<Repeating unit with fluorine atom or iodine atom> The resin (A) may contain a repeating unit having a fluorine atom or an iodine atom in addition to the above-mentioned <repeating unit having an acid-decomposable group> and <repeating unit having an acid group>. In addition, the "repeating unit having a fluorine atom or an iodine atom" described here is preferably the same as the "repeating unit having a lactone group, a sultone group, or a carbonate group" and the "repeating unit having a photoacid generating group" described later. Repeating unit> and other types of repeating units belonging to group A are different.

作為具有氟原子或碘原子的重複單元，較佳為式（C）所表示的重複單元。The repeating unit having a fluorine atom or an iodine atom is preferably a repeating unit represented by formula (C).

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L₅ 表示單鍵或酯基。 R₉ 表示氫原子、或者可具有氟原子或碘原子的烷基。 R₁₀ 表示氫原子、可具有氟原子或碘原子的烷基、可具有氟原子或碘原子的環烷基、可具有氟原子或碘原子的芳基、或者將該些組合而成的基。L ₅ represents a single bond or an ester group. R ₉ represents a hydrogen atom or an alkyl group which may have a fluorine atom or an iodine atom. R ₁₀ represents a hydrogen atom, an alkyl group which may have a fluorine atom or an iodine atom, a cycloalkyl group which may have a fluorine atom or an iodine atom, an aryl group which may have a fluorine atom or an iodine atom, or a group formed by combining these.

以下例示具有氟原子或碘原子的重複單元。The repeating unit having a fluorine atom or an iodine atom is exemplified below.

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相對於樹脂（A）中的全部重複單元，具有氟原子或碘原子的重複單元的含量較佳為0莫耳%以上，更佳為5莫耳%以上，進而佳為10莫耳%以上。另外，作為其上限值，較佳為50莫耳%以下，更佳為45莫耳%以下，進而佳為40莫耳%以下。再者，如上所述，具有氟原子或碘原子的重複單元中不包含＜具有酸分解性基的重複單元＞及＜具有酸基的重複單元＞，因此所述具有氟原子或碘原子的重複單元的含量亦是指除了＜具有酸分解性基的重複單元＞及＜具有酸基的重複單元＞以外的具有氟原子或碘原子的重複單元的含量。The content of the repeating unit having a fluorine atom or an iodine atom relative to all repeating units in the resin (A) is preferably 0 mol% or more, more preferably 5 mol% or more, and still more preferably 10 mol% or more. In addition, the upper limit is preferably 50 mol% or less, more preferably 45 mol% or less, and still more preferably 40 mol% or less. Furthermore, as described above, the repeating unit having a fluorine atom or an iodine atom does not include the <repeating unit having an acid-decomposable group> and <repeating unit having an acid group>, so the repeating unit having a fluorine atom or an iodine atom The content of the unit also refers to the content of the repeating unit having a fluorine atom or an iodine atom other than the <repeating unit having an acid-decomposable group> and the <repeating unit having an acid group>.

樹脂（A）的重複單元中，相對於樹脂（A）的全部重複單元，含有氟原子及碘原子中的至少一者的重複單元的合計含量較佳為20莫耳%以上，更佳為30莫耳%以上，進而佳為40莫耳%以上。上限值並無特別限制，例如為100莫耳%以下。再者，作為含有氟原子及碘原子中的至少一者的重複單元，例如可列舉具有氟原子或碘原子且具有酸分解性基的重複單元、具有氟原子或碘原子且具有酸基的重複單元、及具有氟原子或碘原子的重複單元。In the repeating unit of the resin (A), the total content of the repeating unit containing at least one of a fluorine atom and an iodine atom relative to all the repeating units of the resin (A) is preferably 20 mol% or more, more preferably 30 Mole% or more, more preferably 40 mole% or more. The upper limit is not particularly limited, and is, for example, 100 mol% or less. Furthermore, as a repeating unit containing at least one of a fluorine atom and an iodine atom, for example, a repeating unit having a fluorine atom or an iodine atom and an acid-decomposable group, and a repeating unit having a fluorine atom or an iodine atom and an acid group can be cited Unit and repeating unit having fluorine atom or iodine atom.

＜具有內酯基、磺內酯基或碳酸酯基的重複單元＞樹脂（A）亦可含有具有選自由內酯基、磺內酯基及碳酸酯基所組成的群組中的至少一種的重複單元（以下，亦總稱為「具有內酯基、磺內酯基或碳酸酯基的重複單元」）。具有內酯基、磺內酯基或碳酸酯基的重複單元亦較佳為不具有六氟丙醇基等酸基。<Repeating units having a lactone group, a sultone group, or a carbonate group> The resin (A) may also contain a repeating unit having at least one selected from the group consisting of a lactone group, a sultone group, and a carbonate group (hereinafter, also collectively referred to as "having a lactone group, a sultone group Or the repeating unit of the carbonate group"). It is also preferable that the repeating unit having a lactone group, a sultone group, or a carbonate group does not have an acid group such as a hexafluoropropanol group.

作為內酯基或磺內酯基，只要具有內酯結構或磺內酯結構即可。內酯結構或磺內酯結構較佳為5員環內酯結構～7員環內酯結構或5員環磺內酯結構～7員環磺內酯結構。其中，更佳為其他環結構以形成雙環結構或螺結構的形態於5員環內酯結構～7員環內酯結構中進行縮環而成者、或者其他環結構以形成雙環結構或螺結構的形態於5員環磺內酯結構～7員環磺內酯結構中進行縮環而成者。樹脂（A）較佳為具有如下重複單元，所述重複單元具有自下述通式（LC1-1）～（LC1-21）中的任一者所表示的內酯結構、或者下述通式（SL1-1）～（SL1-3）中的任一者所表示的磺內酯結構的環員原子中去掉一個以上的氫原子而成的內酯基或磺內酯基。另外，內酯基或磺內酯基亦可與主鏈直接鍵結。例如，內酯基或磺內酯基的環員原子亦可構成樹脂（A）的主鏈。As a lactone group or a sultone group, what is necessary is just to have a lactone structure or a sultone structure. The lactone structure or the sultone structure is preferably a 5-membered cyclic lactone structure to a 7-membered cyclic lactone structure or a 5-membered cyclic sultone structure to a 7-membered cyclic sultone structure. Among them, it is more preferable that other ring structures are condensed in the form of a 5-membered ring lactone structure to a 7-membered ring lactone structure to form a bicyclic structure or a spiro structure, or other ring structures are formed to form a bicyclic structure or a spiro structure. The form is formed by condensing rings in the 5-membered cyclic sultone structure to the 7-membered cyclic sultone structure. The resin (A) preferably has a repeating unit having a lactone structure represented by any one of the following general formulas (LC1-1) to (LC1-21), or the following general formula A lactone group or a sultone group obtained by removing one or more hydrogen atoms from the ring member atoms of the sultone structure represented by any one of (SL1-1) to (SL1-3). In addition, the lactone group or sultone group may be directly bonded to the main chain. For example, the ring member atoms of the lactone group or the sultone group may also constitute the main chain of the resin (A).

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所述內酯結構或磺內酯結構部分亦可具有取代基（Rb₂ ）。作為較佳的取代基（Rb₂ ），可列舉碳數1～8的烷基、碳數4～7的環烷基、碳數1～8的烷氧基、碳數1～8的烷氧基羰基、羧基、鹵素原子、羥基、氰基及酸分解性基等。n₂ 表示0～4的整數。於n2為2以上時，多個存在的Rb₂ 可不同，另外多個存在的Rb₂ 彼此可鍵結而形成環。The lactone structure or the sultone structure part may also have a substituent (Rb ₂ ). Preferred substituents (Rb ₂ ) include alkyl groups having 1 to 8 carbons, cycloalkyl groups having 4 to 7 carbons, alkoxy groups having 1 to 8 carbons, and alkoxy groups having 1 to 8 carbons. Carbonyl group, carboxyl group, halogen atom, hydroxyl group, cyano group, acid decomposable group, etc. n ₂ represents an integer of 0-4. When n2 is 2 or more, multiple existing Rb ₂ may be different, and multiple existing Rb ₂ may be bonded to each other to form a ring.

作為含有具有通式（LC1-1）～（LC1-21）中的任一者所表示的內酯結構或通式（SL1-1）～（SL1-3）中的任一者所表示的磺內酯結構的基的重複單元，例如可列舉下述通式（AI）所表示的重複單元等。It contains a lactone structure represented by any one of the general formulas (LC1-1) to (LC1-21) or a sulfonate represented by any one of the general formulas (SL1-1) to (SL1-3) Examples of the repeating unit of the group of the lactone structure include repeating units represented by the following general formula (AI).

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通式（AI）中，Rb₀ 表示氫原子、鹵素原子或碳數1～4的烷基。作為Rb₀ 的烷基可具有的較佳的取代基，可列舉羥基及鹵素原子。作為Rb₀ 的鹵素原子，可列舉：氟原子、氯原子、溴原子及碘原子等。Rb₀ 較佳為氫原子或甲基。 Ab表示單鍵、伸烷基、具有單環或多環的脂環烴結構的二價連結基、醚基、酯基、羰基、羧基、或者將該些組合而成的二價基。其中，較佳為單鍵或-Ab₁ -CO₂ -所表示的連結基。Ab₁ 為直鏈狀或支鏈狀的伸烷基、或者單環或多環的伸環烷基，較佳為亞甲基、伸乙基、伸環己基、伸金剛烷基或伸降冰片基。 V表示自通式（LC1-1）～（LC1-21）中的任一者所表示的內酯結構的環員原子中去掉一個氫原子而成的基、或者自通式（SL1-1）～（SL1-3）中的任一者所表示的磺內酯結構的環員原子中去掉一個氫原子而成的基。In the general formula (AI), Rb ₀ represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms. Preferable substituents that the alkyl group of Rb ₀ may have include a hydroxyl group and a halogen atom. Examples of the halogen atom of Rb ₀ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Rb _{0 is} preferably a hydrogen atom or a methyl group. Ab represents a single bond, an alkylene group, a divalent linking group having a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether group, an ester group, a carbonyl group, a carboxyl group, or a divalent group formed by combining these. Among them, a single bond or a linking group represented by _{-Ab 1} -CO _{2-is preferred.} Ab ₁ is a linear or branched alkylene group, or a monocyclic or polycyclic cycloalkylene group, preferably methylene, ethylene, cyclohexylene, adamantyl or norbornane base. V represents a group obtained by removing one hydrogen atom from the ring member atoms of the lactone structure represented by any of the general formulas (LC1-1) to (LC1-21), or from the general formula (SL1-1) A group obtained by removing one hydrogen atom from the ring member atoms of the sultone structure represented by any one of ~(SL1-3).

於在具有內酯基或磺內酯基的重複單元中存在光學異構體的情況下，可使用任意的光學異構體。另外，可單獨使用一種光學異構體，亦可混合使用多種光學異構體。於主要使用一種光學異構體的情況下，其光學純度（ee）較佳為90以上，更佳為95以上。When an optical isomer is present in the repeating unit having a lactone group or a sultone group, any optical isomer can be used. In addition, one kind of optical isomer may be used alone, or a plurality of optical isomers may be used in combination. In the case of mainly using one optical isomer, its optical purity (ee) is preferably 90 or more, more preferably 95 or more.

作為碳酸酯基，較佳為環狀碳酸酯基。作為具有環狀碳酸酯基的重複單元，較佳為下述通式（A-1）所表示的重複單元。The carbonate group is preferably a cyclic carbonate group. The repeating unit having a cyclic carbonate group is preferably a repeating unit represented by the following general formula (A-1).

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通式（A-1）中，R_A ¹ 表示氫原子、鹵素原子或一價有機基（較佳為甲基）。 n表示0以上的整數。 R_A ² 表示取代基。於n為2以上的情況下，多個存在的R_A ² 可分別相同亦可不同。 A表示單鍵或二價連結基。作為所述二價連結基，較佳為伸烷基、具有單環或多環的脂環烴結構的二價連結基、醚基、酯基、羰基、羧基、或者將該些組合而成的二價基。 Z表示與式中的-O-CO-O-所表示的基一起形成單環或多環的原子團。In the general formula (A-1), R _A ¹ represents a hydrogen atom, a halogen atom, or a monovalent organic group (preferably a methyl group). n represents an integer of 0 or more. R _A ² represents a substituent. When n is 2 or more, a plurality of R _A ² may be the same or different. A represents a single bond or a divalent linking group. The divalent linking group is preferably an alkylene group, a divalent linking group having a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether group, an ester group, a carbonyl group, a carboxyl group, or a combination thereof Divalent base. Z represents an atomic group that forms a monocyclic or polycyclic ring together with the group represented by -O-CO-O- in the formula.

以下例示具有內酯基、磺內酯基或碳酸酯基的重複單元。The repeating unit having a lactone group, a sultone group, or a carbonate group is exemplified below.

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相對於樹脂（A）中的全部重複單元，具有內酯基、磺內酯基或碳酸酯基的重複單元的含量較佳為1莫耳%以上，更佳為10莫耳%以上。另外，作為其上限值，較佳為85莫耳%以下，更佳為80莫耳%以下，進而佳為70莫耳%以下，尤佳為60莫耳%以下。The content of the repeating unit having a lactone group, a sultone group, or a carbonate group is preferably 1 mol% or more, and more preferably 10 mol% or more with respect to all the repeating units in the resin (A). In addition, as the upper limit, it is preferably 85 mol% or less, more preferably 80 mol% or less, further preferably 70 mol% or less, and particularly preferably 60 mol% or less.

＜具有光酸產生基的重複單元＞樹脂（A）亦可含有具有藉由光化射線或放射線的照射而產生酸的基（以下亦稱為「光酸產生基」）的重複單元作為所述以外的重複單元。該情況下，可認為所述具有光酸產生基的重複單元相當於後述的藉由光化射線或放射線的照射而產生酸的化合物（亦稱為「光酸產生劑」）。作為所述重複單元，例如可列舉下述通式（4）所表示的重複單元。＜Repeating unit with photoacid generating group＞ The resin (A) may contain a repeating unit having a group that generates an acid by irradiation with actinic rays or radiation (hereinafter also referred to as a "photoacid generating group") as a repeating unit other than the above. In this case, it can be considered that the repeating unit having a photoacid generating group corresponds to a compound that generates an acid by irradiation with actinic rays or radiation (also referred to as a "photoacid generator") described later. As said repeating unit, the repeating unit represented by the following general formula (4) is mentioned, for example.

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R⁴¹ 表示氫原子或甲基。L⁴¹ 表示單鍵或二價連結基。L⁴² 表示二價連結基。R⁴⁰ 表示藉由光化射線或放射線的照射而分解並在側鏈產生酸的結構部位。R ⁴¹ represents a hydrogen atom or a methyl group. L ⁴¹ represents a single bond or a divalent linking group. L ⁴² represents a divalent linking group. R ⁴⁰ represents a structural site that is decomposed by irradiation with actinic rays or radiation to generate acid in the side chain.

以下例示具有光酸產生基的重複單元。The repeating unit having a photoacid generating group is exemplified below.

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除此以外，作為通式（4）所表示的重複單元，例如可列舉日本專利特開2014-041327號公報的段落[0094]～[0105]中記載的重複單元。In addition, as the repeating unit represented by the general formula (4), for example, the repeating unit described in paragraphs [0094] to [0105] of JP 2014-041327 A can be cited.

相對於樹脂（A）中的全部重複單元，具有光酸產生基的重複單元的含量較佳為1莫耳%以上，更佳為5莫耳%以上。另外，作為其上限值，較佳為40莫耳%以下，更佳為35莫耳%以下，進而佳為30莫耳%以下。The content of the repeating unit having a photoacid generating group is preferably 1 mol% or more, and more preferably 5 mol% or more with respect to all the repeating units in the resin (A). In addition, the upper limit is preferably 40 mol% or less, more preferably 35 mol% or less, and still more preferably 30 mol% or less.

＜通式（V-1）或下述通式（V-2）所表示的重複單元＞樹脂（A）亦可具有下述通式（V-1）或下述通式（V-2）所表示的重複單元。下述通式（V-1）及下述通式（V-2）所表示的重複單元較佳為與所述重複單元不同的重複單元。<Repeating unit represented by general formula (V-1) or the following general formula (V-2)> The resin (A) may have a repeating unit represented by the following general formula (V-1) or the following general formula (V-2). The repeating unit represented by the following general formula (V-1) and the following general formula (V-2) is preferably a repeating unit different from the repeating unit.

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式中， R₆ 及R₇ 分別獨立地表示氫原子、羥基、烷基、烷氧基、醯氧基、氰基、硝基、胺基、鹵素原子、酯基（-OCOR或-COOR：R為碳數1～6的烷基或氟化烷基）或羧基。作為烷基，較佳為碳數1～10的直鏈狀、支鏈狀或環狀的烷基。 n₃ 表示0～6的整數。 n₄ 表示0～4的整數。 X₄ 為亞甲基、氧原子或硫原子。以下例示通式（V-1）或（V-2）所表示的重複單元。In the formula, R ₆ and R ₇ each independently represent a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, a halogen atom, an ester group (-OCOR or -COOR: R Is an alkyl group having 1 to 6 carbons or a fluorinated alkyl group) or a carboxy group. As the alkyl group, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms is preferred. n ₃ represents an integer of 0-6. n ₄ represents an integer of 0-4. X ₄ is a methylene group, an oxygen atom or a sulfur atom. The repeating unit represented by general formula (V-1) or (V-2) is exemplified below.

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＜用於降低主鏈的運動性的重複單元＞就可抑制產生酸的過度擴散或顯影時的圖案倒塌的觀點而言，樹脂（A）較佳為玻璃轉移溫度（Tg）高者。Tg較佳為大於90℃，更佳為大於100℃，進而佳為大於110℃，尤佳為大於125℃。再者，過高的Tg化會導致於顯影液中的溶解速度降低，因此Tg較佳為400℃以下，更佳為350℃以下。再者，本說明書中，樹脂（A）等的聚合物的玻璃轉移溫度（Tg）藉由以下的方法計算出。首先，藉由Bicerano法分別計算出僅由聚合物中所含的各重複單元構成的均聚物的Tg。以後，將計算出的Tg稱為「重複單元的Tg」。其次，計算出各重複單元相對於聚合物中的全部重複單元的質量比例（%）。其次，使用Fox的式（記載於「材料快報（Materials Letters）」62（2008）3152等中），計算出各質量比例中的Tg，將該些進行總和，設為聚合物的Tg（℃）。 Bicerano法記載於「聚合物性能預測（Prediction of polymer properties)｣, 馬塞爾·德克爾公司（Marcel Dekker Inc）, 紐約（New York）（1993）等中。另外，基於Bicerano法的Tg的計算可使用聚合物的物性概算軟體MDL聚合物（Polymer）（MDL信息系統公司（MDL Information Systems, Inc.））來進行。<Repeating unit used to reduce the mobility of the main chain> The resin (A) is preferably one having a high glass transition temperature (Tg) from the viewpoint of suppressing generation of excessive acid diffusion or pattern collapse during development. Tg is preferably greater than 90°C, more preferably greater than 100°C, further preferably greater than 110°C, and particularly preferably greater than 125°C. Furthermore, too high Tg will cause the dissolution rate in the developer to decrease, so Tg is preferably 400°C or less, more preferably 350°C or less. In addition, in this specification, the glass transition temperature (Tg) of the polymer, such as resin (A), is calculated by the following method. First, by the Bicerano method, the Tg of a homopolymer composed only of each repeating unit contained in the polymer is calculated. Hereinafter, the calculated Tg is referred to as "Tg of the repeating unit". Next, the mass ratio (%) of each repeating unit relative to all repeating units in the polymer is calculated. Next, using Fox’s formula (described in "Materials Letters" 62 (2008) 3152, etc.), calculate the Tg in each mass ratio, and sum these to be the Tg (℃) of the polymer . The Bicerano method is described in "Prediction of polymer properties", Marcel Dekker Inc, New York (1993), etc. In addition, the calculation of Tg based on the Bicerano method can be performed using polymer physical property estimation software MDL polymer (Polymer) (MDL Information Systems, Inc.).

為了增大樹脂（A）的Tg（較佳為使Tg超過90℃），較佳為使樹脂（A）的主鏈的運動性降低。降低樹脂（A）的主鏈的運動性的方法可列舉以下的（a）～（e）的方法。（a）向主鏈中導入體積大的取代基（b）向主鏈中導入多個取代基（c）向主鏈附近導入誘發樹脂（A）間的相互作用的取代基（d）以環狀結構形成主鏈（e）環狀結構與主鏈的連結再者，樹脂（A）較佳為具有均聚物的Tg顯示130℃以上的重複單元。再者，均聚物的Tg顯示130℃以上的重複單元的種類並無特別限制，只要是藉由Bicerano法計算出的均聚物的Tg為130℃以上的重複單元即可。再者，根據後述的式（A）～式（E）所表示的重複單元中的官能基的種類，相當於均聚物的Tg顯示130℃以上的重複單元。In order to increase the Tg of the resin (A) (it is preferable to make the Tg exceed 90° C.), it is preferable to reduce the mobility of the main chain of the resin (A). As a method of reducing the mobility of the main chain of the resin (A), the following methods (a) to (e) can be cited. (A) Introduce bulky substituents into the main chain (B) Introduce multiple substituents into the main chain (C) Introduction of substituents that induce the interaction between resins (A) near the main chain (D) Form the main chain with a ring structure (E) The connection between the ring structure and the main chain Furthermore, it is preferable that the resin (A) has a repeating unit whose Tg of a homopolymer shows 130 degreeC or more. In addition, the type of the repeating unit whose Tg of the homopolymer shows 130°C or higher is not particularly limited, as long as it is a repeating unit whose Tg of the homopolymer calculated by the Bicerano method is 130°C or higher. In addition, depending on the type of the functional group in the repeating unit represented by the formula (A) to the formula (E) described later, the Tg corresponding to the homopolymer shows a repeating unit of 130° C. or more.

（式（A）所表示的重複單元）作為所述（a）的具體的達成方法的一例，可列舉在樹脂（A）中導入式（A）所表示的重複單元的方法。(Repeating unit represented by formula (A)) As an example of the concrete achievement method of the said (a), the method of introducing the repeating unit represented by formula (A) into resin (A) is mentioned.

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式（A）中，R_A 表示具有多環結構的基。R_x 表示氫原子、甲基或乙基。所謂具有多環結構的基是指具有多個環結構的基，多個環結構可縮合亦可不縮合。作為式（A）所表示的重複單元的具體例，可列舉下述重複單元。In the formula _(A), R A represents a group having a polycyclic structure. R _x represents a hydrogen atom, a methyl group or an ethyl group. The group having a polycyclic structure refers to a group having a plurality of ring structures, and the plurality of ring structures may or may not be condensed. As a specific example of the repeating unit represented by formula (A), the following repeating unit can be mentioned.

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所述式中，R表示氫原子、甲基或乙基。 Ra表示氫原子、烷基、環烷基、芳基、芳烷基、烯基、羥基、烷氧基、醯氧基、氰基、硝基、胺基、鹵素原子、酯基（-OCOR'''或-COOR'''：R'''為碳數1～20的烷基或氟化烷基）或羧基。再者，所述烷基、所述環烷基、所述芳基、所述芳烷基及所述烯基亦可分別具有取代基。另外，Ra所表示的基中的與碳原子鍵結的氫原子可經氟原子或碘原子取代。另外，R'及R''分別獨立地表示烷基、環烷基、芳基、芳烷基、烯基、羥基、烷氧基、醯氧基、氰基、硝基、胺基、鹵素原子、酯基（-OCOR'''或-COOR'''：R'''為碳數1～20的烷基或氟化烷基）或羧基。再者，所述烷基、所述環烷基、所述芳基、所述芳烷基及所述烯基亦可分別具有取代基。另外，R'及R''所表示的基中的與碳原子鍵結的氫原子可經氟原子或碘原子取代。 L表示單鍵或二價連結基。作為二價連結基，例如可列舉-COO-、-CO-、-O-、-S、-SO-、-SO₂ -、伸烷基、伸環烷基、伸烯基、以及該些的多個連結而成的連結基等。 m及n分別獨立地表示0以上的整數。m及n的上限並無特別限制，2以下的情況較多，1以下的情況更多。In the formula, R represents a hydrogen atom, a methyl group, or an ethyl group. Ra represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, a hydroxyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, a halogen atom, an ester group (-OCOR'"Or-COOR"':R'" is an alkyl group having 1 to 20 carbons or a fluorinated alkyl group) or a carboxyl group. In addition, the alkyl group, the cycloalkyl group, the aryl group, the aralkyl group, and the alkenyl group may each have a substituent. In addition, the hydrogen atom bonded to the carbon atom in the group represented by Ra may be substituted with a fluorine atom or an iodine atom. In addition, R'and R'' each independently represent an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, a hydroxyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, and a halogen atom. , Ester group (-OCOR''' or -COOR''': R''' is an alkyl group with 1 to 20 carbons or a fluorinated alkyl group) or a carboxyl group. In addition, the alkyl group, the cycloalkyl group, the aryl group, the aralkyl group, and the alkenyl group may each have a substituent. In addition, the hydrogen atom bonded to the carbon atom in the groups represented by R′ and R″ may be substituted with a fluorine atom or an iodine atom. L represents a single bond or a divalent linking group. As the divalent linking group, for example, -COO-, -CO-, -O-, -S, -SO-, -SO ₂ -, alkylene, cycloalkylene, alkenylene, and these Multiple connection bases, etc. m and n each independently represent an integer of 0 or more. The upper limit of m and n is not particularly limited, and there are many cases of 2 or less, and more cases of 1 or less.

（式（B）所表示的重複單元）作為所述（b）的具體的達成方法的一例，可列舉在樹脂（A）中導入式（B）所表示的重複單元的方法。(Repeating unit represented by formula (B)) As an example of the concrete achievement method of said (b), the method of introducing the repeating unit represented by formula (B) into resin (A) is mentioned.

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式（B）中，R_b1 ～R_b4 分別獨立地表示氫原子或有機基，R_b1 ～R_b4 中的至少兩個以上表示有機基。另外，於有機基的至少一個為於重複單元中的主鏈直接連結有環結構的基的情況下，其他有機基的種類並無特別限制。另外，於有機基的任一者均並非為於重複單元中的主鏈直接連結有環結構的基的情況下，有機基的至少兩個以上為除了氫原子以外的構成原子的數量為3個以上的取代基。In formula (B), R _b1 to R _b4 each independently represent a hydrogen atom or an organic group, and at least two of _{R b1} to R _{b4 represent an organic group.} In addition, when at least one of the organic groups is a group in which a ring structure is directly connected to the main chain in the repeating unit, the type of other organic groups is not particularly limited. In addition, when none of the organic groups is a group in which a ring structure is directly connected to the main chain of the repeating unit, at least two of the organic groups have three constituent atoms other than hydrogen atoms. The above substituents.

作為式（B）所表示的重複單元的具體例，可列舉下述重複單元。As a specific example of the repeating unit represented by formula (B), the following repeating unit can be mentioned.

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所述式中，R分別獨立地表示氫原子或有機基。作為有機基，可列舉可具有取代基的烷基、環烷基、芳基、芳烷基及烯基等有機基。 R'分別獨立地表示烷基、環烷基、芳基、芳烷基、烯基、羥基、烷氧基、醯氧基、氰基、硝基、胺基、鹵素原子、酯基（-OCOR''或-COOR''：R''為碳數1～20的烷基或氟化烷基）或羧基。再者，所述烷基、所述環烷基、所述芳基、所述芳烷基及所述烯基亦可分別具有取代基。另外，R'所表示的基中的與碳原子鍵結的氫原子可經氟原子或碘原子取代。 m表示0以上的整數。m的上限並無特別限制，2以下的情況較多，1以下的情況更多。In the above formula, R each independently represents a hydrogen atom or an organic group. Examples of the organic group include an optionally substituted organic group such as an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group. R'each independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, a hydroxyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, a halogen atom, an ester group (-OCOR "Or -COOR": R" is an alkyl group having 1 to 20 carbons or a fluorinated alkyl group) or a carboxyl group. In addition, the alkyl group, the cycloalkyl group, the aryl group, the aralkyl group, and the alkenyl group may each have a substituent. In addition, the hydrogen atom bonded to the carbon atom in the group represented by R′ may be substituted with a fluorine atom or an iodine atom. m represents an integer of 0 or more. The upper limit of m is not particularly limited, and there are many cases of 2 or less, and more cases of 1 or less.

（式（C）所表示的重複單元）作為所述（c）的具體的達成方法的一例，可列舉在樹脂（A）中導入式（C）所表示的重複單元的方法。(Repeating unit represented by formula (C)) As an example of a specific method of achieving the (c), a method of introducing a repeating unit represented by the formula (C) into the resin (A) can be cited.

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式（C）中，R_c1 ～R_c4 分別獨立地表示氫原子或有機基，R_c1 ～R_c4 中的至少一個為自主鏈碳起在原子數3以內具有氫鍵性的氫原子的基。其中，較佳為在誘發樹脂（A）的主鏈間的相互作用的基礎上，在原子數2以內（更靠主鏈附近側）具有氫鍵性的氫原子。In formula (C), R _c1 to R _c4 each independently represent a hydrogen atom or an organic group, _{and at least one of R c1} to R _c4 is a group having a hydrogen-bonding hydrogen atom with 3 or less autonomous carbon atoms. Among them, it is preferable to induce an interaction between the main chains of the resin (A) and have a hydrogen atom having hydrogen bonding properties within 2 atoms (more on the side near the main chain).

作為式（C）所表示的重複單元的具體例，可列舉下述重複單元。As a specific example of the repeating unit represented by formula (C), the following repeating unit can be mentioned.

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所述式中，R表示有機基。作為有機基，可列舉可具有取代基的烷基、環烷基、芳基、芳烷基、烯基及酯基（-OCOR或-COOR：R為碳數1～20的烷基或氟化烷基）等。 R'表示氫原子或有機基。作為有機基，可列舉烷基、環烷基、芳基、芳烷基及烯基等有機基。再者，有機基中的氫原子亦可經氟原子或碘原子取代。In the formula, R represents an organic group. Examples of the organic group include optionally substituted alkyl, cycloalkyl, aryl, aralkyl, alkenyl, and ester groups (-OCOR or -COOR: R is an alkyl group having 1 to 20 carbons or fluorinated Alkyl) and so on. R'represents a hydrogen atom or an organic group. Examples of the organic group include organic groups such as an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group. Furthermore, the hydrogen atom in the organic group may be substituted with a fluorine atom or an iodine atom.

