Positive resist composition and patterning process

Abstract

A positive resist composition is provided comprising (A) a resin comprising recurring units having adamantane ring and recurring units having cyclopentyl so that the resin may increase its alkali solubility under the action of acid, (B) a mixture of sulfonium salts, and (C) a solvent. By coating the resist composition as a resist film, forming a protective film thereon, and effecting immersion lithography, a pattern of good profile is formed at a high resolution.

Claims

1. A positive resist composition comprising (A) a resin comprising acid labile group-containing recurring units so that the resin may increase its alkali solubility under the action of acid, (B) a sulfonium salt, and (C) a solvent, the resin as component (A) consisting of recurring units having the general formula (1), recurring units having the general formula (2) as the acid labile group-containing recurring units, and recurring units having the general formula (5), ##STR00043## wherein R.sup.1 is methyl or ethyl, and R.sup.2 is hydrogen or methyl, ##STR00044## wherein p is 0, 1 or 2, component (B) being a mixture of a sulfonium salt having the general formula (3) and a sulfonium salt having the general formula (4): ##STR00045## wherein R.sup.3, R.sup.4 and R.sup.5 are each independently hydrogen or a straight, branched or cyclic C.sub.1-C.sub.20 monovalent hydrocarbon group which may contain a heteroatom, R.sup.6 is each independently a straight, branched or cyclic C.sub.7-C.sub.30 monovalent hydrocarbon group which may contain a heteroatom, and R.sup.7 is each independently hydrogen or a straight, branched or cyclic C.sub.1-C.sub.30 monovalent hydrocarbon group which may contain a heteroatom.

2. The resist composition of claim 1 wherein component (B) is present in an amount of 0.5 to 10 parts by weight per 100 parts by weight of component (A).

3. The resist composition of claim 1 wherein R.sup.2 is methyl.

4. The resist composition of claim 1 wherein R.sup.1 is ethyl.

5. The resist composition of claim 1 wherein R.sup.6 is a group selected from the group consisting of the following formulae: ##STR00046##

6. A pattern forming process comprising the steps of applying a positive resist composition onto a substrate, baking to form a resist film, forming a protective film on the resist film, exposing the resist film to high-energy radiation of wavelength 180 to 250 nm through water by immersion lithography, and developing the resist film in an alkaline developer, said positive resist composition comprising (A) a resin comprising acid labile group-containing recurring units so that the resin may increase its alkali solubility under the action of acid, (B) a sulfonium salt, and (C) a solvent, the resin as component (A) comprising recurring units having the general formula (1) and recurring units having the general formula (2) as the acid labile group-containing recurring units, ##STR00047## wherein R.sup.1 is methyl or ethyl, and R.sup.2 is hydrogen or methyl, component (B) being a mixture of a sulfonium salt having the general formula (3) and a sulfonium salt having the general formula (4): ##STR00048## wherein R.sup.3, R.sup.4 and R.sup.5 are each independently hydrogen or a straight, branched or cyclic C.sub.1-C.sub.20 monovalent hydrocarbon group which may contain a heteroatom, R.sup.6 is each independently a straight, branched or cyclic C.sub.7-C.sub.30 monovalent hydrocarbon group which may contain a heteroatom, and R.sup.7 is each independently hydrogen or a straight, branched or cyclic C.sub.1-C.sub.30 monovalent hydrocarbon group which may contain a heteroatom.

7. The process of claim 6 wherein the resin as component (A) further comprises recurring units having the general formula (5): ##STR00049## wherein p is 0, 1 or 2.

8. The process of claim 6 wherein component (B) is present in an amount of 0.5 to 10 parts by weight per 100 parts by weight of component (A).

