TW202112844A - Active-ray-sensitive or radiation-sensitive resin composition, active-ray-sensitive or radiation-sensitive film, pattern formation method, and electronic device manufacturing method - Google Patents
Active-ray-sensitive or radiation-sensitive resin composition, active-ray-sensitive or radiation-sensitive film, pattern formation method, and electronic device manufacturing method Download PDFInfo
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- TW202112844A TW202112844A TW109129623A TW109129623A TW202112844A TW 202112844 A TW202112844 A TW 202112844A TW 109129623 A TW109129623 A TW 109129623A TW 109129623 A TW109129623 A TW 109129623A TW 202112844 A TW202112844 A TW 202112844A
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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、及電子元件的製造方法。 更詳細而言,本發明是有關於感光化射線性或感放射線性樹脂組成物及感光化射線性或感放射線性膜、以及使用該些的圖案形成方法、及電子元件的製造方法,所述感光化射線性或感放射線性樹脂組成物藉由光化射線或放射線的照射進行反應而性質發生變化,且可用於半導體或積體電路(Integrated Circuit,IC)等的電子元件製造步驟、作為固體攝像元件即互補金屬氧化物半導體(Complementary Metal Oxide Semiconductor,CMOS)影像感測器的主要結構構件的光電二極體的製造步驟、液晶、熱能頭(thermal head)等的電路基板的製造、壓印用模具結構體的製作、以及其他感光蝕刻加工(photofabrication)步驟、平版印刷版、酸硬化性組成物。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. In more detail, the present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition, an actinic ray-sensitive or radiation-sensitive film, a pattern forming method using these, and a method of manufacturing an electronic component. The photosensitive ray-sensitive or radiation-sensitive resin composition reacts with actinic rays or radiation to change its properties, and can be used in the manufacturing process of electronic components such as semiconductors and integrated circuits (IC), as a solid The manufacturing process of photodiode, which is the main structural component of the imaging element, that is, the Complementary Metal Oxide Semiconductor (CMOS) image sensor, and the manufacturing and imprinting of circuit boards such as liquid crystals and thermal heads For the production of mold structures, other photofabrication steps, lithographic printing plates, and acid-curable compositions.
自KrF準分子雷射(248 nm)用抗蝕劑以後,為了彌補由光吸收所引起的感度下降,而使用利用化學增幅的圖案形成方法。例如,於正型的化學增幅法中,首先,曝光部中包含的光酸產生劑藉由光照射而分解並產生酸。然後,於曝光後的烘烤(PEB:Post Exposure Bake)過程等中,藉由所產生的酸的觸媒作用而使感光化射線性或感放射線性樹脂組成物中包含的鹼不溶性的基變化成鹼可溶性的基。之後,例如使用鹼性溶液進行顯影。藉此,將曝光部去除,而獲得所期望的圖案。 於所述方法中,作為鹼性顯影液,已提出有各種鹼性顯影液。例如,通常使用2.38質量%TMAH(四甲基氫氧化銨水溶液)的水系鹼性顯影液作為該鹼性顯影液。Since the resist for KrF excimer laser (248 nm), in order to compensate for the decrease in sensitivity caused by light absorption, a patterning method using chemical amplification has been used. For example, in the positive chemical amplification method, first, the photoacid generator contained in the exposure part is decomposed by light irradiation to generate acid. Then, in the post-exposure baking (PEB: Post Exposure Bake) process, etc., the alkali-insoluble group contained in the sensitizing radiation or radiation-sensitive resin composition is changed by the catalytic action of the generated acid. Into alkali-soluble base. After that, for example, an alkaline solution is used for development. Thereby, the exposure part is removed, and a desired pattern is obtained. In the method, as the alkaline developer, various alkaline developers have been proposed. For example, an aqueous alkaline developer of 2.38% by mass TMAH (tetramethylammonium hydroxide aqueous solution) is generally used as the alkaline developer.
為了半導體元件的微細化,曝光光源的短波長化及投影透鏡的高數值孔徑(高NA(Numerical Aperture))化得到發展,目前正在開發將具有193 nm的波長的ArF準分子雷射作為光源的曝光機。作為進一步提高解析力的技術,可列舉使投影透鏡與試樣之間充滿高折射率的液體(以下,亦稱為「液浸液」)的方法(即,液浸法)。For the miniaturization of semiconductor elements, the short wavelength of the exposure light source and the high numerical aperture (high NA (Numerical Aperture)) of the projection lens have been developed. Currently, an ArF excimer laser with a wavelength of 193 nm is being developed as the light source. Exposure machine. As a technique to further improve the resolution, a method of filling the space between the projection lens and the sample with a high refractive index liquid (hereinafter also referred to as "liquid immersion liquid") (that is, liquid immersion method) can be cited.
作為先前的感光化射線性或感放射線性樹脂組成物,已知有多種,例如已知有專利文獻1中所記載者。 於專利文獻1中記載一種光阻劑組成物,其含有:具有包含藉由酸的作用而解離的酸解離性基的結構單元的聚合體、感放射線性酸產生體、及溶媒。 [現有技術文獻] [專利文獻]As the conventional sensitizing radiation-sensitive or radiation-sensitive resin composition, various types are known. For example, the one described in Patent Document 1 is known. Patent Document 1 describes a photoresist composition containing a polymer having a structural unit including an acid dissociable group dissociated by the action of an acid, a radiation-sensitive acid generator, and a solvent. [Prior Art Literature] [Patent Literature]
[專利文獻1]日本專利特開2015-57638號公報[Patent Document 1] Japanese Patent Laid-Open No. 2015-57638
[發明所欲解決之課題] 對由感光化射線性或感放射線性樹脂組成物所形成的感光化射線性或感放射線性膜進行曝光及顯影而獲得的圖案的剖面形狀一般理想的是矩形。 然而,特別是於使用厚膜(例如,膜厚為1 μm以上)的感光化射線性或感放射線性膜的情況下,存在所獲得的厚膜的圖案的剖面形狀的矩形性降低的問題。例如於利用正型的圖案形成方法形成空間部的線寬與抗蝕劑膜厚的縱橫比為5以上的線與空間圖案的情況下,所獲得的圖案的空間部的線寬於圖案上部變寬,朝向下部變窄,要求以較先前技術更高的水準提高矩形性。[The problem to be solved by the invention] The cross-sectional shape of the pattern obtained by exposing and developing the photosensitive ray-sensitive or radiation-sensitive film formed of the photosensitive ray-sensitive or radiation-sensitive resin composition is generally rectangular. However, particularly in the case of using a thick film (for example, a film thickness of 1 μm or more) sensitizing radiation-sensitive or radiation-sensitive film, there is a problem that the rectangularity of the cross-sectional shape of the pattern of the obtained thick film is reduced. For example, in the case of using a positive pattern forming method to form a line and space pattern with an aspect ratio of the line width of the space portion to the resist film thickness of 5 or more, the line width of the space portion of the obtained pattern becomes larger than that of the upper part of the pattern. Wide and narrow toward the lower part, it is required to improve the rectangularity at a higher level than the prior art.
本發明的目的在於提供一種於厚膜的圖案形成中所獲得的圖案的剖面形狀的矩形性優異的感光化射線性或感放射線性樹脂組成物、及感光化射線性或感放射線性膜、以及使用了所述感光化射線性或感放射線性樹脂組成物的圖案形成方法及電子元件的製造方法。The object of the present invention is to provide a photosensitive ray-sensitive or radiation-sensitive resin composition, a photosensitive ray-sensitive or radiation-sensitive film, and a photosensitive ray-sensitive or radiation-sensitive resin composition having excellent rectangularity in the cross-sectional shape of the pattern obtained in the pattern formation of a thick film, and The pattern formation method and the manufacturing method of the electronic component using the said sensitizing radiation-sensitive or radiation-sensitive resin composition.
[解決課題之手段] 於用以解決所述課題的手段中包含以下的態樣。[Means to solve the problem] The following aspects are included in the means for solving the above-mentioned problems.
[1] 一種感光化射線性或感放射線性樹脂組成物,其固體成分濃度為10質量%以上,所述感光化射線性或感放射線性樹脂組成物中, 所述感光化射線性或感放射線性樹脂組成物含有樹脂(A)、光酸產生劑(B-1)、光酸產生劑(B-2)、及酸擴散控制劑(D), 自所述光酸產生劑(B-1)產生的酸的pKa未滿0, 自所述光酸產生劑(B-2)產生的酸的pKa大於自所述光酸產生劑(B-1)產生的酸的pKa, 相對於所述光酸產生劑(B-1)的含量,所述光酸產生劑(B-2)的含量為0.001質量%以上且0.10質量%以下。 [2] 如[1]所述的感光化射線性或感放射線性樹脂組成物,其中於將自所述光酸產生劑(B-1)產生的酸的pKa設為E1 、將自所述光酸產生劑(B-2)產生的酸的pKa設為E2 的情況下,E2 -E1 為3以上。 [3] 如[1]或[2]所述的感光化射線性或感放射線性樹脂組成物,其中相對於所述光酸產生劑(B-1)的含量,所述酸擴散控制劑(D)的含量為0.5質量%以上且10.0質量%以下。 [4] 如[1]至[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,其中所述樹脂(A)為具有藉由酸的作用進行分解而極性增大的基的樹脂。 [5] 如[1]至[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,其中所述樹脂(A)為包含具有酚性羥基的重複單元的樹脂。 [6] 如[5]所述的感光化射線性或感放射線性樹脂組成物,其中所述樹脂(A)具有源自羥基苯乙烯的重複單元。 [7] 如[1]至[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,其中所述樹脂(A)為包含下述通式(I)所表示的重複單元的樹脂。[1] A sensitizing ray-sensitive or radiation-sensitive resin composition having a solid content concentration of 10% by mass or more, in the sensitizing ray-sensitive or radiation-sensitive resin composition, The resin composition contains a resin (A), a photoacid generator (B-1), a photoacid generator (B-2), and an acid diffusion control agent (D). The photoacid generator (B-1) ) The pKa of the acid generated is less than 0, and the pKa of the acid generated from the photoacid generator (B-2) is greater than the pKa of the acid generated from the photoacid generator (B-1), relative to the The content of the photo acid generator (B-1), and the content of the photo acid generator (B-2) is 0.001% by mass or more and 0.10% by mass or less. [2] The sensitizing radiation-sensitive or radiation-sensitive resin composition according to [1], wherein the pKa of the acid generated from the photoacid generator (B-1) is E 1 , and the When the pKa of the acid generated by the photoacid generator (B-2) is E 2 , E 2 -E 1 is 3 or more. [3] The sensitizing radiation-sensitive or radiation-sensitive resin composition according to [1] or [2], wherein the acid diffusion control agent ( The content of D) is 0.5% by mass or more and 10.0% by mass or less. [4] The sensitizing radiation-sensitive or radiation-sensitive resin composition according to any one of [1] to [3], wherein the resin (A) is decomposed by the action of an acid to increase its polarity. The base resin. [5] The actinic radiation-sensitive or radiation-sensitive resin composition according to any one of [1] to [4], wherein the resin (A) is a resin containing a repeating unit having a phenolic hydroxyl group. [6] The actinic radiation-sensitive or radiation-sensitive resin composition according to [5], wherein the resin (A) has a repeating unit derived from hydroxystyrene. [7] The sensitizing ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [6], wherein the resin (A) is composed of repeats represented by the following general formula (I) Unit resin.
[化1] [化1]
通式(I)中, R41 、R42 及R43 各自獨立地表示氫原子、烷基、環烷基、鹵素原子、氰基或烷氧基羰基。其中,R42 可與Ar4 鍵結而形成環,該情況下的R42 表示單鍵或伸烷基。 X4 表示單鍵、-COO-、或-CONR64 -,R64 表示氫原子或烷基。 L4 表示單鍵或二價連結基。 Ar4 表示(n+1)價的芳香族烴基,於與R42 鍵結而形成環的情況下,表示(n+2)價的芳香族烴基。 n表示1~5的整數。 [8] 如[1]至[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,其中所述酸擴散控制劑(D)為鹼性化合物(DA)、藉由光化射線或放射線的照射而鹼性降低或消失的鹼性化合物(DB)、具有氮原子且具有藉由酸的作用而脫離的基的低分子化合物(DD)、或於陽離子部具有氮原子的鎓鹽化合物(DE)。 [9] 如[1]至[8]中任一項所述的感光化射線性或感放射線性樹脂組成物,其中所述酸擴散控制劑(D)為具有下述式(D1)~式(D5)中任一者所表示的結構的化合物。In the general formula (I), R 41 , R 42 and R 43 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. Among them, R 42 may be bonded to Ar 4 to form a ring. In this case, R 42 represents a single bond or an alkylene group. X 4 represents a single bond, -COO-, or -CONR 64 -, and R 64 represents a hydrogen atom or an alkyl group. L 4 represents a single bond or a divalent linking group. Ar 4 represents an (n+1)-valent aromatic hydrocarbon group, and when it bonds with R 42 to form a ring, it represents an (n+2)-valent aromatic hydrocarbon group. n represents an integer of 1-5. [8] The sensitizing radiation-sensitive or radiation-sensitive resin composition according to any one of [1] to [7], wherein the acid diffusion control agent (D) is a basic compound (DA), Basic compound (DB) whose basicity is reduced or disappeared by the irradiation of actinic rays or radiation, low-molecular compound (DD) that has a nitrogen atom and a group that is detached by the action of an acid, or has a nitrogen atom in the cation part The onium salt compound (DE). [9] The sensitizing radiation-sensitive or radiation-sensitive resin composition according to any one of [1] to [8], wherein the acid diffusion control agent (D) has the following formulas (D1) to (D5) A compound having a structure represented by any one of them.
[化2] [化2]
式(D1)及式(D5)中, R200 、R201 及R202 分別獨立地表示氫原子、烷基、環烷基或芳基。R201 與R202 可相互鍵結而形成環。 R203 、R204 、R205 及R206 分別獨立地表示烷基。 [10] 如[1]至[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,其中所述光酸產生劑(B-2)為下述式d1-1~式d1-3中任一者所表示的化合物。In formula (D1) and formula (D5), R 200 , R 201 and R 202 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group. R 201 and R 202 may be bonded to each other to form a ring. R 203 , R 204 , R 205 and R 206 each independently represent an alkyl group. [10] The sensitizing radiation-sensitive or radiation-sensitive resin composition according to any one of [1] to [9], wherein the photoacid generator (B-2) is the following formula d1-1 to A compound represented by any one of formula d1-3.
[化3] [化3]
式d1-1~式d1-3中, R51 表示有機基。 Z2c 表示烴基。其中,Z2c 表示的烴基設為於與硫原子鄰接的碳原子未鍵結氟原子者。 R52 表示有機基,Y3 表示單鍵或二價連結基,Rf表示取代基。R52 與Rf可鍵結而形成環。 M+ 表示銨陽離子、鋶陽離子或錪陽離子。 [11] 如[1]至[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,其中所述光酸產生劑(B-2)為下述式C-1~式C-3中任一者所表示的化合物。In formula d1-1 to formula d1-3, R 51 represents an organic group. Z 2c represents a hydrocarbon group. Here , the hydrocarbon group represented by Z 2c is one where a fluorine atom is not bonded to a carbon atom adjacent to a sulfur atom. R 52 represents an organic group, Y 3 represents a single bond or a divalent linking group, and Rf represents a substituent. R 52 and Rf may bond to form a ring. M + represents an ammonium cation, a cation or an iodonium cation. [11] The sensitizing radiation-sensitive or radiation-sensitive resin composition according to any one of [1] to [9], wherein the photoacid generator (B-2) is the following formula C-1 to A compound represented by any one of formula C-3.
[化4] [化4]
式C-1~式C-3中, R1 、R2 、及R3 分別獨立地表示有機基。 L1 表示連結陽離子部位與陰離子部位的二價連結基或單鍵。 -X- 表示選自-COO- 、-SO3 - 、-SO2 - 、及-N- -R4 中的陰離子部位。R4 表示於與鄰接的氮原子的連結部位具有羰基、磺醯基、及亞磺醯基中至少一種的一價取代基。 R1 、R2 、R3 、R4 、及L1 可相互鍵結而形成環結構。另外,於式C-3中,將R1 ~R3 中的兩個合併表示一個二價取代基,亦可藉由雙鍵而與氮原子鍵結。 [12] 一種感光化射線性或感放射線性膜,其由如[1]至[11]中任一項所述的感光化射線性或感放射線性樹脂組成物形成,且膜厚為1 μm以上。 [13] 一種圖案形成方法,具有: (i)利用如[1]至[11]中任一項所述的感光化射線性或感放射線性樹脂組成物於基板上形成膜厚為1 μm以上的感光化射線性或感放射線性膜的步驟; (ii)對所述感光化射線性或感放射線性膜照射光化射線或放射線的步驟;以及 (iii)使用顯影液對照射了所述光化射線或放射線的感光化射線性或感放射線性膜進行顯影的步驟。 [14] 一種電子元件的製造方法,包括如[13]所述的圖案形成方法。In formula C-1 to formula C-3, R 1 , R 2 , and R 3 each independently represent an organic group. L 1 represents a divalent linking group or a single bond connecting a cationic site and an anionic site. -X - represents a group selected -COO -, -SO 3 -, -SO 2 -, and -N - anionic sites in -R 4. R 4 represents a monovalent substituent having at least one of a carbonyl group, a sulfinyl group, and a sulfinyl group at the connection site to the adjacent nitrogen atom. R 1 , R 2 , R 3 , R 4 , and L 1 may be bonded to each other to form a ring structure. In addition, in formula C-3, combining two of R 1 to R 3 represents a divalent substituent, which may also be bonded to a nitrogen atom by a double bond. [12] A sensitizing ray-sensitive or radiation-sensitive film formed of the sensitizing ray-sensitive or radiation-sensitive resin composition as described in any one of [1] to [11], and having a film thickness of 1 μm the above. [13] A pattern forming method comprising: (i) using the sensitizing radiation-sensitive or radiation-sensitive resin composition as described in any one of [1] to [11] to form a film thickness of 1 μm or more on a substrate (Ii) the step of irradiating the sensitizing or radiation-sensitive film with actinic rays or radiation; and (iii) using a developer to irradiate the light The step of developing the sensitized or radiation-sensitive film of chemical rays or radiation. [14] A method of manufacturing an electronic component, including the pattern forming method as described in [13].
[發明的效果] 根據本發明,可提供於厚膜的圖案形成中所獲得的圖案的剖面形狀的矩形性優異的感光化射線性或感放射線性樹脂組成物、及感光化射線性或感放射線性膜、以及使用了所述感光化射線性或感放射線性樹脂組成物的圖案形成方法及電子元件的製造方法。[Effects of the invention] According to the present invention, it is possible to provide an actinic ray-sensitive or radiation-sensitive resin composition, an actinic ray-sensitive or radiation-sensitive resin composition, and an actinic ray-sensitive or radiation-sensitive film having excellent rectangularity in the cross-sectional shape of the pattern obtained in the pattern formation of a thick film, and use The pattern formation method of the sensitizing radiation-sensitive or radiation-sensitive resin composition and the manufacturing method of the electronic component are described.
以下,對本發明的內容進行詳細說明。 以下記載的結構要件的說明有時是基於本發明的代表性實施態樣而成,本發明並不限定於此種實施態樣。 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中與不具有取代基的基(原子團)一併亦包含具有取代基的基(原子團)。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。Hereinafter, the content of the present invention will be described in detail. The description of the structural elements described below may be based on a representative embodiment of the present invention, and the present invention is not limited to such an embodiment. Regarding the expression of the group (atomic group) in this specification, the expression that does not describe substituted and unsubstituted includes a group (atomic group) having a substituent together with a group (atomic group) that does not have 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定。取代基的數量例如可為一個、兩個、三個、或其以上。作為取代基的例子,可列舉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, the type of the substituent, the position of the substituent, and the number of the substituent when it is referred to as "may have a substituent" in this specification are not particularly limited. The number of substituents can be, for example, one, two, three, or more. 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;甲基巰基及第三丁基巰基等烷基巰基;苯基巰基及對甲苯基巰基等芳基巰基;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;甲醯基;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 Aphthyl, isobutyryl, acrylic, methacrylic and methoxalyl groups; alkyl mercapto groups such as methyl mercapto and tertiary butyl mercapto; phenyl mercapto and p-tolyl mercapto Alkyl; Cycloalkyl; Aryl; Heteroaryl; Hydroxy; Carboxy; Carboxylic; Sulfo; Cyano; Alkylaminocarbonyl; Arylaminocarbonyl; Sulfonamide; Silyl group; amino group; monoalkylamino group; dialkylamino group; arylamino group, nitro group; methanoyl group; and combinations of these.
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。只要無特別說明,則本說明書中的「光」是指光化射線或放射線。 所謂本說明書中的「曝光」,只要無特別說明,則不僅包含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曝光。 本說明書中,所謂「~」是以包含其前後所記載的數值作為下限值及上限值的含義使用。The "actinic rays" or "radiation rays" in this specification 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 electrons. Beam (EB: Electron Beam) and so on. Unless otherwise specified, the "light" in this specification refers to actinic rays or radiation. The "exposure" in this manual, unless otherwise specified, includes not only exposure using the bright line spectrum of a mercury lamp, extreme ultraviolet, extreme ultraviolet, X-ray, and EUV light represented by excimer lasers, etc. Including exposure using particle beams such as electron beams and ion beams. In this specification, the term "to" is used to include the numerical values described before and after it as the lower limit and the upper limit.
本說明書中,(甲基)丙烯酸酯表示丙烯酸酯及甲基丙烯酸酯,(甲基)丙烯酸表示丙烯酸及甲基丙烯酸。 本說明書中,樹脂成分的重量平均分子量(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)(股)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)(股)製造的TSK gel Multipore HXL-M、管柱溫度:40℃、流速:1.0 mL/min、檢測器:示差折射率檢測器(Refractive Index Detector))所得的聚苯乙烯換算值。In this specification, (meth)acrylate means acrylate and methacrylate, and (meth)acrylic means acrylic and methacrylic acid. In this specification, the weight average molecular weight (Mw), number average molecular weight (Mn), and degree of dispersion (also called molecular weight distribution) (Mw/Mn) of the resin components are defined as the use of gel permeation chromatography (Gel Permeation Chromatography). GPC measurement (solvent: tetrahydrofuran, flow rate (sample injection volume): 10 μL, column: manufactured by Tosoh (stock), HLC-8120GPC manufactured by Tosoh (stock)) TSK gel Multipore HXL-M, column temperature: 40°C, flow rate: 1.0 mL/min, detector: Refractive Index Detector (Refractive Index Detector).
本說明書中關於組成物中的各成分的量,於組成物中存在多種相當於各成分的物質的情況下,只要無特別說明,則是指組成物中存在的相當的多種物質的合計量。 本說明書中「步驟」這一用語不僅包含獨立的步驟,即便於與其他步驟無法明確地加以區分的情況下,只要達成步驟的所期望的目的,則亦包含於本用語中。 本說明書中所謂「總固體成分」,是指自組成物的總組成中去除溶劑後的成分的總質量。另外,所謂「固體成分」,如所述般是去除溶劑後的成分,例如於25℃下可為固體,亦可為液體。 本說明書中,「質量%」與「重量%」為相同含義,「質量份」與「重量份」為相同含義。 另外,本說明書中,兩個以上的較佳態樣的組合為更佳的態樣。Regarding the amount of each component in the composition in this specification, when there are multiple substances corresponding to each component in the composition, unless otherwise specified, it means the total amount of the corresponding multiple substances present in the composition. The term "step" in this specification includes not only independent steps, but even when it cannot be clearly distinguished from other steps, as long as the desired purpose of the step is achieved, it is also included in this term. The "total solid content" in this specification refers to the total mass of the components after removing the solvent from the total composition of the composition. In addition, the so-called "solid content" is a component after removing the solvent as described above, and for example, it may be a solid or a liquid at 25°C. In this manual, "mass%" and "weight%" have the same meaning, and "parts by mass" and "parts by weight" have the same meaning. In addition, in this specification, a combination of two or more preferable aspects is a more preferable aspect.
(感光化射線性或感放射線性樹脂組成物) 本發明的感光化射線性或感放射線性樹脂組成物(以下,亦簡稱為「組成物」)為固體成分濃度為10質量%以上的感光化射線性或感放射線性樹脂組成物, 所述感光化射線性或感放射線性樹脂組成物含有樹脂(A)、光酸產生劑(B-1)、光酸產生劑(B-2)、及酸擴散控制劑(D), 所述光酸產生劑(B-1)的pKa未滿0, 所述光酸產生劑(B-2)的pKa大於所述光酸產生劑(B-1)的pKa, 相對於所述光酸產生劑(B-1)的含量,所述光酸產生劑(B-2)的含量為0.001質量%以上且0.10質量%以下。(Acceptable radiation or radiation-sensitive resin composition) The actinic radiation or radiation-sensitive resin composition of the present invention (hereinafter also referred to as "composition") is an actinic radiation or radiation-sensitive resin composition having a solid content of 10% by mass or more. The sensitizing radiation or radiation-sensitive resin composition contains resin (A), photoacid generator (B-1), photoacid generator (B-2), and acid diffusion control agent (D), The pKa of the photoacid generator (B-1) is less than 0, The pKa of the photo acid generator (B-2) is greater than the pKa of the photo acid generator (B-1), The content of the photo acid generator (B-2) relative to the content of the photo acid generator (B-1) is 0.001% by mass or more and 0.10% by mass or less.
本發明的感光化射線性或感放射線性樹脂組成物較佳為所謂的抗蝕劑組成物,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,可為鹼顯影用的抗蝕劑組成物,亦可為有機溶劑顯影用的抗蝕劑組成物。 本發明的組成物典型而言較佳為化學增幅型的抗蝕劑組成物。The actinic radiation-sensitive or radiation-sensitive resin composition of the present invention is preferably a so-called resist composition, and 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. Typically, the composition of the present invention is preferably a chemically amplified resist composition.
本發明者發現,藉由所述感光化射線性或感放射線性樹脂組成物,可獲得厚膜的、且剖面形狀的矩形性優異的圖案。其理由並不明確,但可如以下般推測。 作為典型的感光化射線性或感放射線性樹脂組成物的抗蝕劑組成物含有樹脂、光酸產生劑(B-1)、酸擴散控制劑及溶劑。於基板上塗佈抗蝕劑組成物等而形成膜厚1 μm以上的厚膜抗蝕劑膜的情況下,於厚膜抗蝕劑膜中,與薄膜的情況相比,溶劑難以揮發,因此於較接近基板之側(基板界面側)更遠離基板之側(空氣界面側)的區域,樹脂或光酸產生劑容易進行濃縮(大量存在(即偏向存在)於較接近基板之側(基板界面側)更遠離基板之側(空氣界面側))。另一方面,酸擴散控制劑均勻分佈於厚膜抗蝕劑膜整體。若對此種狀態的厚膜抗蝕劑膜進行曝光,則於遠離基板之側(空氣界面側)的區域產生大量酸,因此酸容易擴散,圖案的剖面形狀的矩形性降低。 相對於此,認為於本發明中,藉由添加特定量的產生較自光酸產生劑(B-1)產生的酸更弱的酸的光酸產生劑(B-2),光酸產生劑(B-2)亦與光酸產生劑(B-1)同樣地偏向存在於遠離基板之側(空氣界面側)的區域,可適度地抑制自光酸產生劑(B-1)產生的酸的擴散,從而可提高圖案的剖面形狀的矩形性。The inventors of the present invention have found that the above-mentioned actinic radiation-sensitive or radiation-sensitive resin composition can obtain a thick film and a pattern excellent in the rectangularity of the cross-sectional shape. The reason is not clear, but it can be estimated as follows. The resist composition, which is a typical sensitizing radiation-sensitive or radiation-sensitive resin composition, contains a resin, a photoacid generator (B-1), an acid diffusion control agent, and a solvent. When a resist composition or the like is applied on a substrate to form a thick film resist film with a film thickness of 1 μm or more, in the thick film resist film, the solvent is less volatile than in the case of a thin film. In the area closer to the substrate (substrate interface side) and farther away from the substrate (air interface side), the resin or photoacid generator is easy to concentrate (exist in a large amount (that is, biased)) on the side closer to the substrate (substrate interface) Side) farther away from the substrate (air interface side)). On the other hand, the acid diffusion control agent is uniformly distributed over the entire thick film resist film. If the thick resist film in this state is exposed, a large amount of acid is generated in the area far from the substrate (air interface side), so the acid is easily diffused, and the rectangularity of the cross-sectional shape of the pattern is reduced. In contrast to this, it is considered that in the present invention, by adding a specific amount of a photoacid generator (B-2) that generates an acid weaker than the acid generated from the photoacid generator (B-1), the photoacid generator (B-2) Similar to the photoacid generator (B-1), it is also present in the region away from the substrate (air interface side), and the acid generated from the photoacid generator (B-1) can be moderately suppressed Diffusion, thereby improving the rectangularity of the cross-sectional shape of the pattern.
以下,對本發明的感光化射線性或感放射線性樹脂組成物中包含的各成分的詳情進行說明。Hereinafter, the details of each component contained in the sensitizing radiation or radiation sensitive resin composition of the present invention will be described.
<樹脂(A)> 本發明的感光化射線性或感放射線性樹脂組成物含有樹脂(A)。 樹脂(A)較佳為具有藉由酸的作用進行分解而極性增大的基(酸分解性基)的樹脂。樹脂(A)較佳為藉由酸的作用而極性增大、對於顯影液的溶解性發生變化的樹脂。<Resin (A)> The actinic radiation-sensitive or radiation-sensitive resin composition of the present invention contains resin (A). The resin (A) is preferably a resin having a group (acid-decomposable group) that is decomposed by the action of an acid to increase the polarity. The resin (A) is preferably a resin whose polarity increases due to the action of an acid and the solubility to the developer is changed.
樹脂(A)較佳為至少將乙烯性不飽和化合物聚合而成的樹脂。 所述乙烯性不飽和化合物較佳為具有一個~四個乙烯性不飽和鍵,更佳為一個。進而所述乙烯性不飽和化合物較佳為作為單量體的單體。 另外,所述乙烯性不飽和化合物的分子量較佳為28~1,000,更佳為50~800,特佳為100~600。The resin (A) is preferably a resin obtained by polymerizing at least an ethylenically unsaturated compound. The ethylenically unsaturated compound preferably has one to four ethylenically unsaturated bonds, more preferably one. Furthermore, the ethylenically unsaturated compound is preferably a monomer which is a monomer. In addition, the molecular weight of the ethylenically unsaturated compound is preferably 28 to 1,000, more preferably 50 to 800, and particularly preferably 100 to 600.
樹脂(A)更佳為含有具有酸分解性基的結構單元的樹脂。 於該情況下,於後述的本發明的圖案形成方法中,於採用鹼性顯影液作為顯影液的情況下,可較佳地形成正型圖案,於採用有機系顯影液作為顯影液的情況下,可較佳地形成負型圖案。The resin (A) is more preferably a resin containing a structural unit having an acid-decomposable group. In this case, in the pattern forming method of the present invention described later, when an alkaline developer is used as the developer, a positive pattern can be preferably formed, and when an organic developer is used as the developer, , Can preferably form a negative pattern.
〔具有酸分解性基的結構單元〕 樹脂(A)較佳為含有具有酸分解性基的結構單元(亦稱為「重複單元」)。〔Structural units with acid-decomposable groups〕 The resin (A) preferably contains a structural unit having an acid-decomposable group (also referred to as "repeating unit").
作為樹脂(A),可適宜使用公知的樹脂。例如可較佳地使用美國專利申請案公開第2016/0274458號說明書的段落0055~段落0191、美國專利申請案公開第2015/0004544號說明書的段落0035~段落0085、美國專利申請案公開第2016/0147150號說明書的段落0045~段落0090中所揭示的公知的樹脂作為樹脂(A)。As the resin (A), a known resin can be suitably used. For example, paragraph 0055 to paragraph 0191 of U.S. Patent Application Publication No. 2016/0274458 Specification, Paragraph 0035 to Paragraph 0085 of U.S. Patent Application Publication No. 2015/0004544 Specification, and U.S. Patent Application Publication No. 2016/ The well-known resin disclosed in paragraph 0045 to paragraph 0090 of Specification No. 0147150 is referred to as resin (A).
酸分解性基較佳為具有極性基由藉由酸的作用進行分解而脫離的基(脫離基)保護的結構。 作為極性基,可列舉:羧基、酚性羥基、磺酸基、磺醯胺基、磺醯基醯亞胺基、(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(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 decomposed by the action of an acid to be released (a leaving group) protected. Examples of polar groups include carboxyl groups, phenolic hydroxyl groups, sulfonic acid groups, sulfonamido groups, sulfonamido groups, (alkylsulfonyl groups) (alkylcarbonyl) methylene groups, (alkylsulfonyl groups). (Alkyl)(alkylcarbonyl)amido, bis(alkylcarbonyl)methylene, bis(alkylcarbonyl)amido, bis(alkylsulfonyl)methylene, bis(alkyl) Acidic groups such as sulfonyl)imino group, tris(alkylcarbonyl)methylene, and tris(alkylsulfonyl)methylene (groups dissociated in 2.38% by mass tetramethylammonium hydroxide aqueous solution) , And alcoholic hydroxyl groups.
再者,所謂醇性羥基,是指鍵結於烴基、且直接鍵結於芳香環上的羥基(酚性羥基)以外的羥基,作為羥基,α位經氟原子等拉電子性基取代的脂肪族醇基(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 other than the hydroxyl group (phenolic hydroxyl group) that is directly bonded to the aromatic ring and is bonded to a hydrocarbon group. As a hydroxyl group, an aliphatic group substituted with an electron withdrawing group such as a fluorine atom at the α-position Except for group alcohol groups (for example, hexafluoroisopropanol groups, etc.). The alcoholic hydroxyl group is preferably a hydroxyl group having a pKa (acid dissociation constant) of 12 or more and 20 or less.
作為較佳的極性基,可列舉:羧基、酚性羥基、及磺酸基。As a preferable polar group, a carboxyl group, a phenolic hydroxyl group, and a sulfonic acid group are mentioned.
作為酸分解性基而較佳的基為利用藉由酸的作用而脫離的基(脫離基)對該些基的氫原子進行取代的基。 作為藉由酸的作用而脫離的基(脫離基),例如可列舉:-C(R36 )(R37 )(R38 )、-C(R36 )(R37 )(OR39 )、及-C(R01 )(R02 )(OR39 )等。 式中,R36 ~R39 分別獨立地表示烷基、環烷基、芳基、芳烷基或烯基。R36 與R37 可相互鍵結而形成環。 R01 及R02 分別獨立地表示氫原子、烷基、環烷基、芳基、芳烷基或烯基。A preferable group as an acid-decomposable group is a group in which the hydrogen atom of these groups is substituted with a group that is released by the action of an acid (a leaving group). Examples of the group to be released by the action of an acid (a leaving group) include -C(R 36 )(R 37 )(R 38 ), -C(R 36 )(R 37 )(OR 39 ), and -C(R 01 )(R 02 )(OR 39 ) and so on. In the formula, R 36 to R 39 each independently represent an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. R 36 and R 37 may be bonded to each other to form a ring. R 01 and R 02 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group.
R36 ~R39 、R01 及R02 的烷基較佳為碳數1~8的烷基,例如可列舉:甲基、乙基、丙基、正丁基、第二丁基、己基、及辛基等。 R36 ~R39 、R01 及R02 的環烷基可為單環型,亦可為多環型。作為單環型,較佳為碳數3~8的環烷基,例如可列舉:環丙基、環丁基、環戊基、環己基、及環辛基等。作為多環型,較佳為碳數6~20的環烷基,例如可列舉:金剛烷基、降冰片基、異冰片基、莰基、二環戊基、α-蒎烯基、三環癸烷基、四環十二烷基、及雄甾烷基等。再者,環烷基中的至少一個碳原子可經氧原子等雜原子取代。 R36 ~R39 、R01 及R02 的芳基較佳為碳數6~10的芳基,例如可列舉:苯基、萘基、及蒽基等。 R36 ~R39 、R01 及R02 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、及萘基甲基等。 R36 ~R39 、R01 及R02 的烯基較佳為碳數2~8的烯基,例如可列舉:乙烯基、烯丙基、丁烯基、及環己烯基等。 作為R36 與R37 相互鍵結而形成的環,較佳為環烷基(單環或多環)。作為環烷基,較佳為環戊基、及環己基等單環的環烷基、或降冰片基、四環癸烷基、四環十二烷基、及金剛烷基等多環的環烷基。The alkyl group of R 36 to R 39 , R 01 and R 02 is preferably an alkyl group having 1 to 8 carbon atoms, for example, methyl, ethyl, propyl, n-butyl, sec-butyl, hexyl, And octyl and so on. The cycloalkyl groups of R 36 to R 39 , R 01 and R 02 may be monocyclic or polycyclic. The monocyclic type is preferably a cycloalkyl group having 3 to 8 carbon atoms, and examples thereof include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl. The polycyclic type is preferably a cycloalkyl group having 6 to 20 carbon atoms, for example, adamantyl group, norbornyl group, isobornyl group, camphenyl group, dicyclopentyl group, α-pinenyl group, tricyclic group Decyl, tetracyclododecyl, and androstanyl, etc. Furthermore, at least one carbon atom in the cycloalkyl group may be substituted with a hetero atom such as an oxygen atom. The aryl group of R 36 to R 39 , R 01 and R 02 is preferably an aryl group having 6 to 10 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, and an anthryl group. The aralkyl group of R 36 to R 39 , R 01 and R 02 is preferably an aralkyl group having 7 to 12 carbons, and examples thereof include benzyl, phenethyl, and naphthylmethyl. The alkenyl groups of R 36 to R 39 , R 01 and R 02 are preferably alkenyl groups having 2 to 8 carbon atoms, and examples thereof include vinyl groups, allyl groups, butenyl groups, and cyclohexenyl groups. The ring formed by bonding R 36 and R 37 to each other is preferably a cycloalkyl group (monocyclic or polycyclic). The cycloalkyl group is preferably a monocyclic cycloalkyl group such as cyclopentyl and cyclohexyl, or a polycyclic ring such as norbornyl, tetracyclodecyl, tetracyclododecyl, and adamantyl. alkyl.
作為酸分解性基,較佳為枯基酯基、烯醇酯基、縮醛酯基、或三級烷基酯基等,更佳為縮醛基、或三級烷基酯基。The acid-decomposable group is preferably a cumyl ester group, an enol ester group, an acetal ester group, or a tertiary alkyl ester group, and more preferably an acetal group or a tertiary alkyl ester group.
