TW202115133A - Actinic ray-sensitive or radiation-sensitive resin composition, actinic ray-sensitive or radiation-sensitive film, method for forming pattern, and method for producing electronic device - Google Patents
Actinic ray-sensitive or radiation-sensitive resin composition, actinic ray-sensitive or radiation-sensitive film, method for forming pattern, and method for producing electronic device Download PDFInfo
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Abstract
Description
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、感光化射線性或感放射線性膜、圖案形成方法、以及電子元件的製造方法。The present invention relates to a photosensitive ray-sensitive or radiation-sensitive resin composition, a photosensitive ray-sensitive or radiation-sensitive film, a pattern forming method, and a manufacturing method of electronic components.
於積體電路（Integrated Circuit，IC）及大規模積體電路（Large Scale Integrated circuit，LSI）等半導體元件的製造製程中，藉由使用感光性組成物的微影來進行微細加工。 作為微影的方法，可列舉於由感光性組成物形成抗蝕劑膜後對所得的膜進行曝光，然後進行顯影的方法。尤其是，近年來，進行了在曝光時使用電子束（Electron Beam，EB）、極紫外線（Extreme ultraviolet，EUV）光的研究。 專利文獻1揭示了一種抗蝕劑組成物，含有因酸的作用而對顯影液的溶解性發生變化的基材成分（A）、及藉由曝光而產生酸的酸產生劑成分（B），且所述基材成分（A）具有特定的結構，所述酸產生劑成分（B）具有特定的結構。 [現有技術文獻] [專利文獻]In the manufacturing process of semiconductor components such as Integrated Circuit (IC) and Large Scale Integrated Circuit (LSI), microfabrication is performed by using photolithography of photosensitive composition. As a method of lithography, a method of forming a resist film from a photosensitive composition, exposing the resulting film, and then developing it can be cited. In particular, in recent years, research has been conducted using electron beam (EB) and extreme ultraviolet (EUV) light for exposure. Patent Document 1 discloses a resist composition containing a substrate component (A) whose solubility to a developer changes due to the action of an acid, and an acid generator component (B) that generates acid by exposure. In addition, the base component (A) has a specific structure, and the acid generator component (B) has a specific structure. [Prior Art Literature] [Patent Literature]
[專利文獻1]日本專利特開2012-203261號公報 [專利文獻2]日本專利特開2012-208200號公報[Patent Document 1] Japanese Patent Laid-Open No. 2012-203261 [Patent Document 2] Japanese Patent Laid-Open No. 2012-208200
[發明所欲解決之課題] 近年來，要求使用EB、EUV光形成的圖案的超微細化，例如，存在如下情況：在線與空間圖案的形成中，要求盡可能減小線部的線寬，或者增大鄰接的線部的線寬，盡可能減小線部間的間隔。 為了應對此種要求，一般考慮調整用於形成圖案的抗蝕劑組成物的組成，但在確保獲得的圖案的粗糙度性能的同時，對線寬極微小的圖案或鄰接的線部的間隔極微小的圖案進行解析非常困難。 再者，已知有上述專利文獻2中記載的正型感光性組成物，但並未進行使用EB、EUV光形成的圖案的超微細化。[The problem to be solved by the invention] In recent years, ultra-fine patterns formed using EB and EUV light have been required. For example, there are cases where the formation of line and space patterns requires reducing the line width of the line as much as possible, or increasing the line width of the adjacent line. Line width, minimize the space between lines as much as possible. In order to meet such requirements, it is generally considered to adjust the composition of the resist composition used to form the pattern. However, while ensuring the roughness performance of the pattern obtained, the spacing between patterns with extremely small line widths or adjacent lines is extremely small. It is very difficult to analyze small patterns. Furthermore, the positive photosensitive composition described in the above-mentioned Patent Document 2 is known, but the pattern formed by using EB or EUV light has not been ultrafine.
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，能夠降低傾倒前線寬，能夠增大橋接前線寬，從而能夠形成解析性的裕度優異，進而粗糙度性能優異的圖案。 另外，本發明的課題在於提供一種有關所述感光化射線性或感放射線性樹脂組成物的感光化射線性或感放射線性樹脂膜、圖案形成方法及電子元件的製造方法。 [解決課題之手段]Therefore, the subject of the present invention is to provide a sensitized radiation-sensitive or radiation-sensitive resin composition that can reduce the line width before dumping, and can increase the line width before bridging, so as to form an excellent resolution margin and thus excellent roughness performance. pattern. In addition, the subject of the present invention is to provide an actinic ray-sensitive or radiation-sensitive resin film, a pattern formation method, and a manufacturing method of an electronic component related to the sensitized ray-sensitive or radiation-sensitive resin composition. [Means to solve the problem]
本發明者等人發現藉由以下結構可解決所述課題。The inventors of the present invention found that the problem can be solved by the following structure.
[1] 一種感光化射線性或感放射線性樹脂組成物，含有： （A）樹脂，包含具有由下述通式（1a）表示的部分結構及下述通式（1b）表示的部分結構的至少一者、及芳香族基的重複單元（a1）；以及 （B）藉由光化射線或放射線的照射而產生酸的化合物， 所述樹脂（A）不包含具有環氧基及/或氧雜環丁基的重複單元。[1] A sensitized radiation or radiation-sensitive resin composition containing: (A) A resin containing at least one of a partial structure represented by the following general formula (1a) and a partial structure represented by the following general formula (1b), and a repeating unit (a1) of an aromatic group; and (B) A compound that generates acid by irradiation of actinic rays or radiation, The resin (A) does not contain repeating units having epoxy groups and/or oxetanyl groups.
[化1]
所述通式（1a）中， R1 及R2 分別獨立地表示氫原子或有機基。R1 與R2 可彼此鍵結而形成環。 *表示鍵結位置。 所述通式（1b）中， R3 分別獨立地表示氫原子或有機基。 R4 分別獨立地表示氫原子或有機基。 *表示鍵結位置。In the general formula (1a), R 1 and R 2 each independently represent a hydrogen atom or an organic group. R 1 and R 2 may be bonded to each other to form a ring. * Indicates the position of the bond. In the general formula (1b), R 3 each independently represents a hydrogen atom or an organic group. R 4 each independently represents a hydrogen atom or an organic group. * Indicates the position of the bond.
[2] 如[1]所述的感光化射線性或感放射線性樹脂組成物，其中所述重複單元（a1）由下述通式（2a）或通式（2b）表示。[2] The sensitizing radiation-sensitive or radiation-sensitive resin composition according to [1], wherein the repeating unit (a1) is represented by the following general formula (2a) or general formula (2b).
[化2]
所述通式（2a）中， X1 表示氫原子、鹵素原子、氰基、或有機基。 Y1 表示單鍵或二價連結基。 Z1 表示單鍵或（n1 +1）價連結基。 R21 及R22 分別獨立地表示氫原子或有機基。R21 與R22 可彼此鍵結而形成環。 n1 表示1以上的整數。於n1 表示2以上的整數的情況下，多個R21 可相同亦可不同，多個R22 可相同亦可不同。 X1 、Y1 、Z1 、R21 及R22 的至少一者包含芳香族基。 所述通式（2b）中， X2 表示氫原子、鹵素原子、氰基、或有機基。 Y2 表示單鍵或二價連結基。 Z2 表示單鍵或（n2 +1）價連結基。 R23 表示氫原子或有機基。 R24 表示氫原子或有機基。 n2 表示1以上的整數。於n2 表示2以上的整數的情況下，多個R23 可相同亦可不同，多個R24 可相同亦可不同。 X2 、Y2 、Z2 、R23 及R24 的至少一者包含芳香族基。In the general formula (2a), X 1 represents a hydrogen atom, a halogen atom, a cyano group, or an organic group. Y 1 represents a single bond or a divalent linking group. Z 1 represents a single bond or (n 1 +1) valence linking group. R 21 and R 22 each independently represent a hydrogen atom or an organic group. R 21 and R 22 may be bonded to each other to form a ring. n 1 represents an integer of 1 or more. When n 1 represents an integer of 2 or more, a plurality of R 21 may be the same or different, and a plurality of R 22 may be the same or different. At least one of X 1 , Y 1 , Z 1 , R 21, and R 22 includes an aromatic group. In the general formula (2b), X 2 represents a hydrogen atom, a halogen atom, a cyano group, or an organic group. Y 2 represents a single bond or a divalent linking group. Z 2 represents a single bond or (n 2 +1) valence linking group. R 23 represents a hydrogen atom or an organic group. R 24 represents a hydrogen atom or an organic group. n 2 represents an integer of 1 or more. When n 2 represents an integer of 2 or more, a plurality of R 23 may be the same or different, and a plurality of R 24 may be the same or different. At least one of X 2 , Y 2 , Z 2 , R 23 and R 24 includes an aromatic group.
[3] 如[2]所述的感光化射線性或感放射線性樹脂組成物，其中所述由通式（2a）或通式（2b）表示的重複單元為下述通式（3）所表示的重複單元。[3] The sensitizing radiation-sensitive or radiation-sensitive resin composition according to [2], wherein the repeating unit represented by the general formula (2a) or the general formula (2b) is a repeating unit represented by the following general formula (3) unit.
[化3]
所述通式（3）中， X3 表示氫原子、鹵素原子、烷基、環烷基、或氰基。 Y3 表示單鍵或二價連結基。 Ar表示芳香族基。 Z3 表示單鍵或（n+1）價連結基。 R31 及R32 分別獨立地表示氫原子或有機基。R31 與R32 可彼此鍵結而形成環。 n表示1以上的整數。於n表示2以上的整數的情況下，多個R31 可相同亦可不同，多個R32 可相同亦可不同。In the general formula (3), X 3 represents a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, or a cyano group. Y 3 represents a single bond or a divalent linking group. Ar represents an aromatic group. Z 3 represents a single bond or (n+1) valence linking group. R 31 and R 32 each independently represent a hydrogen atom or an organic group. R 31 and R 32 may be bonded to each other to form a ring. n represents an integer of 1 or more. When n represents an integer of 2 or more, a plurality of R 31 may be the same or different, and a plurality of R 32 may be the same or different.
[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，其中相對於樹脂（A）的全部重複單元，樹脂（A）中的所述重複單元（a1）的含量為10莫耳%以上。[4] The sensitizing radiation-sensitive or radiation-sensitive resin composition according to any one of [1] to [3], wherein the repeating unit (A) in the resin (A) is relative to all the repeating units of the resin (A) a1) The content is more than 10 mol%.
[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，其中所述重複單元（a1）、及所述重複單元（a1）以外的重複單元的至少一者具有酸分解性基。[5] The sensitizing radiation-sensitive or radiation-sensitive resin composition according to any one of [1] to [4], wherein at least the repeating unit (a1) and the repeating unit other than the repeating unit (a1) One has an acid-decomposable group.
[6] 如[3]～[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，其中所述通式（3）中的Y3 表示單鍵、-COO-、或-CONR6 -，R6 表示氫原子或烷基。[6] The sensitizing radiation-sensitive or radiation-sensitive resin composition according to any one of [3] to [5], wherein Y 3 in the general formula (3) represents a single bond, -COO-, Or -CONR 6 -, R 6 represents a hydrogen atom or an alkyl group.
[7] 如[3]～[6]中任一項所述的感光化射線性或感放射線性樹脂組成物，其中所述通式（3）中的R31 及R32 分別獨立地表示氫原子、烷基、環烷基、芳基、烷基羰基、芳基羰基、烷基磺醯基、或芳基磺醯基。[7] The sensitizing radiation-sensitive or radiation-sensitive resin composition according to any one of [3] to [6], wherein R 31 and R 32 in the general formula (3) each independently represent hydrogen Atom, alkyl, cycloalkyl, aryl, alkylcarbonyl, arylcarbonyl, alkylsulfonyl, or arylsulfonyl.
[8] 如[3]～[7]中任一項所述的感光化射線性或感放射線性樹脂組成物，其中所述通式（3）由下述通式（4）表示。[8] The sensitizing radiation-sensitive or radiation-sensitive resin composition according to any one of [3] to [7], wherein the general formula (3) is represented by the following general formula (4).
[化4]
通式（4）中， X4 表示氫原子、鹵素原子、烷基、環烷基或氰基。 Y4 表示單鍵或二價連結基。 R41 表示氫原子、烷基、環烷基、芳基、烷基羰基、芳基羰基、烷基磺醯基、或芳基磺醯基。In the general formula (4), X 4 represents a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, or a cyano group. Y 4 represents a single bond or a divalent linking group. R 41 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkylcarbonyl group, an arylcarbonyl group, an alkylsulfonyl group, or an arylsulfonyl group.
[9] 如[8]所述的感光化射線性或感放射線性樹脂組成物，其中，所述通式（4）中的R41 表示烷基羰基或芳基羰基。 [10] 如[1]～[9]中任一項所述的感光化射線性或感放射線性樹脂組成物，其中所述組成物是抗蝕劑組成物。 [11] 一種感光化射線性或感放射線性膜，其是使用如[1]～[10]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。[9] The actinic radiation-sensitive or radiation-sensitive resin composition according to [8], wherein R 41 in the general formula (4) represents an alkylcarbonyl group or an arylcarbonyl group. [10] The sensitizing radiation-sensitive or radiation-sensitive resin composition according to any one of [1] to [9], wherein the composition is a resist composition. [11] A sensitizing radiation or radiation-sensitive film formed using the sensitizing radiation or radiation-sensitive resin composition according to any one of [1] to [10].
[12] 一種圖案形成方法，包括：使用如[1]～[10]中任一項所述的感光化射線性或感放射線性樹脂組成物，在基板上形成抗蝕劑膜的步驟； 將所述抗蝕劑膜進行曝光的步驟；以及 使用顯影液將所述曝光後的抗蝕劑膜顯影而形成圖案的步驟。 [13] 一種電子元件的製造方法，包括如[12]所述的圖案形成方法。 [發明的效果][12] A pattern forming method, comprising: forming a resist film on a substrate using the sensitizing radiation-sensitive or radiation-sensitive resin composition as described in any one of [1] to [10]; The step of exposing the resist film; and The step of developing the exposed resist film using a developing solution to form a pattern. [13] A manufacturing method of an electronic component includes the pattern forming method as described in [12]. [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，能夠降低傾倒前線寬，能夠增大橋接前線寬，從而能夠形成解析性的裕度優異，進而粗糙度性能優異的圖案。 另外，根據本發明，可提供一種有關所述感光化射線性或感放射線性樹脂組成物的感光化射線性或感放射線性樹脂膜、圖案形成方法及電子元件的製造方法。According to the present invention, it is possible to provide a photosensitive radiation-sensitive or radiation-sensitive resin composition, which can reduce the line width before pouring and increase the line width before bridging, thereby being able to form a pattern with excellent resolution margin and excellent roughness performance. In addition, according to the present invention, it is possible to provide an actinic ray-sensitive or radiation-sensitive resin film, a pattern forming method, and a manufacturing method of an electronic component related to the sensitized ray-sensitive or radiation-sensitive resin composition.
以下，說明用於實施本發明的形態的一例。 再者，本說明書中，使用「～」而表示的數值範圍是指包含「～」的前後所記載的數值作為下限值及上限值的範圍的含義。Hereinafter, an example of a form for implementing the present invention will be described. In addition, in this specification, the numerical range shown using "-" means the meaning of the range including the numerical value described before and after "-" as the lower limit and the upper limit.
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.
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」。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".
所謂本說明書中的「(甲基)丙烯酸基」為包含丙烯酸基及甲基丙烯酸基的總稱，且是指「丙烯酸基及甲基丙烯酸基中的至少一種」。同樣地，所謂「(甲基)丙烯酸」是指「丙烯酸及甲基丙烯酸中的至少一種」。The "(meth)acryl group" in this specification is a general term including an acrylic group and a methacryl group, and means "at least one of an acrylic group and a methacryl group". Similarly, "(meth)acrylic acid" means "at least one of acrylic acid and methacrylic acid".
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。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.
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）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, 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 by device (Tosoh HLC-8120GPC) (solvent: tetrahydrofuran, flow rate (sample injection volume): 10 μL, column: TSK gel Multipore HXL-M manufactured by Tosoh) , Column temperature: 40℃, flow rate: 1.0 mL/min, detector: Refractive Index Detector (Refractive Index Detector) obtained by polystyrene conversion value.
1 Å為1×10-10 m。1 Å is 1×10 -10 m.
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：高級化學發展有限公司（Advanced Chemistry Development）（ACD/Labs）Solaris系統用軟體V8.14版（Software V8.14 for Solaris）（1994-2007 ACD/Labs）。Software package 1: Advanced Chemistry Development (ACD/Labs) Solaris system software V8.14 (Software V8.14 for Solaris) (1994-2007 ACD/Labs).
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，可列舉基於熱力學循環，計算並算出溶媒中的H+ 解離自由能量的方法。（再者，本說明書中，作為所述溶媒，通常使用水，於在水中無法求出pKa的情況下，使用二甲基亞碸（dimethylsulfoxide，DMSO）） 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 and calculating the H + dissociation free energy in the solvent based on the thermodynamic cycle can be cited. (Furthermore, in this specification, water is usually used as the solvent, and dimethylsulfoxide (DMSO) is used when the pKa cannot be obtained in water.) Regarding the calculation method of H + dissociation free energy, For example, the calculation can be performed by density functional theory (Density Functional Theory, DFT). In addition to this, various other methods have been reported in the literature, and they 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。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.
關於本說明書中的基（原子團）的表述，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。Regarding the expression of the group (atomic group) in this specification, 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.
另外，本說明書中，提及「可具有取代基」時的取代基的種類、取代基的位置及取代基的數量並無特別限制。取代基的數量例如可為一個、兩個、三個或三個以上。作為取代基的例子，可列舉除氫原子以外的一價非金屬原子團，例如可自以下的取代基T中選擇。In addition, in this specification, the type of substituent, the position of the substituent, and the number of substituents when it is mentioned that "may have a substituent" are not particularly limited. The number of substituents may be one, two, three, or three or more, for example. Examples of the substituent include a monovalent non-metal atomic group other than a hydrogen atom. For example, it can be selected from the following substituents T.
（取代基T） 作為取代基T，可列舉：氟原子、氯原子、溴原子及碘原子等鹵素原子；甲氧基、乙氧基及第三丁氧基等烷氧基；苯氧基及對甲苯氧基等芳氧基；甲氧基羰基、丁氧基羰基及苯氧基羰基等烷氧基羰基；乙醯氧基、丙醯氧基及苯甲醯氧基等醯氧基；乙醯基、苯甲醯基、異丁醯基、丙烯醯基、甲基丙烯醯基及甲氧草醯基（methoxalyl）等醯基；甲基巰基（sulfanyl）及第三丁基巰基等烷基巰基；苯基巰基及對甲苯巰基等芳基巰基；烷基；環烷基；芳基；雜芳基；羥基；羧基；甲醯基；磺基；氰基；烷基胺基羰基；芳基胺基羰基；磺醯胺基；矽烷基；胺基；單烷基胺基；二烷基胺基；芳基胺基、硝基；以及該些的組合。(Substituent T) Examples of the substituent T include halogen atoms such as fluorine atom, chlorine atom, bromine atom, and iodine atom; alkoxy groups such as methoxy, ethoxy, and tert-butoxy; phenoxy and p-tolyloxy, etc. Aryloxy; alkoxycarbonyl groups such as methoxycarbonyl, butoxycarbonyl and phenoxycarbonyl; acetyloxy groups such as acetoxy, propoxy and benzyloxy; acetoxy, benzyl Sulfanyl, isobutyryl, acryloyl, methacryloyl and methoxalyl (methoxalyl); methyl mercapto (sulfanyl) and tertiary butyl mercapto groups such as alkyl mercapto; Aryl mercapto groups such as toluene mercapto groups; alkyl groups; cycloalkyl groups; aryl groups; heteroaryl groups; hydroxyl groups; carboxy groups; carboxamides; sulfo groups; cyano groups; alkylaminocarbonyl groups; arylaminocarbonyl groups; sulfonamides Silyl group; amino group; monoalkylamino group; dialkylamino group; arylamino group, nitro group; and combinations of these.
[感光化射線性或感放射線性樹脂組成物] 對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」）進行說明。 本發明的抗蝕劑組成物可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。 本發明的組成物典型而言為化學增幅型抗蝕劑組成物。[Sensitizing radiation-sensitive or radiation-sensitive resin composition] The actinic radiation-sensitive or radiation-sensitive resin composition (hereinafter, also referred to as "resist composition") of the present invention will be described. The resist composition of the present invention may be a positive type resist composition or 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 composition of the present invention is typically a chemically amplified resist composition.
本發明的感光化射線性或感放射線性樹脂組成物含有：（A）樹脂，包含重複單元（a1），所述重複單元（a1）具有由後述通式（1a）所表示的部分結構及由後述通式（1b）所表示的部分結構的至少一者、及芳香族基；以及（B）藉由光化射線或放射線的照射而產生酸的化合物。 根據此種結構，能夠降低傾倒前線寬，能夠增大橋接前線寬，從而能夠形成解析性的裕度優異，且粗糙度性能優異的圖案。 此處，「傾倒前線寬」是指在線部不傾倒的情況下能夠形成（解析）的線寬。 「橋接前線寬」是指在鄰接的線部不接觸的情況下能夠形成（解析）的線寬。 「解析性的裕度」是指自橋接前線寬減去傾倒前線寬而得的值。該值越大，解析性的容許度（線部中可形成的線寬的範圍）越大，意味著越優異。 本發明能夠表現出所述效果的機制雖未必明確，但本發明者等人如以下般考慮。The sensitizing radiation-sensitive or radiation-sensitive resin composition of the present invention contains: (A) a resin, including a repeating unit (a1), the repeating unit (a1) having a partial structure represented by the following general formula (1a) and consisting of At least one of the partial structures represented by the general formula (1b) described below and an aromatic group; and (B) a compound that generates an acid by irradiation with actinic rays or radiation. According to this structure, the line width before dumping can be reduced, the line width before bridging can be increased, and a pattern with excellent resolution margin and excellent roughness performance can be formed. Here, the "line width before falling" refers to the line width that can be formed (analyzed) without falling over the line. The "line width before bridging" refers to the line width that can be formed (analyzed) when adjacent lines are not in contact. The "analytic margin" is the value obtained by subtracting the line width before dumping from the line width before bridging. The larger the value, the larger the tolerance for resolution (the range of the line width that can be formed in the line portion), which means the better. Although the mechanism by which the present invention can exhibit the aforementioned effects is not necessarily clear, the inventors of the present invention consider as follows.
首先，本發明的感光化射線性或感放射線性樹脂組成物中，樹脂（A）包含重複單元（a1），所述重複單元（a1）具有由後述通式（1a）所表示的部分結構及由後述通式（1b）表示的部分結構的至少一者、以及芳香族基。 此處，通式（1a）所表示的部分結構及後述的通式（1b）所表示的部分結構中的至少一者具有極性非常高的磺醯胺基。因此，由上述組成物形成的感光化射線性或感放射線性膜與基板的表面能之差變小，因此推測感光化射線性或感放射線性膜與基板的密接性提高，即使線部的線寬極微小，線部亦不易傾倒。 但是，如上所述，作為高極性基的磺醯胺基雖然使感光化射線性或感放射線性膜與基板的密接性提高，但另一方面認為曝光部與未曝光部之間的對顯影液的溶解對比度有降低的傾向。First, in the sensitizing radiation-sensitive or radiation-sensitive resin composition of the present invention, the resin (A) includes a repeating unit (a1) having a partial structure represented by the general formula (1a) described below and At least one of the partial structures represented by the following general formula (1b) and an aromatic group. Here, at least one of the partial structure represented by general formula (1a) and the partial structure represented by general formula (1b) described later has a very polar sulfonamide group. Therefore, the difference between the surface energy of the sensitizing radiation or radiation-sensitive film formed of the above composition and the substrate becomes small. Therefore, it is presumed that the adhesion of the sensitizing radiation or radiation-sensitive film to the substrate is improved, even if the line The width is extremely small, and the line is not easy to fall. However, as described above, although the sulfonamide group, which is a highly polar group, improves the adhesion between the sensitized radiation or the radiation-sensitive film and the substrate, it is considered that the contrast between the exposed part and the unexposed part is opposed to the developing solution. The dissolution contrast tends to decrease.
具體而言，在使用鹼顯影液形成正型圖案的情況下，在未曝光部亦被磺醯胺基高極性化（未曝光部成為容易被鹼顯影液溶解的狀態），藉此所述溶解對比度降低，進而難以形成線部的線寬極微小的圖案。另外，亦難以形成鄰接的線部的間隔極微小的圖案（其原因在於，即使要增大鄰接的線部的線寬，盡可能減小線部間的間隔，亦由於上述溶解對比度的降低，難以藉由鹼顯影液使線部與線部之間溶解，線部與線部變得容易相連（橋接））。另外，在使用有機系顯影液形成負型圖案的情況下，在未曝光部亦被磺醯胺基高極性化（未曝光部成為不易被有機系顯影液溶解的狀態），藉此所述溶解對比度降低，進而難以形成線部的線寬極微小的圖案。另外，亦難以形成鄰接的線部的間隔極微小的圖案（其原因在於，即使要增大鄰接的線部的線寬，盡可能減小線部間的間隔，亦由於所述溶解對比度的降低，難以藉由有機系顯影液溶解未曝光部，線部與線部容易相連（橋接））。Specifically, when an alkaline developer is used to form a positive pattern, the unexposed area is also highly polarized by the sulfonamide group (the unexposed area becomes a state that is easily dissolved by the alkaline developer), thereby the dissolution The contrast is lowered, and it is difficult to form a pattern with an extremely small line width in the line portion. In addition, it is also difficult to form a pattern with very small intervals between adjacent line portions (the reason is that even if the line width of adjacent line portions is to be increased, and the interval between the line portions is reduced as much as possible, it is also due to the aforementioned reduction in dissolution contrast. It is difficult to dissolve between the line part and the line part by the alkali developer, and the line part and the line part become easy to connect (bridge)). In addition, when an organic developer is used to form a negative pattern, the unexposed part is also highly polarized by the sulfonamide group (the unexposed part becomes a state that is not easily dissolved by the organic developer), thereby dissolving The contrast is lowered, and it is difficult to form a pattern with an extremely small line width in the line portion. In addition, it is also difficult to form a pattern with very small intervals between adjacent lines (the reason is that even if the line width of adjacent lines is to be increased, and the interval between the lines is reduced as much as possible, it is also due to the reduction in the dissolution contrast. , It is difficult to dissolve the unexposed part by the organic developer, and the line part and the line part are easily connected (bridging)).
但是，若要對高極性的磺醯胺基賦予碳數多的烷基之類的疏水基來維持溶解對比度，則會損害所述的密接性提高的效果，無法解析線寬極微小的圖案。反覆進行努力研究的結果發現，具有包含磺醯胺基及芳香族基的所述重複單元的樹脂（A）可兼顧密接性提高與溶解對比度下降的抑制。推測主要原因是芳香族基是疏水性基，分子間相互作用強，表面能大。 如此，由於與基板的高密接性，線部不易傾倒，而且，曝光部與未曝光部之間的對顯影液的溶解對比度不會受損，因此認為根據本發明的結構，可降低傾倒前線寬。However, if a hydrophobic group such as an alkyl group having a large carbon number is added to a highly polar sulfonamide group to maintain the dissolution contrast, the effect of improving the adhesion described above is impaired, and it is impossible to analyze patterns with extremely minute line widths. As a result of diligent studies, it was found that the resin (A) having the repeating unit containing a sulfonamide group and an aromatic group can achieve both improvement in adhesion and suppression of decrease in dissolution contrast. It is speculated that the main reason is that the aromatic group is a hydrophobic group, with strong intermolecular interaction and large surface energy. In this way, due to the high adhesion to the substrate, the line part is not easy to fall, and the dissolution contrast of the developer between the exposed part and the unexposed part is not impaired. Therefore, it is considered that the structure of the present invention can reduce the line width before dumping. .