（式（D）所表示的重複單元）作為所述（d）的具體的達成方法的一例，可列舉在樹脂（A）中導入式（D）所表示的重複單元的方法。(Repeating unit represented by formula (D)) As an example of a specific method of achieving the above (d), a method of introducing a repeating unit represented by formula (D) into the resin (A) can be cited.

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式（D）中，「Cyclic」表示以環狀結構形成主鏈的基。環的構成原子數並無特別限制。In formula (D), "Cyclic" represents a group that forms a main chain with a cyclic structure. The number of atoms constituting the ring is not particularly limited.

作為式（D）所表示的重複單元的具體例，可列舉下述重複單元。As a specific example of the repeating unit represented by formula (D), the following repeating unit can be mentioned.

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所述式中，R分別獨立地表示氫原子、烷基、環烷基、芳基、芳烷基、烯基、羥基、烷氧基、醯氧基、氰基、硝基、胺基、鹵素原子、酯基（-OCOR''或-COOR''：R''為碳數1～20的烷基或氟化烷基）或羧基。再者，所述烷基、所述環烷基、所述芳基、所述芳烷基及所述烯基亦可分別具有取代基。另外，R所表示的基中的與碳原子鍵結的氫原子可經氟原子或碘原子取代。所述式中，R'分別獨立地表示烷基、環烷基、芳基、芳烷基、烯基、羥基、烷氧基、醯氧基、氰基、硝基、胺基、鹵素原子、酯基（-OCOR''或-COOR''：R''為碳數1～20的烷基或氟化烷基）或羧基。再者，所述烷基、所述環烷基、所述芳基、所述芳烷基及所述烯基亦可分別具有取代基。另外，R'所表示的基中的與碳原子鍵結的氫原子可經氟原子或碘原子取代。 m表示0以上的整數。m的上限並無特別限制，2以下的情況較多，1以下的情況更多。In the formula, R each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, a hydroxyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, and a halogen group. Atom, ester group (-OCOR" or -COOR": R" is an alkyl or fluorinated alkyl group having 1 to 20 carbons) or a carboxyl group. In addition, the alkyl group, the cycloalkyl group, the aryl group, the aralkyl group, and the alkenyl group may each have a substituent. In addition, the hydrogen atom bonded to the carbon atom in the group represented by R may be substituted with a fluorine atom or an iodine atom. In the formula, R'each independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, a hydroxyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, a halogen atom, Ester group (-OCOR" or -COOR": R" is an alkyl group or fluorinated alkyl group having 1 to 20 carbons) or a carboxyl group. In addition, the alkyl group, the cycloalkyl group, the aryl group, the aralkyl group, and the alkenyl group may each have a substituent. In addition, the hydrogen atom bonded to the carbon atom in the group represented by R′ may be substituted with a fluorine atom or an iodine atom. m represents an integer of 0 or more. The upper limit of m is not particularly limited, and there are many cases of 2 or less, and more cases of 1 or less.

（式（E）所表示的重複單元）作為所述（e）的具體的達成方法的一例，可列舉在樹脂（A）中導入式（E）所表示的重複單元的方法。(Repeating unit represented by formula (E)) As an example of a specific method of achieving the above (e), a method of introducing a repeating unit represented by formula (E) into the resin (A) can be cited.

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式（E）中，Re分別獨立地表示氫原子或有機基。作為有機基，可列舉可具有取代基的烷基、環烷基、芳基、芳烷基及烯基等。「Cyclic」是包含主鏈的碳原子的環狀基。環狀基中所含的原子數並無特別限制。In formula (E), Re each independently represents a hydrogen atom or an organic group. As an organic group, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, etc. which may have a substituent are mentioned. "Cyclic" is a cyclic group containing carbon atoms of the main chain. The number of atoms contained in the cyclic group is not particularly limited.

作為式（E）所表示的重複單元的具體例，可列舉下述重複單元。As a specific example of the repeating unit represented by formula (E), the following repeating unit can be mentioned.

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所述式中，R分別獨立地表示氫原子、烷基、環烷基、芳基、芳烷基及烯基、羥基、烷氧基、醯氧基、氰基、硝基、胺基、鹵素原子、酯基（-OCOR''或-COOR''：R''為碳數1～20的烷基或氟化烷基）或羧基。再者，所述烷基、所述環烷基、所述芳基、所述芳烷基及所述烯基亦可分別具有取代基。另外，R所表示的基中的與碳原子鍵結的氫原子可經氟原子或碘原子取代。 R'分別獨立地表示氫原子、烷基、環烷基、芳基、芳烷基及烯基、羥基、烷氧基、醯氧基、氰基、硝基、胺基、鹵素原子、酯基（-OCOR''或-COOR''：R''為碳數1～20的烷基或氟化烷基）或羧基。再者，所述烷基、所述環烷基、所述芳基、所述芳烷基及所述烯基亦可分別具有取代基。另外，R'所表示的基中的與碳原子鍵結的氫原子可經氟原子或碘原子取代。 m表示0以上的整數。m的上限並無特別限制，2以下的情況較多，1以下的情況更多。另外，式（E-2）、式（E-4）、式（E-6）及式（E-8）中，兩個R可彼此鍵結而形成環。In the above formula, R each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, a hydroxyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, and a halogen Atom, ester group (-OCOR" or -COOR": R" is an alkyl or fluorinated alkyl group having 1 to 20 carbons) or a carboxyl group. In addition, the alkyl group, the cycloalkyl group, the aryl group, the aralkyl group, and the alkenyl group may each have a substituent. In addition, the hydrogen atom bonded to the carbon atom in the group represented by R may be substituted with a fluorine atom or an iodine atom. R'each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group and an alkenyl group, a hydroxyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, a halogen atom, and an ester group (-OCOR" or -COOR": R" is an alkyl group or fluorinated alkyl group having 1 to 20 carbons) or a carboxyl group. In addition, the alkyl group, the cycloalkyl group, the aryl group, the aralkyl group, and the alkenyl group may each have a substituent. In addition, the hydrogen atom bonded to the carbon atom in the group represented by R′ may be substituted with a fluorine atom or an iodine atom. m represents an integer of 0 or more. The upper limit of m is not particularly limited, and there are many cases of 2 or less, and more cases of 1 or less. In addition, in formula (E-2), formula (E-4), formula (E-6), and formula (E-8), two Rs may be bonded to each other to form a ring.

相對於樹脂（A）中的全部重複單元，式（E）所表示的重複單元的含量較佳為5莫耳%以上，更佳為10莫耳%以上。另外，作為其上限值，較佳為60莫耳%以下，更佳為55莫耳%以下。The content of the repeating unit represented by the formula (E) is preferably 5 mol% or more, and more preferably 10 mol% or more with respect to all the repeating units in the resin (A). In addition, the upper limit is preferably 60 mol% or less, and more preferably 55 mol% or less.

＜具有選自內酯基、磺內酯基、碳酸酯基、羥基、氰基及鹼可溶性基中的至少一種基的重複單元＞樹脂（A）亦可含有具有選自內酯基、磺內酯基、碳酸酯基、羥基、氰基及鹼可溶性基中的至少一種基的重複單元。作為樹脂（A）所含有的具有內酯基、磺內酯基或碳酸酯基的重複單元，可列舉所述＜具有內酯基、磺內酯基或碳酸酯基的重複單元＞中說明的重複單元。較佳的含量亦如所述＜具有內酯基、磺內酯基或碳酸酯基的重複單元＞中說明般。<Repeating unit having at least one group selected from a lactone group, a sultone group, a carbonate group, a hydroxyl group, a cyano group, and an alkali-soluble group> The resin (A) may also contain a repeating unit having at least one group selected from a lactone group, a sultone group, a carbonate group, a hydroxyl group, a cyano group, and an alkali-soluble group. Examples of the repeating unit having a lactone group, a sultone group, or a carbonate group contained in the resin (A) include those described in the above-mentioned <repeat unit having a lactone group, sultone group, or carbonate group>. Repeating unit. The preferable content is also as described in the above-mentioned "Repeating unit having a lactone group, a sultone group or a carbonate group".

樹脂（A）亦可含有具有羥基或氰基的重複單元。藉此，基板密接性、顯影液親和性提高。具有羥基或氰基的重複單元較佳為具有經羥基或氰基取代的脂環烴結構的重複單元。具有羥基或氰基的重複單元較佳為不具有酸分解性基。作為具有羥基或氰基的重複單元，可列舉下述通式（AIIa）～（AIId）所表示的重複單元。The resin (A) may also contain a repeating unit having a hydroxyl group or a cyano group. Thereby, substrate adhesion and developer affinity are improved. The repeating unit having a hydroxyl group or a cyano group is preferably a repeating unit having an alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group. The repeating unit having a hydroxyl group or a cyano group preferably does not have an acid-decomposable group. Examples of the repeating unit having a hydroxyl group or a cyano group include repeating units represented by the following general formulas (AIIa) to (AIId).

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通式（AIIa）～（AIId）中， R₁ c表示氫原子、甲基、三氟甲基或羥基甲基。 R₂ c～R₄ c分別獨立地表示氫原子、羥基或氰基。其中，R₂ c～R₄ c中的至少一個表示羥基或氰基。較佳為R₂ c～R₄ c中的一個或兩個為羥基，其餘為氫原子。更佳為R₂ c～R₄ c中的兩個為羥基，其餘為氫原子。In the general formulas (AIIa) to (AIId), R ₁ c represents a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group. R ₂ c to R ₄ c each independently represent a hydrogen atom, a hydroxyl group, or a cyano group. Among them, _{at least one of R 2} c to R ₄ c represents a hydroxyl group or a cyano group. Preferably, one or two of R ₂ c to R ₄ c are hydroxyl groups, and the rest are hydrogen atoms. More preferably, two of R ₂ c to R ₄ c are hydroxyl groups, and the rest are hydrogen atoms.

相對於樹脂（A）中的全部重複單元，具有羥基或氰基的重複單元的含量較佳為5莫耳%以上，更佳為10莫耳%以上。另外，作為其上限值，較佳為40莫耳%以下，更佳為35莫耳%以下，進而佳為30莫耳%以下。The content of the repeating unit having a hydroxyl group or a cyano group relative to all repeating units in the resin (A) is preferably 5 mol% or more, and more preferably 10 mol% or more. In addition, the upper limit is preferably 40 mol% or less, more preferably 35 mol% or less, and still more preferably 30 mol% or less.

以下列舉具有羥基或氰基的重複單元的具體例，但本發明並不限定於該些。Specific examples of repeating units having a hydroxyl group or a cyano group are listed below, but the present invention is not limited to these.

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樹脂（A）亦可含有具有鹼可溶性基的重複單元。作為鹼可溶性基，可列舉羧基、磺醯胺基、磺醯亞胺基、雙磺醯亞胺基、α位經拉電子性基取代的脂肪族醇基（例如六氟異丙醇基），較佳為羧基。藉由樹脂（A）含有具有鹼可溶性基的重複單元，接觸孔用途中的解析性增加。作為具有鹼可溶性基的重複單元，可列舉來源於丙烯酸及甲基丙烯酸的重複單元之類的於樹脂的主鏈直接鍵結有鹼可溶性基的重複單元、或者經由連結基於樹脂的主鏈鍵結有鹼可溶性基的重複單元。再者，連結基亦可具有單環或多環的環狀烴結構。作為具有鹼可溶性基的重複單元，較佳為來源於丙烯酸或甲基丙烯酸的重複單元。The resin (A) may contain a repeating unit having an alkali-soluble group. Examples of alkali-soluble groups include carboxyl groups, sulfonamide groups, sulfonamide groups, bissulfonamide groups, and aliphatic alcohol groups substituted with electron-withdrawing groups at the α position (for example, hexafluoroisopropanol group). Preferably it is a carboxyl group. Since the resin (A) contains a repeating unit having an alkali-soluble group, the resolution for contact hole applications is increased. Examples of the repeating unit having an alkali-soluble group include repeating units derived from acrylic acid and methacrylic acid, such as repeating units derived from acrylic acid and methacrylic acid, to which an alkali-soluble group is directly bonded to the main chain of the resin, or to be bonded via a resin-based main chain. Repeating units with alkali-soluble groups. Furthermore, the linking group may have a monocyclic or polycyclic cyclic hydrocarbon structure. The repeating unit having an alkali-soluble group is preferably a repeating unit derived from acrylic acid or methacrylic acid.

相對於樹脂（A）中的全部重複單元，具有鹼可溶性基的重複單元的含量較佳為0莫耳%以上，更佳為3莫耳%以上，進而佳為5莫耳%以上。作為其上限值，較佳為20莫耳%以下，更佳為15莫耳%以下，進而佳為10莫耳%以下。The content of the repeating unit having an alkali-soluble group relative to all repeating units in the resin (A) is preferably 0 mol% or more, more preferably 3 mol% or more, and still more preferably 5 mol% or more. The upper limit is preferably 20 mol% or less, more preferably 15 mol% or less, and still more preferably 10 mol% or less.

以下示出具有鹼可溶性基的重複單元的具體例，但本發明並不限定於此。具體例中，Rx表示H、CH₃ 、CH₂ OH或CF₃ 。Although the specific example of the repeating unit which has an alkali-soluble group is shown below, this invention is not limited to this. In specific examples, Rx represents H, CH ₃ , CH ₂ OH or CF ₃ .

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作為具有選自內酯基、羥基、氰基及鹼可溶性基中的至少一種基的重複單元，較佳為具有選自內酯基、羥基、氰基及鹼可溶性基中的至少兩個的重複單元，更佳為具有氰基與內酯基的重複單元，進而佳為具有於通式（LC1-4）所表示的內酯結構上取代有氰基的結構的重複單元。As a repeating unit having at least one group selected from a lactone group, a hydroxyl group, a cyano group, and an alkali-soluble group, it is preferable to have a repeating unit having at least two selected from a lactone group, a hydroxyl group, a cyano group, and an alkali-soluble group The unit is more preferably a repeating unit having a cyano group and a lactone group, and still more preferably a repeating unit having a cyano group substituted on the lactone structure represented by the general formula (LC1-4).

＜具有脂環烴結構、不顯示酸分解性的重複單元＞樹脂（A）亦可含有具有脂環烴結構、不顯示酸分解性的重複單元。藉此，可減少液浸曝光時低分子成分從抗蝕劑膜向液浸液中的溶出。作為所述重複單元，例如可列舉源自(甲基)丙烯酸1-金剛烷酯、(甲基)丙烯酸二金剛烷酯、(甲基)丙烯酸三環癸酯或(甲基)丙烯酸環己酯的重複單元等。<Repeating units with an alicyclic hydrocarbon structure and not showing acid decomposability> The resin (A) may contain a repeating unit that has an alicyclic hydrocarbon structure and does not show acid decomposability. This can reduce the elution of low-molecular components from the resist film into the liquid immersion liquid during liquid immersion exposure. Examples of the repeating unit include 1-adamantyl (meth)acrylate, diadamantyl (meth)acrylate, tricyclodecyl (meth)acrylate, or cyclohexyl (meth)acrylate. The repeating unit and so on.

＜不具有羥基及氰基的任一者的、通式（III）所表示的重複單元＞樹脂（A）亦可含有不具有羥基及氰基的任一者的、通式（III）所表示的重複單元。<Repeating unit represented by general formula (III) which does not have either a hydroxyl group or a cyano group> The resin (A) may contain a repeating unit represented by general formula (III) that does not have any of a hydroxyl group and a cyano group.

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通式（III）中，R₅ 表示具有至少一個環狀結構且不具有羥基及氰基的任一者的烴基。 Ra表示氫原子、烷基或-CH₂ -O-Ra₂ 基。式中，Ra₂ 表示氫原子、烷基或醯基。In the general formula (III), R ₅ represents a hydrocarbon group that has at least one cyclic structure and does not have any of a hydroxyl group and a cyano group. Ra represents a hydrogen atom, an alkyl group, or a -CH ₂ -O-Ra ₂ group. In the formula, Ra ₂ represents a hydrogen atom, an alkyl group or an acyl group.

R₅ 所具有的環狀結構包括單環式烴基及多環式烴基。作為單環式烴基，例如可列舉碳數3～12（更佳為碳數3～7）的環烷基、或碳數3～12的環烯基。The cyclic structure of R ₅ includes a monocyclic hydrocarbon group and a polycyclic hydrocarbon group. Examples of the monocyclic hydrocarbon group include cycloalkyl groups having 3 to 12 carbon atoms (more preferably 3 to 7 carbon atoms) or cycloalkenyl groups having 3 to 12 carbon atoms.

作為多環式烴基，可列舉環集合烴基及交聯環式烴基。作為交聯環式烴基，可列舉二環式烴環、三環式烴環及四環式烴環等。另外，作為交聯環式烴環，亦包含5員～8員環烷烴環縮合了多個而成的稠環。作為交聯環式烴基，較佳為降冰片基、金剛烷基、雙環辛基或三環[5,2,1,0^2,6 ]癸基，更佳為降冰片基或金剛烷基。Examples of the polycyclic hydrocarbon group include a ring assembly hydrocarbon group and a crosslinked cyclic hydrocarbon group. As a crosslinked cyclic hydrocarbon group, a bicyclic hydrocarbon ring, a tricyclic hydrocarbon ring, a tetracyclic hydrocarbon ring, etc. are mentioned. In addition, the crosslinked cyclic hydrocarbon ring also includes a condensed ring in which a plurality of 5-membered to 8-membered cycloalkane rings are condensed. The crosslinked cyclic hydrocarbon group is preferably norbornyl, adamantyl, bicyclooctyl or tricyclo[5,2,1,0 ^2,6 ]decyl, more preferably norbornyl or adamantyl.

脂環式烴基可具有取代基，作為取代基，可列舉鹵素原子、烷基、經保護基保護的羥基、以及經保護基保護的胺基。作為鹵素原子，較佳為溴原子、氯原子或氟原子。作為烷基，較佳為甲基、乙基、丁基或第三丁基。所述烷基亦可進而具有取代基，作為取代基，可列舉鹵素原子、烷基、經保護基保護的羥基、或者經保護基保護的胺基。The alicyclic hydrocarbon group may have a substituent, and examples of the substituent include a halogen atom, an alkyl group, a hydroxyl group protected with a protecting group, and an amino group protected with a protecting group. As the halogen atom, a bromine atom, a chlorine atom or a fluorine atom is preferred. As the alkyl group, a methyl group, an ethyl group, a butyl group, or a tertiary butyl group is preferable. The alkyl group may further have a substituent, and examples of the substituent include a halogen atom, an alkyl group, a hydroxyl group protected with a protective group, or an amino group protected with a protective group.

作為保護基，例如可列舉烷基、環烷基、芳烷基、經取代的甲基、經取代的乙基、烷氧基羰基及芳烷氧基羰基。作為烷基，較佳為碳數1～4的烷基。作為經取代的甲基，較佳為甲氧基甲基、甲氧基硫代甲基、苄氧基甲基、第三丁氧基甲基或2-甲氧基乙氧基甲基。作為經取代的乙基，較佳為1-乙氧基乙基或1-甲基-1-甲氧基乙基。作為醯基，較佳為甲醯基、乙醯基、丙醯基、丁醯基、異丁醯基、戊醯基及三甲基乙醯基等碳數1～6的脂肪族醯基。作為烷氧基羰基，較佳為碳數1～4的烷氧基羰基。Examples of the protective group include an alkyl group, a cycloalkyl group, an aralkyl group, a substituted methyl group, a substituted ethyl group, an alkoxycarbonyl group, and an aralkoxycarbonyl group. As the alkyl group, an alkyl group having 1 to 4 carbon atoms is preferred. As the substituted methyl group, methoxymethyl, methoxythiomethyl, benzyloxymethyl, tert-butoxymethyl, or 2-methoxyethoxymethyl is preferable. As the substituted ethyl group, 1-ethoxyethyl or 1-methyl-1-methoxyethyl is preferable. As the acyl group, aliphatic acyl groups having 1 to 6 carbon atoms such as formyl, acetyl, propionyl, butyryl, isobutyryl, pentyl, and trimethylacetyl are preferred. The alkoxycarbonyl group is preferably an alkoxycarbonyl group having 1 to 4 carbon atoms.

相對於樹脂（A）中的全部重複單元，不具有羥基及氰基的任一者的、通式（III）所表示的重複單元的含量較佳為0莫耳%～40莫耳%，更佳為0莫耳%～20莫耳%。以下列舉通式（III）所表示的重複單元的具體例，但本發明並不限定於該些。式中，Ra表示H、CH₃ 、CH₂ OH或CF₃ 。The content of the repeating unit represented by the general formula (III) that does not have any of a hydroxyl group and a cyano group relative to all the repeating units in the resin (A) is preferably 0 mol% to 40 mol%, and more Preferably, it is 0 mol% to 20 mol%. Specific examples of the repeating unit represented by the general formula (III) are listed below, but the present invention is not limited to these. In the formula, Ra represents H, CH ₃ , CH ₂ OH or CF ₃ .

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＜其他重複單元＞進而，樹脂（A）亦可具有所述重複單元以外的重複單元。例如樹脂（A）亦可包含選自由具有氧硫雜環己烷（oxathiane）環基的重複單元、具有噁唑啉酮（oxazolone）環基的重複單元、具有二噁烷環基的重複單元、以及具有乙內醯脲環基的重複單元所組成的群組中的重複單元。以下例示所述重複單元。＜Other repeating units＞ Furthermore, resin (A) may have a repeating unit other than the said repeating unit. For example, the resin (A) may also include a repeating unit selected from the group consisting of a repeating unit having an oxathiane ring group, a repeating unit having an oxazolone ring group, a repeating unit having a dioxane ring group, And repeating units in the group consisting of repeating units having hydantoin ring groups. The repeating unit is exemplified below.

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樹脂（A）除了所述重複結構單元以外，亦可為了調節耐乾式蝕刻性、標準顯影液適應性、基板密接性、抗蝕劑輪廓、解析力、耐熱性及感度等而具有各種重複結構單元。In addition to the repeating structural unit, the resin (A) may also have various repeating structural units for adjusting dry etching resistance, standard developer compatibility, substrate adhesion, resist profile, resolution, heat resistance, sensitivity, etc. .

作為樹脂（A），亦較佳為（尤其是於本發明的抗蝕劑組成物用作ArF用感光化射線性或感放射線性樹脂組成物的情況下）重複單元全部由(甲基)丙烯酸酯系重複單元構成。該情況下，可使用重複單元全部為甲基丙烯酸酯系重複單元者、重複單元全部為丙烯酸酯系重複單元者、重複單元全部由甲基丙烯酸酯系重複單元與丙烯酸酯系重複單元構成者中的任一者，較佳為丙烯酸酯系重複單元為全部重複單元的50莫耳%以下。As the resin (A), it is also preferable (especially when the resist composition of the present invention is used as a sensitizing radiation or radiation sensitive resin composition for ArF) that all repeating units are made of (meth)acrylic acid Consisting of ester-based repeating units. In this case, it is possible to use those whose repeating units are all methacrylate-based repeating units, those whose repeating units are all acrylate-based repeating units, and those whose repeating units are all composed of methacrylate-based repeating units and acrylate-based repeating units. Any of the acrylate-based repeating units is preferably 50 mol% or less of all repeating units.

樹脂（A）可按照常規方法（例如自由基聚合）合成。藉由GPC法，以聚苯乙烯換算值計，樹脂（A）的重量平均分子量較佳為1,000～200,000，更佳為3,000～20,000，進而佳為5,000～15,000。藉由將樹脂（A）的重量平均分子量設為1,000～200,000，可進一步抑制耐熱性及耐乾式蝕刻性的劣化。另外，亦可進一步抑制顯影性的劣化及黏度變高而製膜性劣化的情況。樹脂（A）的分散度（分子量分佈）通常為1～5，較佳為1～3，更佳為1.2～3.0，進而佳為1.2～2.0。分散度越小，解析度及抗蝕劑形狀更優異，進而抗蝕劑圖案的側壁更平滑，粗糙度性能亦更優異。The resin (A) can be synthesized according to a conventional method (for example, radical polymerization). According to the GPC method, the weight average molecular weight of the resin (A) is preferably 1,000 to 200,000, more preferably 3,000 to 20,000, and still more preferably 5,000 to 15,000 in terms of polystyrene conversion value. By setting the weight average molecular weight of the resin (A) to 1,000 to 200,000, the deterioration of heat resistance and dry etching resistance can be further suppressed. In addition, it is also possible to further suppress the deterioration of the developability and the increase in the viscosity and the deterioration of the film formability. The degree of dispersion (molecular weight distribution) of the resin (A) is usually 1 to 5, preferably 1 to 3, more preferably 1.2 to 3.0, and still more preferably 1.2 to 2.0. The smaller the dispersion, the better the resolution and the shape of the resist, and the sidewalls of the resist pattern are smoother and the roughness performance is also better.

本發明的抗蝕劑組成物中，相對於組成物的總固體成分，樹脂（A）的含量較佳為50質量%～99.9質量%，更佳為60質量%～99.0質量%。再者，所謂固體成分是指去除組成物中的溶劑後的成分，若為溶劑以外的成分，則即使是液狀成分，亦視為固體成分。另外，樹脂（A）可使用一種，亦可併用多種。In the resist composition of the present invention, the content of the resin (A) is preferably 50% by mass to 99.9% by mass, and more preferably 60% by mass to 99.0% by mass relative to the total solid content of the composition. In addition, the so-called solid content refers to the component after removing the solvent in the composition, and if it is a component other than the solvent, even if it is a liquid component, it is regarded as a solid component. In addition, one kind of resin (A) may be used, or a plurality of kinds may be used in combination.

[酸擴散控制劑] 本發明的抗蝕劑組成物亦可含有酸擴散控制劑。酸擴散控制劑作為如下淬滅劑發揮作用，所述淬滅劑捕獲曝光時由光酸產生劑等所產生的酸，抑制多餘的產生酸所引起的未曝光部中的酸分解性樹脂的反應。作為酸擴散控制劑，例如可使用如下化合物等作為酸擴散控制劑：鹼性化合物（DA）；藉由光化射線或放射線的照射而鹼性降低或消失的鹼性化合物（DB）；以及在陽離子部具有氮原子的鎓鹽化合物（DE）。本發明的抗蝕劑組成物中，可適宜使用公知的酸擴散控制劑。例如可較佳地使用美國專利申請公開2016/0070167A1號說明書的段落[0627]～[0664]、美國專利申請公開2015/0004544A1號說明書的段落[0095]～[0187]、美國專利申請公開2016/0237190A1號說明書的段落[0403]～[0423]及美國專利申請公開2016/0274458A1號說明書的段落[0259]～[0328]中揭示的公知的化合物作為酸擴散控制劑。[Acid Diffusion Control Agent] The resist composition of the present invention may also contain an acid diffusion control agent. The acid diffusion control agent functions as a quencher that captures the acid generated by the photoacid generator during exposure, and suppresses the reaction of the acid-decomposable resin in the unexposed portion caused by the excessive generation of acid . As the acid diffusion control agent, for example, the following compounds can be used as the acid diffusion control agent: basic compound (DA); basic compound (DB) whose basicity decreases or disappears by irradiation with actinic rays or radiation; and An onium salt compound (DE) having a nitrogen atom in the cation part. In the resist composition of the present invention, a known acid diffusion control agent can be suitably used. For example, paragraphs [0627] to [0664] of the specification of U.S. Patent Application Publication No. 2016/0070167A1, paragraphs [0095] to [0187] of specification of U.S. Patent Application Publication No. 2015/0004544A1, and U.S. Patent Application Publication 2016/ Known compounds disclosed in paragraphs [0403] to [0423] of specification 0237190A1 and paragraphs [0259] to [0328] of specification U.S. Patent Application Publication 2016/0274458A1 serve as acid diffusion control agents.

＜鹼性化合物（DA）＞作為鹼性化合物（DA），較佳為具有下述式（A）～（E）所表示的結構的化合物。＜Basic compound (DA)＞ The basic compound (DA) is preferably a compound having a structure represented by the following formulas (A) to (E).

[化67]

[化67]

通式（A）及（E）中， R²⁰⁰ 、R²⁰¹ 及R²⁰² 可相同亦可不同，分別獨立地表示氫原子、烷基（較佳為碳數1～20）、環烷基（較佳為碳數3～20）或芳基（碳數6～20）。R²⁰¹ 與R²⁰² 可彼此鍵結而形成環。 R²⁰³ 、R²⁰⁴ 、R²⁰⁵ 及R²⁰⁶ 可相同亦可不同，分別獨立地表示碳數1～20的烷基。In the general formulas (A) and (E), R ²⁰⁰ , R ²⁰¹ and R ²⁰² may be the same or different, and each independently represents a hydrogen atom, an alkyl group (preferably carbon number 1-20), a cycloalkyl group (more Preferably, it is a carbon number 3-20) or an aryl group (a carbon number 6-20). R ²⁰¹ and R ²⁰² may be bonded to each other to form a ring. R ²⁰³ , R ²⁰⁴ , R ²⁰⁵ and R ²⁰⁶ may be the same or different, and each independently represents an alkyl group having 1 to 20 carbon atoms.

通式（A）及（E）中的烷基可具有取代基亦可未經取代。關於所述烷基，作為具有取代基的烷基，較佳為碳數1～20的胺基烷基、碳數1～20的羥基烷基、或碳數1～20的氰基烷基。通式（A）及（E）中的烷基更佳為未經取代。The alkyl group in general formulas (A) and (E) may have a substituent or may be unsubstituted. As for the alkyl group, the alkyl group having a substituent is preferably an aminoalkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms, or a cyanoalkyl group having 1 to 20 carbon atoms. The alkyl group in the general formulas (A) and (E) is more preferably unsubstituted.

