# Patent

## Title
Resist composition and pattern forming process

## Abstract

A resist composition is provided comprising a polymer comprising recurring units (a) having an oxazolidinedione, thioxooxazolidinone, thiazolidinedione or thioxothiazolidinone structure and recurring unit (b1) having an acid labile group-substituted carboxyl group and/or recurring units (b2) having an acid labile group-substituted phenolic hydroxyl group. The resist composition suppresses acid diffusion, exhibits a high resolution, and forms a pattern of satisfactory profile with low edge roughness.

## Background
CROSS-REFERENCE TO RELATED APPLICATION
This non-provisional application claims priority under 35 U.S.C. 5119(a) on Patent Application NO. 2015-148563 filed in Japan on Jul. 28, 2015, the entire contents of which are lo hereby incorporated by reference.
TECHNICAL FIELD
This invention relates to a resist composition and a patterning process using the composition.
BACKGROUND ART
To meet the demand for higher integration density and operating speed of LSIs, the effort to reduce the pattern rule is in rapid progress. The wide-spreading flash memory market and the demand for increased storage capacities drive forward the miniaturization technology. As the advanced miniaturization technology, manufacturing of microelectronic devices at the 65-nm node by the ArF lithography has been implemented in a mass scale. Manufacturing of 45-nm node devices by the next generation ArF immersion lithography is approaching to the verge of high-volume application. The candidates for the next generation 32-nm node include ultra-high NA lens immersion lithography using a liquid having a higher refractive index than water in combination with a high refractive index lens and a high refractive index resist film, extreme ultraviolet (EUV) lithography of 13.5 nm wavelength, and double patterning version of the ArF lithography, on which active research efforts have been made.
With respect to high-energy radiation of very short wavelength such as EB or X-ray, hydrocarbons used in resist materials have little absorption. Then resist materials based on polyhvdroxystvrene composed mainly of hydrocarbon are under consideration.
The exposure system for mask manufacturing made a transition from the laser beam exposure system to the EH exposure system to increase the accuracy of line width. Since a further size reduction became possible by increasing the accelerating voltage of the electron gun in the EB exposure system, the accelerating voltage increased from 10 kV to 30 kV and reached 50 kV in the current mainstream system, with a voltage of 100 kV being under investigation.
As the accelerating voltage increases, a lowering of sensitivity of resist film becomes of concern. As the accelerating voltage increases, the influence of forward scattering in a resist film becomes so reduced that the contrast of electron image writing energy is improved to ameliorate resolution and dimensional control. However, electrons can pass straightforward through the resist film so that the resist film becomes less sensitive. Since the mask exposure tool is designed for exposure by direct continuous writing, a lowering of sensitivity of resist film leads to an undesirably reduced throughput. Due, to a need for higher sensitivity, chemically amplified resist compositions are studied.
As the feature size reduces, image blurs due to acid diffusion become a problem. To insure resolution for fine patterns with a size of 45 nm et seq., not Only an improvement In dissolution contrast is important as previously reported, but control of acid diffusion is also important as reported in Non-Patent Document 1. Since chemically amplified resist compositions are designed such that sensitivity and contrast are enhanced by acid diffusion, an attempt to minimize acid diffusion by reducing the temperature and/or time of post-exposure bake (PEE) fails, resulting in drastic reductions of sensitivity and contrast,
A triangular tradeoff relationship among sensitivity, resolution, and edge roughness has been pointed out. Specifically, a resolution improvement requires to suppress acid diffusion whereas a short acid diffusion distance leads to a loss of sensitivity.
The addition of an acid generator capable of generating a bulky acid is an effective means for suppressing acid diffusion. It was then proposed to incorporate in a polymer recurring units derived from an onium salt having a polymerizable unsaturated bond as acid generator. Patent Document 1 discloses a sulfonium salt having oolvmerizable unsaturated bond capable of generating a specific sulfonic lo acid and a similar iodonium salt. Patent Document 2 discloses a sulfonium salt having sulfonic acid directly attached to the backbone.
Besides the bulky acid generation, another approach for suppressing acid diffusion is also under study. Patent is Documents 3 to 8 describe nitrogen-containing adhesive groups. The presence of an electron pair in nitrogen atom is effective for control of acid diffusion. However, nitrogen atom not only retards acid diffusion, but also inhibits acid catalyzed reaction. In such case, deprotection reaction does not take place, or even when deprotection reaction takes place, a slow reaction rate leads to a loss of contrast.
CITATION LIST
Patent Document 1: JP-A 2006-045311 (U.S. Pat. No. 7,482,108)
Patent Document 2: JP-A 2006-178317
Patent Document 3: JP-A 2011-203656
Patent Document 4: WO 2011/024953
Patent Document 5: WO 2012/043102
Patent Document 6: WO 2013/129342
Patent Document 7: JP-A 2012-062371
Patent Document 8: JP-A 2012-197382
Non-Patent Document 1: SPIE Vol. 6520 65203L-1 (2007)
SUMMARY OF INVENTION
An object of the present invention is to provide a resist composition which suppresses acid diffusion, exhibits a high resolution surpassing prior art resist compositions, and forms a pattern of satisfactory profile with low edge roughness (LER, LWR); and a patterning process using the resist composition.
Making extensive investigations in search for a resist material capable of meeting the current requirements including high sensitivity, high resolution, and minimal edge roughness, the inventors have found that better results are obtained by using a polymer comprising recurring units having an oxazolidinedione, thioxooxazolidinone, thiazolidinedione or thioxothiazolidinone structure as base resin to formulate a resist composition, typically chemically amplified resist composition.
Toward the goals of suppressing acid diffusion and enhancing dissolution contrast, the inventors have further found that when a polymer comprising recurring units having a carboxyl group substituted with an acid labile group and/or recurring units having a phenolic hydroxyl group substituted with an acid labile group, and recurring units having an oxazolidinedione, thioxooxazolidinone, thiazolidinedione or thioxothiazolidinone structure is used as base resin in a resist composition, typically chemically amplified resist composition, the resulting resist composition exhibits a high sensitivity, a very high contrast of alkaline dissolution rate before and after exposure, full suppression of acid diffusion, and high resolution, and forms a pattern of satisfactory profile with minimal edge roughness. The resist composition is fully useful in commercial application and best suited as the fine pattern-forming material for the manufacture of VLSIs and photomasks.
Since the resist composition allows an acid generator to be effectively decomposed, it has many advantages including a high sensitivity, full suppression of acid diffusion, high resolution, minimal edge roughness, process adaptability, and a good pattern profile after exposure. Because of these advantages, the resist composition is. best suited as the fine pattern-forming material for the manufacture of VLSIs and masks.
In one aspect, the invention provides a resist composition comprising as base resin a polymer comprising recurring units represented by the formula (a) and recurring units having a carboxyl group substituted with an acid labile group and/or recurring units having a phenolic hydroxyl group substituted with an acid labile group, the polymer having a weight average molecular weight of 1,000 to 500,000.




Herein R1 is hydrogen or methyl, R2 and R3 are each independently hydrogen or a straight, branched or cyclic C1-C6 alkyl group, X1 is a single bond, a C1-C12 linking group containing an ester moiety, ether moiety or lactone ring, phenylene or naphthvlene group, X2 and X3 are each independently oxygen or sulfur, and a is a positive number in the range: 0<a<1.0.

In a preferred embodiment, the recurring units having a carboxyl group substituted with an acid labile group are represented by the formula (b1) and the recurring units having a phenolic hydroxyl group substituted with an acid labile group are represented by the formula (b2).




Herein R4 and R6 are each independently hydrogen or methyl, R5 and R9 are each independently an acid labile group, R7 is a single bond or a straight or branched C1-C6 alkylene group, R8 is hydrogen, fluorine, trifluoromethyl, cyano, or a straight, branched or cyclic C1-C6 alkyl, acyl, alkoxy, acyloxy or alkoxycarbonyl group, p is 1 or 2, q is an integer of 0 to 4, Y1 is a single bond, a C1-C12 linking group containing an ester moiety, ether moiety or lactone ring, phenylene or naphthylene group, Y2 is a single bond, —C(═O)—O— or —C(═O)—NH—, b1 and b2 are numbers in the range: 0≦b1<1.0, 0≦b2<1.0, and 0<b1+b2<1.0.

In a preferred embodiment the polymer further comprises recurring units having an adhesive group selected from among hydroxyl, carboxyl, lactone ring, carbonate, thiocarbonate, carbonyl, cyclic acetal, ether, ester, sulfonic acid ester, cyano, amide, and —O—C(═O)-G- wherein G is —S— or —NH—.
In a preferred embodiment, the polymer further comprises recurring units of at least one type selected from recurring units represented by the formulae (d1) to (d3).




Herein R20, R24, and R28 are each independently hydrogen or methyl, R21 is a single bond, phenylene, —O—RA—, or —C(═O)—Y0—RA—, Y0 is —O— or —NH—, RA is a straight, branched or cyclic C1-C6 alkylene or alkenylene group which may contain a carbonyl, ester, ether or hydroxyl moiety, or phenylene group, R22, R23, R25, R26, R27, R29, R30, and R31 are each independently a straight, branched or cyclic C3-C12 alkyl group which may contain a carbonyl, ester or ether moiety, or a C6-C12 aryl, C7-C20 aralkyl, or mercaptophenyl group, Z1 is a single bond, a straight, branched or cyclic C1-C12 alkylene or C2-C12 alkenylene group which may contain an ether moiety, ester moiety or lactone ring, or C6-C10 arylene group, Z2 is a single bond, methylene, ethylene, phenylene, fluorinated phenylene, —O—R32—, or —C(═O)—Z3—R32—, Z3 is —O— or —NH—, R32 is a straight, branched or cyclic C1-C12 alkylene or C2-C12 alkenyiene group which may contain a carbonyl, ester, ether or hydroxyl moiety, or phenylene group, M− is a non-nucleophilic counter ion, d1, d2 and d3 are numbers in the range: 0≦d1≦0.5, 0≦d2≦0.5, 0≦d3≦0.5, and 0<d1+d2+d3≦0.5.

In a preferred embodiment, the resist composition may further comprise an acid generator, an organic solvent, optionally a basic compound and surfactant.
In another aspect, the invention provides a pattern forming process comprising the steps of applying the resist composition defined above onto a substrate to form a coating, baking, exposing the coating to high-energy radiation, and developing the exposed coating in a developer.
Typically, the high-energy radiation is i-line, KrF excimer laser, ArF excimer laser., electron beam or soft X-ray of wavelength 3 to 15 nm.
The resist composition, typically chemically amplified resist composition is used not only in the lithography for forming semiconductor circuits, but also in the formation of mask circuit patterns, micromachines, and thin-film magnetic head circuits.
Advantageous Effects of Invention
The resist composition is effective for suppressing acid diffusion, exhibits a high resolution, and forms a pattern of satisfactory profile with minimal edge roughness after exposure. Because of these advantages, the resist composition is best suited as a fine pattern-forming material for the manufacture of VLSIs and photomasks and a pattern-forming material for lithography using i-line, KrF excimer laser, ArF excimer laser, EB or EUV.


