# Patent

## Title
Polymers, positive resist compositions and patterning process

## Abstract

A polymer is composed of recurring units of hydroxyvinylnaphthalene, (meth)acrylic units having a lactone ring fused to a bridged ring, and (meth)acrylic units having acid labile groups. A positive resist composition comprising the polymer as a base resin, when exposed to high-energy radiation and developed, exhibits a high sensitivity, a high resolution, and a minimal line edge roughness due to controlled swell during development.

## Background
CROSS-REFERENCE TO RELATED APPLICATION
This non-provisional application claims priority under 35 U.S.C. §119(a) on Patent Application No. 2006-059120 filed in Japan on Mar. 6, 2006, the entire contents of which are hereby incorporated by reference.
This invention relates to positive resist compositions, typically of the chemical amplification type, adapted for exposure to high-energy radiation, which have a significantly high contrast of alkali dissolution rate before and after the exposure, a high sensitivity, a high resolution, a minimal line edge roughness, and good etching resistance, and which are especially suited as micropatterning materials for the manufacture of VLSI or the formation of photomask patterns; polymers useful as a base resin in the resist compositions; and a patterning process using the resist compositions.
BACKGROUND OF THE INVENTION
In the drive for higher integration and operating speeds in LSI devices, the pattern rule is made drastically finer. The rapid advance toward finer pattern rules is grounded on the development of a projection lens with an increased NA, a resist material with improved performance, and exposure light of a shorter wavelength. In particular, the change-over from i-line (365 nm) to shorter wavelength KrF laser (248 nm) brought about a significant innovation, enabling mass-scale production of 0.18 micron rule devices. To the demand for a resist material with a higher resolution and sensitivity, acid-catalyzed chemical amplification positive working resist materials are effective as disclosed in U.S. Pat. Nos. 4,491,628 and 5,310,619 (JP-B 2-27660 and JP-A 63-27829). They now become predominant resist materials especially adapted for deep UV lithography.
Resist materials adapted for KrF excimer lasers enjoyed early use on the 0.3 micron process, passed through the 0.25 micron rule, and currently entered the mass production phase on the 0.18 micron rule. Engineers have started investigation on the 0.15 micron rule, with the trend toward a finer pattern rule being accelerated. A wavelength change-over from KrF to shorter wavelength ArF laser (193 nm) is expected to enable miniaturization of the design rule to 0.13 μm or less. Since conventionally used novolac resins and polyvinylphenol resins have very strong absorption in proximity to 193 nm, they are difficult to use as the base resin for resists. To ensure transparency and dry etching resistance, some engineers investigated acrylic and alicyclic (typically cycloolefin) resins as disclosed in JP-A 9-73173, JP-A 10-10739, JP-A 9-230595 and WO 97/33198.
Among others, a focus is drawn on (meth)acrylic resin base resists featuring a high resolution. One of the (meth)acrylic resins proposed thus far is a combination of (meth)acrylic units having methyladamantane ester as acid labile group units with (meth)acrylic units having lactone ring ester as adhesive group units as disclosed in JP-A 9-90637. Norbornyl lactone is also proposed as an adhesive group having enhanced etching resistance as disclosed in JP-A 2000-26446, JP-A 2000-159758 and JP-A 2002-371114.
Of the outstanding tasks associated with the ArF lithography, it is desired to minimize line edge roughness and to reduce residues following development. One of the factors causing line edge roughness is swelling during development. While the polyhydroxystyrene used as the resist for KrF lithography, in which the phenol moiety is a weak acidic group and has an appropriate alkali solubility, is resistant to swelling, polymers containing hydrophobic cycloaliphatic groups, which must be dissolved using carboxylic acids having a high acidity, are likely to swell during development.
Naphthalene ring is an aromatic having less absorption at wavelength 193 nm. ArF resist compositions based on vinyl naphthalene copolymers are described in J. Photopolym. Sci. Technol., Vol. 11, No. 3, p 489 (1998), JP-A 2004-163877, and JP-A 2002-107933. Since hydroxy-containing naphthalene rings exhibit weak acidity like phenol, they are expected to be effective in preventing swelling during development. Other advantages of naphthalene ring include high etching resistance and a high transmittance of vacuum ultraviolet (EUV) with wavelength 13.5 nm.
SUMMARY OF THE INVENTION
An object of the invention is to provide a positive resist composition, especially chemically amplified positive resist composition, which when exposed to high-energy radiation and developed, exhibits a high sensitivity, a high resolution, high dry etch resistance, and a minimal line edge roughness due to controlled swell during development, and leaves minimal residues following development; a polymer useful as a base resin in the resist composition; and a process for forming a pattern using the resist composition.
In a first aspect, the invention provides a polymer comprising recurring units of the general formulae (1a) and (1b).




Herein R1 is each independently hydrogen or methyl, R2 is a hydrogen atom, C1-C10 acyl group or acid labile group, R3 is hydrogen, methyl or —CO2R8, R4 is hydrogen, methyl or —CH2CO2R8, each of R5 to R7 is hydrogen, methyl, trifluoromethyl or —CO2R9, R8 is hydrogen or a straight, branched or cyclic C1-C15 alkyl group, R9 is a hydrogen atom, straight, branched or cyclic C1-C10 alkyl or fluoroalkyl group or acid labile group, X is —CH2—, —O— or —S—, with the proviso that —CH2— is excluded from X when all of R5 to R7 are hydrogen, n is an integer of 1 to 3, a1 and b1 are numbers in the range: 0<a1<1.0 and 0<b1≦0.8.

Particularly when R2 and R9 are not acid labile groups, that is, none of the recurring units of formulae (1a) and (1b) contain acid labile groups, the preferred polymer further comprises recurring units of the general formula (1c).




Herein R3 and R4 are as defined above, R10 is an acid labile group, and c1 is a number in the range: 0<c1≦0.8.

When exposed to high-energy radiation and developed, a positive resist composition comprising the above polymer as a base resin has a significantly high contrast of alkali dissolution rate before and after the exposure, a high sensitivity, a high resolution, and a minimal line edge roughness due to controlled swell during development, leaves minimal residues following etching, and exhibits good etching resistance. Owing to these advantages, the composition is fully acceptable in industrial practice and especially suited as a micropatterning material for the manufacture of VLSI or the formation of photomask patterns.
The composition is preferably formulated as a chemically amplified positive resist composition comprising (A) the above polymer as a base resin, (B) an organic solvent, and (C) a photoacid generator. With this formulation, in the exposed area, the rate of dissolution of the polymer in a developer liquid is accelerated by acid-catalyzed reaction. Then the chemically amplified positive resist composition has so high a sensitivity that it is very suitable as the micropatterning material which is currently needed for the manufacture of VLSI. The positive resist composition may further include a dissolution inhibitor. The inclusion of a dissolution inhibitor enhances the difference in dissolution rate between the exposed and unexposed areas, leading to a further improvement in resolution. The positive resist composition may further include a basic compound and/or a surfactant. The addition of a basic compound holds down the diffusion rate of acid within the resist film, leading to a further improvement in resolution. The addition of a surfactant improves or controls the applicability of the resist composition.
A pattern may be formed on a semiconductor substrate or mask substrate using the resist composition of the invention, typically by applying the resist composition onto a substrate to form a coating, heat treating the coating, exposing it to high-energy radiation, and developing it with a developer liquid. Heat treatment may also be carried out after the exposure and before the development. The process may, of course, be followed by various steps such as etching, resist removal and cleaning steps. The high-energy radiation typically has a wavelength of 180 to 200 nm. The resist composition containing the inventive polymer as the base resin is especially effective for exposure to high-energy radiation with a wavelength of 180 to 200 nm because its sensitivity to the exposure wavelength in the range is very high.
BENEFITS OF THE INVENTION
The polymers of the invention are obtained through copolymerization of recurring units of hydroxyvinylnaphthalene, (meth)acrylic units having a lactone ring fused to a bridged ring, and (meth)acrylic units having acid labile groups. The polymers are formulated as the base resin to form positive resist compositions which have many advantages including a high sensitivity, a high resolution, minimized line edge roughness, and high etch resistance. The positive resist compositions, especially chemically amplified positive resist compositions, are suited as micropatterning materials for the manufacture of VLSI or the formation of photomask patterns.


DESCRIPTION OF THE PREFERRED EMBODIMENTS
The singular forms “a,” “an” and “the” include plural referents unless the context clearly dictates otherwise.
As used herein, the terminology “(Cx-Cy)”, as applied to a particular unit, such as, for example, a chemical compound or a chemical substituent group, means having a carbon atom content of from “x” carbon atoms to “y” carbon atoms per such unit.
Polymer
The inventors continued research works targeting a positive resist composition which when exposed to high-energy radiation and developed, exhibits a high sensitivity, a high resolution, and a minimal line edge roughness due to controlled swell during development, and leaves minimal residues following development.
It has been found that although the inclusion of naphthol alone as an adhesive group fails to achieve sufficient adhesion, a good balance of hydrophilicity, alkaline solubility and adhesion is arrived at by copolymerizing naphthol with recurring units having hydrophilic lactone of a specific structure as an adhesive group. In particular, when a polymer which is obtained from a combination of (meth)acrylate having a bridged ring-fused lactone group, (meth)acrylate having an acid-labile group, and recurring units having adhesive groups with alkaline solubility as typified by naphthol is used as the base resin, there is provided a positive resist composition which when exposed to high-energy radiation and developed, exhibits a high sensitivity, a high resolution, and a minimal line edge roughness due to controlled swell during development, and leaves minimal residues following development. The composition also has excellent dry etching resistance.
According to the invention, the polymer is defined as comprising recurring units of the general formulae (1a) and (1b).




Herein R1 is each independently hydrogen or methyl, R2 is a hydrogen atom, a C1-C10 acyl group or an acid labile group, R3 is hydrogen, methyl or —CO2R8, and R4 is hydrogen, methyl or —CH2CO2R8. Each of R5 to R7 is hydrogen, methyl, trifluoromethyl or —CO2R9. R8 is each independently hydrogen or a straight, branched or cyclic C1-C15 alkyl group. R9 is a hydrogen atom, a straight, branched or cyclic C1-C10 alkyl or fluoroalkyl group or an acid labile group. X is —CH2—, —O— or —S—, with the proviso that —CH2— is excluded from X when all of R5 to R7 are hydrogen. The subscript n is an integer of 1 to 3, a1 and b1 are numbers in the range: 0<a1<1.0 and 0<b1≦0.8.

Typical examples of the C1-C10 acyl group are acetyl and pivaloyl. Examples of the C1-C15 alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, octyl, decyl, norbornyl, and adamantyl. Similar examples are illustrative of the C1-C10 alkyl group. The fluoroalkyl groups correspond to the foregoing alkyl groups in which some or all hydrogen atoms are substituted by fluorine atoms. The acid labile groups are described later.
When exposed to high-energy radiation and developed, the positive resist composition comprising the above polymer as a base resin has a significantly high contrast of alkali dissolution rate before and after the exposure, a high sensitivity, a high resolution, and a minimal line edge roughness due to controlled swell during development, leaves minimal residues following development, and exhibits good etching resistance. Owing to these advantages, the composition is fully acceptable in industrial practice and especially suited as a micropatterning material for the manufacture of VLSI or the formation of photomask patterns.
The monomer M(1a) from which recurring units of formula (1a) are derived has the following formula.




Herein R1, R2, and n are as defined above.

Illustrative examples of monomer M(1a) are given below.







In one example, the monomer prior to polymerization takes a form wherein R2 is an acetyl group, which may converted to a hydroxyl group through alkaline hydrolysis after polymerization, and as the case may be, the hydrogen atom of the hydroxyl group may then be substituted by an acid labile group. Alternatively, the monomer takes a form wherein R2 is an acid labile group such as acetal, which may converted to a hydroxyl group through hydrolysis with a weak acid such as acetic acid or oxalic acid after polymerization.
The monomer M(1b) from which recurring units of formula (1b) are derived has the following formula.




Herein R3, R4, R5, R6, R7, and X are as defined above.

Illustrative examples of monomer M(1b) are given below, but not limited thereto.













The polymer of the invention comprising recurring units (1a) and (1b) is obtained by copolymerization of monomers M(1a) and M(1b) and used to formulate a positive resist composition. When R2 in the recurring units of formula (1a) and R9 in the recurring units of formula (1b) are not acid labile groups, the polymer is preferably further copolymerized with a monomer M(1c) from which recurring units of the general formula (1c) having acid labile groups are derived, so that a positive resist composition is formulated therefrom.




Herein R3 and R4 are as defined above, and R10 is an acid labile group. The subscript c1 is a number in the range: 0<c1≦0.8 when the polymer of the invention contains these recurring units (1c).

The acid labile groups represented by R2, R9 and R10 in formulae (1a), (1b) and (1c) may be identical or different and selected from a variety of such groups. Preferred are structures in which the hydrogen atom of hydroxyl group or of hydroxyl moiety of carboxyl group is substituted with a group of formula (AL-10) or (AL-11), a tertiary alkyl group of 4 to 40 carbon atoms represented by formula (AL-12), an oxoalkyl group of 4 to 20 carbon atoms, or the like.




In formulae (AL-10) and (AL-11), R51 and R54 each are a monovalent hydrocarbon group, typically a straight, branched or cyclic alkyl group of 1 to 40 carbon atoms, especially 1 to 20 carbon atoms, which may contain a heteroatom such as oxygen, sulfur, nitrogen or fluorine. The subscript “a5” is an integer of 0 to 10. R52 and R53 each are hydrogen or a monovalent hydrocarbon group, typically a straight, branched or cyclic C1-C20 alkyl group, which may contain a heteroatom such as oxygen, sulfur, nitrogen or fluorine. Alternatively, a pair of R52 and R53, R52 and R54, or R53 and R54, taken together, may form a ring with the carbon atom or the carbon and oxygen atoms to which they are attached, the ring having 3 to 20 carbon atoms, especially 4 to 16 carbon atoms.
In formula (AL-12), R55, R56 and R57 each are a monovalent hydrocarbon group, typically a straight, branched or cyclic C1-C20 alkyl group, which may contain a heteroatom such as oxygen, sulfur, nitrogen or fluorine. Alternatively, a pair of R55 and R56, R55 and R57, or R56 and R57, taken together, may form a ring with the carbon atom to which they are attached, the ring having 3 to 20 carbon atoms, especially 4 to 16 carbon atoms.
Illustrative examples of the groups of formula (AL-10) include tert-butoxycarbonyl, tert-butoxycarbonylmethyl, tert-amyloxycarbonyl, tert-amyloxycarbonylmethyl, 1-ethoxyethoxycarbonylmethyl, 2-tetrahydropyranyloxycarbonylmethyl and 2-tetrahydrofuranyloxycarbonylmethyl as well as substituent groups of the following formulae (AL-10)-1 to (AL-10)-10.