樹脂(A)較佳為具有下述式AI所表示的結構單元作為具有酸分解性基的結構單元。The resin (A) preferably has a structural unit represented by the following formula AI as a structural unit having an acid-decomposable group.
[化5] [化5]
式AI中,Xa1 表示氫原子、氟原子以外的鹵素原子、或一價有機基,T表示單鍵或二價連結基,Rx1 ~Rx3 分別獨立地表示烷基或環烷基,Rx1 ~Rx3 的任意兩個可鍵結而形成環結構,亦可不形成環結構。In formula AI, Xa 1 represents a hydrogen atom, a halogen atom other than a fluorine atom, or a monovalent organic group, T represents a single bond or a divalent linking group, Rx 1 to Rx 3 each independently represent an alkyl group or a cycloalkyl group, and Rx Any two of 1 to Rx 3 may be bonded to form a ring structure, or may not form a ring structure.
作為T的二價連結基,可列舉:伸烷基、伸芳基、-COO-Rt-、及-O-Rt-等。式中,Rt表示伸烷基、伸環烷基或伸芳基, T較佳為單鍵或-COO-Rt-。Rt較佳為碳數1~5的鏈狀伸烷基,更佳為-CH2 -、-(CH2 )2 -、或-(CH2 )3 -。T更佳為單鍵。As a divalent linking group of T, an alkylene group, an arylene group, -COO-Rt-, and -O-Rt- etc. are mentioned. In the formula, Rt represents an alkylene group, a cycloalkylene group or an arylene group, and T is preferably a single bond or -COO-Rt-. Rt is preferably a chain alkylene having 1 to 5 carbon atoms, more preferably -CH 2 -, -(CH 2 ) 2 -, or -(CH 2 ) 3 -. T is more preferably a single bond.
Xa1 較佳為氫原子或烷基。 Xa1 的烷基可具有取代基,作為取代基,例如可列舉羥基、及氟原子以外的鹵素原子。 Xa1 的烷基較佳為碳數1~4,可列舉:甲基、乙基、丙基、及羥基甲基等。Xa1 的烷基較佳為甲基。Xa 1 is preferably a hydrogen atom or an alkyl group. The alkyl group of Xa 1 may have a substituent, and examples of the substituent include a hydroxyl group and a halogen atom other than a fluorine atom. The alkyl group of Xa 1 preferably has 1 to 4 carbon atoms, and examples thereof include methyl, ethyl, propyl, and hydroxymethyl. The alkyl group of Xa 1 is preferably a methyl group.
作為Rx1 、Rx2 及Rx3 的烷基,可為直鏈狀,亦可為分支狀,可較佳地列舉:甲基、乙基、正丙基、異丙基、正丁基、異丁基、第三丁基等。作為烷基的碳數,較佳為1~10,更佳為1~5,進而佳為1~3。Rx1 、Rx2 及Rx3 的烷基中,碳間鍵的一部分可為雙鍵。 作為Rx1 、Rx2 及Rx3 的環烷基,較佳為環戊基、環己基等單環的環烷基、或降冰片基、四環癸烷基、四環十二烷基、金剛烷基等多環的環烷基。The alkyl groups of Rx 1 , Rx 2 and Rx 3 may be linear or branched, and preferably include methyl, ethyl, n-propyl, isopropyl, n-butyl, isopropyl Butyl, tertiary butyl, etc. The number of carbon atoms in the alkyl group is preferably 1-10, more preferably 1-5, and still more preferably 1-3. In the alkyl group of Rx 1 , Rx 2 and Rx 3 , a part of the inter-carbon bond may be a double bond. The cycloalkyl group of Rx 1 , Rx 2 and Rx 3 is preferably a monocyclic cycloalkyl group such as cyclopentyl and cyclohexyl, or norbornyl, tetracyclodecyl, tetracyclododecyl, adamantane Polycyclic cycloalkyl groups such as alkyl groups.
作為Rx1 、Rx2 及Rx3 的兩個鍵結而形成的環結構,較佳為環戊基環、環己基環、環庚基環、及環辛烷環等單環的環烷烴環、或降冰片烷環、四環癸烷環、四環十二烷環、及金剛烷環等多環的環烷基環,更佳為環戊基環、環己基環、或金剛烷環。作為Rx1 、Rx2 及Rx3 的兩個鍵結而形成的環結構,亦較佳為下述所示的結構。The ring structure formed by the two bonding of Rx 1 , Rx 2 and Rx 3 is preferably a monocyclic cycloalkane ring such as a cyclopentyl ring, a cyclohexyl ring, a cycloheptyl ring, and a cyclooctane ring, Or polycyclic cycloalkyl rings such as norbornane ring, tetracyclodecane ring, tetracyclododecane ring, and adamantane ring, more preferably cyclopentyl ring, cyclohexyl ring, or adamantane ring. As a ring structure formed by two bonding of Rx 1 , Rx 2 and Rx 3 , the structure shown below is also preferable.
[化6] [化6]
以下列舉相當於式AI所表示的結構單元的單體的具體例,但本發明並不限定於該些具體例。下述具體例相當於式AI中的Xa1 為甲基的情況,Xa1 可任意地取代為氫原子、氟原子以外的鹵素原子、或一價有機基。Specific examples of monomers corresponding to the structural unit represented by formula AI are listed below, but the present invention is not limited to these specific examples. Corresponds to the following specific examples of AI of formula Xa 1 is a methyl group, optionally substituted Xa 1 represents a hydrogen atom, a halogen atom other than fluorine atom, or a monovalent organic group.
[化7] [化7]
樹脂(A)亦較佳為具有美國專利申請案公開第2016/0070167號說明書的段落0336~段落0369中記載的結構單元作為具有酸分解性基的結構單元。It is also preferable that the resin (A) has the structural unit described in paragraph 0336 to paragraph 0369 of the specification of U.S. Patent Application Publication No. 2016/0070167 as the structural unit having an acid-decomposable group.
另外,樹脂(A)可具有美國專利申請案公開第2016/0070167號說明書的段落0363~段落0364中記載的包含藉由酸的作用進行分解而產生醇性羥基的基的結構單元作為具有酸分解性基的結構單元。In addition, the resin (A) may have a structural unit described in paragraphs 0363 to 0364 of the specification of U.S. Patent Application Publication No. 2016/0070167, which includes a group that is decomposed by the action of an acid to generate an alcoholic hydroxyl group as a structural unit having acid decomposition. The structural unit of the sex base.
另外,樹脂(A)較佳為含有具有酚性羥基由藉由酸的作用進行分解而脫離的脫離基保護的結構(酸分解性基)的重複單元作為具有酸分解性基的重複單元。再者,本說明書中,所謂酚性羥基是芳香族烴基的氫原子經羥基取代而成的基。芳香族烴基的芳香環為單環或多環的芳香環,可列舉苯環及萘環等。In addition, the resin (A) preferably contains a repeating unit having a structure (acid-decomposable group) protected by a leaving group in which a phenolic hydroxyl group is decomposed by the action of an acid as a repeating unit having an acid-decomposable group. In addition, in this specification, the phenolic hydroxyl group is a group in which the hydrogen atom of an aromatic hydrocarbon group is substituted with a hydroxyl group. The aromatic ring of the aromatic hydrocarbon group is a monocyclic or polycyclic aromatic ring, and examples thereof include a benzene ring and a naphthalene ring.
作為藉由酸的作用進行分解而脫離的脫離基,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 leaving group decomposed and released by the action of an acid 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)、式(Y2)中,Rx1 ~Rx3 各自獨立地表示烷基(直鏈狀或分支鏈狀)或環烷基(單環或多環)。其中,於Rx1 ~Rx3 全部為烷基(直鏈狀或分支鏈狀)的情況下,較佳為Rx1 ~Rx3 中至少兩個為甲基。 其中,更佳為Rx1 ~Rx3 各自獨立地表示直鏈狀或分支鏈狀的烷基的重複單元,進而佳為Rx1 ~Rx3 各自獨立地表示直鏈狀烷基的重複單元。 Rx1 ~Rx3 中兩個可鍵結而形成單環或多環。 作為Rx1 ~Rx3 的烷基,較佳為甲基、乙基、正丙基、異丙基、正丁基、異丁基、及第三丁基等碳數1~4的烷基。 作為Rx1 ~Rx3 的環烷基,較佳為環戊基、環己基等單環的環烷基、或降冰片基、四環癸烷基、四環十二烷基、及金剛烷基等多環的環烷基。 作為Rx1 ~Rx3 中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、或降冰片基、四環癸烷基、四環十二烷基、及金剛烷基等多環的環烷基。其中,更佳為碳數5~6的單環的環烷基。 Rx1 ~Rx3 中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。 式(Y1)及式(Y2)所表示的基較佳為例如Rx1 為甲基或乙基、Rx2 與Rx3 鍵結而形成所述環烷基的態樣。In formula (Y1) and formula (Y2), Rx 1 to Rx 3 each independently represent an alkyl group (linear or branched chain) 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. Among them, it is more preferred that Rx 1 to Rx 3 each independently represent a repeating unit of a linear or branched alkyl group, and it is more preferred that Rx 1 to Rx 3 each independently represent a repeating unit of a linear alkyl group. Two of Rx 1 to Rx 3 may be bonded to form a monocyclic ring or a polycyclic ring. The alkyl group of Rx 1 to Rx 3 is preferably an alkyl group having 1 to 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 norbornyl, tetracyclodecyl, tetracyclododecyl, and adamantyl Such as polycyclic cycloalkyl. As the cycloalkyl formed by bonding two of Rx 1 to Rx 3 , monocyclic cycloalkyl such as cyclopentyl and cyclohexyl, or norbornyl, tetracyclodecyl, and tetracyclodecyl are preferred. Polycyclic cycloalkyl groups such as dialkyl and adamantyl. Among them, a monocyclic cycloalkyl group having 5 to 6 carbon atoms is more preferred. Among the cycloalkyl groups formed by bonding two 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 group represented by the formula (Y1) and the formula (Y2) is preferably a state in which, for example, Rx 1 is a methyl group or an ethyl group, and Rx 2 and Rx 3 are bonded to form the cycloalkyl group.
式(Y3)中,R36 ~R38 各自獨立地表示氫原子或一價有機基。R37 與R38 可相互鍵結而形成環。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 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 preferably a hydrogen atom.
式(Y4)中,Ar表示芳香族烴基。Rn表示烷基、環烷基、或芳基。Rn與Ar可相互鍵結而形成非芳香族環。Ar更佳為芳基。In formula (Y4), Ar represents an aromatic hydrocarbon group. Rn represents an alkyl group, a cycloalkyl group, or an aryl group. Rn and Ar can bond with each other to form a non-aromatic ring. Ar is more preferably an aryl group.
作為具有酚性羥基由藉由酸的作用進行分解而脫離的脫離基保護的結構(酸分解性基)的重複單元,較佳為具有酚性羥基中的氫原子由式(Y1)~式(Y4)所表示的基保護的結構的重複單元。As a repeating unit having a structure (acid decomposable group) protected by a leaving group that is decomposed by the action of an acid, the phenolic hydroxyl group preferably has a hydrogen atom in the phenolic hydroxyl group from formula (Y1) to formula ( Y4) The repeating unit of the structure protected by the group represented.
作為具有酚性羥基由藉由酸的作用進行分解而脫離的脫離基保護的結構(酸分解性基)的重複單元,較佳為下述通式(AII)所表示的重複單元。The repeating unit having a structure (acid-decomposable group) protected by a leaving group in which a phenolic hydroxyl group is decomposed by the action of an acid is preferably a repeating unit represented by the following general formula (AII).
[化8] [化8]
通式(AII)中, R61 、R62 及R63 各自獨立地表示氫原子、烷基、環烷基、鹵素原子、氰基、或烷氧基羰基。其中,R62 可與Ar6 鍵結而形成環,該情況下的R62 表示單鍵或伸烷基。 X6 表示單鍵、-COO-、或-CONR64 -。R64 表示氫原子或烷基。 L6 表示單鍵或伸烷基。 Ar6 表示(n+1)價的芳香族烴基,於與R62 鍵結而形成環的情況下,表示(n+2)價的芳香族烴基。 於n≧2的情況下,Y2 各自獨立地表示氫原子或藉由酸的作用而脫離的基。其中,Y2 的至少一個表示藉由酸的作用而脫離的基。作為Y2 的藉由酸的作用而脫離的基較佳為式(Y1)~式(Y4)。 n表示1~4的整數。In the general formula (AII), R 61 , R 62 and R 63 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. Among them, R 62 may bond with Ar 6 to form a ring. In this case, R 62 represents a single bond or an alkylene group. X 6 represents a single bond, -COO-, or -CONR 64 -. R 64 represents a hydrogen atom or an alkyl group. L 6 represents a single bond or an alkylene group. Ar 6 represents an (n+1)-valent aromatic hydrocarbon group, and when it bonds with R 62 to form a ring, it represents an (n+2)-valent aromatic hydrocarbon group. In the case of n≧2, Y 2 each independently represents a hydrogen atom or a group released by the action of an acid. Among them, at least one of Y 2 represents a group that is detached by the action of an acid. The group that is detached by the action of acid as Y 2 is preferably formula (Y1) to formula (Y4). n represents an integer of 1-4.
所述各基可具有取代基,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,較佳為碳數8以下者。Each of the above groups may have 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 alkoxycarbonyl group. (C2-6), etc., preferably having a carbon number of 8 or less.
以下,列舉具有酚性羥基由藉由酸的作用進行分解而脫離的脫離基保護的結構(酸分解性基)的重複單元的具體例,但本發明並不限定於該些具體例。Hereinafter, specific examples of a repeating unit having a structure (acid-decomposable group) protected by a leaving group in which a phenolic hydroxyl group is decomposed by the action of an acid are given, but the present invention is not limited to these specific examples.
[化9] [化9]
[化10] [化10]
樹脂(A)可單獨包含一種具有酸分解性基的結構單元,亦可包含兩種以上。The resin (A) may contain one kind of structural unit having an acid-decomposable group alone, or two or more kinds.
相對於樹脂(A)的所有結構單元,樹脂(A)中包含的具有酸分解性基的結構單元的含量(於存在多種具有酸分解性基的結構單元的情況下為其合計)較佳為5莫耳%~90莫耳%,更佳為10莫耳%~80莫耳%,進而佳為15莫耳%~70莫耳%。 再者,本發明中,於以莫耳比規定「結構單元」的含量的情況下,所述「結構單元」與「單體單元」為相同含義。另外,本發明中所述「單體單元」可藉由高分子反應等加以聚合後進行修飾。以下亦相同。The content of the acid-decomposable group-containing structural unit contained in the resin (A) relative to all the structural units of the resin (A) (the total when there are multiple structural units having acid-decomposable groups) is preferably 5 mol% to 90 mol%, more preferably 10 mol% to 80 mol%, and still more preferably 15 mol% to 70 mol%. In addition, in the present invention, when the content of the "structural unit" is defined in molar ratio, the "structural unit" and the "monomer unit" have the same meaning. In addition, the "monomer unit" in the present invention can be modified after being polymerized by a polymer reaction or the like. The following is also the same.
〔具有選自由內酯結構、磺內酯結構、及碳酸酯結構所組成的群組中的至少一種的結構單元〕 樹脂(A)可含有具有選自由內酯結構、磺內酯結構、及碳酸酯結構所組成的群組中的至少一種的結構單元。[Having at least one structural unit selected from the group consisting of a lactone structure, a sultone structure, and a carbonate structure] The resin (A) may contain a structural unit having at least one selected from the group consisting of a lactone structure, a sultone structure, and a carbonate structure.
作為內酯結構或磺內酯結構,只要具有內酯結構或磺內酯結構,則可使用任一種,較佳為5員環~7員環內酯結構或5員環~7員環磺內酯結構,更佳為其他環結構以形成雙環結構、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、螺環結構的形式與5員環~7員環磺內酯結構縮環而成者。進而佳為含有具有下述式LC1-1~式LC1-21的任一者所表示的內酯結構、或下述式SL1-1~式SL1-3的任一者所表示的磺內酯結構的結構單元。另外,內酯結構或磺內酯結構亦可直接鍵結於主鏈。作為較佳的結構,為LC1-1、LC1-4、LC1-5、LC1-8、LC1-16、LC1-21、SL1-1。As the lactone structure or sultone structure, any one may be used as long as it has a lactone structure or a sultone structure, preferably a 5-membered to 7-membered cyclic lactone structure or a 5-membered to 7-membered cyclic sultone Ester structure, more preferably other ring structure in the form of a bicyclic structure, spiro ring structure and 5-membered to 7-membered cyclic lactone structure, or other ring structure in the form of a bicyclic structure, spiro ring structure It is formed by condensing with 5-membered to 7-membered cyclic sultone structure. More preferably, it contains a lactone structure represented by any one of the following formulas LC1-1 to LC1-21, or a sultone structure represented by any one of the following formulas SL1-1 to SL1-3 The structural unit. In addition, the lactone structure or the sultone structure may be directly bonded to the main chain. As a preferable structure, it is LC1-1, LC1-4, LC1-5, LC1-8, LC1-16, LC1-21, SL1-1.
[化11] [化11]
內酯結構部分或磺內酯結構部分可具有取代基(Rb2 )亦可不具有取代基(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2~8的烷氧基羰基、羧基、氟原子以外的鹵素原子、羥基、氰基、及酸分解性基等。更佳為碳數1~4的烷基、氰基、及酸分解性基。n2表示0~4的整數。於n2為2以上時,存在多個的取代基(Rb2 )可相同亦可不同。另外,存在多個的取代基(Rb2 )彼此可鍵結而形成環。The lactone moiety or the sultone moiety may have a substituent (Rb 2 ) or may not 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 alkyl groups having 2 to 8 carbons. An oxycarbonyl group, a carboxyl group, a halogen atom other than a fluorine atom, a hydroxyl group, a cyano group, an acid-decomposable group, etc. More preferred are an alkyl group having 1 to 4 carbon atoms, a cyano group, and an acid-decomposable group. n2 represents an integer of 0-4. When n2 is 2 or more, a plurality of substituents (Rb 2 ) may be the same or different. In addition, a plurality of substituents (Rb 2 ) may be bonded to each other to form a ring.
具有內酯結構或磺內酯結構的結構單元較佳為下述式III所表示的結構單元。 另外,含有具有酸分解性基的結構單元的樹脂較佳為包含下述式III所表示的結構單元。The structural unit having a lactone structure or a sultone structure is preferably a structural unit represented by the following formula III. In addition, the resin containing a structural unit having an acid-decomposable group preferably contains a structural unit represented by the following formula III.
[化12] [化12]
所述式III中, A表示酯鍵(-COO-所表示的基)或醯胺鍵(-CONH-所表示的基)。 n為-R0 -Z-所表示的結構的重覆數,表示0~5的整數,較佳為0或1,更佳為0。於n為0的情況下,不存在-R0 -Z-,A與R8 藉由單鍵而鍵結。 R0 表示伸烷基、伸環烷基、或其組合。R0 於存在多個的情況下分別獨立地表示伸烷基、伸環烷基、或其組合。 Z表示單鍵、醚鍵、酯鍵、醯胺鍵、胺基甲酸酯鍵或脲鍵。Z於存在多個的情況下分別獨立地表示單鍵、醚鍵、酯鍵、醯胺鍵、胺基甲酸酯鍵或脲鍵。 R8 表示具有內酯結構或磺內酯結構的一價有機基。 R7 表示氫原子、氟原子以外的鹵素原子或一價有機基(較佳為甲基)。In the formula III, A represents an ester bond (a group represented by -COO-) or an amide bond (a group represented by -CONH-). n is the number of repetitions of the structure represented by -R 0 -Z-, and represents an integer from 0 to 5, preferably 0 or 1, more preferably 0. When n is 0, -R 0 -Z- does not exist, and A and R 8 are bonded by a single bond. R 0 represents an alkylene group, a cycloalkylene group, or a combination thereof. When there are a plurality of R 0 , each independently represents an alkylene group, a cycloalkylene group, or a combination thereof. Z represents a single bond, ether bond, ester bond, amide bond, urethane bond, or urea bond. When there are a plurality of Z, each independently represents a single bond, an ether bond, an ester bond, an amide bond, a urethane bond, or a urea bond. R 8 represents a monovalent organic group having a lactone structure or a sultone structure. R 7 represents a hydrogen atom, a halogen atom other than a fluorine atom, or a monovalent organic group (preferably a methyl group).
R0 的伸烷基或伸環烷基可具有取代基。 Z較佳為醚鍵、或酯鍵,更佳為酯鍵。The alkylene group or cycloalkylene group of R 0 may have a substituent. Z is preferably an ether bond or an ester bond, more preferably an ester bond.
以下列舉相當於式III所表示的結構單元的單體的具體例、及相當於後述的式A-1所表示的結構單元的單體的具體例,但本發明並不限定於該些具體例。下述的具體例相當於式III中的R7 及後述的式A-1中的RA 1 為甲基的情況,R7 及RA 1 可任意地取代為氫原子、氟原子以外的鹵素原子、或一價有機基。Specific examples of monomers corresponding to the structural unit represented by formula III and specific examples of monomers corresponding to the structural unit represented by formula A-1 described below are listed below, but the present invention is not limited to these specific examples . Specific examples corresponds to the following formula III R 7 and described below in the formula A 1-R A 1 is a methyl group, R 7 and R A 1 is optionally substituted other than a hydrogen atom, a fluorine atom halogen Atom, or monovalent organic group.
[化13] [化13]
除所述單體以外下述所示的單體亦可較佳地用作樹脂(A)的原料。In addition to the monomers described below, the monomers shown below can also be preferably used as the raw material of the resin (A).
[化14] [化14]
樹脂(A)可含有具有碳酸酯結構的結構單元。碳酸酯結構較佳為環狀碳酸酯結構。 具有環狀碳酸酯結構的結構單元較佳為下述式A-1所表示的結構單元。The resin (A) may contain a structural unit having a carbonate structure. The carbonate structure is preferably a cyclic carbonate structure. The structural unit having a cyclic carbonate structure is preferably a structural unit represented by the following formula A-1.
[化15] [化15]
式A-1中,RA 1 表示氫原子、氟原子以外的鹵素原子或一價有機基(較佳為甲基),n表示0以上的整數,RA 2 表示取代基。RA 2 於n為2以上的情況下各自獨立地表示取代基,A表示單鍵、或二價連結基,Z表示與式中的-O-C(=O)-O-所表示的基一起形成單環結構或多環結構的原子團。In Formula A-1, R A 1 represents a hydrogen atom, a halogen atom other than a fluorine atom, or a monovalent organic group (preferably a methyl group), n represents an integer of 0 or more, and R A 2 represents a substituent. R A 2 each independently represents a substituent when n is 2 or more, A represents a single bond or a divalent linking group, and Z represents a group formed with the group represented by -OC(=O)-O- in the formula A group of atoms in a monocyclic structure or a polycyclic structure.
樹脂(A)亦較佳為具有美國專利申請案公開第2016/0070167號說明書的段落0370~段落0414中記載的結構單元作為具有選自由內酯結構、磺內酯結構、及碳酸酯結構所組成的群組中的至少一種的結構單元。The resin (A) preferably has the structural unit described in paragraphs 0370 to 0414 of the specification of US Patent Application Publication No. 2016/0070167 as having a structure selected from a lactone structure, a sultone structure, and a carbonate structure. At least one structural unit in the group.
樹脂(A)可含有具有至少兩個內酯結構的結構單元(a)(以下,亦稱為「結構單元(a)」)。 至少兩個內酯結構例如可為至少兩個內酯結構縮環的結構,且可為至少兩個內酯結構藉由單鍵或連結基而連結的結構。 結構單元(a)所具有的內酯結構並無特別限定,較佳為5員環~7員環內酯結構,且較佳為其他環結構以形成雙環結構、螺環結構的形式與5員環~7員環內酯結構縮環而成者。 所述內酯結構例如可較佳地列舉所述LC1-1~LC1-21的任一者所表示的內酯結構。The resin (A) may contain a structural unit (a) having at least two lactone structures (hereinafter, also referred to as "structural unit (a)"). The at least two lactone structures may be, for example, a structure in which at least two lactone structures are condensed, and may be a structure in which at least two lactone structures are connected by a single bond or a linking group. The lactone structure of the structural unit (a) is not particularly limited, and is preferably a 5-membered to 7-membered cyclic lactone structure, and preferably other ring structures to form a bicyclic structure, a spiro ring structure, and 5-membered ring structure. Ring ~ 7-membered ring lactone structure formed by condensing ring. As the lactone structure, for example, a lactone structure represented by any one of LC1-1 to LC1-21 can be preferably cited.
具有至少兩個內酯結構的結構單元(以下,亦稱為「結構單元(a)」)較佳為下述式L-1所表示的結構單元。The structural unit having at least two lactone structures (hereinafter also referred to as "structural unit (a)") is preferably a structural unit represented by the following formula L-1.
[化16] [化16]
式L-1中,Ra表示氫原子或烷基,Rb表示具有兩個以上內酯結構的部分結構。In formula L-1, Ra represents a hydrogen atom or an alkyl group, and Rb represents a partial structure having two or more lactone structures.
Ra的烷基較佳為碳數1~4的烷基,更佳為甲基或乙基,特佳為甲基。Ra的烷基可經取代。作為取代基,例如可列舉:氟原子、氯原子、溴原子等鹵素原子或巰基、羥基、甲氧基、乙氧基、異丙氧基、第三丁氧基、苄氧基等烷氧基、乙醯基、丙醯基等乙醯氧基。Ra較佳為氫原子、甲基、三氟甲基、及羥基甲基。The alkyl group of Ra is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, and particularly preferably a methyl group. The alkyl group of Ra may be substituted. Examples of the substituent include halogen atoms such as a fluorine atom, a chlorine atom, and a bromine atom, or an alkoxy group such as a mercapto group, a hydroxyl group, a methoxy group, an ethoxy group, an isopropoxy group, a tertiary butoxy group, and a benzyloxy group. , Acetyl, propionyl and other acetoxy groups. Ra is preferably a hydrogen atom, a methyl group, a trifluoromethyl group, and a hydroxymethyl group.
Rb部分結構所具有的內酯結構例如可列舉所述的內酯結構。 Rb的具有兩個以上內酯結構的部分結構例如較佳為至少兩個內酯結構藉由單鍵或連結基而連結的結構、及至少兩個內酯結構縮環的結構。 以下各自說明具有至少兩個內酯結構縮環的結構的結構單元(a1)、及具有至少兩個內酯結構藉由單鍵或連結基而連結的結構的結構單元(a2)。Examples of the lactone structure possessed by the Rb partial structure include the aforementioned lactone structures. The partial structure of Rb having two or more lactone structures is preferably, for example, a structure in which at least two lactone structures are connected by a single bond or a linking group, and a structure in which at least two lactone structures are condensed. The structural unit (a1) having a structure in which at least two lactone structures are condensed and the structural unit (a2) having a structure in which at least two lactone structures are connected by a single bond or a linking group are each explained below.
-具有至少兩個內酯結構縮環的結構的結構單元(a1)- 至少兩個內酯結構縮環的結構較佳為兩個或三個內酯結構縮環的結構,且更佳為兩個內酯結構縮環的結構。 具有至少兩個內酯結構縮環的結構的結構單元(以下,亦稱為「結構單元(a1)」)例如可列舉下述式L-2所表示的結構單元。-Structural unit (a1) having at least two lactone structure condensed rings- The structure in which at least two lactone structures are condensed is preferably a structure in which two or three lactone structures are condensed, and more preferably is a structure in which two lactone structures are condensed. The structural unit (hereinafter, also referred to as "structural unit (a1)") having a structure in which at least two lactone structures have condensed rings may be, for example, a structural unit represented by the following formula L-2.
[化17] [化17]
式L-2中,Ra與式L-1的Ra為相同含義,Re1 ~Re8 分別獨立地表示氫原子或烷基,Me1 表示單鍵或二價連結基,Me2 及Me3 分別獨立地表示二價連結基。In formula L-2, Ra has the same meaning as Ra in formula L-1, Re 1 to Re 8 each independently represent a hydrogen atom or an alkyl group, Me 1 represents a single bond or a divalent linking group, Me 2 and Me 3 , respectively Independently represents a divalent linking group.
Re1 ~Re8 的烷基例如較佳為碳數5以下,且更佳為碳數1。 Re1 ~Re8 的碳數5以下的烷基例如可列舉:甲基、乙基、正丙基、異丙基、正丁基、異丁基、第三丁基、正戊基、異戊基、第二戊基、第三戊基等。 其中,Re1 ~Re8 較佳為氫原子。The alkyl group of Re 1 to Re 8 preferably has a carbon number of 5 or less, and more preferably has a carbon number of 1, for example. Examples of the alkyl groups having 5 or less carbon atoms of Re 1 to Re 8 include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tertiary butyl, n-pentyl, and isopentyl. Group, the second pentyl group, the third pentyl group, etc. Among them, Re 1 to Re 8 are preferably hydrogen atoms.
Me1 的二價連結基例如可列舉:伸烷基、伸環烷基、-O-、-CO-、-COO-、-OCO-、及將該些的兩個以上的基組合而成的基。 Me1 的伸烷基例如較佳為碳數1~10。另外,更佳為碳數1或2,作為碳數1或2的伸烷基,例如較佳為亞甲基或伸乙基。 Me1 的伸烷基可為直鏈狀亦可為分支鏈狀,例如可列舉:亞甲基、乙烷-1,1-二基、乙烷-1,2-二基、丙烷-1,1-二基、丙烷-1,3-二基、丙烷-2,2-二基、戊烷-1,5-二基、己烷-1,6-二基等。 Me1 的伸環烷基例如較佳為碳數5~10,且更佳為碳數5或6。 Me1 的伸環烷基例如可列舉:伸環戊基、伸環己基、伸環庚基、伸環辛基、伸環癸基等。 作為Me1 的二價連結基,將所述兩個以上的基組合而成的基例如較佳為將伸烷基與-COO-組合而成的基、及將-OCO-與伸烷基組合而成的基。另外,將所述兩個以上的基組合而成的基更佳為將亞甲基與-COO-基組合而成的基、及將-COO-基與亞甲基組合而成的基。Examples of the divalent linking group of Me 1 include: alkylene, cycloalkylene, -O-, -CO-, -COO-, -OCO-, and combinations of two or more of these groups. base. The alkylene group of Me 1 preferably has 1 to 10 carbon atoms, for example. In addition, it is more preferably a carbon number of 1 or 2. As the alkylene group having a carbon number of 1 or 2, for example, a methylene group or an ethylene group is preferable. The alkylene group of Me 1 may be linear or branched. Examples include: methylene, ethane-1,1-diyl, ethane-1,2-diyl, propane-1, 1-diyl, propane-1,3-diyl, propane-2,2-diyl, pentane-1,5-diyl, hexane-1,6-diyl, etc. The cycloalkylene group of Me 1 preferably has 5 to 10 carbon atoms, and more preferably has 5 or 6 carbon atoms, for example. Examples of the cycloalkylene group of Me 1 include cyclopentyl, cyclohexyl, heptyl, cyclooctyl, and cyclodecylene. As the divalent linking group of Me 1 , the group formed by combining two or more groups is preferably, for example, a group formed by combining an alkylene group and -COO-, and a combination of -OCO- and an alkylene group Formed base. In addition, the group formed by combining two or more groups is more preferably a group formed by combining a methylene group and a -COO- group, and a group formed by combining a -COO- group and a methylene group.
Me2 及Me3 的二價連結基例如可列舉伸烷基、-O-等。Me2 及Me3 的二價連結基較佳為亞甲基、伸乙基、-O-,更佳為-O-。Examples of the divalent linking group of Me 2 and Me 3 include alkylene and -O-. The divalent linking group of Me 2 and Me 3 is preferably methylene, ethylene, and -O-, and more preferably -O-.
與結構單元(a1)相對應的單體例如可藉由日本專利特開2015-160836號公報中所記載的方法來合成。The monomer corresponding to the structural unit (a1) can be synthesized, for example, by the method described in JP 2015-160836 A.
以下表示結構單元(a1)的具體例,但本發明並不限定於此。以下的各式中,R9 表示氫原子、甲基、三氟甲基或羥基甲基,*表示與其他結構單元的鍵結位置。Although the specific example of a structural unit (a1) is shown below, this invention is not limited to this. In the following formulae, R 9 represents a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group, and * represents a bonding position with other structural units.
[化18] [化18]
[化19] [化19]
[化20] [化20]
-具有至少兩個內酯結構藉由單鍵或連結基而連結的結構的結構單元(a2)- 至少兩個內酯結構藉由單鍵或連結基而連結的結構較佳為兩個~四個內酯結構藉由單鍵或連結基而連結的結構,且更佳為兩個內酯結構藉由單鍵或連結基而連結的結構。 連結基例如可列舉與後述的式L-3中的M2 的連結基中列舉的基相同的基。 具有兩個以上內酯結構藉由單鍵或連結基而連結的結構的結構單元(以下,亦稱為「結構單元(a2)」)例如可列舉下述式L-3所表示的結構單元。-A structural unit (a2) having a structure in which at least two lactone structures are connected by a single bond or a linking group-A structure in which at least two lactone structures are connected by a single bond or a linking group is preferably two to four A structure in which each lactone structure is connected by a single bond or a linking group, and more preferably a structure in which two lactone structures are connected by a single bond or a linking group. Examples of the linking group include the same groups as those exemplified in the linking group of M 2 in formula L-3 described later. The structural unit (hereinafter, also referred to as "structural unit (a2)") having a structure in which two or more lactone structures are connected by a single bond or a linking group (hereinafter, also referred to as "structural unit (a2)") includes, for example, a structural unit represented by the following formula L-3.
[化21] [化21]
式L-3中,Ra與所述式L-1的Ra為相同含義,M1 及M2 分別獨立地表示單鍵或連結基,Lc1 及Lc2 分別獨立地表示具有內酯結構的基。In the formula L-3, Ra has the same meaning as the Ra in the formula L-1, M 1 and M 2 each independently represent a single bond or a linking group, and Lc 1 and Lc 2 each independently represent a group having a lactone structure. .
M1 的連結基例如可列舉:伸烷基、伸環烷基、-O-、-CO-、-COO-、-OCO-、及將該些的兩個以上的基組合而成的基。 M1 的伸烷基例如較佳為碳數1~10。 M1 的伸烷基可為直鏈狀亦可為分支鏈狀,例如可列舉:亞甲基、乙烷-1,1-二基、乙烷-1,2-二基、丙烷-1,1-二基、丙烷-1,3-二基、丙烷-2,2-二基、戊烷-1,5-二基、己烷-1,6-二基等。 M1 的伸環烷基例如較佳為碳數5~10。 M1 的伸環烷基例如可列舉:伸環戊基、伸環己基、伸環庚基、伸環辛基、伸環癸基等。 作為M1 的連結基,將所述兩個以上的基組合而成的基例如較佳為將伸烷基與-COO-組合而成的基、及將-OCO-與伸烷基組合而成的基。另外,將所述兩個以上的基組合而成的基更佳為將亞甲基與-COO-基組合而成的基、及將-COO-基與亞甲基組合而成的基。 M2 的連結基例如可列舉與M1 的連結基中列舉的基相同的基。Examples of the linking group of M 1 include an alkylene group, a cycloalkylene group, -O-, -CO-, -COO-, -OCO-, and a combination of two or more of these groups. The alkylene group of M 1 preferably has 1 to 10 carbon atoms, for example. The alkylene group of M 1 may be linear or branched, for example, methylene, ethane-1,1-diyl, ethane-1,2-diyl, propane-1, 1-diyl, propane-1,3-diyl, propane-2,2-diyl, pentane-1,5-diyl, hexane-1,6-diyl, etc. The cycloalkylene group of M 1 preferably has 5 to 10 carbon atoms, for example. Examples of the cycloalkylene group of M 1 include cyclopentyl, cyclohexyl, heptyl, cyclooctyl, and cyclodecylene. As the linking group of M 1 , the group formed by combining two or more groups is preferably a group formed by combining an alkylene group and -COO-, and a group formed by combining an alkylene group and -OCO-的基。 The base. In addition, the group formed by combining two or more groups is more preferably a group formed by combining a methylene group and a -COO- group, and a group formed by combining a -COO- group and a methylene group. Examples of the linking group for M 2 include the same groups as those listed for the linking group for M 1.
Lc1 具有的內酯結構例如較佳為5員環~7員環內酯結構,且較佳為其他環結構以形成雙環結構、螺環結構的形式與5員環~7員環內酯結構縮環而成者。所述內酯結構更佳為所述LC1-1~LC1-21的任一者所表示的內酯結構。作為進而佳的內酯結構,可列舉:LC1-1、LC1-4、LC1-5、LC1-6、LC1-13、LC1-14及LC1-17。 Lc1 具有的內酯結構可包含取代基。Lc1 具有的內酯結構可包含的取代基例如可列舉與所述內酯結構的取代基(Rb2 )相同的取代基。 Lc2 具有的內酯結構例如可列舉與Lc1 具有的內酯結構中列舉的內酯結構相同的結構。The lactone structure of Lc 1 is, for example, a 5-membered to 7-membered cyclic lactone structure, and other ring structures are preferably formed in the form of a bicyclic structure, a spiro structure, and a 5-membered to 7-membered cyclic lactone structure Those who condensed the ring. The lactone structure is more preferably a lactone structure represented by any one of LC1-1 to LC1-21. As a further preferable lactone structure, LC1-1, LC1-4, LC1-5, LC1-6, LC1-13, LC1-14, and LC1-17 are mentioned. The lactone structure of Lc 1 may include a substituent. Examples of the substituent that may be included in the lactone structure of Lc 1 include the same substituents as the substituent (Rb 2) of the lactone structure. The lactone structure that Lc 2 has, for example, the same structure as the lactone structure exemplified in the lactone structure that Lc 1 has.
結構單元(a2)中作為所述式L-3所表示的結構單元,較佳為下述式L-4所表示的結構單元。In the structural unit (a2), the structural unit represented by the formula L-3 is preferably a structural unit represented by the following formula L-4.
[化22] [化22]
式L-4中,Ra與所述式L-1的Ra為相同含義,Mf1 及Mf2 分別獨立地表示單鍵或連結基,Rf1 、Rf2 及Rf3 分別獨立地表示氫原子或烷基,Mf1 與Rf1 可相互鍵結而形成環,Mf2 與Rf2 或Rf3 可分別相互鍵結而形成環。In the formula L-4, Ra has the same meaning as the Ra in the formula L-1, Mf 1 and Mf 2 each independently represent a single bond or a linking group, and Rf 1 , Rf 2 and Rf 3 each independently represent a hydrogen atom or In the alkyl group, Mf 1 and Rf 1 may be bonded to each other to form a ring, and Mf 2 and Rf 2 or Rf 3 may be bonded to each other to form a ring.