Description

DESCRIPTION OF PREFERRED EMBODIMENTS

(1) As used herein, the singular forms “a,” “an” and “the” include plural referents unless the context clearly dictates otherwise. “Optional” or “optionally” means that the subsequently described event or circumstances may or may not occur, and that description includes instances where the event or circumstance occurs and instances where it does not. The notation (Cn-Cm) means a group containing from n to m carbon atoms per group. In the chemical formulae, Me stands for methyl, and Ac for acetyl.

(2) The abbreviations and acronyms have the following meaning.

(3) Mw: weight average molecular weight

(4) Mn: number average molecular weight

(5) Mw/Mn: molecular weight distribution or dispersity

(6) GPC: gel permeation chromatography

(7) PAG: photoacid generator

(8) PEB: post-exposure bake

(9) LWR: line width roughness

(10) DOF: depth of focus

(11) As alluded to previously, there is a need for a positive resist composition which is processed to form a resist pattern without raising problems like top-loss even when a protective film is formed thereon, and is effective for preventing any degradation of pattern profile and resolution, especially DOF.

(12) The inventors have found that a positive resist composition comprising (A) a resin comprising recurring units in which carboxylic acid as dissolvable group is protected with a tertiary ester type acid labile group having adamantane ring (i.e., recurring units of formula (1)) and recurring units in which a tertiary ester type acid labile group is a cyclopentyl group having tert-butyl or tert-amyl pendant (i.e., recurring units of formula (2)), (B) a mixture of a sulfonium salt having formula (3) and a sulfonium salt having formula (4), and (C) a solvent is improved in resolution and rectangularity of pattern profile. Thus the resist composition is best suited in precise micropatterning.

(13) The positive resist composition of the invention is improved in DOF performance independent of whether the pattern is an isolated one or a grouped one. Provided that exposure is made in an identical dose while the focus is vertically shifted, the term “DOF” refers to the range of focus that enables to form a resist pattern to a feature size, a deviation of which from the target size falls within a predetermined range, that is, the range of focus that ensures to form a resist pattern substantially faithful to the mask pattern. A larger magnitude of DOF is preferable.

(14) The positive resist composition is defined as comprising (A) a resin comprising acid labile group-containing recurring units so that the resin may increase its alkali solubility under the action of acid, specifically the resin (A) comprising recurring units having the general formula (1) and recurring units having the general formula (2).

(15) ##STR00004##
Herein R.sup.1 is methyl or ethyl, and R.sup.2 is hydrogen or methyl.

(16) The recurring unit having formula (1), which is one of acid labile group-containing recurring units, is the unit in which carboxylic acid as dissolvable group is protected with a tertiary ester type acid labile group having adamantane ring. By incorporating the recurring unit of formula (1) as a constituent unit in a resin adapted to increase its alkali solubility under the action of acid, satisfactory retention performance (DOF of an isolated pattern) is obtainable. When the unit of formula (1) is used alone, however, removal performance and LWR are degraded despite satisfactory retention performance. Although isopropyl-2-adamantyl methacrylate may also be used as the acid labile group, it is too less homo-polymerizable or copolymerizable to form a polymer with a desired molecular weight. A lowering of molecular weight leads to a lowering of acid diffusion suppressing ability, which in turn, invites undesirable reductions of DOF and LWR of an isolated pattern.

(17) The recurring unit having formula (2), which is another acid labile group-containing recurring unit, is the unit in which a tertiary ester type acid labile group is a cyclopentyl group having tert-butyl or tert-amyl pendant. By incorporating the highly branched structural unit of cyclopentyl having tert-butyl or tert-amyl pendant as a constituent unit in a resin adapted to increase its alkali solubility under the action of acid, the dissolution contrast of resist can be enhanced due to moderate lipophilicity and very high acid eliminatability of the acid-dissociable group having cyclopentyl structure. When such component (A) is combined with component (B) to be described below, there is obtained a positive resist composition which forms a pattern with high resolution, especially excellent removal performance (DOF of a grouped pattern), and improved LWR. As compared with the tertiary ester type acid labile group with tert-butyl or tert-amyl pendant, a tertiary ester type acid labile group in the form of a cyclopentyl group having methyl, ethyl, isopropyl or n-butyl pendant is unsatisfactory in that the pattern profile is degraded due to reductions of lipophilicity, acid diffusion control and acid elimination, and hence, DOF performance is degraded, especially DOF of an isolated pattern is reduced.