In formulae (AL-10)-1 to (AL-10)-10, R58 is independently a straight, branched or cyclic C1-C8 alkyl group, C6-C20 aryl group or C7-C20 aralkyl group; R59 is hydrogen or a straight, branched or cyclic C1-C20 alkyl group; R60 is a C6-C20 aryl group or C7-C20 aralkyl group; and “a5” is an integer of 0 to 10.
Illustrative examples of the acetal group of formula (AL-11) include those of the following formulae (AL-11)-1 to (AL-11)-34.










The polymer may be crosslinked within the molecule or between molecules with acid labile groups of formula (AL-11a) or (AL-11b).




Herein R61 and R62 each are hydrogen or a straight, branched or cyclic C1-C8 alkyl group, or R61 and R62, taken together, may form a ring with the carbon atom to which they are attached, and R61 and R62 are straight or branched C1-C8 alkylene groups when they form a ring. R63 is a straight, branched or cyclic C1-C10 alkylene group. Each of b5 and d5 is 0 or an integer of 1 to 10, preferably 0 or an integer of 1 to 5, and c5 is an integer of 1 to 7. “A” is a (c5+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 such as oxygen, sulfur or nitrogen or in which some of the hydrogen atoms attached to carbon atoms may be substituted by hydroxyl, carboxyl, carbonyl groups or fluorine atoms. “B” is —CO—O—, —NHCO—O— or —NHCONH—.
Preferably, “A” is selected from divalent to tetravalent, straight, branched or cyclic C1-C20 alkylene, alkyltriyl and alkyltetrayl groups, and C6-C30 arylene groups, which may be separated by a heteroatom such as oxygen, sulfur or nitrogen or in which some of the hydrogen atoms attached to carbon atoms may be substituted by hydroxyl, carboxyl, acyl groups or halogen atoms. The subscript c5 is preferably an integer of 1 to 3.
The crosslinking acetal groups of formulae (AL-11a) and (AL-11b) are exemplified by the following formulae (AL-11)-35 through (AL-11)-42.




Illustrative examples of the tertiary alkyl of formula (AL-12) include tert-butyl, triethylcarbyl, 1-ethylnorbornyl, 1-methylcyclohexyl, 1-ethylcyclopentyl, and tert-amyl groups as well as those of (AL-12)-1 to (AL-12)-16.







Herein R64 is independently a straight, branched or cyclic C1-C8 alkyl group, C6-C20 aryl group or C7-C20 aralkyl group; R65 and R67 each are hydrogen or a straight, branched or cyclic C1-C20 alkyl group; and R66 is a C6-C20 aryl group or C7-C20 aralkyl group.
With R68 representative of a di- or more valent alkylene or arylene group included as shown in formulae (AL-12)-17 and (AL-12)-18, the polymer may be crosslinked within the molecule or between molecules. In formulae (AL-12)-17 and (AL-12)-18, R64 is as defined above; R68 is a straight, branched or cyclic C1-C20 alkylene group or arylene group which may contain a heteroatom such as oxygen, sulfur or nitrogen; and b6 is an integer of 1 to 3.




The groups represented by R64, R65, R66 and R67 may contain a heteroatom such as oxygen, nitrogen or sulfur, examples of which are illustrated by those of the following formulae (AL-13)-1 to (AL-13)-7.




Of the acid labile groups of formula (AL-12), recurring units having an exo-form structure represented by the formula (AL-12)-19 are preferred.




Herein, R69 is a straight, branched or cyclic C1-C8 alkyl group or a substituted or unsubstituted C6-C20 aryl group; R70 to R75, R78 and R79 are each independently hydrogen or a monovalent hydrocarbon group of 1 to 15 carbon atoms which may contain a heteroatom; and R76 and R77 are hydrogen. Alternatively, a pair of R70 and R71, R72 and R74, R72 and R75, R73 and R75, R73 and R79, R74 and R78, R76 and R77, or R77 and R78 taken together, may form a ring, and in this case, each R is a divalent hydrocarbon group of 1 to 15 carbon atoms which may contain a heteroatom. Also, a pair of R70 and R79, R76 and R79, or R72 and R74 which are attached to adjoining carbon atoms may bond together directly to form a double bond. R77 is hydrogen or a straight, branched or cyclic C1-C15 alkyl group. The formula also represents an enantiomer.
The ester form monomers from which recurring units having an exo-form structure represented by the formula (AL-12)-19:




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.








Also included in the acid labile groups of formula (AL-12) are acid labile groups having furandiyl, tetrahydrofurandiyl or oxanorbornanediyl as represented by the following formula (AL-12)-20.




Herein, R80 and R81 are each independently a straight, branched or cyclic, monovalent hydrocarbon group of 1 to 10 carbon atoms. R80 and R81, taken together, may form an aliphatic hydrocarbon ring of 3 to 20 carbon atoms with the carbon atom to which they are attached. R82 is a divalent group selected from furandiyl, tetrahydrofurandiyl and oxanorbornanediyl. R83 is hydrogen or a straight, branched or cyclic, monovalent hydrocarbon group of 1 to 10 carbon atoms which may contain a heteroatom.

Examples of the monomers from which the recurring units substituted with acid labile groups having furandiyl, tetrahydrofurandiyl and oxanorbornanediyl as represented by the formula:




(wherein R80, R81, R82 and R83 are as defined above) are derived are shown below. Note that Me is methyl and Ac is acetyl.

















While the polymer of the invention includes essentially recurring units of formulae (1a) and (1b) and optionally recurring units of formula (1c) having acid labile groups, it may have copolymerized therein recurring units (1d) having adhesive groups such as hydroxy, cyano, carbonyl or ester groups, other than formulae (1a) and (1b). Examples of monomers M(1d) from which recurring units (1d) are derived are given below.





































In the polymer of the invention, the recurring units (1a), (1b), (1c) and (1d) are present in proportions a1, b1, c1, and d1, respectively, which satisfy the range: 0<a1<1.0, 0<b1≦0.8, 0≦c1≦0.8, and 0≦d1≦0.8, preferably 0.05≦a1≦0.9, 0.05≦b1≦0.7, 0<c1≦0.8, especially 0.15≦c1≦0.7, and 0≦d1≦0.7. It is noted that a1+b1+c1+d1=1. For a polymer comprising recurring units (1a), (1b), (1c) and (1d), a1+b1+c1+d1=1 means that the total of these recurring units is 100 mol % relative to the total of entire recurring units.
The polymer of the invention should preferably have a weight average molecular weight (Mw) in the range of 1,000 to 500,000, more preferably 2,000 to 30,000 as measured by gel permeation chromatography (GPC) using polystyrene standards. With too low a Mw, the resist composition may be less heat resistant. With too high a Mw, the resist composition may lose alkali solubility and give rise to a footing phenomenon after pattern formation.
If a polymer 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 multi-component copolymer 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.
It is understood that on use of the polymer as the base resin, a blend of two or more polymers which differ in compositional ratio, molecular weight or dispersity is acceptable.
The polymer of the invention may be synthesized by any desired method, for example, by dissolving unsaturated bond-containing monomers corresponding to the respective units (a1), (b1), (c1) and (d1) in an organic solvent, adding a radical initiator thereto, and effecting heat polymerization. Examples of the organic solvent which can be used for polymerization include toluene, benzene, tetrahydrofuran, diethyl ether and dioxane. Examples of the polymerization initiator used herein include 2,2′-azobisisobutyronitrile (AIBN), 2,2′-azobis(2,4-dimethylvaleronitrile), dimethyl 2,2-azobis(2-methylpropionate), benzoyl peroxide, and lauroyl peroxide. Preferably the system is heated at 50 to 80° C. for polymerization to take place. The reaction time is about 2 to 100 hours, preferably about 5 to 20 hours. The acid labile group that has been incorporated in the monomers may be kept as such, or the acid labile group may be once removed with an acid catalyst and thereafter protected or partially protected.
Resist Composition
In addition to the polymer, the positive resist composition, especially chemically amplified positive resist composition of the invention may comprise an organic solvent, a compound capable of generating an acid in response to high-energy radiation (photoacid generator), and optionally, a dissolution inhibitor, a basic compound, a surfactant and other additives.
Solvent
The organic solvent used herein may be any organic solvent in which the base resin, photoacid generator, and other components are soluble. Illustrative, non-limiting, examples of the organic solvent include ketones such as cyclohexanone and methyl-2-n-amylketone; 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, propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, and propylene glycol mono-tert-butyl ether acetate; and lactones such as γ-butyrolactone. These solvents may be used alone or in combinations of two or more thereof. Of the above organic solvents, diethylene glycol dimethyl ether, 1-ethoxy-2-propanol and propylene glycol monomethyl ether acetate, and mixtures thereof are preferred because the photoacid generator is most soluble therein.
The organic solvent is preferably used in an amount of about 200 to 1,000 parts by weight, more preferably about 400 to 800 parts by weight per 100 parts by weight of the base resin.
Photoacid Generator
The photoacid generator is a compound capable of generating an acid upon exposure to high-energy radiation and includes the following:

    (i) onium salts of the formula (P1a-1), (P1a-2) or (P1b),
    (ii) diazomethane derivatives of the formula (P2),
    (iii) glyoxime derivatives of the formula (P3),
    (iv) bissulfone derivatives of the formula (P4),
    (v) sulfonic acid esters of N-hydroxyimide compounds of the formula (P5),
    (vi) β-ketosulfonic acid derivatives,
    (vii) disulfone derivatives,
    (viii) nitrobenzylsulfonate derivatives, and
    (ix) sulfonate derivatives.


These photoacid generators are described in detail.
(i) Onium Salts of Formula (P1a-1), (P1a-2) or (P1b):




Herein, R101a, R101b, and R101c independently represent straight, branched or cyclic alkyl, alkenyl, oxoalkyl or oxoalkenyl groups of 1 to 12 carbon atoms, aryl groups of 6 to 20 carbon atoms, or aralkyl or aryloxoalkyl groups of 7 to 12 carbon atoms, wherein some or all of the hydrogen atoms may be replaced by alkoxy or other groups. Also, R101b and R101c, taken together, may form a ring. R101b and R101c each are an alkylene group of 1 to 6 carbon atoms when they form a ring. K− is a non-nucleophilic counter ion.
R101a, R101b, and R101c may be the same or different and are illustrated below. Exemplary alkyl groups include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclopropylmethyl, 4-methylcyclohexyl, cyclohexylmethyl, norbornyl, and adamantyl. Exemplary alkenyl groups include vinyl, allyl, propenyl, butenyl, hexenyl, and cyclohexenyl. Exemplary oxoalkyl groups include 2-oxocyclopentyl and 2-oxocyclohexyl as well as 2-oxopropyl, 2-cyclopentyl-2-oxoethyl, 2-cyclohexyl-2-oxoethyl, and 2-(4-methylcyclohexyl)-2-oxoethyl. Exemplary oxoalkenyl groups include 2-oxo-4-cyclohexenyl and 2-oxo-4-propenyl. Exemplary aryl groups include phenyl and naphthyl; alkoxyphenyl groups such as p-methoxyphenyl, m-methoxyphenyl, o-methoxyphenyl, ethoxyphenyl, p-tert-butoxyphenyl, and m-tert-butoxyphenyl; alkylphenyl groups such as 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, ethylphenyl, 4-tert-butylphenyl, 4-butylphenyl, and dimethylphenyl; alkylnaphthyl groups such as methylnaphthyl and ethylnaphthyl; alkoxynaphthyl groups such as methoxynaphthyl and ethoxynaphthyl; dialkylnaphthyl groups such as dimethylnaphthyl and diethylnaphthyl; and dialkoxynaphthyl groups such as dimethoxynaphthyl and diethoxynaphthyl. Exemplary aralkyl groups include benzyl, phenylethyl, and phenethyl. Exemplary aryloxoalkyl groups are 2-aryl-2-oxoethyl groups such as 2-phenyl-2-oxoethyl, 2-(1-naphthyl)-2-oxoethyl, and 2-(2-naphthyl)-2-oxoethyl. Examples of the non-nucleophilic counter ion represented by K− 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, and alkylsulfonate ions such as mesylate and butanesulfonate.




Herein, R102a and R102b independently represent straight, branched or cyclic alkyl groups of 1 to 8 carbon atoms. R103 represents a straight, branched or cyclic alkylene group of 1 to 10 carbon atoms. R104a and R104b independently represent 2-oxoalkyl groups of 3 to 7 carbon atoms. K− is a non-nucleophilic counter ion.
Illustrative of the groups represented by R102a and R102b are methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, 4-methylcyclohexyl, and cyclohexylmethyl. Illustrative of the groups represented by R103 are methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, 1,4-cyclohexylene, 1,2-cyclohexylene, 1,3-cyclopentylene, 1,4-cyclooctylene, and 1,4-cyclohexanedimethylene. Illustrative of the groups represented by R104a and R104b are 2-oxopropyl, 2-oxocyclopentyl, 2-oxocyclohexyl, and 2-oxocycloheptyl. Illustrative examples of the counter ion represented by K− are the same as exemplified for formulae (P1a-1) and (P1a-2).
(ii) Diazomethane Derivatives of Formula (P2)




Herein, R105 and R106 independently represent straight, branched or cyclic alkyl or halogenated alkyl groups of 1 to 12 carbon atoms, aryl or halogenated aryl groups of 6 to 20 carbon atoms, or aralkyl groups of 7 to 12 carbon atoms.
Of the groups represented by R105 and R106, exemplary alkyl groups include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, amyl, cyclopentyl, cyclohexyl, cycloheptyl, norbornyl, and adamantyl. Exemplary halogenated alkyl groups include trifluoromethyl, 1,1,1-trifluoroethyl, 1,1,1-trichloroethyl, and nonafluorobutyl. Exemplary aryl groups include phenyl; alkoxyphenyl groups such as p-methoxyphenyl, m-methoxyphenyl, o-methoxyphenyl, ethoxyphenyl, p-tert-butoxyphenyl, and m-tert-butoxyphenyl; and alkylphenyl groups such as 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, ethylphenyl, 4-tert-butylphenyl, 4-butylphenyl, and dimethylphenyl. Exemplary halogenated aryl groups include fluorophenyl, chlorophenyl, and 1,2,3,4,5-pentafluorophenyl. Exemplary aralkyl groups include benzyl and phenethyl.
(iii) Glyoxime Derivatives of Formula (P3)