Mf1 的連結基與所述式L-3的M1 的連結基為相同含義。 Mf2 的連結基與所述式L-3的M2 的連結基為相同含義。 Rf1 的烷基例如可列舉碳數1~4的烷基。Rf1 的碳數1~4的烷基較佳為甲基或乙基,更佳為甲基。Rf1 的烷基可具有取代基。Rf1 的烷基可具有的取代基例如可列舉:羥基、甲氧基及乙氧基等烷氧基、氰基、氟原子等鹵素原子。 Rf2 及Rf3 的烷基與Rf1 的烷基為相同含義。The linking group of Mf 1 has the same meaning as the linking group of M 1 of the formula L-3. The linking group of Mf 2 has the same meaning as the linking group of M 2 of the formula L-3. Examples of the alkyl group of Rf 1 include alkyl groups having 1 to 4 carbon atoms. The alkyl group having 1 to 4 carbons in Rf 1 is preferably a methyl group or an ethyl group, and more preferably a methyl group. The alkyl group of Rf 1 may have a substituent. Examples of the substituent that the alkyl group of Rf 1 may have include alkoxy groups such as a hydroxyl group, a methoxy group, and an ethoxy group, and halogen atoms such as a cyano group and a fluorine atom. The alkyl group of Rf 2 and Rf 3 has the same meaning as the alkyl group of Rf 1.
Mf1 與Rf1 可相互鍵結而形成環。Mf1 與Rf1 相互鍵結而形成環的結構例如可列舉所述內酯結構中由所述的LC1-13、LC1-14或LC1-17所表示的內酯結構。 Mf2 與Rf2 或Rf3 可分別相互鍵結而形成環。 Mf2 與Rf2 相互鍵結而形成環的結構例如可列舉所述內酯結構中由所述的LC1-7、LC1-8或LC1-15所表示的內酯結構。 Mf2 與Rf3 相互鍵結而形成環的結構例如可列舉所述內酯結構中由所述的LC1-3~LC1-6的任一者所表示的內酯結構。 以下表示結構單元(a2)的具體例,但本發明並不限定於此。*表示與其他結構單元的鍵結位置。Mf 1 and Rf 1 may be bonded to each other to form a ring. Examples of the structure in which Mf 1 and Rf 1 are bonded to each other to form a ring include the lactone structure represented by LC1-13, LC1-14, or LC1-17 in the lactone structure. Mf 2 and Rf 2 or Rf 3 may be bonded to each other to form a ring. Examples of the structure in which Mf 2 and Rf 2 are bonded to each other to form a ring include the lactone structure represented by LC1-7, LC1-8, or LC1-15 in the lactone structure. Examples of the structure in which Mf 2 and Rf 3 are bonded to each other to form a ring include the lactone structure represented by any one of LC1-3 to LC1-6 in the lactone structure. Although the specific example of a structural unit (a2) is shown below, this invention is not limited to this. * Indicates the bonding position with other structural units.
[化23] [化23]
具有至少兩個內酯結構的結構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物,亦可將多種光學異構物混合而使用。於主要使用一種光學異構物的情況下,其光學純度(對映體過量(enantiomeric excess,ee))較佳為90%以上,更佳為95%以上。The structural unit having at least two lactone structures generally has optical isomers, and any optical isomer may be used. In addition, one kind of optical isomer may be used alone, or a plurality of optical isomers may be mixed and used. In the case of mainly using one optical isomer, its optical purity (enantiomeric excess (ee)) is preferably 90% or more, more preferably 95% or more.
於樹脂(A)含有具有至少兩個內酯結構的結構單元的情況下,相對於樹脂(A)中的所有結構單元,具有至少兩個內酯結構的結構單元的含有率較佳為10莫耳%~60莫耳%,更佳為20莫耳%~50莫耳%,進而佳為30莫耳%~50莫耳%。 亦可併用兩種以上的具有至少兩個內酯結構的結構單元。於含有兩種以上的具有至少兩個內酯結構的重複單元的情況下,較佳為具有至少兩個內酯結構的結構單元的合計含有率為所述範圍。In the case where the resin (A) contains structural units having at least two lactone structures, relative to all the structural units in the resin (A), the content of the structural units having at least two lactone structures is preferably 10 moles. Ear%~60 mol%, more preferably 20 mol%~50 mol%, and still more preferably 30 mol%~50 mol%. Two or more structural units having at least two lactone structures may also be used in combination. When two or more repeating units having at least two lactone structures are contained, it is preferable that the total content of structural units having at least two lactone structures is the above-mentioned range.
樹脂(A)可單獨包含一種具有選自由內酯結構、磺內酯結構、及碳酸酯結構所組成的群組中的至少一種的結構單元,亦可併用兩種以上而包含。The resin (A) may include one type of structural unit having at least one selected from the group consisting of a lactone structure, a sultone structure, and a carbonate structure alone, or two or more types may be used in combination.
於樹脂(A)包含具有選自由內酯結構、磺內酯結構、及碳酸酯結構所組成的群組中的至少一種的結構單元的情況下,相對於樹脂(A)的所有結構單元,樹脂(A)中包含的具有選自由內酯結構、磺內酯結構、及碳酸酯結構所組成的群組中的至少一種的結構單元的含量(於存在多個具有選自由內酯結構、磺內酯結構、及碳酸酯結構所組成的群組中的至少一種的結構單元的情況下為其合計)較佳為5莫耳%~70莫耳%,更佳為10莫耳%~65莫耳%,進而佳為20莫耳%~60莫耳%。In the case where the resin (A) includes a structural unit having at least one selected from the group consisting of a lactone structure, a sultone structure, and a carbonate structure, the resin (A) has at least one structural unit selected from the group consisting of a lactone structure, a sultone structure, and a carbonate structure. (A) The content of a structural unit having at least one selected from the group consisting of a lactone structure, a sultone structure, and a carbonate structure contained in (A) In the case of at least one structural unit in the group consisting of an ester structure and a carbonate structure, the total is preferably 5 mol% to 70 mol%, more preferably 10 mol% to 65 mol% %, more preferably 20 mol% to 60 mol%.
〔具有極性基的結構單元〕 樹脂(A)較佳為含有具有極性基的結構單元。 作為極性基,並無特別限定,可列舉:羥基、氰基、羧基等。再者,對於具有酚性羥基的重複單元將於後敘述。 具有極性基的結構單元較佳為具有經極性基取代的脂環烴結構的結構單元。另外,具有極性基的結構單元較佳為不具有酸分解性基。作為經極性基取代的脂環烴結構中的脂環烴結構,較佳為金剛烷基、或降冰片基。〔Structural units with polar groups〕 The resin (A) preferably contains a structural unit having a polar group. It does not specifically limit as a polar group, A hydroxyl group, a cyano group, a carboxyl group, etc. are mentioned. In addition, the repeating unit having a phenolic hydroxyl group will be described later. The structural unit having a polar group is preferably a structural unit having an alicyclic hydrocarbon structure substituted with a polar group. In addition, the structural unit having a polar group preferably does not have an acid-decomposable group. The alicyclic hydrocarbon structure in the alicyclic hydrocarbon structure substituted with a polar group is preferably an adamantyl group or a norbornyl group.
以下列舉相當於具有極性基的結構單元的單體的具體例,但本發明並不限定於該些具體例。另外,下述具體例記載為甲基丙烯酸酯化合物,但亦可為丙烯酸酯化合物。Specific examples of monomers corresponding to the structural unit having a polar group are listed below, but the present invention is not limited to these specific examples. In addition, the following specific examples are described as methacrylate compounds, but they may also be acrylate compounds.
[化24] [化24]
此外,作為具有極性基的結構單元的具體例,亦可列舉美國專利申請案公開第2016/0070167號說明書的段落0415~段落0433中所揭示的結構單元。 樹脂(A)可單獨包含一種具有極性基的結構單元,亦可併用兩種以上而包含。 於樹脂(A)包含具有極性基的結構單元的情況下,相對於樹脂(A)中的所有結構單元,具有極性基的結構單元的含量較佳為5莫耳%~40莫耳%,更佳為5莫耳%~30莫耳%,進而佳為10莫耳%~25莫耳%。In addition, as a specific example of the structural unit having a polar group, the structural unit disclosed in paragraph 0415 to paragraph 0433 of the specification of U.S. Patent Application Publication No. 2016/0070167 can also be cited. Resin (A) may contain the structural unit which has a polar group individually by 1 type, and may use 2 or more types together. In the case where the resin (A) contains a structural unit having a polar group, relative to all the structural units in the resin (A), the content of the structural unit having a polar group is preferably 5 mol% to 40 mol%, and more It is preferably from 5 mol% to 30 mol%, and more preferably from 10 mol% to 25 mol%.
〔不具有酸分解性基及極性基中任一者的結構單元〕 樹脂(A)可進而具有不具有酸分解性基及極性基中任一者的結構單元。不具有酸分解性基及極性基中任一者的結構單元較佳為具有脂環烴結構。作為不具有酸分解性基及極性基中任一者的結構單元,例如可列舉美國專利申請案公開第2016/0026083號說明書的段落0236~段落0237中所記載的結構單元。以下表示相當於不具有酸分解性基及極性基中任一者的結構單元的單體的較佳例。[Structural units that do not have any of acid-decomposable groups and polar groups] The resin (A) may further have a structural unit that does not have any of an acid-decomposable group and a polar group. The structural unit that does not have any of an acid-decomposable group and a polar group preferably has an alicyclic hydrocarbon structure. As a structural unit that does not have any of an acid-decomposable group and a polar group, for example, the structural unit described in paragraph 0236 to paragraph 0237 of the specification of U.S. Patent Application Publication No. 2016/0026083 can be cited. The preferable example of the monomer corresponding to the structural unit which does not have any of an acid-decomposable group and a polar group is shown below.
[化25] [化25]
此外,作為不具有酸分解性基及極性基中任一者的結構單元的具體例,亦可列舉美國專利申請案公開第2016/0070167號說明書的段落0433中所揭示的結構單元。 樹脂(A)可單獨包含一種不具有酸分解性基及極性基中任一者的結構單元,亦可併用兩種以上而包含。 於樹脂(A)包含不具有酸分解性基及極性基中任一者的結構單元的情況下,相對於樹脂(A)中的所有結構單元,不具有酸分解性基及極性基中任一者的結構單元的含量較佳為5莫耳%~40莫耳%,更佳為5莫耳%~30莫耳%,進而佳為5莫耳%~25莫耳%。In addition, as a specific example of a structural unit that does not have any of an acid-decomposable group and a polar group, the structural unit disclosed in paragraph 0433 of the specification of U.S. Patent Application Publication No. 2016/0070167 can also be cited. The resin (A) may contain one kind of structural unit that does not have any of an acid-decomposable group and a polar group alone, or may contain two or more kinds in combination. When the resin (A) contains a structural unit that does not have any of an acid-decomposable group and a polar group, relative to all the structural units in the resin (A), it does not have any of the acid-decomposable group or the polar group The content of the structural unit is preferably 5 mol%-40 mol%, more preferably 5 mol%-30 mol%, and still more preferably 5 mol%-25 mol%.
〔重複單元(a3)〕 樹脂(A)可進而具有以下的重複單元(a3)。 重複單元(a3)為源自製成均聚物時的玻璃轉移溫度為50℃以下的單體(亦稱為「單體a3」)的重複單元。 另外,重複單元(a3)為非酸分解性的重複單元。因而,重複單元(a3)不具有酸分解性基。[Repeat unit (a3)] The resin (A) may further have the following repeating unit (a3). The repeating unit (a3) is a repeating unit derived from a monomer (also referred to as "monomer a3") having a glass transition temperature of 50° C. or less when it is made into a homopolymer. In addition, the repeating unit (a3) is a non-acid-decomposable repeating unit. Therefore, the repeating unit (a3) does not have an acid-decomposable group.
(均聚物的玻璃轉移溫度的測定方法) 關於均聚物的玻璃轉移溫度,於存在目錄值或文獻值的情況下採用該值,於無目錄值或文獻值的情況下,利用示差掃描量熱測定(DSC:Differential scanning calorimetry)法進行測定。供於Tg測定的均聚物的重量平均分子量(Mw)設為18000,分散度(Mw/Mn)設為1.7。作為DSC裝置,使用日本TA儀器(TA Instruments Japan)(股)製造的熱分析DSC示差掃描量熱計Q1000型,以升溫速度10℃/min進行測定。 再者,供於Tg測定的均聚物只要使用相對應的單體並藉由公知的方法合成即可,例如可藉由一般的滴加聚合法等合成。以下示出一例。 將丙二醇單甲醚乙酸酯(PGMEA)54質量份於氮氣流下加熱至80℃。於攪拌該液體的同時,花費6小時滴加包含相對應的單體21質量%、2,2'-偶氮雙異丁酸二甲酯0.35質量%的PGMEA溶液125質量份。滴加結束後,於80℃下進而攪拌2小時。將反應液放置冷卻後,以大量的甲醇/水(質量比9:1)進行再沈澱、過濾,並將所獲得的固體加以乾燥,藉此獲得均聚物(Mw:18000、Mw/Mn:1.7)。將所獲得的均聚物供於DSC測定。DSC裝置及升溫速度如所述般。(Method for measuring the glass transition temperature of homopolymers) Regarding the glass transition temperature of the homopolymer, the value is used when there is a catalog value or a literature value, and when there is no catalog value or a literature value, it is measured by the differential scanning calorimetry (DSC: Differential scanning calorimetry) method. . The weight average molecular weight (Mw) of the homopolymer used for the Tg measurement was set to 18000, and the degree of dispersion (Mw/Mn) was set to 1.7. As a DSC device, a thermal analysis DSC differential scanning calorimeter Q1000 manufactured by TA Instruments Japan Co., Ltd. was used, and the measurement was performed at a temperature increase rate of 10° C./min. In addition, the homopolymer used for Tg measurement may be synthesized by a known method using a corresponding monomer, for example, it can be synthesized by a general dropping polymerization method or the like. An example is shown below. 54 parts by mass of propylene glycol monomethyl ether acetate (PGMEA) was heated to 80°C under a nitrogen stream. While stirring the liquid, 125 parts by mass of a PGMEA solution containing 21% by mass of the corresponding monomer and 0.35% by mass of dimethyl 2,2'-azobisisobutyrate was added dropwise over 6 hours. After the dropwise addition, it was further stirred at 80°C for 2 hours. After the reaction liquid was left to cool, it was re-precipitated and filtered with a large amount of methanol/water (mass ratio 9:1), and the obtained solid was dried to obtain a homopolymer (Mw: 18000, Mw/Mn: 1.7). The obtained homopolymer was subjected to DSC measurement. The DSC device and the heating rate are as described above.
單體a3只要製成均聚物時的玻璃轉移溫度(Tg)為50℃以下,則並無特別限定,就提高點圖案的解析性、及抑制蝕刻時可能產生的抗蝕劑圖案側壁的粗糙度的觀點而言,製成均聚物時的Tg較佳為30℃以下。將單體a3製成均聚物時的Tg的下限並無特別限定,較佳為-80℃以上,更佳為-70℃以上,進而佳為-60℃以上,特佳為-50℃以上。藉由將單體a3製成均聚物時的Tg的下限設為所述範圍,可抑制加熱時圖案的流動性,進一步提高點圖案的垂直性,因此較佳。Monomer a3 is not particularly limited as long as the glass transition temperature (Tg) when it is made into a homopolymer is 50°C or less, and it improves the resolution of the dot pattern and suppresses the roughness of the sidewall of the resist pattern that may occur during etching. From the viewpoint of temperature, the Tg when it is made into a homopolymer is preferably 30°C or less. The lower limit of Tg when the monomer a3 is made into a homopolymer is not particularly limited, but is preferably -80°C or higher, more preferably -70°C or higher, further preferably -60°C or higher, particularly preferably -50°C or higher . By setting the lower limit of the Tg when the monomer a3 is a homopolymer to the above range, the fluidity of the pattern during heating can be suppressed, and the verticality of the dot pattern can be further improved, which is preferable.
作為重複單元(a3),就可更容易揮發殘留溶劑的方面而言,較佳為具有可於鏈中包含雜原子且碳數為2以上的非酸分解性烷基的重複單元。本說明書中所謂「非酸分解性」,是指具有不會因光酸產生劑產生的酸而發生脫離/分解反應的性質。 即,所謂「非酸分解性烷基」,更具體而言可列舉:不會藉由光酸產生劑產生的酸的作用而自樹脂(A)脫離的烷基、或不會藉由光酸產生劑產生的酸的作用而分解的烷基。 非酸分解性烷基可為直鏈狀及分支鏈狀中任一種。 以下,對具有可於鏈中包含雜原子且碳數為2以上的非酸分解性烷基的重複單元進行說明。As the repeating unit (a3), it is preferable to have a repeating unit having a non-acid-decomposable alkyl group having a carbon number of 2 or more that can contain a hetero atom in the chain in terms of being able to more easily volatilize the residual solvent. The term "non-acid decomposability" in this specification refers to a property that does not cause a separation/decomposition reaction due to the acid generated by the photoacid generator. That is, the so-called "non-acid decomposable alkyl group", more specifically, include: an alkyl group that is not detached from the resin (A) by the action of an acid generated by a photoacid generator, or an alkyl group that is not decomposed by a photoacid An alkyl group that is decomposed by the action of the acid generated by the generator. The non-acid-decomposable alkyl group may be either linear or branched. Hereinafter, a repeating unit having a non-acid-decomposable alkyl group having a carbon number of 2 or more that can include a hetero atom in the chain will be described.
作為可於鏈中包含雜原子且碳數為2以上的非酸分解性烷基,並無特別限定,例如可列舉碳數為2~20的烷基、及鏈中含有雜原子的碳數2~20的烷基。 作為鏈中含有雜原子的碳數2~20的烷基,例如可列舉一個或兩個以上的-CH2 -經-O-、-S-、-CO-、-NR6 -、或將該些組合兩個以上而成的二價有機基取代的烷基。所述R6 表示氫原子、或碳數為1~6的烷基。 作為可於鏈中包含雜原子且碳數為2以上的非酸分解性烷基,具體而言可列舉:甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基、壬基、癸基、月桂基、硬脂基、異丁基、第二丁基、1-乙基戊基、及2-乙基己基、以及該些的一個或兩個以上的-CH2 -經-O-或-O-CO-取代的一價烷基。The non-acid-decomposable alkyl group with a carbon number of 2 or more that may contain a hetero atom in the chain is not particularly limited. Examples include an alkyl group with 2 to 20 carbon atoms and a chain with a heteroatom containing 2 carbon atoms. ~20 alkyl. Examples of alkyl groups having 2 to 20 carbon atoms containing heteroatoms in the chain include one or two or more -CH 2 -via -O-, -S-, -CO-, -NR 6 -, or the like These combine two or more to form a divalent organic-substituted alkyl group. The R 6 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Examples of non-acid-decomposable alkyl groups that can contain heteroatoms in the chain and have a carbon number of 2 or more include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl groups. , Nonyl, decyl, lauryl, stearyl, isobutyl, sec-butyl, 1-ethylpentyl, and 2-ethylhexyl, and one or more of these -CH 2 -A monovalent alkyl group substituted with -O- or -O-CO-.
作為可於鏈中包含雜原子且碳數為2以上的非酸分解性烷基的碳數,較佳為2以上且16以下,更佳為2以上且10以下,進而佳為2以上且8以下。碳數為2以上的非酸分解性烷基的碳數的下限較佳為4以上。 再者,碳數為2以上的非酸分解性烷基可具有取代基(例如取代基T)。The carbon number of the non-acid-decomposable alkyl group having a hetero atom and a carbon number of 2 or more is preferably 2 or more and 16 or less, more preferably 2 or more and 10 or less, and still more preferably 2 or more and 8 the following. The lower limit of the carbon number of the non-acid-decomposable alkyl group having 2 or more carbon atoms is preferably 4 or more. In addition, the non-acid-decomposable alkyl group having 2 or more carbon atoms may have a substituent (for example, substituent T).
重複單元(a3)較佳為下述通式(1-2)所表示的重複單元。The repeating unit (a3) is preferably a repeating unit represented by the following general formula (1-2).
[化26] [化26]
通式(1-2)中,R1 表示氫原子、鹵素原子、烷基、或環烷基。R2 表示可於鏈中包含雜原子且碳數為2以上的非酸分解性烷基。In the general formula (1-2), R 1 represents a hydrogen atom, a halogen atom, an alkyl group, or a cycloalkyl group. R 2 represents a non-acid-decomposable alkyl group having a carbon number of 2 or more that may contain a hetero atom in the chain.
作為R1 所表示的鹵素原子,並無特別限定,例如可列舉:氟原子、氯原子、溴原子及碘原子等。 作為R1 所表示的烷基,並無特別限定,例如可列舉碳數1~10的烷基,具體而言可列舉:甲基、乙基、及第三丁基等。其中較佳為碳數1~3的烷基,更佳為甲基。 作為R1 所表示的環烷基,並無特別限定,例如可列舉碳數5~10的環烷基,更具體而言可列舉環己基等。 其中,作為R1 ,較佳為氫原子或甲基。The halogen atom represented by R 1 is not particularly limited, and examples thereof include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The alkyl group represented by R 1 is not particularly limited, and examples thereof include alkyl groups having 1 to 10 carbon atoms, and specific examples include methyl, ethyl, and tertiary butyl groups. Among them, an alkyl group having 1 to 3 carbon atoms is preferred, and a methyl group is more preferred. The cycloalkyl group represented by R 1 is not particularly limited, and examples thereof include cycloalkyl groups having 5 to 10 carbon atoms, and more specifically, cyclohexyl groups and the like. Among them, as R 1 , a hydrogen atom or a methyl group is preferred.
R2 所表示的可於鏈中包含雜原子且碳數為2以上的非酸分解性烷基的定義及較佳態樣如所述般。The definition and preferable aspects of the non-acid-decomposable alkyl group having a carbon number of 2 or more and which may include a hetero atom in the chain represented by R 2 are as described above.
另外,就可更容易揮發殘留溶劑的方面而言,重複單元(a3)可為具有可於鏈中包含雜原子且具有羧基或羥基的非酸分解性烷基、或者可於環員中包含雜原子且具有羧基或羥基的非酸分解性環烷基的重複單元。 以下,對具有可於鏈中包含雜原子且具有羧基或羥基的非酸分解性烷基、或者可於環員中包含雜原子且具有羧基或羥基的非酸分解性環烷基的重複單元進行說明。In addition, in terms of easier volatilization of the residual solvent, the repeating unit (a3) may be a non-acid-decomposable alkyl group that may include a heteroatom in the chain and has a carboxyl group or a hydroxyl group, or may include a heteroatom in the ring member. A repeating unit of non-acid-decomposable cycloalkyl having a carboxyl group or a hydroxyl group. Hereinafter, the repeating unit having a non-acid-decomposable alkyl group which can contain a hetero atom in the chain and has a carboxyl group or a hydroxyl group, or a non-acid-decomposable cycloalkyl group which can contain a hetero atom in the ring member and has a carboxyl group or a hydroxyl group is carried out. Description.
作為非酸分解性烷基,可為直鏈狀及分支鏈狀中任一種。 非酸分解性烷基的碳數較佳為2以上,就均聚物的Tg設為50℃以下的觀點而言,所述非酸分解性烷基的碳數的上限例如較佳為20以下。The non-acid-decomposable alkyl group may be either linear or branched. The carbon number of the non-acid-decomposable alkyl group is preferably 2 or more. From the viewpoint that the Tg of the homopolymer is 50°C or less, the upper limit of the carbon number of the non-acid-decomposable alkyl group is preferably 20 or less, for example. .
作為可於鏈中包含雜原子的非酸分解性烷基,並無特別限定,例如可列舉碳數為2~20的烷基、及於鏈中含有雜原子的碳數2~20的烷基。再者,所述烷基中的氫原子的至少一個經羧基或羥基取代。 作為鏈中含有雜原子的碳數2~20的烷基,例如可列舉一個或兩個以上的-CH2 -經-O-、-S-、-CO-、-NR6 -、或將該些組合兩個以上而成的二價有機基取代的烷基。所述R6 表示氫原子、或碳數為1~6的烷基。The non-acid-decomposable alkyl group that can contain a hetero atom in the chain is not particularly limited, and examples include an alkyl group having 2 to 20 carbon atoms and an alkyl group having 2 to 20 carbon atoms that contain a hetero atom in the chain. . Furthermore, at least one of the hydrogen atoms in the alkyl group is substituted with a carboxyl group or a hydroxyl group. Examples of alkyl groups having 2 to 20 carbon atoms containing heteroatoms in the chain include one or two or more -CH 2 -via -O-, -S-, -CO-, -NR 6 -, or the like These combine two or more to form a divalent organic-substituted alkyl group. The R 6 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
作為可於鏈中包含雜原子的非酸分解性烷基的碳數,就抗龜裂性更優異(不易產生龜裂)的方面而言,較佳為2~16,更佳為2~10,進而佳為2~8。 再者,非酸分解性烷基可具有取代基(例如取代基T)。 作為具有於鏈中含有雜原子且具有羧基的非酸分解性烷基的重複單元的具體例,例如可列舉下述結構的重複單元。As the carbon number of the non-acid-decomposable alkyl group which can contain a hetero atom in the chain, it is preferably 2-16, more preferably 2-10 in terms of more excellent crack resistance (less cracks are generated) , More preferably 2-8. Furthermore, the non-acid-decomposable alkyl group may have a substituent (for example, the substituent T). As a specific example of the repeating unit which has a non-acid-decomposable alkyl group which contains a hetero atom in a chain and has a carboxyl group, the repeating unit of the following structure is mentioned, for example.
[化27] [化27]
非酸分解性環烷基的碳數較佳為5以上,就均聚物的Tg設為50℃以下的觀點而言,所述非酸分解性環烷基的碳數的上限例如較佳為20以下,更佳為16以下,進而佳為10以下。The carbon number of the non-acid-decomposable cycloalkyl group is preferably 5 or more. From the viewpoint that the Tg of the homopolymer is set to 50°C or less, the upper limit of the carbon number of the non-acid-decomposable cycloalkyl group is, for example, 20 or less, more preferably 16 or less, and still more preferably 10 or less.
作為可於環員中包含雜原子的非酸分解性環烷基,並無特別限定,例如可列舉碳數為5~20的環烷基(更具體而言為環己基)、及於環員中含有雜原子的碳數5~20的環烷基。再者,所述環烷基中的氫原子的至少一個經羧基或羥基取代。 作為於環員中含有雜原子的碳數5~20的環烷基,例如可列舉一個或兩個以上的-CH2 -經-O-、-S-、-CO-、-NR6 -、或將該些組合兩個以上而成的二價有機基取代的環烷基。所述R6 表示氫原子、或碳數為1~6的烷基。 再者,非酸分解性環烷基可具有取代基(例如取代基T)。The non-acid-decomposable cycloalkyl group that may contain a heteroatom in the ring member is not particularly limited. For example, a cycloalkyl group having 5 to 20 carbon atoms (more specifically, a cyclohexyl group), and a ring member C5-20 cycloalkyl group containing heteroatoms. Furthermore, at least one of the hydrogen atoms in the cycloalkyl group is substituted with a carboxyl group or a hydroxyl group. Examples of the cycloalkyl group having 5 to 20 carbon atoms and containing a hetero atom in the ring member include one or two or more -CH 2 -, -O-, -S-, -CO-, -NR 6 -, Or a divalent organic-substituted cycloalkyl group formed by combining two or more of these. The R 6 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Furthermore, the non-acid-decomposable cycloalkyl group may have a substituent (for example, the substituent T).
作為具有可於鏈中包含雜原子且具有羧基或羥基的非酸分解性烷基、或者可於環員中包含雜原子且具有羧基或羥基的非酸分解性環烷基的重複單元,就本發明的效果更優異的方面而言,其中較佳為下述通式(1-3)所表示的重複單元。As a repeating unit having a non-acid-decomposable alkyl group that can contain a heteroatom in the chain and have a carboxyl group or a hydroxyl group, or a non-acid-decomposable cycloalkyl group that can contain a heteroatom in the ring member and have a carboxyl group or a hydroxyl group, it is essential In terms of more excellent effects of the invention, the repeating unit represented by the following general formula (1-3) is particularly preferred.
[化28] [化28]
通式(1-3)中,R3 表示氫原子、鹵素原子、烷基、或環烷基。R4 表示可於鏈中包含雜原子且具有羧基或羥基的非酸分解性烷基、或者可於環員中包含雜原子且具有羧基或羥基的非酸分解性環烷基。In the general formula (1-3), R 3 represents a hydrogen atom, a halogen atom, an alkyl group, or a cycloalkyl group. R 4 represents a non-acid-decomposable alkyl group which may include a hetero atom in the chain and has a carboxyl group or a hydroxyl group, or a non-acid-decomposable cycloalkyl group which may include a hetero atom in a ring member and has a carboxyl group or a hydroxyl group.
通式(1-3)中,R3 與所述R1 為相同含義,較佳態樣亦相同。In the general formula (1-3), R 3 and R 1 have the same meaning, and preferred aspects are also the same.
R4 所表示的可於鏈中包含雜原子且具有羧基或羥基的非酸分解性烷基、或者可於環員中包含雜原子且具有羧基或羥基的非酸分解性環烷基的定義及較佳態樣如所述般。 其中,作為R4 ,較佳為可於環員中包含雜原子且具有羧基或羥基的非酸分解性環烷基。 另外,例如下述結構的重複單元等亦可列舉為較佳的重複單元。The definition of a non-acid-decomposable alkyl group which may contain a heteroatom in the chain and has a carboxyl or hydroxyl group represented by R 4, or a non-acid-decomposable cycloalkyl group which may contain a heteroatom in the ring member and has a carboxyl or hydroxyl group and The preferred aspect is as described. Among them, R 4 is preferably a non-acid-decomposable cycloalkyl group which can include a hetero atom in the ring member and has a carboxyl group or a hydroxyl group. In addition, for example, repeating units of the following structures can also be cited as preferred repeating units.
[化29] [化29]
作為單體a3,例如可列舉:丙烯酸乙酯(-22℃)、丙烯酸正丙酯(-37℃)、丙烯酸異丙酯(-5℃)、丙烯酸正丁酯(-55℃)、甲基丙烯酸正丁酯(20℃)、丙烯酸正己酯(-57℃)、甲基丙烯酸正己酯(-5℃)、甲基丙烯酸正辛酯(-20℃)、丙烯酸2-乙基己酯(-70℃)、丙烯酸異壬酯(-82℃)、甲基丙烯酸月桂酯(-65℃)、丙烯酸2-羥基乙酯(-15℃)、甲基丙烯酸2-羥基丙酯(26℃)、琥珀酸1-[2-(甲基丙烯醯氧基)乙基]酯(9℃)、甲基丙烯酸2-乙基己酯(-10℃)、丙烯酸第二丁酯(-26℃)、甲氧基聚乙二醇單甲基丙烯酸酯(n=2)(-20℃)、丙烯酸十六烷基酯(35℃)等。再者,括號內表示製成均聚物時的Tg(℃)。Examples of monomer a3 include ethyl acrylate (-22°C), n-propyl acrylate (-37°C), isopropyl acrylate (-5°C), n-butyl acrylate (-55°C), methyl N-Butyl acrylate (20°C), n-hexyl acrylate (-57°C), n-hexyl methacrylate (-5°C), n-octyl methacrylate (-20°C), 2-ethylhexyl acrylate (- 70℃), isononyl acrylate (-82℃), lauryl methacrylate (-65℃), 2-hydroxyethyl acrylate (-15℃), 2-hydroxypropyl methacrylate (26℃), 1-[2-(methacryloxy)ethyl] succinate (9°C), 2-ethylhexyl methacrylate (-10°C), second butyl acrylate (-26°C), Methoxy polyethylene glycol monomethacrylate (n=2) (-20°C), cetyl acrylate (35°C), etc. In addition, the Tg (°C) when it is made into a homopolymer is shown in parentheses.
再者,甲氧基聚乙二醇單甲基丙烯酸酯(n=2)為下述結構的化合物。In addition, methoxy polyethylene glycol monomethacrylate (n=2) is a compound of the following structure.
[化30] [化30]
單體a3較佳為丙烯酸正丁酯、甲基丙烯酸正己酯、甲基丙烯酸正辛酯、甲基丙烯酸2-乙基己酯、丙烯酸2-乙基己酯、甲基丙烯酸月桂酯、丙烯酸十六烷基酯、丙烯酸2-羥基乙酯、及下述MA-5所表示的化合物。Monomer a3 is preferably n-butyl acrylate, n-hexyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate, 2-ethylhexyl acrylate, lauryl methacrylate, ten acrylate Hexaalkyl ester, 2-hydroxyethyl acrylate, and the compound represented by MA-5 below.
[化31] [化31]
樹脂(A)可僅包含一種重複單元(a3),亦可包含兩種以上。 於樹脂(A)具有重複單元(a3)的情況下,相對於樹脂(A)的所有重複單元,重複單元(a3)的含量(於存在多個重複單元(a3)的情況下為其合計)較佳為5莫耳%以上,更佳為10莫耳%以上,且較佳為50莫耳%以下,更佳為40莫耳%以下,進而佳為30莫耳%以下。其中,相對於樹脂(A)的所有重複單元,樹脂(A)中的重複單元(a3)的含量(於存在多個重複單元(a3)的情況下為其合計)較佳為5莫耳%~50莫耳%,更佳為5莫耳%~40莫耳%,進而佳為5莫耳%~30莫耳%。The resin (A) may include only one type of repeating unit (a3), or two or more types. When the resin (A) has a repeating unit (a3), the content of the repeating unit (a3) relative to all repeating units of the resin (A) (the total when there are multiple repeating units (a3)) It is preferably 5 mol% or more, more preferably 10 mol% or more, and preferably 50 mol% or less, more preferably 40 mol% or less, and still more preferably 30 mol% or less. Among them, the content of the repeating unit (a3) in the resin (A) (the total when there are multiple repeating units (a3)) is preferably 5 mol% relative to all repeating units of the resin (A) ~50 mol%, more preferably 5 mol% to 40 mol%, and still more preferably 5 mol% to 30 mol%.
〔具有酚性羥基的重複單元(a4)〕 樹脂(A)較佳為包含具有酚性羥基的重複單元(a4)。 藉由樹脂(A)含有重複單元(a4),鹼顯影時的溶解速度更優異,且耐蝕刻性優異。 樹脂(A)更佳為包含於側鏈具有酚性羥基的重複單元(a4)的樹脂。[Repeating unit with phenolic hydroxyl group (a4)] The resin (A) preferably contains a repeating unit (a4) having a phenolic hydroxyl group. Since the resin (A) contains the repeating unit (a4), the dissolution rate during alkali development is more excellent, and the etching resistance is excellent. The resin (A) is more preferably a resin containing a repeating unit (a4) having a phenolic hydroxyl group in the side chain.
作為具有酚性羥基的重複單元,並無特別限定,可列舉源自羥基苯乙烯的重複單元、或源自(甲基)丙烯酸羥基苯乙烯酯的重複單元。作為具有酚性羥基的重複單元,較佳為下述通式(I)所表示的重複單元。 即,樹脂(A)較佳為包含下述通式(I)所表示的重複單元的樹脂。It does not specifically limit as a repeating unit which has a phenolic hydroxyl group, The repeating unit derived from hydroxystyrene, or the repeating unit derived from hydroxystyrene (meth)acrylate is mentioned. The repeating unit having a phenolic hydroxyl group is preferably a repeating unit represented by the following general formula (I). That is, the resin (A) is preferably a resin containing a repeating unit represented by the following general formula (I).
[化32] [化32]
通式(I)中, R41 、R42 及R43 各自獨立地表示氫原子、烷基、環烷基、鹵素原子、氰基或烷氧基羰基。其中,R42 可與Ar4 鍵結而形成環,該情況下的R42 表示單鍵或伸烷基。 X4 表示單鍵、-COO-、或-CONR64 -,R64 表示氫原子或烷基。 L4 表示單鍵或二價連結基。 Ar4 表示(n+1)價的芳香族烴基,於與R42 鍵結而形成環的情況下,表示(n+2)價的芳香族烴基。 n表示1~5的整數。In the general formula (I), R 41 , R 42 and R 43 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. Among them, R 42 may be bonded to Ar 4 to form a ring. In this case, R 42 represents a single bond or an alkylene group. X 4 represents a single bond, -COO-, or -CONR 64 -, and R 64 represents a hydrogen atom or an alkyl group. L 4 represents a single bond or a divalent linking group. Ar 4 represents an (n+1)-valent aromatic hydrocarbon group, and when it bonds with R 42 to form a ring, it represents an (n+2)-valent aromatic hydrocarbon group. n represents an integer of 1-5.
出於使通式(I)所表示的重複單元高極化的目的,亦較佳為n為2以上的整數、或X4 為-COO-、或-CONR64 -。For the purpose of highly polarizing the repeating unit represented by the general formula (I), it is also preferable that n is an integer of 2 or more, or X 4 is -COO- or -CONR 64 -.
作為通式(I)中的R41 、R42 、及R43 所表示的烷基,較佳為可具有取代基的甲基、乙基、丙基、異丙基、正丁基、第二丁基、己基、2-乙基己基、辛基、及十二烷基等碳數20以下的烷基,更佳為碳數8以下的烷基,進而佳為碳數3以下的烷基。 As the alkyl group represented by R 41 , R 42 , and R 43 in the general formula (I), preferred are optionally substituted methyl, ethyl, propyl, isopropyl, n-butyl, and second The alkyl group having 20 or less carbon atoms, such as butyl, hexyl, 2-ethylhexyl, octyl, and dodecyl, is more preferably an alkyl group having 8 or less carbon atoms, and still more preferably an alkyl group having 3 or less carbon atoms.
作為通式(I)中的R41 、R42 、及R43 所表示的環烷基,可為單環,亦可為多環。較佳為可具有取代基的環丙基、環戊基、及環己基等碳數3個~8個且單環的環烷基。 作為通式(I)中的R41 、R42 、及R43 所表示的鹵素原子,可列舉:氟原子、氯原子、溴原子及碘原子等,較佳為氟原子。 作為通式(I)中的R41 、R42 、及R43 所表示的烷氧基羰基中包含的烷基,較佳為與所述R41 、R42 、及R43 中的烷基相同者。 The cycloalkyl group represented by R 41 , R 42 , and R 43 in the general formula (I) may be a monocyclic ring or a polycyclic ring. Preferably, it is a monocyclic cycloalkyl group having 3 to 8 carbon atoms, such as cyclopropyl, cyclopentyl, and cyclohexyl which may have a substituent. Examples of the halogen atom represented by R 41 , R 42 , and R 43 in the general formula (I) include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like, and a fluorine atom is preferred. The alkyl group included in the alkoxycarbonyl group represented by R 41 , R 42 , and R 43 in the general formula (I) is preferably the same as the alkyl group in the above-mentioned R 41 , R 42 , and R 43 By.