作為鹼性化合物（DA），較佳為胍、胺基吡咯啶、吡唑、吡唑啉、哌嗪、胺基嗎啉、胺基烷基嗎啉或哌啶，更佳為具有咪唑結構、二氮雜雙環結構、氫氧化鎓結構、羧酸鎓鹽結構、三烷基胺結構、苯胺結構或吡啶結構的化合物、具有羥基及/或醚鍵的烷基胺衍生物、或者具有羥基及/或醚鍵的苯胺衍生物。The basic compound (DA) is preferably guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine or piperidine, and more preferably has an imidazole structure, Diazabicyclic structure, onium hydroxide structure, onium carboxylate structure, trialkylamine structure, aniline structure, or pyridine structure compound, alkylamine derivative with hydroxyl and/or ether bond, or hydroxyl and/or Or ether bond aniline derivatives.

＜藉由光化射線或放射線的照射而鹼性降低或消失的鹼性化合物（DB）＞藉由光化射線或放射線的照射而鹼性降低或消失的鹼性化合物（DB）（以下，亦稱為「化合物（DB）」）為如下化合物：具有質子受體（acceptor）性官能基且藉由光化射線或放射線的照射而分解，質子受體性降低、消失或者由質子受體性變化為酸性。<Basic compound (DB) whose alkalinity decreases or disappears by irradiation with actinic rays or radiation> The basic compound (DB) (hereinafter also referred to as "compound (DB)") whose basicity decreases or disappears by irradiation with actinic rays or radiation is a compound that has a proton acceptor (acceptor) functional group and It is decomposed by the irradiation of actinic rays or radiation, and the proton-accepting property decreases or disappears or changes from proton-accepting property to acidity.

所謂質子受體性官能基，是具有可與質子發生靜電相互作用的基或電子的官能基，例如是指環狀聚醚等具有巨環結構的官能基、或含有具有無助於π共軛的非共有電子對的氮原子的官能基。所謂具有無助於π共軛的非共有電子對的氮原子，例如是具有下述式所表示的部分結構的氮原子。The so-called proton-accepting functional group is a functional group having a group or electrons that can interact with protons electrostatically. For example, it refers to a functional group having a macrocyclic structure such as a cyclic polyether, or a functional group that does not contribute to π conjugation. The functional group of the nitrogen atom of the non-shared electron pair. The nitrogen atom having a non-shared electron pair that does not contribute to π-conjugation is, for example, a nitrogen atom having a partial structure represented by the following formula.

[化68]

作為質子受體性官能基的較佳的部分結構，例如可列舉冠醚結構、氮雜冠醚結構、一級胺結構～三級胺結構、吡啶結構、咪唑結構及吡嗪結構。Examples of preferable partial structures of the proton-accepting functional group include a crown ether structure, an aza crown ether structure, a primary amine structure to a tertiary amine structure, a pyridine structure, an imidazole structure, and a pyrazine structure.

化合物（DB）藉由光化射線或放射線的照射而分解並產生質子受體性降低或消失或者由質子受體性變化為酸性的化合物。此處，所謂質子受體性的降低或消失或者由質子受體性變化為酸性，是在質子受體性官能基上加成質子而引起的質子受體性的變化，具體而言，是指於由具有質子受體性官能基的化合物（DB）與質子生成質子加成物時，其化學平衡中的平衡常數減少。質子受體性可藉由進行pH測定來確認。The compound (DB) is decomposed by irradiation with actinic rays or radiation to produce a compound in which the proton acceptor property decreases or disappears, or the proton acceptor property changes to acidity. Here, the decrease or disappearance of proton acceptor or the change from proton acceptor to acidity refers to the change in proton acceptor caused by the addition of protons to the proton acceptor functional group. Specifically, it means When a compound having a proton-accepting functional group (DB) and a proton generate a proton adduct, the equilibrium constant in the chemical equilibrium decreases. The proton acceptability can be confirmed by performing a pH measurement.

藉由光化射線或放射線的照射而化合物（DB）分解所產生的化合物的酸解離常數pKa較佳為滿足pKa＜-1，更佳為滿足-13＜pKa＜-1，進而佳為滿足-13＜pKa＜-3。The acid dissociation constant pKa of the compound produced by the decomposition of the compound (DB) by irradiation with actinic rays or radiation preferably satisfies pKa<-1, more preferably satisfies -13<pKa<-1, and more preferably satisfies- 13<pKa<-3.

再者，所謂酸解離常數pKa可藉由所述方法求出。In addition, the so-called acid dissociation constant pKa can be obtained by the above-mentioned method.

＜具有氮原子且具有因酸的作用而脫離的基的低分子化合物（DD）＞具有氮原子且具有因酸的作用而脫離的基的低分子化合物（DD）（以下，亦稱為「化合物（DD）」）較佳為在氮原子上具有因酸的作用而脫離的基的胺衍生物。作為因酸的作用而脫離的基，較佳為縮醛基、碳酸酯基、胺甲酸酯基、三級酯基、三級羥基或半胺縮醛醚基，更佳為胺甲酸酯基或半胺縮醛醚基。化合物（DD）的分子量較佳為100～1000，更佳為100～700，進而佳為100～500。化合物（DD）亦可在氮原子上具有含有保護基的胺甲酸酯基。作為構成胺甲酸酯基的保護基，由下述通式（d-1）表示。<Low-molecular-weight compounds (DD) having a nitrogen atom and a group detached by the action of an acid> The low-molecular compound (DD) having a nitrogen atom and a group released by the action of an acid (hereinafter also referred to as "compound (DD)") preferably has a group released by the action of an acid on the nitrogen atom Amine derivatives. The group to be removed by the action of an acid is preferably an acetal group, a carbonate group, a urethane group, a tertiary ester group, a tertiary hydroxyl group, or a semiamine acetal ether group, and more preferably a urethane group Group or semi-amine acetal ether group. The molecular weight of the compound (DD) is preferably 100-1000, more preferably 100-700, and still more preferably 100-500. The compound (DD) may have a urethane group containing a protective group on the nitrogen atom. The protecting group constituting the urethane group is represented by the following general formula (d-1).

[化69]

[化69]

通式（d-1）中， R_b 分別獨立地表示氫原子、烷基（較佳為碳數1～10）、環烷基（較佳為碳數3～30）、芳基（較佳為碳數3～30）、芳烷基（較佳為碳數1～10）或烷氧基烷基（較佳為碳數1～10）。R_b 可相互連結而形成環。 R_b 表示的烷基、環烷基、芳基及芳烷基可分別獨立地經羥基、氰基、胺基、吡咯啶基（pyrrolidino）、哌啶基、嗎啉基、側氧基等官能基、烷氧基或者鹵素原子取代。關於R_b 表示的烷氧基烷基，亦同樣。In the general formula (d-1), R _b each independently represents a hydrogen atom, an alkyl group (preferably with a carbon number of 1 to 10), a cycloalkyl group (preferably with a carbon number of 3 to 30), an aryl group (preferably It is a carbon number of 3-30), an aralkyl group (preferably a carbon number of 1-10), or an alkoxyalkyl group (preferably a carbon number of 1-10). R _b may be connected to each other to form a ring. The alkyl group, cycloalkyl group, aryl group and aralkyl group represented by R _b can be independently functionalized by hydroxyl, cyano, amino, pyrrolidino, piperidinyl, morpholino, pendant oxy, etc. Group, alkoxy or halogen atom substitution. The same applies to the alkoxyalkyl group represented by _{R b.}

作為R_b ，較佳為直鏈狀或支鏈狀的烷基、環烷基或芳基，更佳為直鏈狀或支鏈狀的烷基或環烷基。作為兩個R_b 相互連結而形成的環，可列舉脂環式烴、芳香族烴、雜環式烴及其衍生物等。作為通式（d-1）所表示的基的具體結構，可列舉美國專利公報US2012/0135348A1號說明書的段落[0466]中揭示的結構，但並不限制於此。As R _b , a linear or branched alkyl group, a cycloalkyl group, or an aryl group is preferable, and a linear or branched alkyl group or a cycloalkyl group is more preferable. Examples of the ring formed by linking two R _{b to} each other include alicyclic hydrocarbons, aromatic hydrocarbons, heterocyclic hydrocarbons, and derivatives thereof. As a specific structure of the group represented by the general formula (d-1), the structure disclosed in paragraph [0466] of the specification of U.S. Patent Publication US2012/0135348A1 can be cited, but it is not limited to this.

化合物（DD）較佳為下述通式（6）所表示的化合物。The compound (DD) is preferably a compound represented by the following general formula (6).

[化70]

[化70]

通式（6）中， l表示0～2的整數，m表示1～3的整數，滿足l+m=3。 R_a 表示氫原子、烷基、環烷基、芳基或芳烷基。於l為2時，兩個R_a 可相同亦可不同，兩個R_a 可相互連結且與式中的氮原子一起形成雜環。所述雜環中亦可含有式中的氮原子以外的雜原子。 R_b 與所述通式（d-1）中的R_b 為相同含義，較佳的例子亦相同。通式（6）中，作為R_a 的烷基、環烷基、芳基及芳烷基可分別獨立地經如下基取代，所述基與關於作為R_b 的烷基、環烷基、芳基及芳烷基可被取代的基而敘述的基相同。In the general formula (6), l represents an integer from 0 to 2, and m represents an integer from 1 to 3, and satisfies l+m=3. R _a represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group. When 1 is 2, two _Ras may be the same or different, and two _Ras may be connected to each other and form a heterocyclic ring together with the nitrogen atom in the formula. The heterocyclic ring may contain heteroatoms other than the nitrogen atom in the formula. And R _b in the general formula (d-1) R _b is the same meaning, preferred examples are also the same. In the general formula (6), the alkyl group, cycloalkyl group, aryl group, and aralkyl group _{as R a} may be independently substituted with a group that is related to the alkyl group, cycloalkyl group, and aryl group _{as R b.} The group and the aralkyl group which may be substituted are the same as those described above.

作為所述R_a 的烷基、環烷基、芳基及芳烷基（該些基可經所述基取代）的具體例，可列舉與關於R_b 敘述的具體例相同的基。作為本發明中的尤佳的化合物（DD）的具體例，可列舉美國專利申請公開2012/0135348A1號說明書的段落[0475]中揭示的化合物，但並不限制於此。Examples of the R _a is alkyl, cycloalkyl, aryl and aralkyl group (the group may be substituted with those of the group) Specific examples include the specific examples described on the same R _b group. As a specific example of a particularly desirable compound (DD) in the present invention, the compound disclosed in paragraph [0475] of the specification of U.S. Patent Application Publication No. 2012/0135348A1 can be cited, but it is not limited thereto.

＜在陽離子部具有氮原子的鎓鹽化合物（DE）＞在陽離子部具有氮原子的鎓鹽化合物（DE）（以下，亦稱為「化合物（DE）」）較佳為在陽離子部具有包含氮原子的鹼性部位的化合物。鹼性部位較佳為胺基，更佳為脂肪族胺基。進而佳為與鹼性部位中的氮原子鄰接的原子全部為氫原子或碳原子。另外，就鹼性提高的觀點而言，較佳為拉電子性的官能基（羰基、磺醯基、氰基及鹵素原子等）不直接鍵結於氮原子上。作為化合物（DE）的較佳的具體例，可列舉美國專利申請公開2015/0309408A1號說明書的段落[0203]中揭示的化合物，但並不限制於此。<Onium salt compound (DE) having a nitrogen atom in the cation part> The onium salt compound (DE) having a nitrogen atom in the cation part (hereinafter also referred to as “compound (DE)”) is preferably a compound having a basic part including a nitrogen atom in the cation part. The basic part is preferably an amine group, and more preferably an aliphatic amine group. Furthermore, it is preferable that all the atoms adjacent to the nitrogen atom in the basic site are hydrogen atoms or carbon atoms. In addition, from the viewpoint of improving basicity, it is preferable that the electron-withdrawing functional group (carbonyl group, sulfonyl group, cyano group, halogen atom, etc.) is not directly bonded to the nitrogen atom. As a preferable specific example of the compound (DE), the compound disclosed in paragraph [0203] of the specification of U.S. Patent Application Publication No. 2015/0309408A1 can be cited, but it is not limited thereto.

以下示出酸擴散控制劑的較佳例。Preferred examples of acid diffusion control agents are shown below.

[化71]

[化71]

於本發明的抗蝕劑組成物中含有酸擴散控制劑的情況下，相對於組成物的總固體成分，酸擴散控制劑的含量（存在多種時為其合計）較佳為0.1質量%～11.0質量%，更佳為0.1質量%～10.0質量%，進而佳為0.1質量%～8.0質量%，尤佳為0.1質量%～5.0質量%。本發明的抗蝕劑組成物中，酸擴散控制劑可單獨使用一種，亦可併用兩種以上。When the acid diffusion control agent is contained in the resist composition of the present invention, the content of the acid diffusion control agent relative to the total solid content of the composition (when there are multiple types, the total amount) is preferably 0.1% by mass to 11.0 % By mass, more preferably 0.1% by mass to 10.0% by mass, still more preferably 0.1% by mass to 8.0% by mass, and particularly preferably 0.1% by mass to 5.0% by mass. In the resist composition of the present invention, the acid diffusion control agent may be used alone or in combination of two or more.

[疏水性樹脂] 本發明的抗蝕劑組成物除了所述樹脂（A）以外，亦可含有與樹脂（A）不同的疏水性樹脂。疏水性樹脂較佳為設計成偏向存在於抗蝕劑膜的表面，但與界面活性劑不同，分子內未必需要具有親水基，亦可無助於均勻地混合極性物質及非極性物質。作為添加疏水性樹脂的效果，可列舉控制抗蝕劑膜表面相對於水的靜態及動態的接觸角、以及抑制氣體逸出等。[Hydrophobic resin] The resist composition of the present invention may contain a hydrophobic resin different from the resin (A) in addition to the resin (A). The hydrophobic resin is preferably designed to be biased to exist on the surface of the resist film, but unlike surfactants, it is not necessary to have a hydrophilic group in the molecule, and it may not help uniformly mix polar and non-polar substances. As an effect of adding a hydrophobic resin, control of the static and dynamic contact angle of the surface of the resist film with respect to water, suppression of gas escape, and the like can be cited.

就向膜表層的偏向存在化的觀點而言，疏水性樹脂較佳為具有「氟原子」、「矽原子」及「樹脂的側鏈部分所包含的CH₃ 部分結構」中的任一種以上，更佳為具有兩種以上。另外，所述疏水性樹脂較佳為具有碳數5以上的烴基。該些基可存在於樹脂的主鏈中，亦可於側鏈進行取代。From the viewpoint of the existence of bias toward the film surface layer, the hydrophobic resin preferably has any one or more of _{"fluorine atom", "silicon atom", and "CH 3 partial structure contained in the side chain part of the resin",} More preferably, there are two or more types. In addition, the hydrophobic resin preferably has a hydrocarbon group with 5 or more carbon atoms. These groups may exist in the main chain of the resin, or may be substituted in the side chain.

於疏水性樹脂含有氟原子及/或矽原子的情況下，疏水性樹脂中的所述氟原子及/或矽原子可包含於樹脂的主鏈中，亦可包含於側鏈中。When the hydrophobic resin contains fluorine atoms and/or silicon atoms, the fluorine atoms and/or silicon atoms in the hydrophobic resin may be included in the main chain of the resin, or may be included in the side chain.

於疏水性樹脂含有氟原子的情況下，作為具有氟原子的部分結構，較佳為具有氟原子的烷基、具有氟原子的環烷基、或者具有氟原子的芳基。具有氟原子的烷基（較佳為碳數1～10，更佳為碳數1～4）為至少一個氫原子經氟原子取代的直鏈狀或支鏈狀的烷基，亦可進而具有氟原子以外的取代基。具有氟原子的環烷基為至少一個氫原子經氟原子取代的單環或多環的環烷基，亦可進而具有氟原子以外的取代基。作為具有氟原子的芳基，可列舉苯基及萘基等芳基中的至少一個氫原子經氟原子取代的基，亦可進而具有氟原子以外的取代基。作為具有氟原子或矽原子的重複單元的例子，可列舉US2012/0251948A1的段落[0519]中所例示者。When the hydrophobic resin contains a fluorine atom, the partial structure having a fluorine atom is preferably an alkyl group having a fluorine atom, a cycloalkyl group having a fluorine atom, or an aryl group having a fluorine atom. The alkyl group having a fluorine atom (preferably with 1 to 10 carbons, more preferably with 1 to 4 carbons) is a linear or branched alkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and may further have Substituents other than fluorine atoms. The cycloalkyl group having a fluorine atom is a monocyclic or polycyclic cycloalkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and may further have a substituent other than a fluorine atom. Examples of the aryl group having a fluorine atom include a group in which at least one hydrogen atom in an aryl group such as a phenyl group and a naphthyl group is substituted with a fluorine atom, and it may further have a substituent other than a fluorine atom. As an example of the repeating unit having a fluorine atom or a silicon atom, those exemplified in paragraph [0519] of US2012/0251948A1 can be cited.

另外，如上所述，疏水性樹脂亦較佳為在側鏈部分含有CH₃ 部分結構。此處，疏水性樹脂中的側鏈部分所具有的CH₃ 部分結構包括乙基及丙基等所具有的CH₃ 部分結構。另一方面，與疏水性樹脂的主鏈直接鍵結的甲基（例如，具有甲基丙烯酸結構的重複單元的α-甲基）由於主鏈的影響，對疏水性樹脂的表面偏向存在化的貢獻小，因此不包含在本發明的CH₃ 部分結構中。In addition, as described above, it is also preferable that the hydrophobic resin contains a CH ₃ partial structure in the side chain portion. Here, the side chain portion of the hydrophobic resin has a partial structure comprising a CH ₃ ₃ ethyl and propyl partial structure possessed CH. On the other hand, the methyl group directly bonded to the main chain of the hydrophobic resin (for example, the α-methyl group of the repeating unit having a methacrylic acid structure) is biased toward the surface of the hydrophobic resin due to the influence of the main chain. The contribution is small, so it is not included in the CH ₃ partial structure of the present invention.

關於疏水性樹脂，可參照日本專利特開2014-010245號公報的段落[0348]～[0415]的記載，將該些內容併入至本說明書中。Regarding the hydrophobic resin, reference can be made to the description of paragraphs [0348] to [0415] of JP 2014-010245 A, and these contents are incorporated into this specification.

再者，作為疏水性樹脂，除此以外，亦可較佳地使用日本專利特開2011-248019號公報、日本專利特開2010-175859號公報、日本專利特開2012-032544號公報記載的樹脂。Furthermore, as the hydrophobic resin, in addition to this, the resins described in Japanese Patent Laid-Open No. 2011-248019, Japanese Patent Laid-Open No. 2010-175859, and Japanese Patent Laid-Open No. 2012-032544 can also be preferably used. .

以下示出相當於構成疏水性樹脂的重複單元的單體的較佳例。Preferred examples of monomers corresponding to repeating units constituting the hydrophobic resin are shown below.

[化72]

[化72]

[化73]

[化73]

於本發明的抗蝕劑組成物含有疏水性樹脂的情況下，相對於組成物的總固體成分，疏水性樹脂的含量較佳為0.01質量%～15.0質量%，更佳為0.1質量%～10.0質量%，進而佳為0.1質量%～7.0質量%，尤佳為0.1質量%～5.0質量%。When the resist composition of the present invention contains a hydrophobic resin, relative to the total solid content of the composition, the content of the hydrophobic resin is preferably 0.01% by mass to 15.0% by mass, more preferably 0.1% by mass to 10.0 % By mass, more preferably 0.1% by mass to 7.0% by mass, and particularly preferably 0.1% by mass to 5.0% by mass.

[界面活性劑] 本發明的抗蝕劑組成物亦可含有界面活性劑。藉由含有界面活性劑，可形成密接性更優異、顯影缺陷更少的圖案。作為界面活性劑，較佳為氟系及/或矽系界面活性劑。作為氟系及/或矽系界面活性劑，例如可列舉美國專利申請公開第2008/0248425號說明書的段落[0276]中記載的界面活性劑。另外，亦可使用艾福拓（Eftop）EF301或EF303（新秋田化成（股）製造）；弗洛德（Fluorad）FC430、431或4430（住友3M（股）製造）；美佳法（Megafac）F171、F173、F176、F189、F113、F110、F177、F120或R08（DIC（股）製造）；沙福隆（Surflon）S-382、SC101、102、103、104、105或106（旭硝子（股）製造）；托利所（Troysol）S-366（特洛伊化學（Troy Chemical）（股）製造）；GF-300或GF-150（東亞合成化學（股）製造）、沙福隆（Surflon）S-393（清水化學（Seimi Chemical）（股）製造）；艾福拓（Eftop）EF121、EF122A、EF122B、RF122C、EF125M、EF135M、EF351、EF352、EF801、EF802或EF601（傑姆柯（Jemco）（股）製造）；PF636、PF656、PF6320或PF6520（歐諾法（OMNOVA）公司製造）；KH-20（旭化成（股）製造）；FTX-204G、208G、218G、230G、204D、208D、212D、218D或222D（奈奧斯（NEOS）（股）製造）。再者，聚矽氧烷聚合物KP-341（信越化學工業（股）製造）亦可作為矽系界面活性劑使用。[Surfactant] The resist composition of the present invention may also contain a surfactant. By containing a surfactant, it is possible to form a pattern with better adhesion and fewer development defects. As the surfactant, fluorine-based and/or silicon-based surfactants are preferred. Examples of the fluorine-based and/or silicon-based surfactants include the surfactants described in paragraph [0276] of the specification of US Patent Application Publication No. 2008/0248425. In addition, Eftop EF301 or EF303 (manufactured by New Akita Chemical Co., Ltd.); Fluorad FC430, 431 or 4430 (manufactured by Sumitomo 3M Co., Ltd.) can also be used; Megafac F171 , F173, F176, F189, F113, F110, F177, F120 or R08 (manufactured by DIC (Stock)); Surflon S-382, SC101, 102, 103, 104, 105 or 106 (Asahi Glass (Stock) Manufacturing); Troysol S-366 (manufactured by Troy Chemical (stock)); GF-300 or GF-150 (manufactured by Dongya Synthetic Chemical Co., Ltd.), saflon (Surflon) S- 393 (manufactured by Seimi Chemical (shares)); Eftop EF121, EF122A, EF122B, RF122C, EF125M, EF135M, EF351, EF352, EF801, EF802 or EF601 (Jemco) (shares) ) Manufacturing); PF636, PF656, PF6320 or PF6520 (manufactured by OMNOVA); KH-20 (manufactured by Asahi Kasei Co., Ltd.); FTX-204G, 208G, 218G, 230G, 204D, 208D, 212D, 218D Or 222D (manufactured by NEOS (stock)). Furthermore, polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicon-based surfactant.

另外，界面活性劑除了所述所示的公知的界面活性劑以外，亦可使用藉由短鏈聚合（telomerization）法（亦稱為調聚物法）或低聚合（oligomerization）法（亦稱為寡聚物法）製造的氟代脂肪族化合物來合成。具體而言，亦可將具備由該氟代脂肪族化合物導出的氟代脂肪族基的聚合物用作界面活性劑。該氟代脂肪族化合物例如可藉由日本專利特開2002-90991號公報中記載的方法合成。作為具有氟代脂肪族基的聚合物，較佳為具有氟代脂肪族基的單體與(聚(氧化烯))丙烯酸酯及/或(聚(氧化烯))甲基丙烯酸酯的共聚物，即使不規則地分佈者亦可進行嵌段共聚。另外，作為聚(氧化烯)基，可列舉聚(氧化乙烯)基、聚(氧化丙烯)基及聚(氧化丁烯)基，另外，亦可為聚(氧化乙烯、氧化丙烯與氧化乙烯的嵌段連結體)或聚(氧化乙烯與氧化丙烯的嵌段連結體)等於相同鏈長內具有不同鏈長的伸烷基的單元。進而，具有氟代脂肪族基的單體與(聚(氧化烯))丙烯酸酯（或甲基丙烯酸酯）的共聚物不僅為二元共聚物，亦可為將不同的兩種以上的具有氟代脂肪族基的單體及不同的兩種以上的(聚(氧化烯))丙烯酸酯（或甲基丙烯酸酯）等同時進行共聚的三元系以上的共聚物。例如，作為市售的界面活性劑，可列舉美佳法（Megafac）F178、F-470、F-473、F-475、F-476、F-472（DIC（股）製造）、具有C₆ F₁₃ 基的丙烯酸酯（或甲基丙烯酸酯）與(聚(氧化烯))丙烯酸酯（或甲基丙烯酸酯）的共聚物、具有C₃ F₇ 基的丙烯酸酯（或甲基丙烯酸酯）、(聚(氧化乙烯))丙烯酸酯（或甲基丙烯酸酯）與(聚(氧化丙烯))丙烯酸酯（或甲基丙烯酸酯）的共聚物。另外，亦可使用美國專利申請公開第2008/0248425號說明書的段落[0280]中記載的氟系及/或矽系以外的界面活性劑。In addition, the surfactant can also be used by short-chain polymerization (telomerization) method (also known as telomerization method) or oligomerization method (also known as oligomerization) in addition to the well-known surfactants shown above. Oligomer method) to produce fluorinated aliphatic compounds. Specifically, a polymer having a fluoroaliphatic group derived from the fluoroaliphatic compound can also be used as a surfactant. The fluorinated aliphatic compound can be synthesized, for example, by the method described in Japanese Patent Laid-Open No. 2002-90991. The polymer having a fluoroaliphatic group is preferably a copolymer of a monomer having a fluoroaliphatic group and (poly(oxyalkylene)) acrylate and/or (poly(oxyalkylene)) methacrylate , Even if the distribution is irregular, block copolymerization can be carried out. In addition, poly(oxyalkylene) groups include poly(oxyethylene) groups, poly(oxypropylene) groups, and poly(oxybutylene) groups. In addition, poly(oxyethylene, propylene oxide, and oxyethylene) groups may be used. Block linker) or poly(block linker of ethylene oxide and propylene oxide) is equal to the unit of alkylene having different chain lengths in the same chain length. Furthermore, the copolymer of a monomer having a fluoroaliphatic group and (poly(oxyalkylene)) acrylate (or methacrylate) is not only a binary copolymer, but also a combination of two or more different types of fluorine A ternary or more copolymer in which monomers of substituted aliphatic groups and two or more different (poly(oxyalkylene)) acrylates (or methacrylates) are simultaneously copolymerized. For example, as commercially available surfactants, Megafac F178, F-470, F-473, F-475, F-476, F-472 (manufactured by DIC (Stock)), C ₆ F _{Copolymers of 13} -group acrylate (or methacrylate) and (poly(oxyalkylene)) acrylate (or methacrylate), acrylate (or methacrylate) with C ₃ F ₇ group, (Poly(oxyethylene)) acrylate (or methacrylate) and (poly(oxypropylene)) acrylate (or methacrylate) copolymer. In addition, the fluorine-based and/or silicon-based surfactants described in paragraph [0280] of the specification of U.S. Patent Application Publication No. 2008/0248425 may also be used.

該些界面活性劑可單獨使用一種，或者亦可將兩種以上組合使用。相對於本發明的抗蝕劑組成物的總固體成分，界面活性劑的含量較佳為0.0001質量%～2質量%，更佳為0.0005質量%～1質量%。These surfactants may be used alone or in combination of two or more. Relative to the total solid content of the resist composition of the present invention, the content of the surfactant is preferably 0.0001% by mass to 2% by mass, more preferably 0.0005% by mass to 1% by mass.

[溶劑] 本發明的抗蝕劑組成物含有溶劑。溶劑較佳為含有（M1）丙二醇單烷基醚羧酸酯、以及（M2）中的至少一者，所述（M2）選自由丙二醇單烷基醚、乳酸酯、乙酸酯、烷氧基丙酸酯、鏈狀酮、環狀酮、內酯及碳酸伸烷基酯所組成的群組中的至少一者。再者，所述溶劑亦可進而含有成分（M1）及（M2）以外的成分。[Solvent] The resist composition of the present invention contains a solvent. The solvent preferably contains at least one of (M1) propylene glycol monoalkyl ether carboxylate and (M2), and the (M2) is selected from the group consisting of propylene glycol monoalkyl ether, lactate, acetate, alkoxy At least one of the group consisting of propyl propionate, chain ketone, cyclic ketone, lactone, and alkylene carbonate. In addition, the solvent may further contain components other than components (M1) and (M2).

本發明者等人發現，若將所述溶劑與所述樹脂（A）組合使用，則組成物的塗佈性提高，且可形成顯影缺陷數少的圖案。其原因雖未必明確，但本發明者等人認為其原因在於，該些溶劑由於所述樹脂（A）的溶解性、沸點及黏度的平衡良好，因此可抑制組成物膜的膜厚不均及旋塗中的析出物的產生等。The inventors of the present invention found that when the solvent is used in combination with the resin (A), the coatability of the composition is improved, and a pattern with a small number of development defects can be formed. Although the reason is not necessarily clear, the present inventors believe that the reason is that these solvents have a good balance of solubility, boiling point, and viscosity of the resin (A), and therefore can suppress unevenness in the film thickness of the composition film. The generation of precipitates in spin coating, etc.

作為成分（M1），較佳為選自由丙二醇單甲醚乙酸酯（PGMEA：propylene glycol monomethylether acetate）、丙二醇單甲醚丙酸酯及丙二醇單***乙酸酯所組成的群組中的至少一種，更佳為丙二醇單甲醚乙酸酯（PGMEA）。As the component (M1), it is preferably at least one selected from the group consisting of propylene glycol monomethyl ether acetate (PGMEA: propylene glycol monomethylether acetate), propylene glycol monomethyl ether propionate, and propylene glycol monoethyl ether acetate , More preferably propylene glycol monomethyl ether acetate (PGMEA).