Herein, R107, R108, and R109 independently represent straight, branched or cyclic alkyl or halogenated alkyl groups of 1 to 12 carbon atoms, aryl or halogenated aryl groups of 6 to 20 carbon atoms, or aralkyl groups of 7 to 12 carbon atoms. Also, R108 and R109, taken together, may form a ring. R108 and R109 each are a straight or branched alkylene group of 1 to 6 carbon atoms when they form a ring. R105 is as defined in formula (P2).
Illustrative examples of the alkyl, halogenated alkyl, aryl, halogenated aryl, and aralkyl groups represented by R107, R108, and R109 are the same as exemplified for R105 and R106. Examples of the alkylene groups represented by R108 and R109 include methylene, ethylene, propylene, butylene, and hexylene.
(iv) Bissulfone Derivatives of Formula (P4)




Herein, R101a and R101b are as defined above.
(v) Sulfonic Acid Esters of N-hydroxyimide Compounds of Formula (P5)




Herein, R110 is an arylene group of 6 to 10 carbon atoms, alkylene group of 1 to 6 carbon atoms, or alkenylene group of 2 to 6 carbon atoms wherein some or all of the hydrogen atoms may be replaced by straight or branched alkyl or alkoxy groups of 1 to 4 carbon atoms, nitro, acetyl, or phenyl groups. R111 is a straight, branched or cyclic alkyl group of 1 to 8 carbon atoms, alkenyl, alkoxyalkyl, phenyl or naphthyl group wherein some or all of the hydrogen atoms may be replaced by alkyl or alkoxy groups of 1 to 4 carbon atoms, phenyl groups (which may have substituted thereon an alkyl or alkoxy of 1 to 4 carbon atoms, nitro, or acetyl group), hetero-aromatic groups of 3 to 5 carbon atoms, or chlorine or fluorine atoms.
Of the groups represented by R110, exemplary arylene groups include 1,2-phenylene and 1,8-naphthylene; exemplary alkylene groups include methylene, ethylene, trimethylene, tetramethylene, phenylethylene, and norbornane-2,3-diyl; and exemplary alkenylene groups include 1,2-vinylene, 1-phenyl-1,2-vinylene, and 5-norbornene-2,3-diyl. Of the groups represented by R111, exemplary alkyl groups are as exemplified for R101a to R101c; exemplary alkenyl groups include vinyl, 1-propenyl, allyl, 1-butenyl, 3-butenyl, isoprenyl, 1-pentenyl, 3-pentenyl, 4-pentenyl, dimethylallyl, 1-hexenyl, 3-hexenyl, 5-hexenyl, 1-heptenyl, 3-heptenyl, 6-heptenyl, and 7-octenyl; and exemplary alkoxyalkyl groups include methoxymethyl, ethoxymethyl, propoxymethyl, butoxymethyl, pentyloxymethyl, hexyloxymethyl, heptyloxymethyl, methoxyethyl, ethoxyethyl, propoxyethyl, butoxyethyl, pentyloxyethyl, hexyloxyethyl, methoxypropyl, ethoxypropyl, propoxypropyl, butoxypropyl, methoxybutyl, ethoxybutyl, propoxybutyl, methoxypentyl, ethoxypentyl, methoxyhexyl, and methoxyheptyl.
Of the substituents on these groups, the alkyl groups of 1 to 4 carbon atoms include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl and tert-butyl; and the alkoxy groups of 1 to 4 carbon atoms include methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, and tert-butoxy. The phenyl groups which may have substituted thereon an alkyl or alkoxy of 1 to 4 carbon atoms, nitro, or acetyl group include phenyl, tolyl, p-tert-butoxyphenyl, p-acetylphenyl and p-nitrophenyl. The hetero-aromatic groups of 3 to 5 carbon atoms include pyridyl and furyl.
Illustrative examples of the photoacid generator include:
onium salts such as diphenyliodonium trifluoromethanesulfonate, (p-tert-butoxyphenyl)phenyliodonium trifluoromethanesulfonate, diphenyliodonium p-toluenesulfonate, (p-tert-butoxyphenyl)phenyliodonium p-toluenesulfonate, triphenylsulfonium trifluoromethanesulfonate, (p-tert-butoxyphenyl)diphenylsulfonium trifluoromethanesulfonate, bis(p-tert-butoxyphenyl)phenylsulfonium trifluoromethanesulfonate, tris(p-tert-butoxyphenyl)sulfonium trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate, (p-tert-butoxyphenyl)diphenylsulfonium p-toluenesulfonate, bis(p-tert-butoxyphenyl)phenylsulfonium p-toluenesulfonate, tris(p-tert-butoxyphenyl)sulfonium p-toluenesulfonate, triphenylsulfonium nonafluorobutanesulfonate, triphenylsulfonium butanesulfonate, trimethylsulfonium trifluoromethanesulfonate, trimethylsulfonium p-toluenesulfonate, cyclohexylmethyl(2-oxocyclohexyl)sulfonium trifluoromethanesulfonate, cyclohexylmethyl(2-oxocyclohexyl)sulfonium p-toluenesulfonate, dimethylphenylsulfonium trifluoromethanesulfonate, dimethylphenylsulfonium p-toluenesulfonate, dicyclohexylphenylsulfonium trifluoromethanesulfonate, dicyclohexylphenylsulfonium p-toluenesulfonate, trinaphthylsulfonium trifluoromethanesulfonate, (2-norbornyl)methyl(2-oxocyclohexyl)sulfonium trifluoromethanesulfonate, ethylenebis[methyl(2-oxocyclopentyl)sulfonium trifluoromethanesulfonate], and 1,2′-naphthylcarbonylmethyltetrahydrothiophenium triflate;
diazomethane derivatives such as bis(benzenesulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(xylenesulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(cyclopentylsulfonyl)diazomethane, bis(n-butylsulfonyl)diazomethane, bis(isobutylsulfonyl)diazomethane, bis(sec-butylsulfonyl)diazomethane, bis(n-propylsulfonyl)diazomethane, bis(isopropylsulfonyl)diazomethane, bis(tert-butylsulfonyl)diazomethane, bis(n-amylsulfonyl)diazomethane, bis(isoamylsulfonyl)diazomethane, bis(sec-amylsulfonyl)diazomethane, bis(tert-amylsulfonyl)diazomethane, 1-cyclohexylsulfonyl-1-(tert-butylsulfonyl)diazomethane, 1-cyclohexylsulfonyl-1-(tert-amylsulfonyl)diazomethane, and 1-tert-amylsulfonyl-1-(tert-butylsulfonyl)diazomethane;
glyoxime derivatives such as bis-O-(p-toluenesulfonyl)-α-dimethylglyoxime, bis-O-(p-toluenesulfonyl)-α-diphenylglyoxime, bis-O-(p-toluenesulfonyl)-α-dicyclohexylglyoxime, bis-O-(p-toluenesulfonyl)-2,3-pentanedioneglyoxime, bis-O-(p-toluenesulfonyl)-2-methyl-3,4-pentanedioneglyoxime, bis-O-(n-butanesulfonyl)-α-dimethylglyoxime, bis-O-(n-butanesulfonyl)-α-diphenylglyoxime, bis-O-(n-butanesulfonyl)-α-dicyclohexylglyoxime, bis-O-(n-butanesulfonyl)-2,3-pentanedioneglyoxime, bis-O-(n-butanesulfonyl)-2-methyl-3,4-pentanedioneglyoxime, bis-O-(methanesulfonyl)-α-dimethylglyoxime, bis-O-(trifluoromethanesulfonyl)-α-dimethylglyoxime, bis-O-(1,1,1-trifluoroethanesulfonyl)-α-dimethylglyoxime, bis-O-(tert-butanesulfonyl)-α-dimethylglyoxime, bis-O-(perfluorooctanesulfonyl)-α-dimethylglyoxime, bis-O-(cyclohexanesulfonyl)-α-dimethylglyoxime, bis-O-(benzenesulfonyl)-α-dimethylglyoxime, bis-O-(p-fluorobenzenesulfonyl)-α-dimethylglyoxime, bis-O-(p-tert-butylbenzenesulfonyl)-α-dimethylglyoxime, bis-O-(xylenesulfonyl)-α-dimethylglyoxime, and bis-O-(camphorsulfonyl)-α-dimethylglyoxime;
bissulfone derivatives such as bisnaphthylsulfonylmethane, bistrifluoromethylsulfonylmethane, bismethylsulfonylmethane, bisethylsulfonylmethane, bispropylsulfonylmethane, bisisopropylsulfonylmethane, bis-p-toluenesulfonylmethane, and bisbenzenesulfonylmethane;
β-ketosulfone derivatives such as 2-cyclohexylcarbonyl-2-(p-toluenesulfonyl)propane and 2-isopropylcarbonyl-2-(p-toluenesulfonyl)propane;
disulfone derivatives such as diphenyl disulfone derivatives and dicyclohexyl disulfone derivatives;
nitrobenzyl sulfonate derivatives such as 2,6-dinitrobenzyl p-toluenesulfonate and 2,4-dinitrobenzyl p-toluenesulfonate;
sulfonic acid ester derivatives such as 1,2,3-tris(methanesulfonyloxy)benzene, 1,2,3-tris(trifluoromethanesulfonyloxy)benzene, and 1,2,3-tris(p-toluenesulfonyloxy)benzene; and
sulfonic acid esters of N-hydroxyimides such as N-hydroxysuccinimide methanesulfonate, N-hydroxysuccinimide trifluoromethanesulfonate, N-hydroxysuccinimide ethanesulfonate, N-hydroxysuccinimide 1-propanesulfonate, N-hydroxysuccinimide 2-propanesulfonate, N-hydroxysuccinimide 1-pentanesulfonate, N-hydroxysuccinimide 1-octanesulfonate, N-hydroxysuccinimide p-toluenesulfonate, N-hydroxysuccinimide p-methoxybenzenesulfonate, N-hydroxysuccinimide 2-chloroethanesulfonate, N-hydroxysuccinimide benzenesulfonate, N-hydroxysuccinimide 2,4,6-trimethylbenzenesulfonate, N-hydroxysuccinimide 1-naphthalenesulfonate, N-hydroxysuccinimide 2-naphthalenesulfonate, N-hydroxy-2-phenylsuccinimide methanesulfonate, N-hydroxymaleimide methanesulfonate, N-hydroxymaleimide ethanesulfonate, N-hydroxy-2-phenylmaleimide methanesulfonate, N-hydroxyglutarimide methanesulfonate, N-hydroxyglutarimide benzenesulfonate, N-hydroxyphthalimide methanesulfonate, N-hydroxyphthalimide benzenesulfonate, N-hydroxyphthalimide trifluoromethanesulfonate, N-hydroxyphthalimide p-toluenesulfonate, N-hydroxynaphthalimide methanesulfonate, N-hydroxynaphthalimide benzenesulfonate, N-hydroxy-5-norbornene-2,3-dicarboxyimide methanesulfonate, N-hydroxy-5-norbornene-2,3-dicarboxyimide trifluoromethanesulfonate, and N-hydroxy-5-norbornene-2,3-dicarboxyimide p-toluenesulfonate.
Preferred among these photoacid generators are onium salts such as triphenylsulfonium trifluoromethanesulfonate, (p-tert-butoxyphenyl)diphenylsulfonium trifluoromethanesulfonate, tris(p-tert-butoxyphenyl)sulfonium trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate, (p-tert-butoxyphenyl)diphenylsulfonium p-toluenesulfonate, tris(p-tert-butoxyphenyl)sulfonium p-toluenesulfonate, trinaphthylsulfonium trifluoromethanesulfonate, cyclohexylmethyl(2-oxocyclohexyl)sulfonium trifluoromethanesulfonate, (2-norbornyl)methyl(2-oxocylohexyl)sulfonium trifluoromethanesulfonate, and 1,2′-naphthylcarbonylmethyltetrahydrothiophenium triflate;
diazomethane derivatives such as bis(benzenesulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(n-butylsulfonyl)diazomethane, bis(isobutylsulfonyl)diazomethane, bis(sec-butylsulfonyl)diazomethane, bis(n-propylsulfonyl)diazomethane, bis(isopropylsulfonyl)diazomethane, and bis(tert-butylsulfonyl)diazomethane;
glyoxime derivatives such as bis-O-(p-toluenesulfonyl)-α-dimethylglyoxime and bis-O-(n-butanesulfonyl)-α-dimethylglyoxime;
bissulfone derivatives such as bisnaphthylsulfonylmethane; and sulfonic acid esters of N-hydroxyimide compounds such as N-hydroxysuccinimide methanesulfonate, N-hydroxysuccinimide trifluoromethanesulfonate, N-hydroxysuccinimide 1-propanesulfonate, N-hydroxysuccinimide 2-propanesulfonate, N-hydroxysuccinimide 1-pentanesulfonate, N-hydroxysuccinimide p-toluenesulfonate, N-hydroxynaphthalimide methanesulfonate, and N-hydroxynaphthalimide benzenesulfonate.
Also useful are photoacid generators of the oxime type described in WO 2004/074242 A2.
These photoacid generators may be used singly or in combinations of two or more thereof. Onium salts are effective for improving rectangularity, while diazomethane derivatives and glyoxime derivatives are effective for reducing standing waves. The combination of an onium salt with a diazomethane or a glyoxime derivative allows for fine adjustment of the profile.
The photoacid generator is preferably added in an amount of 0.1 to 50 parts, and especially 0.5 to 40 parts by weight, per 100 parts by weight of the base resin. Less than 0.1 part of the photoacid generator may generate a less amount of acid upon exposure, sometimes leading to a poor sensitivity and resolution whereas more than 50 parts of the photoacid generator may adversely affect the transmittance and resolution of resist.
Dissolution Inhibitor
To the resist composition, a dissolution inhibitor or regulator may be added. The dissolution inhibitor is a compound having on the molecule at least two phenolic hydroxyl groups, in which an average of from 0 to 100 mol % of all the hydrogen atoms on the phenolic hydroxyl groups are replaced with acid labile groups or a compound having on the molecule at least one carboxyl group, in which an average of 50 to 100 mol % of all the hydrogen atoms on the carboxyl groups are replaced with acid labile groups, both the compounds having a weight average molecular weight within a range of 100 to 1,000, and preferably 150 to 800.
The degree of substitution of the hydrogen atoms on the phenolic hydroxyl groups with acid labile groups is on average at least 0 mol %, and preferably at least 30 mol %, of all the phenolic hydroxyl groups. The upper limit is 100 mol %, and preferably 80 mol %. The degree of substitution of the hydrogen atoms on the carboxyl groups with acid labile groups is on average at least 50 mol %, and preferably at least 70 mol %, of all the carboxyl groups, with the upper limit being 100 mol %.
Preferable examples of such compounds having two or more phenolic hydroxyl groups or compounds having at least one carboxyl group include those of formulas (D1) to (D14) below.