另外，如上所述，曝光部與未曝光部之間對顯影液的溶解對比度不會受損，因此認為根據本發明，可增大橋接前線寬。 如上所述，根據本發明，能夠降低傾倒前線寬，能夠增大橋接前線寬。其結果，認為與橋接前線寬和傾倒前線寬的差相對應的曝光裕度亦優異。In addition, as described above, the dissolution contrast of the developer between the exposed portion and the unexposed portion is not impaired. Therefore, it is considered that the line width before bridging can be increased according to the present invention. As described above, according to the present invention, the line width before dumping can be reduced, and the line width before bridging can be increased. As a result, it is considered that the exposure margin corresponding to the difference between the line width before bridging and the line width before dumping is also excellent.
另外，關於藉由光化射線或放射線的照射而產生酸的化合物（B）（以下亦簡稱為光酸產生劑），由於光酸產生劑具有極性基、或者為離子性化合物等，光酸產生劑彼此之間有容易凝聚的傾向。 但是，在本發明中，樹脂（A）中所含的作為高極性基的磺醯胺基與光酸產生劑相互作用，藉此可抑制所述的光酸產生劑的凝聚。因此，在感光化射線性或感放射線性膜中更均勻地含有光酸產生劑，進而在曝光部內，由光酸產生劑產生的酸與樹脂的反應更均勻地進行，因此認為粗糙度性能更優異。In addition, with regard to the compound (B) that generates acid by irradiation with actinic rays or radiation (hereinafter also referred to as a photoacid generator), since the photoacid generator has a polar group or is an ionic compound, the photoacid generates The agents tend to coagulate easily. However, in the present invention, the sulfonamide group, which is a highly polar group contained in the resin (A), interacts with the photoacid generator, thereby suppressing the aggregation of the photoacid generator. Therefore, the photoacid generator is contained more uniformly in the sensitizing radiation-sensitive or radiation-sensitive film, and the reaction between the acid generated by the photoacid generator and the resin proceeds more uniformly in the exposed part, so it is considered that the roughness performance is better. Excellent.
〔抗蝕劑組成物的成分〕 以下，對抗蝕劑組成物可含有的成分進行詳述。[Components of resist composition] Hereinafter, the components that can be contained in the resist composition are described in detail.
＜（A）包含具有下述通式（1a）所表示的部分結構及下述通式（1b）所表示的部分結構的至少一種、以及芳香族基的重複單元（a1）的樹脂＞ 抗蝕劑組成物含有（A）包含具有後述通式（1a）所表示的部分結構及後述通式（1b）所表示的部分結構的至少一種、以及芳香族基的重複單元（a1）的樹脂（以下，亦成為「樹脂（A）」）。 所述樹脂（A）不包含具有環氧基及/或氧雜環丁基的重複單元。<(A) A resin containing at least one of the partial structure represented by the following general formula (1a) and the partial structure represented by the following general formula (1b), and the repeating unit (a1) of an aromatic group> The resist composition contains (A) a resin containing at least one of a partial structure represented by the general formula (1a) described below and a partial structure represented by the general formula (1b) described below, and an aromatic group repeating unit (a1) (Hereinafter, also referred to as "resin (A)"). The resin (A) does not contain repeating units having epoxy groups and/or oxetanyl groups.
（具有上述通式（1a）所表示的部分結構及上述通式（1b）所表示的部分結構的至少一種、及芳香族基的重複單元（a1））（以下，亦稱為「重複單元（a1）」） 樹脂（A）包含具有由下述通式（1a）表示的部分結構及下述通式（1b）表示的部分結構的至少一種、以及芳香族基的重複單元（a1）。(Having at least one of the partial structure represented by the general formula (1a) and the partial structure represented by the general formula (1b), and the repeating unit (a1) of the aromatic group) (hereinafter, also referred to as "repeating unit ( a1)”) The resin (A) contains at least one of the partial structure represented by the following general formula (1a) and the partial structure represented by the following general formula (1b), and the repeating unit (a1) of an aromatic group.
[化5]
所述通式（1a）中， R1 及R2 分別獨立地表示氫原子或有機基。R1 與R2 可彼此鍵結而形成環。 *表示鍵結位置。 所述通式（1b）中， R3 分別獨立地表示氫原子或有機基。 R4 分別獨立地表示氫原子或有機基。 *表示鍵結位置。In the general formula (1a), R 1 and R 2 each independently represent a hydrogen atom or an organic group. R 1 and R 2 may be bonded to each other to form a ring. * Indicates the position of the bond. In the general formula (1b), R 3 each independently represents a hydrogen atom or an organic group. R 4 each independently represents a hydrogen atom or an organic group. * Indicates the position of the bond.
作為R1 及R2 的有機基並無特別限定，具體而言可列舉：烷基、環烷基、芳基、雜芳基、烷基羰基、芳基羰基、烷基磺醯基或芳基磺醯基。The organic group for R 1 and R 2 is not particularly limited, and specific examples include an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, an alkylcarbonyl group, an arylcarbonyl group, an alkylsulfonyl group, or an aryl group. Sulfonyl.
烷基可為直鏈狀或支鏈狀，較佳為碳數1～20，更佳為碳數1～15。 環烷基可為單環或多環，較佳為碳數3～20，更佳為碳數5～15。 芳基較佳為碳數6～20，更佳為碳數6～15。 雜芳基較佳為碳數為4～20，更佳為碳數4～15。 烷基羰基可為直鏈狀或支鏈狀，較佳為碳數2～20，更佳為碳數2～15。 芳基羰基較佳為碳數7～20，更佳為碳數7～15。 烷基磺醯基可為直鏈狀或支鏈狀，較佳為碳數1～20，更佳為碳數1～15。 芳基磺醯基較佳為碳數6～20，更佳為碳數6～15。The alkyl group may be linear or branched, and preferably has 1 to 20 carbon atoms, and more preferably has 1 to 15 carbon atoms. The cycloalkyl group may be monocyclic or polycyclic, preferably having 3-20 carbons, more preferably 5-15 carbons. The aryl group preferably has 6 to 20 carbon atoms, more preferably 6 to 15 carbon atoms. The heteroaryl group preferably has 4 to 20 carbon atoms, more preferably 4 to 15 carbon atoms. The alkylcarbonyl group may be linear or branched, and preferably has 2 to 20 carbon atoms, more preferably 2 to 15 carbon atoms. The arylcarbonyl group preferably has 7 to 20 carbon atoms, more preferably 7 to 15 carbon atoms. The alkylsulfonyl group may be linear or branched, and preferably has 1-20 carbon atoms, more preferably 1-15 carbon atoms. The arylsulfonyl group preferably has 6 to 20 carbon atoms, more preferably 6 to 15 carbon atoms.
所述有機基可具有酸分解性基。作為酸分解性基，可列舉後述的作為具有酸分解性基的重複單元中的酸分解性基而記載者。The organic group may have an acid-decomposable group. Examples of the acid-decomposable group include those described below as the acid-decomposable group in the repeating unit having an acid-decomposable group.
所述有機基可更具有取代基。進一步的取代基沒有特別限定，但較佳為所述取代基T，更佳為羥基、羧基、烷氧基、烷氧基羰基、及該些的組合。 R1 、R2 較佳為至少任一者為氫原子，更佳為任一者為氫原子。The organic group may further have a substituent. Further substituents are not particularly limited, but the substituents T are preferred, and hydroxy, carboxy, alkoxy, alkoxycarbonyl, and combinations of these are more preferred. Preferably, at least one of R 1 and R 2 is a hydrogen atom, and more preferably any one is a hydrogen atom.
作為R3 的有機基並無特別限定，具體而言可列舉：烷基、環烷基、芳基或雜芳基。 烷基可為直鏈狀或支鏈狀，較佳為碳數1～20，更佳為碳數1～15。 環烷基可為單環或多環，較佳為碳數3～20，更佳為碳數5～15。 芳基較佳為碳數6～20，更佳為碳數6～15。 雜芳基較佳為碳數為4～20，更佳為碳數4～15。The organic group for R 3 is not particularly limited, and specifically includes an alkyl group, a cycloalkyl group, an aryl group, or a heteroaryl group. The alkyl group may be linear or branched, and preferably has 1 to 20 carbon atoms, and more preferably has 1 to 15 carbon atoms. The cycloalkyl group may be monocyclic or polycyclic, preferably having 3-20 carbons, more preferably 5-15 carbons. The aryl group preferably has 6 to 20 carbon atoms, more preferably 6 to 15 carbon atoms. The heteroaryl group preferably has 4 to 20 carbon atoms, more preferably 4 to 15 carbon atoms.
所述有機基可更具有取代基。進一步的取代基並無特別限定，較佳為所述取代基T。The organic group may further have a substituent. The further substituent is not particularly limited, but the substituent T is preferred.
作為R4 的有機基並無特別限定，具體而言可列舉：烷基、環烷基、芳基或雜芳基。 烷基可為直鏈狀或支鏈狀，較佳為碳數1～20，更佳為碳數1～15。 環烷基可為單環或多環，較佳為碳數3～20，更佳為碳數5～15。 芳基較佳為碳數6～20，更佳為碳數6～15。 雜芳基較佳為碳數4～20，更佳為碳數4～15。The organic group for R 4 is not particularly limited, and specific examples include an alkyl group, a cycloalkyl group, an aryl group, or a heteroaryl group. The alkyl group may be linear or branched, and preferably has 1 to 20 carbon atoms, and more preferably has 1 to 15 carbon atoms. The cycloalkyl group may be monocyclic or polycyclic, preferably having 3-20 carbons, more preferably 5-15 carbons. The aryl group preferably has 6 to 20 carbon atoms, more preferably 6 to 15 carbon atoms. The heteroaryl group preferably has 4 to 20 carbon atoms, more preferably 4 to 15 carbon atoms.
所述有機基可更具有取代基。進一步的取代基並無特別限定，較佳為所述取代基T。The organic group may further have a substituent. The further substituent is not particularly limited, but the substituent T is preferred.
重複單元（a1）具有芳香族基。 構成芳香族基的芳香環沒有特別限定，例如可列舉碳數1～20的芳香環，具體而言，可列舉苯環、萘環、蒽環、噻吩環等。較佳為苯環或萘環，更佳為苯環。The repeating unit (a1) has an aromatic group. The aromatic ring constituting the aromatic group is not particularly limited, and examples thereof include aromatic rings having 1 to 20 carbon atoms, and specific examples include a benzene ring, a naphthalene ring, an anthracene ring, and a thiophene ring. Preferably it is a benzene ring or a naphthalene ring, More preferably, it is a benzene ring.
所述芳香族基亦可更具有取代基。進一步的取代基並無特別限定，較佳為所述取代基T。The aromatic group may further have a substituent. The further substituent is not particularly limited, but the substituent T is preferred.
重複單元（a1）較佳為於側鏈上具有所述通式（1a）所表示的部分結構及所述通式（1b）所表示的部分結構的至少一者。The repeating unit (a1) preferably has at least one of the partial structure represented by the general formula (1a) and the partial structure represented by the general formula (1b) on the side chain.
所述重複單元（a1）較佳為由下述通式（2a）或通式（2b）表示。The repeating unit (a1) is preferably represented by the following general formula (2a) or general formula (2b).
[化6]
所述通式（2a）中， X1 表示氫原子、鹵素原子、氰基、或有機基。 Y1 表示單鍵或二價連結基。 Z1 表示單鍵或（n1 +1）價連結基。 R21 及R22 分別獨立地表示氫原子或有機基。R21 與R22 可彼此鍵結而形成環。 n1 表示1以上的整數。於n1 表示2以上的整數的情況下，多個R21 可相同亦可不同，多個R22 可相同亦可不同。 X1 、Y1 、Z1 、R21 及R22 的至少一者包含芳香族基。 所述通式（2b）中， X2 表示氫原子、鹵素原子、氰基、或有機基。 Y2 表示單鍵或二價連結基。 Z2 表示單鍵或（n2 +1）價連結基。 R23 表示氫原子或有機基。 R24 表示氫原子或有機基。 n2 表示1以上的整數。於n2 表示2以上的整數的情況下，多個R23 可相同亦可不同，多個R24 可相同亦可不同。 X2 、Y2 、Z2 、R23 及R24 的至少一者包含芳香族基。In the general formula (2a), X 1 represents a hydrogen atom, a halogen atom, a cyano group, or an organic group. Y 1 represents a single bond or a divalent linking group. Z 1 represents a single bond or (n 1 +1) valence linking group. R 21 and R 22 each independently represent a hydrogen atom or an organic group. R 21 and R 22 may be bonded to each other to form a ring. n 1 represents an integer of 1 or more. When n 1 represents an integer of 2 or more, a plurality of R 21 may be the same or different, and a plurality of R 22 may be the same or different. At least one of X 1 , Y 1 , Z 1 , R 21, and R 22 includes an aromatic group. In the general formula (2b), X 2 represents a hydrogen atom, a halogen atom, a cyano group, or an organic group. Y 2 represents a single bond or a divalent linking group. Z 2 represents a single bond or (n 2 +1) valence linking group. R 23 represents a hydrogen atom or an organic group. R 24 represents a hydrogen atom or an organic group. n 2 represents an integer of 1 or more. When n 2 represents an integer of 2 or more, a plurality of R 23 may be the same or different, and a plurality of R 24 may be the same or different. At least one of X 2 , Y 2 , Z 2 , R 23 and R 24 includes an aromatic group.
作為X1 的有機基並無特別限定，具體而言可列舉：烷基、環烷基、或芳基。 烷基可為直鏈狀或支鏈狀，較佳為碳數1～20，更佳為碳數1～15。 環烷基可為單環或多環，較佳為碳數3～20，更佳為碳數5～15。 芳基較佳為碳數6～20，更佳為碳數6～15。The organic group of X 1 is not particularly limited, and specifically, an alkyl group, a cycloalkyl group, or an aryl group can be mentioned. The alkyl group may be linear or branched, and preferably has 1 to 20 carbon atoms, and more preferably has 1 to 15 carbon atoms. The cycloalkyl group may be monocyclic or polycyclic, preferably having 3-20 carbons, more preferably 5-15 carbons. The aryl group preferably has 6 to 20 carbon atoms, more preferably 6 to 15 carbon atoms.
所述有機基可更具有取代基。進一步的取代基並無特別限定，較佳為所述取代基T。The organic group may further have a substituent. The further substituent is not particularly limited, but the substituent T is preferred.
作為Y1 的2價連結基沒有特別限定，表示伸烷基、伸環烷基、芳香族基、-CO-、-COO-、-SO-、-SO2 -、-CONR5 -及將該些組合兩個以上而成的基，R5 表示氫原子或烷基。 伸烷基可為直鏈狀或支鏈狀，較佳為碳數1～20，進而佳為碳數1～10。 伸環烷基可為單環亦可為多環，較佳為碳數3～20，進而佳為碳數3～10。 芳香族基較佳為碳數6～20的芳香族基，進而佳為碳數6～15的芳香族基。 作為R5 的烷基可為直鏈狀或支鏈狀，較佳為碳數1～20，更佳為碳數1～10。The divalent linking group of Y 1 is not particularly limited, and it represents an alkylene group, a cycloalkylene group, an aromatic group, -CO-, -COO-, -SO-, -SO 2 -, -CONR 5 -and the These groups are a combination of two or more, and R 5 represents a hydrogen atom or an alkyl group. The alkylene group may be linear or branched, and preferably has 1 to 20 carbon atoms, and more preferably has 1 to 10 carbon atoms. The cycloalkylene group may be monocyclic or polycyclic, and preferably has 3 to 20 carbon atoms, and more preferably has 3 to 10 carbon atoms. The aromatic group is preferably an aromatic group having 6 to 20 carbon atoms, and more preferably an aromatic group having 6 to 15 carbon atoms. The alkyl group as R 5 may be linear or branched, and preferably has 1 to 20 carbon atoms, and more preferably has 1 to 10 carbon atoms.
Z1 表示單鍵或（n1 +1）價連結基。 作為Z1 的（n1 +1）價連結基，例如可列舉自所述作為Y1 的2價連結基除去（n1 -1）個氫原子而得的基。Z 1 represents a single bond or (n 1 +1) valence linking group. As the (n 1 +1)-valent linking group of Z 1 , for example, a group obtained by removing (n 1 -1) hydrogen atoms from the above-mentioned divalent linking group as Y 1 is mentioned.
R21 及R22 分別獨立地表示氫原子或有機基。 作為R21 及R22 的有機基與作為R1 及R2 記載的有機基相同。R 21 and R 22 each independently represent a hydrogen atom or an organic group. The organic groups as R 21 and R 22 are the same as the organic groups described as R 1 and R 2.
n1 表示1以上的整數。n1 的上限值並無特別限定，較佳為5以下。 n1 進而佳為1～2的整數。 X1 、Y1 、Z1 、R21 及R22 的至少一者包含芳香族基。n 1 represents an integer of 1 or more. The upper limit of n 1 is not particularly limited, but it is preferably 5 or less. More preferably, n 1 is an integer of 1-2. At least one of X 1 , Y 1 , Z 1 , R 21, and R 22 includes an aromatic group.
作為X2 的有機基與作為X1 記載的有機基相同。 作為Y2 的2價連結基與作為Y1 記載的2價連結基相同。 Z2 表示單鍵或（n2 +1）價連結基。 作為Z2 的（n2 +1）價連結基，例如可列舉自所述作為Y2 的2價連結基除去（n2 -1）個氫原子而得的基。 作為R23 的有機基與作為R3 記載的有機基相同。 作為R24 的有機基與作為R4 記載的有機基相同。The organic group as X 2 is the same as the organic group described as X 1. Y 2 as the divalent linking group and 2 as the divalent Y 1 according to the same link group. Z 2 represents a single bond or (n 2 +1) valence linking group. As the (n 2 +1)-valent linking group of Z 2 , for example, a group obtained by removing (n 2 -1) hydrogen atoms from the above-mentioned divalent linking group as Y 2 is mentioned. The organic group as R 23 is the same as the organic group described as R 3. The organic group as R 24 is the same as the organic group described as R 4.
n2 表示1以上的整數。n2 的上限值並無特別限定，較佳為5以下。 n2 進而佳為1～2的整數。 X2 、Y2 、Z2 、R23 及R24 的至少一者包含芳香族基。n 2 represents an integer of 1 or more. The upper limit of n 2 is not particularly limited, but it is preferably 5 or less. n 2 is more preferably an integer of 1-2. At least one of X 2 , Y 2 , Z 2 , R 23 and R 24 includes an aromatic group.
所述通式（2a）或通式（2b）所表示的重複單元較佳為下述通式（3）所表示的重複單元。The repeating unit represented by the general formula (2a) or the general formula (2b) is preferably a repeating unit represented by the following general formula (3).
[化7]
所述通式（3）中， X3 表示氫原子、鹵素原子、烷基、環烷基、或氰基。 Y3 表示單鍵或二價連結基。 Ar表示芳香族基。 Z3 表示單鍵或（n+1）價連結基。 R31 及R32 分別獨立地表示氫原子或有機基。R31 與R32 可彼此鍵結而形成環。 n表示1以上的整數。於n表示2以上的整數的情況下，多個R31 可相同亦可不同，多個R32 可相同亦可不同。In the general formula (3), X 3 represents a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, or a cyano group. Y 3 represents a single bond or a divalent linking group. Ar represents an aromatic group. Z 3 represents a single bond or (n+1) valence linking group. R 31 and R 32 each independently represent a hydrogen atom or an organic group. R 31 and R 32 may be bonded to each other to form a ring. n represents an integer of 1 or more. When n represents an integer of 2 or more, a plurality of R 31 may be the same or different, and a plurality of R 32 may be the same or different.
作為X3 的烷基與作為X1 的有機基記載的烷基相同。 作為X3 的環烷基與作為X1 的有機基記載的環烷基相同。The alkyl group as X 3 is the same as the alkyl group described as the organic group of X 1. The cycloalkyl group as X 3 is the same as the cycloalkyl group described as the organic group X 1.
作為X3 的烷基、環烷基可更具有取代基。 Y3 表示單鍵或二價連結基。 作為Y3 的2價連結基與作為Y1 記載的2價連結基相同。 Ar表示芳香族基。 芳香族基為2價芳香族基，較佳為碳數6～20的芳香族基，更佳為碳數6～15的芳香族基。 再者，Z3 表示單鍵，且n表示2以上的整數時，Ar表示（n+1）價芳香族基，具體而言，是自上述2價芳香族基中除去（n-1）個氫原子而成的基。 Z3 表示單鍵或（n+1）價連結基。 作為Z3 的（n+1）價連結基，例如可列舉自所述作為Y3 的2價連結基除去（n-1）個氫原子而得的基。 R31 及R32 分別獨立地表示氫原子或有機基。 作為R31 及R32 的有機基與作為R1 及R2 記載的有機基相同。The alkyl group and cycloalkyl group as X 3 may further have a substituent. Y 3 represents a single bond or a divalent linking group. The divalent linking group as Y 3 is the same as the divalent linking group described as Y 1. Ar represents an aromatic group. The aromatic group is a divalent aromatic group, preferably an aromatic group having 6 to 20 carbons, and more preferably an aromatic group having 6 to 15 carbons. In addition, when Z 3 represents a single bond and n represents an integer of 2 or more, Ar represents an (n+1)-valent aromatic group, specifically, (n-1) are removed from the above-mentioned divalent aromatic group A radical made of hydrogen atoms. Z 3 represents a single bond or (n+1) valence linking group. Examples of the (n+1)-valent linking group of Z 3 include groups obtained by removing (n-1) hydrogen atoms from the above-mentioned divalent linking group as Y 3. R 31 and R 32 each independently represent a hydrogen atom or an organic group. The organic groups as R 31 and R 32 are the same as the organic groups described as R 1 and R 2.
n表示1以上的整數。n的上限值並無特別限定，較佳為5以下。 n進而佳為1～2的整數。 所述通式（3）中的Y3 表示單鍵、-COO-或-CONR6 -，R6 較佳為表示氫原子或烷基。 所述通式（3）中的Z3 較佳為表示單鍵。 所述通式（3）中的R31 及R32 較佳為分別獨立地表示氫原子、烷基、環烷基、芳基、烷基羰基、芳基羰基、烷基磺醯基、或芳基磺醯基。 作為R31 及R32 的烷基、環烷基、芳基、烷基羰基、芳基羰基、烷基磺醯基、或芳基磺醯基分別與作為R1 及R2 的有機基記載的烷基、環烷基、芳基、烷基羰基、芳基羰基、烷基磺醯基、或芳基磺醯基相同。n represents an integer of 1 or more. The upper limit of n is not particularly limited, but it is preferably 5 or less. More preferably, n is an integer of 1-2. Y 3 in the general formula (3) represents a single bond, -COO- or -CONR 6 -, and R 6 preferably represents a hydrogen atom or an alkyl group. Z 3 in the general formula (3) preferably represents a single bond. R 31 and R 32 in the general formula (3) preferably each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkylcarbonyl group, an arylcarbonyl group, an alkylsulfonyl group, or an aryl group. Sulfonyl. As the alkyl group, cycloalkyl group, aryl group, alkylcarbonyl group, arylcarbonyl group, alkylsulfonyl group, or arylsulfonyl group of R 31 and R 32 and the organic group of R 1 and R 2, respectively The alkyl group, cycloalkyl group, aryl group, alkylcarbonyl group, arylcarbonyl group, alkylsulfonyl group, or arylsulfonyl group are the same.
作為R31 及R32 的烷基、環烷基、芳基、烷基羰基、芳基羰基、烷基磺醯基、或芳基磺醯基可更具有取代基。The alkyl group, cycloalkyl group, aryl group, alkylcarbonyl group, arylcarbonyl group, alkylsulfonyl group, or arylsulfonyl group as R 31 and R 32 may further have a substituent.
所述通式（3）較佳為由下述通式（4）表示。The general formula (3) is preferably represented by the following general formula (4).
[化8]
通式（4）中， X4 表示氫原子、鹵素原子、烷基、環烷基或氰基。 Y4 表示單鍵或二價連結基。 R41 表示氫原子、烷基、環烷基、芳基、烷基羰基、芳基羰基、烷基磺醯基或芳基磺醯基。In the general formula (4), X 4 represents a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, or a cyano group. Y 4 represents a single bond or a divalent linking group. R 41 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkylcarbonyl group, an arylcarbonyl group, an alkylsulfonyl group, or an arylsulfonyl group.
作為X4 的烷基與作為X1 的有機基記載的烷基相同。 作為X4 的環烷基與作為X1 的有機基記載的環烷基相同。 作為X4 的烷基、環烷基可更具有取代基。The alkyl group as X 4 is the same as the alkyl group described as the organic group of X 1. The cycloalkyl group as X 4 is the same as the cycloalkyl group described as the organic group X 1. The alkyl group and cycloalkyl group as X 4 may further have a substituent.
作為Y4 的2價連結基與作為Y1 記載的2價連結基相同。 作為R41 的烷基、環烷基、芳基、烷基羰基、芳基羰基、烷基磺醯基、或芳基磺醯基分別與作為R1 及R2 的有機基記載的烷基、環烷基、芳基、烷基羰基、芳基羰基、烷基磺醯基、或芳基磺醯基相同。The divalent linking group as Y 4 is the same as the divalent linking group described as Y 1. The alkyl group, cycloalkyl group, aryl group, alkylcarbonyl group, arylcarbonyl group, alkylsulfonyl group, or arylsulfonyl group as R 41 and the alkyl group described as the organic group of R 1 and R 2, respectively Cycloalkyl, aryl, alkylcarbonyl, arylcarbonyl, alkylsulfonyl, or arylsulfonyl are the same.
所述通式（4）中的R41 較佳為表示烷基羰基或芳基羰基。 R 41 in the general formula (4) preferably represents an alkylcarbonyl group or an arylcarbonyl group.
樹脂（A）中的重複單元（a1）的含量相對於樹脂（A）的全部重複單元較佳為7莫耳%～60莫耳%，進而佳為10莫耳%～50莫耳%，特佳為15莫耳%～50莫耳%。 作為較佳的一形態，相對於樹脂（A）中的全部重複單元，樹脂（A）中的重複單元（a1）的含量較佳為10莫耳%以上。The content of the repeating unit (a1) in the resin (A) is preferably 7 mol% to 60 mol%, and more preferably 10 mol% to 50 mol% with respect to all the repeating units of the resin (A). Preferably, it is 15 mol% to 50 mol%. As a preferable aspect, the content of the repeating unit (a1) in the resin (A) is preferably 10 mol% or more with respect to all the repeating units in the resin (A).
樹脂（A）中，重複單元（a1）可單獨使用一種，亦可使用兩種以上。In resin (A), repeating unit (a1) may be used individually by 1 type, and may use 2 or more types.
重複單元（a1）、及所述重複單元（a1）以外的重複單元的至少一者較佳為具有酸分解性基。 關於重複單元（a1）具有酸分解性基時的酸分解性基，作為酸分解性基，可列舉後述的作為具有酸分解性基的重複單元中的酸分解性基而記載者。At least one of the repeating unit (a1) and repeating units other than the repeating unit (a1) preferably has an acid-decomposable group. Regarding the acid-decomposable group when the repeating unit (a1) has an acid-decomposable group, examples of the acid-decomposable group include those described below as the acid-decomposable group in the repeating unit having an acid-decomposable group.
以下，例示相當於重複單元（a1）的重複單元，但本發明並不限定於該些重複單元。Hereinafter, the repeating unit corresponding to the repeating unit (a1) is exemplified, but the present invention is not limited to these repeating units.
[化9]
[化10]
（其他重複單元） 樹脂（A）亦可包含所述重複單元（a1）以外的重複單元。(Other repeating units) The resin (A) may include repeating units other than the repeating unit (a1).