作為成分（M2），較佳為以下者。作為丙二醇單烷基醚，較佳為丙二醇單甲醚（PGME：propylene glycol monomethylether）或丙二醇單***（PGEE）。作為乳酸酯，較佳為乳酸乙酯、乳酸丁酯或乳酸丙酯。作為乙酸酯，較佳為乙酸甲酯、乙酸乙酯、乙酸丁酯、乙酸異丁酯、乙酸丙酯、乙酸異戊酯、甲酸甲酯、甲酸乙酯、甲酸丁酯、甲酸丙酯或乙酸3-甲氧基丁酯。另外，亦較佳為丁酸丁酯。作為烷氧基丙酸酯，較佳為3-甲氧基丙酸甲酯（MMP：methyl 3-Methoxypropionate）或3-乙氧基丙酸乙酯（EEP：ethyl 3-ethoxypropionate）。作為鏈狀酮，較佳為1-辛酮、2-辛酮、1-壬酮、2-壬酮、丙酮、2-庚酮、4-庚酮、1-己酮、2-己酮、二異丁基酮、苯基丙酮、甲基乙基酮、甲基異丁基酮、乙醯丙酮、丙酮基丙酮、紫羅酮、二丙酮醇、乙醯基原醇、苯乙酮、甲基萘基酮或甲基戊基酮。作為環狀酮，較佳為甲基環己酮、異佛爾酮或環己酮。作為內酯，較佳為γ-丁內酯。作為碳酸伸烷基酯，較佳為碳酸伸丙酯。As a component (M2), the following are preferable. As the propylene glycol monoalkyl ether, propylene glycol monomethyl ether (PGME: propylene glycol monomethylether) or propylene glycol monoethyl ether (PGEE) is preferred. As the lactate, ethyl lactate, butyl lactate or propyl lactate is preferred. As the acetate, methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate, isoamyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate or 3-Methoxybutyl acetate. In addition, butyl butyrate is also preferred. As the alkoxy propionate, methyl 3-methoxypropionate (MMP: methyl 3-Methoxypropionate) or ethyl 3-ethoxypropionate (EEP: ethyl 3-ethoxypropionate) is preferred. The chain ketone is preferably 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone, 4-heptanone, 1-hexanone, 2-hexanone, Diisobutyl ketone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetoacetone, acetonyl acetone, ionone, diacetone alcohol, acetopropanol, acetophenone, methyl ethyl ketone Naphthyl ketone or methyl amyl ketone. The cyclic ketone is preferably methylcyclohexanone, isophorone or cyclohexanone. As the lactone, γ-butyrolactone is preferred. As alkylene carbonate, propylene carbonate is preferable.

作為成分（M2），更佳為丙二醇單甲醚（PGME）、乳酸乙酯、3-乙氧基丙酸乙酯、甲基戊基酮、環己酮、乙酸丁酯、乙酸戊酯、γ-丁內酯或碳酸伸丙酯。As the component (M2), propylene glycol monomethyl ether (PGME), ethyl lactate, ethyl 3-ethoxypropionate, methyl amyl ketone, cyclohexanone, butyl acetate, amyl acetate, γ -Butyrolactone or propylene carbonate.

除了所述成分以外，較佳為使用碳數為7以上（較佳為7～14，更佳為7～12，進而佳為7～10）且雜原子數為2以下的酯系溶劑。In addition to the above-mentioned components, it is preferable to use an ester solvent having a carbon number of 7 or more (preferably 7 to 14, more preferably 7 to 12, and still more preferably 7 to 10) and a heteroatom of 2 or less.

作為碳數為7以上且雜原子數為2以下的酯系溶劑，較佳為乙酸戊酯、乙酸2-甲基丁酯、乙酸1-甲基丁酯、乙酸己酯、丙酸戊酯、丙酸己酯、丙酸丁酯、異丁酸異丁酯、丙酸庚酯或丁酸丁酯，更佳為乙酸異戊酯。As the ester solvent having 7 or more carbon atoms and 2 or less heteroatoms, pentyl acetate, 2-methylbutyl acetate, 1-methylbutyl acetate, hexyl acetate, pentyl propionate, Hexyl propionate, butyl propionate, isobutyl isobutyrate, heptyl propionate or butyl butyrate, more preferably isoamyl acetate.

作為成分（M2），較佳為閃點（以下，亦稱為fp）為37℃以上者。作為所述成分（M2），較佳為丙二醇單甲醚（fp：47℃）、乳酸乙酯（fp：53℃）、3-乙氧基丙酸乙酯（fp：49℃）、甲基戊基酮（fp：42℃）、環己酮（fp：44℃）、乙酸戊酯（fp：45℃）、2-羥基異丁酸甲酯（fp：45℃）、γ-丁內酯（fp：101℃）或碳酸伸丙酯（fp：132℃）。該些中，更佳為丙二醇單***、乳酸乙酯、乙酸戊酯或環己酮，進而佳為丙二醇單***或乳酸乙酯。再者，此處，所謂「閃點」是指東京化成工業股份有限公司或西格瑪奧瑞奇（Sigma-Aldrich）公司的試劑目錄中記載的值。As the component (M2), one having a flash point (hereinafter also referred to as fp) of 37°C or higher is preferred. The component (M2) is preferably propylene glycol monomethyl ether (fp: 47°C), ethyl lactate (fp: 53°C), ethyl 3-ethoxypropionate (fp: 49°C), methyl Amyl ketone (fp: 42°C), cyclohexanone (fp: 44°C), amyl acetate (fp: 45°C), methyl 2-hydroxyisobutyrate (fp: 45°C), γ-butyrolactone (Fp: 101°C) or propylene carbonate (fp: 132°C). Among these, propylene glycol monoethyl ether, ethyl lactate, amyl acetate or cyclohexanone is more preferred, and propylene glycol monoethyl ether or ethyl lactate is still more preferred. In addition, here, the "flash point" refers to the value described in the reagent catalog of Tokyo Chemical Industry Co., Ltd. or Sigma-Aldrich.

成分（M1）與成分（M2）在混合溶劑中的混合的質量比（M1/M2）較佳為在「100/0」～「15/85」的範圍內，更佳為在「100/0」～「40/60」的範圍內。若採用所述構成，可進一步減少顯影缺陷數。The mixing mass ratio (M1/M2) of the component (M1) and the component (M2) in the mixed solvent is preferably in the range of "100/0" to "15/85", and more preferably in the range of "100/0" "~"40/60". According to this configuration, the number of development defects can be further reduced.

如上所述，溶劑亦可進而含有成分（M1）及（M2）以外的成分。該情況下，相對於溶劑的總量，成分（M1）及（M2）以外的成分的含量較佳為30質量%以下的範圍內，更佳為5質量%～30質量%的範圍內。As described above, the solvent may further contain components other than the components (M1) and (M2). In this case, the content of components other than the components (M1) and (M2) is preferably within the range of 30% by mass or less, and more preferably within the range of 5% by mass to 30% by mass relative to the total amount of the solvent.

本發明的抗蝕劑組成物中的溶劑的含量較佳為設定為固體成分濃度成為0.5質量%～30質量%，更佳為設定為固體成分濃度成為1質量%～20質量%。如此，本發明的抗蝕劑組成物的塗佈性更優異。再者，如上所述，所謂「固體成分」是指形成抗蝕劑膜的成分，不含溶劑。另外，只要是形成抗蝕劑膜的成分，即使其性狀為液體狀，亦視為固體成分。The content of the solvent in the resist composition of the present invention is preferably set so that the solid content concentration is 0.5% by mass to 30% by mass, and more preferably set so that the solid content concentration is 1% by mass to 20% by mass. In this way, the resist composition of the present invention is more excellent in coatability. In addition, as described above, the "solid content" refers to a component that forms a resist film, and does not contain a solvent. In addition, as long as it is a component that forms a resist film, even if its properties are liquid, it is regarded as a solid component.

＜其他添加劑＞本發明的抗蝕劑組成物亦可進而含有所述以外的樹脂、交聯劑、酸增殖劑、染料、塑化劑、光增感劑、光吸收劑、鹼可溶性樹脂、溶解抑制劑或溶解促進劑等。＜Other additives＞ The resist composition of the present invention may further contain resins, crosslinking agents, acid multipliers, dyes, plasticizers, photosensitizers, light absorbers, alkali-soluble resins, dissolution inhibitors, or dissolutions other than those described above. Promoter, etc.

[抗蝕劑組成物的製備方法] ＜含水率的調整方法＞以下示出將抗蝕劑組成物的含水率減少至規定值以下的方法的一例。以下所示的方法可單獨實施，亦可將兩種以上的方法組合實施。（1）於氮氣環境下及/或乾燥環境下進行抗蝕劑組成物的製備的方法：藉由於氮氣環境下進行構成抗蝕劑組成物的各成分的混合步驟，可抑制抗蝕劑組成物的製備時的水分的混入。另外，於抗蝕劑組成物含有吸濕性高的樹脂（A）及/或吸濕性高的光酸產生劑的情況下，亦較佳為於乾燥環境（例如濕度50%以下）下進行構成抗蝕劑組成物的各成分的混合步驟。（2）減少構成抗蝕劑組成物的各成分（原料成分）自身的含水率的方法：藉由減少構成抗蝕劑組成物的各成分（原料成分）自身的含水率，可減少抗蝕劑組成物的含水率。具體而言，可列舉於抗蝕劑組成物的製備前，對抗蝕劑組成物中調配的各成分（原料成分）進行真空乾燥處理的方法。所述真空乾燥處理可於室溫下進行，亦可於加熱的同時進行。藉由對抗蝕劑組成物中可大量含有的樹脂（A）進行真空乾燥處理，更容易減少最終所得的抗蝕劑組成物的含水率。作為樹脂（A）的真空乾燥處理，可列舉於減壓及加熱下（例：15 mmHg；40℃～60℃）乾燥規定時間（例如，較佳為30分鐘以上且24小時以下，更佳為1小時以上且16小時以下，進而佳為於2小時以上且12小時以下的範圍內進行調整）的處理作為一例。（3）利用分子篩（molecular sieve）進行脫水處理的方法：藉由利用分子篩（例：聯合（Union）昭和股份有限公司製造者）對構成抗蝕劑組成物的各成分（原料成分）自身及/或抗蝕劑組成物進行脫水處理，可減少抗蝕劑組成物的含水率。尤其是利用分子篩對構成抗蝕劑組成物的各成分（原料成分）自身進行脫水處理更容易減少最終所得的抗蝕劑組成物的含水率。[Preparation method of resist composition] ＜How to adjust the moisture content＞ An example of a method of reducing the moisture content of the resist composition below a predetermined value is shown below. The methods shown below can be implemented individually or in combination of two or more methods. (1) The method of preparing the resist composition in a nitrogen environment and/or a dry environment: By performing the mixing step of each component constituting the resist composition in a nitrogen atmosphere, mixing of moisture during the preparation of the resist composition can be suppressed. In addition, when the resist composition contains a highly hygroscopic resin (A) and/or a highly hygroscopic photoacid generator, it is also preferably performed in a dry environment (for example, humidity below 50%) A step of mixing the components constituting the resist composition. (2) A method to reduce the moisture content of each component (raw material component) constituting the resist composition: By reducing the moisture content of each component (raw material component) constituting the resist composition, the moisture content of the resist composition can be reduced. Specifically, a method of vacuum-drying each component (raw material component) blended in the resist composition before the preparation of the resist composition can be cited. The vacuum drying treatment can be carried out at room temperature or while heating. By vacuum drying the resin (A) that can be contained in a large amount in the resist composition, it is easier to reduce the moisture content of the resist composition finally obtained. As the vacuum drying treatment of the resin (A), drying under reduced pressure and heating (for example: 15 mmHg; 40°C to 60°C) for a predetermined time (for example, preferably 30 minutes or more and 24 hours or less, more preferably 1 hour or more and 16 hours or less, more preferably in the range of 2 hours or more and 12 hours or less) treatment as an example. (3) The method of dehydration treatment using molecular sieve: By using molecular sieves (e.g., manufactured by Union Showa Co., Ltd.) to dehydrate each component (raw material component) constituting the resist composition and/or the resist composition, the resist can be reduced The moisture content of the composition. In particular, it is easier to reduce the moisture content of the resist composition finally obtained by dehydrating each component (raw material component) themselves constituting the resist composition using molecular sieves.

以下示出本發明的抗蝕劑組成物的製備方法的具體的一例。抗蝕劑組成物中，較佳為減少金屬原子的含量。A specific example of the preparation method of the resist composition of the present invention is shown below. In the resist composition, it is preferable to reduce the content of metal atoms.

以下，首先說明減少抗蝕劑組成物中的金屬原子的含量的方法的具體的一例，然後說明抗蝕劑組成物的製備方法的具體的一例。作為減少抗蝕劑組成物中的金屬原子的含量的方法，例如可列舉藉由使用過濾器的過濾進行的調整方法。作為過濾器孔徑，較佳為細孔徑未滿100 nm，更佳為10 nm以下，進而佳為5 nm以下。作為過濾器，較佳為聚四氟乙烯製、聚乙烯製或尼龍製過濾器。過濾器亦可由組合了所述過濾器素材與離子交換介質的複合材料構成。過濾器亦可使用預先利用有機溶劑清洗的過濾器。過濾器過濾步驟中，亦可串聯或並聯連接多種過濾器來使用。於使用多種過濾器的情況下，可組合使用孔徑及/或材質不同的過濾器。另外，亦可對各種材料進行多次過濾，多次過濾的步驟可為循環過濾步驟。Hereinafter, a specific example of a method of reducing the content of metal atoms in the resist composition will be described first, and then a specific example of a method of preparing the resist composition will be described. As a method of reducing the content of metal atoms in the resist composition, for example, an adjustment method by filtration using a filter can be cited. The pore diameter of the filter is preferably less than 100 nm, more preferably 10 nm or less, and still more preferably 5 nm or less. As the filter, a filter made of polytetrafluoroethylene, polyethylene, or nylon is preferred. The filter may also be composed of a composite material combining the filter material and the ion exchange medium. The filter can also be a filter that has been cleaned with an organic solvent in advance. In the filter filtration step, multiple filters can also be connected in series or parallel for use. When multiple filters are used, filters with different pore sizes and/or materials can be used in combination. In addition, various materials can also be filtered multiple times, and the step of multiple filtering can be a cyclic filtering step.

另外，作為減少抗蝕劑組成物中的金屬原子的含量的方法，可列舉以下方法等：選擇金屬含量少的原料作為構成抗蝕劑組成物中的各種材料的原料的方法、對構成抗蝕劑組成物中的各種材料的原料進行過濾器過濾的方法、以及利用鐵氟龍（Teflon）（註冊商標）對裝置內進行加襯（lining）等且在盡可能抑制污染（contamination）的條件下進行蒸餾的方法。In addition, as a method of reducing the content of metal atoms in the resist composition, the following methods can be cited: a method of selecting a raw material with a small metal content as a raw material for constituting various materials in the resist composition, and a method for forming a resist composition. The method of filtering the raw materials of various materials in the agent composition, and lining the device with Teflon (registered trademark), etc., and under the condition of suppressing contamination (contamination) as much as possible The method of carrying out the distillation.

另外，作為減少抗蝕劑組成物中的金屬原子的含量的方法，除了所述過濾器過濾之外，亦可利用吸附材進行去除，亦可將過濾器過濾與吸附材組合使用。作為吸附材，可使用公知的吸附材，例如可使用矽膠及沸石等無機系吸附材、以及活性碳等有機系吸附材。另外，為了減少抗蝕劑組成物中的金屬原子的含量，必須防止製造步驟中的金屬雜質的混入。可藉由測定用於清洗製造裝置的清洗液中所含的金屬成分的含量來確認是否自製造裝置中充分地去除了金屬雜質。In addition, as a method for reducing the content of metal atoms in the resist composition, in addition to filtration by the filter, removal by an adsorbent may be used, or a combination of filter filtration and an adsorbent may be used. As the adsorbent, a well-known adsorbent can be used. For example, inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon can be used. In addition, in order to reduce the content of metal atoms in the resist composition, it is necessary to prevent the incorporation of metal impurities in the manufacturing step. It is possible to confirm whether metal impurities are sufficiently removed from the manufacturing device by measuring the content of the metal component contained in the cleaning liquid used for cleaning the manufacturing device.

其次，對抗蝕劑組成物的製備方法的具體的一例進行敘述。於抗蝕劑組成物的製造時，為了使最終所得的抗蝕劑組成物的含水率為規定值以下，利用所述方法對構成抗蝕劑組成物的各成分（原料成分）自身及/或抗蝕劑組成物實施減少含水量的步驟。Next, a specific example of the method of preparing the resist composition will be described. In the production of the resist composition, in order to make the moisture content of the resist composition finally obtained below a predetermined value, the above method is used to compare the components (raw material components) themselves and/or the resist composition. The resist composition implements a step of reducing the water content.

於抗蝕劑組成物的製造中，例如較佳為於使所述樹脂及光酸產生劑等各種成分溶解於溶劑中之後，使用素材不同的多個過濾器進行過濾（亦可為循環過濾）。例如，較佳為將孔徑50 nm的聚乙烯製過濾器、孔徑10 nm的尼龍製過濾器、孔徑3 nm～5 nm的聚乙烯製過濾器排列連接，進行過濾。過濾亦較佳為進行兩次以上的循環過濾的方法。再者，所述過濾步驟亦具有減少抗蝕劑組成物中的金屬原子的含量的效果。過濾器之間的壓力差越小越佳，通常為0.1 MPa以下，較佳為0.05 MPa以下，更佳為0.01 MPa以下。過濾器與填充噴嘴之間的壓力差亦越小越佳，通常為0.5 MPa以下，較佳為0.2 MPa以下，更佳為0.1 MPa以下。另外，作為抗蝕劑組成物的製造中使用過濾器進行循環過濾的方法，例如亦較佳為使用孔徑50 nm的聚四氟乙烯製過濾器進行兩次以上循環過濾的方法。In the manufacture of the resist composition, it is preferable to dissolve various components such as the resin and the photoacid generator in a solvent, and then filter with a plurality of filters with different materials (circulation filtration is also possible) . For example, it is preferable to arrange and connect a polyethylene filter with a pore diameter of 50 nm, a nylon filter with a pore diameter of 10 nm, and a polyethylene filter with a pore diameter of 3 nm to 5 nm to perform filtration. The filtration is also preferably a method of performing cyclic filtration twice or more. Furthermore, the filtering step also has the effect of reducing the content of metal atoms in the resist composition. The pressure difference between the filters is as small as possible, usually 0.1 MPa or less, preferably 0.05 MPa or less, and more preferably 0.01 MPa or less. The pressure difference between the filter and the filling nozzle is also as small as possible, usually 0.5 MPa or less, preferably 0.2 MPa or less, and more preferably 0.1 MPa or less. In addition, as a method of circulating filtration using a filter in the manufacture of the resist composition, for example, a method of circulating filtration using a polytetrafluoroethylene filter with a pore size of 50 nm is also preferable.

抗蝕劑組成物的製造裝置的內部較佳為藉由氮氣等惰性氣體進行氣體置換。藉此，可抑制氧等活性氣體溶解於抗蝕劑組成物中。將抗蝕劑組成物藉由過濾器過濾後填充到潔淨的容器中。填充到容器中的抗蝕劑組成物較佳為冷藏保存。藉此，可抑制經時引起的性能劣化。從抗蝕劑組成物向容器中的填充完成到開始冷藏保存的時間越短越佳，通常為24小時以內，較佳為16小時以內，更佳為12小時以內，進而佳為10小時以內。保存溫度較佳為0℃～15℃，更佳為0℃～10℃，進而佳為0℃～5℃。The inside of the manufacturing apparatus of the resist composition is preferably replaced with an inert gas such as nitrogen. This can prevent active gases such as oxygen from being dissolved in the resist composition. The resist composition is filtered through a filter and then filled into a clean container. The resist composition filled in the container is preferably stored under refrigeration. Thereby, performance degradation caused by time can be suppressed. The shorter the time from the completion of the filling of the resist composition into the container to the start of refrigerated storage, the better, and it is usually within 24 hours, preferably within 16 hours, more preferably within 12 hours, and more preferably within 10 hours. The storage temperature is preferably 0°C to 15°C, more preferably 0°C to 10°C, and still more preferably 0°C to 5°C.

[抗蝕劑膜、圖案形成方法] 使用本發明的抗蝕劑組成物可形成抗蝕劑膜，進而可形成圖案。使用本發明的抗蝕劑組成物的圖案形成方法的順序並無特別限制，但較佳為包括以下步驟。步驟1：使用抗蝕劑組成物於支持體（基板上）形成抗蝕劑膜的步驟步驟2：對抗蝕劑膜進行曝光的步驟步驟3：使用顯影液將曝光後的抗蝕劑膜顯影的步驟以下，對所述各步驟的順序進行詳述。[Resist film, pattern formation method] Using the resist composition of the present invention, a resist film can be formed, and further patterns can be formed. The order of the pattern formation method using the resist composition of the present invention is not particularly limited, but preferably includes the following steps. Step 1: Step of forming a resist film on the support (on the substrate) using the resist composition Step 2: The step of exposing the resist film Step 3: The step of developing the exposed resist film using a developing solution Hereinafter, the order of each step is described in detail.

[步驟1：抗蝕劑膜形成步驟] 步驟1是使用抗蝕劑組成物於支持體（基板上）形成抗蝕劑膜的步驟。抗蝕劑組成物的定義及抗蝕劑組成物的製備方法如上所述。[Step 1: Resist film formation step] Step 1 is a step of forming a resist film on a support (on a substrate) using the resist composition. The definition of the resist composition and the preparation method of the resist composition are as described above.

其次，對使用抗蝕劑組成物於基板上形成抗蝕劑膜的方法進行說明。作為使用抗蝕劑組成物於基板上形成抗蝕劑膜的方法，可列舉於基板上塗佈抗蝕劑組成物的方法。Next, a method of forming a resist film on a substrate using the resist composition will be described. As a method of forming a resist film on a substrate using the resist composition, a method of applying the resist composition on the substrate can be cited.

抗蝕劑組成物可藉由旋轉器或塗佈機等適當的塗佈方法塗佈於積體電路組件的製造中所使用的基板（例：矽、二氧化矽被覆）上。作為塗佈方法，較佳為使用旋轉器的旋轉塗佈。使用旋轉器進行旋轉塗佈時的轉速較佳為1000 rpm～3000 rpm。亦可於抗蝕劑組成物的塗佈後，對基板進行乾燥而形成抗蝕劑膜。再者，亦可視需要於抗蝕劑膜的下層形成各種基底膜（無機膜、有機膜、防反射膜）。The resist composition can be coated on a substrate (for example, silicon, silicon dioxide coating) used in the manufacture of integrated circuit components by an appropriate coating method such as a spinner or a coater. As the coating method, spin coating using a spinner is preferred. The rotation speed when the spinner is used for spin coating is preferably 1000 rpm to 3000 rpm. After coating the resist composition, the substrate may be dried to form a resist film. Furthermore, various base films (inorganic film, organic film, anti-reflection film) may be formed on the lower layer of the resist film as needed.

作為乾燥方法，可列舉進行加熱而乾燥的方法。加熱可藉由通常的曝光機及/或顯影機所具備的機構進行，亦可使用加熱板等進行。加熱溫度較佳為80℃～150℃，更佳為80℃～140℃，進而佳為80℃～130℃。加熱時間較佳為30秒～1000秒，更佳為60秒～800秒，進而佳為60秒～600秒。As a drying method, the method of heating and drying is mentioned. Heating can be performed by a mechanism provided in a normal exposure machine and/or a developing machine, or a hot plate or the like can be used. The heating temperature is preferably 80°C to 150°C, more preferably 80°C to 140°C, and still more preferably 80°C to 130°C. The heating time is preferably 30 seconds to 1000 seconds, more preferably 60 seconds to 800 seconds, and still more preferably 60 seconds to 600 seconds.

抗蝕劑膜的膜厚並無特別限制，就可形成更高精度的微細圖案的方面而言，較佳為10 nm～150 nm，更佳為15 nm～100 nm。The thickness of the resist film is not particularly limited. In terms of forming a finer pattern with higher accuracy, it is preferably 10 nm to 150 nm, and more preferably 15 nm to 100 nm.

再者，亦可於抗蝕劑膜的上層使用頂塗層組成物而形成頂塗層。頂塗層組成物較佳為與抗蝕劑膜不混合，進而可均勻地塗佈於抗蝕劑膜上層。另外，較佳為於頂塗層形成前對抗蝕劑膜進行乾燥。繼而，於所得的抗蝕劑膜上，藉由與所述抗蝕劑膜的形成方法同樣的方法塗佈頂塗層組成物，進而進行乾燥，藉此可形成頂塗層。頂塗層的膜厚較佳為10 nm～200 nm，更佳為20 nm～100 nm。頂塗層組成物例如含有樹脂、添加劑及溶劑。作為所述樹脂，可使用與所述疏水性樹脂同樣的樹脂。相對於頂塗層組成物的總固體成分，樹脂的含量較佳為50質量%～99.9質量%，更佳為60質量%～99.7質量%。再者，此處所述的「固體成分」是指形成頂塗層的成分，不含溶劑。另外，只要是形成頂塗層的成分，即使其性狀為液體狀，亦視為固體成分。作為所述添加劑，可使用所述酸擴散控制劑。另外，亦可使用具有N-氧自由基的化合物之類的具有自由基捕捉基的化合物。作為所述化合物，例如可列舉[4-(苯甲醯氧基)-2,2,6,6-四甲基哌啶氧基]自由基。相對於頂塗層組成物的總固體成分，添加劑的含量較佳為0.01質量%～20質量%，更佳為0.1質量%～15質量%。所述溶劑較佳為不溶解抗蝕劑膜，例如可列舉醇系溶劑（4-甲基-2-戊醇等）、醚系溶劑（二異戊醚等）、酯系溶劑、氟系溶劑及烴系溶劑（正癸烷等）。頂塗層組成物中的溶劑的含量較佳為設定為固體成分濃度成為0.5質量%～30質量%，更佳為設定為成為1質量%～20質量%。另外，頂塗層組成物除了所述添加劑以外，亦可含有界面活性劑，作為所述界面活性劑，可使用本發明的抗蝕劑組成物可含有的界面活性劑。相對於頂塗層組成物的總固體成分，界面活性劑的含量較佳為0.0001質量%～2質量%，更佳為0.0005質量%～1質量%。除此以外，頂塗層並無特別限定，可藉由現有公知的方法形成現有公知的頂塗層，例如可基於日本專利特開2014-059543號公報的段落[0072]～[0082]的記載而形成頂塗層。例如，較佳為於抗蝕劑膜上形成含有如日本專利特開2013-61648號公報中記載的鹼性化合物的頂塗層。頂塗層可含有的鹼性化合物的具體例可列舉本發明的抗蝕劑組成物可含有的鹼性化合物。另外，頂塗層較佳為含有具有至少一個選自由醚鍵、硫醚鍵、羥基、硫醇基、羰基鍵及酯鍵所組成的群組中的基或鍵的化合物。Furthermore, a top coat composition may be used on the upper layer of the resist film to form a top coat. The top coat composition is preferably not mixed with the resist film, and can be evenly coated on the upper layer of the resist film. In addition, it is preferable to dry the resist film before forming the top coat layer. Then, on the obtained resist film, the top coat composition is applied by the same method as the formation method of the resist film, and then dried, whereby the top coat can be formed. The film thickness of the top coating layer is preferably 10 nm to 200 nm, more preferably 20 nm to 100 nm. The top coat composition contains, for example, resin, additives, and solvents. As the resin, the same resin as the hydrophobic resin can be used. The content of the resin is preferably 50% by mass to 99.9% by mass, and more preferably 60% by mass to 99.7% by mass relative to the total solid content of the topcoat composition. In addition, the "solid content" as used herein refers to a component that forms the top coat, and does not contain a solvent. In addition, as long as it is a component that forms a top coat layer, it is regarded as a solid component even if its properties are liquid. As the additive, the acid diffusion control agent can be used. In addition, a compound having a radical scavenging group such as a compound having an N-oxy radical can also be used. Examples of the compound include [4-(benzyloxy)-2,2,6,6-tetramethylpiperidinyloxy] radical. The content of the additive is preferably 0.01% by mass to 20% by mass, and more preferably 0.1% by mass to 15% by mass relative to the total solid content of the topcoat composition. The solvent is preferably one that does not dissolve the resist film. Examples include alcohol-based solvents (4-methyl-2-pentanol, etc.), ether-based solvents (diisoamyl ether, etc.), ester-based solvents, and fluorine-based solvents. And hydrocarbon solvents (n-decane, etc.). The content of the solvent in the topcoat layer composition is preferably set to a solid content concentration of 0.5% by mass to 30% by mass, and more preferably set to be 1% by mass to 20% by mass. In addition, the topcoat composition may contain a surfactant in addition to the additives, and as the surfactant, a surfactant that can be contained in the resist composition of the present invention can be used. The content of the surfactant relative to the total solid content of the top coat composition is preferably 0.0001% by mass to 2% by mass, and more preferably 0.0005% by mass to 1% by mass. In addition, the top coat is not particularly limited, and a conventionally known top coat can be formed by a conventionally known method, for example, based on the description of paragraphs [0072] to [0082] in Japanese Patent Laid-Open No. 2014-059543 And the top coat is formed. For example, it is preferable to form a top coat layer containing a basic compound as described in JP 2013-61648 A on the resist film. Specific examples of the basic compound that can be contained in the top coat layer include the basic compound that can be contained in the resist composition of the present invention. In addition, the top coating layer preferably contains a compound having at least one group or bond selected from the group consisting of an ether bond, a thioether bond, a hydroxyl group, a thiol group, a carbonyl bond, and an ester bond.

[步驟2：曝光步驟] 步驟2是對抗蝕劑膜進行曝光的步驟。作為曝光的方法，可列舉經由規定的遮罩對所形成的抗蝕劑膜照射光化射線或放射線的方法。作為光化射線或放射線，可列舉紅外光、可見光、紫外光、遠紫外光、極紫外光、X射線及電子束，可列舉較佳為250 nm以下、更佳為220 nm以下、尤佳為1 nm～200 nm的波長的遠紫外光，具體而言可列舉KrF準分子雷射（248 nm）、ArF準分子雷射（193 nm）、F₂ 準分子雷射（157 nm）、EUV（13 nm）、X射線及電子束。[Step 2: Exposure Step] Step 2 is a step of exposing the resist film. As a method of exposure, a method of irradiating the formed resist film with actinic rays or radiation through a predetermined mask is mentioned. As actinic rays or radiations, infrared light, visible light, ultraviolet light, extreme ultraviolet light, extreme ultraviolet light, X-rays, and electron beams can be cited. Preferably, it is 250 nm or less, more preferably 220 nm or less, and particularly preferably The far ultraviolet light with a wavelength of 1 nm to 200 nm, specifically, KrF excimer laser (248 nm), ArF excimer laser (193 nm), F ₂ excimer laser (157 nm), EUV ( 13 nm), X-ray and electron beam.