In these formulas, R201 and R202 are each hydrogen or a straight or branched C1-C8 alkyl or alkenyl; R203 is hydrogen, a straight or branched C1-C8 alkyl or alkenyl, or —(R207)h—COOH; R204 is —(CH2)i— (where i=2 to 10), a C6-C10 arylene, carbonyl, sulfonyl, an oxygen atom, or a sulfur atom; R205 is a C1-C10 alkylene, a C6-C10 arylene, carbonyl, sulfonyl, an oxygen atom, or a sulfur atom; R206 is hydrogen, a straight or branched C1-C8 alkyl or alkenyl, or a hydroxyl-substituted phenyl or naphthyl; R207 is a straight or branched C1-C10 alkylene; R208 is hydrogen or hydroxyl; the letter j is an integer from 0 to 5; u and h are each 0 or 1; s, t, s′, t′, s′′, and t′′ are each numbers which satisfy s+t=8, s′+t′=5, and s′′+t′′=4, and are such that each phenyl structure has at least one hydroxyl group; and a is a number such that the compounds of formula (D8) or (D9) have a molecular weight of from 100 to 1,000.
The dissolution inhibitor may be formulated in an amount of 0 to 50 parts, preferably 5 to 50 parts, and more preferably 10 to 30 parts by weight, per 100 parts by weight of the base resin, and may be used singly or as a mixture of two or more thereof. An appropriate amount of the dissolution inhibitor is effective for improving resolution whereas more than 50 parts would lead to slimming of the patterned film, and thus a decline in resolution.
Basic Compound
The basic compound used herein is preferably a compound capable of suppressing the rate of diffusion when the acid generated by the photoacid generator diffuses within the resist film. The inclusion of this type of basic compound holds down the rate of acid diffusion within the resist film, resulting in better resolution. In addition, it suppresses changes in sensitivity following exposure, thus reducing substrate and environment dependence, as well as improving the exposure latitude and the pattern profile.
Examples of suitable basic compounds include primary, secondary, and tertiary aliphatic amines, mixed amines, aromatic amines, heterocyclic amines, nitrogen-containing compounds having carboxyl group, nitrogen-containing compounds having sulfonyl group, nitrogen-containing compounds having hydroxyl group, nitrogen-containing compounds having hydroxyphenyl group, nitrogen-containing alcoholic compounds, amide derivatives, and imide derivatives.
Examples of suitable primary aliphatic amines include ammonia, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, iso-butylamine, sec-butylamine, tert-butylamine, pentylamine, tert-amylamine, cyclopentylamine, hexylamine, cyclohexylamine, heptylamine, octylamine, nonylamine, decylamine, dodecylamine, cetylamine, methylenediamine, ethylenediamine, and tetraethylenepentamine. Examples of suitable secondary aliphatic amines include dimethylamine, diethylamine, di-n-propylamine, di-iso-propylamine, di-n-butylamine, di-iso-butylamine, di-sec-butylamine, dipentylamine, dicyclopentylamine, dihexylamine, dicyclohexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, didodecylamine, dicetylamine, N,N-dimethylmethylenediamine, N,N-dimethylethylenediamine, and N,N-dimethyltetraethylenepentamine. Examples of suitable tertiary aliphatic amines include trimethylamine, triethylamine, tri-n-propylamine, tri-iso-propylamine, tri-n-butylamine, tri-iso-butylamine, tri-sec-butylamine, tripentylamine, tricyclopentylamine, trihexylamine, tricyclohexylamine, triheptylamine, trioctylamine, trinonylamine, tridecylamine, tridodecylamine, tricetylamine, N,N,N′,N′-tetramethylmethylenediamine, N,N,N′,N′-tetramethylethylenediamine, and N,N,N′,N′-tetramethyltetraethylenepentamine.
Examples of suitable mixed amines include dimethylethylamine, methylethylpropylamine, benzylamine, phenethylamine, and benzyldimethylamine.
Examples of suitable aromatic amines include aniline derivatives (e.g., aniline, N-methylaniline, N-ethylaniline, N-propylaniline, N,N-dimethylaniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, ethylaniline, propylaniline, trimethylaniline, 2-nitroaniline, 3-nitroaniline, 4-nitroaniline, 2,4-dinitroaniline, 2,6-dinitroaniline, 3,5-dinitroaniline, and N,N-dimethyltoluidine), diphenyl(p-tolyl)amine, methyldiphenylamine, triphenylamine, phenylenediamine, naphthylamine, and diaminonaphthalene. Examples of suitable heterocyclic amines include pyrrole derivatives (e.g., pyrrole, 2H-pyrrole, 1-methylpyrrole, 2,4-dimethylpyrrole, 2,5-dimethylpyrrole, and N-methylpyrrole), oxazole derivatives (e.g., oxazole and isooxazole), thiazole derivatives (e.g., thiazole and isothiazole), imidazole derivatives (e.g., imidazole, 4-methylimidazole, and 4-methyl-2-phenylimidazole), pyrazole derivatives, furazan derivatives, pyrroline derivatives (e.g., pyrroline and 2-methyl-1-pyrroline), pyrrolidine derivatives (e.g., pyrrolidine, N-methylpyrrolidine, pyrrolidinone, and N-methylpyrrolidone), imidazoline derivatives, imidazolidine derivatives, pyridine derivatives (e.g., pyridine, methylpyridine, ethylpyridine, propylpyridine, butylpyridine, 4-(1-butylpentyl)pyridine, dimethylpyridine, trimethylpyridine, triethylpyridine, phenylpyridine, 3-methyl-2-phenylpyridine, 4-tert-butylpyridine, diphenylpyridine, benzylpyridine, methoxypyridine, butoxypyridine, dimethoxypyridine, 1-methyl-2-pyridone, 4-pyrrolidinopyridine, 1-methyl-4-phenylpyridine, 2-(1-ethylpropyl)pyridine, aminopyridine, and dimethylaminopyridine), pyridazine derivatives, pyrimidine derivatives, pyrazine derivatives, pyrazoline derivatives, pyrazolidine derivatives, piperidine derivatives, piperazine derivatives, morpholine derivatives, indole derivatives, isoindole derivatives, 1H-indazole derivatives, indoline derivatives, quinoline derivatives (e.g., quinoline and 3-quinolinecarbonitrile), isoquinoline derivatives, cinnoline derivatives, quinazoline derivatives, quinoxaline derivatives, phthalazine derivatives, purine derivatives, pteridine derivatives, carbazole derivatives, phenanthridine derivatives, acridine derivatives, phenazine derivatives, 1,10-phenanthroline derivatives, adenine derivatives, adenosine derivatives, guanine derivatives, guanosine derivatives, uracil derivatives, and uridine derivatives.
Examples of suitable nitrogen-containing compounds having carboxyl group include aminobenzoic acid, indolecarboxylic acid, and amino acid derivatives (e.g., nicotinic acid, alanine, alginine, aspartic acid, glutamic acid, glycine, histidine, isoleucine, glycylleucine, leucine, methionine, phenylalanine, threonine, lysine, 3-aminopyrazine-2-carboxylic acid, and methoxyalanine). Examples of suitable nitrogen-containing compounds having sulfonyl group include 3-pyridinesulfonic acid and pyridinium p-toluenesulfonate. Examples of suitable nitrogen-containing compounds having hydroxyl group, nitrogen-containing compounds having hydroxyphenyl group, and nitrogen-containing alcoholic compounds include 2-hydroxypyridine, aminocresol, 2,4-quinolinediol, 3-indolemethanol hydrate, monoethanolamine, diethanolamine, triethanolamine, N-ethyldiethanolamine, N,N-diethylethanolamine, triisopropanolamine, 2,2′-iminodiethanol, 2-aminoethanol, 3-amino-1-propanol, 4-amino-1-butanol, 4-(2-hydroxyethyl)morpholine, 2-(2-hydroxyethyl)pyridine, 1-(2-hydroxyethyl)piperazine, 1-[2-(2-hydroxyethoxy)ethyl]piperazine, piperidine ethanol, 1-(2-hydroxyethyl)pyrrolidine, 1-(2-hydroxyethyl)-2-pyrrolidinone, 3-piperidino-1,2-propanediol, 3-pyrrolidino-1,2-propanediol, 8-hydroxyjulolidine, 3-quinuclidinol, 3-tropanol, 1-methyl-2-pyrrolidine ethanol, 1-aziridine ethanol, N-(2-hydroxyethyl)phthalimide, and N-(2-hydroxyethyl)isonicotinamide.
Examples of suitable amide derivatives include formamide, N-methylformamide, N,N-dimethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, propionamide, and benzamide. Suitable imide derivatives include phthalimide, succinimide, and maleimide.
One or more basic compounds of the following general formula (B)-1 may also be added.

N(X)n(Y)3-n  (B)-1

In the formula, n is equal to 1, 2 or 3; side chain Y is independently hydrogen or a straight, branched or cyclic alkyl group of 1 to 20 carbon atoms which may contain an ether or hydroxyl group; and side chain X is independently selected from groups of the following general formulas (X)-1 to (X)-3, and two or three X's may bond together to form a ring.




In the formulas, R300, R302 and R305 are independently straight or branched alkylene groups of 1 to 4 carbon atoms; R301 and R304 are independently hydrogen, straight, branched or cyclic alkyl groups of 1 to 20 carbon atoms, which may contain at least one hydroxyl, ether, ester group or lactone ring; R303 is a single bond or a straight or branched alkylene group of 1 to 4 carbon atoms; and R306 is a straight, branched or cyclic alkyl group of 1 to 20 carbon atoms, which may contain at least one hydroxyl, ether, ester group or lactone ring.
Illustrative examples of the compounds of formula (B)-1 include tris(2-methoxymethoxyethyl)amine, tris{2-(2-methoxyethoxy)ethyl}amine, tris{2-(2-methoxyethoxymethoxy)ethyl}amine, tris{2-(1-methoxyethoxy)ethyl}amine, tris{2-(1-ethoxyethoxy)ethyl}amine, tris{2-(1-ethoxypropoxy)ethyl}amine, tris[2-{2-(2-hydroxyethoxy)ethoxy}ethyl]amine, 4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8.8.8]hexacosane, 4,7,13,18-tetraoxa-1,10-diazabicyclo[8.5.5]eicosane, 1,4,10,13-tetraoxa-7,16-diazabicyclooctadecane, 1-aza-12-crown-4, 1-aza-15-crown-5, 1-aza-18-crown-6, tris(2-formyloxyethyl)amine, tris(2-acetoxyethyl)amine, tris(2-propionyloxyethyl)amine, tris(2-butyryloxyethyl)amine, tris(2-isobutyryloxyethyl)amine, tris(2-valeryloxyethyl)amine, tris(2-pivaloyloxyethyl)amine, N,N-bis(2-acetoxyethyl)-2-(acetoxyacetoxy)ethylamine, tris(2-methoxycarbonyloxyethyl)amine, tris(2-tert-butoxycarbonyloxyethyl)amine, tris[2-(2-oxopropoxy)ethyl]amine, tris[2-(methoxycarbonylmethyl)oxyethyl]amine, tris[2-(tert-butoxycarbonylmethyloxy)ethyl]amine, tris[2-(cyclohexyloxycarbonylmethyloxy)ethyl]amine, tris(2-methoxycarbonylethyl)amine, tris(2-ethoxycarbonylethyl)amine, N,N-bis(2-hydroxyethyl)-2-(methoxycarbonyl)ethylamine, N,N-bis(2-acetoxyethyl)-2-(methoxycarbonyl)ethylamine, N,N-bis(2-hydroxyethyl)-2-(ethoxycarbonyl)ethylamine, N,N-bis(2-acetoxyethyl)-2-(ethoxycarbonyl)ethylamine, N,N-bis(2-hydroxyethyl)-2-(2-methoxyethoxycarbonyl)ethylamine, N,N-bis(2-acetoxyethyl)-2-(2-methoxyethoxycarbonyl)ethylamine, N,N-bis(2-hydroxyethyl)-2-(2-hydroxyethoxycarbonyl)ethylamine, N,N-bis(2-acetoxyethyl)-2-(2-acetoxyethoxycarbonyl)ethylamine, N,N-bis(2-hydroxyethyl)-2-[(methoxycarbonyl)methoxycarbonyl]-ethylamine, N,N-bis(2-acetoxyethyl)-2-[(methoxycarbonyl)methoxycarbonyl]-ethylamine, N,N-bis(2-hydroxyethyl)-2-(2-oxopropoxycarbonyl)ethylamine, N,N-bis(2-acetoxyethyl)-2-(2-oxopropoxycarbonyl)ethylamine, N,N-bis(2-hydroxyethyl)-2-(tetrahydrofurfuryloxycarbonyl)-ethylamine, N,N-bis(2-acetoxyethyl)-2-(tetrahydrofurfuryloxycarbonyl)-ethylamine, N,N-bis(2-hydroxyethyl)-2-[(2-oxotetrahydrofuran-3-yl)oxy-carbonyl]ethylamine, N,N-bis(2-acetoxyethyl)-2-[(2-oxotetrahydrofuran-3-yl)oxy-carbonyl]ethylamine, N,N-bis(2-hydroxyethyl)-2-(4-hydroxybutoxycarbonyl)ethylamine, N,N-bis(2-formyloxyethyl)-2-(4-formyloxybutoxycarbonyl)-ethylamine, N,N-bis(2-formyloxyethyl)-2-(2-formyloxyethoxycarbonyl)-ethylamine, N,N-bis(2-methoxyethyl)-2-(methoxycarbonyl)ethylamine, N-(2-hydroxyethyl)-bis[2-(methoxycarbonyl)ethyl]amine, N-(2-acetoxyethyl)-bis[2-(methoxycarbonyl)ethyl]amine, N-(2-hydroxyethyl)-bis[2-(ethoxycarbonyl)ethyl]amine, N-(2-acetoxyethyl)-bis[2-(ethoxycarbonyl)ethyl]amine, N-(3-hydroxy-1-propyl)-bis[2-(methoxycarbonyl)ethyl]amine, N-(3-acetoxy-1-propyl)-bis[2-(methoxycarbonyl)ethyl]amine, N-(2-methoxyethyl)-bis[2-(methoxycarbonyl)ethyl]amine, N-butyl-bis[2-(methoxycarbonyl)ethyl]amine, N-butyl-bis[2-(2-methoxyethoxycarbonyl)ethyl]amine, N-methyl-bis(2-acetoxyethyl)amine, N-ethyl-bis(2-acetoxyethyl)amine, N-methyl-bis(2-pivaloyloxyethyl)amine, N-ethyl-bis[2-(methoxycarbonyloxy)ethyl]amine, N-ethyl-bis[2-(tert-butoxycarbonyloxy)ethyl]amine, tris(methoxycarbonylmethyl)amine, tris(ethoxycarbonylmethyl)amine, N-butyl-bis(methoxycarbonylmethyl)amine, N-hexyl-bis(methoxycarbonylmethyl)amine, and β-(diethylamino)-δ-valerolactone.
Also useful are basic compounds having cyclic structure, represented by the following general formula (B)-2.