所述樹脂（A）較佳為含有上述重複單元（a1），且為酸分解性樹脂。 樹脂（A）典型而言是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的樹脂。樹脂（A）具有因酸的作用分解而生成極性基的基（換言之，極性基由因酸的作用而脫離的脫離基所保護的結構）。亦將所述基（結構）稱為酸分解性基。具有酸分解性基的樹脂（即，含有具有酸分解性基的重複單元的樹脂）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。The resin (A) preferably contains the above-mentioned repeating unit (a1) and is an acid-decomposable resin. The resin (A) is typically a resin whose polarity increases due to the action of an acid, its solubility with respect to an alkaline developer increases, and its solubility with respect to an organic solvent decreases. The resin (A) has a group that is decomposed by the action of an acid to generate a polar group (in other words, the polar group is protected by a leaving group that is detached by the action of an acid). The group (structure) is also referred to as an acid-decomposable group. A resin having an acid-decomposable group (that is, a resin containing a repeating unit having an acid-decomposable group) 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.
（具有酸分解性基的重複單元） 樹脂（A）可更含有具有酸分解性基的重複單元（亦稱為「重複單元（a2）」）。(Repeating unit with acid-decomposable group) The resin (A) may further contain a repeating unit having an acid-decomposable group (also referred to as "repeating unit (a2)").
酸分解性基較佳為具有極性基由因酸的作用而脫離的基（脫離基）保護的結構。 作為極性基，例如可列舉：羧基、酚性羥基、氟化醇基、磺酸基、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（典型而言，2.38質量%四甲基氫氧化銨水溶液中解離的基）、以及醇性羥基等。The acid-decomposable group preferably has a structure in which a polar group is protected by a group (a leaving group) detached by the action of an acid. Examples of polar groups include carboxyl groups, phenolic hydroxyl groups, fluorinated alcohol groups, sulfonic acid groups, sulfonamide groups, sulfonylimine groups, (alkylsulfonyl) (alkylcarbonyl)methylene groups, (Alkylsulfonyl)(alkylcarbonyl)amido, bis(alkylcarbonyl)methylene, bis(alkylcarbonyl)amido, bis(alkylsulfonyl)methylene, Acidic groups such as bis(alkylsulfonyl)imino, tris(alkylcarbonyl)methylene, and tris(alkylsulfonyl)methylene (typically, 2.38% by mass tetramethylhydroxide Dissociated groups in ammonium aqueous solution) and alcoholic hydroxyl groups.
再者，所謂醇性羥基，是與烴基鍵結的羥基，是指直接鍵結在芳香環上的羥基（酚性羥基）以外的羥基，作為羥基，α位被氟原子等拉電子基取代的脂肪族醇（例如六氟異丙醇基等）除外。作為醇性羥基，較佳為pKa（酸解離常數）為12以上且20以下的羥基。In addition, the alcoholic hydroxyl group refers to a hydroxyl group bonded to a hydrocarbon group, and refers to a hydroxyl group other than a hydroxyl group (phenolic hydroxyl group) directly bonded to an aromatic ring. As a hydroxyl group, the α-position is substituted by an electron withdrawing group such as a fluorine atom. Aliphatic alcohols (such as hexafluoroisopropanol groups, etc.) are excluded. The alcoholic hydroxyl group is preferably a hydroxyl group having a pKa (acid dissociation constant) of 12 or more and 20 or less.
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。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基（脫離基），例如可列舉式（Y1）～式（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 group to be released by the action of the acid (a leaving group) include groups represented by formula (Y1) to formula (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）、或者芳基（單環或多環）。 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，並無特別限定，可列舉碳數1～20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，並無特別限定，可列舉碳數3～20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。 Rx1 ～Rx3 的芳基較佳為碳數6～14的芳基，例如可列舉：苯基、萘基及蒽基等。 烷基、環烷基及芳基可具有取代基。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), or an aryl group (monocyclic or Multiple loops). 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 not particularly limited. Examples include alkyl groups having 1 to 20 carbon atoms, and methyl, ethyl, n-propyl, isopropyl, n-butyl, and isobutyl are preferred. And C1-C4 alkyl groups such as the tertiary butyl group. The cycloalkyl group of Rx 1 to Rx 3 is not particularly limited. Examples include cycloalkyl groups having 3 to 20 carbon atoms, and monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl, and norbornyl groups are preferred. Polycyclic cycloalkyl groups such as tetracyclodecyl, tetracyclododecyl and adamantyl. The aryl group of Rx 1 to Rx 3 is preferably an aryl group having 6 to 14 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, and an anthryl group. The alkyl group, cycloalkyl group, and aryl group may have a substituent.
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、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，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或羰基等具有雜原子的基取代。 Rx1 ～Rx3 的兩個鍵結而形成的環烷基可具有取代基。As the cycloalkyl formed by the two bonds of Rx 1 to Rx 3 , monocyclic cycloalkyls such as cyclopentyl and cyclohexyl, norbornyl, tetracyclodecyl, and tetracyclododecane are preferred. The polycyclic cycloalkyl group, such as an adamantyl group and an adamantyl group, is more preferably a C5-6 monocyclic cycloalkyl group. 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 heteroatom such as an oxygen atom or a group having a heteroatom such as a carbonyl group. The cycloalkyl group formed by bonding two of Rx 1 to Rx 3 may have a substituent.
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。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.
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).
[化11]
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）或活性化能量變高，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) or activation energy becomes 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.
樹脂（A）較佳為具有縮醛結構。 酸分解性基較佳為具有縮醛結構。縮醛結構例如是羧基、酚性羥基、氟化醇基等極性基被所述式（Y3）所表示的基保護的結構。The resin (A) preferably has an acetal structure. The acid-decomposable group preferably has an acetal structure. The acetal structure is, for example, a structure in which a polar group such as a carboxyl group, a phenolic hydroxyl group, and a fluorinated alcohol group is protected by a group represented by the formula (Y3).
作為具有酸分解性基的重複單元，較佳為式（A）所表示的重複單元。The repeating unit having an acid-decomposable group is preferably a repeating unit represented by formula (A).
[化12]
L1 表示2價連結基，R1 ～R3 分別獨立地表示氫原子或1價取代基，R4 表示藉由酸的作用而分解並脫離的基。 L1 表示二價連結基。作為二價連結基，可列舉-CO-、-O-、-S-、-SO-、-SO2 -、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-、伸芳基。 作為伸芳基，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。L 1 represents a divalent linking group, R 1 to R 3 each independently represent a hydrogen atom or a monovalent substituent, and R 4 represents a group that is decomposed and released by the action of an acid. L 1 represents a divalent linking group. Examples of the divalent linking group include -CO-, -O-, -S-, -SO-, -SO 2 -, hydrocarbon groups (for example, alkylene, cycloalkylene, alkenylene, arylene, etc.) ), as well as the connecting base formed by these multiple connections. Among them, as L 1 , -CO- and an aryl group are preferred. As the arylene group, a phenylene group is preferred. 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.
R1 ～R3 分別獨立地表示氫原子或一價取代基。作為1價取代基，例如可列舉：烷基、環烷基、或鹵素原子。 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。 環烷基可為單環型，亦可為多環型。該環烷基的碳數較佳為3～8。 作為鹵素原子，例如可列舉：氟原子、氯原子、溴原子及碘原子。R 1 to R 3 each independently represent a hydrogen atom or a monovalent substituent. As a monovalent substituent, an alkyl group, a cycloalkyl group, or a halogen atom is mentioned, for example. 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 cycloalkyl group may be monocyclic or polycyclic. The carbon number of the cycloalkyl group is preferably 3-8. As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned, for example.
R4 表示藉由酸的作用而脫離的基（脫離基）。 其中，作為脫離基，可列舉所述式（Y1）～式（Y4）所表示的基，較佳為所述式（Y3）所表示的基。R 4 represents a group released by the action of an acid (a leaving group). Among them, as the leaving group, the group represented by the formula (Y1) to the formula (Y4) is exemplified, and the group represented by the formula (Y3) is preferred.
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).
[化13]
通式（AI）中， Xa1 表示氫原子或烷基。 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）、或者環烷基（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2個可鍵結而形成環烷基（單環或多環）。In the general formula (AI), Xa 1 represents a hydrogen atom or an alkyl group. T represents a single bond or a divalent linking group. Rx 1 to Rx 3 each independently represent an alkyl group (linear or branched) or a cycloalkyl group (monocyclic or polycyclic). 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 cycloalkyl group (monocyclic or polycyclic).
作為Xa1 所表示的烷基，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）、羥基或一價的有機基，例如可列舉碳數5以下的烷基、及碳數5以下的醯基，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 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, for example, an alkyl group having 5 or less carbon atoms and an acyl group having 5 or less carbon atoms, preferably an alkyl group having 3 or less carbon atoms, More preferably, it is methyl. 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。Examples of the divalent linking group of T include alkylene groups, aromatic ring groups, -COO-Rt- groups, and -O-Rt- groups. 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 group 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或羰基等具有雜原子的基取代。 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. 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 heteroatom such as an oxygen atom or a group having a heteroatom such as a carbonyl group. 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).
樹脂（A）可單獨含有一種具有酸分解性基的重複單元，亦可併用且含有兩種以上。Resin (A) may contain the repeating unit which has an acid-decomposable group individually by 1 type, and may use together and contain 2 or more types.
所述重複單元（a1）具有酸分解性基時，所述重複單元（a1）亦相當於重複單元（a2）。When the repeating unit (a1) has an acid-decomposable group, the repeating unit (a1) also corresponds to the repeating unit (a2).
相對於樹脂（A）的全部重複單元，樹脂（A）所含的具有酸分解性基的重複單元的含量（於存在多個具有酸分解性基的重複單元的情況下為其合計）較佳為10莫耳%～90莫耳%，更佳為20莫耳%～80莫耳%，進而佳為25莫耳%～75莫耳%。Relative to all the repeating units of the resin (A), the content of the acid-decomposable group-containing repeating unit contained in the resin (A) (in the case where there are a plurality of acid-decomposable group-containing repeating units, the total is preferable) It is 10 mol% to 90 mol%, more preferably 20 mol% to 80 mol%, and still more preferably 25 mol% to 75 mol%.
（具有內酯基或磺內酯基的重複單元） 樹脂（A）亦可更含有具有內酯基或磺內酯基的重複單元（亦稱為「重複單元（a3）」）。 作為內酯基或磺內酯基，只要具有內酯結構或磺內酯結構則可使用任一種基，較佳為具有5員環～7員環內酯結構或5員環～7員環磺內酯結構的基，更佳為其他環結構以形成雙環結構或螺環結構的形式與5員環～7員環內酯結構縮環而成者，或者其他環結構以形成雙環結構或螺環結構的形式與5員環～7員環磺內酯結構縮環而成者。更佳為含有具有包含下述通式（LC1-1）～通式（LC1-22）的任一個所表示的內酯結構的基、或包含下述通式（SL1-1）或通式（SL1-3）的任一個所表示的磺內酯結構的基的重複單元。另外，具有內酯結構或磺內酯結構的基可直接鍵結於主鏈。 其中，較佳為通式（LC1-1）、通式（LC1-4）、通式（LC1-5）、通式（LC1-8）、通式（LC1-16）、通式（LC1-21）、或通式（LC1-22）所表示的內酯結構、或通式（SL1-1）所表示的磺內酯結構。(Repeating unit with lactone group or sultone group) The resin (A) may further contain a repeating unit having a lactone group or a sultone group (also referred to as "repeating unit (a3)"). As the lactone group or sultone group, any group can be used as long as it has a lactone structure or a sultone structure, and preferably has a 5- to 7-membered cyclic lactone structure or a 5- to 7-membered cyclic sulfonate The base of the lactone structure is more preferably formed by condensing other ring structures to form a bicyclic structure or a spiro ring structure with a 5- to 7-membered ring lactone structure, or other ring structures to form a bicyclic structure or a spiro ring The form of the structure is condensed with the 5-membered to 7-membered cyclic sultone structure. It is more preferable to include a group having a lactone structure represented by any one of the following general formula (LC1-1) to general formula (LC1-22), or to include the following general formula (SL1-1) or general formula ( The repeating unit of the group of the sultone structure represented by any one of SL1-3). In addition, a group having a lactone structure or a sultone structure may be directly bonded to the main chain. Among them, general formula (LC1-1), general formula (LC1-4), general formula (LC1-5), general formula (LC1-8), general formula (LC1-16), general formula (LC1- 21) Or the lactone structure represented by the general formula (LC1-22), or the sultone structure represented by the general formula (SL1-1).
[化14]
內酯結構部分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 moiety or the sultone moiety may 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. n2 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.
作為包含具有內酯結構或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。As a repeating unit containing the group which has a lactone structure or a sultone structure, the repeating unit etc. which are represented by the following general formula (AI), for example are mentioned.
[化15]
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。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表示具有內酯結構或磺內酯結構的基。 作為V的具有內酯結構或磺內酯結構的基，在所述通式（LC1-1）～（LC1-22）所表示的結構及通式（SL1-1）～（SL1-3）所表示的結構中的任一結構中，較佳為自構成內酯結構或磺內酯結構的一個碳原子中去除一個氫原子而成的基。再者，所述去除一個氫原子的碳原子較佳為並非構成取代基（Rb2 ）的碳原子。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 having a lactone structure or a sultone structure. The group having a lactone structure or a sultone structure of V is described in the structure represented by the general formulas (LC1-1) to (LC1-22) and the general formulas (SL1-1) to (SL1-3). In any of the structures shown, a group obtained by removing one hydrogen atom from one carbon atom constituting the lactone structure or the sultone structure is preferred. Furthermore, the carbon atom from which one hydrogen atom is removed is preferably a carbon atom that does not constitute the substituent (Rb 2 ).
含有具有內酯結構或磺內酯結構的基的重複單元通常存在光學異構物，可使用任一種光學異構物。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。The repeating unit containing a group having a lactone structure or a sultone structure usually has an optical isomer, and 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.
以下列舉包含具有內酯結構或磺內酯結構的基的重複單元的具體例，但本發明並不限定於該些。再者，式中Rx表示H、CH3 、CH2 OH或CF3 。Specific examples of the repeating unit including a group having a lactone structure or a sultone structure are listed below, but the present invention is not limited to these. Furthermore, in the formula, Rx represents H, CH 3 , CH 2 OH or CF 3 .
[化16]
[化17]
於樹脂（A）具有重複單元（a3）的情況下，相對於樹脂（A）中的全部重複單元，該重複單元的含量較佳為1莫耳%～50莫耳%，更佳為5莫耳%～40莫耳%，進而佳為10莫耳%～40莫耳%。When the resin (A) has a repeating unit (a3), relative to all repeating units in the resin (A), the content of the repeating unit is preferably 1 mol% to 50 mol%, more preferably 5 mol% Ear%-40 mol%, more preferably 10 mol%-40 mol%.
（具有碳酸酯基的重複單元） 樹脂（A）亦可更含有具有碳酸酯基的重複單元（亦稱為「重複單元（a4）」）。(Repeating unit with carbonate group) The resin (A) may further contain a repeating unit having a carbonate group (also referred to as "repeating unit (a4)").
具有碳酸酯基的重複單元中的碳酸酯基較佳為包含在環狀碳酸酯基中。 具有碳酸酯基的重複單元較佳為通式（A4）所表示的重複單元。The carbonate group in the repeating unit having a carbonate group is preferably contained in a cyclic carbonate group. The repeating unit having a carbonate group is preferably a repeating unit represented by general formula (A4).
[化18]
通式（A4）中， RA 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（較佳為0～3）的整數。 RA 2 表示取代基。於n為2以上的情況下，多個存在的RA2可分別相同亦可不同。 A表示單鍵或二價連結基。所述二價連結基較佳為伸烷基（較佳為碳數1～4）、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、羧酸基、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。 Z與式中的-O-CO-O-所表示的基一起形成的單環或多環較佳為5員環的環狀碳酸酯基，更佳為下述通式（CC1-1）所表示的環狀碳酸酯結構。 即，通式（A4）中的A較佳為與自下述通式（CC1-1）所表示的環狀碳酸酯結構的環員原子中去掉一個氫原子而成的基鍵結。In the general formula (A4), 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 (preferably 0 to 3). R A 2 represents a substituent. In the case where n is 2 or more, a plurality of RA2s 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 (preferably with a carbon number of 1 to 4), a divalent linking group having a monocyclic or polycyclic alicyclic hydrocarbon structure, ether group, ester group, carbonyl group, carboxylic acid Group, or a divalent group formed by combining these groups. Z represents an atomic group that forms a monocyclic or polycyclic ring together with the group represented by -O-CO-O- in the formula. The monocyclic or polycyclic ring formed by Z and the group represented by -O-CO-O- in the formula is preferably a 5-membered cyclic carbonate group, and more preferably is represented by the following general formula (CC1-1) Represents the cyclic carbonate structure. That is, A in the general formula (A4) is preferably bonded to a group obtained by removing one hydrogen atom from the ring member atoms of the cyclic carbonate structure represented by the following general formula (CC1-1).
[化19]
通式（CC1-1）中的環狀碳酸酯結構部分亦可具有取代基（Rb2 ）。作為較佳的取代基（Rb2 ），例如可列舉：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、羧酸基、鹵素原子（較佳為氟原子）、羥基及氰基等。n3表示0或1的整數。The cyclic carbonate structure part in general formula (CC1-1) may have a substituent (Rb 2 ). Preferred substituents (Rb 2 ) include, for example, alkyl groups having 1 to 8 carbons, cycloalkyl groups having 4 to 7 carbons, alkoxy groups having 1 to 8 carbons, and those having 1 to 8 carbons. An alkoxycarbonyl group, a carboxylic acid group, a halogen atom (preferably a fluorine atom), a hydroxyl group, a cyano group, and the like. n3 represents an integer of 0 or 1.
於樹脂（A）具有重複單元（a4）的情況下，相對於樹脂（A）的全部重複單元，該重複單元的含量較佳為1莫耳%～60莫耳%，更佳為5莫耳%～50莫耳%，進而佳為7莫耳%～45莫耳%。 重複單元（a4）可單獨使用一種，亦可使用兩種以上。When the resin (A) has a repeating unit (a4), relative to all repeating units of the resin (A), the content of the repeating unit is preferably 1 mol% to 60 mol%, more preferably 5 mol% %～50 mol%, more preferably 7 mol%～45 mol%. One type of repeating unit (a4) may be used alone, or two or more types may be used.
（具有極性基的重複單元） 樹脂（A）亦可進而包含與重複單元（a1）、重複單元（a3）、重複單元（a4）不同的具有極性基的重複單元（亦稱為「重複單元（a5）」）。(Repeating unit with polar group) The resin (A) may further include a repeating unit having a polar group different from the repeating unit (a1), the repeating unit (a3), and the repeating unit (a4) (also referred to as "repeating unit (a5)").
作為重複單元（a5）所具有的極性基，較佳為選自由磺酸酯基、羧酸基、磺酸基、胺甲酸酯基、醇性羥基、氟化醇基（較佳為六氟異丙醇基）、亞碸基、磺醯基、酮基、醯亞胺基、醯胺基、磺醯亞胺基、氰基、硝基、及酯基所組成的群組中的至少一種基。The polar group of the repeating unit (a5) is preferably selected from the group consisting of sulfonate group, carboxylic acid group, sulfonic acid group, urethane group, alcoholic hydroxyl group, fluorinated alcohol group (preferably hexafluoroalcohol group). At least one of the group consisting of isopropanol group), sulfonylene group, sulfonyl group, keto group, amide group, amide group, sulfonamide group, cyano group, nitro group, and ester group base.
作為較佳的一形態，重複單元（a5）較佳為通式（A5）所表示的重複單元。As a preferable aspect, the repeating unit (a5) is preferably a repeating unit represented by the general formula (A5).
[化20]
通式（A5）中， XQ5 表示氫原子、鹵素原子或一價有機基（較佳為甲基）。 RQ5 表示伸烷基（直鏈狀或支鏈狀。較佳為碳數1～5）或非芳香族性環基。In the general formula (A5), X Q5 represents a hydrogen atom, a halogen atom, or a monovalent organic group (preferably a methyl group). R Q5 represents an alkylene group (straight-chain or branched. Preferably, it has a carbon number of 1 to 5) or a non-aromatic cyclic group.
作為所述非芳香族性環基，例如可列舉單環式烴環基及多環式烴環基。作為單環式烴環基，例如可列舉碳數3～12（較佳為碳數3～7）的環烷烴環基、以及碳數3～12的環烯烴環基。 作為多環式烴環基，例如可列舉環集合烴環基及交聯環式烴環基。 作為交聯環式烴環，例如可列舉：雙環式烴環、三環式烴環及四環式烴環等。另外，交聯環式烴環亦可為縮合有多個5員環烷烴環～8員環烷烴環而成的縮合環。 交聯環式烴環基較佳為降冰片烷環基、金剛烷環基、雙環辛烷環基或三環[5.2.1.02,6 ]癸烷環基。Examples of the non-aromatic cyclic group include a monocyclic hydrocarbon ring group and a polycyclic hydrocarbon ring group. Examples of monocyclic hydrocarbon ring groups include cycloalkane ring groups having 3 to 12 carbon atoms (preferably 3 to 7 carbon atoms) and cycloolefin ring groups having 3 to 12 carbon atoms. As the polycyclic hydrocarbon ring group, for example, a ring assembly hydrocarbon ring group and a crosslinked cyclic hydrocarbon ring group can be cited. As a crosslinked cyclic hydrocarbon ring, a bicyclic hydrocarbon ring, a tricyclic hydrocarbon ring, a tetracyclic hydrocarbon ring, etc. are mentioned, for example. In addition, the crosslinked cyclic hydrocarbon ring may be a condensed ring formed by condensing a plurality of 5-membered cycloalkane rings to 8-membered cycloalkane rings. The crosslinked cyclic hydrocarbon ring group is preferably a norbornane ring group, an adamantane ring group, a bicyclooctane ring group, or a tricyclic [5.2.1.0 2,6 ] decane ring group.
所述烷基及所述非芳香族性環基亦較佳為不具有-(OH)q5 以外的取代基。It is also preferable that the alkyl group and the non-aromatic cyclic group have no substituents other than -(OH)q5.
通式（A5）中，q5表示1～5的整數。 另外，作為較佳的一形態，重複單元（a5）較佳為通式（A6）所表示的重複單元。In general formula (A5), q5 represents an integer of 1-5. In addition, as a preferable aspect, the repeating unit (a5) is preferably a repeating unit represented by the general formula (A6).
[化21]
通式（A6）中， XQ6 表示氫原子、鹵素原子或一價有機基（較佳為甲基）。 RQ6 表示伸烷基（直鏈狀或支鏈狀。較佳為碳數1～5）、非芳香族性環基、或芳香環基、或者組合該些的兩個以上而成的基。In the general formula (A6), X Q6 represents a hydrogen atom, a halogen atom, or a monovalent organic group (preferably a methyl group). R Q6 represents an alkylene group (straight-chain or branched. Preferably, the number of carbon atoms is 1 to 5), a non-aromatic cyclic group, or an aromatic cyclic group, or a group formed by combining two or more of these.
作為所述非芳香族性環基，例如可列舉單環式烴環基及多環式烴環基。 作為單環式烴環基，例如可列舉碳數3～12（較佳為碳數3～7）的環烷烴環基、以及碳數3～12的環烯烴環基。 作為多環式烴環基，例如可列舉環集合烴環基及交聯環式烴環基。 作為交聯環式烴環，例如可列舉：雙環式烴環、三環式烴環及四環式烴環等。另外，交聯環式烴環亦可為縮合有多個5員環烷烴環～8員環烷烴環而成的縮合環。 交聯環式烴環基較佳為降冰片烷環基、金剛烷環基、雙環辛烷環基或三環[5.2.1.02,6 ]癸烷環基。Examples of the non-aromatic cyclic group include a monocyclic hydrocarbon ring group and a polycyclic hydrocarbon ring group. Examples of monocyclic hydrocarbon ring groups include cycloalkane ring groups having 3 to 12 carbon atoms (preferably 3 to 7 carbon atoms) and cycloolefin ring groups having 3 to 12 carbon atoms. As the polycyclic hydrocarbon ring group, for example, a ring assembly hydrocarbon ring group and a crosslinked cyclic hydrocarbon ring group can be cited. As a crosslinked cyclic hydrocarbon ring, a bicyclic hydrocarbon ring, a tricyclic hydrocarbon ring, a tetracyclic hydrocarbon ring, etc. are mentioned, for example. In addition, the crosslinked cyclic hydrocarbon ring may be a condensed ring formed by condensing a plurality of 5-membered cycloalkane rings to 8-membered cycloalkane rings. The crosslinked cyclic hydrocarbon ring group is preferably a norbornane ring group, an adamantane ring group, a bicyclooctane ring group, or a tricyclic [5.2.1.0 2,6 ] decane ring group.
所述芳香環基較佳為碳數6～18的芳香環基，更佳為苯環基、萘環基、蒽環基或伸聯苯環基。The aromatic ring group is preferably an aromatic ring group having 6 to 18 carbon atoms, more preferably a benzene ring group, a naphthalene ring group, an anthracyclyl group or a biphenyl ring group.
所述伸烷基、所述非芳香族性環基及所述芳香環基亦較佳為不具有-(-C(CF3 )2 OH)q6 以外的取代基。It is also preferable that the alkylene group, the non-aromatic cyclic group, and the aromatic cyclic group do not have substituents other than -(-C(CF 3 ) 2 OH) q6.
通式（A6）中，q6表示1～5的整數。In general formula (A6), q6 represents an integer of 1-5.
於樹脂（A）具有重複單元（a5）的情況下，相對於樹脂（A）的全部重複單元，該重複單元的含量較佳為1莫耳%～60莫耳%，更佳為5莫耳%～50莫耳%，進而佳為7莫耳%～45莫耳%。 重複單元（a5）可單獨使用一種，亦可使用兩種以上。When the resin (A) has a repeating unit (a5), the content of the repeating unit is preferably 1 mol% to 60 mol%, more preferably 5 mol%, relative to all the repeating units of the resin (A) %～50 mol%, more preferably 7 mol%～45 mol%. One type of repeating unit (a5) may be used alone, or two or more types may be used.
（具有酚性羥基的重複單元） 樹脂（A）亦可更含有具有下述通式（B2）所表示的酚性羥基的重複單元（亦稱為「重複單元a6」）。(Repeating unit with phenolic hydroxyl group) The resin (A) may further contain a repeating unit (also referred to as "repeating unit a6") having a phenolic hydroxyl group represented by the following general formula (B2).
[化22]
通式（B2）中，X表示氫原子、烷基或鹵素原子。 所述烷基可為直鏈狀亦可為支鏈狀。所述烷基的碳數較佳為1～10。 所述烷基的取代基較佳為羥基或鹵素原子。於所述烷基具有取代基的情況下，較佳為僅具有羥基及/或鹵素原子作為取代基。所述烷基較佳為-CH3 。In the general formula (B2), X represents a hydrogen atom, an alkyl group, or a halogen atom. The alkyl group may be linear or branched. The carbon number of the alkyl group is preferably 1-10. The substituent of the alkyl group is preferably a hydroxyl group or a halogen atom. When the said alkyl group has a substituent, it is preferable to have only a hydroxyl group and/or a halogen atom as a substituent. The alkyl group is preferably -CH 3 .
通式（B2）中，X4 表示單鍵、-COO-或-CONR64 -，R64 表示氫原子或烷基（可為直鏈狀亦可為支鏈狀。較佳為碳數1～5）。-COO-中的羰基碳較佳為與重複單元的主鏈直接鍵結。In the general formula (B2), X 4 represents a single bond, -COO- or -CONR 64 -, and R 64 represents a hydrogen atom or an alkyl group (which may be linear or branched. The carbon number is preferably 1 to 5). The carbonyl carbon in -COO- is preferably directly bonded to the main chain of the repeating unit.