DESCRIPTION OF EMBODIMENTS
The singular forms “a,” “an” and “the” include plural referents unless the context clearly dictates otherwise. “Optional” or “optionally” means that the subsequently described event or circumstances may or may not occur, and that description includes instances where the event or circumstance occurs and instances where it does not. The notation (Cn-Cm) means a group containing from n to m carbon atoms per group. In the chemical formula, the broken line designates a valence bond, Me is methyl, Ac is acetyl, and Ph is phenyl.
The abbreviations have the following meaning.
EB: electron beam
EUV: extreme ultraviolet
PAG: nhotoacid generator
PEB: post-exposure bake
LER: line edge roughness
LWR: line width roughness
Mw: weight average molecular weight
Mw/Mn: molecular weight distribution or dispersity
GPC: gel permeation chromatography
Resist Composition
Base Resin
A first embodiment of the invention is a resist composition comprising a base resin which includes a polymer comprising recurring units represented by the formula (a), also referred to as recurring units (a), and recurring units having a carboxyl group whose hydrogen atom is substituted by an acid labile group and/or recurring units having a phenolic hydroxyl group whose hydrogen atom is substituted by an acid labile group. The polymer is sometimes referred to as “base polymer.”




Herein R1 is hydrogen or methyl, R2 and R3 are each independently hydrogen or a straight, branched or cyclic C1-C6 alkyl group, X1 is a single bond, a C1-C12 linking group containing an ester moiety, ether moiety or lactone ring, a phenyiene, or naphthylene group, X2 and X3 are each independently oxygen or sulfur, and a is a positive number the range: 0<a<1.0.
Monomers Ma from which recurring units (a) are derived include those represented by the formula (Ma).




Herein R1 to R3 and X1 to X3 are as defined above.

The monomer Ma may be synthesized, for example, by amidation reaction of a compound having the formula (a1) with a compound having the formula (a2).




In the formulae, R1 to R3 and X1 to X3 are as defined above. X4 is hydrogen, halogen such as chlorine or bromine, or a group of the following formula:




wherein R1 and X1 are as defined above.

Examples of the monomer Ma are shown below, but not limited thereto. Herein R1 is as defined above.













The recurring unit (a) is characterized by inclusion of an oxazolidinedione, thioxooxazolidinone, thiazolidinedione or thioxothiazolidinone structure. While the amide or carbamate group containing both nitrogen and oxygen atoms has the drawback that deprotection reaction is inhibited due to an extreme effect of suppressing acid diffusion, the recurring unit (a) having an oxazolidinedione, thioxooxazolidinone, thiazolidinedione or thioxothiazolidinone derivative bonded to the main chain via amide bond does not inhibit acid-catalyzed deprotection reaction because the presence of three carbonyl groups or two carbonyl groups and one thiocarbonyl group around the nitrogen atom prevents the nitrogen atom from exerting basicity. Yet, the unpaired electron in the nitrogen atom is highly effective for is suppressing acid diffusion. Three carbonyl groups provide for adhesion, and the unpaired electron in the nitrogen atom suppresses acid diffusion. As a result, pattern collapse is prevented and edge roughness (LWR) is mitigated.
Preferably, the recurring units having a carboxyl group substituted with an acid labile group are represented by the formula (b1) and the recurring units having a phenolic hydroxyl group substituted with an acid labile group are represented by the formula (b2). Notably, these units are also referred to as recurring units (b1) and (b2).




Herein R4 and R6 are each independently hydrogen or methyl, R5 and R9 are each independently an acid labile group, R7 is a single bond or a straight or branched C1-C6 alkylene group, R8 is hydrogen, fluorine, trifluoromethyl, cyano, or a straight, branched or cyclic C1-C6 alkyl, acyl, alkoxy, acyloxy or alkoxycarbonyl group, p is 1 or 2, q is an integer of 0 to 4, Y1 is a single bond, a C1-C12 linking group containing an ester moiety, ether moiety or lactone ring, a phenylene or naphthylene group, and Y2 is a single bond, —C(═O)—O— or —C(O)—NH—.
The monomer Mb1 from which recurring unit (b1) is derived has the formula (Mb1), and the monomer Mb2 from which recurring unit (b2) is derived has the formula (Mb2).




Herein R4 to R9, Yl, Y2, p and q are as defined above.

Of the groups Y1, the C1-C12 linking group containing lactone ring is exemplified below.




Examples of the monomer Mbl are given below, but not limited thereto. R4 and R5 are as defined above.










Examples of the monomer Mb2 are given below, but not limited thereto. R6 and R9 are as defined above.







In formulae (b1) and (b2), the acid labile groups represented by R8 and R9 may be selected from a variety of such groups. The acid labile groups may be the same or different and preferably include groups of the following formulae (A-1) to (A-3).




In formula (A-1), RL1 is a tertiary alkyl group of 4 to 20 carbon atoms, preferably 4 to 15 carbon atoms, trialkylsilyl group in which each alkyl moiety is of carbon atoms, oxoalkyl group of 4 to 20 carbon atoms, or a group of formula (A-3). A1 is an integer of 0 to 6.
Suitable tertiary alkyl groups include t-butyl, t-pentyl, 1,1-diethylpropyl, 1-ethylcyclopentyl, 1-butylcyclopentyl, 1-ethylcyclohexyl, 1-butylcyclohexyl, 1-ethyl-2-cyclopentenyl, 1-ethyl-2-cyclohexenyl, and 2-methyl-2-adamantyl. Suitable trialkylsilyl groups include trimethylsilyl, triethylsilyl, and dimethyl-t-butylsilyl. Suitable oxoalkyl groups include 3-oxocyclohexyl, 4-methyl-2-oxooxan-4-yl, and 5-methyl-2-oxooxolan-5-yl.
Examples of the acid labile group having formula (A-1) include t-butoxycarbonyl, t-butoxycarbonylmethyl, t-pentyloxycarbonyl, t-pentyloxycarbonylmethyl, 1,1-diethylpropyloxycarbonyl, 1,1-diethylpropyloxycarbonylmethyl, 1-ethylcyclopentyloxycarbonyl, 1-ethylcyclopentyloxycarbonylmethyl, 1-ethyl-2-cyclopentenyloxycarbonyl, 1-ethyl-2-cyclopentenyloxycarbonylmethyl, 1-ethoxyethoxycarbonylmethyl, 2-tetrahydropyranyloxycarbonylmethyl, and 2-tetrahydrofuranyloxycarbonylmethyl.
Of the acid labile groups of formula (A-1), groups having the following formulae (A-1)-1 to (A-1)-10 are preferred.







In the above formulae, RL8 is each independently a straight, branched or cyclic C1-C10 alkyl group or a C6-C20 aryl group. RL9 is hydrogen or a straight, branched or cyclic C1-C10 alkyl group. RL10 is a straight, branched or cyclic C2-C10 alkyl group or C6-C20 aryl group. A1 is an integer of 0 to 6.
In formula (A-2), RL2 and RL3 are each independently hydrogen or a straight, branched or cyclic alkyl group of 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms. Suitable alkyl groups include methyl, ethyl, propyl, isopropyl, n-butyl, s-butyl, t-butyl, cyclopentyl, cyclohexyl, 2-ethylhexyl, and n-octyl. RL4 is a monovalent hydrocarbon group of 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms, which may contain a heteroatom such as oxygen. Suitable monovalent hydrocarbon groups include straight, branched or cyclic alkyl groups and substituted forms of these alkyl groups in which some hydrogen atoms are substituted by hydroxyl, alkoxy, oxo, amino, or alkylamino groups. Examples of the substituted alkyl groups are shown below.




A pair of RL2 and RL3, RL2 and RL4, or RL3 and RL4 may bond together to form a ring with the carbon atom or carbon and oxygen atoms to which they are attached. In this event, the ring-forming combination of RL2 and RL3, RL2 and RL4, or LL3 and RL4 is a straight or branched alkylene group of 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms while the carbon count of the ring preferably ranges from 3 to 10, more preferably from 4 to 10.
Of the acid labile groups of formula (A-2), the straight and branched ones are exemplified by groups having the following formulae (A-2)-1 to (A-2)-69.






















Of the acid labile groups of formula (A-2), the cyclic ones are, for example, tetrahydrofuran-2-yl, 2-methyltetrahydrofuran-2-yl, tetrahydropyran-2-yl, and 2-methyltetrahydropyran-2-yl.
Other examples of acid labile groups include those of the following formula (A-2a) or (A-2b) while the base polymer may be crosslinked within the molecule or between molecules with these acid labile groups.




Herein RL11 and RL12 each are hydrogen or a straight, branched or cyclic C1-C6 alkyl group. RL11 and RL12 may bond together to form a ring with the carbon atom to which they are attached, and the ring-forming combination of RL40 and RL41 is a straight or branched C1-C8 alkylene group. RL13 is a straight, branched or cyclic C1-C10 alkylene group. Each of B1 and D1 is an integer of 0 to 10, preferably an integer of 0 to 5, and C1 is an integer of 1 to 7, preferably 1 to 3.
“A” is a (C1+1)-valent aliphatic or alicyclic saturated hydrocarbon group, aromatic hydrocarbon group or heterocyclic group having 1 to 50 carbon atoms, which may be separated by a heteroatom or in which a carbon-bonded hydrogen atom may be substituted by hydroxyl, carboxyl, acyl moiety or fluorine atom. Preferably, “A” is selected from straight, branched or cyclic C1-C20 alkylene, alkyltriyl and alkyltetrayl groups, and C6-C30 arylene groups. “B” is —CO—O—, —NHCO—O— or —NHCONH—.
The crosslinking acetal groups of formulae (A-2a) and (A-2b) are exemplified by the following formulae (A-2)-70 through (A-2)-77.




In formula (A-3), RL5, RL6 and RL7 are each independently a monovalent hydrocarbon group, typically a straight, branched or cyclic C1-C20 alkyl group or straight, branched or cyclic C2-C20 alkenyl group, which may contain a heteroatom such as oxygen, sulfur, nitrogen or fluorine. A pair of RL5 and RL6, RL5 and RL7, or RL6 and RL7 may bond together to form a C3-C20 ring with the carbon atom to which they are attached.
Exemplary tertiary alkyl groups of formula (A-3) include t-butyl, triethylcarbyl, 1-ethylnorbornyl, 1-methylcyclohexyl, 1-ethylcyclopentyl, 2-(2-methyl)adamantyl, 2-(2-ethyl)adamantyl, and t-pentyl.
Of the tertiary alkyl groups of formula (A-3), groups having the following formulae (A-3)-1 to (A-3)-18 are also useful.










Herein RL14 is each independently a straight, branched or cyclic C1-C8 alkyl group or C6-C20 aryl group, typically phenyl. RL15 and RL17 are each independently hydrogen or a straight, branched or cyclic C1-C20 alkyl group. RL16 is a C6-C20 aryl group, typically phenyl.
Other acid labile groups include those having the formulae (A-3)-19 and (A-3)-20, The polymer may be crosslinked within the molecule or between molecules with these acid labile groups.