(18) Examples of the recurring unit having formula (1) are shown below.

(19) ##STR00005##

(20) Examples of the recurring unit having formula (2) are shown below.

(21) ##STR00006##

(22) In addition to the recurring units having formula (1) and the recurring units having formula (2), the resin (A) preferably further comprises recurring units having the general formula (5). Inclusion of recurring units containing a lactone ring is effective for rendering the resist film more adherent to the substrate in forming a fine size pattern.

(23) ##STR00007##
Herein p is 0, 1 or 2.

(24) Examples of the recurring unit having formula (5) are shown below, but not limited thereto.

(25) ##STR00008##

(26) In addition to the recurring units having formulae (1), (2) and (5), the resin (A) may further comprise recurring units having a fused lactone ring. With fused lactone ring-containing recurring units incorporated, the resin becomes easier to adjust rectangularity in forming a fine size pattern. The content of the fused lactone ring-containing recurring unit should preferably be up to 20 mol % based on the total recurring units. Within this range, the risk of pattern collapse resistance and LWR being degraded due to swell is eliminated. Although the fused lactone ring-containing recurring unit is optional, the content of this unit, when incorporated, is preferably at least 3 mol %, more preferably 5 to 15 mol %.

(27) Examples of the fused lactone ring-containing recurring unit are shown below, but not limited thereto.

(28) ##STR00009## ##STR00010## ##STR00011##

(29) In addition to the recurring units having formulae (1) and (2) and lactone ring-containing recurring units, the resin as component (A) may further comprise other recurring units, if necessary, for example, units containing carboxyl and fluoroalkyl groups. The content of the carboxyl-containing recurring unit should preferably be up to 10 mol % based on the total recurring units. This range avoids any detrimental impact on pattern rectangularity, eliminates the risk of pattern collapse resistance being degraded due to swell, and is sometimes effective for dissolution rate control.

(30) Also, units having a bridged ring structure (excluding units of formula (1) and fused lactone ring-containing units) may be incorporated in the resin. As long as the content of the bridged ring structure-containing recurring unit is less than 10 mol % based on the total recurring units, no detrimental effects are exerted on pattern collapse upon development and LWR.

(31) Examples of the carboxyl-containing unit, fluoroalkyl-containing unit and bridged ring structure-containing unit are shown below, but not limited thereto.

(32) ##STR00012## ##STR00013##

(33) The resin as component (A) may be synthesized, for example, by mixing and dissolving suitable monomers selected from monomers corresponding to the essential recurring units having formulae (1) and (2), lactone units having formula (5), and other optional units in an organic solvent and effecting polymerization by the batch polymerization or dropwise polymerization method while adding a polymerization initiator or chain transfer agent if necessary.

(34) As the polymerization initiator, any commercially available radical polymerization initiators may be used. The preferred radical polymerization initiators are azo and peroxide initiators. The initiators may be used alone or in admixture. The amount of the initiator used may be selected in accordance with the desired molecular weight, monomers, and synthesis conditions such as polymerization temperature and polymerization mode.

(35) Of the polymerization initiators, suitable azo initiators include 2,2′-azobisisobutyronitrile (AIBN), 2,2′-azobis(2,4-dimethylvaleronitrile), dimethyl 2,2′-azobis(2-methylpropionate), 2,2′-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis(cyclohexane-1-carbonitrile), and 4,4′-azobis(4-cyanovaleric acid); and suitable peroxide initiators include benzoyl peroxide, decanoyl peroxide, lauroyl peroxide, succinic acid peroxide, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxypivaloate, and 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate.