通式（B2）中，L4 表示單鍵或伸烷基（可為直鏈狀亦可為支鏈狀。較佳為碳數1～20）。In the general formula (B2), L 4 represents a single bond or an alkylene group (which may be linear or branched. It preferably has 1 to 20 carbon atoms).
通式（B2）中，Ar4 表示（n+1）價芳香環基。所述芳香環基較佳為苯環基、萘環基及蒽環基等碳數6～18的伸芳基、或噻吩環基、呋喃環基、吡咯環基、苯並噻吩環基、苯並呋喃環基、苯並吡咯環基、三嗪環基、咪唑環基、苯並咪唑環基、***環基、噻二唑環基及噻唑環基等含有雜環的芳香環基，更佳為苯環基。In the general formula (B2), Ar 4 represents an (n+1)-valent aromatic ring group. The aromatic ring group is preferably a phenyl ring group, a naphthalene ring group, an anthracyclyl group, and other carbon 6 to 18 arylidene groups, or a thiophene ring group, a furan ring group, a pyrrolyl ring group, a benzothiophene ring group, or a benzene ring group. Aromatic ring groups containing heterocycles, such as oxofuran ring group, benzopyrrole ring group, triazine ring group, imidazole ring group, benzimidazole ring group, triazole ring group, thiadiazole ring group and thiazole ring group, more It is preferably a phenyl ring group.
通式（B2）中，n表示1～5的整數。（n+1）價芳香環基亦可進而具有取代基。In general formula (B2), n represents an integer of 1-5. The (n+1)-valent aromatic ring group may further have a substituent.
作為所述R64 的烷基、L4 的伸烷基及Ar4 的（n+1）價芳香環基可具有的取代基，例如可列舉：鹵素原子（較佳為氟原子）、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。另外，作為Ar4 的（n+1）價芳香環基可具有的取代基，例如亦可列舉烷基（可為直鏈狀亦可為支鏈狀。較佳為碳數1～20）。Examples of substituents that the alkyl group of R 64 , the alkylene group of L 4 and the (n+1)-valent aromatic ring group of Ar 4 may have include halogen atoms (preferably fluorine atoms), methoxy Alkoxy groups such as ethoxy, ethoxy, hydroxyethoxy, propoxy, hydroxypropoxy and butoxy; aryl groups such as phenyl, etc. In addition, as a substituent that the (n+1)-valent aromatic ring group of Ar 4 may have, for example, an alkyl group (which may be linear or branched. Preferably, it has 1 to 20 carbon atoms).
以下，示出重複單元（a6）的具體例，但本發明並不限定於此。式中，a表示1或2。Hereinafter, specific examples of the repeating unit (a6) are shown, but the present invention is not limited to this. In the formula, a represents 1 or 2.
[化23]
[化24]
[化25]
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1～3的整數。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 an integer of 1-3.
[化26]
於樹脂（A）具有重複單元（a6）的情況下，相對於樹脂（A）的全部重複單元，該重複單元的含量較佳為1莫耳%～75莫耳%，更佳為5莫耳%～70莫耳%，進而佳為10莫耳%～70莫耳%。重複單元（a6）可單獨使用一種，亦可使用兩種以上。When the resin (A) has a repeating unit (a6), the content of the repeating unit is preferably 1 mol% to 75 mol%, more preferably 5 mol%, relative to all the repeating units of the resin (A) %～70 mol%, more preferably 10 mol%～70 mol%. One type of repeating unit (a6) may be used alone, or two or more types may be used.
另外，樹脂（A）亦可更含有下述式（D）所表示的重複單元（亦稱為「重複單元（a7）」）。In addition, the resin (A) may further contain a repeating unit represented by the following formula (D) (also referred to as "repeating unit (a7)").
[化27]
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，例如可列舉下述重複單元。Examples of the repeating unit represented by formula (D) include the following repeating units.
[化28]
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）或羧酸基。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）或羧酸基。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 group or fluorinated alkyl group having 1 to 20 carbons) or a carboxylic acid 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 or fluorinated alkyl group having 1 to 20 carbons) or a carboxylic acid 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.
於樹脂（A）含有式（D）所表示的重複單元（重複單元（a7））的情況下，相對於樹脂（A）的全部重複單元，該重複單元的含量較佳為1莫耳%～50莫耳%，更佳為3莫耳%～40莫耳%，進而佳為5莫耳%～30莫耳%。 重複單元（a7）可單獨使用一種，亦可使用兩種以上。When the resin (A) contains the repeating unit (repeating unit (a7)) represented by the formula (D), the content of the repeating unit is preferably 1 mol% to all the repeating units of the resin (A). 50 mol%, more preferably 3 mol% to 40 mol%, and still more preferably 5 mol% to 30 mol%. One type of repeating unit (a7) may be used alone, or two or more types may be used.
另外，樹脂（A）亦可更含有下述式（E）所表示的重複單元（亦稱為「重複單元（a8）」）。In addition, the resin (A) may further contain a repeating unit represented by the following formula (E) (also referred to as "repeating unit (a8)").
[化29]
式（E）中，Re分別獨立地表示氫原子或有機基。作為有機基，例如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, for example. "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，例如可列舉下述重複單元。Examples of the repeating unit represented by formula (E) include the following repeating units.
[化30]
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）或羧酸基。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）或羧酸基。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）、式（E-8）、及式（E-13）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 group. Atom, ester group (-OCOR" or -COOR": R" is an alkyl group or fluorinated alkyl group having 1 to 20 carbons) or a carboxylic acid 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 having 1 to 20 carbons or a fluorinated alkyl group) or a carboxylic acid 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), formula (E-8), and formula (E-13), two Rs may be bonded to each other to form a ring.
於樹脂（A）含有式（E）所表示的重複單元（a8）的情況下，相對於樹脂（A）的全部重複單元，該重複單元的含量較佳為1莫耳%～50莫耳%，更佳為3莫耳%～40莫耳%，進而佳為5莫耳%～35莫耳%。 重複單元（a8）可單獨使用一種，亦可使用兩種以上。When the resin (A) contains the repeating unit (a8) represented by the formula (E), the content of the repeating unit is preferably 1 mol% to 50 mol% relative to all the repeating units of the resin (A) , More preferably from 3 mol% to 40 mol%, further preferably from 5 mol% to 35 mol%. One type of repeating unit (a8) may be used alone, or two or more types may be used.
關於樹脂（A），在不妨礙本發明效果的範圍內，作為其他重複單元，可含有上述以外的重複單元，例如，可含有具有光酸產生基的重複單元。Regarding the resin (A), within a range that does not hinder the effects of the present invention, as other repeating units, repeating units other than those described above may be included, for example, repeating units having a photoacid generating group may be included.
具有光酸產生劑的重複單元並無特別限定，較佳為通式（A7）所述表示的重複單元（亦稱為「重複單元（a9）」）。The repeating unit having the photoacid generator is not particularly limited, but is preferably the repeating unit represented by the general formula (A7) (also referred to as "repeating unit (a9)").
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通式（A7）中，兩個Xf分別獨立地表示氫原子、氟原子或經至少一個氟原子取代的烷基（較佳為CF3 ）。兩個Xf中，至少一者較佳為氫原子以外。 所述烷基可為直鏈狀亦可為支鏈狀。所述烷基的碳數較佳為1～10。所述烷基較佳為僅具有氟原子作為取代基。In the general formula (A7), two Xf each independently represent a hydrogen atom, a fluorine atom, or an alkyl group substituted with at least one fluorine atom (preferably CF 3 ). At least one of the two Xf is preferably other than a hydrogen atom. The alkyl group may be linear or branched. The carbon number of the alkyl group is preferably 1-10. The alkyl group preferably has only a fluorine atom as a substituent.
通式（A7）中，R1 及R2 分別獨立地表示氫原子、氟原子或烷基，於存在多個時的R1 及R2 可分別相同亦可不同。 所述烷基可為直鏈狀亦可為支鏈狀。所述烷基的碳數較佳為1～10。所述烷基的取代基較佳為氟原子。於所述烷基具有取代基的情況下，較佳為僅具有氟原子作為取代基。In the general formula (A7), R 1 and R 2 each independently represent a hydrogen atom, a fluorine atom, or an alkyl group, and when there are a plurality of R 1 and R 2, they may be the same or different. The alkyl group may be linear or branched. The carbon number of the alkyl group is preferably 1-10. The substituent of the alkyl group is preferably a fluorine atom. When the alkyl group has a substituent, it preferably has only a fluorine atom as the substituent.
通式（A7）中，L表示二價連結基，存在多個時的L可相同亦可不同。 L的二價連結基可列舉-COO-、-CO-、-O-、-S-、-SO-、-SO2 -、伸烷基、伸環烷基、伸烯基、以及將該些的多個連結而成的連結基等，較佳為總碳數為12以下的連結基。In the general formula (A7), L represents a divalent linking group, and when there are a plurality of L groups, L may be the same or different. The divalent linking group of L includes -COO-, -CO-, -O-, -S-, -SO-, -SO 2 -, alkylene, cycloalkylene, alkenylene, and these The linking group formed by connecting a plurality of, etc. is preferably a linking group having a total carbon number of 12 or less.
通式（A7）中，x表示1～20的整數，y表示0～10的整數，z表示0～10的整數。In general formula (A7), x represents an integer of 1-20, y represents an integer of 0-10, and z represents an integer of 0-10.
通式（A7）中，X7 表示氫原子、烷基或鹵素原子。 作為X7 表示烷基時的烷基，可列舉直鏈狀或支鏈狀的碳數1～10的烷基，較佳為甲基、乙基、或丙基，更佳為甲基或乙基，進而佳為甲基。 作為所述烷基具有取代基的情況下的取代基，可列舉所述取代基T記載的取代基。 作為X7 表示鹵素原子的情況下的鹵素原子，可列舉氟原子、氯原子、溴原子、或碘原子，較佳為氟原子。In the general formula (A7), X 7 represents a hydrogen atom, an alkyl group, or a halogen atom. Examples of the alkyl group when X 7 represents an alkyl group include linear or branched alkyl groups having 1 to 10 carbon atoms, preferably methyl, ethyl, or propyl, more preferably methyl or ethyl The group is more preferably a methyl group. Examples of the substituent when the alkyl group has a substituent include the substituents described in the substituent T. Examples of the halogen atom in the case where X 7 represents a halogen atom include a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, and a fluorine atom is preferred.
通式（A7）中，M+ 表示陽離子。M+ 的詳情例如可使用與後述的通式（PA-1）中的M+ 相同的陽離子。In the general formula (A7), M + represents a cation. For details of M + , for example, the same cation as M + in the general formula (PA-1) described later can be used.
於樹脂（A）具有重複單元（a9）的情況下，相對於樹脂（A）的全部重複單元，該重複單元的含量較佳為1莫耳%～30莫耳%，更佳為3莫耳%～25莫耳%，進而佳為5莫耳%～20莫耳%。 重複單元（a9）可單獨使用一種，亦可使用兩種以上。When the resin (A) has a repeating unit (a9), relative to all repeating units of the resin (A), the content of the repeating unit is preferably 1 mol% to 30 mol%, more preferably 3 mol% % To 25 mol%, more preferably 5 mol% to 20 mol%. One type of repeating unit (a9) may be used alone, or two or more types may be used.
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4,500～15,000。若將樹脂（A）的重量平均分子量設為1,000～200,000，則可防止耐熱性及耐乾式蝕刻性的劣化，進而可防止顯影性的劣化及黏度變高而製膜性劣化。 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越優異，進而抗蝕劑圖案的側壁越平滑，粗糙度性能越優異。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 4,500 to 15,000 in terms of polystyrene conversion value. If the weight average molecular weight of the resin (A) is 1,000 to 200,000, the deterioration of heat resistance and dry etching resistance can be prevented, and the deterioration of developability and the increase in viscosity and the deterioration of film forming properties can be prevented. 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 resist shape, and the smoother the sidewall of the resist pattern, the better the roughness performance.
相對於樹脂（A）中的全部重複單元，樹脂（A）中的具有芳香族基的重複單元的含量較佳為10莫耳%～100莫耳%，進而佳為15莫耳%～100莫耳%。 具有芳香族基的重複單元的含量可藉由1 H-核磁共振（Nuclear Magnetic Resonance，NMR）或13 C-NMR進行測定。Relative to all the repeating units in the resin (A), the content of the repeating unit having an aromatic group in the resin (A) is preferably 10 mol% to 100 mol%, and more preferably 15 mol% to 100 mol% ear%. The content of the repeating unit having an aromatic group can be determined by 1 H-nuclear magnetic resonance (Nuclear Magnetic Resonance, NMR) or 13 C-NMR.
抗蝕劑組成物中，於總固體成分中，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%。另外，樹脂（A）可使用一種，亦可使用兩種以上。In the resist composition, in the total solid content, the content of the resin (A) is preferably 50% by mass to 99.9% by mass, more preferably 60% by mass to 99.0% by mass. In addition, one type of resin (A) may be used, or two or more types may be used.
＜（B）藉由光化射線或放射線的照射而產生酸的化合物＞ 抗蝕劑組成物亦可含有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、或光酸產生劑（B））。光酸產生劑是藉由曝光（較佳為電子束（EB）、EUV光的曝光）而產生酸的化合物。 光酸產生劑可為低分子化合物的形態，亦可為組入至聚合物的一部分中的形態。另外，亦可併用低分子化合物的形態與組入至聚合物的一部分中的形態。 於光酸產生劑為低分子化合物的形態的情況下，分子量較佳為3000以下，更佳為2000以下，進而佳為1000以下。 於光酸產生劑為併入至聚合物的一部分中的形態的情況下，可併入至樹脂（A）的一部分中，亦可併入至與樹脂（A）不同的樹脂中。 本發明中，光酸產生劑較佳為低分子化合物的形態。 光酸產生劑並無特別限定，其中，較佳為藉由電子束（EB）、EUV光的照射而產生有機酸的化合物，更佳為分子中具有氟原子或碘原子的光酸產生劑。 作為所述有機酸，例如可列舉：磺酸（脂肪族磺酸、芳香族磺酸及樟腦磺酸等）、羧酸（脂肪族羧酸、芳香族羧酸及芳烷基羧酸等）、羰基磺醯亞胺酸、雙(烷基磺醯基)醯亞胺酸及三(烷基磺醯基)甲基化物酸等。<(B) Compounds that generate acid by irradiation with actinic rays or radiation> The resist composition may also contain a compound that generates acid by irradiation with actinic rays or radiation (also referred to as a photoacid generator or a photoacid generator (B)). The photoacid generator is a compound that generates acid by exposure (preferably exposure of electron beam (EB) or EUV light). The photoacid generator may be in the form of a low-molecular compound, or may be incorporated in a part of the polymer. In addition, the form of the low-molecular compound and the form incorporated into a part of the polymer may be used together. When the photoacid generator is in the form of a low-molecular compound, the molecular weight is preferably 3000 or less, more preferably 2000 or less, and still more preferably 1000 or less. When the photoacid generator is a form incorporated into a part of the polymer, it may be incorporated into a part of the resin (A), or may be incorporated into a resin different from the resin (A). In the present invention, the photoacid generator is preferably in the form of a low-molecular compound. The photoacid generator is not particularly limited. Among them, a compound that generates an organic acid by irradiation with electron beam (EB) or EUV light is preferred, and a photoacid generator having a fluorine atom or an iodine atom in the molecule is more preferred. As the organic acid, for example, sulfonic acid (aliphatic sulfonic acid, aromatic sulfonic acid, camphorsulfonic acid, etc.), carboxylic acid (aliphatic carboxylic acid, aromatic carboxylic acid, aralkyl carboxylic acid, etc.), Carbonylsulfonimidic acid, bis(alkylsulfonyl)imidic acid and tris(alkylsulfonyl)methide acid, etc.
由光酸產生劑產生的酸的體積並無特別限制，就抑制由曝光產生的酸向非曝光部的擴散且使解析性良好的方面而言，較佳為240 Å3 以上，更佳為305 Å3 以上，進而佳為350 Å3 以上，尤佳為400 Å3 以上。再者，就感度或在塗佈溶劑中的溶解性的方面而言，由光酸產生劑產生的酸的體積較佳為1500 Å3 以下，更佳為1000 Å3 以下，進而佳為700 Å3 以下。 所述體積的值使用富士通股份有限公司製造的「WinMOPAC」求出。於計算所述體積的值時，首先，輸入各例的酸的化學結構，其次，將該結構作為初始結構，藉由使用分子力學（Molecular Mechanics，MM）3法的分子力場計算，確定各酸的最穩定立體構象，然後，對該些最穩定立體構象進行使用參數型號（Parameterized Model number，PM）3法的分子軌道計算，可計算出各酸的「佔有體積（accessible volume）」。The volume of the acid generated by the photoacid generator is not particularly limited. In terms of suppressing the diffusion of the acid generated by exposure to the non-exposed area and improving the resolution, it is preferably 240 Å 3 or more, more preferably 305 Å 3 or more, more preferably 350 Å 3 or more, and particularly preferably 400 Å 3 or more. Furthermore, it is a sense in terms of the solubility of the solvent or in a coating, the volume of the acid generated from the photoacid generator is preferably 1500 Å 3 or less, more preferably 1000 Å 3 or less, and further good as 700 Å 3 or less. The value of the volume is obtained using "WinMOPAC" manufactured by Fujitsu Co., Ltd. When calculating the value of the volume, firstly, input the chemical structure of the acid of each example, and secondly, use the structure as the initial structure, and determine the molecular force field calculation using the 3 method of Molecular Mechanics (MM). The most stable three-dimensional conformation of the acid, and then the most stable three-dimensional conformation is calculated using the parameterized model number (PM) 3 method to calculate the "accessible volume" of each acid.
由光酸產生劑產生的酸的結構並無特別限制，就抑制酸的擴散且使解析性良好的方面而言，較佳為由光酸產生劑產生的酸與樹脂（A）之間的相互作用強。就該方面而言，於由光酸產生劑產生的酸為有機酸的情況下，較佳為例如除了磺酸基、羧酸基、羰基磺醯亞胺酸基、雙磺醯亞胺酸基及三磺醯基甲基化物酸基等有機酸基以外，進而具有極性基。 作為極性基，例如可列舉：醚基、酯基、醯胺基、醯基、磺基、磺醯氧基、磺醯胺基、硫醚基、硫酯基、脲基、碳酸酯基、胺甲酸酯基、羥基及巰基。 產生的酸所具有的極性基的數量並無特別限制，較佳為一個以上，更佳為兩個以上。其中，就抑制過度的顯影的方面而言，極性基的數量較佳為未滿6個，更佳為未滿4個。The structure of the acid generated by the photoacid generator is not particularly limited. In terms of suppressing the diffusion of the acid and improving the resolution, the interaction between the acid generated by the photoacid generator and the resin (A) is preferred. The effect is strong. In this respect, when the acid generated by the photoacid generator is an organic acid, for example, it is preferably in addition to a sulfonic acid group, a carboxylic acid group, a carbonyl sulfonylimine group, and a bissulfonylimine group. In addition to organic acid groups such as trisulfonyl methide acid groups, it has a polar group. Examples of polar groups include ether groups, ester groups, amide groups, amide groups, sulfo groups, sulfonyloxy groups, sulfonamide groups, thioether groups, thioester groups, urea groups, carbonate groups, and amines. Formate, hydroxyl and mercapto groups. The number of polar groups that the generated acid has is not particularly limited, and it is preferably one or more, and more preferably two or more. Among them, in terms of suppressing excessive development, the number of polar groups is preferably less than six, and more preferably less than four.
光酸產生劑較佳為產生以下例示的酸的光酸產生劑。再者，對一部分例子標註體積的計算值（單位為Å3 ）。The photoacid generator is preferably a photoacid generator that generates the acid exemplified below. Furthermore, mark the calculated value of the volume (unit is Å 3 ) for some examples.
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就本發明的效果更優異的方面而言，光酸產生劑較佳為具有陰離子及陽離子的光酸產生劑。In terms of more excellent effects of the present invention, the photoacid generator is preferably a photoacid generator having anions and cations.
（通式（PA-1）所表示的化合物） 光酸產生劑較佳為含有通式（PA-1）所表示的化合物。(Compound represented by general formula (PA-1)) The photoacid generator preferably contains a compound represented by general formula (PA-1).
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通式（PA-1）中，A1 及A2 分別獨立地表示-SO2 -RP 或-CO-RP 。RP 表示有機基。 通式（PA-1）中存在的兩個RP 可相同亦可不同。 通式（PA-1）中存在的兩個RP 的碳數較佳為分別獨立地為1～25，更佳為1～15。 通式（PA-1）中存在的兩個RP 的除氫原子以外的原子的數量較佳為分別獨立地為2～30，更佳為4～20。 RP 較佳為通式（RF）所表示的基。 -LRF -RRF （RF）Formula (PA-1) in, A 1 and A 2 each independently represent -SO 2 -R P or -CO-R P. R P represents an organic group. The two R P present in the general formula (PA-1) may be the same or different. Formula (1-PA) in the presence of two carbon atoms for R P corresponds each independently is preferably from 1 to 25, more preferably 1 to 15. The number of atoms other than two hydrogen atoms for R P corresponds formula (PA-1) is preferably present in each independently from 2 to 30, more preferably 4 to 20. R P is preferably a group represented by the general formula (RF). -L RF -R RF (RF)
通式（RF）中，LRF 表示單鍵或二價連結基。 作為所述二價連結基，例如可列舉：-COO-、-CONH-、-CO-、-O-、-S-、-SO-、-SO2 -、伸烷基（可為直鏈狀亦可為支鏈狀。較佳為碳數1～6）、伸環烷基（較佳為碳數3～15）、伸烯基（可為直鏈狀亦可為支鏈狀。較佳為碳數2～6）以及將該些的多個組合而成的二價連結基等。 另外，該些二價連結基在可能的情況下可具有的取代基較佳為鹵素原子，更佳為氟原子。例如，所述伸烷基（亦包括將多個組合而成的二價連結基中可包含的伸烷基）亦較佳為成為全氟伸烷基。 所述二價連結基較佳為-伸烷基-COO-或-伸烷基-SO2 -。-伸烷基-COO-及-伸烷基-SO2 -較佳為伸烷基存在於N-側。In the general formula (RF), L RF represents a single bond or a divalent linking group. Examples of the divalent linking group include: -COO-, -CONH-, -CO-, -O-, -S-, -SO-, -SO 2 -, alkylene groups (which may be linear It can also be branched. Preferably it has 1 to 6 carbons, cycloalkylene (preferably 3 to 15 carbons), and alkenylene (which can be straight or branched. It is preferred. These are 2-6 carbon atoms and a divalent linking group formed by combining a plurality of these. In addition, the substituents that these divalent linking groups may have when possible are preferably halogen atoms, and more preferably fluorine atoms. For example, the alkylene group (including the alkylene group that may be contained in the divalent linking group formed by combining a plurality of groups) is also preferably a perfluoroalkylene group. The divalent linking group is preferably -alkylene-COO- or -alkylene-SO 2 -. -Alkylene-COO- and -alkylene-SO 2 -Preferably, the alkylene is present on the N-side.
通式（RF）中，RRF 表示環烷基或烷基。 於RRF 為環烷基的情況下，所述環烷基可為單環亦可為多環。 所述環烷基的碳數較佳為3～15，更佳為5～10。 作為所述環烷基，例如可列舉：降冰片基及十氫化萘基（decalinyl）、金剛烷基。 所述環烷基可具有的取代基較佳為烷基（可為直鏈狀亦可為支鏈狀。較佳為碳數1～5）。所述環烷基亦較佳為不具有除此以外的取代基。 作為所述環烷基的環員原子的碳原子中的一個以上的碳原子亦可經羰基碳原子及/或雜原子取代。例如，環烷基中的與LRF鍵結的碳原子（-CH＜）亦可經氮原子（-N＜）取代。 於RRF 為烷基的情況下，所述烷基可為直鏈狀亦可為支鏈狀。 所述烷基的碳數較佳為1～10，更佳為1～5。 所述烷基可具有的取代基較佳為環烷基、氟原子或氰基。所述烷基亦較佳為不具有該些以外的取代基。 作為所述取代基的環烷基的例子例如可同樣地列舉於RRF 為環烷基的情況下說明的環烷基。 於所述烷基具有作為所述取代基的氟原子的情況下，所述烷基可成為全氟烷基，亦可不成為全氟烷基。於所述烷基具有作為所述取代基的氟原子的情況下，所述烷基的一部分或全部亦較佳為全氟甲基。In the general formula (RF), R RF represents a cycloalkyl group or an alkyl group. When R RF is a cycloalkyl group, the cycloalkyl group may be monocyclic or polycyclic. The carbon number of the cycloalkyl group is preferably 3-15, more preferably 5-10. Examples of the cycloalkyl group include norbornyl group, decalinyl group, and adamantyl group. The substituent that the cycloalkyl group may have is preferably an alkyl group (which may be linear or branched. It preferably has 1 to 5 carbon atoms). The cycloalkyl group preferably has no other substituents. One or more carbon atoms among the carbon atoms of the ring member atoms of the cycloalkyl group may be substituted with carbonyl carbon atoms and/or heteroatoms. For example, the carbon atom (-CH<) bonded to LRF in the cycloalkyl group may be substituted with a nitrogen atom (-N<). When R RF is an alkyl group, the alkyl group may be linear or branched. The carbon number of the alkyl group is preferably 1-10, more preferably 1-5. The substituent that the alkyl group may have is preferably a cycloalkyl group, a fluorine atom, or a cyano group. It is also preferable that the alkyl group does not have substituents other than these. Examples of the cycloalkyl group as the substituent are similarly exemplified in the cycloalkyl group described in the case where R RF is a cycloalkyl group. When the alkyl group has a fluorine atom as the substituent, the alkyl group may or may not be a perfluoroalkyl group. When the alkyl group has a fluorine atom as the substituent, a part or all of the alkyl group is also preferably a perfluoromethyl group.
通式（PA-1）中，「A1 -N- -A2 」中所含的兩個RP 可彼此鍵結而形成環。In the general formula (PA-1), two R P contained in "A 1 -N -- A 2 "may be bonded to each other to form a ring.
通式（PA-1）中，M+ 表示陽離子。 M+ 的陽離子較佳為有機陽離子。 所述有機陽離子較佳為分別獨立地為通式（ZaI）所表示的陽離子（陽離子（ZaI））或通式（ZaII）所表示的陽離子（陽離子（ZaII））。In the general formula (PA-1), M + represents a cation. The cation of M + is preferably an organic cation. The organic cations are preferably cations represented by general formula (ZaI) (cations (ZaI)) or cations represented by general formula (ZaII) (cations (ZaII)), respectively.
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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、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）中的陽離子，例如可列舉後述的陽離子（ZaI-1）、陽離子（ZaI-2）、通式（ZaI-3b）所表示的陽離子（陽離子（ZaI-3b））、以及通式（ZaI-4b）所表示的陽離子（陽離子（ZaI-4b））。Examples of the cation in the general formula (ZaI) include the cation (ZaI-1), the cation (ZaI-2), the cation represented by the general formula (ZaI-3b) (the cation (ZaI-3b)), and A 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.
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，例如可列舉：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，所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 Examples include methyl, ethyl, propyl, n-butyl, sec-butyl, tert-butyl, cyclopropyl, cyclobutyl, cyclohexyl, and the like.
R201 ～R203 的芳基、烷基及環烷基可具有的取代基分別獨立地較佳為烷基（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、羥基或苯硫基。 所述取代基在可能的情況下可進而具有取代基，例如所述烷基可具有鹵素原子作為取代基且成為三氟甲基等鹵化烷基。The substituents that the aryl group, alkyl group and cycloalkyl group of R 201 to R 203 may have are each independently preferably an alkyl group (for example, carbon number 1-15), cycloalkyl group (for example, carbon number 3-15), aryl group Group (for example, carbon number 6-14), alkoxy (for example, carbon number 1-15), cycloalkylalkoxy (for example, carbon number 1-15), halogen atom, hydroxyl group, or thiophenyl group. The substituent may further have a substituent when possible. For example, the alkyl group may have a halogen atom as a substituent and 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 的不含芳香環的有機基通常為碳數1～30，較佳為碳數1～20。 R201 ～R203 較佳為分別獨立地為烷基、環烷基、烯丙基或乙烯基，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 containing 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 preferably each independently 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-oxocycloalkane Group or alkoxycarbonylmethyl group, more preferably a linear or branched 2-oxoalkyl group.