Herein RL14 is as defined above, RL18 is a (E1+1)-valent, straight, branched or cyclic C1-C20 aliphatic hydrocarbon group or di- to tetravalent C6-C20 aromatic hydrocarbon group, which may contain a heteroatom such as oxygen, sulfur or nitrogen, and E1 is an integer of 1 to 3.
Of recurring units having acid labile groups of formula (A-3), recurring units of (meth)acrylate having an exo-form structure represented by the formula (A-3)-21 are preferred.




Herein, R4 is as defined above; RLc1 is a straight, branched or cyclic C1-C8 alkyl group or an optionally substituted C6-20 aryl group; RLc2 to RLc7, RLc10 and RLc11 are each independently hydrogen or a monovalent Cl-C1, hydrocarbon group which may contain a heteroatom; and RLc8 and RLc9 are hydrogen. Alternatively, a pair of RLc2 and RLc3, RLc4 and RLc6, RLc4 and RLc7, RLc5 and RLc7, RLc5 and RLc11, RLc6 and RLc10, RLc8 and RLc9, or RLc9 and RLc10, taken together, may form a ring with the carbon atom to which they are attached, and in that event, the ring-forming combination is a divalent C1-C15 hydrocarbon group which may contain a heteroatom. Also, a pair of RLc2 and RLc11, RLc8 and RLc11, or RLc4 and RLc6 which are attached to vicinal carbon atoms may bond together directly to form a double bond. The formula also represents an enantiomer.

Examples of the monomer from which recurring units having an exo-form structure represented by formula (A-3)-21 are derived are described in U.S. Pat. No. 6,448,420 (JP-A 2000-327633). Illustrative non-limiting examples of suitable monomers are given below. R4 is as defined above.







Also included in the recurring units having an acid labile group of formula (A-3) are recurring units of (meth)acrylate having furandiyl, tetrahydrofurandiyl or oxanorbornanediyl group as represented by the following formula (A-3)-22.




Herein, R4 is as defined above; RLc12 and RLc13 are each independently a straight, branched or cyclic C1-C10 monovalent hydrocarbon group, or RLc12 and RLc13, taken together, may form an aliphatic ring with the carbon atom to which they are attached. RLc14 is furandiyl, tetrehydrofurandiyl or oxanorbornanediyl. RLc15 is hydrogen or a straight, branched or cyclic C1-C10 monovalent hydrocarbon group which may contain a heteroatom. Examples of the monomer from which the recurring units having formula (A-3)-22 are derived are shown below, but not limited thereto.

















An acid labile group having the following formula (A-3)-23 is also exemplary of the acid labile group having formula (A-3). When the base polymer contains the acid labile group having formula (A-3)-23, recurring units (b1) substituted with this acid labile group are preferably incorporated.




Herein RL100 is hydrogen, halogen, cyano, C1-C4 alkyl, C1-C4 alkoxy, C2-C5 acyl, C2-C5 alkoxycarbonyl, or C6-C10 aryl group, and K1 is an integer of 1 to 4.

Examples of the monomer from which recurring units substituted with the acid labile group of formula (A-3)-23 are derived are given below, but not limited thereto. R4 is as defined above.







An acid labile group having the following formula (A-3)-24 is also exemplary of the acid labile group having formula (A-3). When the polymer contains the acid labile group having formula (A-3)-24, recurring units (b1) substituted with this acid labile group are preferably incorporated.




Herein RL101 and RL102 are each independently hydrogen, halogen, cyano, hydroxyl, C1-C4 alkyl, C1-C4 alkoxy, C2-C5 acyl, C2-C5 alkoxycarbonyl, or C6-C10 aryl group; R is hydrogen, a straight, branched or cyclic C1-C12 alkyl group which may contain an oxygen or sulfur atom, C2-C12 alkenyl, C2-C12 alkynyl, or C4-C10 aryl group; RL103, RL104, R105, and RL106 each are hydrogen, or a pair of RL103 and RL104, RL104 and RL105, or RL105 and RL106 may bond together to form a benzene ring; k2 and k3 each are an integer of 1 to 4.
Examples of the monomer from which recurring units having the acid labile group of formula (A-3)-24 are derived are given below, but not limited thereto. R4 is as defined above.

























An acid labile group having the following formula (A-3)-25 is also exemplary of the acid labile group having formula (A-3). When the polymer contains the acid labile group having formula (A-3)-25, recurring units (b1) substituted with this acid labile group are preferably incorporated.




Herein R is as defined above. RL107 is each independently hydrogen or a straight, branched or cyclic C1-C6 alkyl group, and in case k4 is 2 or more, RL107 may bond together to form a non-aromatic ring of 2 to 8 carbon atoms; the circle Z denotes a divalent link between carbons CA and C8, selected from among ethylene, propylene, butylene and pentylene; RL107 is not hydrogen when Z denotes ethylene or propylene; RL108 is each independently hydrogen, hydroxyl, nitro, halogen, cyano, C1-C4 alkyl, C1-C4 alkoxy, C2-C5 acyl, C2-C5 alkoxycarbonyl or C6-C10 aryl group; k4 and k5 each are an integer of 1 to 4.
Examples of the monomer from which recurring units having the acid labile group of formula (A-3)-25 are derived are given below, but not limited thereto. R4 is as defined above.





































An acid labile group having the following formula (A-3)-26 is also exemplary of the acid labile group having formula (A-3). When the polymer contains the acid labile group having formula (A-3)-26, recurring units (bl) substituted with this acid labile group are preferably incorporated.




Herein R is as defined above; RL109 and RL110 are each independently hydrogen, hydroxyl, nitro, halogen, cyano, C1-C4 alkyl, C1-C4 alkoxy, C2-C5 acyl, C2-C5 alkoxycarbonyl or C6-C10 aryl group; and k6 and k7 each are an integer of 1 to 4.
Examples of the monomer from which recurring units having the acid labile group of formula (A-3)-26 are derived are given below, but not limited thereto. R4 is as defined above.



















An acid labile group having the following formula (A-3)-27 is also exemplary of the acid labile group having formula (A-3). When the polymer contains the acid labile group having formula (A-3)-27, recurring units (b1) substituted with this acid labile group are preferably incorporated.




Herein R is as defined above; RL111 and RL112 are each independently hydrogen, hydroxyl, nitro, halogen, cyano, C1-C4 alkyl, C1-C4 alkoxy, C2-C5 acyl, C2-C5 alkoxycarbonyl or C6-C10 aryl group; K8 and k9 each are an integer of 1 to 4; and J is methylene, ethylene, vinylene or —CH2—S—.
Examples of the monomer from which recurring units having the acid labile group of formula (A-3)-27 are derived are given below, but not limited thereto. R4 is as defined above.






















An acid labile group having the following formula (A-3)-28 is also exemplary of the acid labile group haying formula (A-3). When the polymer contains the acid labile group having formula (A-3)-28, recurring units (b1) substituted with this acid labile group are preferably incorporated.




Herein R is as defined above; RL113 and RL114 are each independently hydrogen, hydroxyl, halogen, cyano, C1-C4 alkyl, C1-C4 alkoxy, C2-C5 acyl, C2-C5 alkoxycarbonyl or C6-C10 aryl group; k10 and k11 each are an integer of 1 to 4; and L is carbonyl, ether, sulfide, —S(═O)— or —S(═O)2—.
Examples of the monomer from which recurring units having the acid labile group of formula (A-3)-28 are derived are given below, but not limited thereto. R4 is as defined above.


































In a more preferred embodiment, the base polymer may further comprise recurring units (c) having an adhesive group. The adhesive group is selected from among hydroxyl, carboxyl, lactone ring, carbonate, thiocarbonate, carbonyl, cyclic acetal, ether, ester, sulfonic acid ester, cyano, amide, and —O—C(═O)-G- wherein G is —S— or —NH—. Examples of the monomer from which the recurring units (c) are derived are shown below, but not limited thereto.
































































In the case of a monomer having a hydroxyl group, the hydroxyl group may be replaced by an acetal group susceptible to deprotection with acid, typically ethoxyethoxy, prior to polymerization, and the polymerization be followed by deprotection with weak acid and water. Alternatively, the hydroxyl group may be replaced by an acetyl, formyl, pivaloyl or similar group prior to polymerization, and the polymerization be followed by alkaline hydrolysis.
In a more preferred embodiment, the base polymer may further comprise recurring units derived from sulfonium salts represented by the following formulae (d1) to (d3), which are also referred to as recurring units (d1) to (d3).




Herein R20, R24, and R28 eachare hydrogen or methyl, R21 is a single bond, phenylene, —O—RA—, or —C(═O)—Y0—RA— wherein Y) is —O— or —NH— and RA is a straight, branched or cyclic C1-C6 alkylene or alkenylene group which may contain a carbonyl (—CO—), ester (—COO—), ether (—O—) or hydroxyl moiety, or phenylene group. R22, R23, R25, R26, R27, R29, R30, and R31 are each independently a straight, branched or cyclic C1-C12 alkyl group which may contain a carbonyl, ester or ether moiety, a C6-C12 aryl group, C7-C20 aralkyl group, or mercaptophenyl group. Z1 is a single bond or a straight, branched or cyclic C1-C12 alkylene or C2-C12 alkenylene group which may contain an ether moiety, ester moiety or lactone ring, or C6-C10 arylene group. Z2 is a single bond, methylene, ethylene, phenylene, fluorinated phenylene, —O—R32—, or —C(═O)—Z3—R32— wherein Z3 is —O— or —NH— and R32 is a straight, branched or cyclic C1-C12 alkylene or C2-C12 alkenylene group which may contain a carbonyl, ester, ether or hydroxyl moiety, or phenvlene group. M− is a non-nucleophilic counter ion.

Binding an acid generator to the polymer backbone is effective for reducing acid diffusion and preventing the resolution from lowering due to blur by acid diffusion. Additionally, edge roughness (LER, LWR) is improved because the acid generator is uniformly dispersed.
Examples of the non-nucleophilic counter ion represented by M− include halide ions such as chloride and bromide ions; fluoroalkylsulfonate ions such as triflate, 1,1,1-trifluoroethanesulfonate, and nonafluorobutanesulfonate; arylsulfonate ions such as tosylate, benzenesulfonate, 4-fluorobenzenesulfonate, and 1,2,3,4,5-pentafluorobenzenesulfonate; alkylsulfonate ions such as mesylate and butanesulfonate; imidates such as bis(trifluoromethylsulfonyl)imide, bis(perfluoroethylsulfonyl)imide and bis(perfluorobutylsulfonyl)imide; methidates such as tris(trifluoromethylsulfonyl)methide and tris(perfluoroethylsulfonyl)methide.
Other non-nucleophilic counter ions include sulfonates having fluorine substituted at α-position as represented by the formula (K-1) and sulfonates having fluorine substituted at α- and β-positions as represented by the formula (K-2).




In formula (K-1), R41 is hydrogen, or a straight, branched or cyclic C1-C20 alkyl group, C2-C20 alkenyl group, or C6-C20 aryl group, which may have an ether, ester, carbonyl moiety, lactone ring or fluorine. In formula (K-2), R42 is hydrogen, or a straight, branched or cyclic C1-C30 alkyl or acyl group. C2-C20 alkenyl group, or C6-C20 aryl or aryloxy group, which may have an ether, ester, carbonyl moiety or lactone ring.