(36) As the chain transfer agent, any commercially available agents may be used. Among others, thiol compounds are preferred, including well-known primary, secondary and tertiary thiol compounds. The chain transfer agent may be used alone or in admixture. The amount of the chain transfer agent used may be selected in accordance with the desired molecular weight, monomers, and synthesis conditions such as polymerization temperature and polymerization mode. Exemplary chain transfer agents include 1-octanethiol, 2-mercaptoethanol, thiolactic acid, thioglycolic acid, mercaptopropionic acid, cyclohexyl mercaptan, t-dodecyl mercaptan, 1,4-butanedithiol, 1,8-octanedithiol, butanediol bis(thioglycolate), hexanediol bis(thioglycolate), 1,3,5-benzenetrithiol, trimethyloipropane tris(thioglycolate), and pentaerythritol tetrakis(thioglycolate).

(37) Any solvent may be used for polymerization as long as monomers are dissolvable therein and a polymer produced by polymerization reaction does not precipitate during polymerization reaction. Suitable solvents include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl isopentyl ketone, methyl pentyl ketone, cyclohexanone; alcohols such as isopropyl alcohol, isobutyl alcohol, n-butyl alcohol, isopentyl alcohol; ether alcohols such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether; esters such as methyl acetate, ethyl acetate, isopropyl acetate, propyl acetate, butyl acetate, methyl propionate, methyl lactate, ethyl lactate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate; ethers such as tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether; aromatic hydrocarbons such as toluene, xylene; N,N-dimethylformamide, acetonitrile, etc.

(38) While the resin (A) is composed of recurring units as defined above, they are preferably incorporated in the following compositional ratio. Provided that a total content of recurring units having formula (1) is “a” mol %, a total content of recurring units having formula (2) is “b” mol %, and a total content of recurring units containing lactone ring is “c” mol %, the compositional ratio of recurring units in the resin preferably meets: a+b+c=100 mol %, 5<a≦50, 5≦b≦60, and 20≦c≦70, more preferably a+b+c=100 mol %, 10<a≦40, 10≦b≦60, and 30≦c≦60.

(39) The resin (A) should preferably have a weight average molecular weight (Mw) in the range of 1,000 to 500,000, and more preferably 7,000 to 13,000, as measured by GPC versus polystyrene standards. A resin with too low a Mw may be soluble in water whereas a resin with too high a Mw has a possibility of losing alkaline solubility or causing defects during spin coating.

(40) Also essentially the positive resist composition comprises a mixture of a sulfonium salt having the general formula (3) and a sulfonium salt having the general formula (4) as component (B).

(41) ##STR00014##
Herein R.sup.3, R.sup.4 and R.sup.5 are each independently hydrogen or a straight, branched or cyclic C.sub.1-C.sub.20 monovalent hydrocarbon group which may contain a heteroatom, R.sup.6 is each independently a straight, branched or cyclic C.sub.7-C.sub.30 monovalent hydrocarbon group which may contain a heteroatom, and R.sup.7 is each independently hydrogen or a straight, branched or cyclic C.sub.1-C.sub.30 monovalent hydrocarbon group which may contain a heteroatom.

(42) Examples of groups R.sup.3, R.sup.4 and R.sup.5 in formula (3) include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, tert-amyl, n-pentyl, n-hexyl, cyclopentyl, cyclohexyl, ethylcyclopentyl, butylcyclopentyl, ethylcyclohexyl, butylcyclohexyl, adamantyl, ethyladamantyl, butyladamantyl. Also included are substituted forms of the foregoing in which a heteroatom group such as —O—, —S—, —SO—, —SO.sub.2—, —NH—, —C(═O)—, —C(═O)O— or —C(═O)NH— intervenes in any carbon-carbon bond, or any hydrogen atom is substituted by a functionality such as —OH, —NH.sub.2, —CHO or —CO.sub.2H.

(43) Examples of the group R.sup.6 in formulae (3) and (4) are shown below, but not limited thereto.