作為所述各基中的較佳的取代基,例如可列舉:烷基、環烷基、芳基、胺基、醯胺基、脲基、胺基甲酸酯基、羥基、羧基、鹵素原子、烷氧基、硫醚基、醯基、醯氧基、烷氧基羰基、氰基、及硝基等,取代基的碳數較佳為8以下。Examples of preferred substituents in each of the above groups include alkyl groups, cycloalkyl groups, aryl groups, amino groups, amide groups, ureido groups, urethane groups, hydroxyl groups, carboxyl groups, and halogen atoms. , Alkoxy group, thioether group, acyl group, acyloxy group, alkoxycarbonyl group, cyano group, nitro group, etc., the carbon number of the substituent is preferably 8 or less.
Ar4 表示(n+1)價的芳香族烴基。n為1時的二價芳香族烴基可具有取代基,例如較佳為伸苯基、甲伸苯基、伸萘基、及伸蒽基等碳數6~18的伸芳基、或包含例如噻吩、呋喃、吡咯、苯并噻吩、苯并呋喃、苯并吡咯、三嗪、咪唑、苯并咪唑、***、噻二唑、及噻唑等雜環的芳香族烴基。Ar 4 represents an (n+1)-valent aromatic hydrocarbon group. When n is 1, the divalent aromatic hydrocarbon group may have a substituent. For example, phenylene, phenylene, naphthylene, and anthracenyl are preferably arylene groups having 6 to 18 carbon atoms, or include, for example, Heterocyclic aromatic hydrocarbon groups such as thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, and thiazole.
作為n為2以上的整數時的(n+1)價的芳香族烴基的具體例,可較佳地列舉自二價芳香族烴基的所述具體例中去除(n-1)個任意的氫原子而成的基。 (n+1)價的芳香族烴基可進而具有取代基。As a specific example of the (n+1) valence aromatic hydrocarbon group when n is an integer of 2 or more, it is preferable to remove (n-1) arbitrary hydrogens from the specific examples of the divalent aromatic hydrocarbon group. A base made of atoms. The (n+1)-valent aromatic hydrocarbon group may further have a substituent.
作為所述烷基、環烷基、烷氧基羰基及(n+1)價的芳香族烴基可具有的取代基,例如可列舉:於通式(I)中的R41 、R42 、及R43 中列舉的烷基;甲氧基、乙氧基、羥基乙氧基、丙氧基、羥基丙氧基、及丁氧基等烷氧基;苯基等芳基等。 作為由X4 所表示的-CONR64 -(R64 表示氫原子或烷基)中的R64 的烷基,較佳為可具有取代基的甲基、乙基、丙基、異丙基、正丁基、第二丁基、己基、2-乙基己基、辛基、及十二烷基等碳數20以下的烷基,更佳為碳數8以下的烷基。 作為X4 ,較佳為單鍵、-COO-、或-CONH-,更佳為單鍵、或-COO-。Examples of the substituents that the alkyl group, cycloalkyl group, alkoxycarbonyl group, and (n+1)-valent aromatic hydrocarbon group may have include: R 41 , R 42 , and in the general formula (I) Alkyl groups exemplified in R 43 ; alkoxy groups such as methoxy, ethoxy, hydroxyethoxy, propoxy, hydroxypropoxy, and butoxy; aryl groups such as phenyl, and the like. The alkyl group of R 64 in -CONR 64- (R 64 represents a hydrogen atom or an alkyl group) represented by X 4 is preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, which may have a substituent, Alkyl groups with 20 or less carbon atoms, such as n-butyl, sec-butyl, hexyl, 2-ethylhexyl, octyl, and dodecyl, are more preferably alkyl groups with 8 or less carbon atoms. X 4 is preferably a single bond, -COO-, or -CONH-, and more preferably a single bond or -COO-.
作為L4 的二價連結基較佳為伸烷基,作為伸烷基,較佳為可具有取代基的亞甲基、伸乙基、伸丙基、伸丁基、伸己基、及伸辛基等碳數1~8的伸烷基。 作為Ar4 ,較佳為可具有取代基的碳數6~18的芳香族烴基,更佳為苯環基、萘環基、或伸聯苯環基。其中,通式(I)所表示的重複單元較佳為源自羥基苯乙烯的重複單元。即,Ar4 較佳為苯環基。The divalent linking group of L 4 is preferably an alkylene group, and the alkylene group is preferably an optionally substituted methylene, ethylene, propylene, butylene, hexylene, and octylene group. Alkylene groups having 1 to 8 carbon atoms. Ar 4 is preferably an optionally substituted aromatic hydrocarbon group having 6 to 18 carbon atoms, more preferably a benzene ring group, a naphthalene ring group, or a biphenyl ring group. Among them, the repeating unit represented by the general formula (I) is preferably a repeating unit derived from hydroxystyrene. That is, Ar 4 is preferably a benzene ring group.
n表示1~5的整數,較佳為表示1~3的整數,更佳為表示1或2,進而佳為表示1。n represents an integer of 1 to 5, preferably represents an integer of 1 to 3, more preferably represents 1 or 2, and more preferably represents 1.
以下表示具有酚性羥基的重複單元的具體例,但本發明並不限定於此。式中,a表示1或2。Although the specific example of the repeating unit which has a phenolic hydroxyl group is shown below, this invention is not limited to this. In the formula, a represents 1 or 2.
[化33] [化33]
樹脂(A)可單獨具有一種重複單元(a4),亦可併用兩種以上而具有。 於樹脂(A)包含重複單元(a4)的情況下,相對於樹脂(A)中的所有重複單元,樹脂(A)中重複單元(a4)的含量較佳為40莫耳%以上,更佳為50莫耳%以上,進而佳為60莫耳%以上。另外,相對於樹脂(A)中的所有重複單元,重複單元(a4)的含量較佳為85莫耳%以下,更佳為80莫耳%以下。The resin (A) may have one type of repeating unit (a4) alone, or two or more of them may be used in combination. When the resin (A) contains the repeating unit (a4), relative to all the repeating units in the resin (A), the content of the repeating unit (a4) in the resin (A) is preferably 40 mol% or more, more preferably It is 50 mol% or more, more preferably 60 mol% or more. In addition, with respect to all the repeating units in the resin (A), the content of the repeating unit (a4) is preferably 85 mol% or less, and more preferably 80 mol% or less.
樹脂(A)除具有所述結構單元以外,可出於調節耐乾式蝕刻性或標準顯影液適應性、基板密接性、抗蝕劑輪廓、以及作為抗蝕劑的一般的必要特性的解析力、耐熱性、感度等目的而具有各種結構單元。作為此種結構單元,可列舉相當於其他單量體的結構單元,但並不限定於該些。Resin (A) has the above-mentioned structural units, and can be used to adjust dry etching resistance or standard developer suitability, substrate adhesion, resist profile, and general necessary characteristics as a resist. It has various structural units for the purpose of heat resistance and sensitivity. As such a structural unit, the structural unit corresponding to other monomers can be mentioned, but it is not limited to these.
作為其他單量體,例如可列舉選自丙烯酸酯類、甲基丙烯酸酯類、丙烯醯胺類、甲基丙烯醯胺類、烯丙基化合物、乙烯基醚類、及乙烯基酯類等中的具有一個加成聚合性不飽和鍵的化合物等。 除此以外,只要為可與相當於所述各種結構單元的單量體進行共聚的加成聚合性的不飽和化合物,則亦可進行共聚。 於樹脂(A)中,各結構單元的含有莫耳比是為了調節各種性能而適宜設定。Examples of other monomers include those selected from acrylic esters, methacrylic esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers, and vinyl esters. The compound with an addition polymerizable unsaturated bond, etc. In addition to this, as long as it is an addition polymerizable unsaturated compound copolymerizable with a monomer corresponding to the various structural units described above, it may be copolymerized. In the resin (A), the molar ratio of each structural unit is appropriately set in order to adjust various properties.
於本發明的感光化射線性或感放射線性樹脂組成物為氟氬(ArF)雷射曝光用時,就ArF光的透過性的觀點而言,樹脂(A)較佳為實質上不具有芳香族基。更具體而言,樹脂(A)的所有結構單元中,具有芳香族基的結構單元較佳為整體的5莫耳%以下,更佳為3莫耳%以下,理想的是0莫耳%,即進而佳為不含有具有芳香族基的結構單元。另外,樹脂(A)較佳為具有單環或多環的脂環烴結構。When the sensitized radiation or radiation-sensitive resin composition of the present invention is used for fluorine-argon (ArF) laser exposure, from the viewpoint of the permeability of ArF light, the resin (A) is preferably substantially free of aroma. Family base. More specifically, among all the structural units of the resin (A), the structural unit having an aromatic group is preferably 5 mol% or less of the whole, more preferably 3 mol% or less, and ideally 0 mol%, That is, it is more preferable not to contain a structural unit having an aromatic group. In addition, the resin (A) preferably has a monocyclic or polycyclic alicyclic hydrocarbon structure.
樹脂(A)亦較佳為結構單元全部包含(甲基)丙烯酸酯系結構單元。於該情況下,可使用結構單元全部為甲基丙烯酸酯系結構單元的樹脂、結構單元全部為丙烯酸酯系結構單元的樹脂、結構單元全部由甲基丙烯酸酯系結構單元與丙烯酸酯系結構單元形成的樹脂的任一種樹脂,但較佳為丙烯酸酯系結構單元相對於樹脂(A)的所有結構單元而為50莫耳%以下。It is also preferable that the resin (A) all include a (meth)acrylate-based structural unit in the structural unit. In this case, resins whose structural units are all methacrylate-based structural units, resins whose structural units are all acrylate-based structural units, and whose structural units are all composed of methacrylate-based structural units and acrylate-based structural units can be used. It is any resin of the resin to be formed, but it is preferable that the acrylic structural unit is 50 mol% or less with respect to all the structural units of resin (A).
於本發明的感光化射線性或感放射線性樹脂組成物為氟化氪(KrF)曝光用、電子束(EB)曝光用或極紫外線(EUV)曝光用時,樹脂(A)較佳為包含具有芳香族烴基的結構單元。樹脂(A)更佳為包含具有酚性羥基的結構單元。 作為具有酚性羥基的結構單元,例如可列舉所述重複單元(a4)。 於本發明的感光化射線性或感放射線性樹脂組成物為KrF曝光用、EB曝光用或EUV曝光用時,樹脂(A)較佳為具有酚性羥基的氫原子由藉由酸的作用進行分解而脫離的基(脫離基)保護的結構。 相對於樹脂(A)中的所有結構單元,樹脂(A)中包含的具有芳香族烴基的結構單元的含量較佳為30莫耳%~100莫耳%,更佳為40莫耳%~100莫耳%,進而佳為50莫耳%~100莫耳%。When the sensitized radiation or radiation-sensitive resin composition of the present invention is used for exposure of krypton fluoride (KrF), electron beam (EB) or extreme ultraviolet (EUV) exposure, the resin (A) preferably contains Structural units with aromatic hydrocarbon groups. The resin (A) more preferably contains a structural unit having a phenolic hydroxyl group. As a structural unit which has a phenolic hydroxyl group, the said repeating unit (a4) is mentioned, for example. When the sensitized radiation-sensitive or radiation-sensitive resin composition of the present invention is used for KrF exposure, EB exposure, or EUV exposure, the resin (A) preferably has a hydrogen atom having a phenolic hydroxyl group by the action of an acid. The structure protected by the decomposing radical (departing radical). Relative to all the structural units in the resin (A), the content of the structural unit having an aromatic hydrocarbon group contained in the resin (A) is preferably 30 mol% to 100 mol%, more preferably 40 mol% to 100 mol% Mole%, more preferably 50 mole% to 100 mole%.
樹脂(A)的重量平均分子量較佳為1,000~200,000,更佳為2,000~100,000,進而佳為3,000~50,000,特佳為3,000~30,000。 分散度(Mw/Mn)較佳為1.0~3.0,更佳為1.0~2.6,進而佳為1.0~2.0,特佳為1.1~2.0。The weight average molecular weight of the resin (A) is preferably 1,000 to 200,000, more preferably 2,000 to 100,000, still more preferably 3,000 to 50,000, particularly preferably 3,000 to 30,000. The degree of dispersion (Mw/Mn) is preferably 1.0 to 3.0, more preferably 1.0 to 2.6, still more preferably 1.0 to 2.0, and particularly preferably 1.1 to 2.0.
作為樹脂(A)的具體例,可列舉實施例中所使用的樹脂A-1~樹脂A-7,但並不限定於此。As a specific example of resin (A), resin A-1-resin A-7 used in an Example can be mentioned, but it is not limited to this.
樹脂(A)可單獨使用一種,亦可併用兩種以上。 相對於本發明的感光化射線性或感放射線性樹脂組成物的總固體成分,樹脂(A)的含量較佳為20質量%以上,更佳為40質量%以上,進而佳為60質量%以上,特佳為80質量%以上。上限並無特別限制,較佳為99.5質量%以下,更佳為99質量%以下。The resin (A) may be used singly, or two or more of them may be used in combination. The content of the resin (A) is preferably 20% by mass or more, more preferably 40% by mass or more, and still more preferably 60% by mass or more with respect to the total solid content of the sensitized radiation or radiation-sensitive resin composition of the present invention , Particularly preferably above 80% by mass. The upper limit is not particularly limited, but is preferably 99.5% by mass or less, and more preferably 99% by mass or less.
〔具有酚性羥基的鹼可溶性樹脂〕 於本發明的感光化射線性或感放射線性樹脂組成物含有後述的交聯劑(G)的情況下,本發明的感光化射線性或感放射線性樹脂組成物較佳為含有具有酚性羥基的鹼可溶性樹脂(以下,亦稱為「樹脂(C)」)。樹脂(C)較佳為含有具有酚性羥基的結構單元。 於該情況下,典型而言可較佳地形成負型圖案。 交聯劑(G)可為擔載於樹脂(C)上的形態。 再者,樹脂(C)中,相當於藉由酸的作用而極性增大的樹脂者作為藉由酸的作用而極性增大的樹脂來處理。另外,於該情況下,本發明的感光化射線性或感放射線性樹脂組成物可包含藉由酸的作用而極性增大的樹脂作為樹脂(C),另外亦可至少包含藉由酸的作用而極性增大的樹脂以外的樹脂(C)、與藉由酸的作用而極性增大的樹脂。 樹脂(C)可含有所述酸分解性基。 作為樹脂(C)具有的具有酚性羥基的結構單元,並無特別限定,較佳為所述重複單元(a4)。〔Alkali-soluble resin with phenolic hydroxyl group〕 When the actinic radiation or radiation-sensitive resin composition of the present invention contains the crosslinking agent (G) described later, the actinic radiation or radiation-sensitive resin composition of the present invention preferably contains a phenolic hydroxyl group. The alkali-soluble resin (hereinafter, also referred to as "resin (C)"). The resin (C) preferably contains a structural unit having a phenolic hydroxyl group. In this case, typically, a negative pattern can be preferably formed. The crosslinking agent (G) may be in a form supported on the resin (C). In addition, among the resins (C), those corresponding to the resin whose polarity is increased by the action of acid are treated as the resin whose polarity is increased by the action of acid. In addition, in this case, the sensitized radiation-sensitive or radiation-sensitive resin composition of the present invention may include a resin whose polarity is increased by the action of an acid as the resin (C), and may also include at least Resins (C) other than resins with increased polarity and resins with increased polarity due to the action of acid. The resin (C) may contain the acid decomposable group. It does not specifically limit as a structural unit which has a phenolic hydroxyl group which resin (C) has, Preferably it is the said repeating unit (a4).
樹脂(C)可單獨使用一種,亦可併用兩種以上。 於本發明的感光化射線性或感放射線性樹脂組成物含有樹脂(C)的情況下,本發明的感光化射線性或感放射線性樹脂組成物的總固體成分中的樹脂(C)的含量較佳為30質量%以上,更佳為40質量%以上,進而佳為50質量%以上。上限並無特別限制,較佳為99質量%以下,更佳為90質量%以下,進而佳為85質量%以下。 作為樹脂(C),可較佳地使用美國專利申請案公開第016/0282720號說明書的段落0142~段落0347中所揭示的樹脂。The resin (C) may be used singly, or two or more of them may be used in combination. When the photosensitive ray-sensitive or radiation-sensitive resin composition of the present invention contains resin (C), the content of resin (C) in the total solid content of the photosensitive ray-sensitive or radiation-sensitive resin composition of the present invention It is preferably 30% by mass or more, more preferably 40% by mass or more, and still more preferably 50% by mass or more. The upper limit is not particularly limited, but is preferably 99% by mass or less, more preferably 90% by mass or less, and still more preferably 85% by mass or less. As the resin (C), the resins disclosed in paragraphs 0142 to 0347 of the specification of U.S. Patent Application Publication No. 016/0282720 can be preferably used.
〔疏水性樹脂〕 本發明的感光化射線性或感放射線性樹脂組成物亦較佳為含有疏水性樹脂(亦稱為「疏水性樹脂(E)」)。 本發明的感光化射線性或感放射線性樹脂組成物較佳為至少包含藉由酸的作用而極性增大的樹脂以外的疏水性樹脂(E)、與藉由酸的作用而極性增大的樹脂。 藉由本發明的感光化射線性或感放射線性樹脂組成物含有疏水性樹脂(E),可控制感光化射線性或感放射線性膜的表面的靜態/動態的接觸角。藉此,可改善顯影特性、抑制逸氣、提高液浸曝光中的液浸液追隨性、以及減少液浸缺陷等。 疏水性樹脂(E)較佳為以偏向存在於抗蝕劑膜的表面的方式設計,但與界面活性劑不同,未必需要於分子內具有親水基,可無助於將極性物質/非極性物質均勻地混合。 另外,於本發明中,具有氟原子的樹脂作為疏水性樹脂及後述的含氟樹脂來處理。另外,含有具有所述酸分解性基的結構單元的樹脂較佳為不具有氟原子。〔Hydrophobic resin〕 It is also preferable that the actinic radiation-sensitive or radiation-sensitive resin composition of the present invention contains a hydrophobic resin (also referred to as "hydrophobic resin (E)"). The sensitized radiation-sensitive or radiation-sensitive resin composition of the present invention preferably contains at least a hydrophobic resin (E) other than a resin whose polarity is increased by the action of an acid, and a hydrophobic resin (E) whose polarity is increased by the action of an acid. Resin. When the photosensitive ray-sensitive or radiation-sensitive resin composition of the present invention contains the hydrophobic resin (E), the static/dynamic contact angle of the surface of the photosensitive ray-sensitive or radiation-sensitive film can be controlled. Thereby, the development characteristics can be improved, outgassing can be suppressed, the followability of the liquid immersion liquid in the liquid immersion exposure can be improved, and the liquid immersion defect can be reduced. The hydrophobic resin (E) is preferably designed to be biased toward the surface of the resist film. However, unlike surfactants, it does not necessarily have a hydrophilic group in the molecule, and it does not help remove polar/non-polar substances. Mix evenly. In addition, in the present invention, a resin having a fluorine atom is treated as a hydrophobic resin and a fluorine-containing resin described later. Moreover, it is preferable that the resin containing the structural unit which has the said acid-decomposable group does not have a fluorine atom.
就偏向存在於膜表層的觀點而言,疏水性樹脂(E)較佳為包含具有選自由「氟原子」、「矽原子」、及「樹脂的側鏈部分中所含有的CH3 部分結構」所組成的群組中的至少一種的結構單元的樹脂。 於疏水性樹脂(E)包含氟原子或矽原子的情況下,疏水性樹脂(E)中的所述氟原子或矽原子可包含於樹脂的主鏈中,亦可包含於側鏈中。From the viewpoint of being biased in the surface layer of the film, the hydrophobic resin (E) preferably has a structure selected from the group consisting of "fluorine atom", "silicon atom", and "CH 3 partial structure contained in the side chain part of the resin" At least one structural unit resin in the group consisting of. When the hydrophobic resin (E) contains fluorine atoms or silicon atoms, the fluorine atoms or silicon atoms in the hydrophobic resin (E) may be included in the main chain of the resin or may be included in the side chain.
疏水性樹脂(E)較佳為具有至少一個選自下述(x)~(z)的群組中的基。 (x)酸基 (y)藉由鹼性顯影液的作用進行分解而對於鹼性顯影液的溶解度增大的基(以下,亦稱為極性轉換基) (z)藉由酸的作用而分解的基The hydrophobic resin (E) preferably has at least one group selected from the group of (x) to (z) below. (X) Acid group (Y) A group that is decomposed by the action of an alkaline developer to increase its solubility in an alkaline developer (hereinafter, also referred to as a polarity conversion group) (Z) The base decomposed by the action of acid
作為酸基(x),可列舉:酚性羥基、羧酸基、氟化醇基、磺酸基、磺醯胺基、磺醯基醯亞胺基、(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。 作為酸基,較佳為氟化醇基(較佳為六氟異丙醇基)、磺醯亞胺基、或雙(烷基羰基)亞甲基。Examples of the acid group (x) include: phenolic hydroxyl group, carboxylic acid group, fluorinated alcohol group, sulfonic acid group, sulfonamide group, sulfonamide group, (alkylsulfonyl group) (alkyl Carbonyl)methylene, (alkylsulfonyl)(alkylcarbonyl)imino, bis(alkylcarbonyl)methylene, bis(alkylcarbonyl)imino, bis(alkylsulfonyl) Group) methylene, bis(alkylsulfonyl)imino group, tri(alkylcarbonyl)methylene, tri(alkylsulfonyl)methylene, etc. As the acid group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), a sulfoximine group, or a bis(alkylcarbonyl)methylene group is preferable.
作為藉由鹼性顯影液的作用進行分解而對於鹼性顯影液的溶解度增大的基(y),例如可列舉:內酯基、羧酸酯基(-COO-)、酸酐基(-C(O)OC(O)-)、酸醯亞胺基(-NHCONH-)、羧酸硫酯基(-COS-)、碳酸酯基(-OC(O)O-)、硫酸酯基(-OSO2 O-)、及磺酸酯基(-SO2 O-)等,較佳為內酯基或羧酸酯基(-COO-)。 包含該些基的結構單元為該些基直接鍵結於樹脂的主鏈的結構單元,例如可列舉由丙烯酸酯及甲基丙烯酸酯形成的結構單元等。該結構單元中該些基可經由連結基而鍵結於樹脂的主鏈。或者,該結構單元亦可於聚合時使用具有該些基的聚合起始劑或鏈轉移劑而導入至樹脂的末端。作為具有內酯基的結構單元,例如可列舉與先前的樹脂(A)一項中說明的具有內酯結構的結構單元相同者。As the group (y) that is decomposed by the action of the alkaline developer to increase the solubility in the alkaline developer, for example, a lactone group, a carboxylate group (-COO-), an acid anhydride group (-C (O)OC(O)-), acid imino group (-NHCONH-), carboxylic acid thioester group (-COS-), carbonate group (-OC(O)O-), sulfate group (- OSO 2 O-), sulfonate group (-SO 2 O-), etc., preferably a lactone group or a carboxylate group (-COO-). The structural unit including these groups is a structural unit in which these groups are directly bonded to the main chain of the resin, and examples thereof include structural units formed of acrylate and methacrylate. These groups in the structural unit may be bonded to the main chain of the resin via the linking group. Alternatively, the structural unit may be introduced to the end of the resin using a polymerization initiator or chain transfer agent having these groups at the time of polymerization. As a structural unit which has a lactone group, what is the same as the structural unit which has a lactone structure demonstrated in the previous resin (A) section is mentioned, for example.
具有藉由鹼性顯影液的作用進行分解而對於鹼性顯影液的溶解度增大的基(y)的結構單元的含量以疏水性樹脂(E)中的所有結構單元為基準,較佳為1莫耳%~100莫耳%,更佳為3莫耳%~98莫耳%,進而佳為5莫耳%~95莫耳%。The content of the structural unit having the group (y) that is decomposed by the action of the alkaline developer to increase the solubility of the alkaline developer is based on all the structural units in the hydrophobic resin (E), and is preferably 1 Mole% to 100 mole%, more preferably 3 mole% to 98 mole%, and still more preferably 5 mole% to 95 mole%.
疏水性樹脂(E)中的具有藉由酸的作用而分解的基(z)的結構單元可列舉與樹脂(A)中列舉的具有酸分解性基的結構單元相同者。具有藉由酸的作用而分解的基(z)的結構單元可具有氟原子及矽原子的至少任一者。相對於樹脂(E)中的所有結構單元,具有藉由酸的作用而分解的基(z)的結構單元的含量較佳為1莫耳%~80莫耳%,更佳為10莫耳%~80莫耳%,進而佳為20莫耳%~60莫耳%。In the hydrophobic resin (E), the structural unit having a group (z) that is decomposed by the action of an acid may be the same as the structural unit having an acid-decomposable group listed in the resin (A). The structural unit having a group (z) that is decomposed by the action of an acid may have at least any one of a fluorine atom and a silicon atom. Relative to all the structural units in the resin (E), the content of the structural unit having the group (z) decomposed by the action of an acid is preferably 1 mol% to 80 mol%, more preferably 10 mol% ~80 mol%, more preferably 20 mol% to 60 mol%.
疏水性樹脂(E)可進而具有與所述結構單元不同的結構單元。The hydrophobic resin (E) may further have a structural unit different from the above-mentioned structural unit.
相對於疏水性樹脂(E)中包含的所有結構單元,包含氟原子的結構單元較佳為10莫耳%~100莫耳%,更佳為30莫耳%~100莫耳%。另外,相對於疏水性樹脂(E)中包含的所有結構單元,包含矽原子的結構單元較佳為10莫耳%~100莫耳%,更佳為20莫耳%~100莫耳%。With respect to all the structural units contained in the hydrophobic resin (E), the structural unit containing a fluorine atom is preferably 10 mol% to 100 mol%, and more preferably 30 mol% to 100 mol%. In addition, with respect to all the structural units contained in the hydrophobic resin (E), the structural unit containing silicon atoms is preferably 10 mol% to 100 mol%, and more preferably 20 mol% to 100 mol%.
另一方面,特別是於疏水性樹脂(E)於側鏈部分包含CH3 部分結構的情況下,疏水性樹脂(E)實質上不含有氟原子及矽原子的形態亦較佳。另外,疏水性樹脂(E)較佳為實質上僅包含如下的結構單元,所述結構單元僅包含選自碳原子、氧原子、氫原子、氮原子及硫原子中的原子。On the other hand, particularly when the hydrophobic resin (E) contains a CH 3 partial structure in the side chain portion, the hydrophobic resin (E) is also preferably in a form that does not substantially contain fluorine atoms and silicon atoms. In addition, the hydrophobic resin (E) preferably contains substantially only structural units that only contain atoms selected from carbon atoms, oxygen atoms, hydrogen atoms, nitrogen atoms, and sulfur atoms.
疏水性樹脂(E)的標準聚苯乙烯換算的重量平均分子量較佳為1,000~100,000,更佳為1,000~50,000。The weight average molecular weight in terms of standard polystyrene of the hydrophobic resin (E) is preferably 1,000 to 100,000, more preferably 1,000 to 50,000.
疏水性樹脂(E)中包含的殘存單體及寡聚物成分的合計含量較佳為0.01質量%~5質量%,更佳為0.01質量%~3質量%。另外,分散度(Mw/Mn)較佳為1~5的範圍,更佳為1~3的範圍。The total content of the remaining monomer and oligomer components contained in the hydrophobic resin (E) is preferably 0.01% by mass to 5% by mass, more preferably 0.01% by mass to 3% by mass. In addition, the degree of dispersion (Mw/Mn) is preferably in the range of 1 to 5, and more preferably in the range of 1 to 3.
作為疏水性樹脂(E),可單獨使用公知的樹脂,或者作為該些的混合物適宜選擇來使用。例如可較佳地使用美國專利申請案公開第2015/0168830號說明書的段落0451~段落0704、美國專利申請案公開第2016/0274458號說明書的段落0340~段落0356中所揭示的公知的樹脂作為疏水性樹脂(E)。另外,美國專利申請案公開第2016/0237190號說明書的段落0177~段落0258中所揭示的結構單元亦作為構成疏水性樹脂(E)的結構單元而較佳。As the hydrophobic resin (E), well-known resins can be used alone, or a mixture of these can be appropriately selected and used. For example, the well-known resins disclosed in paragraphs 0451 to 0704 of the specification of U.S. Patent Application Publication No. 2015/0168830 and paragraphs 0340 to 0356 of the specification of U.S. Patent Application Publication No. 2016/0274458 can be preferably used as hydrophobic Resin (E). In addition, the structural unit disclosed in paragraph 0177 to paragraph 0258 of the specification of US Patent Application Publication No. 2016/0237190 is also preferable as a structural unit constituting the hydrophobic resin (E).
-含氟樹脂- 疏水性樹脂(E)較佳為包含氟原子的樹脂(亦稱為「含氟樹脂」)。 於疏水性樹脂(E)包含氟原子的情況下,較佳為含有具有氟原子的烷基、具有氟原子的環烷基、或具有氟原子的芳基作為具有氟原子的部分結構的樹脂。-Fluorine-containing resin- The hydrophobic resin (E) is preferably a resin containing fluorine atoms (also referred to as "fluorine-containing resin"). When the hydrophobic resin (E) contains a fluorine atom, it is preferably a resin containing an alkyl group having a fluorine atom, a cycloalkyl group having a fluorine atom, or an aryl group having a fluorine atom as a partial structure having a fluorine atom.
具有氟原子的烷基為至少一個氫原子經氟原子取代的直鏈狀或分支鏈狀的烷基,較佳為碳數1~10,更佳為碳數1~4。 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。 作為具有氟原子的芳基,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者。The alkyl group having a fluorine atom is a linear or branched alkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and preferably has 1 to 10 carbon atoms, and more preferably has 1 to 4 carbon 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. Examples of the aryl group having a fluorine atom include those 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.
作為具有氟原子的烷基、具有氟原子的環烷基、及具有氟原子的芳基,較佳為式F2~式F4所表示的基。The alkyl group having a fluorine atom, the cycloalkyl group having a fluorine atom, and the aryl group having a fluorine atom are preferably groups represented by formula F2 to formula F4.
[化34] [化34]
式F2~式F4中, R57 ~R68 分別獨立地表示氫原子、氟原子或烷基(直鏈狀或分支鏈狀)。其中,R57 ~R61 的至少一個、R62 ~R64 的至少一個、及R65 ~R68 的至少一個分別獨立地表示氟原子或至少一個氫原子經氟原子取代的烷基。 較佳為R57 ~R61 及R65 ~R67 全部為氟原子。R62 、R63 及R68 較佳為至少一個氫原子經氟原子取代的烷基(較佳為碳數1~4),更佳為碳數1~4的全氟烷基。R62 與R63 可相互連結而形成環。In Formula F2 to Formula F4, R 57 to R 68 each independently represent a hydrogen atom, a fluorine atom, or an alkyl group (linear or branched chain). Among them, at least one of R 57 to R 61 , at least one of R 62 to R 64 , and at least one of R 65 to R 68 each independently represent a fluorine atom or an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom. Preferably, all of R 57 to R 61 and R 65 to R 67 are fluorine atoms. R 62 , R 63 and R 68 are preferably an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom (preferably a carbon number of 1 to 4), more preferably a carbon number of 1 to 4 perfluoroalkyl group. R 62 and R 63 may be connected to each other to form a ring.
其中,就本發明的效果更優異的方面而言,含氟樹脂較佳為具有鹼分解性。 所謂含氟樹脂具有鹼分解性是指於pH值為10的緩衝液2 mL與THF 8 mL的混合液中添加含氟樹脂100 mg,於40℃下靜置,10分鐘後含氟樹脂中的分解性基的總量的30 mol%以上進行水解。再者,分解率可由NMR分析所得的原料與分解物的比來算出。Among them, it is preferable that the fluorine-containing resin has alkali decomposability in terms of more excellent effects of the present invention. The so-called alkali decomposability of fluorine-containing resin means that 100 mg of fluorine-containing resin is added to a mixture of 2 mL of pH 10 buffer solution and 8 mL of THF, and the mixture is allowed to stand at 40°C. After 10 minutes, the content of fluorine-containing resin is 30 mol% or more of the total amount of decomposable groups undergoes hydrolysis. In addition, the decomposition rate can be calculated from the ratio of the raw material to the decomposition product obtained by NMR analysis.
就焦點深度的容許度、圖案直線性、改善顯影特性、抑制逸氣、提高液浸曝光中的液浸液追隨性及減少液浸缺陷的觀點而言,含氟樹脂較佳為具有式X所表示的結構單元。 另外,就焦點深度的容許度、圖案直線性、改善顯影特性、抑制逸氣、提高液浸曝光中的液浸液追隨性及減少液浸缺陷的觀點而言,本發明的感光化射線性或感放射線性樹脂組成物較佳為進而包含具有式X所表示的結構單元的含氟樹脂。From the viewpoints of focus depth tolerance, pattern linearity, improvement of development characteristics, suppression of outgassing, improvement of liquid immersion liquid followability in liquid immersion exposure, and reduction of liquid immersion defects, the fluorine-containing resin is preferably one of formula X Represents the structural unit. In addition, from the viewpoints of the tolerance of the focal depth, the linearity of the pattern, the improvement of the development characteristics, the suppression of outgassing, the improvement of the followability of the liquid immersion in the liquid immersion exposure, and the reduction of the liquid immersion defect, the sensitizing radiation of the present invention may be The radiation-sensitive resin composition preferably further includes a fluorine-containing resin having a structural unit represented by formula X.
[化35] [化35]
式X中,Z表示鹵素原子、R11 OCH2 -所表示的基、或R12 OC(=O)CH2 -所表示的基,R11 及R12 分別獨立地表示取代基,X表示氧原子、或硫原子。L表示(n+1)價的連結基,R10 表示具有藉由鹼性水溶液的作用進行分解而於鹼性水溶液中的含氟樹脂的溶解度增大的基的基,n表示正的整數,於n為2以上的情況下,多個R10 可相互相同亦可不同。In formula X, Z represents a halogen atom, a group represented by R 11 OCH 2 -, or a group represented by R 12 OC(=O)CH 2 -, R 11 and R 12 each independently represent a substituent, and X represents oxygen Atom, or sulfur atom. L represents a (n+1) valent linking group, R 10 represents a group having a group that increases the solubility of the fluororesin in the alkaline aqueous solution by decomposing by the action of the alkaline aqueous solution, n represents a positive integer, When n is 2 or more, a plurality of R 10 may be the same as or different from each other.
作為Z的鹵素原子,例如可列舉:氟原子、氯原子、溴原子、及碘原子,較佳為氟原子。 作為R11 及R12 的取代基,例如可列舉:烷基(較佳為碳數1~4)、環烷基(較佳為碳數6~10)、及芳基(較佳為碳數6~10)。另外,作為R11 及R12 的取代基可進而具有取代基,作為此種進一步的取代基,可列舉:烷基(較佳為碳數1~4)、鹵素原子、羥基、烷氧基(較佳為碳數1~4)、及羧基。 作為L的連結基較佳為二價連結基或三價連結基(換言之,n較佳為1或2),更佳為二價連結基(換言之,n較佳為1)。作為L的連結基較佳為選自由脂肪族基、芳香族基及該些的組合所組成的群組中的連結基。 例如,於n為1、作為L的連結基為二價連結基的情況下,作為二價脂肪族基,可列舉:伸烷基、伸烯基、伸炔基、或聚伸烷氧基。其中,較佳為伸烷基或伸烯基,更佳為伸烷基。 二價脂肪族基可為鏈狀結構,亦可為環狀結構,但較環狀結構而言,較佳為鏈狀結構,較具有分支的鏈狀結構而言,較佳為直鏈狀結構。二價脂肪族基可具有取代基,作為取代基,可列舉:鹵素原子(氟原子、氯原子、溴原子、碘原子)、羥基、羧基、胺基、氰基、芳基、烷氧基、芳氧基、醯基、烷氧基羰基、芳氧基羰基、醯氧基、單烷基胺基、二烷基胺基、芳基胺基、及二芳基胺基。 作為二價芳香族基,可列舉伸芳基。其中,較佳為伸苯基、及伸萘基。 二價芳香族基可具有取代基,不僅可列舉所述二價脂肪族基中的取代基的例子,而且可列舉烷基。 另外,作為L,可為自所述式LC1-1~式LC1-21或式SL1-1~式SL-3所表示的結構去除兩個任意位置的氫原子後的二價基。 於n為2以上的情況下,作為(n+1)價的連結基的具體例,可列舉自所述二價連結基的具體例去除任意(n-1)個氫原子而成的基。 作為L的具體例,例如可列舉以下的連結基。Examples of the halogen atom of Z include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferred. Examples of the substituents of R 11 and R 12 include alkyl groups (preferably carbon number 1 to 4), cycloalkyl groups (preferably carbon number 6 to 10), and aryl groups (preferably carbon number 6~10). In addition, the substituents of R 11 and R 12 may further have substituents, and examples of such further substituents include alkyl groups (preferably with 1 to 4 carbon atoms), halogen atoms, hydroxyl groups, and alkoxy groups ( Preferably, it is a carbon number 1 to 4) and a carboxyl group. The linking group as L is preferably a divalent linking group or a trivalent linking group (in other words, n is preferably 1 or 2), and more preferably a divalent linking group (in other words, n is preferably 1). The linking group as L is preferably a linking group selected from the group consisting of an aliphatic group, an aromatic group, and a combination of these. For example, when n is 1, and the linking group as L is a divalent linking group, examples of the divalent aliphatic group include an alkylene group, an alkenylene group, an alkynylene group, or a polyalkyleneoxy group. Among them, an alkylene group or an alkenylene group is preferred, and an alkylene group is more preferred. The divalent aliphatic group can be a chain structure or a cyclic structure, but it is preferably a chain structure than a cyclic structure, and a linear structure is more preferable for a branched chain structure . The divalent aliphatic group may have a substituent. Examples of the substituent include halogen atoms (fluorine atom, chlorine atom, bromine atom, iodine atom), hydroxyl group, carboxyl group, amino group, cyano group, aryl group, alkoxy group, Aryloxy, acyl, alkoxycarbonyl, aryloxycarbonyl, acyloxy, monoalkylamino, dialkylamino, arylamino, and diarylamino. As the divalent aromatic group, an aryl group can be mentioned. Among them, phenylene and naphthylene are preferred. The divalent aromatic group may have a substituent, and not only examples of the substituent in the divalent aliphatic group but also an alkyl group can be mentioned. In addition, L may be a divalent group obtained by removing two hydrogen atoms at any positions from the structure represented by the above-mentioned formulas LC1-1 to LC1-21 or formulas SL1-1 to SL-3. When n is 2 or more, as a specific example of the (n+1)-valent linking group, a group obtained by removing arbitrary (n-1) hydrogen atoms from the specific example of the divalent linking group can be cited. As a specific example of L, the following linking group can be mentioned, for example.