Herein X is as defined above, and R307 is a straight or branched alkylene group of 2 to 20 carbon atoms which may contain one or more carbonyl, ether, ester or sulfide groups.

Illustrative examples of the compounds having formula (B)-2 include 1-[2-(methoxymethoxy)ethyl]pyrrolidine, 1-[2-(methoxymethoxy)ethyl]piperidine, 4-[2-(methoxymethoxy)ethyl]morpholine, 1-[2-[(2-methoxyethoxy)methoxy]ethyl]pyrrolidine, 1-[2-[(2-methoxyethoxy)methoxy]ethyl]piperidine, 4-[2-[(2-methoxyethoxy)methoxy]ethyl]morpholine, 2-(1-pyrrolidinyl)ethyl acetate, 2-piperidinoethyl acetate, 2-morpholinoethyl acetate, 2-(1-pyrrolidinyl)ethyl formate, 2-piperidinoethyl propionate, 2-morpholinoethyl acetoxyacetate, 2-(1-pyrrolidinyl)ethyl methoxyacetate, 4-[2-(methoxycarbonyloxy)ethyl]morpholine, 1-[2-(t-butoxycarbonyloxy)ethyl]piperidine, 4-[2-(2-methoxyethoxycarbonyloxy)ethyl]morpholine, methyl 3-(1-pyrrolidinyl)propionate, methyl 3-piperidinopropionate, methyl 3-morpholinopropionate, methyl 3-(thiomorpholino)propionate, methyl 2-methyl-3-(1-pyrrolidinyl)propionate, ethyl 3-morpholinopropionate, methoxycarbonylmethyl 3-piperidinopropionate, 2-hydroxyethyl 3-(1-pyrrolidinyl)propionate, 2-acetoxyethyl 3-morpholinopropionate, 2-oxotetrahydrofuran-3-yl 3-(1-pyrrolidinyl)propionate, tetrahydrofurfuryl 3-morpholinopropionate, glycidyl 3-piperidinopropionate, 2-methoxyethyl 3-morpholinopropionate, 2-(2-methoxyethoxy)ethyl 3-(1-pyrrolidinyl)propionate, butyl 3-morpholinopropionate, cyclohexyl 3-piperidinopropionate, α-(1-pyrrolidinyl)methyl-γ-butyrolactone, β-piperidino-γ-butyrolactone, β-morpholino-δ-valerolactone, methyl 1-pyrrolidinylacetate, methyl piperidinoacetate, methyl morpholinoacetate, methyl thiomorpholinoacetate, ethyl 1-pyrrolidinylacetate, and 2-methoxyethyl morpholinoacetate.
Also, basic compounds having cyano group, represented by the following general formulae (B)-3 to (B)-6 are useful.




Herein, X, R307 and n are as defined above, and R308 and R309 are each independently a straight or branched alkylene group of 1 to 4 carbon atoms.

Illustrative examples of the basic compounds having cyano group, represented by formulae (B)-3 to (B)-6, include 3-(diethylamino)propiononitrile, N,N-bis(2-hydroxyethyl)-3-aminopropiononitrile, N,N-bis(2-acetoxyethyl)-3-aminopropiononitrile, N,N-bis(2-formyloxyethyl)-3-aminopropiononitrile, N,N-bis(2-methoxyethyl)-3-aminopropiononitrile, N,N-bis[2-(methoxymethoxy)ethyl]-3-aminopropiononitrile, methyl N-(2-cyanoethyl)-N-(2-methoxyethyl)-3-aminopropionate, methyl N-(2-cyanoethyl)-N-(2-hydroxyethyl)-3-aminopropionate, methyl N-(2-acetoxyethyl)-N-(2-cyanoethyl)-3-aminopropionate, N-(2-cyanoethyl)-N-ethyl-3-aminopropiononitrile, N-(2-cyanoethyl)-N-(2-hydroxyethyl)-3-aminopropiononitrile, N-(2-acetoxyethyl)-N-(2-cyanoethyl)-3-aminopropiononitrile, N-(2-cyanoethyl)-N-(2-formyloxyethyl)-3-aminopropiononitrile, N-(2-cyanoethyl)-N-(2-methoxyethyl)-3-aminopropiononitrile, N-(2-cyanoethyl)-N-[2-(methoxymethoxy)ethyl]-3-aminopropiono-nitrile, N-(2-cyanoethyl)-N-(3-hydroxy-1-propyl)-3-aminopropiononitrile, N-(3-acetoxy-1-propyl)-N-(2-cyanoethyl)-3-aminopropiononitrile, N-(2-cyanoethyl)-N-(3-formyloxy-1-propyl)-3-aminopropiono-nitrile, N-(2-cyanoethyl)-N-tetrahydrofurfuryl-3-aminopropiononitrile, N,N-bis(2-cyanoethyl)-3-aminopropiononitrile, diethylaminoacetonitrile, N,N-bis(2-hydroxyethyl)aminoacetonitrile, N,N-bis(2-acetoxyethyl)aminoacetonitrile, N,N-bis(2-formyloxyethyl)aminoacetonitrile, N,N-bis(2-methoxyethyl)aminoacetonitrile, N,N-bis[2-(methoxymethoxy)ethyl]aminoacetonitrile, methyl N-cyanomethyl-N-(2-methoxyethyl)-3-aminopropionate, methyl N-cyanomethyl-N-(2-hydroxyethyl)-3-aminopropionate, methyl N-(2-acetoxyethyl)-N-cyanomethyl-3-aminopropionate, N-cyanomethyl-N-(2-hydroxyethyl)aminoacetonitrile, N-(2-acetoxyethyl)-N-(cyanomethyl)aminoacetonitrile, N-cyanomethyl-N-(2-formyloxyethyl)aminoacetonitrile, N-cyanomethyl-N-(2-methoxyethyl)aminoacetonitrile, N-cyanomethyl-N-[2-(methoxymethoxy)ethyl)aminoacetonitrile, N-cyanomethyl-N-(3-hydroxy-1-propyl)aminoacetonitrile, N-(3-acetoxy-1-propyl)-N-(cyanomethyl)aminoacetonitrile, N-cyanomethyl-N-(3-formyloxy-1-propyl)aminoacetonitrile, N,N-bis(cyanomethyl)aminoacetonitrile, 1-pyrrolidinepropiononitrile, 1-piperidinepropiononitrile, 4-morpholinepropiononitrile, 1-pyrrolidineacetonitrile, 1-piperidineacetonitrile, 4-morpholineacetonitrile, cyanomethyl 3-diethylaminopropionate, cyanomethyl N,N-bis(2-hydroxyethyl)-3-aminopropionate, cyanomethyl N,N-bis(2-acetoxyethyl)-3-aminopropionate, cyanomethyl N,N-bis(2-formyloxyethyl)-3-aminopropionate, cyanomethyl N,N-bis(2-methoxyethyl)-3-aminopropionate, cyanomethyl N,N-bis[2-(methoxymethoxy)ethyl]-3-aminopropionate, 2-cyanoethyl 3-diethylaminopropionate, 2-cyanoethyl N,N-bis(2-hydroxyethyl)-3-aminopropionate, 2-cyanoethyl N,N-bis(2-acetoxyethyl)-3-aminopropionate, 2-cyanoethyl N,N-bis(2-formyloxyethyl)-3-aminopropionate, 2-cyanoethyl N,N-bis(2-methoxyethyl)-3-aminopropionate, 2-cyanoethyl N,N-bis[2-(methoxymethoxy)ethyl]-3-aminopropionate, cyanomethyl 1-pyrrolidinepropionate, cyanomethyl 1-piperidinepropionate, cyanomethyl 4-morpholinepropionate, 2-cyanoethyl 1-pyrrolidinepropionate, 2-cyanoethyl 1-piperidinepropionate, and 2-cyanoethyl 4-morpholinepropionate.
The basic compound is preferably formulated in an amount of 0.001 to 2 parts, and especially 0.01 to 1 part by weight, per 100 parts by weight of the base resin. Less than 0.001 part of the basic compound achieves no or little addition effect whereas more than 2 parts would result in too low a sensitivity.
Other Components
In the positive resist composition, a compound having a group ≡C—COOH in the molecule may be blended. Exemplary, non-limiting compounds having a carboxyl group include one or more compounds selected from Groups I and II below. Including this compound improves the PED stability of the resist and ameliorates edge roughness on nitride film substrates.
Group I:
Compounds in which some or all of the hydrogen atoms on the phenolic hydroxyl groups of the compounds of general formulas (A1) to (A10) below have been replaced by —R401—COOH (wherein R401 is a straight or branched alkylene of 1 to 10 carbon atoms), and in which the molar ratio C/(C+D) of phenolic hydroxyl groups (C) to ≡C—COOH groups (D) in the molecule is from 0.1 to 1.0.







In these formulas, R408 is hydrogen or methyl; R402 and R403 are each hydrogen or a straight or branched C1-C8 alkyl or alkenyl; R404 is hydrogen, a straight or branched C1-C8 alkyl or alkenyl, or a —(R409)h—COOR′ group (R′ being hydrogen or —R409—COOH); R405 is —(CH2)i— (wherein i is 2 to 10), a C6-C10 arylene, carbonyl, sulfonyl, an oxygen atom, or a sulfur atom; R406 is a C1-C10 alkylene, a C6-C10 arylene, carbonyl, sulfonyl, an oxygen atom, or a sulfur atom; R407 is hydrogen, a straight or branched C1-C8 alkyl or alkenyl, or a hydroxyl-substituted phenyl or naphthyl; R409 is a straight or branched C1-C10 alkyl or alkenyl or a —R411—COOH group; R410 is hydrogen, a straight or branched C1-C8 alkyl or alkenyl, or a —R411—COOH group; R411 is a straight or branched C1-C10 alkylene; h is an integer of 1 to 4, j is an integer from 0 to 3; s1, t1, s2, t2, s3, t3, s4, and t4 are each numbers which satisfy s1+t1=8, s2+t2=5, s3+t3=4, and s4+t4=6, and are such that each phenyl structure has at least one hydroxyl group; u is an integer of 1 to 4; κ is a number such that the compound of formula (A6) may have a weight average molecular weight of 1,000 to 5,000; and λ is a number such that the compound of formula (A7) may have a weight average molecular weight of 1,000 to 10,000.
Group II:
Compounds of general formulas (A11) to (A15) below.




In these formulas, R402, R403, and R411 are as defined above; R412 is hydrogen or hydroxyl; s5 and t5 are numbers which satisfy s5≧0, t5≧0, and s5+t5=5; and h′ is 0 or 1.
Illustrative, non-limiting examples of the compound having a carboxyl group include compounds of the general formulas AI-1 to AI-14 and AII-1 to AII-10 below.







In the above formulas, R′′ is hydrogen or a —CH2COOH group such that the —CH2COOH group accounts for 10 to 100 mol % of R′′ in each compound, κ and λ are as defined above.