Understandably, when a polymer having copolymerized therein recurring units of at least one type selected from units (d1) to (d3) is used as the base resin in a resist composition, the addition of a PAG to be described later may be omitted.
The base polymer may have further copolymerized therein recurring units of any type selected from units having the formulae (e1) to (e5), which are also referred to as recurring units (e1) to (e5).




Herein R110 to R114 each are hydrogen C1-C30 alkyl, partially or entirely halo-substituted C1-C30 alkyl, hydroxyl, C1-C30 alkoxy, acyl, C2-C30 alkoxycarbonyl, C6-C10 aryl, halogen, or 1,1,1,3,3,3-hexafluoro-2-propanol group; and X9 is a methylene, ether or sulfide group.

Additional recurring units (f) may be copolymerized in the base polymer. Exemplary recurring units (f) are derived from styrene, vinylnaphthalene, vinylanthracene, vinylpyrene, methyleneindane, and the like.
The base polymer defined herein may be synthesized by any desired methods, for example, by dissolving suitable monomers selected from the monomers corresponding to recurring units (a) to (f) in an organic solvent, adding a radical polymerization initiator thereto, and effecting heat polymerization. Examples of the organic solvent which can be used for polymerization include toluene, benzene, tetrahydrofuran, diethyl ether, dioxane, cyclohexane, cyclopentane, methyl ethyl ketone, and γ-butyrolactone. Examples of the polymerization initiator used herein include 2,2′-azobisisobutyronitrile (AIBN), 2,2′-azobis(2,4-dimethyl-valeronitrile), dimethyl 2,2-azobis(2-methylpropionate), benzoyl peroxide, and laurayl peroxide. Preferably the system is heated at 50 to 80° C. for polymerization to take place. The reaction time is 2 to 100 hours, preferably 5 to 20 hours.
When hydroxystyrene or hydroxyvinylnaphthalene is copolymerized, an alternative method is possible. Specifically, acetoxystyrene or acetoxyvinylnaphthalene is used instead of hydroxystyrene or hydroxyvinylnaphthalene, and after polymerization, the acetoxy group is deprotected by alkaline hydrolysis, for conversion to hydroxystyrene or hydroxyvinylnaphthalene units. For alkaline hydrolysis, a base such as aqueous ammonia or triethylamine may be used. The reaction temperature is −20° C. to 100° C., preferably 0° C. to 60° C., and the reaction time is 0.2 to 100 hours, preferably 0.5 to 20 hours.
In the base polymer, recurring units (a) and (b) may be incorporated in the following molar fraction: 0<a<1.0, 0≦b1<1.0, 0≦b2<1.0, 0<b1+b2<1.0, and 0.1≦a+b1+b2≦1.0, the fraction of recurring units (c) is in the range: 0≦c≦0.9, where unit (c) is incorporated, 0<c≦0.9 and 0.2≦a+b1+b2+c≦1.0; more preferably 0.02≦a≦0.8, 0≦b1≦0.8, 0≦b2≦0.8, 0.1≦b1+b2≦0.8, 0.1≦c≦0.88; even more preferably 0.05≦a≦0.75, 0≦b1≦0.7, 0≦b2≦0.7, 0.1≦b1+b2≦0.75, 0.15≦c≦0.85; and most preferably 0.07≦a≦0.7, 0≦b1≦0.65, 0≦b2≦0.65, 0.1≦b1+b2≦0.7, 0.2≦c≦0.83. The sum is preferably in a range: 0.2≦a+b1+b2+c≦1.0, more preferably 0.3≦a+b1+b2+c≦1.0, and even more preferably 0.4≦a+b1+b2+c≦1.0.
The fraction of recurring units (d1) to (d3) is in the range: 0≦d1≦0.5, 0≦d2≦0.5, 0≦d3≦0.5, and 0≦d1+d2+d3≦0.5, and where any of units (d1) to (d3) is incorporated, 0<d1+d2+d3≦0.5; preferably 0≦d1≦0.4, 0≦d2≦0.4, 0≦d3≦0.4, and 0<d1+d2+d3≦0.4; more preferably 0≦d1≦0.3, 0≦d2≦0.3, 0≦d3≦0.3, and 0<d1+d2+d3≦0.3; and even more preferably 0≦d1≦0.2, 0≦d2≦0.2, 0≦d3≦0.2, and 0<d1+d2+d3≦0.25. The sum is preferably in a range; 0.2≦a+b1+b2+c+d1+d2+d3≦1.0, more preferably 0.4≦a+b1+b2+c+d1+d2+d3≦1.0. Where any of units (d1) to (d3) is incorporated, the preferred range is 0<d1+d2+d3≦0.5.
The fraction of recurring units (e1) to (e5) is in the range: 0≦e1≦0.5, 0≦e2≦0.5, 0≦e3≦0.5, 0≦e4≦0.5, 0≦e5≦0.5, and 0≦e1+e2+e3+e4+e5≦0.5, and where any of units (e1) to (e5) is incorporated, 0<e1+e2+e3+e4+e5≦0.5; preferably 0≦e1≦0.4, 0≦e2≦0.4, 0≦e3≦0.4, 0≦e4≦0.4, 0≦e5≦0.4, and 0<e1+e2+e3+e4+e5≦0.4; more preferably 0≦e1≦0.3, 0≦e2≦0.3, 0≦e3≦0.3, 0≦e4≦0.3, 0≦e5≦0.3, and 0<e1+e2+e3+e4+e5≦0.3.
The fraction of recurring units (f) is in the range: 0≦f≦0.5, preferably 0≦f≦0.4, more preferably 0≦f≦0.3. It is preferred that a+b1+b2+c+d1+d2+d3+e1+e2+e3+e4+e5+f=1.
The base polymer should have a weight average molecular weight (MW) in the range of 1,000 to 500,000, and preferably 2,000 to 30,000, as measured versus polystyrene standards by GPC using tetrahydrofuran solvent. With Mw≧1,000, the resist composition is heat resistant. A polymer with Mw≦500,000 is fully alkali soluble and avoids a footing phenomenon after pattern formation.
If a multi-component copolymer has a wide molecular weight distribution or dispersity (Mw/Mn), which indicates the presence of lower and higher molecular weight polymer fractions, there is a possibility that foreign matter is left on the pattern or the pattern profile is degraded. The influences of molecular weight and dispersity become stronger as the pattern rule becomes finer. Therefore, the base polymer should preferably have a narrow dispersity (Mw/Mn) of 1.0 to 2.0, especially 1.0 to 1.5, in order to provide a resist composition suitable for micropatterning to a small feature size.
The polymer defined above is advantageously used as a base resin in a resist composition, typically chemically amplified resist composition. In this context, not only a single inventive polymer may be used as the base resin, but also a blend of two or more inventive polymers which differ in compositional ratio, molecular weight or dispersity or a blend of an inventive polymer and a polymer free of recurring unit (a) is acceptable.
Acid Generator
An acid generator may be added to a resist composition so that it may function as a chemically amplified resist composition. Typical of the acid generator used herein is a photoacid generator (PAG) capable of generating an acid in response to actinic light or radiation.
The PAG is any compound capable of generating an acid upon exposure to high-energy radiation. Suitable PAGs include sulfonium salts, iodonium salts, sulfonyldiazo e ne, N-sulfonyloxyimide, and oxime-O-sulfonate acid generators. Exemplary PAGs are described in U.S. Pat. No. 7,537,880 (JP-A 2008-111103, paragraphs [0122] to [0142]).
As the PAG, compounds having the formula (1) or (2) are also preferably used.




In formula (1), R101, R102 and R103 are each independently a straight, branched or cyclic C1-C20 monovalent hydrocarbon group which may contain a heteroatom, any two or more of R101, R102 and R103 may bond together to form a ring with the sulfur atom to which they are attached.
In formula (I), X− is an anion selected from the formulae (1A) to (1D),




In formula (1A), Rfa is fluorine or a straight, branched or cyclic C1-C40 monovalent hydrocarbon group which may contain a heteroatom.
Of the anions of formula (1A), a structure having formula (1A′) is preferred.




In formula (1A′), R104 is hydrogen or trifluoromethyl, preferably trifluoromethyl. R105 is a straight, branched or cyclic C1-C38 monovalent hydrocarbon group which may contain a heteroatom. Suitable heteroatoms include oxygen, nitrogen, sulfur and halogen, with oxygen being preferred. Of the monovalent hydrocarbon groups, those of 6 to 30 carbon atoms are preferred because a high resolution is available in fine pattern formation. Suitable monovalent hydrocarbon groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, pentyl, neopentyl, cyclopentyl, hexyl, cyclohexyl, 3-cyclohexenyl, heptyl, 2-ethylhexyl, nonyl, undecyl, tridecyl, pentadecyl, heptadecyl, 1-adamantyl, 2-adamantyl, 1-adamantylmethyl, norbornyl, norbornylmethyl, tricyclodecanyl, tetracyclododecanyl, tetracyclododecanylmethyl, dicyclohexylmethyl, icosanyl, allyl, benzyl, diphenylmethyl, tetrahydrofurvl, methoxymethyl, ethoxymethyl, methylthiomethyl, acetamidomethyl, trifluoroethyl, (2-methoxyethoxy)methyl, acetoxymethyl, 2-carboxy-1-cyclohexyl, 2-oxopropyl, 4-oxo-1-adamantyl, and 3-oxocyclohexyl. Also included are the foregoing groups in which at least one hydrogen is rep/aced by a radical containing a heteroatom such as oxygen, sulfur, nitrogen or halogen, or in which a radical containing a heteroatom such as oxygen, sulfur or nitrogen intervenes between carbon atoms, so that the group may contain a hydroxyl, cyano, carbonyl, ether, ester, sulfonic acid ester, carbonate, lactone ring, sultone ring, carboxylic acid anhydride or haloalkyl radical.
With respect to the synthesis of the sulfonium salt having an anion of formula (1A′), reference is made to JP-A 2007-145797, JP-A 2008-106045, JP-A 2009-007327, and JP-A 2009-258695. Also useful are the sulfonium salts described in JP-A 2010-215608, JP-A 2012-041320, JP-A 2012-106986, and JP-A 2012-153644.
Examples of the sulfonium salt having an anion of formula (1A) are shown below, but not limited thereto.



