(44) ##STR00015## ##STR00016##

(45) Examples of group R.sup.7 in formula (4) include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, tert-amyl, n-pentyl, n-hexyl, cyclopentyl, cyclohexyl, ethylcyclopentyl, butylcyclopentyl, ethylcyclohexyl, butylcyclohexyl, adamantyl, ethyladamantyl, butyladamantyl. Also included are substituted forms of the foregoing in which a heteroatom group such as —O—, —S—, —SO—, —SO.sub.2—, —NH—, —C(═O)—, —C(═O)O— or —C(═O)NH— intervenes in any carbon-carbon bond, or any hydrogen atom is substituted by a functionality such as —OH, —NH.sub.2, —CHO or —CO.sub.2H.

(46) An appropriate amount of component (B) is 0.5 to 10 parts by weight per 100 parts by weight of component (A) because this range of component (B) ensures to take full advantage of the invention.

(47) The weight ratio of the sulfonium salt of formula (3) to the sulfonium salt of formula (4) is 0.1 to 50.

(48) The positive resist composition further comprises (C) a solvent. Any organic solvent may be used as component (C) as long as the resin (A), sulfonium salts (B) and other additives are soluble therein. With the organic solvent included, the resist composition becomes easier to apply to the substrate or the like. Exemplary solvents include ketones such as cyclohexanone and methyl-2-n-pentyl ketone; alcohols such as 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, and diacetone alcohol; ethers such as propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, and diethylene glycol dimethyl ether; esters such as propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, and propylene glycol mono-tert-butyl ether acetate; and lactones such as γ-butyrolactone, which may be used alone or in admixture. Inter alia, diethylene glycol dimethyl ether, 1-ethoxy-2-propanol, PGMEA, and mixtures thereof are preferred because the acid generator is most soluble therein.

(49) An appropriate amount of component (C) is 200 to 5,000 parts by weight, more preferably 400 to 4,000 parts by weight per 100 parts by weight of component (A).

(50) To the resist composition, a compound which is decomposed with an acid to generate another acid, that is, acid amplifier compound may be added. For this compound, reference should be made to JP-A 2009-269953. In the resist composition, an appropriate amount of the acid amplifier compound is up to 2 parts, and especially up to 1 part by weight per 100 parts by weight of the base resin. An amount of the acid amplifier compound which is up to 2 parts eliminates the risk of making diffusion control difficult and hence, the risk of resolution and pattern profile being degraded.

(51) To the positive resist composition, an organic acid derivative or a compound having a Mw of up to 3,000 which changes its solubility in alkaline developer under the action of an acid, also referred to as dissolution inhibitor, may be added. Reference may be made to JP-A 2009-269953. By blending the dissolution inhibitor, the difference in dissolution rate between exposed and unexposed regions may be accordingly increased, and the resolution be further improved.

(52) To the positive resist composition, a basic compound may be added. By blending the basic compound, the resist composition may be further improved in resolution. Suitable basic compounds include primary, secondary and tertiary amine compounds, specifically amine compounds having hydroxyl, ether, ester, lactone ring, cyano or sulfonic acid ester as described in JP-A 2008-111103, paragraphs [0146]-[0164] (U.S. Pat. No. 7,537,880), and carbamate compounds as described in JP-A 2001-166476. An appropriate amount of the basic compound is 0 to 4 parts by weight per 100 parts by weight of the base resin. When used, the amount of the basic compound is preferably at least 0.1 part by weight.

(53) To the positive resist composition, a surfactant may be added. Although the surfactant used herein is not particularly limited, alkali-soluble surfactants as described in JP-A 2008-122932 may be used. When added, the surfactant is effective for facilitating or controlling the coating step of the resist composition. It is acceptable to use a mixture of surfactants. An appropriate (total) amount of the surfactant(s) added is 0.001 to 20 parts, more preferably 0.01 to 10 parts by weight per 100 parts by weight of the base resin.