The compound is added in an amount ranging from 0 to 5 parts, preferably 0.1 to 5 parts, more preferably 0.1 to 3 parts, further preferably 0.1 to 2 parts by weight, per 100 parts by weight of the base resin. More than 5 parts of the compound can reduce the resolution of the resist composition.
The positive resist composition of the invention may further include a surfactant which is commonly used for improving the coating characteristics.
Illustrative, non-limiting, examples of the surfactant include nonionic surfactants, for example, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether, polyoxyethylene alkylaryl ethers such as polyoxyethylene octylphenol ether and polyoxyethylene nonylphenol ether, polyoxyethylene polyoxypropylene block copolymers, sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monopalmitate, and sorbitan monostearate, and polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan tristearate; fluorochemical surfactants such as EFTOP EF301, EF303 and EF352 (Tohkem Products Co., Ltd.), Megaface F171, F172 and F173 (Dai-Nippon Ink & Chemicals, Inc.), Fluorad FC430 and FC431 (Sumitomo 3M Co., Ltd.), Asahiguard AG710, Surflon S-381, S-382, SC101, SC102, SC103, SC104, SC105, SC106, Surfynol E1004, KH-10, KH-20, KH-30 and KH-40 (Asahi Glass Co., Ltd.); organosiloxane polymers KP341, X-70-092 and X-70-093 (Shin-Etsu Chemical Co., Ltd.), acrylic acid or methacrylic acid Polyflow No. 75 and No. 95 (Kyoeisha Ushi Kagaku Kogyo Co., Ltd.). Inter alia, FC430, Surflon S-381, Surfynol E1004, KH-20 and KH-30 are preferred. These surfactants may be used alone or in admixture.
To the positive resist composition, the surfactant is added in an amount of up to 2 parts, preferably up to 1 part by weight, per 100 parts by weight of the base resin.
For the microfabrication of integrated circuits, any well-known lithography may be used to form a resist pattern from the positive resist composition of the invention, especially the chemically amplified positive resist composition comprising the polymer comprising recurring units of formula (1a) and recurring units of formula (1b), organic solvent, photoacid generator and optional components according to the invention although the technology is not limited thereto.
The resist composition is applied onto a substrate (on which an integrated circuit is to be formed, e.g., Si, SiO2, SiN, SiON, TiN, WSi, BPSG, SOG, organic antireflective film, Cr, CrO, CrON, MoSi, etc.) 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 about 1 to 10 minutes, preferably 80 to 120° C. for 1 to 5 minutes. The resulting resist film is generally 0.01 to 2.0 μm thick.
A relationship between a reduced thickness of resist film and an etch selectivity ratio between resist film and processable substrate imposes severer limits on the process. Under consideration is the tri-layer process in which a resist layer, a silicon-containing intermediate layer, an undercoat layer having a high carbon density and high etch resistance, and a processable substrate are laminated in sequence from top to bottom. On etching with oxygen gas, hydrogen gas, ammonia gas or the like, a high etch selectivity ratio is available between the silicon-containing intermediate layer and the undercoat layer, which allows for thickness reduction of the silicon-containing intermediate layer. A relatively high etch selectivity ratio is also available between the monolayer resist and the silicon-containing intermediate layer, which allows for thickness reduction of the monolayer resist. The method for forming the undercoat layer in this case includes a coating and baking method and a CVD method. In the case of coating, novolac resins and resins obtained by polymerization of fused ring-containing olefins are used. In the CVD film formation, gases such as butane, ethane, propane, ethylene and acetylene are used. For the silicon-containing intermediate layer, either a coating method or a CVD method may be employed. The coating method uses silsesquioxane, POSS® and the like while the CVD method uses silane gases as the reactant. The silicon-containing intermediate layer may have an antireflection function with a light absorbing ability and have photo-absorptive groups like phenyl groups, or it may be a SiON film. An organic film may be formed between the silicon-containing intermediate layer and the photoresist, and the organic film in this case may be an organic antireflective coating.
After the photoresist film is formed, deionized water rinsing (or post-soaking) may be carried out for extracting the photoacid generator and the like from the film surface or washing away particles, or a protective film may be coated.
With a mask having a desired pattern placed above the resist film, the resist film is then exposed to actinic radiation such as UV, deep-UV, electron beams, x-rays, excimer laser light, γ-rays and synchrotron radiation, preferably having an exposure wavelength of up to 300 nm, more preferably 180 to 200 nm. The exposure dose is preferably about 1 to 200 mJ/cm2, more preferably about 10 to 100 mJ/cm2. The film is further baked on a hot plate at 60 to 150° C. for 1 to 5 minutes, preferably 80 to 120° C. for 1 to 3 minutes (post-exposure baking=PEB).
Thereafter the resist film is developed with a developer in the form of an aqueous base solution, for example, 0.1 to 5 wt %, preferably 2 to 3 wt % aqueous solution of tetramethylammonium hydroxide (TMAH) for 0.1 to 3 minutes, preferably 0.5 to 2 minutes by conventional techniques such as dip, puddle or spray techniques. In this way, a desired resist pattern is formed on the substrate. It is appreciated that the resist composition of the invention is suited for micro-patterning using such high-energy radiation as deep UV with a wavelength of 254 to 193 nm, vacuum UV with a wavelength of 157 nm, electron beams, soft x-rays, x-rays, excimer laser light, γ-rays and synchrotron radiation, and best suitable for micro-patterning using high-energy radiation in the wavelength range of 180 to 200 nm.
Immersion lithography can be applied to the resist composition of the invention. The ArF immersion lithography uses a liquid having a refractive index of at least 1 and highly transparent at the exposure wavelength such as deionized water or alkanes as the immersion solvent. The immersion lithography involves prebaking a resist film and exposing the resist film to light through a projection lens, with water interposed between the resist film and the projection lens. Since this allows projection lenses to be designed to a numerical aperture (NA) of 1.0 or higher, formation of finer patterns is possible. The immersion lithography is important for the ArF lithography to survive to the 45-nm node, with a further development thereof being accelerated. In the case of immersion lithography, deionized water rinsing (or post-soaking) may be carried out after exposure for removing water droplets left on the resist film, or a protective coating may be applied onto the resist film after pre-baking for preventing any dissolution from the resist and improving water slip on the film surface. The resist protective coating used in the immersion lithography is preferably formed from a solution of a polymer having α-trifluoromethylhydroxy groups which is insoluble in water, but dissolvable in an alkaline developer liquid, in a solvent selected from alcohols of at least 4 carbon atoms, ethers of 8 to 12 carbon atoms, and mixtures thereof.
The technique enabling the ArF lithography to survive to the 32-nm node is a double patterning process. The double patterning process includes a trench process of processing an underlay to a 1:3 trench pattern by a first step of exposure and etching, shifting the position, and forming a 1:3 trench pattern by a second step of exposure for forming a 1:1 pattern; and a line process of processing a first underlay to a 1:3 isolated left pattern by a first step of exposure and etching, shifting the position, processing a second underlay formed below the first underlay by a second step of exposure through the 1:3 isolated left pattern, for forming a half-pitch 1:1 pattern.
The lactone ring, which is used as a hydrophilic group in the prior art ArF resists, has solubility in both alkaline aqueous solution and water. When lactones and acid anhydrides (e.g., maleic anhydride and itaconic anhydride) having high solubility in water are used as the hydrophilic group, a problem arises during immersion in water that water penetrates into the resist from its surface, whereby the resist surface is swollen. By contrast, naphthol is dissolvable in alkaline aqueous solution, but not at all in water, and it is thus believed that the influence of dissolution and swelling during liquid immersion is minimized.
To the resist composition of the invention, the EB and EUV lithography can also be applied. In particular, the polymer having a naphthalene ring with a higher carbon ratio according to the invention is expected to have a high transmittance to EUV radiation at wavelength 13.5 nm.
EXAMPLE
Examples of the invention are given below by way of illustration and not by way of limitation. The abbreviations used herein are AIBN for 2,2′-azobisisobutyronitrile, GPC for gel permeation chromatography, Mw for weight average molecular weight, Mn for number average molecular weight, Mw/Mn for molecular weight distribution or dispersity, NMR for nuclear magnetic resonance, and PGMEA for propylene glycol monomethyl ether acetate. For all polymers, Mw and Mn are determined by GPC versus polystyrene standards.
Synthesis Example 1
A 100-mL flask was charged with 8.1 g of 2-ethyl-2-adamantane methacrylate, 6.3 g of 3-hydroxy-1-adamantyl methacrylate, 6.7 g of 3-oxo-2,7-dioxatricyclo[4.2.1.04,8]-nonan-9-yl methacrylate, 2.6 g of 2-vinyl-6-ethoxyethoxy-naphthalene, and 20 g of tetrahydrofuran as a solvent. The reactor was cooled to −70° C. in a nitrogen atmosphere, followed by three cycles of vacuum evacuation and nitrogen flow. The reactor was warmed up to room temperature, charged with 0.2 g of AIBN as a polymerization initiator, heated at 60° C., and held for 15 hours for reaction. The reaction solution was poured into 500 mL of isopropyl alcohol for precipitation. The white solids were collected by filtration, dissolved again in 200 mL of methyl ethyl ketone, and combined with 5 g of oxalic acid and 3 g of water. Deprotection reaction of ethoxyethoxy groups occurred at 60° C. for 5 hours, followed by three cycles of separatory washing with 500 mL of water. The reaction solution was concentrated and dissolved in 100 mL of acetone. The subsequent precipitation, filtration and drying at 60° C. in a similar manner as above yielded a white polymer.
The polymer was analyzed by 13C-NMR, 1H-NMR, and GPC, with the results shown below.
Copolymer Composition Ratio (Molar Ratio) 2-ethyl-2-adamantane methacrylate:3-hydroxy-1-adamantyl methacrylate:3-oxo-2,7-dioxatricyclo-[4.2.1.04,8]nonan-9-yl methacrylate:2-vinyl-6-hydroxynaphthalene=0.30:0.25:0.30:0.15
Mw=8,100
Mw/Mn=1.72




This polymer is designated Polymer 1.
Synthesis Example 2
A 100-mL flask was charged with 8.1 g of 2-ethyl-2-adamantane methacrylate, 6.3 g of 3-hydroxy-1-adamantyl methacrylate, 8.4 g of 3-oxo-5-methoxycarbonyl-2-oxatricyclo[4.2.1.04,8]-9-nonyl methacrylate, 2.6 g of 2-vinyl-6-ethoxyethoxynaphthalene, and 20 g of tetrahydrofuran as a solvent. The reactor was cooled to −70° C. in a nitrogen atmosphere, followed by three cycles of vacuum evacuation and nitrogen flow. The reactor was warmed up to room temperature, charged with 0.2 g of AIBN as a polymerization initiator, heated at 60° C., and held for 15 hours for reaction. The reaction solution was poured into 500 mL of isopropyl alcohol for precipitation. The white solids were collected by filtration, dissolved again in 200 mL of methyl ethyl ketone, and combined with 5 g of oxalic acid and 3 g of water. Deprotection reaction of ethoxyethoxy groups occurred at 60° C. for 5 hours, followed by three cycles of separatory washing with 500 mL of water. The reaction solution was concentrated and dissolved in 100 mL of acetone. The subsequent precipitation, filtration and drying at 60° C. in a similar manner as above yielded a white polymer.
The polymer was analyzed by 13C-NMR, 1H-NMR, and GPC, with the results shown below.
Copolymer Composition Ratio (Molar Ratio) 2-ethyl-2-adamantane methacrylate:3-hydroxy-1-adamantyl methacrylate:3-oxo-5-methoxycarbonyl-2-oxatricyclo[4.2.1.04,8]-9-nonyl methacrylate:2-vinyl-6-hydroxynaphthalene=0.30:0.25:0.30:0.15
Mw=8,100
Mw/Mn=1.65




This polymer is designated Polymer 2.
Synthesis Example 3
A 100-mL flask was charged with 6.9 g of 3-ethyl-3-exotetracyclo[4.4.0.12,5.17,10]dodecanyl methacrylate, 6.3 g of 3-hydroxy-1-adamantyl methacrylate, 7.8 g of 3-oxo-2,7-dioxatricyclo[4.2.1.04,8]nonan-9-yl methacrylate, 2.6 g of 2-vinyl-6-ethoxyethoxynaphthalene, and 20 g of tetrahydrofuran as a solvent. The reactor was cooled to −70° C. in a nitrogen atmosphere, followed by three cycles of vacuum evacuation and nitrogen flow. The reactor was warmed up to room temperature, charged with 0.2 g of AIBN as a polymerization initiator, heated at 60° C., and held for 15 hours for reaction. The reaction solution was poured into 500 mL of isopropyl alcohol for precipitation. The white solids were collected by filtration, dissolved again in 200 mL of methyl ethyl ketone, and combined with 5 g of oxalic acid and 3 g of water. Deprotection reaction of ethoxyethoxy groups occurred at 60° C. for 5 hours, followed by three cycles of separatory washing with 500 mL of water. The reaction solution was concentrated and dissolved in 100 mL of acetone. The subsequent precipitation, filtration and drying at 60° C. in a similar manner as above yielded a white polymer.
The polymer was analyzed by 13C-NMR, 1H-NMR, and GPC, with the results shown below.
Copolymer Composition Ratio (Molar Ratio) 3-ethyl-3-exotetracyclo[4.4.0.12,5.17,10]dodecanyl methacrylate:3-hydroxy-1-adamantyl methacrylate:3-oxo-2,7-dioxatricyclo[4.2.1.04,8]nonan-9-yl methacrylate:2-vinyl-6-hydroxynaphthalene=0.25:0.25:0.35:0.15
Mw=7,500
Mw/Mn=1.71




This polymer is designated Polymer 3.
Synthesis Example 4
A 100-mL flask was charged with 6.9 g of 3-ethyl-3-exotetracyclo[4.4.0.12,5.17,10]dodecanyl methacrylate, 11.2 g of 3-oxo-2,7-dioxatricyclo[4.2.1.04,8]nonan-9-yl methacrylate, 5.0 g of 3,5-di(2-hydroxy-1,1,1,3,3,3-hexafluoro-2-propyl)cyclohexyl methacrylate, 2.6 g of 2-vinyl-6-ethoxyethoxynaphthalene, and 20 g of tetrahydrofuran as a solvent. The reactor was cooled to −70° C. in a nitrogen atmosphere, followed by three cycles of vacuum evacuation and nitrogen flow. The reactor was warmed up to room temperature, charged with 0.2 g of AIBN as a polymerization initiator, heated at 60° C., and held for 15 hours for reaction. The reaction solution was poured into 500 mL of isopropyl alcohol for precipitation. The white solids were collected by filtration, dissolved again in 200 mL of methyl ethyl ketone, and combined with 5 g of oxalic acid and 3 g of water. Deprotection reaction of ethoxyethoxy groups occurred at 60° C. for 5 hours, followed by three cycles of separatory washing with 500 mL of water. The reaction solution was concentrated and dissolved in 100 mL of acetone. The subsequent precipitation, filtration and drying at 60° C. in a similar manner as above yielded a white polymer.
The polymer was analyzed by 13C-NMR, 1H-NMR, and GPC, with the results shown below.
Copolymer Composition Ratio (Molar Ratio) 3-ethyl-3-exotetracyclo[4.4.0.12,5.17,10]dodecanyl methacrylate:3-oxo-2,7-dioxatricyclo[4.2.1.04,8]-nonan-9-yl methacrylate:3,5-di(2-hydroxy-1,1,1,3,3,3-hexafluoro-2-propyl)cyclohexyl methacrylate:2-vinyl-6-hydroxynaphthalene=0.25:0.50:0.10:0.15
Mw=8,300
Mw/Mn=1.66




This polymer is designated Polymer 4.
Synthesis Example 5
A 100-mL flask was charged with 6.0 g of 1-ethyl-cyclopentyl methacrylate, 6.3 g of 3-hydroxy-1-adamantyl methacrylate, 6.1 g of 3-oxo-2,7-dioxatricyclo-[4.2.1.04,8]nonan-9-yl methacrylate, 2.6 g of 2-vinyl-6-ethoxyethoxynaphthalene, and 20 g of tetrahydrofuran as a solvent. The reactor was cooled to −70° C. in a nitrogen atmosphere, followed by three cycles of vacuum evacuation and nitrogen flow. The reactor was warmed up to room temperature, charged with 0.2 g of AIBN as a polymerization initiator, heated at 60° C., and held for 15 hours for reaction. The reaction solution was poured into 500 mL of isopropyl alcohol for precipitation. The white solids were collected by filtration, dissolved again in 200 mL of methyl ethyl ketone, and combined with 5 g of oxalic acid and 3 g of water. Deprotection reaction of ethoxyethoxy groups occurred at 60° C. for 5 hours, followed by three cycles of separatory washing with 500 mL of water. The reaction solution was concentrated and dissolved in 100 mL of acetone. The subsequent precipitation, filtration and drying at 60° C. in a similar manner as above yielded a white polymer.
The polymer was analyzed by 13C-NMR, 1H-NMR, and GPC, with the results shown below.
Copolymer Composition Ratio (Molar Ratio) 1-ethylcyclopentyl methacrylate:3-hydroxy-1-adamantyl methacrylate:3-oxo-2,7-dioxatricyclo-[4.2.1.04,8]nonan-9-yl methacrylate:2-vinyl-6-hydroxynaphthalene=0.33:0.25:0.27:0.15
Mw=7,100
Mw/Mn=1.82