In formula (IB), Rfb1 and Rfb2 are each independently fluorine or a straight, branched or cyclic C1-C40 monovalent hydrocarbon group which may contain a heteroatom. Suitable monovalent hydrocarbon groups are as exemplified above for R105. Preferably Rfb1 and Rfb2 each are fluorine or a straight C1-C4 fluorinated alkyl group. A pair of Rfb1 and Rfb2 may bond together to form a ring with the linkage (—CF2—SO2—N−—SO2—CF2—) to which they are attached, and preferably the pair is a fluorinated ethylene or fluorinated propylene group.
In formula (1C), Rfc1, Rfc2 and Rfc3 are each independently fluorine or a straight, branched or cyclic C1-C40 monovalent hydrocarbon group which may contain a heteroatom. Suitable monovalent hydrocarbon groups are as exemplified above for R105. Preferably Rfc1, Rfc2 and Rfc3 each are fluorine or a straight C1-C4 fluorinated alkyl group. A pair of Rfc1 and Rfc2 may bond together to form a ring with the the linkage (—CF2—SO2—C−—SO2—CF2—) to which they are attached, and preferably the pair is a fluorinated ethylene or fluorinated propylene group.
In formula (1D), Rfd is a straight, branched or cyclic C1-C40 monovalent hydrocarbon group which may contain a heteroatom. Suitable monovalent hydrocarbon groups are as exemplified above for R105.
With respect to the synthesis of the sulfonium salt having an anion of formula (1D), reference is made to JP-A 2010-215608 and JP-A 2014-133723.
Examples of the sulfonium salt having an anion of formula (1D) are shown below, but not limited thereto.







The compound having the anion of formula (1D) has a sufficient acid strength to cleave acid labile groups in the base polymer because it is free of fluorine at α-position of sulfo group, but has two trifluoromethyl groups at β-position. Thus the compound is a useful PAG.
In formula (2), R201 and R202 are each independently a straight, branched or cyclic C1-C30 monovalent hydrocarbon group which may contain a heteroatom. R203 is a straight, branched or cyclic C1-C30 divalent hydrocarbon group which may contain a heteroatom. Any two or more of R201, R202 and R203 may bond together to form a ring with the sulfur atom to which they are attached. LA is a single bond, ether bond or a straight, branched or cyclic C1-C20 divalent hydrocarbon group which may contain a heteroatom. XA, XB, XC and XD are each independently hydrogen, fluorine or trifluoromethyl, with the proviso that at least one of XA, XB, XC and XD is fluorine or trifluoromethyl, and k is an integer of 0 to 3.
Suitable monovalent hydrocarbon groups include methyl, ethyl, propyl, isopropyl, n-butyl, s-butyl, t-butyl, n-pentyl, t-pentyl, n-hexyl, n-octyl, n-nonyl, n-decyl, cyclopentyl, cyclohexyl, 2-ethylhexyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylbutyl, cyclohexylmethyl, cyclohexylethyl, cyclohexylbutyl, norbornyl, oxanorbornyl, tricyclo[5.2.1.02,6]decanyl, adamantyl, phenyl, naphthyl and anthracenyl. Also included are the foregoing groups in which at least one hydrogen is replaced by a heteroatom such as oxygen, sulfur, nitrogen or halogen, or in which at least one carbon is replaced by a heteroatom such as oxygen, sulfur or nitrogen, so that the group may contain a hydroxyl, cyano, carbonyl, ether bond, ester bond, sulfonic acid ester bond, carbonate bond, lactone ring, sultone ring, carboxylic acid anhydride or haloalkyl radical.
Suitable divalent hydrocarbon groups include linear alkane diyl groups such as methylene, ethylene, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl, nonane-1,9-diyl, decane-1,10-diyl, undecane-1,11-diyl, dodecane-1,12-diyl, tridecane-1,13-diyl, tetradecane-1,14-diyl, pentadecane-1,15-diyl, hexadecane-1,16-diyl, heptadecane-1,17-diyl; saturated cyclic divalent hydrocarbon groups such as eyclopentanediyl, cyclohexanediyl, norbornanediyl, and adamantanediyl; and unsaturated cyclic divalent hydrocarbon groups such as phenylene and naphthylene. Also included are the foregoing groups in which at least one hydrogen atom is replaced by an alkyl group such as methyl, ethyl, propyl, n-butyl or t-butyl, or in which at least one hydrogen atom is replaced by a radical containing a heteroatom such as oxygen, sulfur, nitrogen or halogen, or in which a radical containing a heteroatom such as oxygen, sulfur or nitrogen intervenes between carbon atoms, so that the group may contain a hydroxyl, cyano, carbonyl, ether, ester, sulfonic acid ester, carbonate, lactone ring, sultone ring, carboxylic acid anhydride or haloalkyl radical. Suitable heteroatoms include oxygen, nitrogen, sulfur and halogen, with oxygen being preferred.
Of the PAGs haying formula (2), those having formula (2′) are preferred.




In formula (2′), LA is as defined above. LB is hydrogen or trifluoromethyl, preferably trifluoromethyl. R301, R302 and R303 are each independently hydrogen or a straight, branched or cyclic C1-C20 monovalent hydrocarbon group which may contain a heteroatom. Suitable monovalent hydrocarbon groups are as exemplified above for R105. The subscripts x and y each are an integer of 0 to 5, and z is an integer of 0 to 4.
Examples of the PAG having formula (2) are shown below, but not limited thereto. Herein LB is as defined above.

























Of the foregoing PAGs, those compounds having an anion of formula (1A′) or (1D) are especially preferred because of reduced acid diffusion and high solubility in resist solvent, and those compounds having an anion of formula (2′) are especially preferred because of minimized acid diffusion.
An appropriate amount of the PAG added is 0.01 to 100 parts, more preferably 0.1 to 80 parts by weight per 100 parts by weight of the base resin. The PAGs may be used alone or in admixture.
Organic Solvent
The resist composition may comprise an organic solvent. Examples of the organic solvent are described in U.S. Pat. No. 7,537,880 (JP-A 2008-111103, paragraphs [0144]-[0145]). Specifically, exemplary solvents include ketones such as cyclohexanone and methyl n-pentyl ketone; alcohols such as 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, and 1-ethoxy-2-propanol; ethers such as propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, and diethylene glycol dimethyl ether; esters such as propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, t-butyl acetate, t-butyl propionate, and propylene glycol mono-t-butyl ether acetate; and lactones such as γ-butyrolactone, and mixtures thereof.
An appropriate amount of the organic solvent used is 50 to 10,000 parts, more preferably 100 to 5,000 parts by weight per 100 parts by weight of the base resin.
Other Components
The resist composition may further comprise any additives such as a basic compound, dissolution regulator, surfactant, and acetylene alcohol.
The addition of the basic compound to the resist composition is effective, for example, for reducing the rate of acid diffusion in the resist film, thus contributing to a further improvement in resolution. Exemplary basic compounds include primary, secondary and tertiary amine compounds, specifically amine compounds having a hydroxyl, ether, ester, lactone, cyano or sulfonic ester group, as described in JP-A 2008-111103, paragraphs [0146]-[0164] (U.S. Pat. No. 7,537,880). An appropriate amount of the basic compound added is 0 to 100 parts, more preferably 0.001 to 50 parts by weight per 100 parts by weight of the base resin.
The addition of the surfactant to the resist composition is effective for facilitating or controlling coating operation. Exemplary surfactants are described in JP-A 2006-111103, paragraphs [0165]-[0166]. An appropriate amount of the surfactant added is 0 to 10 parts, more preferably 0.0001 to 5 parts by weight per 100 parts by weight of the base resin.
The addition of the dissolution regulator to the resist composition is effective for exaggerating a difference in dissolution rate between exposed and unexposed regions, thus contributing to a further improvement in resolution. Exemplary dissolution regulators are described in US 2008090172 (JP-A 2008-122932, paragraphs [0155]-[0178]). An appropriate amount of the dissolution regulator added is 0 to 50 parts, more preferably 0 to 40 parts by weight per 100 parts by weight of the base resin.
Exemplary acetylene alcohols are described in JP-A 2008-122932, paragraphs [0179]-[0182]. An appropriate amount of the acetylene alcohol added is 0 to 2%, more preferably 0.02 to 11 by weight of the resist composition.
Also useful are quenchers of polymer type as described in JP-A 2008-289918. The polymeric quencher segregates at the resist surface after coating and thus enhances the rectangularity of resist pattern. When a protective film is applied on the resist film, the polymeric quencher is also effective for preventing any film thickness loss of resist pattern or rounding of pattern top. When the polymeric quencher is added, its amount is arbitrary as long as the benefits of the invention are not impaired.
Also an onium salt of sulfonic acid which is not fluorinated at α-position or carboxylic acid as represented by the formula (3) or (4) is useful as the quencher.




Herein R151, R152 and R153 are each independently hydrogen, halogen exclusive of fluorine, or a straight, branched or cyclic C1-C40 monovalent hydrocarbon group which may contain a heteroatom, any two or more of R151, R152 and R153 may bond together to form a ring with the carbon atom to which they are attached. R154 is a straight, branched or cyclic C1-C40 monovalent hydrocarbon group which may contain a heteroatom. M+ is an onium cation.

The onium salt of sulfonic acid which is not fluorinated at α-position is described in U.S. Pat. No. 8,795,942 (JP-A 2008-158339). The PAGs capable of generating sulfonic acid which is not fluorinated at α-position are exemplified in JP-A 2010-155824, paragraphs [0019]-[0036] and JP-A 2010-215608, paragraphs [0047]-[0082]. The onium salts of carboxylic acid are described in JP 3991462.
The anion in formula (3) or (4) is a conjugated base of weak acid. As used herein, the weak acid indicates an acidity insufficient to deprotect an acid labile group from an acid labile group-containing unit in the base resin. The onium salt haying formula (3) or (4) functions as a quencher when used in combination with an onium salt type PAG having a conjugated base of a strong acid, typically a sulfonic acid which is fluorinated at α-position as the counter anion.
In a system using a mixture of an onium salt capable of generating a strong acid (e.g., α-position fluorinated sulfonic acid) and an onium salt capable of generating a weak acid (e.g., α-position non-fluorinated sulfonic acid or carboxylic acid), if the strong acid generated from the PAG upon exposure to high-energy radiation collides with the unreacted onium salt having a weak acid anion, then a salt exchange occurs whereby the weak acid is released and an onium salt having a strong acid anion is formed. In this course, the strong acid is exchanged into the weak acid having a low catalysis, incurring apparent deactivation of the acid for enabling to control acid diffusion.
In particular, since sulfonium salts and iodonium salts of an α-position non-fluorinated sulfonic acid and a carboxylic acid are photo-decomposable, those portions receiving a high light intensity are reduced in quenching capability and increased in the concentration of an α-position fluorinated sulfonic acid, imide acid, or methide acid. This enables to form a pattern having an improved contrast in exposed area, further improved depth of focus (DOF) and satisfactory dimensional control.
If a PAG capable of generating a strong acid is an onium salt, an exchange from the strong acid generated upon exposure to high-energy radiation to a weak acid as above can take place, but it never happens that the weak acid generated upon exposure to high-energy radiation collides with the unreacted onium salt capable of generating a strong acid to induce a salt exchange. This is because of a likelihood of an onium cation forming an ion pair with a stronger acid anion.
In case the acid labile group is an acetal group which is very sensitive to acid, the acid for eliminating the protective group need not necessarily be an α-fluorinated sulfonic acid, imide acid or methide acid. Sometimes, deprotection reaction may take place even with α-position non-fluorinated sulfonic acid. In this case, since an onium salt of sulfonic acid cannot be used as the quencher, an onium salt of carboxylic acid is preferably used alone as the quencher.
Of the onium salts of a-position non-fluorinated sulfonic acid and carboxylic acid, sulfonium salts of sulfonic acid haying the following formula (3′) and sulfonium salts of carboxylic acid having the following formula (4′) are preferred.