(54) Also a polymeric additive may be added to the positive resist composition for improving the water repellency on surface of a resist film as spin coated. This additive may be used in the topcoatless immersion lithography. These additives have a specific structure with a 1,1,1,3,3,3-hexafluoro-2-propanol residue and are described in JP-A 2007-297590 and JP-A 2008-111103. The water repellency improver to be added to the resist composition should be soluble in the developer and the organic solvent. The water repellency improver of specific structure with a 1,1,1,3,3,3-hexafluoro-2-propanol residue is well soluble in the developer. A polymer having an amino group or amine salt copolymerized as recurring units may serve as the water repellent additive and is effective for preventing evaporation of acid during PEB and any hole pattern opening failure after development. An appropriate amount of the water repellency improver is 0.1 to 20 parts, preferably 0.5 to 10 parts by weight per 100 parts by weight of the base resin.

(55) Process

(56) The positive resist composition as formulated above is effective in forming a pattern of satisfactory profile at a high resolution by a conventional lithography process including patternwise exposure and development (inclusive of multilayer resist process), and particularly by the immersion lithography process including formation of a protective film on a resist film and exposure of the resist film via water.

(57) Another embodiment of the invention is a pattern forming process comprising the steps of applying onto a substrate a positive resist composition comprising (A) a resin comprising acid labile group-containing recurring units having formulae (1) and (2) such that the resin may increase its alkali solubility under the action of acid, (B) a mixture of sulfonium salts having formulae (3) and (4), and (C) a solvent, baking to form a photoresist film, forming a protective film on the photoresist film, exposing the photoresist film to high-energy radiation of wavelength 180 to 250 nm through water by immersion lithography, and developing the resist film in an alkaline developer. The formulae (1), (2), (3) and (4) are as defined above.

(58) Pattern formation using the positive resist composition may be performed by well-known lithography processes. For example, the resist composition is applied to a substrate by a suitable coating technique such as spin coating, and prebaked on a hot plate at a temperature of 60 to 150° C. for 1 to 10 minutes, preferably at 80 to 140° C. for 1 to 5 minutes to form a photoresist film having a thickness of 0.05 to 2.0 μm. The substrate used herein may be a substrate for integrated circuitry fabrication (e.g., Si, SiO.sub.2, SiN, SiON, TiN, WSi, BPSG, SOG, organic antireflective film, etc.) or a substrate for mask circuitry fabrication (e.g., Cr, CrO, CrON, MoSi, etc.).

(59) Then a protective film which is water insoluble is formed on the photoresist film. The water-insoluble protective film is to prevent the resist film from being leached and to improve water slippage at the film surface. It is generally divided into two types. The first type is an organic solvent-strippable protective coating which must be stripped, prior to alkaline development, with an organic solvent in which the resist film is not dissolvable. The second type is an alkali-soluble protective coating which is soluble in an alkaline developer so that it can be removed simultaneously with the removal of solubilized areas of the resist film.

(60) The protective coating of the second type is preferably of a material comprising a polymer having a 1,1,1,3,3,3-hexafluoro-2-propanol residue (which is insoluble in water and soluble in an alkaline developer) as a base in an alcohol solvent of at least 4 carbon atoms, an ether solvent of 8 to 12 carbon atoms or a mixture thereof, as exemplified in JP-A 2007-297590 and JP-A 2008-111103. Alternatively, the aforementioned surfactant which is insoluble in water and soluble in an alkaline developer may be dissolved in an alcohol solvent of at least 4 carbon atoms, an ether solvent of 8 to 12 carbon atoms or a mixture thereof to form a solution, from which the protective film of the second type is formed.

(61) The pattern forming process may involve any additional steps. For example, after formation of the photoresist film, deionized water rinsing (or post-soaking) may be carried out for extracting the acid generator and the like from the film surface or washing away particles, or after exposure, rinsing (or post-soaking) may be carried out for removing water droplets left on the resist film after exposure.