This polymer is designated Polymer 5.
Synthesis Example 6
A 100-mL flask was charged with 6.3 g of 1-(7-oxanorbornan-2-yl)cyclopentyl methacrylate, 6.3 g of 3-hydroxy-1-adamantyl methacrylate, 7.8 g of 3-oxo-2,7-dioxatricyclo[4.2.1.04,8]nonan-9-yl methacrylate, 2.6 g of 2-vinyl-6-ethoxyethoxynaphthalene, and 20 g of tetrahydrofuran as a solvent. The reactor was cooled to −70° C. in a nitrogen atmosphere, followed by three cycles of vacuum evacuation and nitrogen flow. The reactor was warmed up to room temperature, charged with 0.2 g of AIBN as a polymerization initiator, heated at 60° C., and held for 15 hours for reaction. The reaction solution was poured into 500 mL of isopropyl alcohol for precipitation. The white solids were collected by filtration, dissolved again in 200 mL of methyl ethyl ketone, and combined with 5 g of oxalic acid and 3 g of water. Deprotection reaction of ethoxyethoxy groups occurred at 60° C. for 5 hours, followed by three cycles of separatory washing with 500 mL of water. The reaction solution was concentrated and dissolved in 100 mL of acetone. The subsequent precipitation, filtration and drying at 60° C. in a similar manner as above yielded a white polymer.
The polymer was analyzed by 13C-NMR, 1H-NMR, and GPC, with the results shown below.
Copolymer Composition Ratio (Molar Ratio) 1-(7-oxanorbornan-2-yl)cyclopentyl methacrylate: 3-hydroxy-1-adamantyl methacrylate:3-oxo-2,7-dioxatricyclo[4.2.1.04,8]nonan-9-yl methacrylate:2-vinyl-6-hydroxynaphthalene=0.25:0.25:0.35:0.15
Mw=7,400
Mw/Mn=1.73




This polymer is designated Polymer 6.
Synthesis Example 7
A 100-mL flask was charged with 6.3 g of 2-adamantyloxymethyl methacrylate, 6.3 g of 3-hydroxy-1-adamantyl methacrylate, 7.8 g of 3-oxo-2,7-dioxatricyclo-[4.2.1.04,8]nonan-9-yl methacrylate, 2.6 g of 2-vinyl-6-ethoxyethoxynaphthalene, and 20 g of tetrahydrofuran as a solvent. The reactor was cooled to −70° C. in a nitrogen atmosphere, followed by three cycles of vacuum evacuation and nitrogen flow. The reactor was warmed up to room temperature, charged with 0.2 g of AIBN as a polymerization initiator, heated at 60° C., and held for 15 hours for reaction. The reaction solution was poured into 500 mL of isopropyl alcohol for precipitation. The white solids were collected by filtration, dissolved again in 200 mL of methyl ethyl ketone, and combined with 5 g of oxalic acid and 3 g of water.
Deprotection reaction of ethoxyethoxy groups occurred at 60° C. for 5 hours, followed by three cycles of separatory washing with 500 mL of water. The reaction solution was concentrated and dissolved in 100 mL of acetone. The subsequent precipitation, filtration and drying at 60° C. in a similar manner as above yielded a white polymer.
The polymer was analyzed by 13C-NMR, 1H-NMR, and GPC, with the results shown below.
Copolymer Composition Ratio (Molar Ratio) 2-adamantyloxymethyl methacrylate:3-hydroxy-1-adamantyl methacrylate:3-oxo-2,7-dioxatricyclo-[4.2.1.04,8]nonan-9-yl methacrylate:2-vinyl-6-hydroxynaphthalene=0.25:0.25:0.35:0.15
Mw=9,000
Mw/Mn=1.91




This polymer is designated Inventive Polymer 7.
Synthesis Example 8
A 100-mL flask was charged with 6.9 g of 3-ethyl-3-exotetracyclo[4.4.0.12,5.17,10]dodecanyl methacrylate, 5.6 g of 3-oxo-2,7-dioxatricyclo[4.2.1.04,8]nonan-9-yl methacrylate, 8.5 g of 2-vinyl-7-ethoxyethoxynaphthalene, and 20 g of tetrahydrofuran as a solvent. The reactor was cooled to −70° C. in a nitrogen atmosphere, followed by three cycles of vacuum evacuation and nitrogen flow. The reactor was warmed up to room temperature, charged with 0.2 g of AIBN as a polymerization initiator, heated at 60° C., and held for 15 hours for reaction. The reaction solution was poured into 500 mL of isopropyl alcohol for precipitation. The white solids were collected by filtration, dissolved again in 200 mL of methyl ethyl ketone, and combined with 5 g of oxalic acid and 3 g of water. Deprotection reaction of ethoxyethoxy groups occurred at 60° C. for 5 hours, followed by three cycles of separatory washing with 500 mL of water. The reaction solution was concentrated and dissolved in 100 mL of acetone. The subsequent precipitation, filtration and drying at 60° C. in a similar manner as above yielded a white polymer.
The polymer was analyzed by 13C-NMR, 1H-NMR, and GPC, with the results shown below.
Copolymer Composition Ratio (Molar Ratio) 3-ethyl-3-exotetracyclo[4.4.0.12,5.17,10]dodecanyl methacrylate:3-oxo-2,7-dioxatricyclo[4.2.1.04,8]-nonan-9-yl methacrylate:2-vinyl-7-hydroxy-naphthalene=0.25:0.25:0.50
Mw=8,100
Mw/Mn=1.72




This polymer is designated Polymer 8.
Synthesis Example 9
A 100-mL flask was charged with 6.9 g of 3-ethyl-3-exotetracyclo[4.4.0.12,5.17,10]dodecanyl methacrylate, 5.6 g of 3-oxo-2,7-dioxatricyclo[4.2.1.04,8]nonan-9-yl methacrylate, 8.9 g of 1-vinyl-5-ethoxyethoxynaphthalene, and 20 g of tetrahydrofuran as a solvent. The reactor was cooled to −70° C. in a nitrogen atmosphere, followed by three cycles of vacuum evacuation and nitrogen flow. The reactor was warmed up to room temperature, charged with 0.2 g of AIBN as a polymerization initiator, heated at 60° C., and held for 15 hours for reaction. The reaction solution was poured into 500 mL of isopropyl alcohol for precipitation. The white solids were collected by filtration, dissolved again in 200 mL of methyl ethyl ketone, and combined with 5 g of oxalic acid and 3 g of water. Deprotection reaction of ethoxyethoxy groups occurred at 60° C. for 5 hours, followed by three cycles of separatory washing with 500 mL of water. The reaction solution was concentrated and dissolved in 100 mL of acetone. The subsequent precipitation, filtration and drying at 60° C. in a similar manner as above yielded a white polymer.
The polymer was analyzed by 13C-NMR, 1H-NMR, and GPC, with the results shown below.
Copolymer Composition Ratio (Molar Ratio) 3-ethyl-3-exotetracyclo[4.4.0.12,5.17,10]dodecanyl methacrylate:3-oxo-2,7-dioxatricyclo[4.2.1.04,8]-nonan-9-yl methacrylate:1-vinyl-5-hydroxy-naphthalene=0.25:0.25:0.50
Mw=8,700
Mw/Mn=1.77




This polymer is designated Polymer 9.
Synthesis Example 10
A 100-mL flask was charged with 10.8 g of 3-oxo-5-ethylcyclopentyloxycarbonyl-2-oxatricyclo[4.2.1.04,8]-9-nonyl methacrylate, 11.9 g of 2-vinyl-7-ethoxyethoxynaphthalene, and 20 g of tetrahydrofuran as a solvent. The reactor was cooled to −70° C. in a nitrogen atmosphere, followed by three cycles of vacuum evacuation and nitrogen flow. The reactor was warmed up to room temperature, charged with 0.2 g of AIBN as a polymerization initiator, heated at 60° C., and held for 15 hours for reaction. The reaction solution was poured into 500 mL of isopropyl alcohol for precipitation. The white solids were collected by filtration, dissolved again in 200 mL of methyl ethyl ketone, and combined with 5 g of oxalic acid and 3 g of water. Deprotection reaction of ethoxyethoxy groups occurred at 60° C. for 5 hours, followed by three cycles of separatory washing with 500 mL of water. The reaction solution was concentrated and dissolved in 100 mL of acetone. The subsequent precipitation, filtration and drying at 60° C. in a similar manner as above yielded a white polymer.
The polymer was analyzed by 13C-NMR, 1H-NMR, and GPC, with the results shown below.
Copolymer Composition Ratio (Molar Ratio) 3-oxo-5-ethylcyclopentyloxycarbonyl-2-oxatricyclo-[4.2.1.04,8]-9-nonyl methacrylate:2-vinyl-7-hydroxynaphthalene=0.30:0.70
Mw=9,900
Mw/Mn=1.87




This polymer is designated Polymer 10.
Synthesis Example 11
A 100-mL flask was charged with 3.6 g of 3-oxo-5-ethylcyclopentyloxycarbonyl-2-oxatricyclo[4.2.1.04,8]-9-nonyl methacrylate, 11.9 g of 2-vinyl-7-acetoxynaphthalene, 4.8 g of 2-vinyl-7-ethoxyethoxynaphthalene, and 20 g of tetrahydrofuran as a solvent. The reactor was cooled to −70° C. in a nitrogen atmosphere, followed by three cycles of vacuum evacuation and nitrogen flow. The reactor was warmed up to room temperature, charged with 0.2 g of AIBN as a polymerization initiator, heated at 60° C., and held for 15 hours for reaction. The reaction solution was poured into 500 mL of isopropyl alcohol for precipitation. The white solids were collected, dissolved again in 50 mL of methanol and 80 mL of tetrahydrofuran, and combined with 5 g of triethylamine and 3 g of water. Deprotection reaction of acetyl groups occurred at 70° C. for 5 hours, followed by neutralization with acetic acid. The reaction solution was concentrated and dissolved in 100 mL of acetone. The subsequent precipitation, filtration and drying at 60° C. in a similar manner as above yielded a white polymer.
The polymer was analyzed by 13C-NMR, 1H-NMR, and GPC, with the results shown below.
Copolymer Composition Ratio (Molar Ratio) 3-oxo-5-ethylcyclopentyloxycarbonyl-2-oxatricyclo-[4.2.1.04,8]-9-nonyl methacrylate:2-vinyl-7-hydroxynaphthalene:2-vinyl-7-ethoxyethoxy-naphthalene=0.10:0.70:0.20
Mw=9,100
Mw/Mn=1.90




This polymer is designated Polymer 11.
Synthesis Example 12
A 100-mL flask was charged with 6.9 g of 3-ethyl-3-exotetracyclo[4.4.0.12,5.17,10]dodecanyl methacrylate, 3.8 g of 3-hydroxy-1-adamantyl methacrylate, 3.3 g of 3-oxo-2,7-dioxatricyclo[4.2.1.04,8]nonan-9-yl methacrylate, 5.1 g of 2-oxooxofuran-4-yl methacrylate, 2.6 g of 2-vinyl-6-ethoxyethoxynaphthalene, and 20 g of tetrahydrofuran as a solvent. The reactor was cooled to −70° C. in a nitrogen atmosphere, followed by three cycles of vacuum evacuation and nitrogen flow. The reactor was warmed up to room temperature, charged with 0.2 g of AIBN as a polymerization initiator, heated at 60° C., and held for 15 hours for reaction. The reaction solution was poured into 500 mL of isopropyl alcohol for precipitation. The white solids were collected by filtration, dissolved again in 200 mL of methyl ethyl ketone, and combined with 5 g of oxalic acid and 3 g of water. Deprotection reaction of ethoxyethoxy groups occurred at 60° C. for 5 hours, followed by three cycles of separatory washing with 500 mL of water. The reaction solution was concentrated and dissolved in 100 mL of acetone. The subsequent precipitation, filtration and drying at 60° C. in a similar manner as above yielded a white polymer.
The polymer was analyzed by 13C-NMR, 1H-NMR, and GPC, with the results shown below.
Copolymer Composition Ratio (Molar Ratio) 3-ethyl-3-exotetracyclo[4.4.0.12,5.17,10]dodecanyl methacrylate:3-hydroxy-1-adamantyl methacrylate:3-oxo-2,7-dioxatricyclo[4.2.1.04,8]nonan-9-yl methacrylate:2-oxooxofuran-4-yl methacrylate:2-vinyl-6-hydroxynaphthalene=0.25:0.15:0.15:0.30:0.15
Mw=7,900
Mw/Mn=1.79




This polymer is designated Polymer 12.
Comparative Synthesis Example 1
A 100-mL flask was charged with 24.4 g of 2-ethyl-2-adamantane methacrylate, 17.1 g of γ-butyrolactone methacrylate, and 40 g of tetrahydrofuran as a solvent. The reactor was cooled to −70° C. in a nitrogen atmosphere, followed by three cycles of vacuum evacuation and nitrogen flow. The reactor was warmed up to room temperature, charged with 0.2 g of AIBN as a polymerization initiator, heated at 60° C., and held for 15 hours for reaction. The reaction solution was poured into 500 mL of isopropyl alcohol for precipitation. The white solids were collected by filtration and dried at 60° C. under reduced pressure, yielding 36.1 g of a white polymer.
The polymer was analyzed by 13C-NMR, 1H-NMR, and GPC, with the results shown below.
Copolymer Composition Ratio (Molar Ratio) 2-ethyl-2-adamantane methacrylate:γ-butyrolactone methacrylate=0.48:0.52
Mw=12,500
Mw/Mn=1.88




This polymer is designated Comparative Polymer 1.
Comparative Synthesis Example 2
A 100-mL flask was charged with 8.2 g of 3-ethyl-3-exotetracyclo[4.4.0.12,5.17,10]dodecanyl methacrylate, 8.2 g of 3-hydroxy-1-adamantyl methacrylate, 9.2 g of 3-oxo-2,7-dioxatricyclo[4.2.1.04,8]nonan-9-yl methacrylate, and 20 g of tetrahydrofuran as a solvent. The reactor was cooled to −70° C. in a nitrogen atmosphere, followed by three cycles of vacuum evacuation and nitrogen flow. The reactor was warmed up to room temperature, charged with 0.2 g of AIBN as a polymerization initiator, heated at 60° C., and held for 15 hours for reaction. The reaction solution was poured into 500 mL of isopropyl alcohol for precipitation. The white solids were filtered and dried at 60° C. under reduced pressure, yielding a white polymer.
The polymer was analyzed by 13C-NMR, 1H-NMR, and GPC, with the results shown below.
Copolymer Composition Ratio (Molar Ratio) 3-ethyl-3-exotetracyclo[4.4.0.12,5.17,10]dodecanyl methacrylate:3-hydroxy-1-adamantyl methacrylate:3-oxo-2,7-dioxatricyclo[4.2.1.04,8]nonan-9-yl=0.30:0.25:0.45
Mw=8,400
Mw/Mn=1.63