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).
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通式（ZaI-3b）中， R1c ～R5c 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。 R6c 及R7c 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。 Rx 及Ry 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.
R1c ～R5c 中的任意兩個以上、R5c 與R6c 、R6c 與R7c 、R5c 與Rx 以及Rx 與Ry 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，例如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縮合環。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R1c ～R5c 中的任意兩個以上、R6c 與R7c 、以及Rx 與Ry 鍵結而形成的基，例如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。 R5c 與R6c 、以及R5c 與Rx 鍵結而形成的基較佳為單鍵或伸烷基。作為伸烷基，例如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, for example.
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).
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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，亦可為一部分中含有環烷基的基）。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，亦可為一部分中含有環烷基的基）。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，較佳為兩個R15 為伸烷基且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 may be a cycloalkyl group itself, or a group containing a cycloalkyl group in a part). 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 group containing a cycloalkyl group in a part). 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, it is preferable that two R 15 are alkylene groups and 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。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. The alkyl group is more preferably methyl, ethyl, n-butyl or tertiary butyl.
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。 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。 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 carbons or a branched alkyl group having 3 to 10 carbons (for example, methyl, ethyl, propyl, butyl, etc.). Group or pentyl group), or a cycloalkyl group having 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.
（通式（PB）所表示的化合物） 光酸產生劑亦較佳為含有通式（PB）所表示的化合物。 M1 + A- -L-B- M2 + （PB）(Compound represented by general formula (PB)) The photoacid generator preferably contains a compound represented by general formula (PB). M 1 + A -- LB - M 2 + (PB)
通式（PB）所表示的化合物於一分子中包含具有相當於通常的光酸產生劑的功能的結構（相當於「M1 + A- -」的部分）、以及具有相當於酸擴散控制劑的功能的結構（相當於「-B- M2 + 」的部分）此兩者，因此在抗蝕劑膜中，可使所述結構的各自的存在比率固定。 因此，本發明者等人推測，即使於抗蝕劑膜被曝光時，在抗蝕劑膜中產生的酸的量以及擴散亦容易變得均勻，顯影後所獲得的圖案的寬度穩定。Compounds of general formula (PB) comprises a structure represented by the equivalent of having a photoacid generating agent is generally a function (corresponding to "A M 1 + - -" moiety) in one molecule, and having the equivalent of the acid diffusion controller The functional structure (corresponding to the part of "-B - M 2 + ") of the two, so in the resist film, the existence ratio of each of the structures can be fixed. Therefore, the inventors of the present invention speculate that even when the resist film is exposed to light, the amount and diffusion of acid generated in the resist film are likely to become uniform, and the width of the pattern obtained after development is stable.
通式（PB）中，M1 + 及M2 + 分別獨立地表示有機陽離子。 M1 + 及M2 + 的有機陽離子可分別獨立地同樣地使用在關於通式（PA-1）的M+ 的說明中列舉的有機陽離子。In the general formula (PB), M 1 + and M 2 + each independently represent an organic cation. As the organic cations of M 1 + and M 2 + , the organic cations listed in the description of M + of the general formula (PA-1) can be used independently of each other in the same manner.
通式（PB）中，L表示二價有機基。 作為所述二價有機基，例如可列舉-COO-、-CONH-、-CO-、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）、以及將該些的多個組合而成的二價連結基等。 構成所述伸環烷基的環烷烴環的亞甲基的一個以上可經羰基碳及/或雜原子（氧原子等）取代。 該些二價連結基亦較佳為進而具有選自由-O-、-S-、-SO-及-SO2 -所組成的群組中的基。In the general formula (PB), L represents a divalent organic group. As the divalent organic group, for example, -COO-, -CONH-, -CO-, alkylene (preferably carbon number 1 to 6. It may be linear or branched), extension Cycloalkyl (preferably carbon number 3-15), alkenylene group (preferably carbon number 2-6), and a divalent linking group formed by combining a plurality of these. One or more of the methylene groups constituting the cycloalkane ring of the cycloalkylene group may be substituted with a carbonyl carbon and/or a heteroatom (oxygen atom, etc.). The divalent linking groups preferably further have a group selected from the group consisting of -O-, -S-, -SO- and -SO 2 -.
其中，L較佳為下述通式（L）所表示的基。 *A-LA-LB-LC-LD-LE-*B （L）Among them, L is preferably a group represented by the following general formula (L). *A-LA-LB-LC-LD-LE-*B (L)
通式（L）中，*A表示與通式（PB）中的A-的鍵結位置。通式（L）中，*B表示與通式（PB）中的B-的鍵結位置。In the general formula (L), *A represents the bonding position with A- in the general formula (PB). In the general formula (L), *B represents the bonding position with B- in the general formula (PB).
通式（L）中，LA表示-(C(RLA1 )(RLA2 ))XA -。 所述XA表示1以上的整數，較佳為1～10，更佳為1～3。 RLA1 及RLA2 分別獨立地表示氫原子或取代基。 RLA1 及RLA2 的取代基較佳為分別獨立地為氟原子或氟烷基，更佳為氟原子或全氟烷基，進而佳為氟原子或全氟甲基。 於XA為2以上的情況下，存在XA個的RLA1 可分別相同亦可不同。 於XA為2以上的情況下，存在XA個的RLA2 可分別相同亦可不同。 -(C(RLA1 )(RLA2 ))-較佳為-CH2 -、-CHF-、-CH(CF3 )-或-CF2 -。 其中，與通式（PB）中的A- 直接鍵結的-(C(RLA1 )(RLA2 ))-較佳為-CH2 -、-CHF-、-CH(CF3 )-或-CF2 -。 與通式（PB）中的A- 直接鍵結的-(C(RLA1 )(RLA2 ))-以外的-(C(RLA1 )(RLA2 ))-較佳為分別獨立地為-CH2 -、-CHF-或-CF2 -。In the general formula (L), LA represents -(C(R LA1 )(R LA2 )) XA -. The XA represents an integer of 1 or more, preferably 1-10, more preferably 1-3. R LA1 and R LA2 each independently represent a hydrogen atom or a substituent. The substituents of R LA1 and R LA2 are preferably each independently a fluorine atom or a fluoroalkyl group, more preferably a fluorine atom or a perfluoroalkyl group, and still more preferably a fluorine atom or a perfluoromethyl group. When XA is 2 or more, XA R LA1 may be the same or different. When XA is 2 or more, R LA2 in which XA is present may be the same or different. -(C(R LA1 )(R LA2 ))- is preferably -CH 2 -, -CHF-, -CH(CF 3 )- or -CF 2 -. Among them, -(C(R LA1 )(R LA2 ))- which is directly bonded to A- in general formula (PB) is preferably -CH 2 -, -CHF-, -CH(CF 3 )- or- CF 2 -. Other than -(C(R LA1 )(R LA2 ))- which is directly bonded to A- in the general formula (PB) -(C(R LA1 )(R LA2 ))- is preferably each independently- CH 2 -, -CHF- or -CF 2 -.
通式（L）中，LB表示單鍵、酯基（-COO-）或磺醯基（-SO2 -）。In the general formula (L), LB represents a single bond, an ester group (-COO-) or a sulfonyl group (-SO 2 -).
通式（L）中，LC表示單鍵、伸烷基、伸環烷基、或者將該些組合而成的基（「-伸烷基-伸環烷基-」）等）。 所述伸烷基可為直鏈狀亦可為支鏈狀。 所述伸烷基的碳數較佳為1～5，更佳為1～2，進而佳為1，所述伸環烷基的碳數較佳為3～15，更佳為5～10。 所述伸環烷基可為單環亦可為多環。 作為所述伸環烷基，例如可列舉降冰片烷二基及金剛烷二基。 所述伸環烷基可具有的取代基較佳為烷基（可為直鏈狀亦可為支鏈狀。較佳為碳數1～5）。 構成所述伸環烷基的環烷烴環的亞甲基的一個以上可經羰基碳及/或雜原子（氧原子等）取代。 於LC為「-伸烷基-伸環烷基-」的情況下，伸烷基部分較佳為存在於LB側。 於LB為單鍵的情況下，LC較佳為單鍵或伸環烷基。In the general formula (L), LC represents a single bond, an alkylene group, a cycloalkylene group, or a combination of these ("-alkylene group-cycloalkylene group-"), etc.). The alkylene group may be linear or branched. The carbon number of the alkylene group is preferably 1-5, more preferably 1-2, and even more preferably 1, the carbon number of the cycloalkylene group is preferably 3-15, more preferably 5-10. The cycloalkylene group may be monocyclic or polycyclic. Examples of the cycloalkylene group include norbornanediyl and adamantanediyl. The substituent that the cycloalkylene group may have is preferably an alkyl group (which may be linear or branched. Preferably, it has 1 to 5 carbon atoms). One or more of the methylene groups constituting the cycloalkane ring of the cycloalkylene group may be substituted with a carbonyl carbon and/or a heteroatom (oxygen atom, etc.). When LC is "-alkylene-cycloalkylene-", the alkylene moiety is preferably present on the LB side. When LB is a single bond, LC is preferably a single bond or a cycloalkylene group.
通式（L）中，LD表示單鍵、醚基（-O-）、羰基（-CO-）或酯基（-COO-）。In the general formula (L), LD represents a single bond, an ether group (-O-), a carbonyl group (-CO-), or an ester group (-COO-).
通式（L）中，LE表示單鍵或-(C(RLE1 )(RLE2 ))XE -。 所述-(C(RLE1 )(RLE2 ))XE -中的XE表示1以上的整數，較佳為1～10，更佳為1～3。 RLE1 及RLE2 分別獨立地表示氫原子或取代基。 於XE為2以上的情況下，存在XE個的RLE1 可分別相同亦可不同。 於XE為2以上的情況下，存在XE個的RLE2 可分別相同亦可不同。 其中，-(C(RLE1 )(RLE2 ))-較佳為-CH2 -。通式（L）中，於LB、LC及LD為單鍵的情況下，較佳為LE亦為單鍵。In the general formula (L), LE represents a single bond or -(C(R LE1 )(R LE2 )) XE -. XE in the -(C(R LE1 )(R LE2 )) XE-represents an integer of 1 or more, preferably 1-10, more preferably 1-3. R LE1 and R LE2 each independently represent a hydrogen atom or a substituent. When XE is 2 or more, XE R LE1 may be the same or different. When XE is 2 or more, XE R LE2 may be the same or different. Among them, -(C(R LE1 )(R LE2 ))- is preferably -CH 2 -. In the general formula (L), when LB, LC and LD are single bonds, it is preferable that LE is also a single bond.
通式（PB）中，A- 表示酸根陰離子基。 酸根陰離子基是具有陰離子原子的基。 具體而言，A- 較佳為通式（A-1）～（A-2）中的任一者所表示的基。In the general formula (PB), A - represents an acid radical anion group. The acid anion group is a group having an anion atom. Specifically, A -is preferably a group represented by any one of general formulas (A-1) to (A-2).
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通式（A-1）～（A-2）中，*表示鍵結位置。 通式（A-2）中，RA 表示有機基。 RA 較佳為烷基。 所述烷基可為直鏈狀亦可為支鏈狀。 所述烷基的碳數較佳為1～10，更佳為1～5。 所述烷基可具有的取代基較佳為氟原子。 具有氟原子作為取代基的所述烷基可成為全氟烷基，亦可不成為全氟烷基。In the general formulas (A-1) to (A-2), * represents the bonding position. Formula (A-2) in, R A represents an organic group. R A is preferably an alkyl group. The alkyl group may be linear or branched. The carbon number of the alkyl group is preferably 1-10, more preferably 1-5. The substituent that the alkyl group may have is preferably a fluorine atom. The alkyl group having a fluorine atom as a substituent may or may not be a perfluoroalkyl group.
通式（PB）中，B- 表示通式（B-1）～（B-4）中的任一者所表示的基。 B- 較佳為通式（B-1）～（B-3）中的任一者所表示的基，更佳為通式（B-1）～（B-2）中的任一者所表示的基。In general formula (PB), B - represents a group represented by any one of general formulas (B-1) to (B-4). B -is preferably a group represented by any of the general formulas (B-1) to (B-3), more preferably a group represented by any of the general formulas (B-1) to (B-2) Represents the base.
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通式（B-1）～（B-4）中，*表示鍵結位置。 通式（B-1）～（B-4）中，RB 表示有機基。 RB 較佳為環烷基或烷基。 於RB 為環烷基的情況下，所述環烷基的碳數較佳為3～15，更佳為5～10。 所述環烷基可為單環亦可為多環。 作為所述環烷基，例如可列舉降冰片基及金剛烷基。 所述環烷基可具有的取代基較佳為烷基（可為直鏈狀亦可為支鏈狀。較佳為碳數1～5）。 作為所述環烷基的環員原子的碳原子中的一個以上的碳原子可經羰基碳原子取代。 於RB 為烷基的情況下，所述烷基可為直鏈狀亦可為支鏈狀。 所述烷基的碳數較佳為1～10，更佳為1～5。 所述烷基可具有的取代基較佳為環烷基、氟原子或氰基。 作為所述取代基的環烷基的例子可同樣地列舉於RB 為環烷基的情況下說明的環烷基。 於所述烷基具有作為所述取代基的氟原子的情況下，所述烷基可成為全氟烷基，亦可不成為全氟烷基。於所述烷基具有作為所述取代基的氟原子的情況下，所述烷基的一部分或全部亦較佳為全氟甲基。In the general formulas (B-1) to (B-4), * represents the bonding position. In the general formula (B-1) ~ (B -4), R B represents an organic group. R B is preferably a cycloalkyl group or an alkyl group. In the case where R B is a cycloalkyl group, the cycloalkyl group preferably having a carbon number of 3 to 15, more preferably from 5 to 10. The cycloalkyl group may be monocyclic or polycyclic. Examples of the cycloalkyl group include norbornyl group and adamantyl group. The substituent that the cycloalkyl group may have is preferably an alkyl group (which may be linear or branched. It preferably has 1 to 5 carbon atoms). One or more carbon atoms among the carbon atoms of the ring member atoms of the cycloalkyl group may be substituted with a carbonyl carbon atom. Under a case where R B is an alkyl group, the alkyl group may be linear or branched or. The carbon number of the alkyl group is preferably 1-10, more preferably 1-5. The substituent that the alkyl group may have is preferably a cycloalkyl group, a fluorine atom, or a cyano group. Cycloalkyl described case of the Examples of the cycloalkyl group may be substituted in the same manner as R B is exemplified a cycloalkyl group. When the alkyl group has a fluorine atom as the substituent, the alkyl group may or may not be a perfluoroalkyl group. When the alkyl group has a fluorine atom as the substituent, a part or all of the alkyl group is also preferably a perfluoromethyl group.
於通式（PB）所表示的化合物的M1 + 及M2 + 分別經氫原子取代的HA-L-BH所表示的化合物中，HA所表示的基的pKa比BH所表示的基的pKa低。 更具體而言，在對HA-L-BH所表示的化合物求出酸解離常數的情況下，將「HA-L-BH」成為「A- -L-BH」時的pKa設為「HA所表示的基的pKa」，進而將「A- -L-BH」成為「A- -L-B- 」時的pKa設為「BH所表示的基的pKa」。 「HA所表示的基的pKa」及「BH所表示的基的pKa」分別使用「軟體包1」或「高斯（Gaussian）16」求出。 其中，HA所表示的基的pKa較佳為-12.00～1.00，更佳為-7.00～0.50，進而佳為-5.00～0.00。 HB所表示的基的pKa較佳為-4.00～14.00，更佳為-2.00～12.00，進而佳為-1.00～5.00。 HB所表示的基的pKa與HA所表示的基的pKa之差（「HB所表示的基的pKa」-「HA所表示的基的pKa」）較佳為0.10～20.00，更佳為0.50～17.00，進而佳為2.00～15.00。 In the compound represented by HA-L-BH in which M 1 + and M 2 + of the compound represented by the general formula (PB) are each substituted with a hydrogen atom, the pKa of the group represented by HA is higher than the pKa of the group represented by BH low. More specifically, in the case of calculating the acid dissociation constant for the compound represented by HA-L-BH , the pKa when "HA-L-BH" becomes "A-- L-BH" is referred to as "HA The pKa of the base represented by "A -- L-BH ", and the pKa when "A-- LB - " becomes "A--LB -" is further defined as the "pKa of the base represented by BH". "The pKa of the base represented by HA" and "the pKa of the base represented by BH" are obtained using "Package 1" or "Gaussian 16", respectively. Among them, the pKa of the group represented by HA is preferably -12.00 to 1.00, more preferably -7.00 to 0.50, and still more preferably -5.00 to 0.00. The pKa of the group represented by HB is preferably -4.00 to 14.00, more preferably -2.00 to 12.00, and still more preferably -1.00 to 5.00. The difference between the pKa of the group represented by HB and the pKa of the group represented by HA ("pKa of the group represented by HB"-"pKa of the group represented by HA") is preferably 0.10 to 20.00, more preferably 0.50 to 17.00, more preferably 2.00 to 15.00.
（其他光酸產生劑） 抗蝕劑組成物亦可使用所述以外的其他光酸產生劑。 作為其他光酸產生劑，例如可列舉「M+ Z- （M+ 表示陽離子，Z- 表示陰離子）」所表示的化合物（鎓鹽）。(Other photo-acid generators) The resist composition may use photo-acid generators other than those mentioned above. As another photoacid generator, for example, "M + Z - (M + represents a cation, Z - represents an anion)" compound (salt) represented.
「M+ Z- 」所表示的化合物中，M+ 表示陽離子，可列舉與通式（PA-1）中的陽離子相同的陽離子。 「M+ Z- 」所表示的化合物中，Z- 表示陰離子，較佳為引起親核反應的能力顯著低的陰離子。 作為所述陰離子，例如可列舉：磺酸根陰離子（氟烷基磺酸根陰離子等脂肪族磺酸根陰離子、芳香族磺酸根陰離子及樟腦磺酸根陰離子等）、羧酸根陰離子（脂肪族羧酸根陰離子、芳香族羧酸根陰離子及芳烷基羧酸根陰離子等）、以及三(烷基磺醯基)甲基化物陰離子。"M + Z -" compound represented by, M + represents a cation of the same, may include the general formula (PA-1) cations cation. "M + Z -" compound represented by, Z - represents an anion, preferably the ability to cause nucleophilic reaction is significantly low anion. Examples of the anion include sulfonate anions (aliphatic sulfonate anions such as fluoroalkylsulfonate anions, aromatic sulfonate anions, camphorsulfonate anions, etc.), carboxylate anions (aliphatic carboxylate anions, aromatic Group carboxylate anions and aralkyl carboxylate anions, etc.), and tri(alkylsulfonyl) methide anions.
脂肪族磺酸根陰離子及脂肪族羧酸根陰離子中的脂肪族部位可為烷基亦可為環烷基，較佳為碳數1～30的直鏈狀或支鏈狀的烷基、以及碳數3～30的環烷基。The aliphatic part in the aliphatic sulfonate anion and the aliphatic carboxylate anion may be an alkyl group or a cycloalkyl group, preferably a linear or branched alkyl group having 1 to 30 carbon atoms, and a carbon number 3-30 cycloalkyl.
芳香族磺酸根陰離子及芳香族羧酸根陰離子中的芳香環基較佳為碳數6～14的芳基，例如可列舉苯基、甲苯基及萘基。The aromatic ring group in the aromatic sulfonate anion and the aromatic carboxylate anion is preferably an aryl group having 6 to 14 carbon atoms, and examples thereof include a phenyl group, a tolyl group, and a naphthyl group.
作為所述列舉的烷基、環烷基及芳基可具有的取代基，例如可列舉：硝基、氟原子等鹵素原子、羧酸基、羥基、胺基、氰基、烷氧基（較佳為碳數1～15）、環烷基（較佳為碳數3～15）、芳基（較佳為碳數6～14）、烷氧基羰基（較佳為碳數2～7）、醯基（較佳為碳數2～12）、烷氧基羰氧基（較佳為碳數2～7）、烷硫基（較佳為碳數1～15）、烷基磺醯基（較佳為碳數1～15）、烷基亞胺基磺醯基（較佳為碳數1～15）、芳氧基磺醯基（較佳為碳數6～20）、烷基芳氧基磺醯基（較佳為碳數7～20）、環烷基芳氧基磺醯基（較佳為碳數10～20）、烷氧基烷氧基（較佳為碳數5～20）及環烷基烷氧基烷氧基（較佳為碳數8～20）。Examples of the substituents that the alkyl group, cycloalkyl group, and aryl group may have include halogen atoms such as nitro group and fluorine atom, carboxylic acid group, hydroxyl group, amino group, cyano group, and alkoxy group (more Preferred are carbon number 1-15), cycloalkyl (preferably carbon number 3-15), aryl group (preferably carbon number 6-14), alkoxycarbonyl (preferably carbon number 2-7) , Alkyl (preferably carbon number 2-12), alkoxycarbonyloxy (preferably carbon number 2-7), alkylthio (preferably carbon number 1-15), alkylsulfonyl (Preferably carbon number 1-15), alkyliminosulfonyl group (preferably carbon number 1-15), aryloxysulfonyl group (preferably carbon number 6-20), alkyl aryl Oxysulfonyl (preferably carbon number 7-20), cycloalkylaryloxysulfonyl (preferably carbon number 10-20), alkoxy alkoxy (preferably carbon number 5-20) 20) and cycloalkylalkoxyalkoxy (preferably carbon number 8-20).
芳烷基羧酸根陰離子中的芳烷基較佳為碳數7～12的芳烷基，例如可列舉苄基、苯乙基、萘基甲基、萘基乙基及萘基丁基。The aralkyl group in the aralkylcarboxylate anion is preferably an aralkyl group having 7 to 12 carbon atoms, and examples thereof include benzyl, phenethyl, naphthylmethyl, naphthylethyl, and naphthylbutyl.
三(烷基磺醯基)甲基化物陰離子中的烷基較佳為碳數1～5的烷基。作為該些烷基的取代基，例如可列舉：鹵素原子、經鹵素原子取代的烷基、烷氧基、烷硫基、烷氧基磺醯基、芳氧基磺醯基及環烷基芳氧基磺醯基，較佳為氟原子或經氟原子取代的烷基。The alkyl group in the tris(alkylsulfonyl)methide anion is preferably an alkyl group having 1 to 5 carbon atoms. Examples of substituents of these alkyl groups include halogen atoms, alkyl groups substituted with halogen atoms, alkoxy groups, alkylthio groups, alkoxysulfonyl groups, aryloxysulfonyl groups, and cycloalkyl aryl groups. The oxysulfonyl group is preferably a fluorine atom or an alkyl group substituted with a fluorine atom.
作為其他非親核性陰離子，例如可列舉氟化磷（例如PF6 - ）、氟化硼（例如BF4 - ）及氟化銻（例如SbF6 - ）。As other non-nucleophilic anion, and examples thereof include phosphorus fluoride (e.g., PF 6 -), boron trifluoride (e.g., BF 4 -) and antimony trifluoride (e.g., SbF 6 -).
非親核性陰離子較佳為磺酸的至少α位經氟原子取代的脂肪族磺酸根陰離子、經氟原子或具有氟原子的基取代的芳香族磺酸根陰離子、或者烷基經氟原子取代的三(烷基磺醯基)甲基化物陰離子。其中，更佳為全氟脂肪族磺酸根陰離子（較佳為碳數4～8）或具有氟原子的苯磺酸根陰離子，進而佳為九氟丁磺酸根陰離子、全氟辛磺酸根陰離子、五氟苯磺酸根陰離子或3,5-雙(三氟甲基)苯磺酸根陰離子。The non-nucleophilic anion is preferably an aliphatic sulfonate anion substituted with a fluorine atom in at least the α position of a sulfonic acid, an aromatic sulfonate anion substituted with a fluorine atom or a group having a fluorine atom, or an alkyl group substituted with a fluorine atom Tris(alkylsulfonyl)methide anion. Among them, more preferred are perfluoroaliphatic sulfonate anions (preferably carbon number 4-8) or benzenesulfonate anions having a fluorine atom, and more preferred are nonafluorobutanesulfonate anion, perfluorooctanesulfonate anion, five Fluorobenzenesulfonate anion or 3,5-bis(trifluoromethyl)benzenesulfonate anion.
就酸強度的方面而言，為了提高感度，較佳為產生酸的pKa為-1以下。In terms of acid strength, in order to increase sensitivity, it is preferable that the pKa for generating acid is -1 or less.
另外，非親核性陰離子亦較佳為以下的通式（AN1）所表示的陰離子。In addition, the non-nucleophilic anion is also preferably an anion represented by the following general formula (AN1).
[化41]
式中，Xf分別獨立地表示氟原子或經至少一個氟原子取代的烷基。 R1 及R2 分別獨立地表示氫原子、氟原子或烷基，存在多個時的R1 及R2 可分別相同亦可不同。 L表示二價連結基，存在多個時的L可相同亦可不同。 A表示環狀有機基。 x表示1～20的整數，y表示0～10的整數，z表示0～10的整數。In the formula, Xf each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. R 1 and R 2 each independently represent a hydrogen atom, a fluorine atom, or an alkyl group, and when there are a plurality of R 1 and R 2, they may be the same or different. L represents a divalent linking group, and when there are a plurality of L, L may be the same or different. A represents a cyclic organic group. x represents an integer of 1-20, y represents an integer of 0-10, and z represents an integer of 0-10.
對通式（AN1）進行更詳細的說明。 Xf的經氟原子取代的烷基中的烷基的碳數較佳為1～10，更佳為1～4。另外，Xf的經氟原子取代的烷基較佳為全氟烷基。 Xf較佳為氟原子或碳數1～4的全氟烷基。Xf例如可列舉：氟原子、CF3 、C2 F5 、C3 F7 、C4 F9 、CH2 CF3 、CH2 CH2 CF3 、CH2 C2 F5 、CH2 CH2 C2 F5 、CH2 C3 F7 、CH2 CH2 C3 F7 、CH2 C4 F9 及CH2 CH2 C4 F9 等，其中，較佳為氟原子或CF3 。尤佳為兩個Xf為氟原子。The general formula (AN1) is explained in more detail. The carbon number of the alkyl group in the alkyl group substituted with a fluorine atom of Xf is preferably 1-10, more preferably 1-4. In addition, the alkyl group substituted with a fluorine atom of Xf is preferably a perfluoroalkyl group. Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms. Examples of Xf include fluorine atom, CF 3 , C 2 F 5 , C 3 F 7 , C 4 F 9 , CH 2 CF 3 , CH 2 CH 2 CF 3 , CH 2 C 2 F 5 , CH 2 CH 2 C 2 F 5 , CH 2 C 3 F 7 , CH 2 CH 2 C 3 F 7 , CH 2 C 4 F 9 and CH 2 CH 2 C 4 F 9, etc. Among them, a fluorine atom or CF 3 is preferred. It is particularly preferable that two Xf are fluorine atoms.