[化36] [化36]
再者,該些連結基如所述般,可進而具有取代基。In addition, these linking groups may further have a substituent as described above.
作為R10 ,較佳為下述式W所表示的基。 -Y-R20 式WAs R 10 , a group represented by the following formula W is preferred. -YR 20 type W
所述式W中,Y表示藉由鹼性水溶液的作用進行分解而於鹼性水溶液中的溶解度增大的基。R20 表示拉電子性基。In the above-mentioned formula W, Y represents a group that is decomposed by the action of the alkaline aqueous solution to increase the solubility in the alkaline aqueous solution. R 20 represents an electron withdrawing group.
作為Y,可列舉:羧酸酯基(-COO-或OCO-)、酸酐基(-C(O)OC(O)-)、酸醯亞胺基(-NHCONH-)、羧酸硫酯基(-COS-)、碳酸酯基(-OC(O)O-)、硫酸酯基(-OSO2 O-)、及磺酸酯基(-SO2 O-),較佳為羧酸酯基。Examples of Y include: carboxylic acid ester group (-COO- or OCO-), acid anhydride group (-C(O)OC(O)-), acid imino group (-NHCONH-), carboxylic acid thioester group (-COS-), carbonate group (-OC(O)O-), sulfate group (-OSO 2 O-), and sulfonate group (-SO 2 O-), preferably carboxylate group .
作為所述拉電子性基,較佳為下述式EW所示的部分結構。式EW中的*表示與式W中的基Y直接鍵結的結合鍵。As the electron withdrawing group, a partial structure represented by the following formula EW is preferred. The * in the formula EW represents a bonding bond directly bonding to the group Y in the formula W.
[化37] [化37]
式EW中, new 為-C(Rew1 )(Rew2 )-所表示的連結基的重覆數,表示0或1的整數。new 為0的情況下表示單鍵,表示Yew1 直接鍵結。 Yew1 可列舉:鹵素原子、氰基、硝基、後述的-C(Rf1 )(Rf2 )-Rf3 所表示的鹵代(環)烷基、鹵代芳基、氧基、羰基、磺醯基、亞磺醯基、及該些的組合(其中,於Yew1 為鹵素原子、氰基或硝基的情況下,new 為1)。 Rew1 及Rew 2 分別獨立地表示任意的基,例如表示氫原子、烷基(較佳為碳數1~8)、環烷基(較佳為碳數3~10)或芳基(較佳為碳數6~10)。 Rew1 、Rew 2 及Yew1 中至少兩個可相互連結而形成環。 再者,所謂「鹵代(環)烷基」,表示至少一部分進行了鹵化的烷基及環烷基,所謂「鹵代芳基」,表示至少一部分進行了鹵化的芳基。In the formula EW, n ew is the number of repetitions of the linking group represented by -C(R ew1 )(R ew2 )-, and represents an integer of 0 or 1. When n ew is 0, it represents a single bond, which means that Y ew1 is directly bonded. Y ew1 includes halogen atoms, cyano groups, nitro groups, halogenated (cyclo)alkyl groups represented by -C(R f1 )(R f2 )-R f3 described later, halogenated aryl groups, oxy groups, carbonyl groups, A sulfonyl group, a sulfinyl group, and a combination of these (wherein, when Yew1 is a halogen atom, a cyano group, or a nitro group, n ew is 1). R ew1 and R ew 2 each independently represent any group, for example, a hydrogen atom, an alkyl group (preferably carbon number 1-8), cycloalkyl (preferably carbon number 3-10) or an aryl group (more Preferably, the carbon number is 6-10). At least two of R ew1 , R ew 2 and Y ew1 may be connected to each other to form a ring. In addition, the "halogenated (cyclo)alkyl group" means an alkyl group and a cycloalkyl group in which at least a part is halogenated, and the "halogenated aryl group" means an aryl group in which at least a part is halogenated.
作為Yew1 ,較佳為鹵素原子、-C(Rf1 )(Rf2 )-Rf3 所表示的鹵代(環)烷基、或鹵代芳基。Y ew1 is preferably a halogen atom, a halogenated (cyclo)alkyl group represented by -C(R f1 )(R f2 )-R f3, or a halogenated aryl group.
Rf1 表示鹵素原子、全鹵代烷基、全鹵代環烷基、或全鹵代芳基,較佳為氟原子、全氟烷基或全氟環烷基,更佳為氟原子或三氟甲基。 Rf2 及Rf3 分別獨立地表示氫原子、鹵素原子或有機基,Rf2 與Rf3 可連結而形成環。作為有機基,可列舉:烷基、環烷基、及烷氧基,該些可經鹵素原子(較佳為氟原子)取代。Rf2 及Rf3 較佳為(鹵代)烷基或(鹵代)環烷基。Rf2 更佳為表示與Rf1 相同的基、或者與Rf3 連結而形成環。 作為Rf2 與Rf3 連結而形成的環,可列舉(鹵代)環烷基環。R f1 represents a halogen atom, a perhalogenated alkyl group, a perhalogenated cycloalkyl group, or a perhalogenated aryl group, preferably a fluorine atom, a perfluoroalkyl group or a perfluorocycloalkyl group, more preferably a fluorine atom or a trifluoromethyl group base. R f2 and R f3 each independently represent a hydrogen atom, a halogen atom, or an organic group, and R f2 and R f3 may be linked to form a ring. Examples of the organic group include an alkyl group, a cycloalkyl group, and an alkoxy group, and these may be substituted with a halogen atom (preferably a fluorine atom). R f2 and R f3 are preferably (halo)alkyl or (halo)cycloalkyl. More preferably, R f2 represents the same group as R f1 , or is linked to R f3 to form a ring. Examples of the ring formed by linking R f2 and R f3 include a (halogenated) cycloalkyl ring.
作為Rf1 ~Rf3 中的(鹵代)烷基,可為直鏈狀及分支鏈狀的任一種,作為直鏈狀(鹵代)烷基,較佳為碳數1~30,更佳為1~20。The (halogenated) alkyl group in R f1 to R f3 may be linear or branched. The linear (halogenated) alkyl group preferably has 1 to 30 carbon atoms, more preferably It is 1~20.
作為Rf1 ~Rf3 中、或Rf2 與Rf3 連結而形成的環中的(鹵代)環烷基,可為單環型,亦可為多環型。於多環型的情況下,(鹵代)環烷基可為橋環式。即於該情況下,(鹵代)環烷基可具有橋聯結構。 作為該些(鹵代)環烷基,例如可列舉由下式表示者、及該些進行了鹵化的基。再者,環烷基中的碳原子的一部分可經氧原子等雜原子取代。The (halogenated) cycloalkyl group in the ring formed by connecting R f1 to R f3 or R f2 and R f3 may be a monocyclic type or a polycyclic type. In the case of a polycyclic type, the (halo)cycloalkyl group may be a bridged ring type. That is, in this case, the (halo)cycloalkyl group may have a bridge structure. Examples of these (halogenated) cycloalkyl groups include those represented by the following formulae and these halogenated groups. In addition, part of the carbon atoms in the cycloalkyl group may be substituted with heteroatoms such as oxygen atoms.
[化38] [化38]
作為Rf2 及Rf3 中、或Rf2 與Rf3 連結而形成的環中的(鹵代)環烷基,較佳為-C(n) F(2n-2) H所表示的氟環烷基。此處,碳數n並無特別限定,較佳為5~13,更佳為6。As the R f2 and R f3, R f2 and R f3, or formed by connecting ring (halo) cycloalkyl, preferably fluorine cycloalkyl -C (n) F (2n- 2) H expressed by base. Here, the carbon number n is not particularly limited, but is preferably 5-13, more preferably 6.
作為Yew1 中、或Rf1 中的(全)鹵代芳基,可列舉-C(n) F(n-1) 所表示的全氟芳基。此處,碳數n並無特別限定,較佳為5~13,更佳為6。 Examples of the (per)halogenated aryl group in Yew1 or R f1 include perfluoroaryl groups represented by -C (n) F (n-1). Here, the carbon number n is not particularly limited, but is preferably 5-13, more preferably 6.
作為Rew1 、Rew2 及Yew1 中至少兩個可相互連結而形成的環,較佳為環烷基或雜環基。As the ring which at least two of Rew1 , Rew2 and Yew1 can be connected to each other, a cycloalkyl group or a heterocyclic group is preferable.
構成所述式EW所示的部分結構的各基及各環可進而具有取代基。Each group and each ring constituting the partial structure represented by the formula EW may further have a substituent.
所述式W中,R20 較佳為經選自由鹵素原子、氰基及硝基所組成的群組中的一個以上取代的烷基,更佳為經鹵素原子取代的烷基(鹵代烷基),進而佳為氟烷基。經選自由鹵素原子、氰基及硝基所組成的群組中的一個以上取代的烷基的碳數較佳為1~10,更佳為1~5。 更具體而言,R20 較佳為-C(R'1 )(R'f1 )(R'f2 )或-C(R'1 )(R'2 )(R'f1 )所表示的原子團。R'1 及R'2 分別獨立地表示氫原子、或未經拉電子性基取代的(較佳為未經取代的)烷基。R'f1 及R'f2 分別獨立地表示鹵素原子、氰基、硝基、或全氟烷基。 作為R'1 及R'2 的烷基可為直鏈狀亦可為分支鏈狀,較佳為碳數1~6。 作為R'f1 及R'f2 的全氟烷基可為直鏈狀亦可為分支鏈狀,較佳為碳數1~6。 作為R20 的較佳的具體例,可列舉:-CF3 、-C2 F5 、-C3 F7 、-C4 F9 、-CF(CF3 )2 、-CF(CF3 )C2 F5 、-CF2 CF(CF3 )2 、-C(CF3 )3 、-C5 F11 、-C6 F13 、-C7 F15 、-C8 F17 、-CH2 CF3 、-CH2 C2 F5 、-CH2 C3 F7 、-CH(CF3 )2 、-CH(CF3 )C2 F5 、-CH2 CF(CF3 )2 、及-CH2 CN。其中較佳為-CF3 、-C2 F5 、-C3 F7 、-C4 F9 、-CH2 CF3 、-CH2 C2 F5 、-CH2 C3 F7 、-CH(CF3 )2 、或-CH2 CN,更佳為-CH2 CF3 、-CH2 C2 F5 、-CH2 C3 F7 、-CH(CF3 )2 、或-CH2 CN,進而佳為-CH2 C2 F5 、-CH(CF3 )2 、或-CH2 CN,特佳為-CH2 C2 F5 、或-CH(CF3 )2 。In the formula W, R 20 is preferably an alkyl group substituted with one or more selected from the group consisting of a halogen atom, a cyano group, and a nitro group, and more preferably an alkyl group substituted with a halogen atom (haloalkyl) , More preferably a fluoroalkyl group. The number of carbon atoms of the alkyl group substituted by one or more selected from the group consisting of a halogen atom, a cyano group, and a nitro group is preferably 1-10, more preferably 1-5. More specifically, R 20 is preferably an atomic group represented by -C(R' 1 )(R' f1 )(R' f2 ) or -C(R' 1 )(R' 2 )(R' f1 ). R '1 and R' 2 each independently represent a hydrogen atom, or a non-electron withdrawing group-substituted (preferably unsubstituted) alkyl group. R'f1 and R'f2 each independently represent a halogen atom, a cyano group, a nitro group, or a perfluoroalkyl group. As the R '1 and R' 2 is alkyl may be linear chain may also be branched, preferably having 1 to 6 carbon atoms. As R 'f1 and R' f2 is a perfluoroalkyl group may be linear chain may also be branched, preferably having 1 to 6 carbon atoms. Preferred specific examples of R 20 include: -CF 3 , -C 2 F 5 , -C 3 F 7 , -C 4 F 9 , -CF(CF 3 ) 2 , -CF(CF 3 )C 2 F 5 , -CF 2 CF(CF 3 ) 2 , -C(CF 3 ) 3 , -C 5 F 11 , -C 6 F 13 , -C 7 F 15 , -C 8 F 17 , -CH 2 CF 3 , -CH 2 C 2 F 5 , -CH 2 C 3 F 7 , -CH (CF 3 ) 2 , -CH (CF 3 ) C 2 F 5 , -CH 2 CF (CF 3 ) 2 , and -CH 2 CN. Among them, -CF 3 , -C 2 F 5 , -C 3 F 7 , -C 4 F 9 , -CH 2 CF 3 , -CH 2 C 2 F 5 , -CH 2 C 3 F 7 , -CH (CF 3 ) 2 , or -CH 2 CN, more preferably -CH 2 CF 3 , -CH 2 C 2 F 5 , -CH 2 C 3 F 7 , -CH(CF 3 ) 2 , or -CH 2 CN , More preferably -CH 2 C 2 F 5 , -CH(CF 3 ) 2 , or -CH 2 CN, particularly preferably -CH 2 C 2 F 5 , or -CH(CF 3 ) 2 .
作為式X所表示的結構單元,較佳為下述式X-1或式X-2所表示的結構單元,更佳為式X-1所表示的結構單元。The structural unit represented by the formula X is preferably a structural unit represented by the following formula X-1 or formula X-2, and more preferably a structural unit represented by the formula X-1.
[化39] [化39]
式X-1中,R20 表示拉電子性基,L2 表示二價連結基,X2 表示氧原子或硫原子,Z2 表示鹵素原子。 式X-2中,R20 表示拉電子性基,L3 表示二價連結基,X3 表示氧原子或硫原子,Z3 表示鹵素原子。In formula X-1, R 20 represents an electron withdrawing group, L 2 represents a divalent linking group, X 2 represents an oxygen atom or a sulfur atom, and Z 2 represents a halogen atom. In formula X-2, R 20 represents an electron withdrawing group, L 3 represents a divalent linking group, X 3 represents an oxygen atom or a sulfur atom, and Z 3 represents a halogen atom.
作為L2 及L3 的二價連結基的具體例及較佳例與所述式X的作為二價連結基的L中說明者相同。 作為R20 的拉電子性基較佳為所述式EW所示的部分結構,具體例及較佳例亦如所述般,更佳為鹵代(環)烷基。The specific examples and preferred examples of the divalent linking group as L 2 and L 3 are the same as those described in the formula X as the divalent linking group L. The electron withdrawing group as R 20 is preferably a partial structure represented by the formula EW. Specific examples and preferred examples are also as described above, and more preferably a halogenated (cyclo)alkyl group.
所述式X-1中,L2 與R20 不相互鍵結而形成環,所述式X-2中,L3 與R20 不相互鍵結而形成環。In the formula X-1, L 2 and R 20 are not bonded to each other to form a ring, and in the formula X-2, L 3 and R 20 are not bonded to each other to form a ring.
作為X2 及X3 ,較佳為氧原子。 作為Z2 及Z3 ,較佳為氟原子或氯原子,更佳為氟原子。As X 2 and X 3 , an oxygen atom is preferred. As Z 2 and Z 3 , a fluorine atom or a chlorine atom is preferable, and a fluorine atom is more preferable.
另外,作為式X所表示的結構單元,亦較佳為式X-3所表示的結構單元。In addition, the structural unit represented by formula X is also preferably a structural unit represented by formula X-3.
[化40] [化40]
式X-3中,R20 表示拉電子性基,R21 表示氫原子、烷基、或芳基,L4 表示二價連結基,X4 表示氧原子或硫原子,m表示0或1。In formula X-3, R 20 represents an electron withdrawing group, R 21 represents a hydrogen atom, an alkyl group, or an aryl group, L 4 represents a divalent linking group, X 4 represents an oxygen atom or a sulfur atom, and m represents 0 or 1.
作為L4 的二價連結基的具體例及較佳例與式X的作為二價連結基的L中說明者相同。 作為R20 的拉電子性基較佳為所述式EW所示的部分結構,具體例及較佳例亦如所述般,更佳為鹵代(環)烷基。The specific examples and preferred examples of the divalent linking group as L 4 are the same as those described in the formula X as the divalent linking group. The electron withdrawing group as R 20 is preferably a partial structure represented by the formula EW. Specific examples and preferred examples are also as described above, and more preferably a halogenated (cyclo)alkyl group.
再者,所述式X-3中,L4 與R20 不相互鍵結而形成環。 作為X4 ,較佳為氧原子。Furthermore, in the formula X-3, L 4 and R 20 are not bonded to each other to form a ring. X 4 is preferably an oxygen atom.
另外,作為式X所表示的結構單元,亦較佳為式Y-1所表示的結構單元或式Y-2所表示的結構單元。In addition, the structural unit represented by formula X is also preferably a structural unit represented by formula Y-1 or a structural unit represented by formula Y-2.
[化41] [化41]
式Y-1及式Y-2中,Z表示鹵素原子、R11 OCH2 -所表示的基、或R12 OC(=O)CH2 -所表示的基,R11 及R12 分別獨立地表示取代基,R20 表示拉電子性基。In Formula Y-1 and Formula Y-2, Z represents a halogen atom, a group represented by R 11 OCH 2 -, or a group represented by R 12 OC(=O)CH 2 -, and R 11 and R 12 are each independently Represents a substituent, and R 20 represents an electron withdrawing group.
作為R20 的拉電子性基較佳為所述式EW所示的部分結構,具體例及較佳例亦如所述般,更佳為鹵代(環)烷基。The electron withdrawing group as R 20 is preferably a partial structure represented by the formula EW. Specific examples and preferred examples are also as described above, and more preferably a halogenated (cyclo)alkyl group.
作為Z的鹵素原子、R11 OCH2 -所表示的基、及R12 OC(=O)CH2 -所表示的基的具體例及較佳例與所述式X中說明者相同。Specific examples and preferred examples of the halogen atom as Z, the group represented by R 11 OCH 2 -, and the group represented by R 12 OC(=O)CH 2 -are the same as those described in the formula X.
相對於含氟樹脂的所有結構單元,式X所表示的結構單元的含量較佳為10莫耳%~100莫耳%,更佳為20莫耳%~100莫耳%,進而佳為30莫耳%~100莫耳%。Relative to all the structural units of the fluorine-containing resin, the content of the structural unit represented by formula X is preferably 10 mol% to 100 mol%, more preferably 20 mol% to 100 mol%, and further preferably 30 mol% Ear%~100mol%.
以下表示構成疏水性樹脂(E)的結構單元的較佳例。 作為疏水性樹脂(E),可較佳地列舉將該些結構單元任意地組合的樹脂,但並不限定於此。The preferable example of the structural unit which comprises hydrophobic resin (E) is shown below. As the hydrophobic resin (E), a resin in which these structural units are arbitrarily combined can be preferably used, but it is not limited to this.
[化42] [化42]
[化43] [化43]
疏水性樹脂(E)可單獨使用一種,亦可併用兩種以上。 就液浸曝光中的液浸液追隨性與顯影特性的併存的觀點而言,較佳為將表面能量不同的兩種以上的疏水性樹脂(E)混合而使用。The hydrophobic resin (E) may be used singly, or two or more of them may be used in combination. From the viewpoint of coexistence of liquid immersion liquid followability and development characteristics in liquid immersion exposure, it is preferable to mix and use two or more kinds of hydrophobic resins (E) having different surface energies.
於本發明的感光化射線性或感放射線性樹脂組成物包含疏水性樹脂(E)的情況下,相對於本發明的感光化射線性或感放射線性樹脂組成物的總固體成分,疏水性樹脂(E)於組成物中的含量較佳為0.01質量%~10質量%,更佳為0.05質量%~8質量%。When the actinic radiation or radiation-sensitive resin composition of the present invention contains the hydrophobic resin (E), the hydrophobic resin is relative to the total solid content of the actinic radiation or radiation-sensitive resin composition of the present invention. The content of (E) in the composition is preferably 0.01% by mass to 10% by mass, more preferably 0.05% by mass to 8% by mass.
[光酸產生劑] 本發明的組成物包含光酸產生劑(B-1)及光酸產生劑(B-2)中至少兩種光酸產生劑。 自光酸產生劑(B-1)產生的酸的pKa未滿0。 自光酸產生劑(B-2)產生的酸的pKa大於自光酸產生劑(B-1)產生的酸的pKa。 相對於光酸產生劑(B-1)的含量,光酸產生劑(B-2)的含量為0.001質量%以上且0.1質量%以下。[Photo Acid Generator] The composition of the present invention contains at least two photoacid generators among the photoacid generator (B-1) and the photoacid generator (B-2). The pKa of the acid generated from the photoacid generator (B-1) is less than zero. The pKa of the acid generated from the photoacid generator (B-2) is greater than the pKa of the acid generated from the photoacid generator (B-1). The content of the photoacid generator (B-2) is 0.001% by mass or more and 0.1% by mass or less with respect to the content of the photoacid generator (B-1).
於本發明的組成物中,藉由併用產生對於自光酸產生劑(B-1)產生的酸而言相對弱的酸的光酸產生劑(B-2),若藉由光化射線性或放射線的照射而自光酸產生劑(B-1)產生的酸與未反應的光酸產生劑(B-2)碰撞,則藉由鹽交換而釋放出弱酸,產生具有強酸根陰離子的鎓鹽。於該過程中強酸被交換為觸媒能力更低的弱酸,因此於表觀上,酸失活而可控制酸擴散。因而,由本發明的組成物形成的厚膜抗蝕劑膜中,於樹脂(A)及光酸產生劑(B-1)容易濃縮的膜的上部,可適度地抑制自光酸產生劑(B-1)產生的酸的擴散,可提高圖案的剖面形狀的矩形性。In the composition of the present invention, by using a photoacid generator (B-2) that generates an acid that is relatively weak compared to the acid generated from the photoacid generator (B-1), if the photoacid generator (B-2) is activated by actinic rays Or the acid generated from the photoacid generator (B-1) collides with the unreacted photoacid generator (B-2) due to the irradiation of radiation, and the weak acid is released by the salt exchange, and the onium with the strong acid anion is produced. salt. In this process, the strong acid is exchanged for a weak acid with a lower catalytic ability. Therefore, apparently, the acid is deactivated and the acid diffusion can be controlled. Therefore, in the thick film resist film formed from the composition of the present invention, the resin (A) and the photoacid generator (B-1) are easily concentrated on the upper part of the film, and the photoacid generator (B-1) can be moderately suppressed. -1) The diffusion of the generated acid can improve the rectangularity of the cross-sectional shape of the pattern.
於將自光酸產生劑(B-1)產生的酸的pKa設為E1 、將自光酸產生劑(B-2)產生的酸的pKa設為E2 的情況下,E2 -E1 較佳為0.5以上,更佳為3以上,進而佳為6以上。E2 -E1 較佳為20以下,更佳為15以下。When the pKa of the acid generated from the photoacid generator (B-1) is E 1 and the pKa of the acid generated from the photo acid generator (B-2) is E 2 , E 2 -E 1 is preferably 0.5 or more, more preferably 3 or more, and still more preferably 6 or more. E 2 -E 1 is preferably 20 or less, more preferably 15 or less.
自光酸產生劑(B-1)產生的酸的pKa(E1 )未滿0,較佳為-0.01以下,更佳為-1以下,進而佳為-2以下。E1 較佳為-15以上,更佳為-10以上。 The pKa (E 1 ) of the acid generated from the photoacid generator (B-1) is less than 0, preferably -0.01 or less, more preferably -1 or less, and still more preferably -2 or less. E 1 is preferably -15 or more, more preferably -10 or more.
自光酸產生劑(B-2)產生的酸的pKa(E2 )較佳為0.5以上,更佳為1.0以上。E2 較佳為7.0以下,更佳為6.0以下。 The pKa (E 2 ) of the acid generated from the photoacid generator (B-2) is preferably 0.5 or more, more preferably 1.0 or more. E 2 is preferably 7.0 or less, more preferably 6.0 or less.
所謂pKa表示於水溶液中的酸解離常數pKa,例如由化學便覽(II)(修訂4版,1993年,日本化學會編,丸善股份有限公司)定義。酸解離常數pKa的值越低,表示酸強度越大。具體而言,於水溶液中的酸解離常數pKa可藉由使用無限稀釋水溶液,測定25℃下的酸解離常數來實測。或者,亦可使用下述軟體包1,藉由計算來求出基於哈米特取代基常數及公知文獻值的資料庫的值。本說明書中記載的pKa的值全部表示使用該軟體包,藉由計算來求出的值。The so-called pKa represents the acid dissociation constant pKa in an aqueous solution, and is defined, for example, by the Handbook of Chemistry (II) (Revised 4th edition, 1993, The Chemical Society of Japan, Maruzen Co., Ltd.). The lower the value of the acid dissociation constant pKa, the greater the acid strength. Specifically, the acid dissociation constant pKa in an aqueous solution can be measured by measuring the acid dissociation constant at 25° C. using an infinitely diluted aqueous solution. Alternatively, the following software package 1 can also be used to obtain the value of the database based on the Hammett's substituent constant and publicly known literature values by calculation. The values of pKa described in this manual all indicate values obtained by calculations using this 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).
以下,對光酸產生劑(B-1)及光酸產生劑(B-2)進行詳細說明。Hereinafter, the photo acid generator (B-1) and the photo acid generator (B-2) will be described in detail.
<光酸產生劑(B-1)> 本發明的組成物包含光酸產生劑(B-1)。 光酸產生劑(B-1)為藉由光化射線或放射線的照射而產生酸的化合物。 作為光酸產生劑(B-1),較佳為藉由光化射線或放射線的照射而產生有機酸的化合物。例如可列舉:鋶鹽化合物、錪鹽化合物、重氮鎓鹽化合物、鏻鹽化合物、醯亞胺磺酸酯化合物、肟磺酸酯化合物、重氮二碸化合物、二碸化合物、及鄰硝基苄基磺酸酯化合物。<Photoacid generator (B-1)> The composition of the present invention contains a photoacid generator (B-1). The photoacid generator (B-1) is a compound that generates acid by irradiation with actinic rays or radiation. As the photoacid generator (B-1), a compound that generates an organic acid by irradiation with actinic rays or radiation is preferred. Examples include: sulfonium salt compounds, iodonium salt compounds, diazonium salt compounds, phosphonium salt compounds, imine sulfonate compounds, oxime sulfonate compounds, diazonium compounds, disulfide compounds, and o-nitro groups Benzyl sulfonate compound.
作為光酸產生劑(B-1),可單獨使用藉由光化射線或放射線的照射而產生酸的公知的化合物,或者作為該些的混合物適宜選擇來使用。例如可較佳地使用美國專利申請案公開第2016/0070167號說明書的段落0125~段落0319、美國專利申請案公開第2015/0004544號說明書的段落0086~段落0094、美國專利申請案公開第2016/0237190號說明書的段落0323~段落0402中所揭示的公知的化合物作為光酸產生劑(B-1)。As the photoacid generator (B-1), a known compound that generates an acid by irradiation with actinic rays or radiation can be used alone, or a mixture of these can be appropriately selected and used. For example, paragraphs 0125 to 0319 of U.S. Patent Application Publication No. 2016/0070167, paragraphs 0086 to 0094 of U.S. Patent Application Publication No. 2015/0004544, and U.S. Patent Application Publication No. 2016/ The well-known compound disclosed in paragraph 0323 to paragraph 0402 of Specification No. 0237190 is used as a photoacid generator (B-1).
〔式ZI、式ZII或式ZIII所表示的化合物〕 作為光酸產生劑(B-1)的較佳態樣,例如可列舉下述式ZI、式ZII或式ZIII所表示的化合物。[Compounds represented by formula ZI, formula ZII or formula ZIII] As a preferable aspect of the photoacid generator (B-1), for example, a compound represented by the following formula ZI, formula ZII, or formula ZIII can be cited.
[化44] [化44]
所述式ZI中, R201 、R202 及R203 分別獨立地表示有機基。 作為R201 、R202 及R203 的有機基的碳數較佳為1~30,更佳為1~20。 另外,R201 ~R203 中兩個可鍵結而形成環結構,可於環內包含氧原子、硫原子、酯鍵、醯胺鍵、或羰基。作為R201 ~R203 中的兩個鍵結而形成的基,可列舉伸烷基(例如,伸丁基、伸戊基)及-CH2 -CH2 -O-CH2 -CH2 -。 Z- 表示陰離子。In the formula ZI, R 201 , R 202 and R 203 each independently represent an organic group. The number of carbon atoms in the organic group of R 201 , R 202 and R 203 is preferably 1-30, more 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 bond, an amide bond, or a carbonyl group. Examples of the group formed by bonding two of R 201 to R 203 include alkylene (for example, butylene, pentylene) and -CH 2 -CH 2 -O-CH 2 -CH 2 -. Z - represents an anion.
〔式ZI所表示的化合物中的陽離子〕 作為式ZI中的陽離子的較佳態樣,可列舉後述的化合物(ZI-1)、化合物(ZI-2)、化合物(ZI-3)及化合物(ZI-4)中的對應的基。 再者,光酸產生劑(B-1)可為具有多個式ZI所表示的結構的化合物。例如,可為具有式ZI所表示的化合物的R201 ~R203 中的至少一個與式ZI所表示的另一化合物的R201 ~R203 中的至少一個經由單鍵或連結基鍵結而成的結構的化合物。[The cation in the compound represented by the formula ZI] As a preferable aspect of the cation in the formula ZI, the compound (ZI-1), the compound (ZI-2), the compound (ZI-3) and the compound ( The corresponding base in ZI-4). Furthermore, the photoacid generator (B-1) may be a compound having a plurality of structures represented by formula ZI. For example, at least one R ZI another compound of formula may be represented by R is a compound represented by the formula ZI 201 ~ R 203 in 201 ~ R 203 via at least a single bond or a linking group formed by bonding The structure of the compound.
-化合物ZI-1- 首先,對化合物(ZI-1)進行說明。 化合物(ZI-1)為所述式ZI的R201 ~R203 中的至少一個為芳基的芳基鋶化合物、即以芳基鋶作為陽離子的化合物。 芳基鋶化合物中R201 ~R203 可全部為芳基,亦可R201 ~R203 的一部分為芳基且其餘為烷基或環烷基。 作為芳基鋶化合物,例如可列舉:三芳基鋶化合物、二芳基烷基鋶化合物、芳基二烷基鋶化合物、二芳基環烷基鋶化合物、及芳基二環烷基鋶化合物。-Compound ZI-1- First, the compound (ZI-1) will be described. Compound (ZI-1) is an aryl alumium compound in which at least one of R 201 to R 203 of the formula ZI is an aryl group, that is, a compound having an aryl alumium as a cation. In the aryl amber compound, all of R 201 to R 203 may be aryl groups, or part of R 201 to R 203 may be aryl groups and the rest may be alkyl or cycloalkyl groups. As the aryl alumite compound, for example, a triaryl alumite compound, a diaryl alkyl alumite compound, an aryl dialkyl alumite compound, a diaryl cycloalkyl alumite compound, and an aryl dicycloalkyl alumite compound are mentioned.
作為芳基鋶化合物的芳基,較佳為苯基、或萘基,更佳為苯基。芳基可為含有具有氧原子、氮原子、或硫原子等的雜環結構的芳基。作為雜環結構,可列舉:吡咯殘基、呋喃殘基、噻吩殘基、吲哚殘基、苯并呋喃殘基、及苯并噻吩殘基等。於芳基鋶化合物具有兩個以上的芳基的情況下,存在兩個以上的芳基可相同亦可不同。 芳基鋶化合物視需要具有的烷基或環烷基較佳為碳數1~15的直鏈烷基、碳數3~15的分支烷基、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 of the aryl alumium compound 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 compound has two or more aryl groups, the two or more aryl groups may be the same or different. The alkyl group or cycloalkyl group optionally possessed by the aryl cyanide compound is preferably a linear alkyl group having 1 to 15 carbon atoms, a branched alkyl group having 3 to 15 carbon atoms, or a cycloalkyl group having 3 to 15 carbon atoms, for example Examples include methyl, ethyl, propyl, n-butyl, second butyl, tertiary butyl, cyclopropyl, cyclobutyl, and cyclohexyl.
R201 ~R203 的芳基、烷基、及環烷基可分別獨立地具有烷基(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)、鹵素原子、羥基、或苯硫基作為取代基。The aryl group, alkyl group, and cycloalkyl group of R 201 to R 203 may each independently have an alkyl group (for example, carbon number 1-15), cycloalkyl group (for example, carbon number 3-15), and aryl group (for example, carbon number 6-14), an alkoxy group (for example, carbon number 1-15), a halogen atom, a hydroxyl group, or a thiophenyl group as a substituent.
-化合物ZI-2- 其次,對化合物(ZI-2)進行說明。 化合物(ZI-2)為式ZI中的R201 ~R203 分別獨立地為不具有芳香環的有機基的化合物。此處所謂芳香環亦包含含有雜原子的芳香族環。 作為R201 ~R203 的不具有芳香環的有機基較佳為碳數1~30,更佳為碳數1~20。 R201 ~R203 分別獨立地較佳為烷基、環烷基、烯丙基、或乙烯基,更佳為直鏈或分支的2-氧代烷基、2-氧代環烷基、或烷氧基羰基甲基,進而佳為直鏈或分支2-氧代烷基。-Compound ZI-2- Next, the compound (ZI-2) will be described. Compound (ZI-2) is a compound in which R 201 to R 203 in formula ZI are each independently an organic group without an aromatic ring. The aromatic ring referred to here also includes an aromatic ring containing a heteroatom. The organic group having no aromatic ring as R 201 to R 203 preferably has 1 to 30 carbon atoms, and more preferably has 1 to 20 carbon atoms. R 201 to R 203 are each independently preferably an alkyl group, a cycloalkyl group, an allyl group, or a vinyl group, more preferably a linear or branched 2-oxoalkyl group, a 2-oxocycloalkyl group, or The alkoxycarbonylmethyl group is more preferably a linear or branched 2-oxoalkyl group.
作為R201 ~R203 的烷基及環烷基,較佳為可列舉:碳數1~10的直鏈烷基或碳數3~10的分支烷基(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。The alkyl group and cycloalkyl group of R 201 to R 203 preferably include straight chain alkyl groups having 1 to 10 carbon atoms or branched alkyl groups having 3 to 10 carbon atoms (for example, methyl, ethyl, propyl Group, butyl group, and pentyl group), and a cycloalkyl group having 3 to 10 carbon atoms (for example, 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.
-化合物ZI-3- 其次,對化合物(ZI-3)進行說明。 化合物ZI-3為由下述式ZI-3表示、具有苯甲醯甲基鋶鹽結構的化合物。-Compound ZI-3- Next, the compound (ZI-3) will be described. The compound ZI-3 is a compound represented by the following formula ZI-3 and having a benzyl methyl sulfonium salt structure.
[化45] [化45]
式ZI-3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、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 formula ZI-3, 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, and a cycloalkyl group. A carbonyloxy group, a halogen atom, a hydroxyl group, a nitro group, an alkylthio group or an arylthio group, R 6c and R 7c each independently represent a hydrogen atom, an alkyl group, 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 、及Rx 與Ry 可分別鍵結而形成環結構,該環結構可分別獨立地包含氧原子、硫原子、酮基、酯鍵、或醯胺鍵。 作為所述環結構,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、及將該些環組合兩個以上而成的多環稠環。作為環結構,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 structure, and the ring structure may be respectively It independently contains an oxygen atom, a sulfur atom, a keto group, an ester bond, or an amide bond. Examples of the ring structure 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 structure 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 、及Rx 與Ry 鍵結而形成的基,可列舉伸丁基、及伸戊基等。 作為R5c 與R6c 、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,可列舉亞甲基、及伸乙基等。 Zc- 表示陰離子。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 butylene and pentylene. 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. Zc - represents an anion.
-化合物ZI-4- 其次,對化合物(ZI-4)進行說明。 化合物(ZI-4)由下述式ZI-4表示。-Compound ZI-4- Next, the compound (ZI-4) will be described. The compound (ZI-4) is represented by the following formula ZI-4.
[化46] [化46]
式ZI-4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、環烷基、烷氧基、烷氧基羰基、或具有環烷基的基,該些基可具有取代基,R14 分別獨立地表示羥基、烷基、環烷基、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,該些基可具有取代基,R15 分別獨立地表示烷基、環烷基或萘基,該些基可具有取代基,兩個R15 可相互鍵結而形成環。 於兩個R15 相互鍵結而形成環時,可於環骨架內包含氧原子、或氮原子等雜原子。於一態樣中,較佳為兩個R15 為伸烷基,且相互鍵結而形成環結構。 Z- 表示陰離子。In formula ZI-4, l represents an integer from 0 to 2, r represents an integer from 0 to 8, and R 13 represents a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, or A group having a cycloalkyl group, these groups may have a substituent, and R 14 each independently represents a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, a ring An alkylsulfonyl group or a group having a cycloalkyl group, these groups may have a substituent, R 15 each independently represents an alkyl group, a cycloalkyl group or a naphthyl group, these groups may have a substituent, two R 15 Can 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 they are bonded to each other to form a ring structure. Z - represents an anion.
式ZI-4中,R13 、R14 及R15 的烷基為直鏈狀或分支狀,較佳為碳原子數1~10者,更佳為甲基、乙基、正丁基、或第三丁基等。In the formula ZI-4, the alkyl group of R 13 , R 14 and R 15 is linear or branched, preferably having 1 to 10 carbon atoms, more preferably methyl, ethyl, n-butyl, or Tertiary butyl and so on.
〔式ZII所表示的化合物中的陽離子、及式ZIII所表示的化合物〕 其次,對式ZII、及式ZIII進行說明。 式ZII、及式ZIII中,R204 ~R207 各自獨立地表示芳基、烷基或環烷基。 作為R204 ~R207 的芳基,較佳為苯基、或萘基,更佳為苯基。R204 ~R207 的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。作為具有雜環結構的芳基的骨架,例如可列舉:吡咯、呋喃、噻吩、吲哚、苯并呋喃、及苯并噻吩等。 作為R204 ~R207 的烷基及環烷基,較佳為可列舉碳數1~10的直鏈烷基或碳數3~10的分支烷基(例如,甲基、乙基、丙基、丁基、及戊基)、碳數3~10的環烷基(例如環戊基、環己基、及降冰片基)。[Cation in the compound represented by the formula ZII and the compound represented by the formula ZIII] Next, the formula ZII and the formula ZIII will be described. In formula ZII and formula ZIII, R 204 to R 207 each independently represent an aryl group, an alkyl group, or a cycloalkyl group. The aryl group of R 204 to R 207 is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. The aryl group of R 204 to R 207 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 skeleton of the aryl group having a heterocyclic structure include pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene. As the alkyl group and cycloalkyl group of R 204 to R 207 , preferably, a straight chain alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms (e.g., methyl, ethyl, propyl , Butyl, and pentyl), C3-10 cycloalkyl (such as cyclopentyl, cyclohexyl, and norbornyl).