較佳為於曝光後、進行顯影前進行烘烤（加熱）。藉由烘烤促進曝光部的反應，感度及圖案形狀變得更良好。加熱溫度較佳為80℃～150℃，更佳為80℃～140℃，進而佳為80℃～130℃。加熱時間較佳為10秒～1000秒，更佳為10秒～180秒，進而佳為30秒～120秒。加熱可藉由通常的曝光機及/或顯影機所具備的機構進行，亦可使用加熱板等進行。所述步驟亦稱為曝光後烘烤。Preferably, baking (heating) is performed after exposure and before development. By baking to promote the reaction of the exposed part, the sensitivity and pattern shape become better. The heating temperature is preferably 80°C to 150°C, more preferably 80°C to 140°C, and still more preferably 80°C to 130°C. The heating time is preferably 10 seconds to 1000 seconds, more preferably 10 seconds to 180 seconds, and still more preferably 30 seconds to 120 seconds. Heating can be performed by a mechanism provided in a normal exposure machine and/or a developing machine, or a hot plate or the like can be used. This step is also called post-exposure baking.

[步驟3：顯影步驟] 步驟3是使用顯影液將曝光後的抗蝕劑膜顯影而形成圖案的步驟。[Step 3: Development Step] Step 3 is a step of developing the exposed resist film using a developing solution to form a pattern.

作為顯影方法，可列舉：使基板於充滿顯影液的槽中浸漬固定時間的方法（浸漬法）；藉由利用表面張力使顯影液堆積至基板表面並靜置固定時間來進行顯影的方法（覆液（puddle）法）；對基板表面噴射顯影液的方法（噴霧法）；以及一面以固定速度掃描顯影液噴出噴嘴，一面朝以固定速度旋轉的基板上連續噴出顯影液的方法（動態分配法）。另外，亦可在進行顯影的步驟之後，實施一面置換為其他溶劑一面停止顯影的步驟。顯影時間若為未曝光部的樹脂充分溶解的時間，則並無特別限制，較佳為10秒～300秒，更佳為20秒～120秒。顯影液的溫度較佳為0℃～50℃，更佳為15℃～35℃。Examples of the development method include: a method of immersing the substrate in a bath filled with developer for a fixed period of time (dipping method); and a method of developing by depositing the developer on the surface of the substrate using surface tension and allowing it to stand for a fixed period of time (coating method). The puddle method); the method of spraying developer on the surface of the substrate (spray method); and the method of continuously spraying the developer on the substrate rotating at a fixed speed while scanning the developer spray nozzle at a fixed speed (dynamic distribution law). In addition, after performing the development step, a step of stopping development while replacing the side with another solvent may be performed. The development time is not particularly limited as long as the resin in the unexposed part is fully dissolved, and it is preferably 10 seconds to 300 seconds, and more preferably 20 seconds to 120 seconds. The temperature of the developer is preferably 0°C to 50°C, more preferably 15°C to 35°C.

作為顯影液，可列舉鹼性顯影液及有機溶劑顯影液。鹼性顯影液較佳為使用包含鹼的鹼性水溶液。鹼性水溶液的種類並無特別限制，例如可列舉包含以氫氧化四甲基銨為代表的四級銨鹽、無機鹼、一級胺、二級胺、三級胺、醇胺或環狀胺等的鹼性水溶液。其中，鹼性顯影液較佳為以氫氧化四甲基銨（Tetramethyl Ammonium Hydroxide，TMAH）為代表的四級銨鹽的水溶液。鹼性顯影液中亦可添加適量的醇類、界面活性劑等。鹼性顯影液的鹼濃度通常為0.1質量%～20質量%。另外，鹼性顯影液的pH通常為10.0～15.0。Examples of the developer include alkaline developer and organic solvent developer. As the alkaline developer, it is preferable to use an alkaline aqueous solution containing alkali. The type of alkaline aqueous solution is not particularly limited, and examples include quaternary ammonium salts represented by tetramethylammonium hydroxide, inorganic bases, primary amines, secondary amines, tertiary amines, alcohol amines, or cyclic amines. The alkaline aqueous solution. Among them, the alkaline developer is preferably an aqueous solution of a quaternary ammonium salt represented by Tetramethyl Ammonium Hydroxide (TMAH). An appropriate amount of alcohols, surfactants, etc. can also be added to the alkaline developer. The alkali concentration of the alkaline developer is usually 0.1% by mass to 20% by mass. In addition, the pH of the alkaline developer is usually 10.0 to 15.0.

所謂有機溶劑顯影液是指含有有機溶劑的顯影液。有機溶劑顯影液中所含的有機溶劑的蒸氣壓（於為混合溶劑的情況下是作為整體的蒸氣壓）於20℃下較佳為5 kPa以下，更佳為3 kPa以下，進而佳為2 kPa以下。藉由將有機溶劑的蒸氣壓設為5 kPa以下，顯影液於基板上或顯影杯內的蒸發得到抑制，晶圓面內的溫度均勻性提高，結果晶圓面內的尺寸均勻性良化。The so-called organic solvent developer refers to a developer containing an organic solvent. The vapor pressure of the organic solvent contained in the organic solvent developer (in the case of a mixed solvent, the vapor pressure as a whole) at 20°C is preferably 5 kPa or less, more preferably 3 kPa or less, and still more preferably 2 Below kPa. By setting the vapor pressure of the organic solvent to 5 kPa or less, the evaporation of the developer on the substrate or in the developing cup is suppressed, the temperature uniformity in the wafer surface is improved, and the dimensional uniformity in the wafer surface is improved.

作為有機溶劑顯影液中使用的有機溶劑，可列舉公知的有機溶劑，可列舉酯系溶劑、酮系溶劑、醇系溶劑、醯胺系溶劑、醚系溶劑及烴系溶劑。Examples of the organic solvent used in the organic solvent developer include well-known organic solvents, including ester solvents, ketone solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents.

於所述曝光步驟中使用EUV及電子束的情況下，就可抑制抗蝕劑膜的膨潤的方面而言，有機溶劑顯影液中所含的有機溶劑較佳為使用碳原子數為7以上（較佳為7～14，更佳為7～12，進而佳為7～10）且雜原子數為2以下的酯系溶劑。When EUV and electron beams are used in the exposure step, in terms of suppressing swelling of the resist film, the organic solvent contained in the organic solvent developer is preferably used with carbon atoms of 7 or more ( Preferably it is 7-14, More preferably, it is 7-12, More preferably, it is 7-10) and an ester solvent with a heteroatom number of 2 or less.

所述酯系溶劑的雜原子為碳原子及氫原子以外的原子，例如可列舉氧原子、氮原子及硫原子等。雜原子數較佳為2以下。The hetero atom of the ester-based solvent is an atom other than a carbon atom and a hydrogen atom, and examples thereof include an oxygen atom, a nitrogen atom, and a sulfur atom. The number of heteroatoms is preferably 2 or less.

作為碳原子數為7以上且雜原子數為2以下的酯系溶劑，較佳為乙酸戊酯、乙酸異戊酯、乙酸2-甲基丁酯、乙酸1-甲基丁酯、乙酸己酯、丙酸戊酯、丙酸己酯、丙酸丁酯、異丁酸異丁酯、丙酸庚酯或丁酸丁酯等，更佳為乙酸異戊酯。As the ester solvent having 7 or more carbon atoms and 2 or less heteroatoms, pentyl acetate, isoamyl acetate, 2-methylbutyl acetate, 1-methylbutyl acetate, and hexyl acetate are preferred , Pentyl propionate, hexyl propionate, butyl propionate, isobutyl isobutyrate, heptyl propionate or butyl butyrate, etc., more preferably isoamyl acetate.

於所述曝光步驟中使用EUV及電子束的情況下，有機溶劑顯影液中所含的有機溶劑亦可使用所述酯系溶劑及所述烴系溶劑的混合溶劑、或者所述酮系溶劑及所述烴系溶劑的混合溶劑來代替碳原子數為7以上且雜原子數為2以下的酯系溶劑。該情況下，對於抑制抗蝕劑膜的膨潤亦有效。In the case of using EUV and electron beam in the exposure step, the organic solvent contained in the organic solvent developer may also be a mixed solvent of the ester solvent and the hydrocarbon solvent, or the ketone solvent and The mixed solvent of the hydrocarbon-based solvent replaces the ester-based solvent having 7 or more carbon atoms and 2 or less heteroatoms. In this case, it is also effective for suppressing swelling of the resist film.

於將酯系溶劑與烴系溶劑組合使用的情況下，較佳為使用乙酸異戊酯作為酯系溶劑。另外，作為烴系溶劑，就調整抗蝕劑膜的溶解性的方面而言，較佳為飽和烴系溶劑（例如辛烷、壬烷、癸烷、十二烷、十一烷、十六烷等）。When an ester-based solvent and a hydrocarbon-based solvent are used in combination, it is preferable to use isoamyl acetate as the ester-based solvent. In addition, as the hydrocarbon solvent, in terms of adjusting the solubility of the resist film, a saturated hydrocarbon solvent (for example, octane, nonane, decane, dodecane, undecane, hexadecane, etc.) is preferred. Wait).

於將酮系溶劑與烴系溶劑組合使用的情況下，較佳為使用2-庚酮作為酮系溶劑。另外，作為烴系溶劑，就調整抗蝕劑膜的溶解性的方面而言，較佳為飽和烴系溶劑（例如辛烷、壬烷、癸烷、十二烷、十一烷、十六烷等）。When a ketone-based solvent and a hydrocarbon-based solvent are used in combination, it is preferable to use 2-heptanone as the ketone-based solvent. In addition, as the hydrocarbon solvent, in terms of adjusting the solubility of the resist film, a saturated hydrocarbon solvent (for example, octane, nonane, decane, dodecane, undecane, hexadecane, etc.) is preferred. Wait).

於使用所述混合溶劑的情況下，烴系溶劑的含量取決於抗蝕劑膜的溶劑溶解性，因此並無特別限定，只要適宜調整來決定必要量即可。In the case of using the mixed solvent, the content of the hydrocarbon solvent depends on the solvent solubility of the resist film, and therefore is not particularly limited, as long as it is appropriately adjusted to determine the necessary amount.

所述有機溶劑可混合多種，亦可與所述以外的溶劑或水混合使用。其中，為了充分發揮本發明的效果，較佳為作為顯影液整體的含水率未滿10質量%，更佳為實質上不含有水分。顯影液中的有機溶劑（混合多種時為合計）的濃度較佳為50質量%以上，更佳為50質量%～100質量%，進而佳為85質量%～100質量%，尤佳為90質量%～100質量%，最佳為95質量%～100質量%。The organic solvent may be mixed with multiple types, or may be mixed with other solvents or water for use. Among them, in order to fully exhibit the effects of the present invention, it is preferable that the moisture content of the entire developer is less than 10% by mass, and it is more preferable that it contains substantially no moisture. The concentration of the organic solvent in the developer (the total when multiple types are mixed) is preferably 50% by mass or more, more preferably 50% to 100% by mass, still more preferably 85% to 100% by mass, and particularly preferably 90% by mass % To 100% by mass, preferably 95% to 100% by mass.

[其他步驟] 所述圖案形成方法較佳為於步驟3之後包括使用淋洗液進行清洗的步驟。作為於使用顯影液進行顯影的步驟後的淋洗步驟中使用的淋洗液，例如可列舉純水。再者，亦可於純水中添加適量的界面活性劑。亦可於淋洗液中添加適量的界面活性劑。[Other steps] The pattern forming method preferably includes a step of cleaning with an eluent after step 3. As the rinsing liquid used in the rinsing step after the step of performing development using a developer, for example, pure water can be cited. Furthermore, an appropriate amount of surfactant may be added to pure water. It is also possible to add an appropriate amount of surfactant to the eluent.

淋洗步驟的方法並無特別限定，例如可列舉：朝以固定速度旋轉的基板上連續噴出淋洗液的方法（旋轉塗佈法）、使基板於充滿淋洗液的槽中浸漬固定時間的方法（浸漬法）、以及對基板表面噴射淋洗液的方法（噴霧法）等。另外，本發明的圖案形成方法亦可於淋洗步驟後包括加熱步驟（Post Bake）。藉由該步驟，利用烘烤去除殘留於圖案間及圖案內部的顯影液及淋洗液。另外，藉由該步驟，亦具有形成抗蝕劑圖案且改善圖案的表面粗糙度的效果。淋洗步驟後的加熱步驟通常在40℃～250℃（較佳為90℃～200℃）下進行10秒～3分鐘（較佳為30秒～120秒）。The method of the rinsing step is not particularly limited. For example, a method of continuously spraying a rinsing liquid on a substrate rotating at a fixed speed (spin coating method), and a method of immersing the substrate in a tank filled with the rinsing liquid for a fixed period of time Method (dipping method), and method of spraying eluent on the surface of the substrate (spray method), etc. In addition, the pattern forming method of the present invention may also include a heating step (Post Bake) after the rinsing step. Through this step, baking is used to remove the developer and rinsing liquid remaining between and inside the patterns. In addition, this step also has the effect of forming a resist pattern and improving the surface roughness of the pattern. The heating step after the rinsing step is usually performed at 40°C to 250°C (preferably 90°C to 200°C) for 10 seconds to 3 minutes (preferably 30 seconds to 120 seconds).

另外，亦可將所形成的圖案作為遮罩，實施基板的蝕刻處理。即，亦可將步驟3中形成的圖案作為遮罩，加工基板（或下層膜及基板）而於基板上形成圖案。基板（或下層膜及基板）的加工方法並無特別限定，較佳為藉由將步驟3中形成的圖案作為遮罩對基板（或下層膜及基板）進行乾式蝕刻而於基板上形成圖案的方法。乾式蝕刻可為一段蝕刻，亦可為包含多段的蝕刻。於蝕刻為包含多段的蝕刻的情況下，各段的蝕刻可為相同的處理，亦可為不同的處理。蝕刻可使用任一種公知的方法，各種條件等根據基板的種類或用途等適宜決定。例如，可依據「國際光學工程學會會議記錄（Proceeding of Society of Photo-optical Instrumentation Engineers，Proc.of SPIE）」Vol. 6924, 692420（2008）、日本專利特開2009-267112號公報等來實施蝕刻。另外，亦可依據「半導體製程教本第四版 2007年刊行發行人：SEMI日本」的「第4章蝕刻」中記載的方法。其中，作為乾式蝕刻，較佳為氧電漿蝕刻。In addition, the formed pattern may be used as a mask to perform the etching treatment of the substrate. That is, the pattern formed in step 3 may be used as a mask, and the substrate (or the underlayer film and the substrate) may be processed to form a pattern on the substrate. The processing method of the substrate (or the underlying film and the substrate) is not particularly limited, and it is preferable to dry-etch the substrate (or the underlying film and the substrate) by using the pattern formed in step 3 as a mask to form a pattern on the substrate. method. Dry etching may be one-stage etching, or may include multiple-stage etching. When the etching includes multiple stages of etching, the etching of each stage may be the same treatment or different treatments. Any known method can be used for etching, and various conditions and the like are appropriately determined according to the type of substrate, use, and the like. For example, the etching can be performed according to "Proceeding of Society of Photo-optical Instrumentation Engineers (Proc. of SPIE)" Vol. 6924, 692420 (2008), Japanese Patent Laid-Open No. 2009-267112, etc. . In addition, the method described in "Chapter 4 Etching" of "Semiconductor Process Textbook Fourth Edition 2007 Issuer: SEMI Japan" can also be used. Among them, as dry etching, oxygen plasma etching is preferred.

本發明的圖案形成方法中使用的抗蝕劑組成物以外的各種材料（例如顯影液、淋洗液、防反射膜形成用組成物、頂塗層形成用組成物等）中，金屬等雜質（例如Na、K、Ca、Fe、Cu、Mg、Al、Li、Cr、Ni、Sn、Ag、As、Au、Ba、Cd、Co、Pb、Ti、V、W及Zn等）越少越佳。作為該些材料中所含的雜質的含量，例如較佳為1質量ppm以下。In various materials other than the resist composition used in the pattern forming method of the present invention (for example, developer, rinse, composition for forming anti-reflection film, composition for forming top coat, etc.), impurities such as metals ( For example, Na, K, Ca, Fe, Cu, Mg, Al, Li, Cr, Ni, Sn, Ag, As, Au, Ba, Cd, Co, Pb, Ti, V, W, Zn, etc.) The less the better . The content of impurities contained in these materials is preferably 1 mass ppm or less, for example.

作為抗蝕劑組成物以外的各種材料中的金屬等雜質的減少方法，例如可列舉使用過濾器的過濾。作為過濾器孔徑，較佳為細孔徑未滿100 nm，更佳為10 nm以下，進而佳為5 nm以下。作為過濾器，較佳為聚四氟乙烯製、聚乙烯製或尼龍製過濾器。過濾器亦可由組合了所述過濾器素材與離子交換介質的複合材料構成。過濾器亦可使用預先利用有機溶劑清洗的過濾器。過濾器過濾步驟中，亦可串聯或並聯連接多種過濾器來使用。於使用多種過濾器的情況下，可組合使用孔徑及/或材質不同的過濾器。另外，亦可對各種材料進行多次過濾，多次過濾的步驟可為循環過濾步驟。As a method of reducing impurities such as metals in various materials other than the resist composition, for example, filtration using a filter can be cited. The pore diameter of the filter is preferably less than 100 nm, more preferably 10 nm or less, and still more preferably 5 nm or less. As the filter, a filter made of polytetrafluoroethylene, polyethylene, or nylon is preferred. The filter may also be composed of a composite material combining the filter material and the ion exchange medium. The filter can also be a filter that has been cleaned with an organic solvent in advance. In the filter filtration step, multiple filters can also be connected in series or parallel for use. When multiple filters are used, filters with different pore sizes and/or materials can be used in combination. In addition, various materials can also be filtered multiple times, and the step of multiple filtering can be a cyclic filtering step.

另外，作為減少抗蝕劑組成物以外的各種材料中的金屬等雜質的方法，可列舉以下方法等：選擇金屬含量少的原料作為構成各種材料的原料的方法、對構成各種材料的原料進行過濾器過濾的方法、以及利用鐵氟龍（Teflon）（註冊商標）對裝置內進行加襯等且在盡可能抑制污染的條件下進行蒸餾的方法。In addition, as a method of reducing impurities such as metals in various materials other than the resist composition, the following methods can be cited: a method of selecting raw materials with a low metal content as the raw materials constituting various materials, and filtering the raw materials constituting various materials The method of filter filtration and the method of lining the device with Teflon (registered trademark) and distilling under the condition of suppressing pollution as much as possible.

另外，作為減少抗蝕劑組成物以外的各種材料中的金屬等雜質的方法，除了所述過濾器過濾之外，亦可利用吸附材進行雜質的去除，亦可將過濾器過濾與吸附材組合使用。作為吸附材，可使用公知的吸附材，例如可使用矽膠及沸石等無機系吸附材、以及活性碳等有機系吸附材。為了減少抗蝕劑組成物以外的各種材料中所含的金屬等雜質，必須防止製造步驟中的金屬雜質的混入。可藉由測定用於清洗製造裝置的清洗液中所含的金屬成分的含量來確認是否自製造裝置中充分地去除了金屬雜質。In addition, as a method to reduce impurities such as metals in various materials other than the resist composition, in addition to the filter filtration, the adsorption material can also be used to remove impurities, and the filter filtration and the adsorption material can also be combined use. As the adsorbent, a well-known adsorbent can be used. For example, inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon can be used. In order to reduce impurities such as metals contained in various materials other than the resist composition, it is necessary to prevent the mixing of metal impurities in the manufacturing process. It is possible to confirm whether metal impurities are sufficiently removed from the manufacturing device by measuring the content of the metal component contained in the cleaning liquid used for cleaning the manufacturing device.

為了防止伴隨著靜電的帶電、接下來產生的靜電放電引起的藥液配管及各種部件（過濾器、O型環、管等）的故障，亦可於淋洗液等有機系處理液中添加導電性的化合物。導電性的化合物並無特別限制，例如可列舉甲醇。添加量並無特別限制，就維持較佳的顯影特性或淋洗特性的觀點而言，較佳為10質量%以下，更佳為5質量%以下。作為藥液配管，可使用經SUS（不鏽鋼）、或實施了防靜電處理的聚乙烯、聚丙烯或氟樹脂（聚四氟乙烯、全氟烷氧基樹脂等）被膜的各種配管。關於過濾器及O型環，亦同樣地可使用實施了防靜電處理的聚乙烯、聚丙烯或氟樹脂（聚四氟乙烯、全氟烷氧基樹脂等）。In order to prevent malfunctions of the chemical liquid piping and various components (filters, O-rings, tubes, etc.) caused by static electricity and subsequent electrostatic discharge, it is also possible to add conductivity to organic treatment liquids such as eluents Sexual compounds. The conductive compound is not particularly limited, and for example, methanol can be mentioned. The addition amount is not particularly limited, but from the viewpoint of maintaining better development characteristics or rinse characteristics, it is preferably 10% by mass or less, and more preferably 5% by mass or less. As the chemical solution piping, various piping coated with SUS (stainless steel) or antistatic treatment of polyethylene, polypropylene, or fluororesin (polytetrafluoroethylene, perfluoroalkoxy resin, etc.) can be used. Regarding the filter and O-ring, similarly, polyethylene, polypropylene, or fluororesin (polytetrafluoroethylene, perfluoroalkoxy resin, etc.) that has been subjected to antistatic treatment can be used.

對於藉由本發明的方法而形成的圖案，可應用改善圖案的表面粗糙度的方法。作為改善圖案的表面粗糙度的方法，例如可列舉國際公開第2014/002808號中揭示的利用含有氫的氣體的電漿來處理圖案的方法。除此以外，亦可列舉日本專利特開2004-235468號公報、美國專利申請公開第2010/0020297號說明書、日本專利特開2008-83384號公報、以及國際光學工程學會會議記錄（Proc.of SPIE）Vol.8328 83280N-1「用於降低線寬粗糙度與增強蝕刻選擇性的極紫外線抗蝕劑硬化技術（EUV Resist Curing Technique for LWR Reduction and Etch Selectivity Enhancement）」中記載的公知的方法。For the pattern formed by the method of the present invention, a method of improving the surface roughness of the pattern can be applied. As a method of improving the surface roughness of a pattern, for example, a method of processing a pattern using plasma of a hydrogen-containing gas disclosed in International Publication No. 2014/002808 can be cited. In addition, Japanese Patent Laid-Open No. 2004-235468, U.S. Patent Application Publication No. 2010/0020297, Japanese Patent Laid-Open No. 2008-83384, and Proc. of SPIE ) Vol. 8328 83280N-1 "EUV Resist Curing Technique for LWR Reduction and Etch Selectivity Enhancement for reducing line width roughness and enhancing etching selectivity" is a well-known method described in.

於所形成的圖案為線狀的情況下，利用圖案高度除以線寬所得的值求出的縱橫比較佳為2.5以下，更佳為2.1以下，進而佳為1.7以下。於所形成的圖案為溝槽（槽）圖案狀或接觸孔圖案狀的情況下，利用圖案高度除以溝槽寬度或孔徑所得的值求出的縱橫比較佳為4.0以下，更佳為3.5以下，進而佳為3.0以下。When the formed pattern is linear, the aspect ratio calculated by dividing the pattern height by the line width is preferably 2.5 or less, more preferably 2.1 or less, and still more preferably 1.7 or less. When the pattern to be formed is a groove (groove) pattern or a contact hole pattern, the aspect ratio calculated by dividing the pattern height by the groove width or hole diameter is preferably 4.0 or less, more preferably 3.5 or less , And more preferably 3.0 or less.

本發明的圖案形成方法亦可用於定向自組裝（Directed Self-Assembly，DSA）中的引導圖案形成（例如，參照「ASC奈米（ACS Nano）」Vol.4 No.8 4815-4823頁）。The pattern forming method of the present invention can also be used for guiding pattern formation in Directed Self-Assembly (DSA) (for example, refer to "ASC Nano (ACS Nano)" Vol. 4 No. 8 4815-4823).

另外，藉由所述方法而形成的圖案例如可用作日本專利特開平3-270227號公報及日本專利特開2013-164509號公報中揭示的間隔物製程的芯材（core）。In addition, the pattern formed by the method described above can be used as a core of the spacer process disclosed in Japanese Patent Laid-Open No. 3-270227 and Japanese Patent Laid-Open No. 2013-164509, for example.

[電子元件的製造方法] 另外，本發明亦有關於一種包含所述圖案形成方法的電子元件的製造方法。作為所述電子元件，可列舉搭載於電氣電子機器（家電、辦公自動化（Office Automation，OA）、媒體相關機器、光學用機器及通信機器等）中者。[Method of manufacturing electronic components] In addition, the present invention also relates to a manufacturing method of an electronic component including the pattern forming method. Examples of the electronic components include those mounted in electrical and electronic equipment (home appliances, office automation (OA), media-related equipment, optical equipment, communication equipment, etc.).

[組成物收容體] 本發明的組成物收容體包括：收容容器；以及收容在所述收容容器中的感光化射線性或感放射線性樹脂組成物（抗蝕劑組成物）。[Composition container] The composition container of the present invention includes: a container; and an actinic radiation-sensitive or radiation-sensitive resin composition (resist composition) contained in the container.

[收容容器] 作為收容容器，並無特別限制，較佳為收容容器內的與抗蝕劑組成物接觸的區域（例如，所述收容容器內的收容抗蝕劑組成物的收容部的內壁及/或抗蝕劑組成物的流路）由以非金屬為主成分的材料所形成。再者，此處，所謂主成分，是指構成接觸規定成分的區域的80質量%以上。[Container] The storage container is not particularly limited, but it is preferably the area in contact with the resist composition in the storage container (for example, the inner wall and/or the resist The flow path of the etchant composition is formed of a material whose main component is non-metal. In addition, here, the term "main component" means 80% by mass or more of the area constituting the contact with the predetermined component.

作為收容容器內的與抗蝕劑組成物接觸的區域的材料，就抑制以附著在所述區域的水分為核的光酸產生劑B（相當於分子內含有多價鹽結構的光酸產生劑）的凝聚的方面、以及防止伴隨著與收容容器的過度的親和性的來自收容容器的溶出物污染的方面而言，較佳為樹脂，更佳為聚烯烴樹脂或氟系樹脂。As the material of the area in contact with the resist composition in the container, the photoacid generator B (corresponding to the photoacid generator with a multivalent salt structure in the molecule) that uses the moisture attached to the area as the nucleus is suppressed In terms of aggregation of) and in terms of preventing contamination by eluates from the storage container due to excessive affinity with the storage container, a resin is preferable, and a polyolefin resin or a fluororesin is more preferable.

再者，作為與抗蝕劑組成物接觸的區域為氟系樹脂的收容容器的具體例，例如可列舉英特格（Entegris）公司製造的純氟PFA（FluoroPure PFA）複合鼓、日本專利特表平3-502677號公報的第4頁等、國際公開第2004/016526號手冊的第3頁等、以及國際公開第99/46309號手冊的第9頁及第16頁等中記載的容器。Furthermore, as a specific example of a container in which the area in contact with the resist composition is a fluorine-based resin, for example, a pure fluorine PFA (FluoroPure PFA) composite drum manufactured by Entegris, and Japanese Patent Special List The containers described in pages 4, etc. of Hei 3-502677, International Publication No. 2004/016526, Page 3, etc., and International Publication No. 99/46309, Pages 9 and 16, etc.

作為收容容器內的與抗蝕劑組成物接觸的區域的材料，就進一步抑制以附著在所述區域的水分為核的光酸產生劑B的凝聚的方面而言，其中更佳為選自由聚烯烴樹脂及含氟原子的聚烯烴樹脂所組成的群組中的一種以上的樹脂。作為聚烯烴樹脂，較佳為高密度聚乙烯（High Density Polyethylene，HDPE）。作為含氟原子的聚烯烴樹脂，較佳為全氟烷烴（perfluoro alkane，PFA）或聚四氟乙烯（polytetrafluoroethylene，PTFE）。As the material of the area in contact with the resist composition in the storage container, in terms of further suppressing the aggregation of the photoacid generator B with moisture adhering to the area as the nucleus, it is more preferably selected from the group consisting of One or more resins in the group consisting of olefin resin and fluorine atom-containing polyolefin resin. As the polyolefin resin, high density polyethylene (HDPE) is preferred. As the fluorine atom-containing polyolefin resin, perfluoroalkane (PFA) or polytetrafluoroethylene (PTFE) is preferred.

作為收容容器，亦可較佳地使用美國專利申請公開第2015/0227049號說明書、日本專利申請公開第2015-123351號說明書（日本專利特開2015-123351）及日本專利申請公開第2017-13804號說明書（日本專利特開2017-13804）等中記載的容器。As the storage container, U.S. Patent Application Publication No. 2015/0227049, Japanese Patent Application Publication No. 2015-123351 (Japanese Patent Application Laid-Open No. 2015-123351), and Japanese Patent Application Publication No. 2017-13804 can also be preferably used. The container described in the specification (Japanese Patent Laid-Open No. 2017-13804) and the like.

另外，作為收容容器，面向半導體用途，容器內的清潔度高、雜質的溶出少的容器亦可較佳地使用。具體而言，可列舉愛賽璐化學（Aicello Chemical）（股）製造的「清潔瓶（Clean Bottle）」系列以及兒玉（Kodama）樹脂工業（股）製造的「潔淨瓶（Pure Bottle）」等。In addition, as a storage container, for semiconductor applications, a container with high cleanliness in the container and less elution of impurities can also be preferably used. Specifically, the "Clean Bottle" series manufactured by Aicello Chemical (Stock) and the "Pure Bottle" manufactured by Kodama Resin Industry (Stock) can be cited.

收容容器較佳為於填充前清洗容器內部。作為用於所述清洗的液體，並無特別限制，較佳為金屬含有率未滿0.001質量ppt（兆分之一（parts per trillion））。The container is preferably cleaned before filling. The liquid used for the cleaning is not particularly limited, but the metal content is preferably less than 0.001 mass ppt (parts per trillion).