Herein R251, R252 and R253 are each independently a straight, branched or cyclic C1-C20 monovalent hydrocarbon group which may contain a heteroatom, any two or more of R253, R252 and R253 may bond together to form a ring with the atom to which they are attached and intervening atoms. R254 is a straight, branched or cyclic C1-C40 monovalent hydrocarbon group which may contain a heteroatom. R255 and R256 are each independently hydrogen or trifluoromethyl. R257 and R258 are each independently hydrogen, fluorine or trifluoromethyl. R259 is hydrogen, hydroxyl, a straight, branched or cyclic C1-C35 monovalent hydrocarbon group which may contain a heteroatom, or optionally substituted C6-C30 aryl group. The subscript r is an integer of 1 to 3, z1, z2 and z3 are each independently an integer of 0 to 5.
The quencher may be used alone or in admixture of two or more. An appropriate amount of the quencher is 0 to 50 parts, preferably 0.001 to 50 parts, more preferably 0.01 to 20 parts by weight, per 100 parts by weight of the base resin. The inclusion of quencher facilitates adjustment of resist sensitivity and holds down the rate of acid diffusion within the resist film, resulting in better resolution. In addition, it suppresses changes in sensitivity following exposure and reduces substrate and environment dependence, as well as le improving the exposure latitude and the pattern profile. The inclusion of quencher is also effective for improving adhesion to the substrate.
Also a polymeric additive may be added for improving the water repellency on surface of a resist film as spin coated. The water repellency improver may be used in the topcoatless immersion lithography. The preferred water repellency improvers have a specific structure with a 1,1,1,3,3,3-hexafluoro-2-propanol residue, with their examples being described in JP-A 2007-297590 and JP-A 2008-111103. The water repellency improver to be added to the resist composition should be soluble in the organic solvent as the developer. The water repellency improver of specific structure with a 1,1,1,3,3,3-hexalluoro-2-propanol residue is well soluble in the developer. A polymer having an amino group or amine salt copolymerized as recurring units may serve as the water repellency improver and is effective for preventing evaporation of acid during PEB and any hole pattern opening failure after development. An appropriate amount of the water repellency improver is 0.1 to 20 parts, preferably 0.5 to 10 parts by weight per 100 parts by weight of the base resin.
As alluded to previously, the polymer is advantageously used as a base resin in a resist composition. Specifically, the polymer is used as a base resin and combined with any desired components including an organic solvent, acid generator, dissolution regulator, basic compound, and surfactant to formulate a resist composition. This resist composition has a very high sensitivity in that the dissolution rate in developer of the polymer in exposed areas is accelerated by catalytic reaction. In addition, the resist film has a high dissolution contrast, resolution, exposure latitude, and process adaptability, and provides a good pattern profile after exposure, yet better etch resistance, and minimal proximity bias because of restrained acid diffusion. By virtue of these advantages, the composition is fully useful in commercial application and suited as a pattern-forming material for the fabrication of VLSIs. Particularly when an acid generator is included to formulate a chemically amplified resist composition capable of utilizing acid catalyzed reaction, the composition has a higher sensitivity and is further improved in the properties described above.
Process
The resist composition, typically chemically amplified resist composition comprising a base resin containing the polymer, an acid generator, an organic solvent, and a basic compound is used in the fabrication of various integrated circuits. Pattern formation using the resist composition may be performed by well-known lithography processes. The process generally involves coating, prebake, exposure, and development. If necessary, any additional steps may be added.
The resist composition is first applied onto a substrate on which an integrated circuit is to be formed (e.g., Si, SiO2, SiN, SiON, TiN, WSi, BPSG, SOG, or organic antireflective coating) or a substrate on which a mask circuit is to be formed (e.g., Cr, CrO, CrON, or MoSi) by a suitable coating technique such as spin coating, roll coating, flow coating, dip coating, spray coating or doctor coating. The coating is prebaked on a hot plate at a temperature of 60 to 150° C. for 10 seconds to 30 minutes, preferably 80 to 120° C. for 30 seconds to 20 minutes. The resulting resist film is generally 0.1 to 2.0 μm thick.
If desired, a protective film may be formed on the resist film. The protective film is preferably formed of an alkaline developer-soluble composition so that both formation of a resist pattern and stripping of the protective film may be achieved during development. The protective film has the functions of restraining outgassing from the resist film, filtering or cutting off out-of-band (OOB) light having a wavelength of 140 to 300 nm emitted by the EUV laser (other than 13.5 nm), and preventing the resist film from assuming T-top profile or from losing its thickness under environmental imnacts.
The resist film is then exposed to a desired pattern of high-energy radiation such as UV, deep-UV, EUV, EB, x-ray, soft x-ray, excimer laser light, γ-ray or synchrotron radiation directly or through a mask. The exposure dose is preferably about 1 to 200 mJ/cm2, more preferably about 10 to 100 mJ/cm2, or 0.1 to 100 μC/cm2, more preferably 0.5 to 50 μC/cm2. The resist film is further baked (PEB) on a hot plate at 60 to 150° C. for 10 seconds to 30 minutes, preferably 80 to 120° C. for 30 seconds to 20 minutes.
Thereafter the resist film is developed with a developer in the form of an aqueous base solution for 3 seconds to 3 minutes, preferably 5 seconds to 2 minutes by conventional techniques such as dip, puddle or spray techniques. Suitable developers are 0.1 to 10 wt %, preferably 2 to 5 wt % aqueous solutions of tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide (TEAH), tetrapropylammonium hydroxide (TPAH) and tetrabutylammonium hydroxide (TBAH). The resist film in the exposed area is dissolved in the developer whereas the resist film in the unexposed area is not dissolved. In this way, the desired positive pattern is formed on the substrate. It is appreciated that the resist composition of the invention is best suited for micro-patterning using such high-energy radiation as EB, EUV, x-ray, soft x-ray, γ-ray and synchrotron radiation among others.
Although TMAH aqueous solution is generally used as the developer, TEAH, TPAH and TBAH having a longer alkyl chain are effective in inhibiting the resist film from being swollen during development and thus preventing pattern collapse. JP 3429592 describes an example using an aqueous TBAH solution for the development of a polymer comprising recurring units having an alicyclic structure such as adamantane methacrylate and recurring units having an acid labile group such as tert-butyl methacrylate, the polymer being water repellent due to the absence of hydrophilic groups.
The TMAH developer is most often used as 2.38 wt % aqueous solution, which corresponds to 0.26N. The TEAH, TPAH, and TBAH aqueous solutions should preferably have an equivalent normality. The concentration of TEAH, TPAH, and TBAH that corresponds to 0.26N is 3.84 wt %, 5.31 wt %, and 6.78 wt %, respectively.
When a pattern with a line size of 32 nm or less is resolved by the EB and EUV lithography, there arises a phenomenon that lines become wavy, lines merge together, and merged lines collapse. It is believed that this phenomenon occurs because lines are swollen in the developer and the thus expanded lines merge together. Since the swollen lines containing liquid developer are as soft as sponge, they readily collapse under the stress of rinsing. For this reason, the developer using a long-chain alkyl developing agent is effective for preventing film swell and hence, pattern collapse.
In another embodiment, a negative pattern can be formed from the resist composition by organic solvent development. The developer used to this end is at least one solvent selected from among 2-octanone, 2-nonanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-hexanone, 3-hexanone, diisobutyl ketone, methylcyolohexanone, acetophenone, methylacetophenone, pronyl acetate, butyl acetate, isobutyl acetate, pentyl acetate, butenyl acetate, isopentyl acetate, propyl formate, butyl formate, isobutyl formate, pentyl formate, isopentyl formate, methyl valerate, methyl pentenoate, methyl crotonate, ethyl crotonate, methyl propionate, ethyl propionate, ethyl 3-ethoxypropionate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, isobutyl lactate, pentyl lactate, isopentyl lactate, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, methyl benzoate, ethyl benzoate, phenyl acetate, benzyl acetate, methyl phenylacetate, benzyl formate, phenylethyl formate, methyl 3-phenylpropionate, benzyl propionate, ethyl phenylacetate, and 2-phenylethyl acetate.
At the end of development, the resist film is rinsed. As the rinsing liquid, a solvent which is miscible with the developer and does not dissolve the resist film is preferred. Suitable solvents include alcohols of 3 to 10 carbon atoms, ether compounds of 8 to 12 carbon atoms, alkanes, alkenes, and alkynes of 6 to 12 carbon atoms, and aromatic solvents. Specifically, suitable alcohols of 3 to 10 carbon atoms include n-propyl alcohol, isopropyl alcohol, 1-butyl alcohol, 2-butyI alcohol, isobutyl alcohol, t-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, t-pentyl alcohol, neopentyl alcohol, 2-methyl-1-butanol, 3-methyl-1-butanol, 3-methyl-3-pentanol, cyclopentanol, 1-hexanol, 2-hexanol, 3-hexanol, 2,3-dimethyl-2-butanol, 3,3-dimethyl-1-butanol, 3,3-dimethyl-2-butanol, 2-ethyl-1-butanol, 2-methyl-1-pentanol, 2-methyl-2-pentanol, 2-methyl-3-pentanol, 3-methyl-1-pentanol, 3-methyl-2-pentanol, 3-methyl-3-pentanol, 4-methyl-1-pentanol, 4-methyl-2-pentanol, 4-methyl-3-pentanol, cyclohexanol, and 1-octanol. Suitable ether compounds of 8 to 12 carbon atoms include di-n-butyl ether, diisobutyl ether, di-s-butyl ether, di-n-pentyl ether, diisopentyl ether, di-s-pentyl ether, di-t-pentyl ether, and di-n-hexyl ether. Suitable alkanes of 6 to 12 carbon atoms include hexane, heptane, octane, nonane, decane, undecane, dodecane, methylcyclopentane, dimethylcyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, cycloheptane, cyclooctane, and cyclononane. Suitable alkenes of 6 to 12 carbon atoms include hexene, heptene, octene, cyclohexene, methylcyclohexene, dimethylcyclohexene, cycloheptene, and cyclooctene. Suitable alkynes of 6 to 12 carbon atoms include hexyne, heptyne, and octvne. Suitable aromatic solvents include toluene, xylene, ethylbenzene, isopropylbenzene, t-butylbenzene, and mesitylene. The solvents may be used. alone or in admixture.
EXAMPLE
Examples and Comparative Examples are given below for further illustrating the invention, but they should not be construed as limiting the invention thereto. All parts (pbw) are by weight. Mw is a weight average molecular weight as measured versus polystyrene standards by GPC using tetrahydrofuran (THF) solvent.
[1] Synthesis of Monomers
Synthesis Example 1
Synthesis of Monomer 1
Under ice cooling, 92.4 g of methacrylic acid chloride was added dropwise to a solution of 50 g of 5,5-dimethyl-2,4-oxazolidinedione and 3.7 g of 4-(dimethylamino)pyridine in 500 g of THF. Stirring was continued at room temperature for 5 hours, Water was added to the solution to quench the reaction. The reaction product was treated by ordinary aqueous workup and purified by silica gel column chromatography, yielding 112 g of Monomer 1.