R204 ~R207 的芳基、烷基、及環烷基可各自獨立地具有取代基。作為R204 ~R207 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。 Z- 表示陰離子。The aryl group, alkyl group, and cycloalkyl group of R 204 to R 207 may each independently have a substituent. Examples of the substituents that the aryl group, alkyl group, and cycloalkyl group of R 204 to R 207 may have include alkyl groups (for example, carbon numbers 1 to 15), cycloalkyl groups (for example, carbon numbers 3 to 15), Aryl group (for example, carbon number 6-15), alkoxy group (for example, carbon number 1-15), halogen atom, hydroxyl group, phenylthio group, etc. Z - represents an anion.
〔式ZI~式ZII所表示的化合物中的陰離子〕 作為式ZI中的Z- 、式ZII中的Z- 、式ZI-3中的Zc- 、及式ZI-4中的Z- ,較佳為下述式An-1所表示的陰離子。Anionic compounds of formula [~ ZI] represented by Formula ZII ZI of formula Z -, ZII the formula Z -, of the formula ZI-3 Zc -, and ZI-4 of the formula Z -, preferably It is an anion represented by the following formula An-1.
[化47] [化47]
式An-1中,pf表示0~10的整數,qf表示0~10的整數,rf表示1~3的整數,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,於rf為2以上的整數的情況下,多個-C(Xf)2 -可分別相同亦可不同,R4f 及R5f 分別獨立地表示氫原子、氟原子、烷基、或經至少一個氟原子取代的烷基,於pf為2以上的整數的情況下,多個-CR4f R5f -可分別相同亦可不同,Lf 表示二價連結基,於qf為2以上的整數的情況下,多個Lf 可分別相同亦可不同,W表示有機基。In the formula An-1, pf represents an integer from 0 to 10, qf represents an integer from 0 to 10, rf represents an integer from 1 to 3, and Xf each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. When rf is an integer of 2 or more, a plurality of -C(Xf) 2 -may be the same or different, and R 4f and R 5f each independently represent a hydrogen atom, a fluorine atom, an alkyl group, or at least one fluorine atom For the substituted alkyl group, when pf is an integer of 2 or more, a plurality of -CR 4f R 5f -may be the same or different, respectively, L f represents a divalent linking group, and when qf is an integer of 2 or more, A plurality of L f may be the same or different, respectively, and W represents an organic group.
Xf表示氟原子、或經至少一個氟原子取代的烷基。該烷基的碳數較佳為1~10,更佳為1~4。另外,經至少一個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更佳為氟原子或CF3 。特別是兩個Xf較佳為氟原子。Xf represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. The number of carbon atoms in the alkyl group is preferably 1-10, more preferably 1-4. In addition, the alkyl group substituted with at least one fluorine atom is preferably a perfluoroalkyl group. Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms. Xf is more preferably a fluorine atom or CF 3 . In particular, two Xf are preferably fluorine atoms.
R4f 及R5f 分別獨立地表示氫原子、氟原子、烷基、或經至少一個氟原子取代的烷基。存在多個時的R4f 及R5f 可分別相同亦可不同。 作為R4f 及R5f 的烷基可具有取代基,較佳為碳數1~4。R4f 及R5f 較佳為氫原子。 經至少一個氟原子取代的烷基的具體例及較佳態樣與式An-1中的Xf的具體例及較佳態樣相同。R 4f and R 5f each independently represent a hydrogen atom, a fluorine atom, an alkyl group, or an alkyl group substituted with at least one fluorine atom. When there are a plurality of R 4f and R 5f , each may be the same or different. The alkyl group as R 4f and R 5f may have a substituent, and preferably has 1 to 4 carbon atoms. R 4f and R 5f are preferably hydrogen atoms. The specific examples and preferred aspects of the alkyl group substituted with at least one fluorine atom are the same as the specific examples and preferred aspects of Xf in the formula An-1.
Lf 表示二價連結基,存在多個時的Lf 可分別相同亦可不同。 作為二價連結基,例如可列舉:-COO-(-C(=O)-O-)、-OCO-、-CONH-、-NHCO-、-CO-、-O-、-S-、-SO-、-SO2 -、伸烷基(較佳為碳數1~6)、伸環烷基(較佳為碳數3~15)、伸烯基(較佳為碳數2~6)及將該些的多個組合而成的二價連結基等。該些中,較佳為-COO-、-OCO-、-CONH-、-NHCO-、-CO-、-O-、-SO2 -、-COO-伸烷基-、-OCO-伸烷基-、-CONH-伸烷基-或-NHCO-伸烷基-,更佳為-COO-、-OCO-、-CONH-、-SO2 -、-COO-伸烷基-或-OCO-伸烷基-。L f represents a divalent linking group, and when there are a plurality of L fs, they may be the same or different. Examples of the divalent linking group include: -COO-(-C(=O)-O-), -OCO-, -CONH-, -NHCO-, -CO-, -O-, -S-,- SO-, -SO 2 -, alkylene group (preferably carbon number 1 to 6), cycloalkylene group (preferably carbon number 3 to 15), alkenylene group (preferably carbon number 2 to 6) And a divalent linking group formed by combining a plurality of these. Among these, preferred are -COO-, -OCO-, -CONH-, -NHCO- , -CO-, -O-, -SO 2 -, -COO-alkylene-, -OCO-alkylene -, -CONH-alkylene- or -NHCO-alkylene-, more preferably -COO-, -OCO-, -CONH-, -SO 2 -, -COO-alkylene- or -OCO-alkylene alkyl-.
W表示有機基(例如,烷基、環烷基、芳基、雜環基等),較佳為表示包含環狀結構的有機基。該些中,較佳為環狀有機基。 作為環狀有機基,例如可列舉:脂環基、芳基、及雜環基。 脂環基可為單環式,亦可為多環式。作為單環式的脂環基,例如可列舉:環戊基、環己基、及環辛基等單環的環烷基。作為多環式的脂環基,例如可列舉:降冰片基、三環癸烷基、四環癸烷基、四環十二烷基、及金剛烷基等多環的環烷基。其中,較佳為降冰片基、三環癸烷基、四環癸烷基、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。W represents an organic group (for example, an alkyl group, a cycloalkyl group, an aryl group, a heterocyclic group, etc.), and preferably represents an organic group containing a cyclic structure. Among these, a cyclic organic group is preferred. Examples of the cyclic organic group include an alicyclic group, an aryl group, and a heterocyclic group. The alicyclic group may be monocyclic or polycyclic. Examples of the monocyclic alicyclic group include monocyclic cycloalkyl groups such as cyclopentyl, cyclohexyl, and cyclooctyl. Examples of the polycyclic alicyclic group include polycyclic cycloalkyl groups such as norbornyl group, tricyclodecyl group, tetracyclodecyl group, tetracyclododecyl group, and adamantyl group. Among them, alicyclic groups having a bulky structure with 7 or more carbon atoms, such as norbornyl group, tricyclodecyl group, tetracyclodecyl group, tetracyclododecyl group, and adamantyl group, are preferred.
芳基可為單環式,亦可為多環式。作為該芳基,例如可列舉:苯基、萘基、菲基及蒽基。 雜環基可為單環式,亦可為多環式。多環式可進一步抑制酸的擴散。另外,雜環基可具有芳香族性,亦可不具有芳香族性。作為具有芳香族性的雜環,例如可列舉:呋喃環、噻吩環、苯并呋喃環、苯并噻吩環、二苯并呋喃環、二苯并噻吩環、及吡啶環。作為不具有芳香族性的雜環,例如可列舉:四氫吡喃環、內酯環、磺內酯環及十氫異喹啉環。作為內酯環及磺內酯環的例子,可列舉所述樹脂中例示的內酯結構及磺內酯結構。作為雜環基中的雜環,特佳為呋喃環、噻吩環、吡啶環、或十氫異喹啉環。The aryl group may be monocyclic or polycyclic. As this aryl group, a phenyl group, a naphthyl group, a phenanthryl group, and an anthracenyl group are mentioned, for example. The heterocyclic group may be monocyclic or polycyclic. The polycyclic type can further inhibit the diffusion of acid. In addition, the heterocyclic group may be aromatic or not. Examples of the heterocyclic ring having aromaticity include a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, and a pyridine ring. Examples of the heterocyclic ring having no aromaticity include a tetrahydropyran ring, a lactone ring, a sultone ring, and a decahydroisoquinoline ring. Examples of the lactone ring and the sultone ring include the lactone structure and the sultone structure exemplified in the resin. The heterocyclic ring in the heterocyclic group is particularly preferably a furan ring, a thiophene ring, a pyridine ring, or a decahydroisoquinoline ring.
所述環狀有機基可具有取代基。作為該取代基,例如可列舉:烷基(可為直鏈、分支的任一種,較佳為碳數1~12)、環烷基(可為單環、多環、螺環的任一種,較佳為碳數3~20)、芳基(較佳為碳數6~14)、羥基、烷氧基、酯基、醯胺基、胺基甲酸酯基、脲基、硫醚基、磺醯胺基、及磺酸酯基等。再者,構成環狀有機基的碳(有助於環形成的碳)可為羰基碳。The cyclic organic group may have a substituent. Examples of the substituent include an alkyl group (which may be either linear or branched, and preferably has 1 to 12 carbon atoms), cycloalkyl (which may be any one of monocyclic, polycyclic, and spirocyclic rings, Preferably it is carbon number 3-20), aryl group (preferably carbon number 6-14), hydroxyl group, alkoxy group, ester group, amide 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.
作為式An-1所表示的陰離子,可列舉SO3 - -CF2 -CH2 -OCO-(Lf )q'-W、SO3 - -CF2 -CHF-CH2 -OCO-(Lf )q'-W、SO3 - -CF2 -COO-(Lf )q'-W、SO3 - -CF2 -CF2 -CH2 -CH2 -(Lf )q f -W、SO3 - -CF2 -CH(CF3 )-OCO-(Lf )q'-W作為較佳者。此處,Lf 、qf及W與式An-1相同。q'表示0~10的整數。As the anion represented by the formula An-1, SO 3 -- CF 2 -CH 2 -OCO-(L f )q'-W, SO 3 -- CF 2 -CHF-CH 2 -OCO-(L f )q'-W, SO 3 -- CF 2 -COO-(L f )q'-W, SO 3 -- CF 2 -CF 2 -CH 2 -CH 2 -(L f ) q f -W, SO 3 -- CF 2 -CH(CF 3 )-OCO-(L f )q'-W is preferable. Here, L f , qf and W are the same as the formula An-1. q'represents an integer of 0-10.
於一態樣中,作為式ZI中的Z- 、式ZII中的Z- 、式ZI-3中的Zc- 、及式ZI-4中的Z- ,亦較佳為下述式4所表示的陰離子。In one aspect, the ZI formula Z -, ZII the formula Z -, of the formula ZI-3 Zc -, and ZI-4 of the formula Z -, also preferably represented by the following formula 4的 anions.
[化48] [化48]
式4中,XB1 及XB2 分別獨立地表示氫原子、或不具有氟原子的一價有機基。XB1 及XB2 較佳為氫原子。 XB3 及XB4 分別獨立地表示氫原子、或一價有機基。較佳為XB3 及XB4 中至少一者為氟原子或具有氟原子的一價有機基,更佳為XB3 及XB4 兩者為氟原子或具有氟原子的一價有機基。進而佳為XB3 及XB4 兩者為經氟取代的烷基。 Lf 、qf及W與式An-1相同。In Formula 4, X B1 and X B2 each independently represent a hydrogen atom or a monovalent organic group that does not have a fluorine atom. X B1 and X B2 are preferably hydrogen atoms. X B3 and X B4 each independently represent a hydrogen atom or a monovalent organic group. It is preferable that at least one of X B3 and X B4 is a fluorine atom or a monovalent organic group having a fluorine atom, and it is more preferable that both X B3 and X B4 are a fluorine atom or a monovalent organic group having a fluorine atom. More preferably, both X B3 and X B4 are alkyl groups substituted with fluorine. L f , qf and W are the same as the formula An-1.
作為式ZI中的Z- 、式ZII中的Z- 、式ZI-3中的Zc- 、及式ZI-4中的Z- ,較佳為下述式5所表示的陰離子。ZI of formula Z -, ZII the formula Z -, of the formula ZI-3 Zc -, and ZI-4 of the formula Z -, preferably an anion represented by the following formula 5.
[化49] [化49]
式5中,Xa分別獨立地表示氟原子、或經至少一個氟原子取代的烷基,Xb分別獨立地表示氫原子或不具有氟原子的有機基。rf、pf、qf、R4f 、R5f 、Lf 及W的定義及較佳態樣與式An-1相同。In Formula 5, Xa each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom, and Xb each independently represents a hydrogen atom or an organic group having no fluorine atom. The definitions and preferred aspects of rf, pf, qf, R 4f , R 5f , L f and W are the same as the formula An-1.
式ZI中的Z- 、式ZII中的Z- 、式ZI-3中的Zc- 、及式ZI-4中的Z- 可為苯磺酸根陰離子,較佳為藉由分支烷基或環烷基進行了取代的苯磺酸根陰離子。ZI of formula Z -, ZII the formula Z -, of the formula ZI-3 Zc -, and ZI-4 of the formula Z - may be a benzenesulfonate anion, preferably a branched alkyl or by cycloalkyl Benzenesulfonate anion with substituted group.
作為式ZI中的Z- 、式ZII中的Z- 、式ZI-3中的Zc- 、及式ZI-4中的Z- ,亦較佳為下述式SA1所表示的芳香族磺酸根陰離子。Aromatic sulfonate anion, preferably also represented by the following formula SA1 - Z in formula ZI -, Z in formula ZII -, the formula ZI-3 Zc -, and in formula Z ZI-4 .
[化50] [化50]
式SA1中,Ar表示芳基,可進而具有磺酸根陰離子及-(D-RB )以外的取代基。作為可進而具有的取代基,可列舉氟原子、羥基等。In the formula SA1, Ar represents an aryl group, and may further have a sulfonate anion and a substituent other than -(DR B ). Examples of the substituent that may be further include a fluorine atom, a hydroxyl group, and the like.
n表示0以上的整數。n較佳為1~4,更佳為2~3,特佳為3。n represents an integer of 0 or more. n is preferably 1 to 4, more preferably 2 to 3, particularly preferably 3.
D表示單鍵或二價連結基。作為該二價連結基,可列舉:醚基、硫醚基、羰基、亞碸基、碸基、磺酸酯基、酯基、及包含該些中的兩種以上的組合的基等。D represents a single bond or a divalent linking group. Examples of the divalent linking group include an ether group, a thioether group, a carbonyl group, an oxalylene group, an oxalyl group, a sulfonate group, an ester group, and a group containing a combination of two or more of these.
RB 表示烴基。R B represents a hydrocarbon group.
較佳為D為單鍵,RB 為脂肪族烴結構。RB 更佳為異丙基或環己基。D is preferably a single bond, R B is an aliphatic hydrocarbon structure. R B is more preferably isopropyl or cyclohexyl.
以下表示式ZI中的鋶陽離子、及式ZII中的錪陽離子的較佳例。The following shows preferred examples of the alium cation in the formula ZI and the iodonium cation in the formula ZII.
[化51] [化51]
[化52] [化52]
以下表示式ZI、式ZII中的陰離子Z- 、式ZI-3中的Zc- 、及式ZI-4中的Z- 的較佳例。 Preferred examples of the anion Z- in formula ZI, formula ZII, Zc - in formula ZI-3, and Z - in formula ZI-4 are shown below.
[化53] [化53]
[化54] [化54]
可將所述陽離子及陰離子任意地組合而用作光酸產生劑(B-1)。The cation and anion can be combined arbitrarily and used as a photoacid generator (B-1).
光酸產生劑(B-1)為包含陽離子及陰離子的離子性化合物,所述陰離子可包含所述式An-1、下述式An-2及下述式An-3中任一者所表示的離子。The photoacid generator (B-1) is an ionic compound containing a cation and an anion, and the anion may include any of the formula An-1, the following formula An-2, and the following formula An-3. Of ions.
[化55] [化55]
式An-2及式An-3中,Rfa分別獨立地表示具有氟原子的一價有機基,多個Rfa可相互鍵結而形成環。In Formula An-2 and Formula An-3, Rfa each independently represents a monovalent organic group having a fluorine atom, and a plurality of Rfa may be bonded to each other to form a ring.
Rfa較佳為經至少一個氟原子取代的烷基。該烷基的碳數較佳為1~10,更佳為1~4。另外,經至少一個氟原子取代的烷基較佳為全氟烷基。 另外,較佳為多個Rfa相互鍵結而形成環。Rfa is preferably an alkyl group substituted with at least one fluorine atom. The number of carbon atoms in the alkyl group is preferably 1-10, more preferably 1-4. In addition, the alkyl group substituted with at least one fluorine atom is preferably a perfluoroalkyl group. In addition, it is preferable that a plurality of Rfa are bonded to each other to form a ring.
光酸產生劑(B-1)可為低分子化合物的形態,亦可為組入至聚合體的一部分中的形態。另外,亦可併用低分子化合物的形態與組入至聚合體的一部分中的形態。 光酸產生劑(B-1)較佳為低分子化合物的形態。 於光酸產生劑(B-1)為低分子化合物的形態的情況下,分子量較佳為3,000以下,更佳為2,000以下,進而佳為1,000以下。 於光酸產生劑(B-1)為組入至聚合體的一部分中的形態的情況下,可組入至所述樹脂(A)的一部分中,亦可組入至與樹脂(A)不同的樹脂中。The photoacid generator (B-1) 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 in combination. The photoacid generator (B-1) is preferably in the form of a low-molecular compound. When the photoacid generator (B-1) is in the form of a low-molecular compound, the molecular weight is preferably 3,000 or less, more preferably 2,000 or less, and still more preferably 1,000 or less. When the photoacid generator (B-1) is incorporated into a part of the polymer, it may be incorporated into a part of the resin (A), or it may be incorporated differently from the resin (A) In the resin.
光酸產生劑(B-1)可單獨使用一種,亦可併用兩種以上。The photoacid generator (B-1) may be used singly, or two or more of them may be used in combination.
光酸產生劑(B-1)於本發明的組成物中的含量(於存在多種的情況下為其合計)以本發明的組成物的總固體成分為基準,較佳為0.1質量%~35質量%,更佳為0.5質量%~25質量%,進而佳為0.5質量%~20質量%,特佳為1.0質量%~20質量%。The content of the photoacid generator (B-1) in the composition of the present invention (the total when there are multiple types) is based on the total solid content of the composition of the present invention, and is preferably 0.1% by mass to 35 % By mass, more preferably 0.5% by mass to 25% by mass, still more preferably 0.5% by mass to 20% by mass, particularly preferably 1.0% by mass to 20% by mass.
<光酸產生劑(B-2)> 本發明的組成物包含光酸產生劑(B-2)。 光酸產生劑(B-2)為藉由光化射線或放射線的照射而產生酸的化合物。 作為光酸產生劑(B-2),較佳為藉由光化射線或放射線的照射而產生有機酸的化合物。例如可列舉:鋶鹽化合物、錪鹽化合物、重氮鎓鹽化合物、鏻鹽化合物、醯亞胺磺酸酯化合物、肟磺酸酯化合物、重氮二碸化合物、二碸化合物、及鄰硝基苄基磺酸酯化合物。<Photoacid generator (B-2)> The composition of the present invention contains a photoacid generator (B-2). The photoacid generator (B-2) is a compound that generates acid by irradiation with actinic rays or radiation. As the photoacid generator (B-2), a compound that generates an organic acid by irradiation with actinic rays or radiation is preferred. Examples include: sulfonium salt compounds, iodonium salt compounds, diazonium salt compounds, phosphonium salt compounds, imine sulfonate compounds, oxime sulfonate compounds, diazonium compounds, disulfide compounds, and o-nitro groups Benzyl sulfonate compound.
光酸產生劑(B-2)較佳為包含陽離子與陰離子的鹽結構的化合物,更佳為下述式d1-1~式d1-3中任一者所表示的化合物。The photoacid generator (B-2) is preferably a compound containing a salt structure of a cation and an anion, and more preferably a compound represented by any one of the following formulas d1-1 to d1-3.
[化56] [化56]
式d1-1~式d1-3中, R51 表示有機基。 Z2c 表示烴基。其中,Z2c 表示的烴基設為於與硫原子鄰接的碳原子上未鍵結有氟原子。 R52 表示有機基,Y3 表示單鍵或二價連結基,Rf表示取代基。R52 與Rf可鍵結而形成環。 M+ 表示銨陽離子、鋶陽離子或錪陽離子。In formula d1-1 to formula d1-3, R 51 represents an organic group. Z 2c represents a hydrocarbon group. However, the hydrocarbon group represented by Z 2c is assumed to have no fluorine atom bonded to the carbon atom adjacent to the sulfur atom. R 52 represents an organic group, Y 3 represents a single bond or a divalent linking group, and Rf represents a substituent. R 52 and Rf may bond to form a ring. M + represents an ammonium cation, a cation or an iodonium cation.
式d1-1中,R51 表示有機基。 作為有機基,並無特別限定,例如可列舉:烷基、烯基、環烷基、芳基、雜環基、醯基、烷氧基羰基、環烷氧基羰基、芳氧基羰基等。In formula d1-1, R 51 represents an organic group. The organic group is not particularly limited, and examples thereof include an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, a heterocyclic group, an acyl group, an alkoxycarbonyl group, a cycloalkoxycarbonyl group, and an aryloxycarbonyl group.
作為烷基,例如可列舉碳數1~20的烷基,可為直鏈狀或分支狀,較佳為碳數1~10的烷基,更佳為碳數1~5的烷基。 作為烯基,例如可列舉碳數2~5的烯基,可為直鏈狀或分支狀,較佳為碳數2~3的烯基。 作為環烷基,例如可列舉碳數3~20的環烷基,較佳為碳數3~10的環烷基。 所述環烷基可於碳-碳鍵之間具有雜原子。作為雜原子,例如可列舉:氧原子、硫原子、氮原子。 作為芳基,例如可列舉碳數6~14的芳基,較佳為碳數6~10的芳基。 雜環基可為單環式,亦可為多環式。多環式可進一步抑制酸的擴散。另外,雜環基可具有芳香族性,亦可不具有芳香族性。作為具有芳香族性的雜環,例如可列舉:呋喃環、噻吩環、苯并呋喃環、苯并噻吩環、二苯并呋喃環、二苯并噻吩環、及吡啶環。作為不具有芳香族性的雜環,例如可列舉:四氫吡喃環、內酯環、磺內酯環及十氫異喹啉環。作為內酯環及磺內酯環的例子,可列舉所述樹脂中例示的內酯結構及磺內酯結構。作為雜環基中的雜環,特佳為呋喃環、噻吩環、吡啶環、或十氫異喹啉環。 作為醯基,例如可列舉碳數1~20的醯基。 作為烷氧基羰基,可列舉於所述烷基取代有氧基羰基的基。 作為環烷氧基羰基,可列舉於所述環烷基取代有氧基羰基的基。 作為芳氧基羰基,可列舉於所述芳基取代有氧基羰基的基。Examples of the alkyl group include an alkyl group having 1 to 20 carbon atoms, which may be linear or branched, preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 5 carbon atoms. Examples of the alkenyl group include alkenyl groups having 2 to 5 carbon atoms, which may be linear or branched, and are preferably alkenyl groups having 2 to 3 carbon atoms. The cycloalkyl group includes, for example, a cycloalkyl group having 3 to 20 carbon atoms, and a cycloalkyl group having 3 to 10 carbon atoms is preferred. The cycloalkyl group may have a heteroatom between the carbon-carbon bond. As a hetero atom, an oxygen atom, a sulfur atom, and a nitrogen atom are mentioned, for example. Examples of the aryl group include an aryl group having 6 to 14 carbon atoms, and an aryl group having 6 to 10 carbon atoms is preferred. The heterocyclic group may be monocyclic or polycyclic. The polycyclic type can further inhibit the diffusion of acid. In addition, the heterocyclic group may be aromatic or not. Examples of the heterocyclic ring having aromaticity include a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, and a pyridine ring. Examples of the heterocyclic ring having no aromaticity include a tetrahydropyran ring, a lactone ring, a sultone ring, and a decahydroisoquinoline ring. Examples of the lactone ring and the sultone ring include the lactone structure and the sultone structure exemplified in the resin. The heterocyclic ring in the heterocyclic group is particularly preferably a furan ring, a thiophene ring, a pyridine ring, or a decahydroisoquinoline ring. As an acyl group, a C1-C20 acyl group is mentioned, for example. Examples of the alkoxycarbonyl group include those in which the alkyl group is substituted with an oxycarbonyl group. Examples of the cycloalkoxycarbonyl group include groups in which the cycloalkyl group is substituted with an oxycarbonyl group. Examples of the aryloxycarbonyl group include groups in which the aryl group is substituted with an oxycarbonyl group.
所述烷基、烷基、烯基、環烷基、芳基、雜環基、醯基、烷氧基羰基、環烷氧基羰基、及芳氧基羰基可進而具有取代基。作為取代基,例如可列舉所述取代基T。The alkyl group, alkyl group, alkenyl group, cycloalkyl group, aryl group, heterocyclic group, acyl group, alkoxycarbonyl group, cycloalkoxycarbonyl group, and aryloxycarbonyl group may further have a substituent. As a substituent, the said substituent T is mentioned, for example.
式d1-2中,Z2c 表示烴基。 Z2c 表示的烴基可具有取代基。作為取代基,例如可列舉所述取代基T。 Z2c 表示的烴基可於碳-碳鍵之間具有雜原子。作為雜原子,例如可列舉:氧原子、氮原子、硫原子等。 Z2c 表示的烴基並無特別限定,例如較佳為下述式An-2所表示的基。In the formula d1-2, Z 2c represents a hydrocarbon group. The hydrocarbon group represented by Z 2c may have a substituent. As a substituent, the said substituent T is mentioned, for example. The hydrocarbon group represented by Z 2c may have a hetero atom between the carbon-carbon bond. As a hetero atom, an oxygen atom, a nitrogen atom, a sulfur atom, etc. are mentioned, for example. The hydrocarbon group represented by Z 2c is not particularly limited, but is preferably a group represented by the following formula An-2, for example.
[化57] [化57]
式An-2中,pf表示0~10的整數,qf表示0~10的整數,tf表示0~3的整數,R40 及R50 分別獨立地表示氫原子或有機基,於tf為2以上的整數的情況下,多個-CR40 R50 -可分別相同亦可不同,R4f 及R5f 分別獨立地表示氫原子、氟原子、烷基、或經至少一個氟原子取代的烷基,於pf為2以上的整數的情況下,多個-CR4f R5f -可分別相同亦可不同,Lf 表示二價連結基,於qf為2以上的整數的情況下,多個Lf 可分別相同亦可不同,W表示有機基。*表示鍵結位置。其中,式An-2所表示的基設為於與式d1-2中的硫原子鍵結的碳原子上未鍵結有氟原子。In the formula An-2, pf represents an integer from 0 to 10, qf represents an integer from 0 to 10, tf represents an integer from 0 to 3, R 40 and R 50 each independently represent a hydrogen atom or an organic group, and tf is 2 or more In the case of an integer of, a plurality of -CR 40 R 50 -may be the same or different, and R 4f and R 5f each independently represent a hydrogen atom, a fluorine atom, an alkyl group, or an alkyl group substituted with at least one fluorine atom, When pf is an integer of 2 or more, a plurality of -CR 4f R 5f -may be the same or different, respectively, L f represents a divalent linking group, and when qf is an integer of 2 or more, a plurality of L f may be They may be the same or different, and W represents an organic group. * Indicates the position of the bond. However, the group represented by the formula An-2 is set to a carbon atom that is bonded to the sulfur atom in the formula d1-2, and a fluorine atom is not bonded.
R40 及R50 分別獨立地表示氫原子或有機基,較佳為表示氫原子。作為有機基,可列舉與所述R51 相同的有機基。R 40 and R 50 each independently represent a hydrogen atom or an organic group, and preferably represent a hydrogen atom. As the organic group, the same organic group as the above- mentioned R 51 can be mentioned.
式An-2中,pf、qf、R4f 、R5f 、Lf 、及W分別與所述式An-1中的pf、qf、R4f 、R5f 、Lf 、及W相同。In the formula An-2, pf, qf, R 4f, R 5f, L f, and W are of the formula in 1 An-pf, qf, R 4f, R 5f, L f, and W the same.
式d1-3中,R52 表示有機基。作為有機基,可列舉與所述R51 相同的有機基。In formula d1-3, R 52 represents an organic group. As the organic group, the same organic group as the above- mentioned R 51 can be mentioned.
式d1-3中,Y3 表示單鍵或二價連結基。作為二價連結基,例如可列舉:伸烷基、伸環烷基、伸芳基、-O-、-CO-、-COO-、-OCO-、-SO2 -、及將該些的兩種以上的基組合而成的基。 所述伸烷基例如較佳為碳數1~10。另外,更佳為碳數1或2,作為碳數1或2的伸烷基,例如較佳為亞甲基或伸乙基。 所述伸烷基可為直鏈狀亦可為分支鏈狀,例如可列舉:亞甲基、乙烷-1,1-二基、乙烷-1,2-二基、丙烷-1,1-二基、丙烷-1,3-二基、丙烷-2,2-二基、戊烷-1,5-二基、己烷-1,6-二基等。 所述伸環烷基例如較佳為碳數5~10,另外,更佳為碳數5或6。 所述伸環烷基例如可列舉:伸環戊基、伸環己基、伸環庚基、伸環辛基、伸環癸基等。 所述伸芳基例如較佳為碳數6~10。 所述伸芳基例如可列舉伸苯基、伸萘基等。In formula d1-3, Y 3 represents a single bond or a divalent linking group. As the divalent linking group, for example, an alkylene group, a cycloalkylene group, an arylene group, -O-, -CO-, -COO-, -OCO-, -SO 2 -, and two of these A combination of more than one group. The alkylene group preferably has 1 to 10 carbon atoms, for example. In addition, it is more preferably a carbon number of 1 or 2. As the alkylene group having a carbon number of 1 or 2, for example, a methylene group or an ethylene group is preferable. The alkylene group may be linear or branched, for example: methylene, ethane-1,1-diyl, ethane-1,2-diyl, propane-1,1 -Diyl, propane-1,3-diyl, propane-2,2-diyl, pentane-1,5-diyl, hexane-1,6-diyl, etc. The cycloalkylene group preferably has 5 to 10 carbon atoms, and more preferably has 5 or 6 carbon atoms. Examples of the cycloalkylene group include cyclopentyl group, cyclohexylene group, cycloheptyl group, cyclooctyl group, cyclodecylene group and the like. The arylene group preferably has 6 to 10 carbon atoms, for example. Examples of the arylene group include phenylene group, naphthylene group, and the like.
式d1-3中,Rf表示取代基。作為取代基,較佳為有機基。作為有機基,可列舉與所述R51 相同的有機基。Rf較佳為表示包含氟原子的烴基,更佳為表示氟烷基,進而佳為表示碳數1~5的氟烷基。In formula d1-3, Rf represents a substituent. As the substituent, an organic group is preferred. As the organic group, the same organic group as the above- mentioned R 51 can be mentioned. Rf preferably represents a hydrocarbon group containing a fluorine atom, more preferably represents a fluoroalkyl group, and still more preferably represents a fluoroalkyl group having 1 to 5 carbon atoms.
式d1-1~式d1-3中,M+ 表示銨陽離子、鋶陽離子或錪陽離子。M+ 表示鋶陽離子時的較佳態樣與作為所述光酸產生劑(B-1)的較佳態樣而記載的式ZI中的鋶陽離子相同。M+ 表示錪陽離子時的較佳態樣與作為所述光酸產生劑(B-1)的較佳態樣而記載的式ZII中的錪陽離子相同。M+ 表示銨陽離子時的較佳態樣可列舉四級銨陽離子,較佳為四個碳數1~10的烷基進行了取代的銨陽離子。In formula d1-1 to formula d1-3, M + represents an ammonium cation, a cation or an iodonium cation. A preferable aspect when M + represents a cation is the same as the cation in the formula ZI described as a preferable aspect of the photoacid generator (B-1). A preferable aspect when M + represents an iodonium cation is the same as the iodonium cation in the formula ZII described as a preferable aspect of the photoacid generator (B-1). A preferable aspect when M + represents an ammonium cation includes a quaternary ammonium cation, preferably an ammonium cation in which four alkyl groups having 1 to 10 carbon atoms are substituted.
光酸產生劑(B-2)亦可為於同一分子內具有陽離子部位與陰離子部位、且所述陽離子部位與陰離子部位藉由共價鍵而連結的化合物。作為此種態樣的光酸產生劑(B-2),較佳為下述式C-1~式C-3的任一者所表示的化合物。The photoacid generator (B-2) may be a compound having a cation site and an anion site in the same molecule, and the cation site and anion site are linked by a covalent bond. As a photoacid generator (B-2) of this aspect, the compound represented by any one of following formula C-1-formula C-3 is preferable.
[化58] [化58]
式C-1~式C-3中, R1 、R2 、及R3 分別獨立地表示有機基。 L1 表示將陽離子部位與陰離子部位連結的二價連結基或單鍵。 -X- 表示選自-COO- 、-SO3 - 、-SO2 - 、及-N- -R4 中的陰離子部位。R4 表示於與鄰接的氮原子的連結部位具有羰基、磺醯基、及亞磺醯基中至少一者的一價取代基。 R1 、R2 、R3 、R4 、及L1 可相互鍵結而形成環結構。另外,式C-3中,將R1 ~R3 中的兩個合併而表示一個二價取代基,可藉由雙鍵而與氮原子鍵結。In formula C-1 to formula C-3, R 1 , R 2 , and R 3 each independently represent an organic group. L 1 represents a divalent linking group or a single bond connecting a cation site and an anion site. -X - represents a group selected -COO -, -SO 3 -, -SO 2 -, and -N - anionic sites in -R 4. R 4 represents a monovalent substituent having at least one of a carbonyl group, a sulfinyl group, and a sulfinyl group at the connection site to the adjacent nitrogen atom. R 1 , R 2 , R 3 , R 4 , and L 1 may be bonded to each other to form a ring structure. In addition, in formula C-3, two of R 1 to R 3 are combined to represent one divalent substituent, which can be bonded to a nitrogen atom by a double bond.
式C-1~式C-3中,R1 、R2 、及R3 分別獨立地表示有機基。 作為R1 ~R3 中的有機基,可列舉:烷基、環烷基、芳基、烷氧基羰基、環烷氧基羰基、芳氧基羰基、烷基胺基羰基、環烷基胺基羰基、及芳基胺基羰基等。較佳為烷基、環烷基、或芳基。In formula C-1 to formula C-3, R 1 , R 2 , and R 3 each independently represent an organic group. Examples of the organic groups in R 1 to R 3 include alkyl groups, cycloalkyl groups, aryl groups, alkoxycarbonyl groups, cycloalkoxycarbonyl groups, aryloxycarbonyl groups, alkylaminocarbonyl groups, and cycloalkylamines. Carbonyl, and arylaminocarbonyl, etc. Preferably, it is an alkyl group, a cycloalkyl group, or an aryl group.
作為二價連結基的L1 可列舉:直鏈或分支鏈狀伸烷基、伸環烷基、伸芳基、羰基、醚鍵、酯鍵、醯胺鍵、胺基甲酸酯鍵、脲鍵、及將該些的兩種以上組合而成的基等。L1 較佳為伸烷基、伸芳基、醚鍵、酯鍵、或將該些的兩種以上組合而成的基。 Examples of L 1 as the divalent linking group include linear or branched alkylene, cycloalkylene, arylene, carbonyl, ether bond, ester bond, amide bond, urethane bond, urea A bond, and a base formed by combining two or more of these. L 1 is preferably an alkylene group, an arylene group, an ether bond, an ester bond, or a combination of two or more of these.
光酸產生劑(B-2)可為低分子化合物的形態,亦可為組入至聚合體的一部分中的形態。另外,亦可併用低分子化合物的形態與組入至聚合體的一部分中的形態。 光酸產生劑(B-2)較佳為低分子化合物的形態。 於光酸產生劑(B-2)為低分子化合物的形態的情況下,分子量較佳為3,000以下,更佳為2,000以下,進而佳為1,000以下。 於光酸產生劑(B-2)為組入至聚合體的一部分中的形態的情況下,可組入至所述樹脂(A)的一部分中,亦可組入至與樹脂(A)不同的樹脂中。The photoacid generator (B-2) 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 in combination. The photoacid generator (B-2) is preferably in the form of a low-molecular compound. When the photoacid generator (B-2) is in the form of a low-molecular compound, the molecular weight is preferably 3,000 or less, more preferably 2,000 or less, and still more preferably 1,000 or less. When the photoacid generator (B-2) is incorporated into a part of the polymer, it may be incorporated into a part of the resin (A), or it may be incorporated differently from the resin (A) In the resin.
光酸產生劑(B-2)可單獨使用一種,亦可併用兩種以上。The photoacid generator (B-2) may be used alone or in combination of two or more.
相對於光酸產生劑(B-1)的含量,光酸產生劑(B-2)的含量為0.001質量%以上且0.10質量%以下,較佳為0.005質量%以上且0.10質量%以下,更佳為0.01質量%以上且0.10質量%以下,進而佳為0.05質量%以上且0.10質量%以下。The content of the photoacid generator (B-2) relative to the content of the photoacid generator (B-1) is 0.001 mass% or more and 0.10 mass% or less, preferably 0.005 mass% or more and 0.10 mass% or less, more Preferably it is 0.01 mass% or more and 0.10 mass% or less, More preferably, it is 0.05 mass% or more and 0.10 mass% or less.
以下表示光酸產生劑(B-2)的具體例,但本發明並不限定於該些。The specific examples of the photoacid generator (B-2) are shown below, but the present invention is not limited to these.