R1 及R2 的烷基可具有取代基（較佳為氟原子），取代基中的碳數較佳為1～4。取代基較佳為碳數1～4的全氟烷基。R1 及R2 的具有取代基的烷基例如可列舉：CF3 、C2 F5 、C3 F7 、C4 F9 、C5 F11 、C6 F13 、C7 F15 、C8 F17 、CH2 CF3 、CH2 CH2 CF3 、CH2 C2 F5 、CH2 CH2 C2 F5 、CH2 C3 F7 、CH2 CH2 C3 F7 、CH2 C4 F9 及CH2 CH2 C4 F9 等，其中，較佳為CF3 。 R1 及R2 較佳為氟原子或CF3 。The alkyl group of R 1 and R 2 may have a substituent (preferably a fluorine atom), and the number of carbons in the substituent is preferably 1-4. The substituent is preferably a perfluoroalkyl group having 1 to 4 carbon atoms. Examples of the substituted alkyl groups of R 1 and R 2 include CF 3 , C 2 F 5 , C 3 F 7 , C 4 F 9 , C 5 F 11 , C 6 F 13 , C 7 F 15 , and C 8 F 17 , CH 2 CF 3 , CH 2 CH 2 CF 3 , CH 2 C 2 F 5 , CH 2 CH 2 C 2 F 5 , CH 2 C 3 F 7 , CH 2 CH 2 C 3 F 7 , CH 2 C 4 F 9 and CH 2 CH 2 C 4 F 9 etc., among which CF 3 is preferred. R 1 and R 2 are preferably a fluorine atom or CF 3 .
x較佳為1～10的整數，更佳為1～5。 y較佳為0～4的整數，更佳為0。 z較佳為0～5的整數，更佳為0～3的整數。 作為L的二價連結基，例如可列舉：-COO-、-CO-、-O-、-S-、-SO-、-SO2 -、伸烷基、伸環烷基、伸烯基、以及將該些的多個連結而成的連結基等，較佳為總碳數12以下的連結基。其中，較佳為-COO-、-CO-或-O-，更佳為-COO-。x is preferably an integer of 1-10, more preferably 1-5. y is preferably an integer of 0-4, more preferably 0. z is preferably an integer of 0-5, more preferably an integer of 0-3. Examples of the divalent linking group of L include -COO-, -CO-, -O-, -S-, -SO-, -SO 2 -, alkylene, cycloalkylene, alkenylene, And the linking group etc. formed by linking a plurality of these are preferably a linking group having a total carbon number of 12 or less. Among them, -COO-, -CO- or -O- is preferred, and -COO- is more preferred.
A的環狀有機基只要是具有環狀結構者，則並無特別限定，可列舉脂環基、芳香環基及雜環基（不僅包含具有芳香族性者，亦包含不具有芳香族性者）等。 脂環基可為單環亦可為多環，較佳為環戊基、環己基及環辛基等單環的環烷基，除此以外，亦較佳為降冰片基、三環癸基、四環癸基、四環十二烷基及金剛烷基等多環的環烷基。其中，就可抑制曝光後加熱步驟中的膜中擴散性且遮罩誤差增強因子（Mask Error Enhancement Factor，MEEF）提高的方面而言，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。 作為芳香環基，例如可列舉苯環、萘環、菲環及蒽環等。 作為雜環基，例如可列舉源自呋喃環、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等的基。其中，較佳為源自呋喃環、噻吩環或吡啶環的基。The cyclic organic group of A is not particularly limited as long as it has a cyclic structure. Examples include alicyclic groups, aromatic cyclic groups, and heterocyclic groups (not only those having aromatic properties, but also those having non-aromatic properties. )Wait. The alicyclic group may be monocyclic or polycyclic, preferably monocyclic cycloalkyl groups such as cyclopentyl, cyclohexyl, and cyclooctyl. In addition, it is also preferably norbornyl and tricyclodecyl , Tetracyclodecyl, tetracyclododecyl and adamantyl and other polycyclic cycloalkyls. Among them, in terms of suppressing the diffusibility in the film in the heating step after exposure and improving the Mask Error Enhancement Factor (MEEF), norbornyl, tricyclodecyl, and tetracyclodecyl are preferred. Alicyclic group having a bulky structure with 7 or more carbon atoms, such as tetracyclododecyl group, and adamantyl group. As an aromatic ring group, a benzene ring, a naphthalene ring, a phenanthrene ring, an anthracene ring, etc. are mentioned, for example. Examples of heterocyclic groups include groups derived from furan ring, thiophene ring, benzofuran ring, benzothiophene ring, dibenzofuran ring, dibenzothiophene ring, pyridine ring, and the like. Among them, preferred is a group derived from a furan ring, a thiophene ring, or a pyridine ring.
另外，作為環狀有機基，亦可列舉內酯結構，作為具體例，可列舉所述通式（LC1-1）～（LC1-22）所表示的內酯結構。Moreover, as a cyclic organic group, a lactone structure can also be mentioned, As a specific example, the lactone structure represented by the said general formula (LC1-1)-(LC1-22) is mentioned.
所述環狀的有機基可具有取代基。所述取代基可列舉：烷基（可為直鏈狀亦可為支鏈狀，亦可含有環狀結構。較佳為碳數1～12）、環烷基（可為單環及多環中的任一者，於為多環時亦可為螺環。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等。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 have a substituent. Examples of the substituent include: alkyl (which may be linear or branched, and may contain a cyclic structure. Preferably, the number of carbon atoms is 1 to 12), cycloalkyl (which may be monocyclic or polycyclic) Any one of these may be a spiro ring when it is a polycyclic ring. Preferably it is a carbon number of 3-20), an aryl group (preferably a carbon number of 6-14), a hydroxyl group, an alkoxy group, an ester group, and an acyl group Amine group, urethane group, urea group, thioether group, sulfonamide group, sulfonate group, etc. Furthermore, the carbon (carbon that contributes to ring formation) constituting the cyclic organic group may be a carbonyl carbon.
另外，光酸產生劑亦可為具有陽離子部與陰離子部、兩者經共價鍵連結的結構的甜菜鹼化合物。In addition, the photoacid generator may be a betaine compound having a structure in which a cation part and an anion part, and the two are connected by a covalent bond.
作為光酸產生劑，可引用日本專利特開2014-41328號公報的段落[0368]～[0377]以及日本專利特開2013-228681號公報的段落[0240]～[0262]（對應的美國專利申請公開第2015/004533號說明書的[0339]），將該些內容併入至本案說明書中。 另外，作為較佳的具體例，可列舉以下化合物。下述化合物中，於可能的情況下，陰離子與陽離子可任意交換。As the photoacid generator, paragraphs [0368] to [0377] of Japanese Patent Laid-Open No. 2014-41328 and paragraphs [0240] to [0262] of Japanese Patent Laid-Open No. 2013-228681 (corresponding U.S. Patent Application Publication No. 2015/004533 Specification [0339]), and incorporated these contents into the specification of this case. In addition, as preferred specific examples, the following compounds can be cited. In the following compounds, where possible, anions and cations can be exchanged arbitrarily.
[化42]
[化43]
[化44]
[化45]
[化46]
[化47]
抗蝕劑組成物中的光酸產生劑的含量並無特別限制，就本發明的效果更優異的方面而言，相對於組成物的總固體成分，較佳為5質量%以上，更佳為9質量%以上，進而佳為15質量%以上。另外，所述含量較佳為45質量%以下，更佳為40質量%以下，進而佳為35質量%以下。 光酸產生劑可單獨使用一種，亦可使用兩種以上。The content of the photoacid generator in the resist composition is not particularly limited. In terms of the more excellent effect of the present invention, it is preferably 5% by mass or more with respect to the total solid content of the composition, and more preferably 9% by mass or more, more preferably 15% by mass or more. In addition, the content is preferably 45% by mass or less, more preferably 40% by mass or less, and still more preferably 35% by mass or less. One type of photoacid generator may be used alone, or two or more types may be used.
＜（C）溶劑＞ 抗蝕劑組成物亦可含有溶劑。 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。＜(C) Solvent＞ The resist composition may also contain 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過程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, the coating properties of the composition are 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, so that the film thickness unevenness of the composition film and the spin coating process can be suppressed. The production of precipitates and so on.
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）。Component (M1) is preferably at least one selected from the group consisting of propylene glycol monomethylether acetate (PGMEA: propylene glycol monomethylether acetate), propylene glycol monomethyl ether propionate and propylene glycol monoethyl ether acetate, and Preferably, it is propylene glycol monomethyl ether acetate (PGMEA).
成分（M2）較佳為以下溶劑。 丙二醇單烷基醚較佳為丙二醇單甲醚（propylene glycol monomethylether，PGME）及丙二醇單***（propylene glycol monoethyl ether，PGEE）。 乳酸酯較佳為乳酸乙酯、乳酸丁酯或乳酸丙酯。 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。 烷氧基丙酸酯較佳為3-甲氧基丙酸甲酯（methyl 3-Methoxypropionate，MMP）或3-乙氧基丙酸乙酯（ethyl 3-ethoxypropionate，EEP）。 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。 環狀酮較佳為甲基環己酮、異佛爾酮、環戊酮或環己酮。 內酯較佳為γ-丁內酯。 碳酸伸烷基酯較佳為碳酸伸丙酯。The component (M2) is preferably the following solvent. The propylene glycol monoalkyl ether is preferably propylene glycol monomethylether (PGME) and propylene glycol monoethyl ether (PGEE). The lactate is preferably ethyl lactate, butyl lactate or propyl lactate. The acetate is preferably methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate, isoamyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate or acetic acid. -Methoxybutyl ester. In addition, butyl butyrate is also preferred. The alkoxy propionate is preferably methyl 3-Methoxypropionate (MMP) or ethyl 3-ethoxypropionate (EEP). The chain ketone is preferably 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone, 4-heptanone, 1-hexanone, 2-hexanone, diiso Butyl ketone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetoacetone, acetonyl acetone, ionone, diacetone alcohol, acetoacetone, acetophenone, methyl naphthalene Base ketone or methyl amyl ketone. The cyclic ketone is preferably methylcyclohexanone, isophorone, cyclopentanone or cyclohexanone. The lactone is preferably γ-butyrolactone. The alkylene carbonate is preferably propylene carbonate.
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。The component (M2) is more preferably propylene glycol monomethyl ether (PGME), ethyl lactate, ethyl 3-ethoxypropionate, methyl amyl ketone, cyclohexanone, butyl acetate, amyl acetate, and γ-butyl Lactone 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，例如可列舉乙酸戊酯、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、丙酸庚酯及丁酸丁酯等，較佳為乙酸異戊酯。Examples of ester solvents having 7 or more carbon atoms and 2 or less heteroatoms include pentyl acetate, 2-methylbutyl acetate, 1-methylbutyl acetate, hexyl acetate, pentyl propionate, Hexyl propionate, butyl propionate, isobutyl isobutyrate, heptyl propionate, butyl butyrate, etc., preferably isoamyl acetate.
成分（M2）較佳為閃點（以下，亦稱為fp）為37℃以上的溶劑。 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。The component (M2) is preferably a solvent having a flash point (hereinafter also referred to as fp) of 37°C or higher. The component (M2) is preferably propylene glycol monomethyl ether (fp: 47°C), ethyl lactate (fp: 53°C), ethyl 3-ethoxypropionate (fp: 49°C), methylpentyl 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.
溶劑較佳為含有成分（M1）。溶劑更佳為實質上僅包含成分（M1）或者為成分（M1）與其他成分的混合溶劑。於後者的情況下，溶劑進而佳為含有成分（M1）與成分（M2）此兩者。The solvent preferably contains the component (M1). It is more preferable that the solvent contains substantially only the component (M1) or is a mixed solvent of the component (M1) and other components. In the latter case, the solvent further preferably contains both the component (M1) and the component (M2).
成分（M1）與成分（M2）的質量比（M1/M2）較佳為「100/0」～「0/10」，更佳為「100/0」～「15/85」，進而佳為「100/0」～「40/60」，尤佳為「100/0」～「60/40」。 即，於溶劑含有成分（M1）與成分（M2）此兩者的情況下，成分（M1）相對於成分（M2）的質量比較佳為15/85以上，更佳為40/60以上，進而佳為60/40以上。若採用所述構成，則可進一步減少顯影缺陷數。The mass ratio (M1/M2) of the component (M1) to the component (M2) is preferably "100/0" to "0/10", more preferably "100/0" to "15/85", and still more preferably "100/0"～"40/60", especially "100/0"～"60/40". That is, when the solvent contains both the component (M1) and the component (M2), the mass of the component (M1) relative to the component (M2) is preferably 15/85 or more, more preferably 40/60 or more, and further Preferably, it is 60/40 or more. According to this configuration, the number of development defects can be further reduced.
再者，於溶劑含有成分（M1）與成分（M2）此兩者的情況下，成分（M1）相對於成分（M2）的質量比例如設為99/1以下。In addition, when the solvent contains both the component (M1) and the component (M2), the mass ratio of the component (M1) to the component (M2) is set to 99/1 or less, for example.
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5質量%～30質量%。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 5% by mass to 30% by mass relative to the total amount of the solvent.
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，可進一步提高抗蝕劑組成物的塗佈性。 再者，所謂固體成分是指溶劑以外的所有成分。 所謂固體成分濃度，是指除溶劑以外的其他成分的質量相對於抗蝕劑組成物的總質量的質量百分率。The content of the solvent in the resist composition 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 coatability of the resist composition can be further improved. In addition, the term "solid content" refers to all components other than the solvent. The so-called solid content concentration refers to the mass percentage of the mass of components other than the solvent relative to the total mass of the resist composition.
＜（D）酸擴散控制劑＞ 抗蝕劑組成物亦可進而含有酸擴散控制劑。酸擴散控制劑作為捕獲由光酸產生劑所產生的酸的淬滅劑發揮作用，且發揮控制抗蝕劑膜中的酸的擴散現象的作用。 酸擴散控制劑例如可為鹼性化合物。 鹼性化合物較佳為具有下述通式（A）～通式（E）所表示的結構的化合物。＜(D) Acid diffusion control agent＞ The resist composition may further contain an acid diffusion control agent. The acid diffusion control agent functions as a quencher that traps the acid generated by the photoacid generator, and also functions to control the diffusion phenomenon of the acid in the resist film. The acid diffusion control agent may be, for example, a basic compound. The basic compound is preferably a compound having a structure represented by the following general formula (A) to general formula (E).
[化48]
通式（A）及通式（E）中，R200 、R201 及R202 可相同亦可不同，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（較佳為碳數6～20），此處，R201 與R202 亦可彼此鍵結而形成環。In general formula (A) and general formula (E), R 200 , R 201 and R 202 may be the same or different, and represent a hydrogen atom, an alkyl group (preferably with 1 to 20 carbon atoms), a cycloalkyl group (preferably It is a carbon number of 3-20) or an aryl group (preferably a carbon number of 6-20). Here, R 201 and R 202 may also be bonded to each other to form a ring.
關於所述烷基，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。 R203 、R204 、R205 及R206 可相同亦可不同，表示碳數1～20的烷基。 該些通式（A）及通式（E）中的烷基更佳為未經取代。Regarding 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. R 203 , R 204 , R 205 and R 206 may be the same or different, and represent an alkyl group having 1 to 20 carbon atoms. It is more preferable that the alkyl group in these general formula (A) and general formula (E) is unsubstituted.
作為鹼性化合物，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（烷基部分可為直鏈狀亦可為支鏈狀，一部分可經醚基及/或酯基取代。烷基部分的氫原子以外的所有原子的合計數較佳為1～17）、或哌啶等。其中，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等。The basic compound is preferably guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine (the alkyl part may be linear or branched) Part of it may be substituted with ether groups and/or ester groups. The total number of all atoms other than hydrogen atoms in the alkyl part is preferably 1-17), piperidine, or the like. Among them, more preferred are compounds having an imidazole structure, a diazabicyclic structure, an onium hydroxide structure, an onium carboxylate structure, a trialkylamine structure, an aniline structure, or a pyridine structure, and an alkyl group having a hydroxyl group and/or an ether bond. Amine derivatives, or aniline derivatives having a hydroxyl group and/or ether bond, etc.
作為具有咪唑結構的化合物，例如可列舉咪唑、2,4,5-三苯基咪唑及苯並咪唑等。作為具有二氮雜雙環結構的化合物，例如可列舉：1,4-二氮雜雙環[2,2,2]辛烷、1,5-二氮雜雙環[4,3,0]壬-5-烯及1,8-二氮雜雙環[5,4,0]十一-7-烯等。作為具有氫氧化鎓結構的化合物，例如可列舉：三芳基氫氧化鋶、苯甲醯甲基氫氧化鋶及具有2-氧代烷基的氫氧化鋶等。具體而言，可列舉：三苯基氫氧化鋶、三(第三丁基苯基)氫氧化鋶、雙(第三丁基苯基)氫氧化碘、苯甲醯甲基氫氧化噻吩鎓及2-氧代丙基氫氧化噻吩鎓等。具有羧酸鎓鹽結構的化合物是具有氫氧化鎓結構的化合物的陰離子部成為羧酸鹽者，例如可列舉：乙酸鹽、金剛烷-1-羧酸鹽及全氟烷基羧酸鹽等。作為具有三烷基胺結構的化合物，例如可列舉三(正丁基)胺及三(正辛基)胺等。作為苯胺化合物，例如可列舉：2,6-二異丙基苯胺、N,N-二甲基苯胺、N,N-二丁基苯胺及N,N-二己基苯胺等。作為具有羥基及/或醚鍵的烷基胺衍生物，例如可列舉：乙醇胺、二乙醇胺、三乙醇胺、三(甲氧基乙氧基乙基)胺及(HO-C2 H4 -O-C2 H4 )2 N(-C3 H6 -O-CH3 )等。作為具有羥基及/或醚鍵的苯胺衍生物，例如可列舉N,N-雙(羥基乙基)苯胺等。Examples of the compound having an imidazole structure include imidazole, 2,4,5-triphenylimidazole, and benzimidazole. Examples of the compound having a diazabicyclic structure include: 1,4-diazabicyclo[2,2,2]octane, 1,5-diazabicyclo[4,3,0]non-5 -Ene and 1,8-diazabicyclo[5,4,0]undec-7-ene, etc. Examples of the compound having an onium hydroxide structure include triaryl sulfonium hydroxide, benzyl methyl sulfonium hydroxide, and sulfonium hydroxide having a 2-oxoalkyl group. Specifically, examples include: triphenyl sulfonium hydroxide, tris(tertiary butylphenyl) sulfonium hydroxide, bis(tertiary butylphenyl) iodine hydroxide, benzylmethylthiophenium hydroxide, and 2-oxopropyl thiophenium hydroxide and the like. The compound having an onium carboxylate structure is one in which the anion portion of the compound having an onium hydroxide structure becomes a carboxylate, and examples thereof include acetate, adamantane-1-carboxylate, and perfluoroalkylcarboxylate. Examples of the compound having a trialkylamine structure include tri(n-butyl)amine and tri(n-octyl)amine. Examples of the aniline compound include 2,6-diisopropylaniline, N,N-dimethylaniline, N,N-dibutylaniline, and N,N-dihexylaniline. Examples of alkylamine derivatives having hydroxyl groups and/or ether bonds include ethanolamine, diethanolamine, triethanolamine, tris(methoxyethoxyethyl)amine, and (HO-C 2 H 4 -OC 2 H 4 ) 2 N(-C 3 H 6 -O-CH 3 ) and so on. As an aniline derivative which has a hydroxyl group and/or an ether bond, N,N-bis(hydroxyethyl) aniline etc. are mentioned, for example.
作為鹼性化合物，可較佳地列舉具有苯氧基的胺化合物及具有苯氧基的銨鹽化合物。As a basic compound, the amine compound which has a phenoxy group and the ammonium salt compound which has a phenoxy group are mentioned suitably.
作為胺化合物，例如可使用一級、二級及三級胺化合物，較佳為至少一個烷基與氮原子鍵結的胺化合物。胺化合物更佳為三級胺化合物。胺化合物中，若至少一個烷基（較佳為碳數1～20）與氮原子鍵結，則除了烷基以外，環烷基（較佳為碳數3～20）或芳基（較佳為碳數6～12）亦可與氮原子鍵結。 另外，胺化合物較佳為具有氧伸烷基。氧伸烷基的數量於分子內較佳為1以上，更佳為3～9，進而佳為4～6。氧伸烷基中亦較佳為氧伸乙基（-CH2 CH2 O-）、或氧伸丙基（-CH(CH3 )CH2 O-或CH2 CH2 CH2 O-），更佳為氧伸乙基。As the amine compound, for example, primary, secondary, and tertiary amine compounds can be used, and an amine compound in which at least one alkyl group is bonded to a nitrogen atom is preferred. The amine compound is more preferably a tertiary amine compound. In the amine compound, if at least one alkyl group (preferably carbon number 1-20) is bonded to a nitrogen atom, in addition to the alkyl group, a cycloalkyl group (preferably a carbon number 3-20) or an aryl group (preferably It has 6 to 12 carbon atoms) and can also be bonded to a nitrogen atom. In addition, the amine compound preferably has an oxyalkylene group. The number of oxyalkylene groups in the molecule is preferably 1 or more, more preferably 3-9, and still more preferably 4-6. The oxyethylene group is also preferably oxyethylene group (-CH 2 CH 2 O-) or oxyethylene group (-CH(CH 3 )CH 2 O- or CH 2 CH 2 CH 2 O-), More preferred is oxyethylene.
作為銨鹽化合物，例如可列舉一級、二級、三級及四級銨鹽化合物，較佳為至少一個烷基與氮原子鍵結的銨鹽化合物。銨鹽化合物中，若至少一個烷基（較佳為碳數1～20）與氮原子鍵結，則除了烷基以外，環烷基（較佳為碳數3～20）或芳基（較佳為碳數6～12）亦可與氮原子鍵結。 銨鹽化合物較佳為具有氧伸烷基。氧伸烷基的數量於分子內較佳為1以上，更佳為3～9，進而佳為4～6。氧伸烷基中較佳為氧伸乙基（-CH2 CH2 O-）、或氧伸丙基（-CH(CH3 )CH2 O-或-CH2 CH2 CH2 O-），更佳為氧伸乙基。 作為銨鹽化合物的陰離子，例如可列舉鹵素原子、磺酸鹽、硼酸鹽及磷酸鹽等，其中，較佳為鹵素原子或磺酸鹽。鹵素原子較佳為氯原子、溴原子或碘原子。磺酸鹽較佳為碳數1～20的有機磺酸鹽。作為有機磺酸鹽，例如可列舉碳數1～20的烷基磺酸鹽及芳基磺酸鹽。烷基磺酸鹽的烷基亦可具有取代基，作為取代基，例如可列舉：氟原子、氯原子、溴原子、烷氧基、醯基及芳香環基等。作為烷基磺酸鹽，例如可列舉：甲磺酸鹽、乙磺酸鹽、丁磺酸鹽、己磺酸鹽、辛磺酸鹽、苄基磺酸鹽、三氟甲磺酸鹽、五氟乙磺酸鹽及九氟丁磺酸鹽等。作為芳基磺酸鹽的芳基，可列舉苯環基、萘環基及蒽環基。苯環基、萘環基及蒽環基可具有的取代基較佳為碳數1～6的直鏈狀或支鏈狀的烷基、或碳數3～6的環烷基。作為直鏈狀或支鏈狀的烷基及環烷基，例如可列舉：甲基、乙基、正丙基、異丙基、正丁基、異丁基、第三丁基、正己基及環己基等。作為其他取代基，例如可列舉：碳數1～6的烷氧基、鹵素原子、氰基、硝基、醯基及醯氧基等。Examples of the ammonium salt compound include primary, secondary, tertiary, and quaternary ammonium salt compounds, and ammonium salt compounds in which at least one alkyl group is bonded to a nitrogen atom are preferred. In the ammonium salt compound, if at least one alkyl group (preferably carbon number 1-20) is bonded to a nitrogen atom, in addition to the alkyl group, a cycloalkyl group (preferably a carbon number 3-20) or an aryl group (more Preferably, the carbon number is 6-12) and it can also be bonded to the nitrogen atom. The ammonium salt compound preferably has an oxyalkylene group. The number of oxyalkylene groups in the molecule is preferably 1 or more, more preferably 3-9, and still more preferably 4-6. The oxyethylene group is preferably oxyethylene group (-CH 2 CH 2 O-) or oxyethylene group (-CH(CH 3 )CH 2 O- or -CH 2 CH 2 CH 2 O-), More preferred is oxyethylene. As an anion of an ammonium salt compound, a halogen atom, a sulfonate, a borate, a phosphate, etc. are mentioned, for example, Among these, a halogen atom or a sulfonate is preferable. The halogen atom is preferably a chlorine atom, a bromine atom or an iodine atom. The sulfonate is preferably an organic sulfonate having 1 to 20 carbon atoms. Examples of organic sulfonates include alkyl sulfonates and aryl sulfonates having 1 to 20 carbon atoms. The alkyl group of the alkyl sulfonate may have a substituent, and examples of the substituent include a fluorine atom, a chlorine atom, a bromine atom, an alkoxy group, an acyl group, and an aromatic ring group. Examples of alkyl sulfonates include methanesulfonate, ethanesulfonate, butanesulfonate, hexylsulfonate, octylsulfonate, benzylsulfonate, trifluoromethanesulfonate, five Fluoroethanesulfonate and nonafluorobutanesulfonate, etc. Examples of the aryl group of the arylsulfonate include a benzene ring group, a naphthalene ring group, and an anthracene ring group. The substituent which the benzene ring group, naphthyl ring group, and anthracyclyl group may have is preferably a linear or branched alkyl group having 1 to 6 carbon atoms, or a cycloalkyl group having 3 to 6 carbon atoms. Examples of linear or branched alkyl groups and cycloalkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-hexyl, and Cyclohexyl and so on. Examples of other substituents include alkoxy groups having 1 to 6 carbon atoms, halogen atoms, cyano groups, nitro groups, acyl groups, and acyloxy groups.
所謂具有苯氧基的胺化合物及具有苯氧基的銨鹽化合物，是指在胺化合物或銨鹽化合物的烷基的與氮原子為相反側的末端具有苯氧基的化合物。 作為苯氧基的取代基，例如可列舉：烷基、烷氧基、鹵素原子、氰基、硝基、羧酸基、羧酸酯基、磺酸酯基、芳基、芳烷基、醯氧基及芳氧基等。取代基的取代位可為2位～6位中的任一者。取代基的數量可為1～5中的任一者。The amine compound having a phenoxy group and the ammonium salt compound having a phenoxy group refer to a compound having a phenoxy group at the end of the alkyl group of the amine compound or the ammonium salt compound on the opposite side to the nitrogen atom. Examples of the substituent of the phenoxy group include an alkyl group, an alkoxy group, a halogen atom, a cyano group, a nitro group, a carboxylic acid group, a carboxylate group, a sulfonate group, an aryl group, an aralkyl group, and an Oxy and aryloxy, etc. The substitution position of the substituent may be any of the 2-position to the 6-position. The number of substituents may be any one of 1-5.
較佳為於苯氧基與氮原子之間具有至少一個氧伸烷基。氧伸烷基的數量於分子內較佳為1以上，更佳為3～9，進而佳為4～6。氧伸烷基中亦較佳為氧伸乙基（-CH2 CH2 O-）、或氧伸丙基（-CH(CH3 )CH2 O-或-CH2 CH2 CH2 O-），更佳為氧伸乙基。It is preferable to have at least one oxyalkylene group between the phenoxy group and the nitrogen atom. The number of oxyalkylene groups in the molecule is preferably 1 or more, more preferably 3-9, and still more preferably 4-6. The oxyethylene group is also preferably oxyethylene (-CH 2 CH 2 O-) or oxyethylene (-CH(CH 3 )CH 2 O- or -CH 2 CH 2 CH 2 O-) , More preferably oxyethylene.