[抗蝕劑組成物] 抗蝕劑組成物如上所述。 [實施例][Resist composition] The resist composition is as described above. [Example]

以下基於實施例對本發明進行更詳細的說明。以下的實施例中所示的材料、使用量、比例、處理內容及處理順序等只要不脫離本發明的主旨，則可適宜變更。因此，本發明的範圍不由以下所示的實施例限定性地解釋。Hereinafter, the present invention will be described in more detail based on examples. The materials, usage amount, ratio, processing content, processing order, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present invention. Therefore, the scope of the present invention is not limitedly interpreted by the examples shown below.

[感光化射線性或感放射線性樹脂組成物的各種成分] [酸分解性樹脂] 以下示出表4及表9所示的樹脂A（樹脂A-1～A-20）。樹脂A-1～A-20使用按照後述的樹脂A-1的合成方法（合成例1）合成的樹脂。表1中示出後述揭示的各重複單元的組成比（莫耳比；從左依次對應）、重量平均分子量（Mw）及分散度（Mw/Mn）再者，樹脂A-1～A-20的重量平均分子量（Mw）及分散度（Mw/Mn）藉由GPC（載體：四氫呋喃（tetrahydrofuran，THF））進行測定（為聚苯乙烯換算量）。另外，樹脂的組成比（莫耳%比）藉由¹³ C-核磁共振（nuclear magnetic resonance，NMR）進行測定。[Various components of the sensitizing radiation-sensitive or radiation-sensitive resin composition] [Acid decomposable resin] Resin A (resin A-1 to A-20) shown in Table 4 and Table 9 are shown below. As the resins A-1 to A-20, resins synthesized in accordance with the synthesis method of resin A-1 (synthesis example 1) described later were used. Table 1 shows the composition ratio (molar ratio; corresponding from the left), weight average molecular weight (Mw), and dispersion degree (Mw/Mn) of each repeating unit disclosed below. Furthermore, resins A-1 to A-20 The weight average molecular weight (Mw) and degree of dispersion (Mw/Mn) of the product are measured by GPC (carrier: tetrahydrofuran (THF)) (in terms of polystyrene conversion). In addition, the resin composition ratio (mole% ratio ^{) is measured by 13} C-nuclear magnetic resonance (NMR).

[表1] 表1 重複的莫耳比率 Mw Mw/Mn 樹脂A-1 50 50 - - 6500 1.52 樹脂A-2 45 55 - - 8300 1.65 樹脂A-3 40 30 30 - 7800 1.55 樹脂A-4 40 50 10 - 12000 1.68 樹脂A-5 50 50 - - 5500 1.49 樹脂A-6 25 30 30 15 8600 1.63 樹脂A-7 40 10 30 20 9600 1.72 樹脂A-8 40 5 55 - 10200 1.64 樹脂A-9 30 20 40 10 7500 1.54 樹脂A-10 40 10 40 10 7000 1.61 樹脂A-11 40 10 10 40 6500 1.63 樹脂A-12 40 30 30 - 5900 1.59 樹脂A-13 10 30 60 - 5200 1.53 樹脂A-14 25 15 60 - 6200 1.48 樹脂A-15 50 50 - - 7000 1.73 樹脂A-16 30 10 60 - 11500 1.56 樹脂A-17 35 10 55 - 8400 1.58 樹脂A-18 40 10 50 - 9200 1.66 樹脂A-19 25 15 60 - 5700 1.75 樹脂A-20 30 20 50 - 7600 1.56 [Table 1] Table 1 Repeated molar ratio Mw Mw/Mn Resin A-1 50 50 - - 6500 1.52 Resin A-2 45 55 - - 8300 1.65 Resin A-3 40 30 30 - 7800 1.55 Resin A-4 40 50 10 - 12000 1.68 Resin A-5 50 50 - - 5500 1.49 Resin A-6 25 30 30 15 8600 1.63 Resin A-7 40 10 30 20 9600 1.72 Resin A-8 40 5 55 - 10200 1.64 Resin A-9 30 20 40 10 7500 1.54 Resin A-10 40 10 40 10 7000 1.61 Resin A-11 40 10 10 40 6500 1.63 Resin A-12 40 30 30 - 5900 1.59 Resin A-13 10 30 60 - 5200 1.53 Resin A-14 25 15 60 - 6200 1.48 Resin A-15 50 50 - - 7000 1.73 Resin A-16 30 10 60 - 11500 1.56 Resin A-17 35 10 55 - 8400 1.58 Resin A-18 40 10 50 - 9200 1.66 Resin A-19 25 15 60 - 5700 1.75 Resin A-20 30 20 50 - 7600 1.56

以下示出表1所示的樹脂A-1～A-20的結構式。The structural formulae of resins A-1 to A-20 shown in Table 1 are shown below.

[化74]

[化74]

[化75]

[化75]

（合成例1：樹脂A-1的合成）將環己酮（113 g）於氮氣流下加熱為80℃。一邊攪拌所述溶液一邊花6小時滴加下述式M-1所表示的單體（25.5 g）、下述式M-2所表示的單體（31.6 g）、環己酮（210 g）及2,2'-偶氮雙異丁酸二甲酯[V-601，和光純藥工業（股）製造]（6.21 g）的混合溶液，獲得反應液。於滴加結束後，將反應液於80℃下進而攪拌2小時。於將所得的反應液放冷後，在利用大量的甲醇/水（質量比9：1）再沈澱後進行過濾，將所得的固體真空乾燥，藉此獲得52 g的樹脂A-1。(Synthesis example 1: Synthesis of resin A-1) Cyclohexanone (113 g) was heated to 80°C under a stream of nitrogen. While stirring the solution, the monomer represented by the following formula M-1 (25.5 g), the monomer represented by the following formula M-2 (31.6 g), and cyclohexanone (210 g) were added dropwise over 6 hours. And a mixed solution of dimethyl 2,2'-azobisisobutyrate [V-601, manufactured by Wako Pure Chemical Industries, Ltd.] (6.21 g) to obtain a reaction liquid. After completion of the dropwise addition, the reaction solution was further stirred at 80°C for 2 hours. After the obtained reaction liquid was allowed to cool, it was reprecipitated with a large amount of methanol/water (mass ratio 9:1) and then filtered, and the obtained solid was vacuum dried, thereby obtaining 52 g of resin A-1.

[化76]

[化76]

所得的樹脂A-1的由GPC（載體：四氫呋喃（THF））求出的重量平均分子量（Mw：聚苯乙烯換算）為6500，分散度（Mw/Mn）為1.52。藉由¹³ C-NMR（nuclear magnetic resonance）測定的組成比以莫耳比計為50/50。The weight average molecular weight (Mw: polystyrene conversion) of the obtained resin A-1 determined by GPC (carrier: tetrahydrofuran (THF)) was 6,500, and the degree of dispersion (Mw/Mn) was 1.52. The composition ratio measured by ¹³ C-NMR (nuclear magnetic resonance) is 50/50 in molar ratio.

[光酸產生劑] ＜光酸產生劑B＞以下示出表4及表9所示的光酸產生劑B（化合物B-1～B-24）的結構。另外，以下一併示出表4及表9所示的比較用光酸產生劑B-25的結構。比較用光酸產生劑B-25不相當於選自由所述化合物（I）～化合物（III）所組成的群組中的化合物（光酸產生劑B）。[Photo Acid Generator] ＜Photoacid generator B＞ The structures of the photoacid generator B (compounds B-1 to B-24) shown in Table 4 and Table 9 are shown below. In addition, the structure of the photo acid generator B-25 for comparison shown in Table 4 and Table 9 is shown together below. The comparative photo acid generator B-25 does not correspond to a compound (photo acid generator B) selected from the group consisting of the above-mentioned compounds (I) to (III).

[化77]

[化77]

[化78]

[化78]

[化79]

[化79]

＜光酸產生劑C＞以下示出表4及表9所示的光酸產生劑C（化合物C-1～C-21）的結構。＜Photoacid generator C＞ The structure of the photoacid generator C (compounds C-1 to C-21) shown in Table 4 and Table 9 is shown below.

[化80]

[化80]

[化81]

[化81]

[酸擴散控制劑] 以下示出表4及表9所示的酸擴散控制劑D（化合物D-1～D-5）的結構。[Acid Diffusion Control Agent] The structure of the acid diffusion control agent D (compound D-1 to D-5) shown in Table 4 and Table 9 is shown below.

[化82]

[化82]

[疏水性樹脂及頂塗層用樹脂] 表4及表9所示的疏水性樹脂（E-1～E-11）以及表5所示的頂塗層用樹脂（PT-1～PT-3）使用合成的樹脂。表2中示出表4及表9所示的疏水性樹脂以及表5所示的頂塗層用樹脂中的重複單元的莫耳比率、重量平均分子量（Mw）及分散度（Mw/Mn）。再者，疏水性樹脂E-1～E-11及頂塗層用樹脂PT-1～PT-3的重量平均分子量（Mw）及分散度（Mw/Mn）藉由GPC（載體：四氫呋喃（THF））進行測定（為聚苯乙烯換算量）。另外，樹脂的組成比（莫耳%比）藉由¹³ C-NMR（nuclear magnetic resonance）進行測定。[Hydrophobic resin and resin for top coat] The hydrophobic resins (E-1 to E-11) shown in Table 4 and Table 9 and the resins for top coat (PT-1 to PT-3) shown in Table 5 ) Use synthetic resin. Table 2 shows the molar ratio, weight average molecular weight (Mw) and degree of dispersion (Mw/Mn) of the repeating units in the hydrophobic resins shown in Tables 4 and 9 and the topcoat resin shown in Table 5 . Furthermore, the weight average molecular weight (Mw) and dispersion degree (Mw/Mn) of the hydrophobic resins E-1 to E-11 and the top coat resins PT-1 to PT-3 were determined by GPC (carrier: tetrahydrofuran (THF) )) for measurement (in terms of polystyrene conversion amount). In addition, the composition ratio (mole% ratio) of the resin is ^{measured by 13} C-NMR (nuclear magnetic resonance).

[表2] 表2 重複單元1的莫耳比率重複單元2的莫耳比率重複單元3的莫耳比率重複單元4的莫耳比率 Mw Mw/Mn 樹脂E-1 ME-3 60 ME-4 40 10000 1.4 樹脂E-2 ME-15 50 ME-1 50 12000 1.5 樹脂E-3 ME-2 40 ME-13 50 ME-9 5 ME-20 5 6000 1.3 樹脂E-4 ME-19 50 ME-14 50 9000 1.5 樹脂E-5 ME-10 50 ME-2 50 15000 1.5 樹脂E-6 ME-17 50 ME-15 50 10000 1.5 樹脂E-7 ME-7 100 23000 1.7 樹脂E-8 ME-5 100 13000 1.5 樹脂E-9 ME-6 50 ME-16 50 10000 1.7 樹脂E-10 ME-13 10 ME-18 85 ME-9 5 11000 1.4 樹脂E-11 ME-8 80 ME-11 20 13000 1.4 樹脂PT-1 ME-2 40 ME-11 30 ME-9 30 8000 1.6 樹脂PT-2 ME-2 50 ME-12 40 ME-3 10 5000 1.5 樹脂PT-3 ME-3 30 ME-4 70 8500 1.7 [Table 2] Table 2 Molar ratio of repeating unit 1 Molar ratio of repeating unit 2 Molar ratio of repeating unit 3 Molar ratio of repeating unit 4 Mw Mw/Mn Resin E-1 ME-3 60 ME-4 40 10000 1.4 Resin E-2 ME-15 50 ME-1 50 12000 1.5 Resin E-3 ME-2 40 ME-13 50 ME-9 5 ME-20 5 6000 1.3 Resin E-4 ME-19 50 ME-14 50 9000 1.5 Resin E-5 ME-10 50 ME-2 50 15000 1.5 Resin E-6 ME-17 50 ME-15 50 10000 1.5 Resin E-7 ME-7 100 23000 1.7 Resin E-8 ME-5 100 13000 1.5 Resin E-9 ME-6 50 ME-16 50 10000 1.7 Resin E-10 ME-13 10 ME-18 85 ME-9 5 11000 1.4 Resin E-11 ME-8 80 ME-11 20 13000 1.4 Resin PT-1 ME-2 40 ME-11 30 ME-9 30 8000 1.6 Resin PT-2 ME-2 50 ME-12 40 ME-3 10 5000 1.5 Resin PT-3 ME-3 30 ME-4 70 8500 1.7

以下示出表4及表9所示的疏水性樹脂E-1～E-11以及表5所示的頂塗層用樹脂PT-1～PT-3的合成中使用的單體結構。The monomer structures used in the synthesis of the hydrophobic resins E-1 to E-11 shown in Tables 4 and 9 and the topcoat resins PT-1 to PT-3 shown in Table 5 are shown below.

[化83]

[化83]

[界面活性劑] 以下示出表4及表9所示的界面活性劑。 H-1：美佳法（Megafac）F176（DIC（股）製造、氟系界面活性劑） H-2：美佳法（Megafac）R08（DIC（股）製造、氟系及矽系界面活性劑） H-3：PF656（歐諾法（OMNOVA）公司製造、氟系界面活性劑）[Surfactant] The surfactants shown in Table 4 and Table 9 are shown below. H-1: Megafac F176 (manufactured by DIC (Stock), fluorine-based surfactant) H-2: Megafac R08 (manufactured by DIC (stock), fluorine-based and silicon-based surfactants) H-3: PF656 (manufactured by OMNOVA, fluorine-based surfactant)

[溶劑] 以下示出表4及表9所示的溶劑。 F-1：丙二醇單甲醚乙酸酯（PGMEA） F-2：丙二醇單甲醚（PGME） F-3：丙二醇單***（PGEE） F-4：環己酮 F-5：環戊酮 F-6：2-庚酮 F-7：乳酸乙酯 F-8：γ-丁內酯 F-9：碳酸伸丙酯[Solvent] The solvents shown in Table 4 and Table 9 are shown below. F-1: Propylene glycol monomethyl ether acetate (PGMEA) F-2: Propylene glycol monomethyl ether (PGME) F-3: Propylene glycol monoethyl ether (PGEE) F-4: Cyclohexanone F-5: Cyclopentanone F-6: 2-Heptanone F-7: Ethyl lactate F-8: γ-butyrolactone F-9: propylene carbonate

[感光化射線性或感放射線性樹脂組成物的製備及圖案形成：ArF液浸曝光] [感光化射線性或感放射線性樹脂組成物的製備（1）] ＜感光化射線性或感放射線性樹脂組成物Re-1～Re-29、Re-31、Re-33＞首先，將酸分解性樹脂（樹脂A）在15 mmHg及60℃下真空乾燥規定時間（再者，在酸分解性樹脂（樹脂A）的所述乾燥時間為2小時～12小時的範圍內，按照各組成物製備，以使感光化射線性或感放射線性樹脂組成物的各含水率成為表3所示的含水率）。然後，以固體成分濃度成為4質量%的方式混合表4所示的各成分。繼而，將所得的混合液按照最初為孔徑50 nm的聚乙烯製過濾器、其次為孔徑10 nm的尼龍製過濾器、最後為孔徑5 nm的聚乙烯製過濾器的順序進行過濾，藉此製備感光化射線性或感放射線性樹脂組成物（以下，亦稱為樹脂組成物）Re-1～Re-29、Re-31及Re-33。再者，樹脂組成物中，所謂固體成分，是指溶劑以外的所有成分。繼而，將所得的樹脂組成物封入至規定的容器（再者，容器的種類分別示於表6及表7中）中。將封入了樹脂組成物的組成物收容體在溫度23℃、濕度60%的環境下放置4周。將封入至該規定的保管容器中且經過規定期間的樹脂組成物用於後述的圖案形成。[Preparation and pattern formation of sensitizing radiation-sensitive or radiation-sensitive resin composition: ArF liquid immersion exposure] [Preparation of sensitized radiation-sensitive or radiation-sensitive resin composition (1)] <Acceptable radiation or radiation-sensitive resin composition Re-1～Re-29, Re-31, Re-33> First, the acid-decomposable resin (resin A) is vacuum dried at 15 mmHg and 60°C for a predetermined time (in addition, the acid-decomposable resin (resin A) has a drying time in the range of 2 to 12 hours, It was prepared according to each composition so that each moisture content of the sensitizing radiation-sensitive or radiation-sensitive resin composition became the moisture content shown in Table 3). Then, each component shown in Table 4 was mixed so that the solid content concentration might become 4 mass %. Then, the resulting mixed liquid was filtered in the order of a polyethylene filter with a pore size of 50 nm, a nylon filter with a pore size of 10 nm, and a polyethylene filter with a pore size of 5 nm, thereby preparing Sensitizing radiation-sensitive or radiation-sensitive resin composition (hereinafter also referred to as resin composition) Re-1 to Re-29, Re-31, and Re-33. In addition, in the resin composition, the so-called solid content refers to all components other than the solvent. Then, the obtained resin composition was enclosed in a predetermined container (in addition, the kind of container is shown in Table 6 and Table 7, respectively). The composition container encapsulated with the resin composition was left for 4 weeks in an environment with a temperature of 23° C. and a humidity of 60%. The resin composition enclosed in the predetermined storage container and passed a predetermined period of time is used for pattern formation described later.

＜感光化射線性或感放射線性樹脂組成物Re-30、Re-32＞除了於混合各成分前不使酸分解性樹脂（樹脂A）真空乾燥以外，藉由與樹脂組成物Re-1～Re-29、Re-31、Re-33同樣的方法，製備樹脂組成物Re-30、Re-32。繼而，將所得的樹脂組成物封入至規定的容器（再者，容器的種類分別示於表6及表7中）中。將封入了樹脂組成物的組成物收容體於溫度23℃、濕度60%的環境下放置4周。將封入至該規定的保管容器中且經過規定期間的樹脂組成物用於後述的圖案形成。<Acceptable radiation or radiation-sensitive resin composition Re-30, Re-32> Except that the acid-decomposable resin (resin A) was not vacuum-dried before mixing the components, the resin composition Re was prepared by the same method as the resin composition Re-1 to Re-29, Re-31, and Re-33 -30, Re-32. Then, the obtained resin composition was enclosed in a predetermined container (in addition, the kind of container is shown in Table 6 and Table 7, respectively). The composition container in which the resin composition was sealed was left in an environment with a temperature of 23° C. and a humidity of 60% for 4 weeks. The resin composition enclosed in the predetermined storage container and passed a predetermined period of time is used for pattern formation described later.

＜含水率的測定＞對於剛調液後的各樹脂組成物，使用卡爾費歇爾水分計（京都電子工業股份有限公司製造的MKC-510N）按照下述順序測定含水率。具體而言，於23℃的大氣中，將10 mL的抗蝕劑組成物投入至滴定燒瓶中，利用京都電子工業股份有限公司製造的MKC-510N算出含水率。結果示於表3中。＜Measurement of moisture content＞ For each resin composition immediately after the liquid adjustment, the moisture content was measured in the following procedure using a Karl Fischer moisture meter (MKC-510N manufactured by Kyoto Electronics Co., Ltd.). Specifically, 10 mL of the resist composition was put into a titration flask in the atmosphere at 23° C., and the moisture content was calculated using MKC-510N manufactured by Kyoto Electronics Co., Ltd. The results are shown in Table 3.

[表3] 表3 含水率（質量%） Re-1 0.19 Re-2 0.56 Re-3 0.34 Re-4 0.41 Re-5 0.21 Re-6 0.97 Re-7 0.55 Re-8 0.07 Re-9 0.31 Re-10 0.40 Re-11 0.71 Re-12 0.68 Re-13 0.06 Re-14 0.22 Re-15 0.65 Re-16 0.24 Re-17 0.39 Re-18 0.34 Re-19 0.26 Re-20 0.08 Re-21 0.12 Re-22 0.66 Re-23 0.82 Re-24 0.24 Re-25 0.02 Re-26 0.11 Re-27 0.32 Re-28 0.67 Re-29 0.98 Re-30 1.10 Re-31 0.46 Re-32 1.05 Re-33 0.02 [table 3] table 3 Water content (mass%) Re-1 0.19 Re-2 0.56 Re-3 0.34 Re-4 0.41 Re-5 0.21 Re-6 0.97 Re-7 0.55 Re-8 0.07 Re-9 0.31 Re-10 0.40 Re-11 0.71 Re-12 0.68 Re-13 0.06 Re-14 0.22 Re-15 0.65 Re-16 0.24 Re-17 0.39 Re-18 0.34 Re-19 0.26 Re-20 0.08 Re-21 0.12 Re-22 0.66 Re-23 0.82 Re-24 0.24 Re-25 0.02 Re-26 0.11 Re-27 0.32 Re-28 0.67 Re-29 0.98 Re-30 1.10 Re-31 0.46 Re-32 1.05 Re-33 0.02

以下示出表4。再者，表4中，各成分的含量（質量%）是指相對於總固體成分的含量。Table 4 is shown below. In addition, in Table 4, the content (mass %) of each component refers to the content with respect to the total solid content.

[表4] 表4 樹脂A 光酸產生劑B 光酸產生劑C 酸擴散控制劑D 添加樹脂界面活性劑溶劑種類含量（質量%）種類含量（質量%）種類含量（質量%）種類含量（質量%）種類含量（質量%）種類含量（質量%）種類混合比（質量比） Re-1 A-1 89.6 B-1 9.1 C-1 1.0 E-3 0.3 F-1/F-2 70/30 Re-2 A-2 83.3 B-2 9.2 C-2 5.5 E-1/E-2 1.0/1.0 F-1/F-8 85/15 Re-3 A-3 85.1 B-3 11.2 C-3 1.2 E-4 2.5 F-1/F-2/F-8 70/25/5 Re-4 A-4 86.0 B-4 11.0 C-4 0.3 D-5 1.0 E-8 1.6 F-4 100 Re-5 A-5 84.4 B-5 10.6 C-5 4.8 H-1/H-2 0.1/0.1 F-1/F-7 80/20 Re-6 A-6 91.2 B-6 8.1 C-6 0.6 H-3 0.1 F-1/F-3 70/30 Re-7 A-7 90.6 B-7 7.5 C-7 1.9 F-1/F-5 50/50 Re-8 A-8 85.5 B-8 10.2 C-8 3.3 E-5 1.0 F-1/F-9 90/10 Re-9 A-9 86.4 B-9 11.7 C-9 0.3 D-1 0.1 E-9 1.5 F-1/F-6 40/60 Re-10 A-10 84.0 B-10 7.4 C-10 5.4 E-10 3.2 F-1/F-8 90/10 Re-11 A-11 91.9 B-11 4.6 C-11 2.6 E-11 0.8 H-1 0.1 F-1/F-2 80/20 Re-12 A-12 81.5 B-12 13.5 C-12 0.3 D-3 0.5 E-6/E-8 2.1/2.1 F-1 100 Re-13 A-1 81.6 B-13 12.9 C-13 4.1 E-7 1.4 F-7 100 Re-14 A-2 89.3 B-14 5.5 C-14 2.7 E-10 2.5 F-1/F-8 85/15 Re-15 A-1/A-5 45.9/45.9 B-15 4.4 C-15 0.6 E-1 3.2 F-1/F-2 70/30 Re-16 A-11 89.4 B-16 4.8 C-16 4.6 E-3 1.2 F-1/F-8 85/15 Re-17 A-4 88.2 B-17 10.7 C-17 0.6 E-5 0.5 F-1/F-2 70/30 Re-18 A-1 88.6 B-18 10.2 C-18 0.2 E-2 1.0 F-1/F-8 85/15 Re-19 A-5 87.7 B-19 9.1 C-19 1.8 E-3 1.5 F-1/F-2 70/30 Re-20 A-7 84.8 B-20 14.0 C-20 0.4 E-5 0.8 F-1/F-2/F-8 50/40/10 Re-21 A-8 84.7 B-21 12.3 C-21 1.8 E-9 1.2 F-1/F-8 85/15 Re-22 A-9 86.4 B-1 12.1 E-2 1.5 F-1/F-8 85/15 Re-23 A-1 83.7 B-2/B-12 7.3/6.9 C-3 1.1 E-5 1.0 F-1/F-2/F-8 70/25/5 Re-24 A-3 83.3 B-3 12.8 C-12/C-20 2.0/1.0 E-3 0.9 F-1/F-8 85/15 Re-25 A-1 88.9 B-1 9.1 C-1 1.0 E-1 1.0 F-1/F-2 70/30 Re-26 A-1 87.7 B-22 10.2 C-1 1.1 E-1 1.0 F-1/F-2/F-8 50/40/10 Re-27 A-1 77.5 B-23 20.1 C-1 1.4 E-1 1.0 F-1/F-2/F-8 50/40/10 Re-28 A-1 90.5 B-24 7.7 C-1 0.8 E-1 1.0 F-1/F-2/F-8 50/40/10 Re-29 A-1 93.9 B-2 3.8 C-1 1.3 E-1 1.0 F-1/F-2/F-8 50/40/10 Re-30 A-9 85.1 B-2 11.7 C-3 2.0 E-1 1.2 F-1/F-8 85/15 Re-31 A-4 82.1 B-25 15.6 C-18 1.5 E-1 0.8 F-1/F-2/F-8 50/35/15 Re-32 A-5 85.7 B-25 12.0 C-2 1.5 E-1 0.8 F-1/F-2/F-8 50/35/15 Re-33 A-3 87.4 B-3 10.6 C-3 1.2 E-1 0.8 F-1/F-2/F-8 70/25/5 [Table 4] Table 4 Resin A Photo acid generator B Photo acid generator C Acid diffusion control agent D Add resin Surfactant Solvent species Content (mass%) species Content (mass%) species Content (mass%) species Content (mass%) species Content (mass%) species Content (mass%) species Mixing ratio (mass ratio) Re-1 A-1 89.6 B-1 9.1 C-1 1.0 E-3 0.3 F-1/F-2 70/30 Re-2 A-2 83.3 B-2 9.2 C-2 5.5 E-1/E-2 1.0/1.0 F-1/F-8 85/15 Re-3 A-3 85.1 B-3 11.2 C-3 1.2 E-4 2.5 F-1/F-2/F-8 70/25/5 Re-4 A-4 86.0 B-4 11.0 C-4 0.3 D-5 1.0 E-8 1.6 F-4 100 Re-5 A-5 84.4 B-5 10.6 C-5 4.8 H-1/H-2 0.1/0.1 F-1/F-7 80/20 Re-6 A-6 91.2 B-6 8.1 C-6 0.6 H-3 0.1 F-1/F-3 70/30 Re-7 A-7 90.6 B-7 7.5 C-7 1.9 F-1/F-5 50/50 Re-8 A-8 85.5 B-8 10.2 C-8 3.3 E-5 1.0 F-1/F-9 90/10 Re-9 A-9 86.4 B-9 11.7 C-9 0.3 D-1 0.1 E-9 1.5 F-1/F-6 40/60 Re-10 A-10 84.0 B-10 7.4 C-10 5.4 E-10 3.2 F-1/F-8 90/10 Re-11 A-11 91.9 B-11 4.6 C-11 2.6 E-11 0.8 H-1 0.1 F-1/F-2 80/20 Re-12 A-12 81.5 B-12 13.5 C-12 0.3 D-3 0.5 E-6/E-8 2.1/2.1 F-1 100 Re-13 A-1 81.6 B-13 12.9 C-13 4.1 E-7 1.4 F-7 100 Re-14 A-2 89.3 B-14 5.5 C-14 2.7 E-10 2.5 F-1/F-8 85/15 Re-15 A-1/A-5 45.9/45.9 B-15 4.4 C-15 0.6 E-1 3.2 F-1/F-2 70/30 Re-16 A-11 89.4 B-16 4.8 C-16 4.6 E-3 1.2 F-1/F-8 85/15 Re-17 A-4 88.2 B-17 10.7 C-17 0.6 E-5 0.5 F-1/F-2 70/30 Re-18 A-1 88.6 B-18 10.2 C-18 0.2 E-2 1.0 F-1/F-8 85/15 Re-19 A-5 87.7 B-19 9.1 C-19 1.8 E-3 1.5 F-1/F-2 70/30 Re-20 A-7 84.8 B-20 14.0 C-20 0.4 E-5 0.8 F-1/F-2/F-8 50/40/10 Re-21 A-8 84.7 B-21 12.3 C-21 1.8 E-9 1.2 F-1/F-8 85/15 Re-22 A-9 86.4 B-1 12.1 E-2 1.5 F-1/F-8 85/15 Re-23 A-1 83.7 B-2/B-12 7.3/6.9 C-3 1.1 E-5 1.0 F-1/F-2/F-8 70/25/5 Re-24 A-3 83.3 B-3 12.8 C-12/C-20 2.0/1.0 E-3 0.9 F-1/F-8 85/15 Re-25 A-1 88.9 B-1 9.1 C-1 1.0 E-1 1.0 F-1/F-2 70/30 Re-26 A-1 87.7 B-22 10.2 C-1 1.1 E-1 1.0 F-1/F-2/F-8 50/40/10 Re-27 A-1 77.5 B-23 20.1 C-1 1.4 E-1 1.0 F-1/F-2/F-8 50/40/10 Re-28 A-1 90.5 B-24 7.7 C-1 0.8 E-1 1.0 F-1/F-2/F-8 50/40/10 Re-29 A-1 93.9 B-2 3.8 C-1 1.3 E-1 1.0 F-1/F-2/F-8 50/40/10 Re-30 A-9 85.1 B-2 11.7 C-3 2.0 E-1 1.2 F-1/F-8 85/15 Re-31 A-4 82.1 B-25 15.6 C-18 1.5 E-1 0.8 F-1/F-2/F-8 50/35/15 Re-32 A-5 85.7 B-25 12.0 C-2 1.5 E-1 0.8 F-1/F-2/F-8 50/35/15 Re-33 A-3 87.4 B-3 10.6 C-3 1.2 E-1 0.8 F-1/F-2/F-8 70/25/5

[頂塗層組成物的製備] 以下示出表5所示的頂塗層組成物中所含的各種成分。＜樹脂＞作為表5所示的樹脂，使用表2所示的樹脂PT-1～PT-3。＜添加劑＞以下示出表5所示的添加劑的結構。[Preparation of top coat composition] The various components contained in the top coat composition shown in Table 5 are shown below. ＜Resin＞ As the resin shown in Table 5, the resins PT-1 to PT-3 shown in Table 2 were used. ＜Additives＞ The structure of the additives shown in Table 5 is shown below.