Synthesis Example 2
Synthesis of Monomer 2
Under ice cooling, 92.4 g of methacrylic acid chloride was added dropwise to a solution of 45 g of 2,4-thiazolidinedione and 3.7 g of 4-(dimethylamino)pyridine in 500 g of THF. Stirring was continued at room temperature for 5 hours. Water was added to the solution to quench the reaction. The reaction product was treated by ordinary aqueous workup and purified by silica gel column chromatography, yielding 110 g of Monomer 2.




Synthesis Example 3
Synthesis of Monomer 3
Under ice cooling, 92.4 g of methacrylic acid chloride was added dropwise to a solution of 43 g of rhodanine and 3.7 g of 4-(dimethylamino)pyridine in 500 g of THF. Stirring was continued at room temperature for 5 hours. Water was added to the solution to quench the reaction. The reaction product was treated by ordinary aqueous workup and purified by silica gel column chromatography, yielding 106 g of Monomer 3.




Synthesis Example 4
Synthesis of Monomer 4
Under ice cooling, 92.4 g of methacrylic acid chloride was added dropwise to a solution of 57 g of 5,5-dimethyl-2-thioxo-4-oxazolidinone and 3.7 g of 4-(dimethylamino)pyridine in 500 g of THF. Stirring was continued at room temperature for 5 hours. Water was added to the solution to quench the reaction. The reaction product was treated by ordinary aqueous workup and purified by silica gel column chromatography, yielding 114 g of Monomer 4.




[2] Synthesis of Polymers
PAG Monomers 1 and 2 used in Synthesis Examples are shown below by their structure




Synthesis Example 5
Synthesis of Polymer 1
A 2-L flask was charged with 5.6 g of 1-isopropvl-exo-tetraoyolo[4.4.0.12,5.17,10]dodecanyl methacrylate, 3.9 g of 1-isopropylcyclopentyl methacrylate, 5.9 g of Monomer 1, 5.9 g of 2-oxo-4,5-dimethyltetrahydrofuran-4-yl methacrylate, and 40 g of THF as solvent. The reactor was cooled at −70° C. in nitrogen atmosphere, after which vacuum pumping and nitrogen blow were repeated three times. The reactor was warmed up to room temperature, whereupon 1.2 g of azobisisobutyronitrile (AIBN) as polymerization initiator was added. The reactor was heated at 60° C., whereupon reaction ran for 15 hours. The reaction solution was poured into 1 L of isopropyl alcohol for precipitation. The white solid precipitate was collected by filtration and dried in vacuum at 60° C., yielding a white polymer, designated Polymer 1. The polymer was analyzed by 13C- and 1H-NMR and GPC, with the results shown below.
Copolymer Composition Ratio (Molar Ratio)

    
    
        1-isopropyl-exo-tetracyclo[4.4.0.12,5.17,10]dedecanyl methacrylate:1-isopropylcyclopentyl methacrylate:Monomer 1:2-oxo-4,5-dimethyltetrahydrofuran-4-yl methacrylate=0.200.20:0.300.30
        Mw=7,500
        Mw/Mn=1.59
    
    






Synthesis Example 6
A 2-L flask was charged with 5.6 g of 1-isopropyl-exo-tetracyclo[4.4.0.12,5.17,10]dodecanyl methacrylate, 3.9 g of 1-isopropylcyclopentyl methacrylate, 5.6 g of Monomer 2, 5.9 g of 2-oxo-45-dimethyltetrahydrofuran-4-yl methacrylate, and 40 g of THF solvent. The reactor was cooled at −70° C. in nitrogen atmosphere, after which vacuum pumping and nitrogen blow were repeated three times. The reactor was warmed up to room temperature, whereupon 1.2 g of AIBN initiator was added. The reactor was heated at 60° C., whereupon reaction ran for 15 hours. The reaction solution was poured into 1 L of isopropyl alcohol for precipitation. The white solid precipitate was collected by filtration and dried in vacuum at 60° C., yielding a white polymer, designated Polymer 2. The polymer was analyzed by 13C- and 1H-NMR and GPC, with the results shown below.
Copolymer Composition Ratio (Molar Ratio)

    
    
        1-isopropyl-exo-tetracyclo[4.4.0.12,5.17,10]idodecanyl methacrylate:1-isopropylcyclopentyl methacrylate:Monomer 2:2-oxo-4,5-dimethyltetrahydrofuran-4-yl methacrylate=0.20:0.20:0.30:0.30
        Mw=8,900
        Mw/Mn=1.69
    
    






Synthesis Example 7
A 2-L flask was charged with 5.5 g of 1-ethyl-exo-tetracyclo[4.4.0.12,5.17,10]dodecanyl methacrylate, 4.2 g of 1-t-butylcyclopentvl methacrylate, 6.0 g of Monomer 3, 5.9 g of 2-oxo-4,5-dimethyltetrahydrofuran-4-yl methacrylate, and 40 g of THF solvent. The reactor was cooled at −70° C. in nitrogen atmosphere, after which vacuum pumping and nitrogen blow were repeated three times. The reactor was warmed up to room temperature, whereupon 1.2 g of AIBN initiator was added. The reactor was heated at 60° C., whereupon reaction ran for 15 hours. The reaction solution was poured into 1 L of isopropyl alcohol for precipitation. The white solid precipitate was collected by filtration and dried in vacuum at 60° C., yielding a white polymer, designated Polymer 3. The polymer was analyzed by 13C- and 1H-NMR and GPC, with the results shown below.
Copolymer Composition Ratio (Molar Ratio)

    
    
        1-ethyl-exo-tetracyclo[4.4.0.12,5.17,10]dodecanyl methacrylate:1-t-butylcyclopentyl methacrylate:Monomer 3:2-oxo-4,5-dimethyltetrahydrofuran-4-yl methacrylate=0.20:0.20:0.30:0.30
        Mw=8,600
        Mw/Mn=1.81
    
    






Synthesis Example 8
A 2-L flask was charged with 5.5 g of 1-ethyl-exo-tetracyclo[4.4.0.12.5.17,10]dodecanyl methacrylate, 4.2 g of 1-t-butylcyclopentyl methacrylate, 6.4 g of Monomer 4, 5.9 g of 2-oxo-4,5-dimethyltetrahydrofuran-4-yl methacrylate, and 40 g of THF solvent. The reactor was cooled at −70° C. in nitrogen atmosphere, after which vacuum pumping and nitrogen blow were repeated three times. The reactor was warmed up to room temperature, whereupon 1.2 g of AIBN initiator was added. The reactor was heated at 60° C., whereupon reaction ran for 15 hours. The reaction solution was poured into 1 L of isopropyl alcohol for precipitation. The white solid precipitate was collected by filtration and dried in vacuum at 60° C., yielding a white polymer, designated Polymer 4. The polymer was analyzed by 13C- and 1H-NMR and GPC, with the results shown below.
Copolymer Composition Ratio (Molar Ratio)

    
    
        1-ethyl-exo-tetracyclo[4.4.0.12,5.17,10]idodeoanyl methacrylate:1-t-butylcyclopentyl methacrylate:Monomer 4:2-oxo-4,5-dimethyltetrahydrofuran-4-yl methacrylate=0.20:0.20:0.30:0.30
        Mw=8,900
        Mw/Mn=1.71
    
    






Synthesis Example 9
A 2-L flask was charged with 5.2 g of 1-(adamantan-1-yl)-1-methylethyl methacrylate, 3.1 g of 4-(1-methylcyolopentyloxy)styrene, 5.9 g of Monomer 1, 4.4 g of 4-hydroxyphenyl methacrylate, 11.0 g of PAG Monomer 1, and 40 g of THF solvent. The reactor was cooled at −70° C. in nitrogen atmosphere, after which vacuum pumping and nitrogen blow were repeated three times. The reactor was warmed up to room temperature, whereupon 1.2 g of AIBN initiator was added. The reactor was heated at 60° C., whereupon reaction ran for 15 hours. The reaction solution was poured into 1 L of isopropyl alcohol for precipitation. The white solid precipitate was collected by filtration and dried in vacuum at 60° C., yielding a white polymer, designated Polymer 5. The polymer was analyzed by 13C- and 1H-NKR and GPC, with the results shown below.
Copolymer Composition Ratio (Molar Ratio)

    
    
        1-(adamantan-1-yl)-1-methylethyl methacrylate:4-(1-methylcyclopentyloxy)styrene:Monomer 1:4-hydroxyphenyl methacrylate:PAG Monomer 1=0.20:0.15:0.30:0.20:0.15
        Mw=9,100
        Mw/Mn=1.73
    
    






Synthesis Example 10
A 2-L flask was charged with 10.9 g of 4-(1-methyl-cyclohexyloxy)phenyl methacrylate, 4.2 g of Monomer 2, 3.6 g of 4-hydroxyphenyl methacrylate, 15.0 g of PAG Monomer 2, and 40 g of THF solvent. The reactor was cooled at −70° C. in nitrogen atmosphere, after which vacuum pumping and nitrogen blow were repeated three times. The reactor was warmed up to room temperature, whereupon 1.2 g of AIBN initiator was added. The reactor was heated at 60° C., whereupon reaction ran for 15 hours. The reaction solution was poured into 1 L of isopropyl alcohol for precipitation. The white solid precipitate was collected by filtration and dried in vacuum at 60° C., yielding a white polymer, designated Polymer 6. The polymer was analyzed by 13C- and 1H-NMR and GPC, with the results shown below.
Copolymer Composition Ratio (Molar Ratio)

    
    
        4-(1-methylcyclohexyloxy)phenyl methacrylate:Monomer 2:4-hydroxyphenyl methacrylate:PAG Monomer 2=0.40:0.200.200.20
        MW=8,300
        Mw/Mn=1.83
    
    






Comparative Synthesis Example 1
Comparative Polymer I was synthesized by the same procedure as in Synthesis Example 1 aside from omitting Monomer 1.
Copolymer Composition Ratio (Molar Ratio)

    
    
        1-isopropyl-exo-tetracyclo[4.4.0.12,5.17,10]dodecanyl methaorylate:1-isopropyloyclopentyl methacrylate:2-oxo-4,5-dimethyltetrahydrofuran-4-yl methacrylate=0.20:0.20:0.60
        Mw=8,900
        Mw/Mn=1.79
    
    






Comparative Synthesis Example 2
Comparative Polymer 2 was synthesized by the same procedure as in Synthesis Example 9 aside from using 2-oxotetrahydrofuran-3-yl methacrylate instead of Monomer 1.
Copolymer Composition Ratio (Molar Ratio)

    
    
        1-(adamantan-1-yl)-1-methylethyl methacrylate:4-(1-methylcyclopentyloxy)styrene:2-oxotetrahydrofuran-3-yl methacrylate:4-hydroxyphenyl methacrylate:PAG Monomer 1=0.20:0.15:0.30:0.20:0.15
        Mw=9,100
        Mw/Mn=1.78
    
    