具有苯氧基的胺化合物可藉由於將具有苯氧基的一級胺或二級胺、以及鹵代烷基醚加熱並使其反應後，向反應體系中添加強鹼（例如氫氧化鈉、氫氧化鉀及四烷基銨等）的水溶液，進而利用有機溶劑（例如乙酸乙酯及氯仿等）萃取反應生成物而獲得。或者，可藉由將一級胺或二級胺與末端具有苯氧基的鹵代烷基醚加熱並使其反應後，向反應體系中添加強鹼的水溶液，進而利用有機溶劑萃取反應生成物而獲得。The amine compound having a phenoxy group can be obtained by heating and reacting a primary or secondary amine having a phenoxy group and a halogenated alkyl ether, and then adding a strong base (such as sodium hydroxide, potassium hydroxide, etc.) to the reaction system. And an aqueous solution of tetraalkylammonium etc.), and then extract the reaction product with an organic solvent (for example, ethyl acetate and chloroform) to obtain. Alternatively, it can be obtained by heating and reacting a primary amine or a secondary amine and a halogenated alkyl ether having a phenoxy group at the end, adding an aqueous solution of a strong base to the reaction system, and then extracting the reaction product with an organic solvent.
（具有質子受體性官能基且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、消失或者由質子受體性變化為酸性的化合物的化合物（PA）） 抗蝕劑組成物亦可含有：具有質子受體性官能基且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的化合物（以下，亦稱為化合物（PA））來作為酸擴散控制劑。(Compounds (PA) that have a proton-accepting functional group and are decomposed by the irradiation of actinic rays or radiation to produce a compound (PA) whose proton-accepting properties are reduced, disappeared, or changed from proton-accepting properties to acidic properties) The resist composition may also contain: a compound having a proton-accepting functional group that is decomposed by irradiation with actinic rays or radiation to produce a compound whose proton-accepting property decreases or disappears or changes from proton-accepting property to acidity (Hereinafter, it is also referred to as a compound (PA)) as an acid diffusion control agent.
所謂質子受體性官能基，是指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，例如是指具有下述通式所示的部分結構的氮原子。The so-called proton-accepting functional group refers to a functional group having a group or electrons that can electrostatically interact with protons. For example, it refers to a functional group having a macrocyclic structure such as a cyclic polyether, or a functional group containing A functional group that conjugates the nitrogen atom of a non-shared electron pair. 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 general formula.
[化49]
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等。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（PA）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，是指因於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（PA）與質子生成質子加成物時，其化學平衡中的平衡常數減少。The compound (PA) 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 property or the change from proton acceptor property to acidity refers to the change in proton acceptor property caused by the addition of protons to the proton acceptor functional group. Specifically, it means that when a proton adduct is generated from a compound (PA) having a proton-accepting functional group (PA) and a proton, the equilibrium constant in the chemical equilibrium decreases.
作為化合物（PA），例如可引用日本專利特開2014-41328號公報的段落[0421]～段落[0428]、日本專利特開2014-134686號公報的段落[0108]～段落[0116]中記載的化合物，將該些內容併入至本說明書中。As the compound (PA), for example, the descriptions in paragraph [0421] to paragraph [0428] of JP 2014-41328 and paragraph [0108] to paragraph [0116] of JP 2014-134686 can be cited. Compounds, these contents are incorporated into this specification.
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亦可作為酸擴散控制劑使用。所述低分子化合物較佳為於氮原子上具有因酸的作用而脫離的基的胺衍生物。 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。 低分子化合物的分子量較佳為100～1000，更佳為100～700，進而佳為100～500。 低分子化合物亦可於氮原子上具有含有保護基的胺甲酸酯基。A low-molecular compound having a nitrogen atom and having a group detached by the action of an acid can also be used as an acid diffusion control agent. The low-molecular compound is preferably an amine derivative having a group detached by the action of an acid on the nitrogen atom. 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, more preferably a urethane group or Semiamine acetal ether group. The molecular weight of the low-molecular compound is preferably 100-1000, more preferably 100-700, and still more preferably 100-500. The low-molecular compound may also have a urethane group containing a protective group on the nitrogen atom.
酸擴散控制劑的具體例如下所述，但本發明並不限定於此。The specific example of the acid diffusion control agent is as follows, but the present invention is not limited to this.
[化50]
[化51]
[化52]
[化53]
於抗蝕劑組成物含有酸擴散控制劑的情況下，相對於抗蝕劑組成物的總固體成分，酸擴散控制劑的含量較佳為0.001質量%～15質量%，更佳為0.01質量%～8質量%。 酸擴散控制劑可單獨使用一種，亦可使用兩種以上。 另外，於抗蝕劑組成物含有通式（PB）所表示的化合物作為光酸產生劑的情況下，通式（PB）所表示的化合物中含有具有相當於酸擴散控制劑的功能的結構，因此亦較佳為抗蝕劑組成物實質上不含酸擴散控制劑。此處，所謂實質上不含酸擴散控制劑，是指相對於通式（PB）所表示的化合物的含量，酸擴散控制劑的含量為5質量%以下。When the resist composition contains an acid diffusion control agent, the content of the acid diffusion control agent is preferably 0.001% by mass to 15% by mass, more preferably 0.01% by mass relative to the total solid content of the resist composition ～8% by mass. One kind of acid diffusion control agent may be used alone, or two or more kinds may be used. In addition, when the resist composition contains a compound represented by general formula (PB) as a photoacid generator, the compound represented by general formula (PB) contains a structure having a function equivalent to an acid diffusion control agent, Therefore, it is also preferable that the resist composition does not substantially contain an acid diffusion control agent. Here, the term "substantially not containing the acid diffusion control agent" means that the content of the acid diffusion control agent is 5% by mass or less with respect to the content of the compound represented by the general formula (PB).
光酸產生劑與酸擴散控制劑在抗蝕劑組成物中的使用比例較佳為光酸產生劑/酸擴散控制劑（莫耳比）=2.5～300。就感度及解析度的方面而言，莫耳比較佳為2.5以上，就抑制至曝光後加熱處理為止的經時的抗蝕劑圖案的變粗所引起的解析度的降低的方面而言，莫耳比較佳為300以下。光酸產生劑/酸擴散控制劑（莫耳比）更佳為5.0～200，進而佳為7.0～150。The use ratio of the photoacid generator and the acid diffusion control agent in the resist composition is preferably the photoacid generator/acid diffusion control agent (molar ratio)=2.5-300. In terms of sensitivity and resolution, the molar ratio is preferably 2.5 or more. In terms of suppressing the decrease in resolution due to the thickening of the resist pattern over time until the heat treatment after exposure, it is not The ear ratio is preferably 300 or less. The photoacid generator/acid diffusion control agent (mole ratio) is more preferably 5.0 to 200, and still more preferably 7.0 to 150.
作為酸擴散控制劑，例如亦可列舉日本專利特開2013-11833號公報的段落[0140]～[0144]中記載的化合物（胺化合物、含醯胺基的化合物、脲化合物及含氮雜環化合物等）。As the acid diffusion control agent, for example, the compounds described in paragraphs [0140] to [0144] of Japanese Patent Laid-Open No. 2013-11833 (amine compounds, amide group-containing compounds, urea compounds, and nitrogen-containing heterocyclic rings) Compounds, etc.).
＜（E）疏水性樹脂＞ 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。＜(E) Hydrophobic resin＞ The resist composition 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方面而言，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。In terms 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，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，例如可列舉苯基及萘基等芳基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，例如可列舉US2012/0251948A1的段落[0519]中所例示的重複單元。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 of 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 the repeating unit having a fluorine atom or a silicon atom, for example, the repeating unit 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]～段落[0415]的記載，將該些內容併入至本案說明書中。Regarding the hydrophobic resin, reference can be made to the description of paragraph [0348] to paragraph [0415] of JP 2014-010245 A, and these contents are incorporated into the specification of the present application.
再者，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。In addition, as the hydrophobic resin, the resins described in Japanese Patent Application Publication No. 2011-248019, Japanese Patent Application Publication No. 2010-175859, and Japanese Patent Application Publication No. 2012-032544 may also be preferably used.
於抗蝕劑組成物含有疏水性樹脂的情況下，相對於抗蝕劑組成物的總固體成分，疏水性樹脂的含量較佳為0.01質量%～20質量%，更佳為0.1質量%～15質量%。When the resist composition contains a hydrophobic resin, the content of the hydrophobic resin is preferably 0.01% by mass to 20% by mass, and more preferably 0.1% by mass to 15%, relative to the total solid content of the resist composition. quality%.
＜（F）界面活性劑＞ 抗蝕劑組成物亦可含有界面活性劑。若含有界面活性劑，則可形成密接性更優異、顯影缺陷更少的圖案。 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及4430（住友3M（股）製造）；美佳法（Megafac）F171、F173、F176、F189、F113、F110、F177、F120及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及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及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。＜(F) Surfactant＞ The resist composition may also contain a surfactant. If a surfactant is contained, a pattern with more excellent adhesiveness and fewer development defects can be formed. The surfactant is preferably a fluorine-based and/or silicon-based surfactant. 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 and 4430 (manufactured by Sumitomo 3M Co., Ltd.) can also be used; Megafac F171 , F173, F176, F189, F113, F110, F177, F120 and 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, and PF6520 (manufactured by Onofa (OMNOVA)); KH-20 (manufactured by Asahi Kasei (Stock)); FTX-204G, 208G, 218G, 230G, 204D, 208D, 212D, 218D And 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。 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. 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，亦可使用兩種以上。These surfactants may be used singly, or two or more of them may be used.
於抗蝕劑組成物含有界面活性劑的情況下，相對於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%。When the resist composition contains a surfactant, the content of the surfactant is preferably 0.0001% by mass to 2% by mass, and more preferably 0.0005% by mass to 1% by mass relative to the total solid content of the composition.
＜（G）其他添加劑＞ 抗蝕劑組成物亦可進而含有溶解抑制化合物、染料、塑化劑、光增感劑、光吸收劑及/或促進在顯影液中的溶解性的化合物（例如分子量1000以下的酚化合物、或含有羧酸基的脂環族或脂肪族化合物）。＜(G) Other additives＞ The resist composition may further contain a dissolution inhibiting compound, a dye, a plasticizer, a photosensitizer, a light absorber, and/or a compound that promotes solubility in a developer (for example, a phenol compound with a molecular weight of 1000 or less, or Alicyclic or aliphatic compounds containing carboxylic acid groups).
抗蝕劑組成物亦可進而含有溶解抑制化合物。此處，所謂「溶解抑制化合物」是指因酸的作用而分解且在有機系顯影液中的溶解度減少的分子量為3000以下的化合物。The resist composition may further contain a dissolution inhibiting compound. Here, the "dissolution inhibiting compound" refers to a compound having a molecular weight of 3000 or less that is decomposed by the action of an acid and has a reduced solubility in an organic developer.
[用途] 本發明的組成物是有關於一種藉由光化射線或放射線的照射而進行反應且性質發生變化的感光化射線性或感放射線性樹脂組成物。更詳細而言，本發明的組成物是有關於一種在IC（Integrated Circuit）等半導體製造步驟、液晶或熱能頭（thermal head）等電路基板的製造、壓印用模具結構體的製作、其他的感光蝕刻加工（photofabrication）步驟、或平版印刷版或酸硬化性組成物的製造中使用的感光化射線性或感放射線性樹脂組成物。本發明中形成的圖案可用於蝕刻步驟、離子注入步驟、凸塊電極形成步驟、再配線形成步驟及微機電系統（Micro Electro Mechanical Systems，MEMS）等。[use] The composition of the present invention relates to a photosensitive ray-sensitive or radiation-sensitive resin composition that reacts and changes its properties by irradiation with actinic rays or radiation. In more detail, the composition of the present invention is related to the manufacturing process of semiconductors such as IC (Integrated Circuit), the manufacturing of circuit substrates such as liquid crystal or thermal head, the manufacturing of mold structures for imprinting, and others. A photosensitive ray-sensitive or radiation-sensitive resin composition used in the photofabrication step, or the production of a lithographic printing plate or an acid-curable composition. The pattern formed in the present invention can be used in the etching step, ion implantation step, bump electrode formation step, rewiring formation step, Micro Electro Mechanical Systems (MEMS), etc.
[感光化射線性或感放射線性膜] 本發明亦是有關於一種藉由本發明的感光化射線性或感放射線性組成物而形成的感光化射線性或感放射線性膜（亦稱為「抗蝕劑膜」）。此種膜例如藉由將本發明的組成物塗佈在基板等支撐體上而形成。該膜的厚度較佳為0.02 μm～0.1 μm。 作為塗佈在基板上的方法，藉由旋塗、輥塗、流塗、浸塗、噴塗、刮刀塗佈等適當的塗佈方法塗佈在基板上，但較佳為旋轉塗佈，其轉速較佳為1000 rpm～3000 rpm（每分鐘轉數（rotations per minute））。塗佈膜在60℃～150℃下預烘焙1～20分鐘，較佳為在80℃～120℃下預烘焙1～10分鐘形成薄膜。 關於構成被加工基板及其最表層的材料，例如在半導體用晶圓的情況下，可使用矽晶圓，作為成為最表層的材料的例子，可列舉Si、SiO2 、SiN、SiON、TiN、WSi、BPSG、SOG、有機防反射膜等。[Sensitizing ray-sensitive or radiation-sensitive film] The present invention also relates to a sensitizing ray-sensitive or radiation-sensitive film formed by the sensitizing ray or radiation-sensitive composition of the present invention (also called "anti-radiation-sensitive film"). Etchant film”). Such a film is formed, for example, by coating the composition of the present invention on a support such as a substrate. The thickness of the film is preferably 0.02 μm to 0.1 μm. As the method of coating on the substrate, spin coating, roll coating, flow coating, dip coating, spray coating, knife coating and other appropriate coating methods are used to coat the substrate on the substrate, but spin coating is preferred. Preferably, it is 1000 rpm to 3000 rpm (rotations per minute). The coating film is pre-baked at 60°C to 150°C for 1 to 20 minutes, preferably at 80°C to 120°C for 1 to 10 minutes to form a thin film. Regarding the material constituting the substrate to be processed and its outermost layer, for example, in the case of a semiconductor wafer, a silicon wafer can be used. Examples of the material that becomes the outermost layer include Si, SiO 2 , SiN, SiON, TiN, WSi, BPSG, SOG, organic anti-reflection film, etc.
〔圖案形成方法〕 使用所述抗蝕劑組成物的圖案形成方法的順序並無特別限制，但較佳為具有以下步驟。 步驟1：使用抗蝕劑組成物於基板上形成抗蝕劑膜的步驟 步驟2：對抗蝕劑膜（較佳為利用電子束（EB）、EUV光）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而形成圖案的步驟 以下，對所述各步驟的順序進行詳述。[Pattern forming method] The order of the pattern formation method using the resist composition is not particularly limited, but it is preferable to have the following steps. Step 1: Step of forming a resist film on a substrate using a resist composition Step 2: Exposing the resist film (preferably using electron beam (EB), EUV light) Step 3: Use a developer to develop the exposed resist film to form a pattern 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基板上形成抗蝕劑膜的步驟。抗蝕劑組成物的定義如上所述。<Step 1: Resist film formation step> Step 1 is a step of forming a resist film on a substrate using the resist composition. The definition of the resist composition is as described above.
作為使用抗蝕劑組成物於基板上形成抗蝕劑膜的方法，例如可列舉於基板上塗佈抗蝕劑組成物的方法。 再者，較佳為於塗佈前視需要對抗蝕劑組成物進行過濾器過濾。過濾器的細孔徑較佳為0.1 μm以下，更佳為0.05 μm以下，進而佳為0.03 μm以下。另外，過濾器較佳為聚四氟乙烯製、聚乙烯製或尼龍製。As a method of forming a resist film on a substrate using the resist composition, for example, a method of applying the resist composition on the substrate can be cited. Furthermore, it is preferable to filter the resist composition as necessary before coating. The pore size of the filter is preferably 0.1 μm or less, more preferably 0.05 μm or less, and still more preferably 0.03 μm or less. In addition, the filter is preferably made of polytetrafluoroethylene, polyethylene, or nylon.
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零件的製造中所使用的基板（例：矽、二氧化矽被覆）上。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 parts by an appropriate coating method such as a spinner or a coater. The coating method is preferably spin coating using a spinner. 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，例如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實施，亦可使用加熱板等實施。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, for example. 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～65 nm，更佳為15 nm～50 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 65 nm, and more preferably 15 nm to 50 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，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，進而佳為40 nm～80 nm。 關於頂塗層，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後述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 above-mentioned resist film, and then dried to form the top coat. The film thickness of the top coating layer is preferably 10 nm to 200 nm, more preferably 20 nm to 100 nm, and still more preferably 40 nm to 80 nm. The top coat layer is not particularly limited, and a conventionally known top coat layer can be formed by a conventionally known method. For example, it can be formed based on the description in paragraphs [0072] to [0082] of Japanese Patent Laid-Open No. 2014-059543 Top coat. 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 basic compounds that can be contained in the resist composition described later. 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（較佳為利用電子束（EB）、EUV光）進行曝光的步驟。 作為曝光的方法，例如可列舉經由規定的遮罩對所形成的抗蝕劑膜照射電子束（EB）或EUV光的方法。<Step 2: Exposure Step> Step 2 is a step of exposing the resist film (preferably using electron beam (EB), EUV light). As a method of exposure, for example, a method of irradiating the formed resist film with electron beam (EB) or EUV light through a predetermined mask.
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實施，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。 顯影液可為鹼性顯影液，亦可為含有有機溶劑的顯影液（以下，亦稱為有機系顯影液）。<Step 3: Development Step> Step 3 is a step of developing the exposed resist film using a developing solution to form a pattern. The developer may be an alkaline developer or a developer containing an organic solvent (hereinafter, also referred to as an organic developer).
作為顯影方法，例如可列舉：使基板於充滿顯影液的槽中浸漬固定時間的方法（浸漬法）；利用表面張力使顯影液堆積至基板表面並靜止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 tank filled with a developer solution for a fixed period of time (dipping method); a method of depositing the developer solution on the surface of the substrate using surface tension and resting for a fixed period of time for development (coating liquid ( puddle method); a method of spraying developer on the surface of the substrate (spray method); and a 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 method) . 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.
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。As the alkaline developer, it is preferable to use an alkaline aqueous solution containing an 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.
有機系顯影液較佳為含有選自由酮系溶劑、酯系溶劑、醇系溶劑、醯胺系溶劑、醚系溶劑及烴系溶劑所組成的群組中的至少一種有機溶劑的顯影液。The organic developer is preferably a developer containing at least one organic solvent selected from the group consisting of ketone solvents, ester solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents.
作為酮系溶劑，例如可列舉：1-辛酮、2-辛酮、1-壬酮、2-壬酮、丙酮、2-庚酮（甲基戊基酮）、4-庚酮、1-己酮、2-己酮、二異丁基酮、環己酮、甲基環己酮、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、異佛爾酮及碳酸伸丙酯等。Examples of ketone solvents include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone (methylpentyl ketone), 4-heptanone, 1- Hexanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetone, acetonyl acetone, purple Protonone, diacetone alcohol, acetoxynol, acetophenone, methyl naphthyl ketone, isophorone and propylene carbonate, etc.
作為酯系溶劑，例如可列舉：乙酸甲酯、乙酸丁酯、乙酸乙酯、乙酸異丙酯、乙酸戊酯（acetic acid pentyl）、乙酸異戊酯、乙酸戊酯（acetic acid amyl）、丙二醇單甲醚乙酸酯、乙二醇單***乙酸酯、二乙二醇單丁醚乙酸酯、二乙二醇單***乙酸酯、乙基-3-乙氧基丙酸酯、3-甲氧基丁基乙酸酯、3-甲基-3-甲氧基丁基乙酸酯、甲酸甲酯、甲酸乙酯、甲酸丁酯、甲酸丙酯、乳酸乙酯、乳酸丁酯、乳酸丙酯、丁酸丁酯、2-羥基異丁酸甲酯、乙酸異戊酯、異丁酸異丁酯及丙酸丁酯等。Examples of ester solvents include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, acetic acid pentyl, isoamyl acetate, acetic acid amyl, and propylene glycol. Monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropionate, 3 -Methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, Propyl lactate, butyl butyrate, methyl 2-hydroxyisobutyrate, isoamyl acetate, isobutyl isobutyrate and butyl propionate, etc.
作為醇系溶劑、醯胺系溶劑、醚系溶劑及烴系溶劑，例如可使用美國專利申請公開2016/0070167A1號說明書的段落[0715]～段落[0718]中揭示的溶劑。As alcohol-based solvents, amide-based solvents, ether-based solvents, and hydrocarbon-based solvents, for example, the solvents disclosed in paragraphs [0715] to [0718] of the specification of U.S. Patent Application Publication No. 2016/0070167A1 can be used.
所述溶劑可混合多種，亦可與所述以外的溶劑或水混合。作為顯影液整體的含水率較佳為未滿50質量%，更佳為未滿20質量%，進而佳為未滿10質量%，尤佳為實質上不含有水分。 相對於顯影液的總量，有機溶劑相對於有機系顯影液的含量較佳為50質量%以上且100質量%以下，更佳為80質量%以上且100質量%以下，進而佳為90質量%以上且100質量%以下，尤佳為95質量%以上且100質量%以下。A plurality of the solvents may be mixed, or may be mixed with solvents or water other than the above. The moisture content of the entire developer is preferably less than 50% by mass, more preferably less than 20% by mass, still more preferably less than 10% by mass, and particularly preferably contains substantially no water. Relative to the total amount of the developer, the content of the organic solvent relative to the organic developer is preferably 50% by mass or more and 100% by mass or less, more preferably 80% by mass or more and 100% by mass or less, and still more preferably 90% by mass Above and 100% by mass or less, more preferably 95% by mass or more and 100% by mass or less.
＜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。＜Other steps＞ The pattern forming method preferably includes a step of cleaning with an eluent after step 3.
作為於使用鹼性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。As the rinsing liquid used in the rinsing step after the step of performing development using an alkaline 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.
使用有機系顯影液的顯影步驟後的淋洗步驟中使用的淋洗液只要不溶解抗蝕劑圖案即可，並無特別限制，可使用含有一般的有機溶劑的溶液。淋洗液較佳為使用含有選自由烴系溶劑、酮系溶劑、酯系溶劑、醇系溶劑、醯胺系溶劑及醚系溶劑所組成的群組中的至少一種有機溶劑的淋洗液。 作為烴系溶劑、酮系溶劑、酯系溶劑、醇系溶劑、醯胺系溶劑及醚系溶劑的例子，可列舉與含有有機溶劑的顯影液中說明者為相同者。The rinsing liquid used in the rinsing step after the development step using an organic developer is not particularly limited as long as it does not dissolve the resist pattern, and a solution containing a general organic solvent can be used. The eluent is preferably an eluent containing at least one organic solvent selected from the group consisting of hydrocarbon-based solvents, ketone-based solvents, ester-based solvents, alcohol-based solvents, amide-based solvents, and ether-based solvents. Examples of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents include the same as those described in the developer containing an organic solvent.
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℃）下進行通常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), usually 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4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，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 based on "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 4th Edition 2007 Issued by: SEMI Japan" can also be used. Among them, the dry etching is preferably oxygen plasma etching.
抗蝕劑組成物及本發明的圖案形成方法中使用的各種材料（例如溶劑、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）較佳為不含金屬等雜質。該些材料中所含的雜質的含量較佳為1質量ppm以下，更佳為10質量ppb以下，進而佳為100質量ppt以下，尤佳為10質量ppt以下，最佳為1質量ppt以下。此處，作為金屬雜質，例如可列舉：Na、K、Ca、Fe、Cu、Mg、Al、Li、Cr、Ni、Sn、Ag、As、Au、Ba、Cd、Co、Pb、Ti、V、W及Zn等。The resist composition and the various materials used in the pattern forming method of the present invention (for example, solvent, developer, rinsing solution, composition for forming anti-reflection film, composition for forming top coat, etc.) are preferably free of Impurities such as metals. The content of impurities contained in these materials is preferably 1 mass ppm or less, more preferably 10 mass ppb or less, further preferably 100 mass ppt or less, particularly preferably 10 mass ppt or less, and most preferably 1 mass ppt or less. Here, as metal impurities, for example, Na, K, Ca, Fe, Cu, Mg, Al, Li, Cr, Ni, Sn, Ag, As, Au, Ba, Cd, Co, Pb, Ti, V , W and Zn, etc.
作為自各種材料中去除金屬等雜質的方法，例如可列舉使用過濾器的過濾。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。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。 於抗蝕劑組成物的製造中，例如較佳為於使樹脂及光酸產生劑等各成分溶解於溶劑中之後，使用素材不同的多個過濾器進行循環過濾。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的聚乙烯製過濾器排列連接，進行10次以上的循環過濾。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。 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℃。As a method of removing impurities such as metals from various materials, for example, filtration using a filter can be cited. The filter pore size is preferably less than 100 nm, more preferably 10 nm or less, and still more preferably 5 nm or less. The filter is preferably a filter made of polytetrafluoroethylene, polyethylene, or nylon. 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 be filtered multiple times, and the step of multiple filtering can be a cyclic filtering step. In the manufacture of a resist composition, it is preferable to perform cyclic filtration using a plurality of filters with different materials after dissolving each component such as a resin and a photoacid generator in a solvent, for example. 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, and to perform the filtration cycle 10 times or more. 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. 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 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.
另外，作為減少各種材料中所含的金屬等雜質的方法，例如可列舉以下方法等：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 contained in various materials, for example, the following methods can be cited: a method of selecting a raw material with a small metal content as a raw material constituting various materials, a method of filtering a raw material constituting various materials with a filter , And the method of using Teflon (registered trademark) to lining the device, etc., and distilling under the condition of suppressing pollution as much as possible.
除了過濾器過濾之外，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。為了減少所述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。使用後的清洗液中所含的金屬成分的含量較佳為100質量ppt（兆分之一（parts per trillion））以下，更佳為10質量ppt以下，進而佳為1質量ppt以下。In addition to filter filtration, adsorption materials can also be used to remove impurities, and filter filtration and adsorption materials can also be used in combination. 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 the various materials, it is necessary to prevent the mixing of metal impurities in the manufacturing process. It is possible to measure the content of the metal components contained in the cleaning liquid used for cleaning the manufacturing equipment to confirm whether the metal impurities are sufficiently removed from the manufacturing equipment. The content of the metal component contained in the cleaning solution after use is preferably 100 mass ppt (parts per trillion) or less, more preferably 10 mass ppt or less, and still more preferably 1 mass ppt or less.
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方面而言，較佳為10質量%以下，更佳為5質量%以下。 作為藥液配管，例如可使用經SUS（不鏽鋼）、或實施了防靜電處理的聚乙烯、聚丙烯或氟樹脂（聚四氟乙烯或全氟烷氧基樹脂等）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（聚四氟乙烯或全氟烷氧基樹脂等）。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 it is preferably 10% by mass or less, and more preferably 5% by mass or less in terms of maintaining better development characteristics or rinsing characteristics. As the chemical solution piping, for example, various piping coated with SUS (stainless steel) or antistatic treated polyethylene, polypropylene, or fluororesin (polytetrafluoroethylene, perfluoroalkoxy resin, etc.) can be used. Regarding the filter and O-ring, polyethylene, polypropylene, or fluororesin (polytetrafluoroethylene, perfluoroalkoxy resin, etc.) that has been subjected to antistatic treatment can also be used in the same way.
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.
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、以及藉由所述製造方法製造的電子元件。 本發明的電子元件可較佳地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。 [實施例]In addition, the present invention also relates to a manufacturing method of an electronic component including the pattern forming method, and an electronic component manufactured by the manufacturing method. The electronic component of the present invention can be preferably mounted in electrical and electronic equipment (home appliances, office automation (OA), media-related equipment, optical equipment, communication equipment, etc.). [Example]
以下，基於實施例來對本發明進一步進行詳細說明。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，本發明的範圍不應由以下所示的實施例限定性地解釋。 此外，只要無特別說明，則「份」、「%」為質量基準。Hereinafter, the present invention will be described in further 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 should not be limitedly interpreted by the examples shown below. In addition, unless otherwise specified, "parts" and "%" are quality standards.