This polymer is designated Comparative Polymer 2.
Comparative Synthesis Example 3
A 100-mL flask was charged with 6.9 g of 3-ethyl-3-exotetracyclo[4.4.0.12,5.17,10]dodecanyl methacrylate, 5.9 g of 3-hydroxy-1-adamantyl methacrylate, 7.7 g of 5-oxo-4-oxatricyclo[4.2.1.03,7]nonan-2-yl methacrylate, 2.6 g of 2-vinyl-6-hydroxynaphthalene, and 20 g of tetrahydrofuran as a solvent. The reactor was cooled to −70° C. in a nitrogen atmosphere, followed by three cycles of vacuum evacuation and nitrogen flow. The reactor was warmed up to room temperature, charged with 0.2 g of AIBN as a polymerization initiator, heated at 60° C., and held for 15 hours for reaction. The reaction solution was poured into 500 mL of isopropyl alcohol for precipitation. The white solids were filtered and dried at 60° C. under reduced pressure, yielding a white polymer.
The polymer was analyzed by 13C-NMR, 1H-NMR, and GPC, with the results shown below.
Copolymer Composition Ratio (Molar Ratio) 3-ethyl-3-exotetracyclo[4.4.0.12,5.17,10]dodecanyl methacrylate:3-hydroxy-1-adamantyl methacrylate:5-oxo-4-oxatricyclo[4.2.1.03,7]nonan-2-yl methacrylate:2-vinyl-6-hydroxynaphthalene=0.25:0.25:0.35:0.15
Mw=7,700
Mw/Mn=1.75




This polymer is designated Comparative Polymer 3.
Comparative Synthesis Example 4
A 100-mL flask was charged with 6.9 g of 3-ethyl-3-exotetracyclo[4.4.0.12,5.17,10]dodecanyl methacrylate, 5.6 g of 3-oxo-2,7-dioxatricyclo[4.2.1.04,8]nonan-9-yl methacrylate, 6.0 g of 4-hydroxystyrene, and 20 g of tetrahydrofuran as a solvent. The reactor was cooled to −70° C. in a nitrogen atmosphere, followed by three cycles of vacuum evacuation and nitrogen flow. The reactor was warmed up to room temperature, charged with 0.2 g of AIBN as a polymerization initiator, heated at 60° C., and held for 15 hours for reaction. The reaction solution was poured into 500 mL of isopropyl alcohol for precipitation. The white solids were filtered and dried at 60° C. under reduced pressure, yielding a white polymer.
The polymer was analyzed by 13C-NMR, 1H-NMR, and GPC, with the results shown below.
Copolymer Composition Ratio (Molar Ratio) 3-ethyl-3-exotetracyclo[4.4.0.12,5.17,10]dodecanyl methacrylate:3-oxo-2,7-dioxatricyclo[4.2.1.04,8]-nonan-9-yl methacrylate:4-hydroxystyrene=0.25:0.25:0.50
Mw=8,900
Mw/Mn=1.65




This polymer is designated Comparative Polymer 4.
Preparation of Positive Resist Compositions
Resist solutions were prepared by dissolving the polymer (Polymers 1 to 7, 12 and Comparative Polymers 1 to 3) and other components in a solvent in accordance with the formulation shown in Table 1 and passing through a filter with a pore size of 0.2 μm. The components in Table 1 are as follows.
Polymer:
Polymers 1 to 7 and 12 obtained in Synthesis Examples 1 to 7 and 12
Comparative Polymers 1 to 3 obtained in Comparative Synthesis Examples 1 to 3
Photoacid Generator:
PAG1 and PAG2 of the following structural formulae




Basic Compound:

Quencher 1 and Quencher 2 of the following structural formulae




Dissolution Inhibitor:

DRI1 of the following structural formula




Dissolution Regulator:

DRR1 of the following structural formula




Organic Solvent:

PGMEA
Examples 1-11 & Comparative Examples 1-3
ArF Exposure/Patterning Test
On silicon wafers having an antireflective coating (AR-19, Shipley) of 82 nm thick, the resist solutions were spin coated, then baked on a hot plate at 120° C. for 60 seconds to give resist films having a thickness of 150 nm.
The resist films were exposed in steps of 1 mJ/cm2 by means of an ArF excimer laser stepper model NSR-S307E (Nikon Corp., NA 0.85, σ 0.93, 2⁄3 annular illumination). Immediately after exposure, the resist films were baked (PEB) at 110° C. for 60 seconds and then developed for 60 seconds with a 2.38% aqueous solution of tetramethylammonium hydroxide, obtaining positive patterns.
The resist patterns were evaluated. The exposure dose (mJ/cm2) which provided a 1:1 resolution to a 0.08-μm line-and-space pattern was the sensitivity. Using a measuring SEM model S-9380 (Hitachi Ltd.), the 0.08-μm line edge roughness at this exposure dose was measured. A size variation in the range of the optimum exposure dose ±2 mJ/cm2 was determined and reported as an exposure margin.
The resist formulation is shown in Table 1 together with the results of sensitivity, exposure margin, and line edge roughness in the ArF lithography.
















TABLE 1














Line




Photoacid
Basic
Dissolution
Organic

Exposure
edge



Polymer
generator
compound
inhibitor
solvent
Sensitivity
margin
roughness



(pbw)
(pbw)
(pbw)
(pbw)
(pbw)
(mJ/cm2)
(nm/mJ/cm2)
(3σ, nm)
























Example 1
Polymer 1
PAG1
Quencher1
—
PGMEA
29
2.6
7.2



(100)
(6.6)
(0.88)

(800)


Example 2
Polymer 2
PAG1
Quencher1
—
PGMEA
31
2.6
6.1



(100)
(6.6)
(0.88)

(800)


Example 3
Polymer 3
PAG1
Quencher1
—
PGMEA
35
2.8
7.8



(100)
(6.6)
(0.88)

(800)


Example 4
Polymer 4
PAG1
Quencher1
—
PGMEA
31
2.9
7.6



(100)
(6.6)
(0.88)

(800)


Example 5
Polymer 5
PAG1
Quencher1
—
PGMEA
22
2.7
7.1



(100)
(6.6)
(0.88)

(800)


Example 6
Polymer 6
PAG1
Quencher1
—
PGMEA
26
2.8
6.2



(100)
(6.6)
(0.88)

(800)


Example 7
Polymer 7
PAG1
Quencher1
—
PGMEA
28
2.8
7.8



(100)
(6.6)
(0.88)

(800)


Example 8
Polymer 2
PAG2
Quencher1
—
PGMEA
36
2.6
6.5



(100)
(6.6)
(0.88)

(800)


Example 9
Polymer 2
PAG1
Quencher2
—
PGMEA
35
2.8
6.9



(100)
(6.6)
(0.92)

(800)


Example 10
Polymer 2
PAG1
Quencher1
DRI1
PGMEA
28
2.9
6.3



(100)
(6.6)
(0.88)
(10)
(800)


Example 11
Polymer 12
PAG1
Quencher1
—
PGMEA
22
3.1
5.3



(100)
(6.6)
(0.88)

(800)


Comparative
Comparative
PAG1
Quencher1
—
PGMEA
22
6.5
12.5


Example 1
Polymer 1
(6.6)
(0.88)

(800)



(100)


Comparative
Comparative
PAG1
Quencher1
—
PGMEA
29
3.9
9.6


Example 2
Polymer 2
(6.6)
(0.88)

(800)



(100)


Comparative
Comparative
PAG1
Quencher1
—
PGMEA
33
3.5
10.5


Example 3
Polymer 3
(6.6)
(0.88)

(800)



(100)









It is seen from the results of Table 1 that the resist compositions of Examples 1 to 11 have a wide margin in exposure dose and a minimal line edge roughness.
Examples 12-15 & Comparative Examples 4-5
EB Exposure/Patterning Test
Positive resist compositions were prepared by using the polymers synthesized above (Polymers 8 to 10 and Comparative Polymers 3,4), dissolving the polymers and other components in a solvent in accordance with the formulation shown in Table 2, and filtering through a filter having a pore size of 0.2 μm.
Using Clean Track Mark 5 (Tokyo Electron Ltd.), the resist solutions were spin-coated onto 6-inch silicon substrates and pre-baked on a hot plate at 110° C. for 90 seconds to form a resist film of 100 nm thick. Using an e-beam direct writing system HL-800D by Hitachi Ltd., image writing was performed in a vacuum chamber at a HV voltage of 50 keV.
Immediately after the image writing, post-exposure baking (PEB) was effected on a hot plate at 80° C. for 90 seconds, using Clean Track Mark 5 (Tokyo Electron Ltd.). This was followed by puddle development in an aqueous solution of 2.38 wt % tetramethylammonium hydroxide (TMAH) for 30 seconds, giving positive patterns.
The resulting resist patterns were evaluated. The sensitivity was the exposure dose (μC/cm2) which provided a 1:1 resolution to a 0.12-μm line-and-space pattern. The minimum line width (μm) of a L/S pattern which was ascertained separate at this dose was the resolution.
Table 2 reports the formulation of resist compositions and the results of sensitivity and resolution thereof upon EB writing.















TABLE 2








Photoacid

Dissolution
Organic





Polymer
generator
Base
regulator
solvent
Sensitivity
Resolution



(pbw)
(pbw)
(pbw)
(pbw)
(pbw)
(μC/cm2)
(μm)























Example 12
Polymer 8
PAG1
triethanolamine
—
PGMEA
18
0.08



(100)
(10.0)
(0.2)

(1,000)


Example 13
Polymer 9
PAG1
triethanolamine
—
PGMEA
18
0.08



(100)
(10.0)
(0.2)

(1,000)


Example 14
Polymer 10
PAG1
triethanolamine
—
PGMEA
16
0.08



(100)
(10.0)
(0.2)

(1,000)


Example 15
Polymer 9
PAG1
triethanolamine
DRR1
PGMEA
15
0.08



(100)
(10.0)
(0.2)
(10)
(1,000)


Comparative
Comparative
PAG1
triethanolamine
—
PGMEA
16
0.12


Example 4
Polymer 3
(10.0)
(0.2)

(1,000)



(100)


Comparative
Comparative
PAG1
triethanolamine
—
PGMEA
15
0.12


Example 5
Polymer 4
(10.0)
(0.2)

(1,000)



(100)









The data of Table 2 demonstrate that the resist compositions of Examples 12 to 15 have a high sensitivity and high resolution.
Examples 16-25 & Comparative Examples 6-9
Dry Etching Test
Each polymer, 2 g, was thoroughly dissolved in 10 g of PGMEA, and passed through a filter having a pore size of 0.2 μm, obtaining a polymer solution. The polymer solution was spin coated onto a silicon substrate and baked, forming a polymer film of 300 nm thick. Dry etching tests were carried out on the polymer films by etching them under two sets of conditions.
(1) CHF3/CF4 Gas Etching Test
Using a dry etching instrument TE-8500P (Tokyo Electron Ltd.), the polymer film was etched with CHF3/CF4 gas under the following conditions. The difference in polymer film thickness before and after etching was determined.

















Chamber pressure
40.0
Pa



RF power
1300
W



Gap
9
mm



CHF3 gas flow rate
30
ml/min



CF4 gas flow rate
30
ml/min



Ar gas flow rate
100
ml/min



Time
60
sec










(2) Cl2/BCl3 Gas Etching Test

Using a dry etching instrument L-507D-L (Nichiden Anelva K.K.), the polymer film was etched with Cl2/BCl3 gas under the following conditions. The difference in polymer film thickness before and after etching was determined.

















Chamber pressure
40.0
Pa



RF power
300
W



Gap
9
mm



Cl2 gas flow rate
30
ml/min



BCl3 gas flow rate
30
ml/min



CHF3 gas flow rate
100
ml/min



O2 gas flow rate
2
ml/min



Time
60
sec










The results of the etching tests are shown in Table 3.











TABLE 3








CHF3/CF4 gas
Cl2/BCl3 gas




etching rate
etching rate



Polymer
(nm/min)
(nm/min)



















Example 16
Polymer 1
144
188


Example 17
Polymer 2
138
186


Example 18
Polymer 3
126
168


Example 19
Polymer 4
122
163


Example 20
Polymer 5
138
177


Example 21
Polymer 6
150
203


Example 22
Polymer 7
140
180


Example 23
Polymer 8
144
220


Example 24
Polymer 9
144
220


Example 25
Polymer 10
144
220


Comparative
Comparative Polymer 1
158
350


Example 6


Comparative
Comparative Polymer 2
140
260


Example 7


Comparative
Comparative Polymer 3
138
205


Example 8


Comparative
Comparative Polymer 4
138
205


Example 9









As is evident from Tables 1-3, resist compositions using inventive polymers not only exhibit an excellent sensitivity and resolution, and minimized line edge roughness, but also have good dry etching resistance as demonstrated by a minimized difference in film thickness after etching.
While the invention has been described with reference to a preferred embodiment, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the scope of the invention. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed as the best mode contemplated for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims.
All cited patents, patent applications, and other references are incorporated herein by reference in their entirety.
Japanese Patent Application No. 2006-059120 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 polymer comprising recurring units of the general formulae (1a) and (1b):




wherein R1 is each independently hydrogen or methyl, R2 is a hydrogen atom, C1-C10 acyl group or acid labile group, R3 is hydrogen, methyl or —CO2R8, R4 is hydrogen, methyl or —CH2CO2R8, each of R5 to R7 is hydrogen, methyl, trifluoromethyl or —CO2R9, R8 is hydrogen or a straight, branched or cyclic C1-C15 alkyl group, R9 is a hydrogen atom, straight, branched or cyclic C1-C10 alkyl or fluoroalkyl group or acid labile group, X is —CH2—, —O— or —S—, with the proviso that —CH2— is excluded from X when all of R5 to R7 are hydrogen, n is an integer of 1 to 3, a1 and b1 are numbers in the range: 0<a1<1.0 and 0<b1≦0.8.

2. The polymer of claim 1, further comprising recurring units of the general formula (1c):




wherein R3 and R4 are as defined above, R10 is an acid labile group, and c1 is a number in the range: 0<c1≦0.8.

3. A positive resist composition comprising the polymer of claim 1 as a base resin.

4. The positive resist composition of claim 3, further comprising an organic solvent and a photoacid generator, and serving as a chemically amplified resist composition.

5. The positive resist composition of claim 3, further comprising a dissolution inhibitor.

6. The positive resist composition of claim 3, further comprising a basic compound and/or a surfactant.

7. A process for forming a pattern comprising the steps of applying the resist composition of claim 3 onto a substrate, heat treating, exposing to high-energy radiation, and developing with a developer.

8. The pattern forming process of claim 7 wherein the high-energy radiation has a wavelength of 180 to 200 nm.