[化59] [化59]
[化60] [化60]
[化61] [化61]
[化62] [化62]
<酸擴散控制劑(D)> 本發明的感光化射線性或感放射線性樹脂組成物含有酸擴散控制劑(D)。 酸擴散控制劑(D)作為如下淬滅劑發揮作用,所述淬滅劑捕獲曝光時自光酸產生劑等所產生的酸,抑制多餘的產生酸所引起的未曝光部中的酸分解性樹脂的反應。例如可使用鹼性化合物(DA)、藉由光化射線或放射線的照射而鹼性降低或消失的鹼性化合物(DB)、具有氮原子且具有藉由酸的作用而脫離的基的低分子化合物(DD)、或者於陽離子部具有氮原子的鎓鹽化合物(DE)等作為酸擴散控制劑(D)。 其中,本發明的感光化射線性或感放射線性樹脂組成物較佳為包含含氮化合物作為酸擴散控制劑(D),更佳為包含含氮鹼性化合物。 於本發明的感光化射線性或感放射線性樹脂組成物中,可適宜使用公知的酸擴散控制劑。例如,可較佳地使用美國專利申請案公開第2016/0070167號說明書的段落0627~段落0664、美國專利申請案公開第2015/0004544號說明書的段落0095~段落0187、美國專利申請案公開第2016/0237190號說明書的段落0403~段落0423、美國專利申請案公開第2016/0274458號說明書的段落0259~段落0328中所揭示的公知的化合物作為酸擴散控制劑(D)。<Acid diffusion control agent (D)> The actinic radiation-sensitive or radiation-sensitive resin composition of the present invention contains an acid diffusion control agent (D). The acid diffusion control agent (D) functions as a quencher that captures acid generated from a photoacid generator during exposure, and suppresses the acid decomposability in the unexposed portion caused by excess acid generation The reaction of the resin. For example, a basic compound (DA), a basic compound (DB) whose basicity decreases or disappears by irradiation with actinic rays or radiation, and a low-molecular molecule having a nitrogen atom and a group detached by the action of an acid can be used. A compound (DD) or an onium salt compound (DE) having a nitrogen atom in the cation part is used as the acid diffusion control agent (D). Among them, the actinic radiation-sensitive or radiation-sensitive resin composition of the present invention preferably contains a nitrogen-containing compound as the acid diffusion control agent (D), and more preferably contains a nitrogen-containing basic compound. In the sensitizing radiation-sensitive or radiation-sensitive resin composition of the present invention, a known acid diffusion control agent can be suitably used. For example, paragraphs 0627 to 0664 of U.S. Patent Application Publication No. 2016/0070167, paragraphs 0095 to 0187 of U.S. Patent Application Publication No. 2015/0004544, and U.S. Patent Application Publication No. 2016 The well-known compounds disclosed in paragraphs 0403 to 0423 of the specification /0237190 and paragraphs 0259 to 0328 of the specification of U.S. Patent Application Publication No. 2016/0274458 are used as the acid diffusion control agent (D).
〔鹼性化合物(DA)〕 作為鹼性化合物(DA),較佳為可列舉具有下述式(D1)~式(D5)的任一者所表示的結構的化合物。〔Basic Compound (DA)〕 As the basic compound (DA), preferably, a compound having a structure represented by any one of the following formulas (D1) to (D5) is mentioned.
[化63] [化63]
式(D1)及式(D5)中, R200 、R201 及R202 分別獨立地表示氫原子、烷基、環烷基或芳基。R201 與R202 可相互鍵結而形成環。 R203 、R204 、R205 及R206 分別獨立地表示烷基。In formula (D1) and formula (D5), R 200 , R 201 and R 202 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group. R 201 and R 202 may be bonded to each other to form a ring. R 203 , R 204 , R 205 and R 206 each independently represent an alkyl group.
於R200 、R201 及R202 表示烷基的情況下,例如可列舉碳數1~20的烷基,可為直鏈狀或分支狀。關於所述烷基,作為具有取代基的烷基,較佳為碳數1~20的胺基烷基、碳數1~20的羥基烷基、或碳數1~20的氰基烷基。 R203 、R204 、R205 及R206 表示的烷基的具體例及較佳範圍與R200 、R201 及R202 表示烷基時的烷基相同。R203 、R204 、R205 及R206 可相同亦可不同。 式(D1)及式(D5)中的烷基更佳為未經取代。When R 200 , R 201, and R 202 represent an alkyl group, for example, an alkyl group having 1 to 20 carbon atoms may be mentioned, and it may be linear or branched. As for the alkyl group, the alkyl group having a substituent is preferably an aminoalkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms, or a cyanoalkyl group having 1 to 20 carbon atoms. The specific examples and preferred ranges of the alkyl group represented by R 203 , R 204 , R 205 and R 206 are the same as the alkyl group when R 200 , R 201 and R 202 represent an alkyl group. R 203 , R 204 , R 205 and R 206 may be the same or different. The alkyl group in formula (D1) and formula (D5) is more preferably unsubstituted.
於R200 、R201 及R202 表示環烷基的情況下,例如可列舉碳數3~20的環烷基。When R 200 , R 201 and R 202 represent a cycloalkyl group, for example, a cycloalkyl group having 3 to 20 carbon atoms can be cited.
於R200 、R201 及R202 表示芳基的情況下,例如可列舉碳數6~20的芳基。When R 200 , R 201 and R 202 represent an aryl group, for example, an aryl group having 6 to 20 carbon atoms can be cited.
作為鹼性化合物(DA),較佳為胍、胺基吡咯啶、吡唑、吡唑啉、哌嗪、胺基嗎啉、胺基烷基嗎啉、或哌啶等,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。As the basic compound (DA), guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine, piperidine, etc. are preferred, and imidazole is more preferred. Structure, diazabicyclic structure, onium hydroxide structure, onium carboxylate structure, trialkylamine structure, aniline structure or pyridine structure compound, alkylamine derivative with hydroxyl group and/or ether bond, or hydroxyl group And/or aniline derivatives of ether linkages, etc.
〔藉由光化射線或放射線的照射而鹼性降低或消失的鹼性化合物(DB)〕 藉由光化射線或放射線的照射而鹼性降低或消失的鹼性化合物(DB)(以下,亦稱為「化合物(DB)」)為如下化合物:具有質子受體性官能基,且藉由光化射線或放射線的照射進行分解而質子受體性降低、消失、或自質子受體性變化為酸性。[Basic compound (DB) whose alkalinity decreases or disappears by irradiation with actinic rays or radiation] The basic compound (DB) (hereinafter, also referred to as "compound (DB)") whose basicity decreases or disappears by irradiation with actinic rays or radiation is a compound that has a proton-accepting functional group and is Irradiation of actinic rays or radiation decomposes and the proton acceptor property decreases, disappears, or the proton acceptor property changes to acidity.
所謂質子受體性官能基,是具有可與質子發生靜電相互作用的基或電子的官能基,例如是指環狀聚醚等具有巨環結構的官能基、或含有具有無助於π共軛的非共價電子對的氮原子的官能基。所謂具有無助於π共軛的非共價電子對的氮原子,例如為具有下述式所表示的部分結構的氮原子。The so-called proton-accepting functional group is a functional group having a group or electrons that can interact with protons electrostatically. For example, it refers to a functional group having a macrocyclic structure such as a cyclic polyether, or a functional group that does not contribute to π conjugation. The non-covalent electron pair is the functional group of the nitrogen atom. The nitrogen atom having a non-covalent electron pair that does not contribute to π conjugation is, for example, a nitrogen atom having a partial structure represented by the following formula.
[化64] [化64]
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~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 to tertiary amine structure, a pyridine structure, an imidazole structure, and a pyrazine structure.
化合物(DB)藉由光化射線或放射線的照射進行分解而產生質子受體性降低或消失、或者自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、或者自質子受體性變化為酸性,是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(DB)與質子生成質子加成物時,其化學平衡中的平衡常數減少。 質子受體性可藉由進行pH測定來確認。The compound (DB) is decomposed by irradiation with actinic rays or radiation to produce a compound in which the proton acceptor property decreases or disappears, or the proton acceptor property changes to acidity. Here, the decrease or disappearance of proton acceptor, or the change from proton acceptor to acidity, is the change in proton acceptor caused by the addition of protons to the proton acceptor functional group. Specifically, it is It means that when a compound having a proton-accepting functional group (DB) and a proton generate a proton adduct, the equilibrium constant in the chemical equilibrium decreases. The proton acceptability can be confirmed by performing a pH measurement.
藉由光化射線或放射線的照射而化合物(DB)分解所產生的化合物的酸解離常數pKa較佳為滿足pKa<-1,更佳為-13<pKa<-1,進而佳為-13<pKa<-3。The acid dissociation constant pKa of the compound produced by the decomposition of the compound (DB) by irradiation with actinic rays or radiation preferably satisfies pKa<-1, more preferably -13<pKa<-1, and more preferably -13< pKa<-3.
所謂酸解離常數pKa表示於水溶液中的酸解離常數pKa,例如由化學便覽(II)(修訂4版,1993年,日本化學會編,丸善股份有限公司)定義。酸解離常數pKa的值越低,表示酸強度越大。具體而言,於水溶液中的酸解離常數pKa可藉由使用無限稀釋水溶液,測定25℃下的酸解離常數來實測。或者,亦可使用下述軟體包1,藉由計算來求出基於哈米特取代基常數及公知文獻值的資料庫的值。本說明書中記載的pKa的值全部表示使用該軟體包,藉由計算來求出的值。The so-called acid dissociation constant pKa represents the acid dissociation constant pKa in an aqueous solution, and is defined, for example, by the Handbook of Chemistry (II) (Revised 4th edition, 1993, The Chemical Society of Japan, Maruzen Co., Ltd.). The lower the value of the acid dissociation constant pKa, the greater the acid strength. Specifically, the acid dissociation constant pKa in an aqueous solution can be measured by measuring the acid dissociation constant at 25° C. using an infinitely diluted aqueous solution. Alternatively, the following software package 1 can also be used to obtain the value of the database based on the Hammett's substituent constant and publicly known literature values by calculation. The values of pKa described in this manual all indicate values obtained by calculations using this 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).
〔具有氮原子且具有藉由酸的作用而脫離的基的低分子化合物(DD)〕 具有氮原子且具有藉由酸的作用而脫離的基的低分子化合物(DD)(以下,亦稱為「化合物(DD)」)較佳為於氮原子上具有藉由酸的作用而脫離的基的胺衍生物。 作為藉由酸的作用而脫離的基,較佳為縮醛基、碳酸酯基、胺甲酸酯基、三級酯基、三級羥基、或半胺縮醛醚基,更佳為胺甲酸酯基、或半胺縮醛醚基。 化合物(DD)的分子量較佳為100~1000,更佳為100~700,進而佳為100~500。 化合物(DD)可於氮原子上具有含有保護基的胺甲酸酯基。作為構成胺甲酸酯基的保護基,可由下述式d-1表示。[Low-molecular compound (DD) having a nitrogen atom and a group detached by the action of an acid] The low-molecular compound (DD) having a nitrogen atom and a group that is released by the action of an acid (hereinafter, also referred to as "compound (DD)") preferably has a nitrogen atom that is released by the action of an acid -Based amine derivatives. The group to be released by the action of an acid is preferably an acetal group, a carbonate group, a urethane group, a tertiary ester group, a tertiary hydroxyl group, or a semiamine acetal ether group, and more preferably a urethane group Ester group, or semiamine acetal ether group. The molecular weight of the compound (DD) is preferably 100-1000, more preferably 100-700, and still more preferably 100-500. The compound (DD) may have a urethane group containing a protective group on the nitrogen atom. The protecting group constituting the urethane group can be represented by the following formula d-1.
[化65] [化65]
式d-1中, Rb 分別獨立地表示氫原子、烷基(較佳為碳數1~10)、環烷基(較佳為碳數3~30)、芳基(較佳為碳數3~30)、芳烷基(較佳為碳數1~10)、或烷氧基烷基(較佳為碳數1~10)。Rb 可相互連結而形成環。 Rb 表示的烷基、環烷基、芳基、及芳烷基可分別獨立地經羥基、氰基、胺基、吡咯啶基、哌啶基、嗎啉基、側氧基等官能基、烷氧基、或鹵素原子取代。關於Rb 表示的烷氧基烷基亦同樣。In formula d-1, R b each independently represents a hydrogen atom, an alkyl group (preferably carbon number 1-10), cycloalkyl group (preferably carbon number 3-30), aryl group (preferably carbon number 3-30), aralkyl (preferably carbon number 1-10), or alkoxyalkyl (preferably carbon number 1-10). R b may be connected to each other to form a ring. The alkyl group, cycloalkyl group, aryl group, and aralkyl group represented by R b can be independently passed through functional groups such as hydroxyl, cyano, amino, pyrrolidinyl, piperidinyl, morpholinyl, and pendant oxy groups. Alkoxy or halogen atom substitution. The same applies to the alkoxyalkyl group represented by R b.
作為Rb ,較佳為直鏈狀或分支狀的烷基、環烷基、或者芳基,更佳為直鏈狀或分支狀的烷基、或者環烷基。 作為兩個Rb 相互連結而形成的環,可列舉:脂環式烴、芳香族烴、雜環式烴及其衍生物等。 作為式d-1所表示的基的具體結構,可列舉美國專利申請案公開第2012/0135348號說明書的段落0466中所揭示的結構,但並不限定於此。As R b , a linear or branched alkyl group, a cycloalkyl group, or an aryl group is preferable, and a linear or branched alkyl group or a cycloalkyl group is more preferable. Examples of the ring formed by connecting two R b to each other include alicyclic hydrocarbons, aromatic hydrocarbons, heterocyclic hydrocarbons, and derivatives thereof. As a specific structure of the group represented by formula d-1, the structure disclosed in paragraph 0466 of the specification of U.S. Patent Application Publication No. 2012/0135348 can be cited, but it is not limited to this.
化合物(DD)較佳為具有下述式6所表示的結構。The compound (DD) preferably has a structure represented by Formula 6 below.
[化66] [化66]
式6中, l表示0~2的整數,m表示1~3的整數,滿足l+m=3。 Ra 表示氫原子、烷基、環烷基、芳基或芳烷基。於l為2時,兩個Ra 可相同亦可不同,兩個Ra 可相互連結並與式中的氮原子一起形成雜環。可於該雜環中包含式中的氮原子以外的雜原子。 Rb 與所述式d-1中的Rb 為相同含義,較佳例亦相同。 式6中,作為Ra 的烷基、環烷基、芳基、及芳烷基可分別獨立地經如下基取代,所述基與關於作為Rb 的烷基、環烷基、芳基、及芳烷基可進行取代的基而所述的基相同。In Formula 6, l represents an integer from 0 to 2, and m represents an integer from 1 to 3, and satisfies l+m=3. R a represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group. When 1 is 2, two Ras may be the same or different, and two Ras may be connected to each other and form a heterocyclic ring together with the nitrogen atom in the formula. Heteroatoms other than the nitrogen atom in the formula may be included in the heterocyclic ring. R b in the formula 1 d-R b in the same sense, the preferred embodiments are also the same. In Formula 6, the alkyl group, cycloalkyl group, aryl group, and aralkyl group as R a may be independently substituted with a group that is the same as the alkyl group, cycloalkyl group, aryl group, and aryl group as R b. And the aralkyl group may be substituted, and the groups are the same.
作為所述Ra 的烷基、環烷基、芳基、及芳烷基(該些基可經所述基取代)的具體例,可列舉與關於Rb 而所述的具體例相同的基。 作為本發明中特佳的化合物(DD)的具體的結構,可列舉美國專利申請案公開第2012/0135348號說明書的段落0475中所揭示的化合物,但並不限定於此。Specific examples of the above R a is alkyl, cycloalkyl, aryl, and aralkyl groups (the group may be substituted with those of the group) include the specific examples of R b and on the same base . As the specific structure of the particularly preferred compound (DD) in the present invention, the compound disclosed in paragraph 0475 of the specification of U.S. Patent Application Publication No. 2012/0135348 can be cited, but it is not limited to this.
於陽離子部具有氮原子的鎓鹽化合物(DE)(以下,亦稱為「化合物(DE)」)較佳為於陽離子部具有包含氮原子的鹼性部位的化合物。鹼性部位較佳為胺基,更佳為脂肪族胺基。進而佳為鹼性部位中的與氮原子鄰接的原子全部為氫原子或碳原子。另外,就鹼性提高的觀點而言,較佳為拉電子性的官能基(羰基、磺醯基、氰基、及鹵素原子等)不直接鍵結於氮原子。 作為化合物(DE)的較佳的具體的結構,可列舉美國專利申請案公開第2015/0309408號說明書的段落0203中所揭示的化合物,但並不限定於此。The onium salt compound (DE) having a nitrogen atom in the cation part (hereinafter also referred to as "compound (DE)") is preferably a compound having a basic part including a nitrogen atom in the cation part. The basic part is preferably an amine group, and more preferably an aliphatic amine group. More preferably, all atoms adjacent to the nitrogen atom in the basic site are hydrogen atoms or carbon atoms. In addition, from the viewpoint of improving basicity, it is preferable that the electron-withdrawing functional group (carbonyl group, sulfonyl group, cyano group, halogen atom, etc.) is not directly bonded to the nitrogen atom. As a preferable specific structure of the compound (DE), the compound disclosed in paragraph 0203 of the specification of U.S. Patent Application Publication No. 2015/0309408 can be cited, but it is not limited to this.
以下表示其他酸擴散控制劑的較佳例。The following shows preferred examples of other acid diffusion control agents.
[化67] [化67]
[化68] [化68]
[化69] [化69]
於本發明的感光化射線性或感放射線性樹脂組成物中,酸擴散控制劑(D)可單獨使用一種,亦可併用兩種以上。 酸擴散控制劑(D)於本發明的組成物中的含量(於存在多種的情況下為其合計)以本發明的組成物的總固體成分為基準,較佳為0.01質量%~10質量%,更佳為0.01質量%~5質量%。In the sensitizing radiation-sensitive or radiation-sensitive resin composition of the present invention, the acid diffusion control agent (D) may be used alone or in combination of two or more kinds. The content of the acid diffusion control agent (D) in the composition of the present invention (the total when there are multiple types) is based on the total solid content of the composition of the present invention, and is preferably 0.01% by mass to 10% by mass , More preferably 0.01% by mass to 5% by mass.
相對於光酸產生劑(B-1)的含量,酸擴散控制劑(D)的含量較佳為0.5質量%以上且10.0質量%以下,更佳為1.0質量%以上且7.0質量%以下,進而佳為1.5質量%以上且5.0質量%以下。Relative to the content of the photoacid generator (B-1), the content of the acid diffusion control agent (D) is preferably 0.5% by mass or more and 10.0% by mass or less, more preferably 1.0% by mass or more and 7.0% by mass or less, and further Preferably, it is 1.5% by mass or more and 5.0% by mass or less.
<溶劑> 本發明的感光化射線性或感放射線性樹脂組成物較佳為包含溶劑(亦稱為「溶劑(F)」),更佳為包含有機溶劑。 於本發明的感光化射線性或感放射線性樹脂組成物中,可適宜使用公知的抗蝕劑溶劑。例如可較佳地使用美國專利申請案公開第2016/0070167號說明書的段落0665~段落0670、美國專利申請案公開第2015/0004544號說明書的段落0210~段落0235、美國專利申請案公開第2016/0237190號說明書的段落0424~段落0426、美國專利申請案公開第2016/0274458號說明書的段落0357~段落0366中所揭示的公知的溶劑。 作為製備組成物時可使用的溶劑,例如可列舉:烷二醇單烷基醚羧酸酯、烷二醇單烷基醚、乳酸烷基酯、烷氧基丙酸烷基酯、環狀內酯(較佳為碳數4~10)、可具有環的單酮化合物(較佳為碳數4~10)、碳酸伸烷基酯、烷氧基乙酸烷基酯、及丙酮酸烷基酯等有機溶劑。<Solvent> The sensitizing radiation-sensitive or radiation-sensitive resin composition of the present invention preferably contains a solvent (also referred to as "solvent (F)"), and more preferably contains an organic solvent. In the sensitizing radiation-sensitive or radiation-sensitive resin composition of the present invention, a known resist solvent can be suitably used. For example, paragraphs 0665 to 0670 of U.S. Patent Application Publication No. 2016/0070167, paragraphs 0210 to 0235 of U.S. Patent Application Publication No. 2015/0004544, and U.S. Patent Application Publication No. 2016/ A well-known solvent disclosed in paragraph 0424 to paragraph 0426 of specification 0237190, and paragraph 0357 to paragraph 0366 of specification U.S. Patent Application Publication No. 2016/0274458. Examples of solvents that can be used when preparing the composition include: alkanediol monoalkyl ether carboxylate, alkanediol monoalkyl ether, alkyl lactate, alkyl alkoxypropionate, cyclic internal Esters (preferably carbon number 4-10), monoketone compounds that may have a ring (preferably carbon number 4-10), alkylene carbonate, alkyl alkoxy acetate, and alkyl pyruvate And other organic solvents.
作為有機溶劑,亦可使用將結構中含有羥基的溶劑與不含有羥基的溶劑混合而成的混合溶劑。 作為含有羥基的溶劑、及不含有羥基的溶劑,可適宜選擇所述的例示化合物,作為含有羥基的溶劑,較佳為烷二醇單烷基醚、或乳酸烷基酯等,更佳為丙二醇單甲醚(PGME(propylene glycol monomethyl ether):1-甲氧基-2-丙醇)、丙二醇單***(propylene glycol monoethyl ether,PGEE)、2-羥基異丁酸甲酯、或乳酸乙酯。另外,作為不含有羥基的溶劑,較佳為烷二醇單烷基醚乙酸酯、烷基烷氧基丙酸酯、可含有環的單酮化合物、環狀內酯、或乙酸烷基酯等,該些中,更佳為丙二醇單甲醚乙酸酯(PGMEA(propylene glycol monomethyl ether acetate):1-甲氧基-2-乙醯氧基丙烷)、乙基乙氧基丙酸酯、2-庚酮、γ-丁內酯、環己酮、環戊酮或乙酸丁酯,進而佳為丙二醇單甲醚乙酸酯、γ-丁內酯、乙基乙氧基丙酸酯、環己酮、環戊酮或2-庚酮。作為不含有羥基的溶劑,亦較佳為碳酸伸丙酯。該些中,就所形成的層的均勻性的觀點而言,溶劑特佳為包含γ-丁內酯。 含有羥基的溶劑與不含有羥基的溶劑的混合比(質量比)為1/99~99/1,較佳為10/90~90/10,更佳為20/80~60/40。就塗佈均勻性的方面而言,較佳為含有50質量%以上的不含有羥基的溶劑的混合溶劑。 溶劑較佳為包含丙二醇單甲醚乙酸酯,可為丙二醇單甲醚乙酸酯單一溶劑,亦可為含有丙二醇單甲醚乙酸酯的兩種以上的混合溶劑。As the organic solvent, a mixed solvent obtained by mixing a solvent containing a hydroxyl group and a solvent not containing a hydroxyl group in the structure can also be used. As a solvent containing a hydroxyl group and a solvent not containing a hydroxyl group, the exemplified compounds can be appropriately selected. As the solvent containing a hydroxyl group, an alkanediol monoalkyl ether, an alkyl lactate, etc. are preferred, and propylene glycol is more preferred. Monomethyl ether (PGME (propylene glycol monomethyl ether): 1-methoxy-2-propanol), propylene glycol monoethyl ether (PGEE), methyl 2-hydroxyisobutyrate, or ethyl lactate. In addition, as a solvent that does not contain a hydroxyl group, an alkanediol monoalkyl ether acetate, an alkyl alkoxy propionate, a ring-containing monoketone compound, a cyclic lactone, or an alkyl acetate is preferred. Etc. Among these, more preferred are propylene glycol monomethyl ether acetate (PGMEA (propylene glycol monomethyl ether acetate): 1-methoxy-2-acetoxypropane), ethyl ethoxy propionate, 2-heptanone, γ-butyrolactone, cyclohexanone, cyclopentanone or butyl acetate, more preferably propylene glycol monomethyl ether acetate, γ-butyrolactone, ethyl ethoxy propionate, cyclic Hexanone, cyclopentanone or 2-heptanone. As a solvent that does not contain a hydroxyl group, propylene carbonate is also preferred. Among these, from the viewpoint of the uniformity of the formed layer, the solvent particularly preferably contains γ-butyrolactone. The mixing ratio (mass ratio) of the solvent containing a hydroxyl group and the solvent not containing a hydroxyl group is 1/99 to 99/1, preferably 10/90 to 90/10, more preferably 20/80 to 60/40. In terms of coating uniformity, a mixed solvent containing 50% by mass or more of a solvent not containing a hydroxyl group is preferable. The solvent preferably contains propylene glycol monomethyl ether acetate, may be a single solvent of propylene glycol monomethyl ether acetate, or may be a mixed solvent of two or more containing propylene glycol monomethyl ether acetate.
本發明的感光化射線性或感放射線性樹脂組成物的固體成分濃度為10質量%以上,較佳為10質量%~50質量%,更佳為15質量%~45質量%,進而佳為20質量%~40質量%。 所謂固體成分濃度,是除溶劑以外的其他成分的質量相對於本發明的組成物的總質量的質量百分率。The solid content concentration of the sensitized radiation or radiation-sensitive resin composition of the present invention is 10% by mass or more, preferably 10% by mass to 50% by mass, more preferably 15% by mass to 45% by mass, and still more preferably 20% by mass. Mass%~40% by mass. The so-called solid content concentration is the mass percentage of the mass of other components other than the solvent with respect to the total mass of the composition of the present invention.
<交聯劑> 本發明的感光化射線性或感放射線性樹脂組成物可含有藉由酸的作用使樹脂進行交聯的化合物(以下,亦稱為交聯劑(G))。 作為交聯劑(G),可適宜地使用公知的化合物。例如,可較佳地使用美國專利申請案公開第2016/0147154號說明書的段落0379~段落0431、美國專利申請案公開第2016/0282720號說明書的段落0064~段落0141中所揭示的公知的化合物作為交聯劑(G)。 交聯劑(G)為具有可使樹脂進行交聯的交聯性基的化合物,作為交聯性基,可列舉:羥基甲基、烷氧基甲基、醯氧基甲基、烷氧基甲醚基、環氧乙烷環、及氧雜環丁烷環等。 交聯性基較佳為羥基甲基、烷氧基甲基、環氧乙烷環或氧雜環丁烷環。 交聯劑(G)較佳為具有兩個以上交聯性基的化合物(亦包含樹脂)。 交聯劑(G)更佳為具有羥基甲基或烷氧基甲基的酚衍生物、脲系化合物(具有脲結構的化合物)或三聚氰胺系化合物(具有三聚氰胺結構的化合物)。 交聯劑可單獨使用一種,亦可併用兩種以上。 相對於組成物的總固體成分,交聯劑(G)的含量較佳為1質量%~50質量%,更佳為3質量%~40質量%,進而佳為5質量%~30質量%。<Crosslinking agent> The actinic radiation-sensitive or radiation-sensitive resin composition of the present invention may contain a compound that crosslinks the resin by the action of an acid (hereinafter, also referred to as a crosslinking agent (G)). As a crosslinking agent (G), a well-known compound can be used suitably. For example, the well-known compounds disclosed in paragraphs 0379 to 0431 of the specification of U.S. Patent Application Publication No. 2016/0147154 can be preferably used as paragraphs 0064 to paragraph 0141 of the specification of U.S. Patent Application Publication No. 2016/0282720. Crosslinking agent (G). The crosslinking agent (G) is a compound having a crosslinkable group that can crosslink the resin. Examples of the crosslinkable group include: hydroxymethyl, alkoxymethyl, oxymethyl, and alkoxy Methyl ether group, ethylene oxide ring, and oxetane ring, etc. The crosslinkable group is preferably a hydroxymethyl group, an alkoxymethyl group, an oxirane ring or an oxetane ring. The crosslinking agent (G) is preferably a compound (including resins) having two or more crosslinkable groups. The crosslinking agent (G) is more preferably a phenol derivative having a hydroxymethyl group or an alkoxymethyl group, a urea-based compound (a compound having a urea structure), or a melamine-based compound (a compound having a melamine structure). A crosslinking agent may be used individually by 1 type, and may use 2 or more types together. With respect to the total solid content of the composition, the content of the crosslinking agent (G) is preferably 1% by mass to 50% by mass, more preferably 3% by mass to 40% by mass, and still more preferably 5% by mass to 30% by mass.
<界面活性劑> 本發明的感光化射線性或感放射線性樹脂組成物可含有界面活性劑(亦稱為「界面活性劑(H)」),亦可不含有。於含有界面活性劑的情況下,較佳為含有氟系及矽酮系界面活性劑(具體而言,氟系界面活性劑、矽酮系界面活性劑、或具有氟原子與矽原子兩者的界面活性劑)中至少一者。<Surface active agent> The sensitizing radiation-sensitive or radiation-sensitive resin composition of the present invention may or may not contain a surfactant (also referred to as "surfactant (H)"). When a surfactant is contained, it is preferably a fluorine-based and silicone-based surfactant (specifically, a fluorine-based surfactant, a silicone-based surfactant, or those having both fluorine atoms and silicon atoms). Surfactant) at least one of them.
藉由本發明的感光化射線性或感放射線性樹脂組成物含有界面活性劑,於使用波長250 nm以下、特別是波長220 nm以下的曝光光源的情況下,可以良好的感度及解析度獲得密接性及顯影缺陷少的抗蝕劑圖案。 作為氟系或矽酮系界面活性劑,可列舉美國專利申請案公開第2008/0248425號說明書的段落0276中記載的界面活性劑。 另外,亦可使用美國專利申請案公開第2008/0248425號說明書的段落0280中記載的氟系或矽酮系界面活性劑以外的其他界面活性劑。The sensitizing radiation-sensitive or radiation-sensitive resin composition of the present invention contains a surfactant, and when an exposure light source with a wavelength of 250 nm or less, especially a wavelength of 220 nm or less, is used, adhesion can be obtained with good sensitivity and resolution And the resist pattern with few development defects. Examples of the fluorine-based or silicone-based surfactant include the surfactants described in paragraph 0276 of the specification of U.S. Patent Application Publication No. 2008/0248425. In addition, other surfactants other than the fluorine-based or silicone-based surfactants described in paragraph 0280 of the specification of U.S. Patent Application Publication No. 2008/0248425 may be used.
該些界面活性劑可單獨使用一種,亦可併用兩種以上。 於本發明的感光化射線性或感放射線性樹脂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%。 另一方面,藉由界面活性劑的含量相對於組成物的總固體成分而設為0.0001質量%以上,疏水性樹脂的表面偏向存在性提高。藉此,可使感光化射線性或感放射線性膜的表面更疏水,液浸曝光時的水追隨性提高。These surfactants may be used alone or in combination of two or more. When the sensitized radiation-sensitive or radiation-sensitive resin composition of the present invention contains a surfactant, the content of the surfactant relative to the total solid content of the composition is preferably 0.0001% by mass to 2% by mass, and more preferably It is 0.0005 mass% to 1 mass%. On the other hand, when the content of the surfactant is set to 0.0001% by mass or more with respect to the total solid content of the composition, the surface deflection existence of the hydrophobic resin improves. Thereby, the surface of the sensitized radiation-sensitive or radiation-sensitive film can be made more hydrophobic, and the water followability during liquid immersion exposure can be improved.
<其他添加劑> 本發明的感光化射線性或感放射線性樹脂組成物可進而包含其他公知的添加劑。 作為其他添加劑,可列舉:酸增殖劑、染料、塑化劑、光增感劑、光吸收劑、鹼可溶性樹脂、溶解抑制劑、溶解促進劑等。<Other additives> The actinic radiation-sensitive or radiation-sensitive resin composition of the present invention may further contain other well-known additives. Examples of other additives include acid multiplying agents, dyes, plasticizers, photosensitizers, light absorbers, alkali-soluble resins, dissolution inhibitors, dissolution promoters, and the like.
本發明的感光化射線性或感放射線性樹脂組成物較佳為將所述成分溶解於規定的有機溶劑、較佳為所述混合溶劑中,對其進行過濾器過濾後,例如塗佈於規定的支撐體(基板)上而使用。 用於過濾器過濾的過濾器的孔徑大小(pore size)(孔徑)較佳為0.2 μm以下,更佳為0.05 μm以下,進而佳為0.03 μm以下。 另外,於感光化射線性或感放射線性樹脂組成物的固體成分濃度高的情況下(例如,25質量%以上),用於過濾器過濾的過濾器的孔徑大小較佳為3 μm以下,更佳為0.5 μm以下,進而佳為0.3 μm以下。 所述過濾器較佳為聚四氟乙烯製、聚乙烯製、或尼龍製的過濾器。於過濾器過濾中,例如如日本專利特開2002-62667號公報中所揭示般,可進行循環過濾,亦可將多種過濾器串聯或並聯連接來進行過濾。另外,亦可將組成物過濾多次。進而,亦可於過濾器過濾前後對組成物進行脫氣處理等。The sensitizing radiation-sensitive or radiation-sensitive resin composition of the present invention preferably dissolves the components in a predetermined organic solvent, preferably the mixed solvent, and filters it, for example, coating on a predetermined organic solvent. On the support (substrate). The pore size (pore size) of the filter used for filter filtration is preferably 0.2 μm or less, more preferably 0.05 μm or less, and still more preferably 0.03 μm or less. In addition, when the solid content of the sensitized radiation or radiation-sensitive resin composition is high (for example, 25% by mass or more), the pore size of the filter used for filter filtration is preferably 3 μm or less, and more It is preferably 0.5 μm or less, and more preferably 0.3 μm or less. The filter is preferably a filter made of polytetrafluoroethylene, polyethylene, or nylon. In filter filtration, for example, as disclosed in Japanese Patent Laid-Open No. 2002-62667, cyclic filtration can be performed, and multiple filters can also be connected in series or parallel to perform filtration. In addition, the composition may be filtered multiple times. Furthermore, the composition may be degassed before and after filtration by the filter.
包含本發明的感光化射線性或感放射線性樹脂組成物的抗蝕劑膜的膜厚並無特別限定,較佳為1 μm以上,更佳為2 μm以上且50 μm以下,進而佳為2 μm以上且20 μm以下。將組成物中的固體成分濃度設定為適當的範圍使其具有適度的黏度,提高塗佈性或製膜性,藉此可形成此種膜厚。The thickness of the resist film containing the sensitized radiation-sensitive or radiation-sensitive resin composition of the present invention is not particularly limited, but is preferably 1 μm or more, more preferably 2 μm or more and 50 μm or less, and still more preferably 2 μm or more and 20 μm or less. The solid content concentration in the composition is set to an appropriate range to have an appropriate viscosity, and the coating properties or film-forming properties are improved, whereby such a film thickness can be formed.
<用途> 本發明的感光化射線性或感放射線性樹脂組成物為藉由光的照射進行反應而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,本發明的感光化射線性或感放射線性樹脂組成物是有關於一種於積體電路(Integrated Circuit,IC)等的半導體製造步驟、液晶或熱能頭等的電路基板的製造、壓印用模具結構體的製作、其他的感光蝕刻加工步驟、或平版印刷版或者酸硬化性組成物的製造中所使用的感光化射線性或感放射線性樹脂組成物。由本發明的感光化射線性或感放射線性樹脂組成物所形成的抗蝕劑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、及微電子機械系統(Micro Electro Mechanical Systems,MEMS)等。<Use> The actinic ray-sensitive or radiation-sensitive resin composition of the present invention is an actinic ray-sensitive or radiation-sensitive resin composition whose properties are changed by reaction with light irradiation. In more detail, the photosensitive radiation-sensitive or radiation-sensitive resin composition of the present invention relates to a semiconductor manufacturing process such as an integrated circuit (IC), the manufacturing of a circuit board such as a liquid crystal or a thermal head, etc. A photosensitive ray-sensitive or radiation-sensitive resin composition used in the production of a mold structure for imprinting, other photosensitive etching processing steps, or the production of a lithographic printing plate or an acid-curable composition. The resist pattern formed by the sensitized radiation-sensitive or radiation-sensitive resin composition of the present invention can be used in an etching step, an ion implantation step, a bump electrode formation step, a rewiring formation step, and a microelectromechanical system (Micro Electro Mechanical System). Systems, MEMS) etc.
(感光化射線性或感放射線性膜) 本發明的感光化射線性或感放射線性膜(較佳為抗蝕劑膜)為藉由本發明的感光化射線性或感放射線性樹脂組成物而形成的膜。本發明的感光化射線性或感放射線性膜為本發明的感光化射線性或感放射線性樹脂組成物的固化物。 所謂本發明中的固化物,只要為自本發明的感光化射線性或感放射線性樹脂組成物去除至少一部分溶劑者即可。 具體而言,本發明的感光化射線性或感放射線性膜例如可藉由在基板等支撐體上塗佈本發明的感光化射線性或感放射線性樹脂組成物後進行乾燥而獲得。 所謂所述乾燥,是指去除本發明的感光化射線性或感放射線性樹脂組成物中包含的溶劑的至少一部分。 乾燥方法並無特別限定,可使用公知的方法,可列舉利用加熱(例如,70℃~130℃、30秒鐘~300秒鐘)進行的乾燥等。 作為加熱方法,並無特別限定,可使用公知的加熱機構,例如可列舉:加熱器、烘箱、加熱板、紅外線燈、紅外線雷射等。(Sensitized radiation or radiation sensitive film) The actinic radiation or radiation-sensitive film (preferably a resist film) of the present invention is a film formed from the actinic radiation or radiation-sensitive resin composition of the present invention. The actinic radiation or radiation-sensitive film of the present invention is a cured product of the actinic radiation or radiation-sensitive resin composition of the present invention. The cured product in the present invention may be any one having at least a part of the solvent removed from the sensitizing radiation or radiation-sensitive resin composition of the present invention. Specifically, the actinic radiation or radiation-sensitive film of the present invention can be obtained, for example, by coating the actinic radiation or radiation-sensitive resin composition of the present invention on a support such as a substrate and then drying. The drying refers to removing at least a part of the solvent contained in the sensitizing ray-sensitive or radiation-sensitive resin composition of the present invention. The drying method is not particularly limited, and a known method can be used, and examples thereof include drying by heating (for example, 70° C. to 130° C., 30 seconds to 300 seconds). It does not specifically limit as a heating method, A well-known heating mechanism can be used, For example, a heater, an oven, a hotplate, an infrared lamp, an infrared laser, etc. are mentioned.