[感光化射線性或感放射線性樹脂組成物的各種成分][Various components of sensitized radiation or radiation sensitive resin composition]
〔樹脂（A）〕 ＜單體（M1）的合成＞〔Resin (A)〕 ＜Synthesis of monomer (M1)＞
[化54]
向苯甲醯磺胺39 g中加入丙酮310 ml及0.5 mol/l氫氧化鈉水溶液310 ml，在冰冷卻下攪拌的同時滴加甲基丙烯醯氯15.6 g。在室溫（25℃）下攪拌5小時後，向反應液中加入1 mol/l鹽酸20 ml，進行過濾。向得到的固體中加入丙酮750 ml，邊攪拌邊加熱回流，過濾除去不溶物。一邊攪拌得到的丙酮溶液一邊加入1000 ml水，就會析出白色結晶，將其過濾，得到25.0 g單體（M1）（收率51%）。1 H-NMR（DMSO-d6:ppm）δ:12.45（br）、10.22（s）、7.94（m）、7.86（d）、7.62（t）、7.49（t）、5.86（s）、5.60（s）、1.96（s）Add 310 ml of acetone and 310 ml of 0.5 mol/l sodium hydroxide aqueous solution to 39 g of benzalkonium sulfonamide, and add 15.6 g of methacrylic acid chloride dropwise while stirring under ice cooling. After stirring for 5 hours at room temperature (25°C), 20 ml of 1 mol/l hydrochloric acid was added to the reaction solution and filtered. 750 ml of acetone was added to the obtained solid, heated to reflux with stirring, and filtered to remove insoluble materials. While stirring the resulting acetone solution and adding 1000 ml of water, white crystals were precipitated, which was filtered to obtain 25.0 g of monomer (M1) (yield 51%). 1 H-NMR (DMSO-d6: ppm) δ: 12.45 (br), 10.22 (s), 7.94 (m), 7.86 (d), 7.62 (t), 7.49 (t), 5.86 (s), 5.60 ( s), 1.96 (s)
＜單體（M6）的合成＞＜Synthesis of monomer (M6)＞
[化55]
（單體（M5）的合成） 向4-乙醯氧基苯甲酸25 g中加入150 ml甲苯及0.5 gN,N'-二甲基甲醯胺，再加入19.8 g亞硫醯氯，在70℃下加熱攪拌2小時。冷卻到室溫（25℃）後，減壓蒸餾除去殘留的亞硫醯氯及溶媒，得到4-乙醯氧基苯甲醯氯的甲苯溶液30.3 g（濃度91.7質量%）。向4-甲基丙烯醯胺苯磺醯胺30g中加入N,N'-二甲基乙醯胺180 ml、三乙胺17.0 g、及4-二甲基胺基吡啶1.4 g，在冰冷卻下攪拌的同時，滴加全部的上述製備的4-乙醯氧基苯甲醯氯的甲苯溶液。在室溫下攪拌10小時後，向0.5 mol/l鹽酸1000 ml中加入反應液，進行過濾，得到白色固體。向所述固體中加入丙酮970 ml，邊攪拌邊加熱回流，過濾除去不溶物。一邊攪拌得到的丙酮溶液一邊加入1100 ml水，就會析出白色結晶，將其過濾。向該結晶中加入乙酸乙酯/二異丙醚=80/20（質量比）的混合溶媒350 g，進行攪拌並過濾，得到16.0 g單體（M5）（收率32%）。1 H-NMR（DMSO-d6:ppm）δ:12.48（br）、10.22（s）、8.01-7.88（m）、7.26（d）、5.86（s）、5.60（s）、2.29（s）、1.96（s）(Synthesis of monomer (M5)) To 25 g of 4-acetoxybenzoic acid, 150 ml of toluene and 0.5 g of N,N'-dimethylformamide were added, and 19.8 g of sulfite Heat and stir at ℃ for 2 hours. After cooling to room temperature (25° C.), the remaining thiol chloride and solvent were distilled off under reduced pressure to obtain 30.3 g of a toluene solution of 4-acetoxybenzyl chloride (concentration 91.7% by mass). Add 180 ml of N,N'-dimethylacetamide, 17.0 g of triethylamine, and 1.4 g of 4-dimethylaminopyridine to 30 g of 4-methacrylamide benzenesulfonamide, and cool in ice. While stirring, all of the toluene solution of 4-acetoxybenzyl chloride prepared above was added dropwise. After stirring for 10 hours at room temperature, the reaction solution was added to 1000 ml of 0.5 mol/l hydrochloric acid and filtered to obtain a white solid. Add 970 ml of acetone to the solid, heat to reflux while stirring, and filter to remove insoluble materials. While stirring the resulting acetone solution, add 1100 ml of water to precipitate white crystals, which are filtered. 350 g of a mixed solvent of ethyl acetate/diisopropyl ether=80/20 (mass ratio) was added to the crystals, stirred and filtered to obtain 16.0 g of monomer (M5) (yield 32%). 1 H-NMR (DMSO-d6: ppm) δ: 12.48 (br), 10.22 (s), 8.01-7.88 (m), 7.26 (d), 5.86 (s), 5.60 (s), 2.29 (s), 1.96(s)
（單體M6的合成） 向15 g單體（M5）中加入0.5 mol/l氫氧化鈉水溶液240 ml及80 ml甲醇，在室溫下攪拌5小時。過濾反應液除去不溶物後，加入乙酸乙酯300 ml進行分液操作。向水層中加入水600 ml，邊攪拌邊滴加濃鹽酸36 ml，白色結晶析出。將其過濾，得到單體（M6）11.5 g（收率86%）。1 H-NMR（DMSO-d6:ppm）δ:12.11（br）、10.36（s）、10.20（s）、7.92（m）、7.75（d）、6.80（d）、5.85（s）、5.59（s）、1.95（s）(Synthesis of monomer M6) To 15 g of monomer (M5), 240 ml of 0.5 mol/l sodium hydroxide aqueous solution and 80 ml of methanol were added, and the mixture was stirred at room temperature for 5 hours. After filtering the reaction solution to remove insoluble materials, 300 ml of ethyl acetate was added for liquid separation. 600 ml of water was added to the water layer, 36 ml of concentrated hydrochloric acid was added dropwise while stirring, white crystals precipitated. This was filtered to obtain 11.5 g of monomer (M6) (yield 86%). 1 H-NMR (DMSO-d6: ppm) δ: 12.11 (br), 10.36 (s), 10.20 (s), 7.92 (m), 7.75 (d), 6.80 (d), 5.85 (s), 5.59 ( s), 1.95 (s)
＜單體（M3）的合成＞＜Synthesis of monomer (M3)＞
[化56]
（單體M11的合成） 在4-乙烯基磺酸鈉40 g中加入370 ml乙腈及7.4 gN,N'-二甲基甲醯胺而得的溶液中，在冰冷卻下加入亞硫醯氯47.7 g，在50℃下加熱攪拌4小時。冷卻至室溫（25℃）後，在冰冷卻下向92 g氨水溶液（濃度25質量%）與500 g水的混合液中加入反應液，在室溫（25℃）下攪拌1小時。用600 ml乙酸乙酯萃取反應液兩次，將得到的有機層用水600 ml洗滌後，加入硫酸鈉。過濾硫酸鈉後減壓蒸餾除去溶媒，得到單體（M11）20.0 g（收率56%）。1 H-NMR（DMSO-d6:ppm）δ:7.79（d）、7.66（d）、7.35（br）、6.81（dd）、5.99（d）、5.42（d）(Synthesis of monomer M11) To a solution obtained by adding 370 ml of acetonitrile and 7.4 g of N,N'-dimethylformamide to 40 g of sodium 4-vinylsulfonate, add sulfite chloride under ice cooling 47.7 g, heated and stirred at 50°C for 4 hours. After cooling to room temperature (25°C), the reaction solution was added to a mixture of 92 g of aqueous ammonia (concentration 25% by mass) and 500 g of water under ice cooling, and stirred at room temperature (25°C) for 1 hour. The reaction solution was extracted twice with 600 ml of ethyl acetate, the obtained organic layer was washed with 600 ml of water, and sodium sulfate was added. After filtering sodium sulfate, the solvent was distilled off under reduced pressure to obtain 20.0 g of monomer (M11) (yield 56%). 1 H-NMR (DMSO-d6: ppm) δ: 7.79 (d), 7.66 (d), 7.35 (br), 6.81 (dd), 5.99 (d), 5.42 (d)
（單體M3的合成） 向單體（M11）15 g中加入四氫呋喃200 ml、三乙胺10.8 g、4-二甲基胺基吡啶1.0 g，在冰冷卻下攪拌的同時滴加氯化苯甲醯12.7 g。在室溫（25℃）下攪拌10小時後，向反應液中加入水400 ml，用乙酸乙酯200 ml進行兩次萃取。得到的有機層用水200 ml洗滌3次後，加入硫酸鈉。過濾硫酸鈉後減壓蒸餾除去溶媒，用矽膠管柱層析法（洗滌液:乙酸乙酯/正己烷=50/50（體積比））精製得到的殘留物。向管柱精製的固體中加入乙酸乙酯25 ml，邊攪拌邊加熱回流。冷卻至室溫（25℃）後，加入正己烷30 ml時析出白色結晶，將其過濾，得到單體（M3）5.0 g（收率21%）。1 H-NMR（DMSO-d6:ppm）δ:12.54（br）、7.97（d）、7.86（d）、7.73（d）、7.63（t）、7.49（t）、6.84（dd）、6.04（d）、5.48（d）(Synthesis of monomer M3) To 15 g of monomer (M11), 200 ml of tetrahydrofuran, 10.8 g of triethylamine, and 1.0 g of 4-dimethylaminopyridine were added, and chlorobenzene was added dropwise while stirring under ice cooling. Formaldehyde 12.7 g. After stirring for 10 hours at room temperature (25°C), 400 ml of water was added to the reaction solution, and extraction was performed twice with 200 ml of ethyl acetate. After the obtained organic layer was washed three times with 200 ml of water, sodium sulfate was added. After the sodium sulfate is filtered, the solvent is distilled off under reduced pressure, and the residue is purified by silica gel column chromatography (washing solution: ethyl acetate/n-hexane=50/50 (volume ratio)). Add 25 ml of ethyl acetate to the solid purified by the column, and heat to reflux while stirring. After cooling to room temperature (25°C), white crystals precipitated when 30 ml of n-hexane was added, which was filtered to obtain 5.0 g of monomer (M3) (yield 21%). 1 H-NMR (DMSO-d6: ppm) δ: 12.54 (br), 7.97 (d), 7.86 (d), 7.73 (d), 7.63 (t), 7.49 (t), 6.84 (dd), 6.04 ( d), 5.48 (d)
＜樹脂（A-1）的合成＞＜Synthesis of resin (A-1)＞
[化57]
使0.78 g單體（M1）、7.8 g單體（Mb1）、1.3 g單體（Md7）、及0.54 g聚合起始劑V-601（和光純藥工業（股）製造）溶解在41.1 g環己酮中。在反應容器中加入17.8 g環己酮及3.12 g單體（M1），在85℃下加熱溶解，在氮氣氣氛下用4小時向85℃的體系中滴加上述製備的單體與起始劑的混合溶液。將反應溶液加熱攪拌2小時後，將其放置冷卻至室溫（25℃）為止。將上述反應溶液滴加到455 g甲醇與水的混合溶媒（甲醇/水=40/60（質量比））中，使聚合物沈澱，進行過濾。將得到的聚合物溶解在丙酮50 g中，滴加到455 g正庚烷與乙酸乙酯的混合溶媒（正庚烷/乙酸乙酯=90/10（質量比））中。過濾沈澱的聚合物，使用上述正庚烷與乙酸乙酯的混合溶媒195 g，進行過濾後的聚合物的洗滌。將洗滌後的聚合物在40℃下送風乾燥，得到10.0 g樹脂（A-1）。由GPC所得的重量平均分子量為13000，分子量分散度（Mw/Mn）為1.95。1 H-NMR（DMSO-d6:ppm）δ:12.41、9.63、8.13-7.29、2.23-0.64Dissolve 0.78 g monomer (M1), 7.8 g monomer (Mb1), 1.3 g monomer (Md7), and 0.54 g polymerization initiator V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) in 41.1 g ring In hexanone. Add 17.8 g of cyclohexanone and 3.12 g of monomer (M1) into the reaction vessel, heat to dissolve at 85°C, and add dropwise the monomer and initiator prepared above to the system at 85°C for 4 hours under a nitrogen atmosphere的mixed solution. After heating and stirring the reaction solution for 2 hours, it was left to cool to room temperature (25°C). The above reaction solution was added dropwise to a mixed solvent of 455 g of methanol and water (methanol/water=40/60 (mass ratio)) to precipitate the polymer, and then filtered. The obtained polymer was dissolved in 50 g of acetone and added dropwise to a mixed solvent of 455 g of n-heptane and ethyl acetate (n-heptane/ethyl acetate = 90/10 (mass ratio)). The precipitated polymer was filtered, and 195 g of the above-mentioned mixed solvent of n-heptane and ethyl acetate was used to wash the filtered polymer. The washed polymer was blown and dried at 40°C to obtain 10.0 g of resin (A-1). The weight average molecular weight obtained by GPC is 13,000, and the molecular weight dispersion (Mw/Mn) is 1.95. 1 H-NMR (DMSO-d6: ppm) δ: 12.41, 9.63, 8.13-7.29, 2.23-0.64
除了變更使用的單體以外，用與上述樹脂A-1的合成例同樣的方法合成了表1所示的樹脂（A）。 樹脂（A）的組成比（莫耳比）藉由1 H-NMR或13 C-NMR測定而算出。 樹脂（A）的重量平均分子量（Mw:聚苯乙烯換算）、分散度（Mw/Mn）是藉由GPC（溶媒:四氫呋喃（tetrahydrofuran，THF））測定而算出。再者，表1中針對各樹脂示出了重複單元的組成比（莫耳比）、具有芳香族基的重複單元的含量（莫耳比）、重量平均分子量、分散度。 重複單元1對應於重複單元（a1）。 再者，樹脂（RA-1）～（RA-4）不是樹脂（A），但為了方便記載在表1中。Except for changing the monomers used, the resin (A) shown in Table 1 was synthesized by the same method as the synthesis example of the above-mentioned resin A-1. The composition ratio (molar ratio) of the resin (A) is calculated by 1 H-NMR or 13 C-NMR measurement. The weight average molecular weight (Mw: polystyrene conversion) and the degree of dispersion (Mw/Mn) of the resin (A) were calculated by GPC (solvent: tetrahydrofuran (THF)) measurement. In addition, Table 1 shows the composition ratio (molar ratio) of the repeating unit, the content (molar ratio) of the repeating unit having an aromatic group, the weight average molecular weight, and the degree of dispersion for each resin. Repeating unit 1 corresponds to repeating unit (a1). In addition, resins (RA-1) to (RA-4) are not resins (A), but are listed in Table 1 for convenience.
[表1]
以下，示出各樹脂（A-1～A-47、RA-1～RA-4）的各自具有的重複單元。Hereinafter, the repeating unit each resin (A-1 to A-47, RA-1 to RA-4) has is shown.
[化58]
[化59]
[化60]
[化61]
〔光酸產生劑〕 使用以下所示的光酸產生劑。〔Photoacid generator〕 Use the photoacid generator shown below.
[化62]
[化63]
[化64]
[化65]
〔酸擴散控制劑〕 使用以下所示的酸擴散控制劑。〔Acid diffusion control agent〕 Use the acid diffusion control agent shown below.
[化66]
〔疏水性樹脂〕 以下示出疏水性樹脂E（樹脂E-1）的結構。 再者，疏水性樹脂E-1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-NMR進行測定。 疏水性樹脂E-1的重量平均分子量（Mw）為15000，分散度（Mw/Mn）為1.50，組成比以莫耳比計為50/50。[Hydrophobic resin] The structure of hydrophobic resin E (resin E-1) is shown below. In addition, the weight average molecular weight (Mw) and the degree of dispersion (Mw/Mn) of the hydrophobic resin E-1 were measured by GPC (carrier: tetrahydrofuran (THF)) (in terms of polystyrene conversion). In addition, the composition ratio (mole ratio) of the resin was measured by 13 C-NMR. The weight average molecular weight (Mw) of the hydrophobic resin E-1 is 15,000, the degree of dispersion (Mw/Mn) is 1.50, and the composition ratio is 50/50 in terms of molar ratio.
[化67]
〔界面活性劑〕 使用以下所示的界面活性劑。 W-1：美格夫克（MEGAFACE）F176（迪愛生（DIC）（股）製造；氟系） W-2：美格夫克（MEGAFACE）R08（DIC（股）製造）（氟系及矽系）〔Interface active agent〕 Use the surfactant shown below. W-1: MEGAFACE F176 (manufactured by DIC (stock); fluorine series) W-2: MEGAFACE R08 (manufactured by DIC) (fluorine-based and silicon-based)
〔溶劑〕 使用以下所示的溶劑。 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〕 Use the solvents 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
[抗蝕劑組成物的製備] 以固體成分濃度成為2.0質量%的方式混合表2中所示的各成分。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，亦稱為抗蝕劑組成物）。 再者，於抗蝕劑組成物中，所謂固體成分，是指溶劑以外的所有成分。於實施例及比較例中使用所得的樹脂組成物。 以下的「樹脂（A）」欄、「光酸產生劑（B）」欄、「酸擴散控制劑（D）」欄、「疏水性樹脂（E）」欄及「界面活性劑」欄中記載的各成分的含量（添加量）表示各成分相對於全部固體成分的比例（質量%）。[Preparation of resist composition] The components shown in Table 2 were mixed so that the solid content concentration became 2.0% 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 a resist composition). In addition, in the resist composition, the so-called solid content refers to all components other than the solvent. The obtained resin composition was used in Examples and Comparative Examples. The following "Resin (A)" column, "Photoacid generator (B)" column, "Acid diffusion control agent (D)" column, "Hydrophobic resin (E)" column and "Surfactant" column The content (addition amount) of each component in the represents the ratio (mass %) of each component to the total solid content.
[表2]
[表2（續）]
[圖案形成] 〔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3所示的抗蝕劑組成物（抗蝕劑組成物的組成參照表2），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），對所得的具有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] 〔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. The resist composition shown in Table 3 was applied thereon (see Table 2 for the composition of the resist composition), and baked at 100° C. for 60 seconds to form a resist film with a thickness of 30 nm. Using EUV exposure equipment (manufactured by Exitech, Micro Exposure Tool, NA 0.3, Quadrupole, External Sigma 0.68, Internal Sigma 0.36), the obtained resist film 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.
〔評價〕 [粗糙度性能]（線寬粗糙度（Line Width Roughness，LWR）性能） 針對以解析線寬為平均20 nm的線圖案時的最佳曝光量進行解析的20 nm（1：1）的線與空間圖案，使用測長掃描式電子顯微鏡（SEM（日立製作所（股）的S-9380II））自圖案上部進行觀察時，在50個部位觀測線寬，用3σ評價其測定偏差，並設為LWR（nm）。值越小，表示性能越良好。〔Evaluation〕 [Roughness performance] (Line Width Roughness (LWR) performance) For the line and space pattern of 20 nm (1:1) analyzed with the optimal exposure when the line pattern with an average line width of 20 nm is analyzed, a length measuring scanning electron microscope (SEM (Hitachi, Ltd.) S-9380II)) When observing from the top of the pattern, observe the line width at 50 locations, evaluate the measurement deviation with 3σ, and set it as LWR (nm). The smaller the value, the better the performance.
[傾倒前線寬] 一邊改變曝光量，一邊測量了線與空間圖案的線寬。此時，將在10 μm見方範圍內圖案無傾倒地解析的最小線寬的平均值作為傾倒前線寬。該值越小，表示圖案傾倒的裕度越大，性能越好。[Line width before dumping] While changing the exposure, the line width of the line and space pattern was measured. At this time, the average value of the smallest line width analyzed without falling over in the 10 μm square range was used as the line width before dumping. The smaller the value, the greater the margin for pattern dumping and the better the performance.
[橋接前線寬] 一邊改變曝光量，一邊測量了線與空間圖案的線寬。此時，將在10 μm見方範圍內無橋接地解析的最大線寬的平均值作為橋接前線寬。該值越大，表示對於橋接的裕度越大，性能越好。[Bridge front line width] While changing the exposure, the line width of the line and space pattern was measured. At this time, the average value of the maximum line width in the 10 μm square range without bridge ground analysis is used as the line width before the bridge. The larger the value, the greater the margin for bridging and the better the performance.
[解析性的裕度] 是自上述橋接前線寬減去上述傾倒前線寬的值，值越大，解析性的裕度越寬，越較佳。[Analytic Margin] It is the value obtained by subtracting the line width before dumping from the line width before bridging. The larger the value, the wider the resolution margin, and the better.
將評價結果示於表3中。The evaluation results are shown in Table 3.
[表3]
如所述表3所示，關於本發明的抗蝕劑組成物，確認了於利用有機溶劑顯影形成圖案的情況下，能夠降低傾倒前線寬，能夠增大橋接前線寬，從而解析性的裕度優異、進而粗糙度性能優異。另一方面，比較例的抗蝕劑組成物中，該些性能不充分。As shown in Table 3, it was confirmed that the resist composition of the present invention can reduce the line width before pouring and increase the line width before bridging when the pattern is formed by organic solvent development. Excellent, and thus excellent roughness performance. On the other hand, in the resist composition of the comparative example, these performances were not sufficient.
〔EUV曝光、鹼顯影〕 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4所示的抗蝕劑組成物（抗蝕劑組成物的組成參照表2），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。 與所述同樣地，進行了粗糙度性能、傾倒前線寬、橋接前線寬、及解析性的裕度的評價。〔EUV exposure, alkali 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. The resist composition shown in Table 4 was applied thereon (see Table 2 for the composition of the resist composition), and baked at 100° C. for 60 seconds to form a resist film with a thickness of 30 nm. 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. In the same manner as described above, the roughness performance, the line width before dumping, the line width before bridging, and the margin of resolution were evaluated.
將評價結果示於下述表4中。The evaluation results are shown in Table 4 below.
[表4]
如所述表4所示，關於本發明的抗蝕劑組成物，確認了於利用鹼顯影形成圖案的情況下，能夠降低傾倒前線寬、能夠增大橋接前線寬、從而解析性的裕度優異、進而粗糙度性能優異。另一方面，比較例的抗蝕劑組成物中，該些性能不充分。As shown in Table 4, it was confirmed that the resist composition of the present invention can reduce the line width before dumping and increase the line width before bridging when forming a pattern by alkali development, and thus has excellent resolution margin. , And excellent roughness performance. On the other hand, in the resist composition of the comparative example, these performances were not sufficient.
〔EB曝光、鹼顯影〕 使用旋塗機將表5所示的抗蝕劑組成物（關於抗蝕劑組成物的組成參照表2）均勻地塗佈在實施了六甲基二矽氮烷處理的矽基板上。之後，於加熱板上以120℃進行90秒加熱乾燥，形成膜厚35 nm的抗蝕劑膜。 使用電子束照射裝置（（股）日立製作所製造的HL750，加速電壓50 keV），對得到的抗蝕劑膜藉由線寬24 nm的1:1線與空間圖案的6%半色調遮罩進行了電子束照射。照射後，立即於加熱板上以110℃進行60秒鐘加熱。進而，使用濃度2.38質量%的四甲基氫氧化銨水溶液在23℃下顯影60秒，用純水淋洗30秒後，旋轉乾燥得到正型圖案。〔EB exposure, alkali development〕 The resist composition shown in Table 5 (refer to Table 2 for the composition of the resist composition) was uniformly coated on the silicon substrate treated with hexamethyldisilazane using a spin coater. After that, heating and drying were performed on a hot plate at 120° C. for 90 seconds to form a resist film with a film thickness of 35 nm. Using an electron beam irradiation device ((stock) HL750 manufactured by Hitachi, acceleration voltage 50 keV), the obtained resist film was processed with a 6% halftone mask with a line width of 24 nm and a 1:1 line and a space pattern. The electron beam is irradiated. Immediately after irradiation, heating was performed on a hot plate at 110°C for 60 seconds. Furthermore, a tetramethylammonium hydroxide aqueous solution with a concentration of 2.38% by mass was used for development at 23° C. for 60 seconds, rinsed with pure water for 30 seconds, and spin-dried to obtain a positive pattern.
〔評價〕 [粗糙度性能]（線寬粗糙度（line width roughness，LWR）性能） 針對以解析線寬為平均24 nm的線圖案時的最佳曝光量進行解析的20 nm（1：1）的線與空間圖案，使用測長掃描式電子顯微鏡（SEM（日立製作所（股）的S-9380II））自圖案上部進行觀察時，在50個部位觀測線寬，用3σ評價其測定偏差，並設為LWR（nm）。值越小，表示性能越良好。〔Evaluation〕 [Roughness performance] (line width roughness (LWR) performance) For the line and space pattern of 20 nm (1:1) analyzed with the optimal exposure when the line pattern with an average line width of 24 nm is analyzed, a length measuring scanning electron microscope (SEM (Hitachi, Ltd.) S-9380II)) When observing from the top of the pattern, observe the line width at 50 locations, evaluate the measurement deviation with 3σ, and set it as LWR (nm). The smaller the value, the better the performance.
與所述同樣地，進行了傾倒前線寬、橋接前線寬、及解析性的裕度的評價。In the same manner as described above, the line width before dumping, the line width before bridging, and the margin of resolution were evaluated.
將評價結果示於下述表5中。The evaluation results are shown in Table 5 below.
[表5]
如所述表5所示，關於本發明的抗蝕劑組成物，確認了於利用鹼顯影形成圖案的情況下，能夠降低傾倒前線寬、能夠增大橋接前線寬、從而解析性的裕度優異、進而粗糙度性能優異。另一方面，比較例的抗蝕劑組成物中，該些性能不充分。 [產業上的可利用性]As shown in Table 5, it was confirmed that the resist composition of the present invention can reduce the line width before dumping and increase the line width before bridging when forming a pattern by alkali development, and thus has excellent resolution margin. , And excellent roughness performance. On the other hand, in the resist composition of the comparative example, these performances were not sufficient. [Industrial availability]
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，能夠降低傾倒前線寬，能夠增大橋接前線寬，從而能夠形成解析性的裕度優異，進而粗糙度性能優異的圖案。 另外，根據本發明，可提供一種有關所述感光化射線性或感放射線性樹脂組成物的感光化射線性或感放射線性樹脂膜、圖案形成方法及電子元件的製造方法。According to the present invention, it is possible to provide a photosensitive radiation-sensitive or radiation-sensitive resin composition, which can reduce the line width before pouring and increase the line width before bridging, thereby being able to form a pattern with excellent resolution margin and excellent roughness performance. In addition, according to the present invention, it is possible to provide an actinic ray-sensitive or radiation-sensitive resin film, a pattern forming method, and a manufacturing method of an electronic component related to the sensitized ray-sensitive or radiation-sensitive resin composition.
已詳細且參照特定的實施方式對本發明進行了說明，對於本領域從業人員而言明確的是，可不脫離本發明的精神與範圍而施加各種變更或修正。 本申請案是基於2019年9月30日提出申請的日本專利申請案（日本專利特願2019-179963）者，將其內容作為參照而編入至本申請案中。The present invention has been described in detail with reference to specific embodiments, and it is clear to those skilled in the art that various changes or modifications can be added without departing from the spirit and scope of the present invention. This application is based on a Japanese patent application (Japanese Patent Application No. 2019-179963) filed on September 30, 2019, and the content is incorporated into this application as a reference.
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| JP2003241382A (en) * | 2002-02-22 | 2003-08-27 | Fuji Photo Film Co Ltd | Positive resist composition |
| JP5514687B2 (en) * | 2010-09-29 | 2014-06-04 | 富士フイルム株式会社 | Actinic ray-sensitive or radiation-sensitive resin composition, actinic ray-sensitive or radiation-sensitive film, and pattern forming method |
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