[化84]

[化84]

＜界面活性劑＞作為表5所示的界面活性劑，使用所述界面活性劑H-3。＜Surface active agent＞ As the surfactant shown in Table 5, the surfactant H-3 was used.

＜溶劑＞以下示出表5所示的溶劑。 FT-1：4-甲基-2-戊醇（4-methyl-2-pentanol，MIBC） FT-2：正癸烷 FT-3：二異戊醚＜Solvent＞ The solvents shown in Table 5 are shown below. FT-1: 4-methyl-2-pentanol (MIBC) FT-2: n-decane FT-3: Diisoamyl ether

＜頂塗層組成物的製備＞以固體成分濃度成為3質量%的方式混合表5所示的各成分，繼而，將所得的混合液按照最初為孔徑50 nm的聚乙烯製過濾器、其次為孔徑10 nm的尼龍製過濾器、最後為孔徑5 nm的聚乙烯製過濾器的順序進行過濾，藉此製備頂塗層組成物。再者，此處所述的固體成分，是指溶劑以外的所有成分。將所得的頂塗層組成物在實施例中使用。<Preparation of top coat composition> The components shown in Table 5 were mixed so that the solid content concentration became 3% by mass, and then the resulting mixture was adjusted to a polyethylene filter with a pore diameter of 50 nm, a nylon filter with a pore diameter of 10 nm, and Finally, filtration was performed sequentially with a polyethylene filter with a pore diameter of 5 nm, thereby preparing a top coat composition. In addition, the solid content mentioned here refers to all components other than the solvent. The obtained top coating composition was used in the examples.

[表5] 表5 樹脂添加劑界面活性劑溶劑種類質量[g] 種類質量[g] 種類質量[g] 種類混合比（質量） TC-1 PT-1 10 DT-1/DT-2 1.3/0.06 FT-1/FT-2 70/30 TC-2 PT-2 10 DT-3/DT-4 0.04/0.06 H-3 0.005 FT-1/FT-3 75/25 TC-3 PT-3 10 DT-5 0.05 FT-1/FT-3 10/90 [table 5] table 5 Resin additive Surfactant Solvent species Mass [g] species Mass [g] species Mass [g] species Mixing ratio (quality) TC-1 PT-1 10 DT-1/DT-2 1.3/0.06 FT-1/FT-2 70/30 TC-2 PT-2 10 DT-3/DT-4 0.04/0.06 H-3 0.005 FT-1/FT-3 75/25 TC-3 PT-3 10 DT-5 0.05 FT-1/FT-3 10/90

[圖案形成（1）：ArF液浸曝光、有機溶劑顯影] 於矽晶圓上塗佈有機防反射膜形成用組成物ARC29SR（布魯爾科技（Brewer Science）公司製造），在205℃下進行60秒烘烤，形成膜厚98 nm的防反射膜。於其上塗佈表4所示的各樹脂組成物（封入至規定的保管容器中且經過規定期間的樹脂組成物），在100℃下進行60秒烘烤，形成膜厚90 nm的抗蝕劑膜（感光化射線性或感放射線性膜）。再者，關於實施例1-5、實施例1-6及實施例1-7，於抗蝕劑膜的上層形成頂塗膜（所使用的頂塗層組成物的種類示於表6中）。頂塗膜的膜厚均設為100 nm。針對抗蝕劑膜，使用ArF準分子雷射液浸掃描儀（ASML公司製造；XT1700i、NA 1.20、偶極（Dipole）、外西格瑪0.950、內西格瑪0.850、Y偏向），經由線寬45 nm的1：1線與空間圖案的6%半色調遮罩進行曝光。液浸液使用超純水。於將曝光後的抗蝕劑膜在90℃下進行60秒烘烤後，利用乙酸正丁酯顯影30秒，繼而利用4-甲基-2-戊醇淋洗30秒。然後，將其旋轉乾燥而獲得負型的圖案。[Pattern formation (1): ArF liquid immersion exposure, organic solvent development] The organic anti-reflection film formation composition ARC29SR (manufactured by Brewer Science) was coated on a silicon wafer, and baked at 205°C for 60 seconds to form an anti-reflection film with a thickness of 98 nm. Each resin composition shown in Table 4 (resin composition sealed in a predetermined storage container for a predetermined period of time) was coated on it, and baked at 100°C for 60 seconds to form a resist with a film thickness of 90 nm. Agent film (sensitized radiation or radiation-sensitive film). Furthermore, regarding Examples 1-5, Examples 1-6, and Examples 1-7, a top coating film was formed on the upper layer of the resist film (the type of top coating composition used is shown in Table 6) . The film thickness of the top coating film was all set to 100 nm. For the resist film, an ArF excimer laser immersion scanner (manufactured by ASML; XT1700i, NA 1.20, Dipole, outer sigma 0.950, inner sigma 0.850, Y-bias) was used, and the line width 45 nm 1:1 line and space pattern 6% halftone mask for exposure. Ultrapure water is used for the immersion liquid. After the exposed resist film was baked at 90°C for 60 seconds, it was developed with n-butyl acetate for 30 seconds, and then rinsed with 4-methyl-2-pentanol for 30 seconds. Then, it was spin-dried to obtain a negative pattern.

＜缺陷評價＞於形成所述線寬45 nm的圖案後，然後利用UVision5（AMAT公司製造）檢測矽晶圓上的缺陷分佈，且使用SEMVisionG4（AMAT公司製造），觀察缺陷的形狀。再者，圖案晶圓所產生的缺陷例如以圖1及圖2般的圖像來觀察。計算出每片矽晶圓的缺陷數，按照以下的評價基準進行評價。缺陷數越少，表示結果越良好。（評價基準）「S」：缺陷數為50個以下「A」：缺陷數超過50個且為200個以下「B」：缺陷數超過200個且為300個以下「C」：缺陷數超過300個且為400個以下「D」：缺陷數超過400個且為500個以下「E」：缺陷數超過500個＜Defect evaluation＞ After forming the pattern with the line width of 45 nm, UVision5 (manufactured by AMAT) was used to detect the defect distribution on the silicon wafer, and SEMVisionG4 (manufactured by AMAT) was used to observe the shape of the defect. Furthermore, the defects generated in the patterned wafer can be observed with the images shown in FIGS. 1 and 2, for example. The number of defects per silicon wafer is calculated and evaluated according to the following evaluation criteria. The smaller the number of defects, the better the result. (Evaluation criteria) "S": The number of defects is less than 50 "A": The number of defects exceeds 50 and is less than 200 "B": The number of defects exceeds 200 and is less than 300 "C": The number of defects exceeds 300 and is less than 400 "D": The number of defects exceeds 400 and is less than 500 "E": The number of defects exceeds 500

＜評價結果＞以上的評價試驗的結果示於表6中。再者，表6中記載的收容容器如下所述。「A」：收容部的內壁為玻璃的收容容器。「B」：收容部的內壁為聚乙烯（PE）的收容容器。「C」：收容部的內壁為聚四氟乙烯（PTFE）的收容容器。另外，所謂表6中的「量比T」由下述式（1X）所表示。式（1X）：量比T=選自由化合物（I）～化合物（III）所組成的群組中的化合物（相當於光酸產生劑B）相對於組成物中的固體成分量的含有率（含量）（質量%）/相對於組成物的總質量的含水率（質量%）＜Evaluation result＞ The results of the above evaluation test are shown in Table 6. In addition, the storage containers described in Table 6 are as follows. "A": The inner wall of the container is a glass container. "B": The inner wall of the container is a container made of polyethylene (PE). "C": The inner wall of the container is a polytetrafluoroethylene (PTFE) container. In addition, the "quantity ratio T" in Table 6 is represented by the following formula (1X). Formula (1X): Amount ratio T=The content ratio of a compound (corresponding to the photoacid generator B) selected from the group consisting of compound (I) to compound (III) with respect to the solid content in the composition ( Content) (mass%)/water content relative to the total mass of the composition (mass%)

[表6] 表6 感光化射線性或感放射線性樹脂組成物含水率（質量%）量比T 容器頂塗層組成物缺陷實施例1-1 Re-1 0.19 48.5 A - A 實施例1-2 Re-2 0.56 16.4 A - C 實施例1-3 Re-3 0.34 33.0 A - B 實施例1-4 Re-4 0.41 27.2 A - B 實施例1-5 Re-5 0.21 50.3 A TC-1 A 實施例1-6 Re-6 0.97 8.3 A TC-2 C 實施例1-7 Re-7 0.55 13.8 A TC-3 C 實施例1-8 Re-8 0.07 146.0 A - A 實施例1-9 Re-9 0.31 37.1 A - B 實施例1-10 Re-10 0.40 18.4 A - B 實施例1-11 Re-11 0.71 6.5 A - C 實施例1-12 Re-12 0.68 19.7 A - C 實施例1-13 Re-25 0.02 454.6 A - B 實施例1-14 Re-1 0.19 48.5 B - S 實施例1-15 Re-1 0.19 48.5 C - S 實施例1-16 Re-26 0.11 92.7 A - A 實施例1-17 Re-27 0.32 62.8 A - B 實施例1-18 Re-29 0.98 3.9 A - D 實施例1-19 Re-33 0.02 530.0 A - D 比較例1-1 Re-30 1.10 10.7 A - E 比較例1-2 Re-31 0.46 33.9 A - E 比較例1-3 Re-32 1.05 11.4 A - E [Table 6] Table 6 Sensitizing radiation or radiation sensitive resin composition Water content (mass%) Quantity ratio T container Top coat composition defect Example 1-1 Re-1 0.19 48.5 A - A Example 1-2 Re-2 0.56 16.4 A - C Example 1-3 Re-3 0.34 33.0 A - B Example 1-4 Re-4 0.41 27.2 A - B Example 1-5 Re-5 0.21 50.3 A TC-1 A Example 1-6 Re-6 0.97 8.3 A TC-2 C Example 1-7 Re-7 0.55 13.8 A TC-3 C Example 1-8 Re-8 0.07 146.0 A - A Example 1-9 Re-9 0.31 37.1 A - B Example 1-10 Re-10 0.40 18.4 A - B Example 1-11 Re-11 0.71 6.5 A - C Example 1-12 Re-12 0.68 19.7 A - C Example 1-13 Re-25 0.02 454.6 A - B Example 1-14 Re-1 0.19 48.5 B - S Example 1-15 Re-1 0.19 48.5 C - S Example 1-16 Re-26 0.11 92.7 A - A Example 1-17 Re-27 0.32 62.8 A - B Example 1-18 Re-29 0.98 3.9 A - D Examples 1-19 Re-33 0.02 530.0 A - D Comparative example 1-1 Re-30 1.10 10.7 A - E Comparative example 1-2 Re-31 0.46 33.9 A - E Comparative example 1-3 Re-32 1.05 11.4 A - E

如表6所示，明確了根據本發明的抗蝕劑組成物，即使於保管規定期間後，亦可形成缺陷得到抑制的圖案。另外，根據實施例1-1～實施例1-13、實施例1-16～實施例1-19的對比（尤其是實施例1-6與實施例1-18、實施例1-13與實施例1-19的對比），明確了於所述式（1X）所表示的量比T為4.0～500.0的情況下，所形成的圖案的缺陷抑制性能更優異。進而，明確了於相對於組成物的總質量而言含水率為0.50質量%以下（較佳為0.03質量%～0.30質量%）的情況下，所形成的圖案的缺陷抑制性能更優異。另外，根據實施例1-1、實施例1-14及實施例1-15的對比，明確了於收容容器的收容部的內壁為選自由聚烯烴樹脂及含氟原子的聚烯烴樹脂所組成的群組中的一種以上的樹脂的情況下，所形成的圖案的缺陷抑制性能更優異。另一方面，明確了比較例的抗蝕劑組成物不滿足所期望的要求。As shown in Table 6, it is clarified that the resist composition of the present invention can form a pattern in which defects are suppressed even after storage for a predetermined period of time. In addition, according to the comparison of Example 1-1 to Example 1-13, Example 1-16 to Example 1-19 (especially Example 1-6 and Example 1-18, Example 1-13 and the implementation Comparison of Examples 1-19), it is clarified that when the amount ratio T represented by the formula (1X) is 4.0 to 500.0, the defect suppression performance of the formed pattern is more excellent. Furthermore, it was clarified that when the moisture content is 0.50% by mass or less (preferably 0.03% by mass to 0.30% by mass) with respect to the total mass of the composition, the defect suppression performance of the formed pattern is more excellent. In addition, according to the comparison of Example 1-1, Example 1-14, and Example 1-15, it is clear that the inner wall of the container in the container is composed of polyolefin resins and polyolefin resins containing fluorine atoms. In the case of one or more resins in the group, the defect suppression performance of the formed pattern is more excellent. On the other hand, it was clarified that the resist composition of the comparative example did not meet the desired requirements.

[圖案形成（2）：ArF液浸曝光、鹼水溶液顯影] 於矽晶圓上塗佈有機防反射膜形成用組成物ARC29SR（布魯爾科技（Brewer Science）公司製造），在205℃下進行60秒烘烤，形成膜厚98 nm的防反射膜。於其上塗佈表4所示的各樹脂組成物（封入至規定的保管容器中且經過規定期間的樹脂組成物），在100℃下進行60秒烘烤，形成膜厚90 nm的抗蝕劑膜。再者，關於實施例2-3、實施例2-4及實施例2-5，於抗蝕劑膜的上層形成頂塗膜（所使用的頂塗層組成物的種類示於表7中）。頂塗膜的膜厚均設為100 nm。針對抗蝕劑膜，使用ArF準分子雷射液浸掃描儀（ASML公司製造；XT1700i、NA 1.20、偶極、外西格瑪0.950、內西格瑪0.850、Y偏向），經由線寬45 nm的1：1線與空間圖案的6%半色調遮罩進行曝光。液浸液使用超純水。於將曝光後的抗蝕劑膜在90℃下進行60秒烘烤後，利用氫氧化四甲基銨水溶液（2.38質量%）顯影30秒，繼而利用純水淋洗30秒。然後，將其旋轉乾燥而獲得正型的圖案。對於所得的正型的圖案，實施所述[圖案形成（1）：ArF液浸曝光、有機溶劑顯影]中所得的負型的圖案中實施的＜缺陷評價＞。[Pattern formation (2): ArF liquid immersion exposure, alkaline aqueous solution development] The organic anti-reflection film formation composition ARC29SR (manufactured by Brewer Science) was coated on a silicon wafer, and baked at 205°C for 60 seconds to form an anti-reflection film with a thickness of 98 nm. Each resin composition shown in Table 4 (resin composition sealed in a predetermined storage container for a predetermined period of time) was coated on it, and baked at 100°C for 60 seconds to form a resist with a film thickness of 90 nm.剂膜。 Film. Furthermore, regarding Example 2-3, Example 2-4, and Example 2-5, a top coating film was formed on the upper layer of the resist film (the types of top coating composition used are shown in Table 7) . The film thickness of the top coating film was all set to 100 nm. For the resist film, use the ArF excimer laser immersion scanner (manufactured by ASML; XT1700i, NA 1.20, dipole, outer sigma 0.950, inner sigma 0.850, Y bias), passing through a line width of 45 nm 1:1 Expose the 6% halftone mask of the line and space pattern. Ultrapure water is used for the immersion liquid. After the exposed resist film was baked at 90°C for 60 seconds, it was developed with a tetramethylammonium hydroxide aqueous solution (2.38% by mass) for 30 seconds, and then rinsed with pure water for 30 seconds. Then, it was spin-dried to obtain a positive pattern. With respect to the obtained positive pattern, the <defect evaluation> implemented in the negative pattern obtained in the aforementioned [Pattern Formation (1): ArF Immersion Exposure, Organic Solvent Development] was carried out.

＜評價結果＞以上的評價試驗的結果示於表7中。再者，表7中記載的收容容器如下所述。「A」：收容部的內壁為玻璃的收容容器。「B」：收容部的內壁為聚乙烯（PE）的收容容器。「C」：收容部的內壁為聚四氟乙烯（PTFE）的收容容器。另外，所謂表7中的「量比T」由下述式（1X）所表示。式（1X）：量比T=選自由化合物（I）～化合物（III）所組成的群組中的化合物（相當於光酸產生劑B）相對於組成物中的固體成分量的含有率（含量）（質量%）/相對於組成物的總質量的含水率（質量%）＜Evaluation result＞ The results of the above evaluation test are shown in Table 7. In addition, the storage containers described in Table 7 are as follows. "A": The inner wall of the container is a glass container. "B": The inner wall of the container is a container made of polyethylene (PE). "C": The inner wall of the container is a polytetrafluoroethylene (PTFE) container. In addition, the "quantity ratio T" in Table 7 is represented by the following formula (1X). Formula (1X): Amount ratio T=The content ratio of a compound (corresponding to the photoacid generator B) selected from the group consisting of compound (I) to compound (III) with respect to the solid content in the composition ( Content) (mass%)/water content relative to the total mass of the composition (mass%)

[表7] 表7 感光化射線性或感放射線性樹脂組成物含水率（質量%）量比T 容器頂塗層組成物缺陷實施例2-1 Re-13 0.06 214.8 A - A 實施例2-2 Re-14 0.22 24.6 A - A 實施例2-3 Re-15 0.65 6.7 A TC-1 C 實施例2-4 Re-16 0.24 19.8 A TC-2 A 實施例2-5 Re-17 0.39 27.5 A TC-3 B 實施例2-6 Re-18 0.34 30.1 A - B 實施例2-7 Re-19 0.26 34.4 A - A 實施例2-8 Re-20 0.08 174.8 A - A 實施例2-9 Re-21 0.12 106.4 A - A 實施例2-10 Re-22 0.66 18.4 A - C 實施例2-11 Re-23 0.82 17.3 A - C 實施例2-12 Re-24 0.24 52.9 A - A 實施例2-13 Re-25 0.02 454.6 A - B 實施例2-14 Re-13 0.06 214.8 B - S 實施例2-15 Re-13 0.06 214.8 C - S 實施例2-16 Re-28 0.67 11.5 A - C 實施例2-17 Re-29 0.98 3.9 A - D 實施例2-18 Re-33 0.02 530.0 A - D 比較例2-1 Re-30 1.10 10.7 A - E 比較例2-2 Re-31 0.46 33.9 A - E 比較例2-3 Re-32 1.05 11.4 A - E [Table 7] Table 7 Sensitizing radiation or radiation sensitive resin composition Water content (mass%) Quantity ratio T container Top coat composition defect Example 2-1 Re-13 0.06 214.8 A - A Example 2-2 Re-14 0.22 24.6 A - A Example 2-3 Re-15 0.65 6.7 A TC-1 C Example 2-4 Re-16 0.24 19.8 A TC-2 A Example 2-5 Re-17 0.39 27.5 A TC-3 B Example 2-6 Re-18 0.34 30.1 A - B Example 2-7 Re-19 0.26 34.4 A - A Example 2-8 Re-20 0.08 174.8 A - A Example 2-9 Re-21 0.12 106.4 A - A Example 2-10 Re-22 0.66 18.4 A - C Example 2-11 Re-23 0.82 17.3 A - C Example 2-12 Re-24 0.24 52.9 A - A Example 2-13 Re-25 0.02 454.6 A - B Example 2-14 Re-13 0.06 214.8 B - S Example 2-15 Re-13 0.06 214.8 C - S Example 2-16 Re-28 0.67 11.5 A - C Example 2-17 Re-29 0.98 3.9 A - D Example 2-18 Re-33 0.02 530.0 A - D Comparative example 2-1 Re-30 1.10 10.7 A - E Comparative example 2-2 Re-31 0.46 33.9 A - E Comparative example 2-3 Re-32 1.05 11.4 A - E

如表7所示，明確了根據本發明的抗蝕劑組成物，即使於保管規定期間後，亦可形成缺陷得到抑制的圖案。另外，根據實施例2-1～實施例2-13、實施例2-16～實施例2-18，明確了於所述式（1X）所表示的量比T為4.0～500.0的情況下，所形成的圖案的缺陷抑制性能更優異。進而，明確了於相對於組成物的總質量而言含水率為0.50質量%以下（較佳為0.03質量%～0.30質量%）的情況下，所形成的圖案的缺陷抑制性能更優異。另外，根據實施例2-1、實施例2-14及實施例2-15的對比，明確了於收容容器的收容部的內壁為選自由聚烯烴樹脂及含氟原子的聚烯烴樹脂所組成的群組中的一種以上的樹脂的情況下，所形成的圖案的缺陷抑制性能更優異。另一方面，明確了比較例的抗蝕劑組成物不滿足所期望的要求。As shown in Table 7, it is clarified that the resist composition of the present invention can form a pattern in which defects are suppressed even after storage for a predetermined period of time. In addition, according to Example 2-1 to Example 2-13, and Example 2-16 to Example 2-18, it has been clarified that when the amount ratio T represented by the formula (1X) is 4.0 to 500.0, The defect suppression performance of the formed pattern is more excellent. Furthermore, it was clarified that when the moisture content is 0.50% by mass or less (preferably 0.03% by mass to 0.30% by mass) with respect to the total mass of the composition, the defect suppression performance of the formed pattern is more excellent. In addition, according to the comparison of Example 2-1, Example 2-14, and Example 2-15, it is clear that the inner wall of the receiving portion of the storage container is composed of polyolefin resins and polyolefin resins containing fluorine atoms. In the case of one or more resins in the group, the defect suppression performance of the formed pattern is more excellent. On the other hand, it was clarified that the resist composition of the comparative example did not meet the desired requirements.

[感光化射線性或感放射線性樹脂組成物的製備及圖案形成：EUV曝光] [感光化射線性或感放射線性樹脂組成物的製備（2）] ＜感光化射線性或感放射線性樹脂組成物Re-34～Re-54、Re-56、Re-58＞首先，將酸分解性樹脂在15 mmHg及60℃下真空乾燥規定時間（再者，在酸分解性樹脂（樹脂A）的所述乾燥時間為2小時～12小時的範圍內，按照各組成物製備，以使感光化射線性或感放射線性樹脂組成物的各含水率成為表8所示的含水率）。然後，以固體成分濃度成為2質量%的方式混合表9所示的各成分。繼而，將所得的混合液按照最初為孔徑50 nm的聚乙烯製過濾器、其次為孔徑10 nm的尼龍製過濾器、最後為孔徑5 nm的聚乙烯製過濾器的順序進行過濾，藉此製備感光化射線性或感放射線性樹脂組成物（以下，亦稱為樹脂組成物）Re-34～Re-54、Re-56、Re-58。再者，樹脂組成物中，所謂固體成分，是指溶劑以外的所有成分。繼而，將所得的樹脂組成物封入至規定的容器（再者，容器的種類分別示於表10及表11中）中。將封入了樹脂組成物的組成物收容體在溫度23℃、濕度60%的環境下放置4周。將封入至該規定的保管容器中且經過規定期間的樹脂組成物用於後述的圖案形成。[Preparation and pattern formation of sensitized radiation-sensitive or radiation-sensitive resin composition: EUV exposure] [Preparation of sensitized radiation-sensitive or radiation-sensitive resin composition (2)] <Acceptable radiation or radiation-sensitive resin composition Re-34～Re-54, Re-56, Re-58> First, the acid-decomposable resin is vacuum-dried at 15 mmHg and 60°C for a predetermined time (in addition, the acid-decomposable resin (resin A) is within the range of 2 to 12 hours for the drying time, according to each composition Prepared so that each moisture content of the sensitizing radiation-sensitive or radiation-sensitive resin composition becomes the moisture content shown in Table 8). Then, the components shown in Table 9 were mixed so that the solid content concentration became 2% by mass. Then, the obtained mixed liquid was filtered in the order of a polyethylene filter with a pore size of 50 nm, a nylon filter with a pore size of 10 nm, and a polyethylene filter with a pore size of 5 nm. Sensitizing radiation-sensitive or radiation-sensitive resin composition (hereinafter also referred to as resin composition) Re-34 to Re-54, Re-56, and Re-58. In addition, in the resin composition, the so-called solid content refers to all components other than the solvent. Then, the obtained resin composition was enclosed in a predetermined container (in addition, the types of containers are shown in Table 10 and Table 11, respectively). The composition container encapsulated with the resin composition was left for 4 weeks in an environment with a temperature of 23° C. and a humidity of 60%. The resin composition enclosed in the predetermined storage container and passed a predetermined period of time is used for pattern formation described later.

＜感光化射線性或感放射線性樹脂組成物Re-55、Re-57＞除了於混合各成分前不使酸分解性樹脂（樹脂A）真空乾燥以外，藉由與樹脂組成物Re-34～Re-54、Re-56及Re-58同樣的方法，製備樹脂組成物Re-55及Re-57。繼而，將所得的樹脂組成物封入至規定的容器（再者，容器的種類分別示於表10及表11中）中。將封入了樹脂組成物的組成物收容體在溫度23℃、濕度60%的環境下放置4周。將封入至該規定的保管容器中且經過規定期間的樹脂組成物用於後述的圖案形成。<Acceptable radiation or radiation-sensitive resin composition Re-55, Re-57> The resin composition Re was prepared by the same method as the resin composition Re-34～Re-54, Re-56 and Re-58 except that the acid-decomposable resin (resin A) was not vacuum dried before mixing the components. -55 and Re-57. Then, the obtained resin composition was enclosed in a predetermined container (in addition, the types of containers are shown in Table 10 and Table 11, respectively). The composition container encapsulated with the resin composition was left for 4 weeks in an environment with a temperature of 23° C. and a humidity of 60%. The resin composition enclosed in the predetermined storage container and passed a predetermined period of time is used for pattern formation described later.

＜含水率的測定＞對於剛調液後的各樹脂組成物，使用卡爾費歇爾水分計（京都電子工業股份有限公司製造的MKC-510N）按照下述順序測定含水率。具體而言，於23℃的大氣中，將10 mL的抗蝕劑組成物投入至滴定燒瓶中，利用京都電子工業股份有限公司製造的MKC-510N算出含水率。結果示於表8中。＜Measurement of moisture content＞ For each resin composition immediately after the liquid adjustment, the moisture content was measured in the following procedure using a Karl Fischer moisture meter (MKC-510N manufactured by Kyoto Electronics Co., Ltd.). Specifically, 10 mL of the resist composition was put into a titration flask in the atmosphere at 23° C., and the moisture content was calculated using MKC-510N manufactured by Kyoto Electronics Co., Ltd. The results are shown in Table 8.

[表8] 表8 含水率（質量%） Re-34 0.11 Re-35 0.94 Re-36 0.46 Re-37 0.56 Re-38 0.17 Re-39 0.06 Re-40 0.19 Re-41 0.33 Re-42 0.46 Re-43 0.13 Re-44 0.38 Re-45 0.93 Re-46 0.08 Re-47 0.54 Re-48 0.35 Re-49 0.54 Re-50 0.01 Re-51 0.26 Re-52 0.22 Re-53 0.70 Re-54 0.02 Re-55 1.08 Re-56 0.37 Re-57 1.07 Re-58 0.91 [Table 8] Table 8 Water content (mass%) Re-34 0.11 Re-35 0.94 Re-36 0.46 Re-37 0.56 Re-38 0.17 Re-39 0.06 Re-40 0.19 Re-41 0.33 Re-42 0.46 Re-43 0.13 Re-44 0.38 Re-45 0.93 Re-46 0.08 Re-47 0.54 Re-48 0.35 Re-49 0.54 Re-50 0.01 Re-51 0.26 Re-52 0.22 Re-53 0.70 Re-54 0.02 Re-55 1.08 Re-56 0.37 Re-57 1.07 Re-58 0.91

以下示出表9。再者，表9中，各成分的含量（質量%）是指相對於總固體成分的含量。Table 9 is shown below. In addition, in Table 9, the content (mass %) of each component refers to the content with respect to the total solid content.