本發明的感光化射線性或感放射線性膜中包含的成分與本發明的感光化射線性或感放射線性樹脂組成物中包含的成分中去除溶劑後的成分相同,較佳態樣亦相同。 本發明的感光化射線性或感放射線性膜中包含的各成分的含量相當於將本發明的感光化射線性或感放射線性樹脂組成物的溶劑以外的各成分的含量的說明中的「總固體成分」的記載替換為「感光化射線性或感放射線性膜的總質量」而得者。The components contained in the sensitizing radiation or radiation-sensitive film of the present invention are the same as the components included in the sensitizing radiation or radiation-sensitive resin composition of the present invention after removing the solvent, and preferred aspects are also the same. The content of each component contained in the sensitizing radiation or radiation-sensitive film of the present invention corresponds to the "total content" in the description of the content of each component other than the solvent of the sensitizing radiation or radiation-sensitive resin composition of the present invention. The description of "solid content" is replaced with "total mass of sensitizing radiation or radiation sensitive film".
本發明的感光化射線性或感放射線性膜的厚度較佳為1 μm以上,更佳為2 μm以上且50 μm以下,進而佳為2 μm以上且20 μm以下。The thickness of the sensitizing radiation-sensitive or radiation-sensitive film of the present invention is preferably 1 μm or more, more preferably 2 μm or more and 50 μm or less, and still more preferably 2 μm or more and 20 μm or less.
(圖案形成方法) 本發明的圖案形成方法為具有如下步驟的圖案形成方法,即 (i)利用本發明的感光化射線性或感放射線性樹脂組成物於基板上形成膜厚為1 μm以上的感光化射線性或感放射線性膜的步驟; (ii)對感光化射線性或感放射線性膜照射光化射線或放射線的步驟;以及 (iii)使用顯影液對照射了光化射線或放射線的感光化射線性或感放射線性膜進行顯影的步驟。(Pattern formation method) The pattern forming method of the present invention is a pattern forming method having the following steps, namely (I) The step of using the photosensitive ray-sensitive or radiation-sensitive resin composition of the present invention to form a photosensitive ray-sensitive or radiation-sensitive film with a film thickness of 1 μm or more on a substrate; (Ii) The step of irradiating actinic rays or radiation to the sensitized ray-sensitive or radiation-sensitive film; and (Iii) A step of using a developing solution to develop an actinic ray-sensitive or radiation-sensitive film irradiated with actinic rays or radiation.
<步驟(i) 成膜步驟> 本發明的圖案形成方法包括步驟(i)(成膜步驟)。作為成膜步驟中的感光化射線性或感放射線性膜的形成方法,例如可列舉利用所述感光化射線性或感放射線性膜的項目中所述的乾燥來形成感光化射線性或感放射線性膜的方法。<Step (i) Film forming step> The pattern forming method of the present invention includes step (i) (film forming step). As a method of forming the sensitizing radiation or radiation sensitive film in the film forming step, for example, the drying described in the item of the sensitizing radiation or radiation sensitive film can be used to form the sensitizing radiation or radiation sensitive film. Sexual film method.
〔基板(支撐體)〕 基板並無特別限定,除了IC等的半導體製造步驟、或者液晶或熱能頭等的電路基板的製造步驟以外,可使用於其他感光蝕刻加工的微影步驟等中一般而言使用的基板。作為支撐體的具體例,可列舉:矽、SiO2 、及SiN等無機基板等。[Substrate (support)] The substrate is not particularly limited. In addition to semiconductor manufacturing steps such as ICs, or circuit substrate manufacturing steps such as liquid crystals or thermal heads, it can be used in other photolithography steps such as photolithographic processing. Language substrate used. Specific examples of the support include inorganic substrates such as silicon, SiO 2, and SiN.
<步驟(ii) 曝光步驟> 步驟(ii)(曝光步驟)為藉由光對感光化射線性或感放射線性膜進行曝光的步驟。 曝光方法可為液浸曝光。 本發明的圖案形成方法可包括多次曝光步驟。 曝光中所使用的光(光化射線或放射線)的種類只要考慮光酸產生劑的特性及欲獲得的圖案形狀等來選擇即可,可列舉:紅外光、可見光、紫外光、遠紫外光、極紫外光(EUV)、X射線、及電子束等,較佳為遠紫外光。 例如,較佳為波長250 nm以下的光化射線,更佳為220 nm以下,進而佳為1 nm~200 nm。 具體而言,作為所使用的光,為KrF準分子雷射(248 nm)、ArF準分子雷射(193 nm)、F2 準分子雷射(157 nm)、X射線、EUV(13 nm)、或電子束等,較佳為KrF準分子雷射、EUV或電子束。 於KrF準分子雷射的情況下,作為曝光量,較佳為5 mJ/cm2 ~200 mJ/cm2 ,更佳為10 mJ/cm2 ~150 mJ/cm2 。於電子束的情況下,以成為0.1 μC/cm2 ~20 μC/cm2 左右、較佳為3 μC/cm2 ~10 μC/cm2 左右的方式進行曝光,於極紫外線的情況下,以成為0.1 mJ/cm2 ~20 mJ/cm2 左右、較佳為3 mJ/cm2 ~15 mJ/cm2 左右的方式進行曝光。<Step (ii) Exposure Step> Step (ii) (exposure step) is a step of exposing the sensitized radiation or radiation-sensitive film with light. The exposure method may be liquid immersion exposure. The pattern forming method of the present invention may include multiple exposure steps. The type of light (actinic rays or radiation) used in the exposure can be selected in consideration of the characteristics of the photoacid generator and the shape of the pattern to be obtained. Examples include infrared light, visible light, ultraviolet light, far ultraviolet light, Extreme ultraviolet light (EUV), X-ray, electron beam, etc. are preferably extreme ultraviolet light. For example, it is preferably an actinic ray with a wavelength of 250 nm or less, more preferably 220 nm or less, and still more preferably 1 nm to 200 nm. Specifically, the light used is KrF excimer laser (248 nm), ArF excimer laser (193 nm), F 2 excimer laser (157 nm), X-ray, EUV (13 nm) , Or electron beam, etc., preferably KrF excimer laser, EUV or electron beam. In the case of a KrF excimer laser, the exposure amount is preferably 5 mJ/cm 2 to 200 mJ/cm 2 , and more preferably 10 mJ/cm 2 to 150 mJ/cm 2 . In the case of an electron beam, exposure is performed so that it becomes about 0.1 μC/cm 2 to 20 μC/cm 2 , preferably about 3 μC/cm 2 to 10 μC/cm 2 , and in the case of extreme ultraviolet light, The exposure is performed so that it becomes about 0.1 mJ/cm 2 to 20 mJ/cm 2 , preferably about 3 mJ/cm 2 to 15 mJ/cm 2.
<步驟(iii) 顯影步驟> 步驟(iii)(顯影步驟)中所使用的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),較佳為鹼性水溶液。<Step (iii) Development step> The developer used in step (iii) (development step) may be an alkaline developer, or a developer containing an organic solvent (hereinafter, also referred to as an organic developer), and is preferably an alkaline aqueous solution.
〔鹼性顯影液〕 作為鹼性顯影液,可較佳地使用以四甲基氫氧化銨為代表的四級銨鹽,除此之外亦可使用無機鹼、一級胺~三級胺、烷醇胺、及環狀胺等的鹼性水溶液。 進而,所述鹼性顯影液可含有適當量的醇類、及界面活性劑的至少一種。鹼性顯影液的鹼濃度較佳為0.1質量%~20質量%。鹼性顯影液的pH較佳為10~15。 使用鹼性顯影液進行顯影的時間較佳為10秒~300秒。 鹼性顯影液的鹼濃度、pH、及顯影時間可根據所形成的圖案而適宜調整。〔Alkaline developer〕 As the alkaline developer, a quaternary ammonium salt represented by tetramethylammonium hydroxide can be preferably used. In addition to this, inorganic bases, primary to tertiary amines, alkanolamines, and cyclic amines can also be used. Alkaline aqueous solutions such as amines. Furthermore, the alkaline developer may contain an appropriate amount of at least one of alcohols and surfactants. The alkali concentration of the alkaline developer is preferably 0.1% by mass to 20% by mass. The pH of the alkaline developer is preferably 10-15. The time for developing using an alkaline developer is preferably 10 seconds to 300 seconds. The alkali concentration, pH, and development time of the alkaline developer can be appropriately adjusted according to the formed pattern.
〔有機系顯影液〕 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。〔Organic developer〕 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.
-酮系溶劑- 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、乙醯基丙酮、丙酮基丙酮、紫羅酮、二丙酮基醇、乙醯基甲醇(acetyl carbinol)、苯乙酮、甲基萘基酮、異佛爾酮、及碳酸伸丙酯等。-Ketone solvent- 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, acetylacetone, acetonylacetone, Ionone, diacetone alcohol, acetyl carbinol, acetophenone, methyl naphthyl ketone, isophorone, and propylene carbonate, etc.
-酯系溶劑- 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、乙酸異戊酯、乙酸戊酯、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。-Ester solvent- Examples of ester solvents include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, amyl acetate, 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, 2 -Methyl hydroxyisobutyrate, isoamyl acetate, isobutyl isobutyrate, and butyl propionate, etc.
-其他溶劑- 作為醇系溶劑、醯胺系溶劑、醚系溶劑、及烴系溶劑,可使用美國專利申請案公開第2016/0070167號說明書的段落0715~段落0718中所揭示的溶劑。-Other solvents- As alcohol-based solvents, amide-based solvents, ether-based solvents, and hydrocarbon-based solvents, the solvents disclosed in paragraphs 0715 to 0718 of the specification of U.S. Patent Application Publication No. 2016/0070167 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%,特佳為實質上不含有水分。 相對於顯影液的總量,有機系顯影液中的有機溶劑的含量較佳為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,特佳為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 water 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 in 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, particularly preferably 95% by mass or more and 100% by mass or less.
-界面活性劑- 有機系顯影液視需要可含有適當量的公知的界面活性劑。 相對於顯影液的總質量,界面活性劑的含量較佳為0.001質量%~5質量%,更佳為0.005質量%~2質量%,進而佳為0.01質量%~0.5質量%。-Surfactant- The organic developer may contain a known surfactant in an appropriate amount as necessary. The content of the surfactant relative to the total mass of the developer is preferably 0.001% by mass to 5% by mass, more preferably 0.005% by mass to 2% by mass, and still more preferably 0.01% by mass to 0.5% by mass.
-酸擴散控制劑- 有機系顯影液亦可包含所述的酸擴散控制劑。-Acid diffusion control agent- The organic developer may also contain the acid diffusion control agent described above.
〔顯影方法〕 作為顯影方法,例如可應用: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的方法(覆液(puddle)法);對基板表面噴霧顯影液的方法(噴霧法);或者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)等。〔Development method〕 As a development method, for example, a method of immersing a substrate in a tank filled with a developer solution for a fixed period of time (dipping method); a method of using surface tension to deposit the developer solution on the surface of the substrate and standing still for a fixed period of time (puddle method) ); the method of spraying developer on the surface of the substrate (spray method); or the method of continuously spraying the developer on the substrate rotating at a fixed speed while scanning the developer spray nozzle at a fixed speed (dynamic distribution method), etc.
亦可將使用鹼性水溶液進行顯影的步驟(鹼顯影步驟)、及使用包含有機溶劑的顯影液進行顯影的步驟(有機溶劑顯影步驟)組合。藉此,可不僅僅溶解中間的曝光強度的區域而進行圖案形成,因此可形成更微細的圖案。It is also possible to combine the step of developing using an alkaline aqueous solution (alkaline development step) and the step of developing using a developer containing an organic solvent (organic solvent development step). This allows pattern formation not only to dissolve the intermediate exposure intensity area, and therefore it is possible to form a finer pattern.
<前加熱步驟、曝光後加熱步驟> 本發明的圖案形成方法較佳為於曝光步驟之前包括前加熱(PB:PreBake)步驟。 本發明的圖案形成方法可包括多次前加熱步驟。 本發明的圖案形成方法較佳為於曝光步驟之後且顯影步驟之前包括曝光後加熱(PEB:Post Exposure Bake)步驟。 本發明的圖案形成方法可包括多次曝光後加熱步驟。 加熱溫度於前加熱步驟及曝光後加熱步驟中的任一步驟中均較佳為70℃~130℃,更佳為80℃~120℃。 加熱時間於前加熱步驟及曝光後加熱步驟中的任一步驟中均較佳為30秒~300秒,更佳為30秒~180秒,進而佳為30秒~90秒。 加熱可藉由曝光裝置及顯影裝置所包括的機構進行,亦可使用加熱板等進行。<Pre-heating step, post-exposure heating step> The pattern forming method of the present invention preferably includes a pre-heating (PB: PreBake) step before the exposure step. The pattern forming method of the present invention may include multiple pre-heating steps. The pattern forming method of the present invention preferably includes a post-exposure heating (PEB: Post Exposure Bake) step after the exposure step and before the development step. The pattern forming method of the present invention may include a heating step after multiple exposures. The heating temperature is preferably 70°C to 130°C, more preferably 80°C to 120°C in any of the pre-heating step and the post-exposure heating step. The heating time in any of the pre-heating step and the post-exposure heating step is preferably 30 seconds to 300 seconds, more preferably 30 seconds to 180 seconds, and still more preferably 30 seconds to 90 seconds. Heating can be performed by the mechanism included in the exposure device and the developing device, or by using a heating plate or the like.
<抗蝕劑底層膜形成步驟> 本發明的圖案形成方法可於成膜步驟之前進而包括形成抗蝕劑底層膜的步驟(抗蝕劑底層膜形成步驟)。 抗蝕劑底層膜形成步驟為於抗蝕劑膜與支撐體之間形成抗蝕劑底層膜(例如,旋塗式玻璃(Spin On Glass,SOG)、旋塗碳(Spin On Carbon,SOC)、抗反射膜等)的步驟。作為抗蝕劑底層膜,可適宜使用公知的有機系或無機系的材料。<Steps of forming resist underlayer film> The pattern forming method of the present invention may further include a step of forming a resist underlayer film (resist underlayer film forming step) before the film forming step. The step of forming a resist underlayer film is to form a resist underlayer film (for example, spin on glass (Spin On Glass, SOG), spin on carbon (Spin On Carbon, SOC), etc.) between the resist film and the support. Anti-reflective film, etc.) steps. As the resist underlayer film, a known organic or inorganic material can be suitably used.
<保護膜形成步驟> 本發明的圖案形成方法可於顯影步驟之前進而包括形成保護膜的步驟(保護膜形成步驟)。 保護膜形成步驟為於抗蝕劑膜的上層形成保護膜(頂塗層)的步驟。作為保護膜,可適宜使用公知的材料。例如可較佳地使用美國專利申請案公開第2007/0178407號說明書、美國專利申請案公開第2008/0085466號說明書、美國專利申請案公開第2007/0275326號說明書、美國專利申請案公開第2016/0299432號說明書、美國專利申請案公開第2013/0244438號說明書、國際公開第2016/157988號中所揭示的保護膜形成用組成物。作為保護膜形成用組成物,較佳為包含所述酸擴散控制劑者。 亦可於含有所述疏水性樹脂的抗蝕劑膜的上層形成保護膜。<Protection film formation procedure> The pattern forming method of the present invention may further include a step of forming a protective film (protective film forming step) before the development step. The protective film forming step is a step of forming a protective film (top coat layer) on the upper layer of the resist film. As the protective film, a known material can be suitably used. For example, U.S. Patent Application Publication No. 2007/0178407 Specification, U.S. Patent Application Publication No. 2008/0085466 Specification, U.S. Patent Application Publication No. 2007/0275326 Specification, U.S. Patent Application Publication No. 2016/ The protective film forming composition disclosed in specification 0299432, specification of U.S. Patent Application Publication No. 2013/0244438, and International Publication No. 2016/157988. The composition for forming a protective film is preferably one containing the acid diffusion control agent. You may form a protective film on the upper layer of the resist film containing the said hydrophobic resin.
<淋洗步驟> 本發明的圖案形成方法較佳為於顯影步驟之後,包括使用淋洗液進行清洗的步驟(淋洗步驟)。<Rinse step> The pattern forming method of the present invention preferably includes a step of washing with a rinse solution (rinsing step) after the development step.
〔使用鹼性顯影液的顯影步驟的情況〕 使用鹼性顯影液的顯影步驟之後的淋洗步驟中使用的淋洗液例如可使用純水。純水可含有適當量的界面活性劑。於該情況下,於顯影步驟或淋洗步驟之後,可追加利用超臨界流體去除附著於圖案上的顯影液或淋洗液的處理。進而,於淋洗處理或者利用超臨界流體的處理後,可進行加熱處理以去除圖案中殘存的水分。[In the case of the development step using alkaline developer] As the rinse solution used in the rinse step after the development step using the alkaline developer, for example, pure water can be used. The pure water may contain an appropriate amount of surfactant. In this case, after the development step or the rinsing step, a process of removing the developing solution or the rinsing solution adhering to the pattern with a supercritical fluid may be added. Furthermore, after the rinsing treatment or the treatment with a supercritical fluid, heat treatment may be performed to remove water remaining in the pattern.
〔使用有機系顯影液的顯影步驟的情況〕 使用包含有機溶劑的顯影液的顯影步驟之後的淋洗步驟中使用的淋洗液只要不溶解抗蝕劑圖案,則並無特別限制,可使用包含一般的有機溶劑的溶液。作為淋洗液,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、及醚系溶劑的具體例,可列舉與包含有機溶劑的顯影液中所說明的具體例相同者。 作為此時的淋洗步驟中使用的淋洗液,更佳為含有一元醇的淋洗液。[In the case of a development step using an organic developer] The rinsing liquid used in the rinsing step after the development step using a developer containing an organic solvent 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. As the eluent, it is preferable to use an eluent containing at least one organic solvent selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents. Lotion. Specific examples of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents include the same ones as those described in the developer containing an organic solvent. As the rinsing liquid used in the rinsing step at this time, a rinsing liquid containing a monohydric alcohol is more preferable.
作為淋洗步驟中使用的一元醇,可列舉直鏈狀、分支狀、或環狀的一元醇。具體而言可列舉:1-丁醇、2-丁醇、3-甲基-1-丁醇、第三丁醇、1-戊醇、2-戊醇、1-己醇、4-甲基-2-戊醇、1-庚醇、1-辛醇、2-己醇、環戊醇、2-庚醇、2-辛醇、3-己醇、3-庚醇、3-辛醇、4-辛醇、及甲基異丁基甲醇。作為碳數5以上的一元醇,可列舉:1-己醇、2-己醇、4-甲基-2-戊醇、1-戊醇、3-甲基-1-丁醇、及甲基異丁基甲醇等。Examples of monohydric alcohols used in the rinsing step include linear, branched, or cyclic monohydric alcohols. Specific examples include: 1-butanol, 2-butanol, 3-methyl-1-butanol, tertiary butanol, 1-pentanol, 2-pentanol, 1-hexanol, 4-methyl -2-pentanol, 1-heptanol, 1-octanol, 2-hexanol, cyclopentanol, 2-heptanol, 2-octanol, 3-hexanol, 3-heptanol, 3-octanol, 4-octanol, and methyl isobutyl methanol. Examples of monohydric alcohols having 5 or more carbon atoms include 1-hexanol, 2-hexanol, 4-methyl-2-pentanol, 1-pentanol, 3-methyl-1-butanol, and methyl Isobutyl methanol and so on.
各成分可混合多種,亦可與所述以外的有機溶劑混合而使用。 淋洗液中的含水率較佳為10質量%以下,更佳為5質量%以下,進而佳為3質量%以下。藉由將含水率設為10質量%以下,可獲得良好的顯影特性。Each component may mix multiple types, and may mix and use with organic solvents other than the said. The water content in the rinsing liquid is preferably 10% by mass or less, more preferably 5% by mass or less, and still more preferably 3% by mass or less. By setting the moisture content to 10% by mass or less, good development characteristics can be obtained.
淋洗液可含有適當量的界面活性劑。 於淋洗步驟中,使用包含有機溶劑的淋洗液,對使用有機系顯影液進行了顯影的基板進行清洗處理。清洗處理的方法並無特別限定,例如可應用: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)、或者對基板表面噴霧淋洗液的方法(噴霧法)等。其中,較佳為利用旋轉塗佈法進行清洗處理,清洗後使基板以2,000 rpm~4,000 rpm(轉/分鐘)的轉速旋轉,自基板上去除淋洗液。另外,亦較佳為於淋洗步驟之後包括加熱步驟(後烘烤(Post Bake))。藉由所述加熱步驟,殘留於圖案間及圖案內部的顯影液及淋洗液被去除。於淋洗步驟之後的加熱步驟中,加熱溫度較佳為40℃~160℃,更佳為70℃~95℃。加熱時間較佳為10秒~3分鐘,更佳為30秒~90秒。The eluent may contain an appropriate amount of surfactant. In the rinsing step, a rinsing liquid containing an organic solvent is used to clean the substrate that has been developed with an organic developer. The method of cleaning treatment is not particularly limited. For example, it can be applied: a method of continuously spraying 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 rinsing liquid for a fixed period of time (Dipping method), or a method of spraying rinsing liquid on the surface of the substrate (spray method), etc. Among them, it is preferable to perform a cleaning process by a spin coating method. After cleaning, the substrate is rotated at a rotation speed of 2,000 rpm to 4,000 rpm (revolutions per minute) to remove the eluent from the substrate. In addition, it is also preferable to include a heating step (Post Bake) after the rinsing step. Through the heating step, the developer and rinsing liquid remaining between and inside the patterns are removed. In the heating step after the rinsing step, the heating temperature is preferably 40°C to 160°C, more preferably 70°C to 95°C. The heating time is preferably 10 seconds to 3 minutes, more preferably 30 seconds to 90 seconds.
<表面粗糙度的改善> 對於藉由本發明的圖案形成方法而形成的圖案,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,例如可列舉美國專利申請案公開第2015/0104957號說明書中所揭示的藉由含有氫的氣體的電漿來處理抗蝕劑圖案的方法。除此以外,亦可應用日本專利特開2004-235468號公報、美國專利申請案公開第2010/0020297號說明書、「國際光學工程學會會議記錄(Proc. of SPIE(The International Society for Optical Engineering))」(Vol. 8328 83280N-1)「用於LWR減少與蝕刻選擇性增強的EUV抗試劑熟化技術(EUV Resist Curing Technique for LWR Reduction and Etch Selectivity Enhancement)」中所記載的公知的方法。 另外,藉由所述方法而形成的抗蝕劑圖案例如可用作日本專利特開平3-270227號公報及美國專利申請案公開第2013/0209941號說明書中所揭示的間隔物製程的芯材(Core)。<Improvement of surface roughness> For the pattern formed by the pattern forming 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 the pattern, for example, a method of processing a resist pattern by a plasma containing hydrogen-containing gas disclosed in the specification of U.S. Patent Application Publication No. 2015/0104957 can be cited. In addition to this, Japanese Patent Laid-Open No. 2004-235468, U.S. Patent Application Publication No. 2010/0020297, "Proc. of SPIE (The International Society for Optical Engineering)) "(Vol. 8328 83280N-1) "EUV Resist Curing Technique for LWR Reduction and Etch Selectivity Enhancement" is a well-known method described in "EUV Resist Curing Technique for LWR Reduction and Etch Selectivity Enhancement." In addition, the resist pattern formed by the method can be used, for example, as a core material for the spacer process disclosed in Japanese Patent Laid-Open No. 3-270227 and U.S. Patent Application Publication No. 2013/0209941 ( Core).
(電子元件的製造方法) 本發明的電子元件的製造方法包含本發明的圖案形成方法。藉由本發明的電子元件的製造方法製造的電子元件可較佳地搭載於電氣電子設備(例如,家電、辦公自動化(Office Automation,OA)相關設備、媒體相關設備、光學用設備、及通訊設備等)中。 [實施例](Method of manufacturing electronic components) The manufacturing method of the electronic component of this invention includes the pattern formation method of this invention. The electronic components manufactured by the method of manufacturing electronic components of the present invention can be preferably mounted on electrical and electronic equipment (for example, home appliances, office automation (OA) related equipment, media related equipment, optical equipment, and communication equipment, etc.) )in. [Example]
以下列舉實施例來對本發明的實施形態進行更具體的說明。以下的實施例所示的材料、使用量、比例、處理內容、及處理順序等只要不脫離本發明的實施形態的主旨,則可適宜變更。因而,本發明的實施形態的範圍並不限定於以下所示的具體例。再者,只要無特別說明,則「份」、「%」為質量基準。Examples are listed below to more specifically describe the embodiments of the present invention. The materials, usage amount, ratio, processing content, and processing order shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the embodiment of the present invention. Therefore, the scope of the embodiments of the present invention is not limited to the specific examples shown below. In addition, unless otherwise specified, "parts" and "%" are quality standards.
<樹脂(A)> 以下表示所使用的樹脂(A-1~A-7)的結構。 再者,樹脂的重量平均分子量(Mw)、數量平均分子量(Mn)、及分散度(Mw/Mn)如所述般,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(各重複單元相對於所有重複單元的含有比率 單位:莫耳%)藉由13 C-核磁共振(Nuclear Magnetic Resonance,NMR)進行測定。Pd表示分子量分佈(Mw/Mn)。<Resin (A)> The structure of the resin (A-1 to A-7) used is shown below. Furthermore, the weight average molecular weight (Mw), number average molecular weight (Mn), and degree of dispersion (Mw/Mn) of the resin are measured by GPC (carrier: tetrahydrofuran (THF)) as described above. Styrene conversion amount). In addition, the composition ratio of the resin (the content ratio of each repeating unit to all repeating units, unit: mole % ) was measured by 13 C-nuclear magnetic resonance (NMR). Pd represents the molecular weight distribution (Mw/Mn).
[化70] [化70]
[化71] [化71]
再者,所述樹脂的各重複單元的含有比率的單位為莫耳%。In addition, the unit of the content ratio of each repeating unit of the resin is mole %.
將與本說明書及實施例中的樹脂的各重複單元相對應的單體製成均聚物時的玻璃轉移溫度(Tg)的值可參照PCT/JP2018/018239(國際公開第2018/212079號)的記載。Refer to PCT/JP2018/018239 (International Publication No. 2018/212079) for the value of the glass transition temperature (Tg) when the monomer corresponding to each repeating unit of the resin in this specification and the examples is made into a homopolymer. The record.
<光酸產生劑(B-1)> 以下表示所使用的光酸產生劑(B-1)的結構。Bu表示正丁基。<Photoacid generator (B-1)> The structure of the photoacid generator (B-1) used is shown below. Bu represents n-butyl.
[化72] [化72]
[化73] [化73]
<光酸產生劑(B-2)> 以下表示所使用的光酸產生劑(B-2)的結構。<Photoacid generator (B-2)> The structure of the photoacid generator (B-2) used is shown below.
[化74] [化74]
<酸擴散控制劑> 以下表示所使用的酸擴散控制劑的結構。<Acid diffusion control agent> The structure of the acid diffusion control agent used is shown below.
[化75] [化75]
下述表示所使用的界面活性劑。 W-1:PF6320(歐諾法(OMNOVA)(股)製造) W-2:美佳法(Megafac)F176(迪愛生(DIC)(股)製造;氟系) W-3:聚矽氧烷聚合物KP-341(信越化學工業(股)製造;矽系)The following shows the surfactants used. W-1: PF6320 (manufactured by OMNOVA (stock)) W-2: Megafac F176 (manufactured by DIC (stock); fluorine series) W-3: Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.; silicon-based)
下述表示所使用的溶劑。 SL-1:丙二醇單甲醚(1-甲氧基-2-丙醇) SL-2:丙二醇單甲醚乙酸酯(1-甲氧基-2-乙醯氧基丙烷) SL-3:2-庚酮 SL-4:乳酸乙酯 SL-5:γ-丁內酯 SL-6:碳酸伸丙酯The following shows the solvents used. SL-1: Propylene glycol monomethyl ether (1-methoxy-2-propanol) SL-2: Propylene glycol monomethyl ether acetate (1-methoxy-2-acetoxypropane) SL-3: 2-Heptanone SL-4: Ethyl Lactate SL-5: γ-butyrolactone SL-6: Propyl Carbonate
<感光化射線性或感放射線性樹脂組成物的製備> 將表1所示的各成分以成為表1中記載的固體成分濃度(質量%)的方式混合來獲得溶液。繼而,利用具有3 μm的孔徑大小的聚乙烯過濾器對所獲得的溶液進行過濾,藉此製備感光化射線性或感放射線性樹脂組成物(抗蝕劑組成物)。 於抗蝕劑組成物中,於本實施例中所謂固體成分,是指溶劑以外的所有成分。於實施例及比較例中使用所獲得的抗蝕劑組成物。 於表1中,溶劑以外的各成分的含量(質量%)是指相對於亦包含溶劑在內的抗蝕劑組成物整體的含有比率。另外,於表1中記載使用的溶劑相對於所有溶劑的含有比率(質量%)。 表1中,「(B-2)的量相對於(B-1)的量」表示光酸產生劑(B-2)的含量(質量%)相對於光酸產生劑(B-1)的含量。 光酸產生劑(B-2)以規定量溶解於使用的溶劑中,加以稀釋來調整濃度。 表1中,光酸產生劑(B-1)一欄的「pKa」為自光酸產生劑(B-1)產生的酸的pKa,光酸產生劑(B-2)一欄的「pKa」為自光酸產生劑(B-2)產生的酸的pKa,酸擴散控制劑一欄的「pKa」為酸擴散控制劑的共軛酸的pKa。<Preparation of sensitized radiation or radiation-sensitive resin composition> Each component shown in Table 1 was mixed so that it might become a solid content concentration (mass %) described in Table 1, and a solution was obtained. Then, the obtained solution was filtered with a polyethylene filter having a pore size of 3 μm, thereby preparing a sensitizing radiation-sensitive or radiation-sensitive resin composition (resist composition). In the resist composition, the so-called solid content in this embodiment refers to all components other than the solvent. The obtained resist composition was used in Examples and Comparative Examples. In Table 1, the content (mass %) of each component other than the solvent means the content ratio with respect to the entire resist composition including the solvent. In addition, the content ratio (mass %) of the solvents used with respect to all solvents is described in Table 1. In Table 1, "the amount of (B-2) relative to the amount of (B-1)" represents the content (mass%) of the photoacid generator (B-2) relative to the photoacid generator (B-1) content. The photoacid generator (B-2) is dissolved in the solvent used in a predetermined amount and diluted to adjust the concentration. In Table 1, the "pKa" in the column of the photoacid generator (B-1) is the pKa of the acid generated from the photoacid generator (B-1), and the "pKa" in the column of the photoacid generator (B-2) "Is the pKa of the acid generated from the photoacid generator (B-2), and the "pKa" in the acid diffusion control agent column is the pKa of the conjugate acid of the acid diffusion control agent.
[表1]
光酸產生劑(B-2)的含量如以下般測定。 製備抗蝕劑組成物的10質量%乙腈溶液,利用孔徑0.20 μm的聚四氟乙烯(PTFE)製過濾器(DISMIC-25JP,愛多邦得科(ADVANTEC)公司製造)進行過濾,利用使用了WAX系管柱(DB-HeavyWAX(#123-7162),安捷倫科技(Agilent Technologies)公司製造)的FID檢測器(Agilent-6890A,安捷倫科技(Agilent Technologies)公司製造)的氣相層析(GC)裝置(Agilent-6890A,安捷倫科技(Agilent Technologies)公司製造)法進行分析。藉由使用各化合物的絕對校準曲線法,對(B-2)的含量進行定量。The content of the photoacid generator (B-2) is measured as follows. A 10% by mass acetonitrile solution of the resist composition was prepared, and filtered with a polytetrafluoroethylene (PTFE) filter (DISMIC-25JP, manufactured by ADVANTEC) with a pore size of 0.20 μm. Gas chromatography (GC) of WAX series column (DB-HeavyWAX (#123-7162), manufactured by Agilent Technologies) FID detector (Agilent-6890A, manufactured by Agilent Technologies) The analysis was performed using a device (Agilent-6890A, manufactured by Agilent Technologies) method. The content of (B-2) was quantified by using the absolute calibration curve method of each compound.
<圖案形成方法(1):KrF曝光、鹼性水溶液顯影> 使用東京電子製造的旋塗機「ACT-8」,於實施了六甲基二矽氮烷處理的8吋Si基板(先進材料技術(Advanced Materials Technology)公司製造(以下,亦稱為「基板」))上不設置抗反射層,於基板靜止的狀態下滴加所述製備的抗蝕劑組成物。於滴加結束後使基板旋轉,將其轉速以500 rpm維持3秒鐘,之後以100 rpm維持2秒鐘,進而以500 rpm維持3秒鐘,再次以100 rpm維持2秒鐘後,提高至膜厚設定轉速(1200 rpm)而維持60秒鐘。之後,於加熱板上以130℃進行60秒鐘加熱乾燥,從而形成膜厚3 μm的正型抗蝕劑膜。 對於該抗蝕劑膜,介隔具有進行縮小投影曝光及顯影後形成的圖案的空間部的線寬250 nm、線部的線寬750 nm的線與空間圖案的遮罩,使用KrF準分子雷射掃描器(艾司莫耳(ASML)製造,PAS5500/850C,波長248 nm),於NA=0.68、σ=0.60的曝光條件下進行圖案曝光。於照射後在130℃下進行60秒烘烤,使用2.38質量%四甲基氫氧化銨(TMAH)水溶液作為鹼性顯影液並浸漬60秒鐘後,利用純水淋洗30秒鐘並加以乾燥,從而形成空間部的線寬250 nm、線部的線寬750 nm的線與空間圖案。 藉由所述順序,獲得具有基板與形成於基板表面的圖案的評價用圖案晶圓。<Pattern formation method (1): KrF exposure, alkaline aqueous solution development> Using the spin coater "ACT-8" manufactured by Tokyo Electronics, on an 8-inch Si substrate (Advanced Materials Technology) that has been treated with hexamethyldisilazane (hereinafter, also referred to as "substrate" )) No anti-reflective layer is provided on the substrate, and the prepared resist composition is added dropwise while the substrate is in a static state. After the dripping is completed, the substrate is rotated, and the rotation speed is maintained at 500 rpm for 3 seconds, then at 100 rpm for 2 seconds, then at 500 rpm for 3 seconds, and again at 100 rpm for 2 seconds, and then increase to The film thickness is set at a rotation speed (1200 rpm) and maintained for 60 seconds. After that, heating and drying were performed on a hot plate at 130°C for 60 seconds to form a positive resist film with a film thickness of 3 μm. For this resist film, a mask having a line and space pattern with a line width of 250 nm and a line width of 750 nm in the space part of the pattern formed after reduced projection exposure and development was used, and KrF excimer mine was used. Scanner (manufactured by ASML, PAS5500/850C, wavelength 248 nm), pattern exposure was performed under the exposure conditions of NA=0.68 and σ=0.60. After irradiation, bake at 130°C for 60 seconds, use 2.38% by mass tetramethylammonium hydroxide (TMAH) aqueous solution as an alkaline developer and immerse for 60 seconds, rinse with pure water for 30 seconds and dry , So as to form a line and space pattern with a line width of 250 nm in the space part and a line width of 750 nm in the line part. According to the above procedure, a patterned wafer for evaluation having a substrate and a pattern formed on the surface of the substrate was obtained.
<性能評價> [圖案的矩形性] 觀察空間部的線寬250 nm/線部的線寬750 nm/膜厚3 μm的線與空間圖案的剖面形狀,使用測長掃描式電子顯微鏡(SEM,日立製作所(股)的S-9380II),分別測定五處自抗蝕劑圖案的上部表面沿膜厚方向朝向基板0.3 μm的部分的空間部的線寬(HT )、自抗蝕劑圖案的上部表面沿膜厚方向朝向基板1.5 μm的部分的空間部的線寬(HM )、以及自抗蝕劑圖案的上部表面沿膜厚方向朝向基板2.7 μm的部分的空間部的線寬(HB ),求出平均值,並示於下述表3。另外,表3中,對於評價為A或B者,亦記載了HT 與目標臨界尺寸(Critical Dimension,CD)(250 nm)的差。HT 與目標CD的差的值越小越佳。 另外,使用所獲得的值以下述表2中記載的基準進行評價,示於下述表3。<Performance evaluation> [Pattern rectangularity] Observe the cross-sectional shape of the line and space pattern with a line width of 250 nm/line width of 750 nm/film thickness of 3 μm in the space part, using a length measuring scanning electron microscope (SEM, S-9380II of Hitachi, Ltd.), measured the line width (H T ) of the space from the upper surface of the resist pattern toward the 0.3 μm part of the substrate in the film thickness direction, and the distance from the resist pattern. The line width (H M ) of the space where the upper surface faces the substrate 1.5 μm in the film thickness direction, and the line width (H M) of the space where the upper surface of the resist pattern faces the substrate 2.7 μm in the film thickness direction B ), calculate the average value, and show it in Table 3 below. Further, in Table 3, for the evaluation of A or B who also describes the difference between the target critical dimension H T (Critical Dimension, CD) (250 nm) in the. Value of the difference H T and the target CD is smaller the better. In addition, the obtained values were used for evaluation based on the criteria described in Table 2 below, and are shown in Table 3 below.
[表2]
[表3]
於比較例1~比較例3中,HT 與目標CD的差的值的偏差大,無法算出值。Comparative Example 3 in Comparative Example 1, the difference between the offset value and the target CD H T is large, the value can not be calculated.
根據表3的結果,由本發明的組成物獲得的厚膜的圖案剖面形狀具有優異的矩形性。 [產業上之可利用性]According to the results of Table 3, the pattern cross-sectional shape of the thick film obtained from the composition of the present invention has excellent rectangularity. [Industrial availability]
根據本發明,可提供於厚膜的圖案形成中所獲得的圖案的剖面形狀的矩形性優異的感光化射線性或感放射線性樹脂組成物、及感光化射線性或感放射線性膜、以及使用了所述感光化射線性或感放射線性樹脂組成物的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 an actinic ray-sensitive or radiation-sensitive resin composition, an actinic ray-sensitive or radiation-sensitive resin composition, and an actinic ray-sensitive or radiation-sensitive film having excellent rectangularity in the cross-sectional shape of the pattern obtained in the pattern formation of a thick film, and use The pattern formation method of the sensitizing radiation-sensitive or radiation-sensitive resin composition and the manufacturing method of the electronic component are described.
雖然詳細地且參照特定的實施態樣對本發明進行了說明,但對於本發明所屬技術領域中具有通常知識者而言明確的是,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8月30日申請的日本專利申請案(日本專利特願2019-158895)者,其內容作為參照而被併入至本申請案中。Although the present invention has been described in detail with reference to specific embodiments, it is clear to those having ordinary knowledge in the technical field to which the present invention pertains 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. 2019-158895) filed on August 30, 2019, and the content is incorporated into this application as a reference.
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