[3] ArF Lithography Patterning
Examples 1-1 to 1-5 and Comparative Example 1-1
3.1 Preparation of Resist Composition
Positive resist compositions (R-1 to R-5) were prepared by dissolving components in a solvent in accordance with the recipe shown in Table 1, and filtering through a filter having a pore size of 0.2 μm. The solvent contained 100 ppm of surfactant FC-4430 (3M-Sumitomo Co., Ltd.). The components in Table 1 are as identified below.
Organic Solvents:
PGMEA (propylene glycol monomethyl ether acetate)
GBL (γ-butyrolactone)

    Acid generator: PAG1 of the following structural formula






    Quencher: Quencher 1 of the following structural formu






    Additive: Water repellent polymer 1 (Mw=12,100, Mw/Mn=1.78) of the following structural formula


















TABLE 1







Acid


Organic


Resist
Polymer
generator
Quencher
Additive
solvent


composition
(pbw)
(pbw)
(pbw)
(pbw)
(pbw)







R-1
Polymer 1
PAG 1
Quencher 1
Water repellent
PGMEA (2,500)



(100)
(8.0)
(3.0)
polymer 1
GBL (500)






(3)


R-2
Polymer 2
PAG 1
Quencher 1
Water repellent
PGMEA (2,500)



(100)
(8.0)
(3.0)
polymer 1
GBL (500)






(3)


R-3
Polymer 3
PAG 1
Quencher 1
Water repellent
PGMEA (2,500)



(100)
(8.0)
(3.0)
polymer 1
GBL (500)






(3)


R-4
Polymer 4
PAG 1
Quencher 1
Water repellent
PGMEA (2,500)



(100)
(8.0)
(3.0)
polymer 1
GBL (500)






(3)


R-5
Comparative
PAG 1
Quencher 1
Water repellent
PGMEA (2,500)



Polymer 1
(8.0)
(3.0)
polymer 1
GBL (500)



(100)


(3)









3.2 ArF Lithography Patterning Test

On a substrate (silicon wafer), a spin-on carbon film ODL-101 (Shin-Etsu Chemical Co.; Ltd.) having a carbon content of 80 wt % was deposited to a thickness of 160 nm and a silicon-containing spin-on hard mask SHB-A940 having a Ito silicon content of 43 wt % was deposited thereon to a thickness of 35 nm. On this substrate for trilayer process, the resist composition (R-1 to R-5) was spin coated and baked on a hot plate at 80° C. for 60 seconds to form a resist film of 80 nm thick.
Using an ArF excimer laser immersion lithography scanner NSR-610C (Nikon Corp., NA 1.30, a 0.98/0.78, cross-pole opening 20 deg., azimuthally polarized illumination), exposure was performed in a varying dose through a 6% halftone phase shift mask bearing a lattice pattern with a pitch of 90 nm and a line width of 30 nm (on-wafer size). After the exposure, the wafer was baked (PEB) at the temperature shown in Table 2 for 60 seconds and developed. Specifically, butyl acetate or 2-heptanone was iniected from a development nozzle while the wafer was spun at 30 rpm for 3 seconds, which was followed by stationary puddle development for 27 seconds. The wafer was spin dried, yielding a negative pattern.
A hole pattern resulted from image reversal by solvent development. By observation under TDSEM (CG-4000, Hitachi High-Technologies Corp.), fifty (50) holes were picked up and measured for diameter, from which a variation (3σ) was computed as critical dimension uniformity (CDU). A cross-sectional profile of the hole pattern was observed under electron microscope (S-4300, Hitachi High-Technologies Corp.). The results are shown in Table 2.













TABLE 2











Hole size



Resist
PEB


variation



com-
temp.
Dose

3σ



position
(° C.)
(mJ/cm2)
Developer
(nm)





















Example 1-1
R-1
95
34
n-butyl acetate
2.1


Example 1-2
R-2
95
35
n-butyl acetate
2.3


Example 1-3
R-3
95
26
n-butyl acetate
2.2


Example 1-4
R-4
95
27
n-butyl acetate
2.2


Example 1-5
R-1
95
25
2-heptanone
2.3


Comparative
R-5
90
42
n-butyl acetate
4.0


Example 1-1









As is evident from the data in Table 2, the resist compositions within the scope of the invention ensure that the pattern obtained after organic solvent development is improved in CDU.
[4] EB Lithography
Examples 2-1 to 2-2 and Comparative Example 2-1
4.1 Preparation of Resist Composition
Positive resist compositions (R-6 to R-8) were prepared by dissolving components in a solvent in accordance with the recipe shown in Table 3, and filtering through a filter having a pore size of 0.2 μm. The solvent contained 100 ppm of surfactant FC-4430 (3M-Sumitomo Coe, Ltd.). The components in Table 3 are as identified below.
Organic Solvents:
PGMEA (propylene glycol monomethyl ether acetate)
PGME (propylene glycol monomethyl ether)
CyH (cyclohexanone)

    Basic compound: Amine 1 of the following structural formula

















TABLE 3








Basic




Resist
Polymer
compound
Organic solvent



composition
(pbw)
(pbw)
(pbw)







Example 2-1
R-6
Polymer 5
Amine 1
PGMEA (500)




(100)
(1.0)
CyH (1,200)






PGME (200)


Example 2-2
R-7
Polymer 6
Amine 1
PGMEA (500)




(100)
(1.0)
CyH (1,200)






PGME (200)


Comparative
R-8
Comparative
Amine 1
PGMEA (500)


Example 2-1

Polymer 2
(1.0)
CyH (1,200)




(100)

PGME (200)









4.2 EB Lithography Patterning Test

Using a coater/developer system Clean Track Mark 5 (Tokyo Electron Ltd.), the positive resist composition (R-6 to R-8) was spin coated onto a silicon substrate of diameter 6 inches (which had been vapor primed with hexamethyldisilazane) and prebaked on a hot plate at 110° C. for 60 seconds to form a resist film of 100 nm thick. Using a system HL-800D (Hitachi Ltd.) at a HV voltage of 50 kV, the resist film was exposed imagewise to EB in a vacuum chamber.
Using Clean Track Mark 5, immediately after the exposure, the resist film was baked (PEB) on a hot plate at the temperature shown in Table 4 for 60 seconds and puddle developed in a 2.38 wt % TMAH aqueous solution for 30 seconds to form a positive pattern.
Resolution is a minimum size at the exposure dose (sensitivity) that provides a 1:1 resolution of a 100-nm line-and-space pattern. The 100-nm L/S pattern was measured for roughness (LWR) under SEM. The results are shown in Table 4.













TABLE 4







Resist
PEB temp.
Sensitivity
Resolution
LWR



composition
(° C.)
(μC/cm2)
(nm)
(nm)





















Example 2-1
R-6
85
28.9
75
5.4


Example 2-2
R-7
85
30.3
75
5.2


Comparative
R-8
85
30.5
80
6.1


Example 2-1









Japanese Patent Application No. 2015-148563 is incorporated herein by reference.
Although some preferred embodiments have been described, many modifications and variations may be made thereto in light of the above teachings. It is therefore to be understood that the invention may be practiced otherwise than as specifically described without departing from the scope of the appended claims.

## Claims

1. A resist composition comprising as base resin a polymer comprising recurring units represented by the formula (a) and recurring units having a carboxyl group substituted with an acid labile group and/or recurring units having a phenolic hydroxyl group substituted with an acid labile group, the polymer having a weight average molecular weight of 1,000 to 500,000,




wherein R1 is hydrogen or methyl, R2 and R3 are each independently hydrogen or a straight, branched or cyclic C1-C6 alkyl group, X1 is a single bond, a C1-C12 linking group containing an ester moiety, ether moiety or lactone ring, phenylene or naphthylene group, X2 and X3 are each independently oxygen or sulfur, and a is a positive number in the range: 0<a<1.0.

2. The resist composition of claim 1 wherein the recurring units having a carboxyl group substituted with an acid labile group are represented by the formula (b1) and the recurring units having a phenolic hydroxyl group substituted with an acid labile group are represented by the formula (b2):




wherein R4 and R6 are each independently hydrogen or methyl. R5 and R9 are each independently an acid labile group, R7 is a single bond or a straight or branched C1-C6 alkylene group, R6 is hydrogen, fluorine, trifluoromethyl, cyano, or a straight, branched or cyclic C1-C6 alkyl, acyl, alkoxy, acyloxy or alkoxycarbonyl group, p is 1 or 2, q is an integer of 0 to 4, Y1 is a single bond, a C1-C12 linking group containing an ester moiety, ether moiety or lactone ring, phenylene or naphthylene group, Y2 is a single bond, —C(═O)—O— or —C(═O)—NH—, b1 and b2 are numbers in the range: 0≦b1<1.0, 0≦b2<1.0, and 0<b1+b2<1.0.

3. The resist composition of claim 1 wherein the polymer further comprises recurring units having an adhesive group selected from the group consisting of hydroxyl, carboxyl, lactone ring, carbonate, thiocarbonate, carbonyl, cyclic acetal, ether, ester, sulfonic acid ester, cyano, amide, and —O—C(═O)-G- wherein G is —S— or —NH—.

4. The resist composition of claim 1 wherein the polymer further comprises recurring units of at least one type selected from recurring units represented by the formulae (d1) to (d3):




wherein R20, R24, and R28 are each independently hydrogen or methyl, R21 is a single bond, phenylene, —O—RA—, or —C(═O)—Y0—RA—, Y0 is —O— or —NH—, RA is a straight, branched or cyclic C1-C6 alkylene or alkenylene group which may contain a carbonyl, ester, ether or hydroxyl moiety, or phenylene group, R22, R23, R25, R26, R27, R29, R30, and R31 are each independently a straight, branched or cyclic C1-C12 alkyl group which may contain a carbonyl, ester or ether moiety, or a C6-C12 aryl, C7-C20 aralkyl, or meroaptophenyl group, Z1 is a single bond, a straight, branched or cyclic C1-C12 alkylene or C2-C12 alkenylene group which may contain an ether moiety, ester moiety or lactone ring, or C6-C10 arylene group, Z2 is a single bond, methylene, ethylene, phenylene, fluorinated phenylene, —O—R32—, or —C(═O)—Z3—R32—, Z3 is —O— or —NH—, R32 is a straight, branched or cyclic C1-C12 alkylene or C2-C12 alkenylene group which may contain a carbonyl, ester, ether or hydroxyl moiety, or phenylene group, M− is a non-nucleophilic counter ion, d1, d2 and d3 are numbers in the range: 0≦d1≦0.5, 0≦d2≦0.5, 0≦d3≦0.5, and 0<d1+d2+d3≦0.5.

5. The resist composition of claim 1, further comprising an acid generator and an organic solvent.

6. The resist composition of claim 5, further comprising a basic compound and/or a surfactant.

7. A pattern forming process comprising the steps of applying the resist composition of claim 1 onto a substrate to form a coating, baking, exposing the coating to high-energy radiation, and developing the exposed coating in a developer.

8. The process of claim 7 wherein the high-energy radiation is i-line, KrF excimer laser, ArF excimer laser, electron beam or soft X-ray of wavelength 3 to 15 nm.