[表9] 表9 樹脂A 光酸產生劑B 光酸產生劑C 酸擴散控制劑D 添加樹脂界面活性劑溶劑種類含量（質量%）種類含量（質量%）種類含量（質量%）種類含量（質量%）種類含量（質量%）種類含量（質量%）種類混合比（質量比） Re-34 A-6 83.8 B-14 14.9 C-14 1.2 F-1/F-8 85/15 Re-35 A-15 86.7 B-2 9.8 C-2 3.5 F-1/F-2/F-8 70/25/5 Re-36 A-16 94.4 B-3 4.2 C-3 1.3 D-2 0.1 F-4 100 Re-37 A-17 84.3 B-4 10.5 C-4 5.2 F-1/F-2 70/30 Re-38 A-13 85.2 B-8 8.7 C-8/C-10 1.0/4.7 D-4/D-1 0.1/0.3 F-1/F-8 85/15 Re-39 A-5 93.0 B-10 4.7 C-10 2.3 F-1/F-8 85/15 Re-40 A-14 86.9 B-1 13.1 F-1/F-2 70/30 Re-41 A-18 91.8 B-5 6.4 C-5 1.7 H-1 0.1 F-1/F-8 85/15 Re-42 A-20 90.6 B-7 4.8 C-1/C-7 2.3/2.3 F-1/F-2/F-8 50/40/10 Re-43 A-12 90.5 B-11 7.9 C-11 1.5 F-1/F-9 90/10 Re-44 A-13 78.1 B-11/B-15 7.3/11.8 C-15 2.8 F-1/F-6 40/60 Re-45 A-19 92.3 B-6 4.1 C-6 2.4 E-5 1.2 F-1/F-8 90/10 Re-46 A-1 87.7 B-9 9.4 C-9 2.9 F-1/F-2 80/20 Re-47 A-15/A-16 44.4/44.4 B-12 8.7 C-12 2.5 F-1 100 Re-48 A-4 84.4 B-13 11.5 C-13 4.1 F-1/F-2 70/30 Re-49 A-19 85.9 B-16 7.7 C-16 4.9 D-1 1.5 F-1/F-8 85/15 Re-50 A-17 94.4 B-3 4.8 C-2 0.8 F-1/F-2 70/30 Re-51 A-6 77.3 B-22 20.5 C-2 2.2 F-1/F-2/F-8 50/40/10 Re-52 A-6 65.9 B-23 31.0 C-2 3.1 F-1/F-2/F-8 50/40/10 Re-53 A-6 90.2 B-24 8.4 C-2 1.4 F-1/F-2/F-8 50/40/10 Re-54 A-6 62.7 B-2 35.5 C-2 1.8 F-1/F-2/F-8 50/40/10 Re-55 A-18 88.5 B-5 10.5 C-3 1.1 F-1/F-8 85/15 Re-56 A-4 76.1 B-25 22.0 C-18 1.9 F-1/F-2/F-8 50/35/15 Re-57 A-14 81.3 B-25 17.3 C-2 1.4 F-1/F-2/F-8 50/35/15 Re-58 A-17 91.3 B-4 3.5 C-4 5.2 F-1/F-2 70/30 [Table 9] Table 9 Resin A Photo acid generator B Photo acid generator C Acid diffusion control agent D Add resin Surfactant Solvent species Content (mass%) species Content (mass%) species Content (mass%) species Content (mass%) species Content (mass%) species Content (mass%) species Mixing ratio (mass ratio) Re-34 A-6 83.8 B-14 14.9 C-14 1.2 F-1/F-8 85/15 Re-35 A-15 86.7 B-2 9.8 C-2 3.5 F-1/F-2/F-8 70/25/5 Re-36 A-16 94.4 B-3 4.2 C-3 1.3 D-2 0.1 F-4 100 Re-37 A-17 84.3 B-4 10.5 C-4 5.2 F-1/F-2 70/30 Re-38 A-13 85.2 B-8 8.7 C-8/C-10 1.0/4.7 D-4/D-1 0.1/0.3 F-1/F-8 85/15 Re-39 A-5 93.0 B-10 4.7 C-10 2.3 F-1/F-8 85/15 Re-40 A-14 86.9 B-1 13.1 F-1/F-2 70/30 Re-41 A-18 91.8 B-5 6.4 C-5 1.7 H-1 0.1 F-1/F-8 85/15 Re-42 A-20 90.6 B-7 4.8 C-1/C-7 2.3/2.3 F-1/F-2/F-8 50/40/10 Re-43 A-12 90.5 B-11 7.9 C-11 1.5 F-1/F-9 90/10 Re-44 A-13 78.1 B-11/B-15 7.3/11.8 C-15 2.8 F-1/F-6 40/60 Re-45 A-19 92.3 B-6 4.1 C-6 2.4 E-5 1.2 F-1/F-8 90/10 Re-46 A-1 87.7 B-9 9.4 C-9 2.9 F-1/F-2 80/20 Re-47 A-15/A-16 44.4/44.4 B-12 8.7 C-12 2.5 F-1 100 Re-48 A-4 84.4 B-13 11.5 C-13 4.1 F-1/F-2 70/30 Re-49 A-19 85.9 B-16 7.7 C-16 4.9 D-1 1.5 F-1/F-8 85/15 Re-50 A-17 94.4 B-3 4.8 C-2 0.8 F-1/F-2 70/30 Re-51 A-6 77.3 B-22 20.5 C-2 2.2 F-1/F-2/F-8 50/40/10 Re-52 A-6 65.9 B-23 31.0 C-2 3.1 F-1/F-2/F-8 50/40/10 Re-53 A-6 90.2 B-24 8.4 C-2 1.4 F-1/F-2/F-8 50/40/10 Re-54 A-6 62.7 B-2 35.5 C-2 1.8 F-1/F-2/F-8 50/40/10 Re-55 A-18 88.5 B-5 10.5 C-3 1.1 F-1/F-8 85/15 Re-56 A-4 76.1 B-25 22.0 C-18 1.9 F-1/F-2/F-8 50/35/15 Re-57 A-14 81.3 B-25 17.3 C-2 1.4 F-1/F-2/F-8 50/35/15 Re-58 A-17 91.3 B-4 3.5 C-4 5.2 F-1/F-2 70/30

[圖案形成（3）：EUV曝光、有機溶劑顯影] 於矽晶圓上塗佈下層膜形成用組成物AL412（布魯爾科技（Brewer Science）公司製造），在205℃下進行60秒烘烤，形成膜厚20 nm的基底膜。於其上塗佈表8所示的各樹脂組成物（封入至規定的保管容器中且經過規定期間的樹脂組成物），在100℃下進行60秒烘烤，形成膜厚30 nm的抗蝕劑膜。使用EUV曝光裝置（埃庫斯泰克（Exitech）公司製造、微型曝光設備（Micro Exposure Tool）、NA 0.3、四極（Quadrupole）、外西格瑪0.68、內西格瑪0.36），對具有所得的抗蝕劑膜的矽晶圓進行圖案照射。再者，作為遮罩（reticle），使用線尺寸=20 nm、且線：空間=1：1的遮罩（mask）。於將曝光後的抗蝕劑膜在90℃下進行60秒烘烤後，利用乙酸正丁酯顯影30秒，將其旋轉乾燥而獲得負型的圖案。[Pattern formation (3): EUV exposure, organic solvent development] The underlayer film formation composition AL412 (manufactured by Brewer Science) was coated on the silicon wafer, and baked at 205°C for 60 seconds to form a base film with a thickness of 20 nm. Each resin composition shown in Table 8 (resin composition sealed in a predetermined storage container and passed a predetermined period of time) was coated on it, and baked at 100°C for 60 seconds to form a resist with a thickness of 30 nm.剂膜。 Film. Using EUV exposure equipment (manufactured by Exitech, Micro Exposure Tool, NA 0.3, Quadrupole, Out Sigma 0.68, Ne Sigma 0.36), the resist film obtained The silicon wafer is patterned. Furthermore, as a reticle, a mask with line size=20 nm and line:space=1:1 is used. After the exposed resist film was baked at 90°C for 60 seconds, it was developed with n-butyl acetate for 30 seconds, and it was spin-dried to obtain a negative pattern.

＜缺陷評價＞於形成所述線寬20 nm的圖案後，然後利用UVision5（AMAT公司製造）檢測矽晶圓上的缺陷分佈，且使用SEMVisionG4（AMAT公司製造），觀察缺陷的形狀。再者，圖案晶圓所產生的缺陷例如以圖1及圖2般的圖像來觀察。計算出每片矽晶圓的缺陷數，按照以下的評價基準進行評價。缺陷數越少，表示結果越良好。（評價基準）「S」：缺陷數為50個以下「A」：缺陷數超過50個且為200個以下「B」：缺陷數超過200個且為300個以下「C」：缺陷數超過300個且為400個以下「D」：缺陷數超過400個且為500個以下「E」：缺陷數超過500個＜Defect evaluation＞ After the pattern with the line width of 20 nm is formed, UVision5 (manufactured by AMAT) is used to detect the defect distribution on the silicon wafer, and SEMVisionG4 (manufactured by AMAT) is used to observe the shape of the defect. Furthermore, the defects generated in the patterned wafer can be observed with the images shown in FIGS. 1 and 2, for example. The number of defects per silicon wafer is calculated and evaluated according to the following evaluation criteria. The smaller the number of defects, the better the result. (Evaluation criteria) "S": The number of defects is less than 50 "A": The number of defects exceeds 50 and is less than 200 "B": The number of defects exceeds 200 and is less than 300 "C": The number of defects exceeds 300 and is less than 400 "D": The number of defects exceeds 400 and is less than 500 "E": The number of defects exceeds 500

＜評價結果＞以上的評價試驗的結果示於表10中。再者，表10中記載的收容容器如下所述。「A」：收容部的內壁為玻璃的收容容器。「B」：收容部的內壁為聚乙烯（PE）的收容容器。「C」：收容部的內壁為聚四氟乙烯（PTFE）的收容容器。另外，所謂表10中的「量比T」由下述式（1X）所表示。式（1X）：量比T=選自由化合物（I）～化合物（III）所組成的群組中的化合物（相當於光酸產生劑B）相對於組成物中的固體成分量的含有率（含量）（質量%）/相對於組成物的總質量的含水率（質量%）＜Evaluation result＞ The results of the above evaluation test are shown in Table 10. In addition, the storage container described in Table 10 is as follows. "A": The inner wall of the container is a glass container. "B": The inner wall of the container is a container made of polyethylene (PE). "C": The inner wall of the container is a polytetrafluoroethylene (PTFE) container. In addition, the "quantity ratio T" in Table 10 is represented by the following formula (1X). Formula (1X): Amount ratio T=The content ratio of a compound (corresponding to the photoacid generator B) selected from the group consisting of compound (I) to compound (III) with respect to the solid content in the composition ( Content) (mass%)/water content relative to the total mass of the composition (mass%)

[表10] 表10 感光化射線性或感放射線性樹脂組成物含水率（質量%）量比T 容器缺陷實施例3-1 Re-34 0.11 138.2 A A 實施例3-2 Re-35 0.94 10.4 A C 實施例3-3 Re-36 0.46 9.2 A B 實施例3-4 Re-37 0.56 18.8 A C 實施例3-5 Re-38 0.17 50.6 A A 實施例3-6 Re-39 0.06 82.5 A A 實施例3-7 Re-40 0.19 70.0 A A 實施例3-8 Re-41 0.33 19.4 A B 實施例3-9 Re-50 0.01 480.0 A B 實施例3-10 Re-34 0.11 138.2 B S 實施例3-11 Re-34 0.11 138.2 C S 實施例3-12 Re-53 0.70 12.0 A C 實施例3-13 Re-54 0.02 1775.0 A D 實施例3-14 Re-58 0.91 3.8 A D 比較例3-1 Re-55 1.08 9.7 A E 比較例3-2 Re-56 0.37 59.5 A E 比較例3-3 Re-57 1.07 16.2 A E [Table 10] Table 10 Sensitizing radiation or radiation sensitive resin composition Water content (mass%) Quantity ratio T container defect Example 3-1 Re-34 0.11 138.2 A A Example 3-2 Re-35 0.94 10.4 A C Example 3-3 Re-36 0.46 9.2 A B Example 3-4 Re-37 0.56 18.8 A C Example 3-5 Re-38 0.17 50.6 A A Example 3-6 Re-39 0.06 82.5 A A Example 3-7 Re-40 0.19 70.0 A A Example 3-8 Re-41 0.33 19.4 A B Example 3-9 Re-50 0.01 480.0 A B Example 3-10 Re-34 0.11 138.2 B S Example 3-11 Re-34 0.11 138.2 C S Example 3-12 Re-53 0.70 12.0 A C Example 3-13 Re-54 0.02 1775.0 A D Example 3-14 Re-58 0.91 3.8 A D Comparative example 3-1 Re-55 1.08 9.7 A E Comparative example 3-2 Re-56 0.37 59.5 A E Comparative example 3-3 Re-57 1.07 16.2 A E

如表10所示，明確了根據本發明的抗蝕劑組成物，即使於保管規定期間後，亦可形成缺陷得到抑制的圖案。另外，根據實施例3-1～實施例3-9、實施例3-12～實施例3-14的對比，明確了於所述式（1X）所表示的量比T為4.0～500.0的情況下，所形成的圖案的缺陷抑制性能更優異。進而，明確了於相對於組成物的總質量而言含水率為0.50質量%以下（較佳為0.03質量%～0.30質量%）的情況下，所形成的圖案的缺陷抑制性能更優異。另外，根據實施例3-1、實施例3-10及實施例3-11的對比，明確了於收容容器的收容部的內壁為選自由聚烯烴樹脂及含氟原子的聚烯烴樹脂所組成的群組中的一種以上的樹脂的情況下，所形成的圖案的缺陷抑制性能更優異。另一方面，明確了比較例的抗蝕劑組成物明確了不滿足所期望的要求。As shown in Table 10, it is clarified that the resist composition of the present invention can form a pattern with suppressed defects even after storage for a predetermined period of time. In addition, according to the comparison of Example 3-1 to Example 3-9 and Example 3-12 to Example 3-14, it is clear that the amount ratio T represented by the above formula (1X) is 4.0 to 500.0 Next, the defect suppression performance of the formed pattern is more excellent. Furthermore, it was clarified that when the moisture content is 0.50% by mass or less (preferably 0.03% by mass to 0.30% by mass) with respect to the total mass of the composition, the defect suppression performance of the formed pattern is more excellent. In addition, according to the comparison of Example 3-1, Example 3-10, and Example 3-11, it is clear that the inner wall of the container in the container is composed of polyolefin resin and polyolefin resin containing fluorine atoms. In the case of one or more resins in the group, the defect suppression performance of the formed pattern is more excellent. On the other hand, it was clarified that the resist composition of the comparative example did not satisfy the desired requirements.

[圖案形成（4）：EUV曝光、鹼水溶液顯影] 於矽晶圓上塗佈下層膜形成用組成物AL412（布魯爾科技（Brewer Science）公司製造），在205℃下進行60秒烘烤，形成膜厚20 nm的基底膜。於其上塗佈表11所示的各樹脂組成物（封入至規定的保管容器中且經過規定期間的樹脂組成物），在100℃下進行60秒烘烤，形成膜厚30 nm的抗蝕劑膜。使用EUV曝光裝置（埃庫斯泰克（Exitech）公司製造、微型曝光設備（Micro Exposure Tool）、NA 0.3、四極、外西格瑪0.68、內西格瑪0.36），對具有所得的抗蝕劑膜的矽晶圓進行圖案照射。再者，作為遮罩（reticle），使用線尺寸=20 nm、且線：空間=1：1的遮罩（mask）。於將曝光後的抗蝕劑膜在90℃下進行60秒烘烤後，利用氫氧化四甲基銨水溶液（2.38質量%）顯影30秒，繼而利用純水淋洗30秒。然後，將其旋轉乾燥而獲得正型的圖案。對於所得的正型的圖案，實施所述[圖案形成（3）：EUV曝光、有機溶劑顯影]中所得的負型的圖案中實施的＜缺陷評價＞。[Pattern formation (4): EUV exposure, development with aqueous alkali solution] The underlayer film formation composition AL412 (manufactured by Brewer Science) was coated on the silicon wafer, and baked at 205°C for 60 seconds to form a base film with a thickness of 20 nm. Each resin composition shown in Table 11 (resin composition sealed in a predetermined storage container for a predetermined period of time) was coated on it, and baked at 100°C for 60 seconds to form a resist with a thickness of 30 nm.剂膜。 Film. Using EUV exposure equipment (manufactured by Exitech, Micro Exposure Tool, NA 0.3, quadrupole, outer sigma 0.68, inner sigma 0.36), the silicon wafer with the obtained resist film Perform pattern illumination. Furthermore, as a reticle, a mask with line size=20 nm and line:space=1:1 is used. After the exposed resist film was baked at 90°C for 60 seconds, it was developed with a tetramethylammonium hydroxide aqueous solution (2.38% by mass) for 30 seconds, and then rinsed with pure water for 30 seconds. Then, it was spin-dried to obtain a positive pattern. About the obtained positive-type pattern, the <defect evaluation> implemented in the negative-type pattern obtained in the aforementioned [Pattern Formation (3): EUV Exposure, Organic Solvent Development] was carried out.

＜評價結果＞以上的評價試驗的結果示於表11中。再者，表11中記載的收容容器如下所述。「A」：收容部的內壁為玻璃的收容容器。「B」：收容部的內壁為聚乙烯（PE）的收容容器。「C」：收容部的內壁為聚四氟乙烯（PTFE）的收容容器。另外，所謂表11中的「量比T」由下述式（1X）所表示。式（1X）：量比T=選自由化合物（I）～化合物（III）所組成的群組中的化合物（相當於光酸產生劑B）相對於組成物中的固體成分量的含有率（含量）（質量%）/相對於組成物的總質量的含水率（質量%） [表11] 表11 感光化射線性或感放射線性樹脂組成物含水率（質量%）量比T 容器缺陷實施例4-1 Re-42 0.46 10.4 A B 實施例4-2 Re-43 0.13 62.6 A A 實施例4-3 Re-44 0.38 50.7 A B 實施例4-4 Re-45 0.93 4.4 A C 實施例4-5 Re-46 0.08 113.9 A A 實施例4-6 Re-47 0.54 16.2 A C 實施例4-7 Re-48 0.35 32.5 A B 實施例4-8 Re-49 0.54 14.3 A C 實施例4-9 Re-50 0.01 480.0 A B 實施例4-10 Re-42 0.46 10.4 B S 實施例4-11 Re-42 0.46 10.4 C S 實施例4-12 Re-51 0.26 78.8 A A 實施例4-13 Re-52 0.22 140.9 A A 實施例4-14 Re-54 0.02 1775.0 A D 實施例4-15 Re-58 0.91 3.8 A D 比較例4-1 Re-55 1.08 9.7 A E 比較例4-2 Re-56 0.37 59.5 A E 比較例4-3 Re-57 1.07 16.2 A E <Evaluation results> The results of the above evaluation tests are shown in Table 11. In addition, the storage containers described in Table 11 are as follows. "A": The inner wall of the container is a glass container. "B": The inner wall of the container is a container made of polyethylene (PE). "C": The inner wall of the container is a polytetrafluoroethylene (PTFE) container. In addition, the "quantity ratio T" in Table 11 is represented by the following formula (1X). Formula (1X): Amount ratio T=The content ratio of a compound (corresponding to the photoacid generator B) selected from the group consisting of compound (I) to compound (III) with respect to the solid content in the composition ( Content) (mass%)/water content relative to the total mass of the composition (mass%) [Table 11] Table 11 Sensitizing radiation or radiation sensitive resin composition Water content (mass%) Quantity ratio T container defect Example 4-1 Re-42 0.46 10.4 A B Example 4-2 Re-43 0.13 62.6 A A Example 4-3 Re-44 0.38 50.7 A B Example 4-4 Re-45 0.93 4.4 A C Example 4-5 Re-46 0.08 113.9 A A Example 4-6 Re-47 0.54 16.2 A C Example 4-7 Re-48 0.35 32.5 A B Example 4-8 Re-49 0.54 14.3 A C Example 4-9 Re-50 0.01 480.0 A B Example 4-10 Re-42 0.46 10.4 B S Example 4-11 Re-42 0.46 10.4 C S Example 4-12 Re-51 0.26 78.8 A A Example 4-13 Re-52 0.22 140.9 A A Example 4-14 Re-54 0.02 1775.0 A D Example 4-15 Re-58 0.91 3.8 A D Comparative example 4-1 Re-55 1.08 9.7 A E Comparative example 4-2 Re-56 0.37 59.5 A E Comparative example 4-3 Re-57 1.07 16.2 A E

如表11所示，明確了根據本發明的抗蝕劑組成物，即使於保管規定期間後，亦可形成缺陷得到抑制的圖案。另外，根據實施例4-1～實施例4-9、實施例4-12～實施例4-15的對比，明確了於所述式（1X）所表示的量比T為4.0～500.0的情況下，所形成的圖案的缺陷抑制性能更優異。進而，明確了於相對於組成物的總質量而言含水率為0.50質量%以下（較佳為0.03質量%～0.30質量%）的情況下，所形成的圖案的缺陷抑制性能更優異。另外，根據實施例4-1、實施例4-10及實施例4-11的對比，明確了於收容容器的收容部的內壁為選自由聚烯烴樹脂及含氟原子的聚烯烴樹脂所組成的群組中的一種以上的樹脂的情況下，所形成的圖案的缺陷抑制性能更優異。另一方面，明確了比較例的抗蝕劑組成物不滿足所期望的要求。As shown in Table 11, it is clarified that the resist composition of the present invention can form a pattern in which defects are suppressed even after storage for a predetermined period of time. In addition, according to the comparison of Example 4-1 to Example 4-9 and Example 4-12 to Example 4-15, it is clear that the amount ratio T represented by the above formula (1X) is 4.0 to 500.0 Next, the defect suppression performance of the formed pattern is more excellent. Furthermore, it was clarified that when the moisture content is 0.50% by mass or less (preferably 0.03% by mass to 0.30% by mass) with respect to the total mass of the composition, the defect suppression performance of the formed pattern is more excellent. In addition, according to the comparison of Example 4-1, Example 4-10, and Example 4-11, it is clear that the inner wall of the receiving portion of the storage container is composed of polyolefin resins and polyolefin resins containing fluorine atoms. In the case of one or more resins in the group, the defect suppression performance of the formed pattern is more excellent. On the other hand, it was clarified that the resist composition of the comparative example did not meet the desired requirements.

無no

圖1是用於說明圖案形成後缺陷評價的評價方法的示意圖，是利用測長掃描式電子顯微鏡（Scanning Electron Microscope，SEM）觀察到的缺陷的一例。圖2是用於說明圖案形成後缺陷評價的評價方法的示意圖，是利用測長掃描式電子顯微鏡（SEM）觀察到的缺陷的另一例。FIG. 1 is a schematic diagram for explaining the evaluation method of defect evaluation after pattern formation, and is an example of defects observed with a scanning electron microscope (Scanning Electron Microscope, SEM). 2 is a schematic diagram for explaining the evaluation method of defect evaluation after pattern formation, and is another example of defects observed with a length measuring scanning electron microscope (SEM).

Claims

一種感光化射線性或感放射線性樹脂組成物，包含：因酸的作用分解而極性增大的樹脂；藉由光化射線或放射線的照射而產生酸的化合物；以及溶劑，所述藉由光化射線或放射線的照射而產生酸的化合物包含選自由下述化合物（I）～下述化合物（III）所組成的群組中的一種以上，相對於所述組成物的總質量，含水率為1.00質量%以下；化合物（I）：具有下述結構部位X與下述結構部位Y分別各一個且藉由光化射線或放射線的照射而產生酸的化合物，所述酸包含源自下述結構部位X的下述第一酸性部位與源自下述結構部位Y的下述第二酸性部位結構部位X：包含陰離子部位A₁ ^- 與陽離子部位M₁ ⁺ 且藉由光化射線或放射線的照射而形成HA₁ 所表示的第一酸性部位的結構部位結構部位Y：包含陰離子部位A₂ ^- 與陽離子部位M₂ ⁺ 且藉由光化射線或放射線的照射而形成與由所述結構部位X形成的所述第一酸性部位的結構不同的HA₂ 所表示的第二酸性部位的結構部位其中，化合物（I）滿足下述條件I；條件I：所述化合物（I）中，將所述結構部位X中的所述陽離子部位M₁ ⁺ 及所述結構部位Y中的所述陽離子部位M₂ ⁺ 取代為H⁺ 而成的化合物PI具有源自將所述結構部位X中的所述陽離子部位M₁ ⁺ 取代為H⁺ 而成的HA₁ 所表示的酸性部位的酸解離常數a1、以及源自將所述結構部位Y中的所述陽離子部位M₂ ⁺ 取代為H⁺ 而成的HA₂ 所表示的酸性部位的酸解離常數a2，且所述酸解離常數a2大於所述酸解離常數a1；化合物（II）：具有兩個以上所述結構部位X、與所述結構部位Y且藉由光化射線或放射線的照射而產生酸的化合物，所述酸包含兩個以上源自所述結構部位X的所述第一酸性部位、與源自所述結構部位Y的所述第二酸性部位其中，化合物（II）滿足下述條件II；條件II：所述化合物（II）中，將所述結構部位X中的所述陽離子部位M₁ ⁺ 及所述結構部位Y中的所述陽離子部位M₂ ⁺ 取代為H⁺ 而成的化合物PII具有源自將所述結構部位X中的所述陽離子部位M₁ ⁺ 取代為H⁺ 而成的HA₁ 所表示的酸性部位的酸解離常數a1、以及源自將所述結構部位Y中的所述陽離子部位M₂ ⁺ 取代為H⁺ 而成的HA₂ 所表示的酸性部位的酸解離常數a2，且所述酸解離常數a2大於所述酸解離常數a1；化合物（III）：具有兩個以上所述結構部位X、與下述結構部位Z且藉由光化射線或放射線的照射而產生酸的化合物，所述酸包含兩個以上源自所述結構部位X的所述第一酸性部位、與所述結構部位Z 結構部位Z：可中和酸的非離子性的有機部位。A photosensitive ray-sensitive or radiation-sensitive resin composition, comprising: a resin that is decomposed by the action of an acid and increased in polarity; a compound that generates an acid by irradiation of actinic rays or radiation; and a solvent, The compound that generates acid by irradiation with chemical rays or radiation includes one or more selected from the group consisting of the following compound (I) to the following compound (III), and the water content is relative to the total mass of the composition 1.00% by mass or less; Compound (I): A compound having one each of the following structural part X and the following structural part Y and generating an acid by irradiation with actinic rays or radiation, the acid including the following structure The following first acidic site of site X and the following second acidic site derived from the following structural site Y. Structural site X includes an anion site A ₁ ^- and a cation site M ₁ ⁺ and is irradiated with actinic rays or radiation And the structural site that forms the first acidic site represented by _{HA 1} _{The structural site Y: includes the anion site A 2} ^- and the cationic site M ₂ ⁺ and is formed by the irradiation of actinic rays or radiation and is formed by the structural site X _{The structure of the second acidic site represented by HA 2} having a different structure of the first acidic site, wherein the compound (I) satisfies the following condition I; Condition I: in the compound (I), the structure the cation site site X and M ₁ ⁺ is the cation site in the structural site of M ₂ ⁺ Y substituent having a cation portion derived from the structure of the site X in the compound obtained by PI H ⁺ M ₁ ⁺ is substituted with an acid dissociation constant a1 solution of acid sites represented by H ⁺ from the HA _1, as well as from the cation site structure of the portion M ₂ ⁺ Y is substituted with H ⁺ from the HA ₂ The acid dissociation constant a2 of the acidic site is represented, and the acid dissociation constant a2 is greater than the acid dissociation constant a1; compound (II): having two or more of the structural site X, and the structural site Y, and by A compound that generates an acid by irradiation of actinic rays or radiation, the acid comprising two or more of the first acidic site derived from the structural site X and the second acidic site derived from the structural site Y Wherein, the compound (II) satisfies the following condition II; Condition II: in the compound (II), the cationic site M ₁ ⁺ in the structural site X and the cationic site in the structural site Y The compound PII formed by substituting M ₂ ⁺ with H ⁺ has acid dissociation constant a1 derived from the acidic site represented by _{HA 1} _{formed by substituting the cation site M 1} ⁺ with H ^{+ in the structural site X} And the acid dissociation constant a2 derived from _{the acidic site represented by HA 2} formed by substituting the cationic site M ₂ ⁺ with H ^{+ in} the structural site Y, and the acid dissociation constant a2 is greater than the acid dissociation Constant a1; Compound (III): It has two or more of the above-mentioned structural parts X, and the following structural parts Z, and by actinic radiation A compound that generates an acid by irradiation of rays or radiation, the acid comprising two or more of the first acidic site derived from the structural site X, and the structural site Z. Structural site Z: non-ion that can neutralize the acid Sexual organic parts.

如請求項1所述的感光化射線性或感放射線性樹脂組成物，其中相對於所述組成物的總質量，所述含水率為0.50質量%以下。The photosensitive radiation-sensitive or radiation-sensitive resin composition according to claim 1, wherein the moisture content is 0.50% by mass or less with respect to the total mass of the composition.

如請求項1所述的感光化射線性或感放射線性樹脂組成物，其中相對於所述組成物的總質量，所述含水率為0.30質量%以下。The photosensitive radiation-sensitive or radiation-sensitive resin composition according to claim 1, wherein the moisture content is 0.30% by mass or less with respect to the total mass of the composition.

如請求項1所述的感光化射線性或感放射線性樹脂組成物，其中相對於所述組成物的總質量，所述含水率為0.03質量%～0.30質量%。The sensitized radiation-sensitive or radiation-sensitive resin composition according to claim 1, wherein the moisture content is 0.03% by mass to 0.30% by mass relative to the total mass of the composition.

如請求項1至請求項4中任一項所述的感光化射線性或感放射線性樹脂組成物，其中下述式（1X）所表示的量比T為4.0～500.0；式（1X）：量比T=選自由所述化合物（I）～所述化合物（III）所組成的群組中的化合物相對於組成物中的固體成分量的含有率（質量%）/相對於所述組成物的總質量的含水率（質量%）。The sensitizing radiation-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 4, wherein the amount ratio T represented by the following formula (1X) is 4.0-500.0; Formula (1X): Amount ratio T=The content ratio (mass %) of a compound selected from the group consisting of the compound (I) to the compound (III) relative to the solid content in the composition (mass %)/relative The moisture content (mass%) of the total mass of the composition.

一種抗蝕劑膜，是使用如請求項1至請求項5中任一項所述的感光化射線性或感放射線性樹脂組成物而形成。A resist film is formed using the sensitizing radiation-sensitive or radiation-sensitive resin composition according to any one of Claims 1 to 5.

一種圖案形成方法，包括：使用如請求項1至請求項5中任一項所述的感光化射線性或感放射線性樹脂組成物於支持體上形成抗蝕劑膜的步驟；對所述抗蝕劑膜進行曝光的步驟；以及使用顯影液對所述經曝光的抗蝕劑膜進行顯影的步驟。A pattern forming method includes: A step of forming a resist film on a support using the sensitized radiation-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 5; A step of exposing the resist film; and A step of developing the exposed resist film using a developing solution.

一種電子元件的製造方法，包括如請求項7所述的圖案形成方法。A manufacturing method of an electronic component includes the pattern forming method as described in claim 7.

一種組成物收容體，包括：收容容器；以及收容在所述收容容器中的如請求項1至請求項5中任一項所述的感光化射線性或感放射線性樹脂組成物。A composition container, comprising: a container; and the photosensitive radiation-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 5 contained in the container.

如請求項9所述的組成物收容體，其中所述收容容器內的與所述感光化射線性或感放射線性樹脂組成物接觸的區域的材料為樹脂。The composition container according to claim 9, wherein the material of the area in contact with the photosensitive ray-sensitive or radiation-sensitive resin composition in the container is a resin.

如請求項9或請求項10所述的組成物收容體，其中所述收容容器內的與所述感光化射線性或感放射線性樹脂組成物接觸的區域的材料為選自由聚烯烴樹脂及含氟原子的聚烯烴樹脂所組成的群組中的一種以上。The composition container according to claim 9 or claim 10, wherein the material of the area in contact with the photosensitive ray-sensitive or radiation-sensitive resin composition in the storage container is selected from polyolefin resins and One or more types of polyolefin resins containing fluorine atoms.