(62) Next, a mask having a desired pattern is disposed over the substrate, water is held between the mask and the substrate, and the resist film is exposed to high-energy radiation of wavelength 180 to 250 nm such as deep-UV or excimer laser by the immersion lithography. An appropriate exposure dose is in the range of 1 to 200 mJ/cm.sup.2, more preferably 10 to 100 mJ/cm.sup.2. The positive resist composition of the invention is best suited for micropatterning using deep-UV or excimer laser radiation of wavelength 180 to 250 nm.

(63) The resist film is then baked (PEB) on a hot plate at 60 to 150° C. for 1 to 5 minutes, and preferably at 80 to 140° C. for 1 to 3 minutes. Finally, development is carried out using as the developer an aqueous alkaline solution, such as a 0.1 to 5 wt %, preferably 2 to 3 wt %, aqueous solution of tetramethylammonium hydroxide (TMAH), this being done by a conventional method such as dip, puddle, or spray development for a period of 0.1 to 3 minutes, and preferably 0.5 to 2 minutes. In this way the desired pattern is formed on the substrate.

EXAMPLE

(64) Examples are given below by way of illustration and not by way of limitation.

(65) A series of resins were used in the test. Table 1 shows the compositional ratio (molar ratio) of recurring units incorporated in these resins and their molecular weight (Mw). Notably, the molecular weight Mw is measured by GPC versus polystyrene standards. Table 2 shows the structure of respective recurring units. Among the resins in Table 1, Resins P1 to P9 correspond to the resin as essential component (A) in the inventive resist composition.

(66) TABLE-US-00001 TABLE 1 Unit 1 Unit 2 Unit 3 Unit 4 Resin (molar ratio) (molar ratio) (molar ratio) (molar ratio) Mw P1 A-1 (0.25) A-8 (0.15) L-1 (0.60) — 8,500 P2 A-1 (0.25) A-8 (0.25) L-1 (0.50) — 8,100 P3 A-1 (0.15) A-8 (0.35) L-1 (0.50) — 9,000 P4 A-1 (0.25) A-8 (0.25) L-3 (0.50) — 9,100 P5 A-1 (0.30) A-9 (0.10) L-1 (0.60) — 8,800 P6 A-2 (0.25) A-8 (0.25) L-1 (0.50) — 8,000 P7 A-1 (0.25) A-9 (0.25) L-3 (0.50) — 9,000 P8 A-1 (0.30) A-8 (0.10) L-1 (0.50) L-3 (0.10) 8,700 P9 A-1 (0.25) A-8 (0.15) A-9 (0.10) L-1 (0.50) 8,500 P10 A-1 (0.25) A-4 (0.25) L-1 (0.50) — 7,900 P11 A-2 (0.25) A-5 (0.25) L-1 (0.50) — 7,500 P12 A-1 (0.25) A-6 (0.25) L-1 (0.50) — 8,000 P13 A-1 (0.25) A-4 (0.25) L-2 (0.50) — 8,800 P14 A-1 (0.25) A-7 (0.25) L-1 (0.50) — 7,800 P15 A-1 (0.15) A-4 (0.35) L-1 (0.50) — 7,600 P16 A-1 (0.15) A-8 (0.35) L-1 (0.50) — 7,300 P17 A-1 (0.50) L-1 (0.25) H-1 (0.25) — 7,900 P18 A-2 (0.50) L-1 (0.25) H-1 (0.25) — 7,100 P19 A-1 (0.40) A-4 (0.15) L-4 (0.45) — 8,100 P20 A-1 (0.25) A-8 (0.25) L-4 (0.50) — 8,300 P21 A-1 (0.25) A-10 (0.25) L-4 (0.50) — 8,500 P22 A-1 (0.25) A-2 (0.20) L-4 (0.30) H-1 (0.25) 8,000 P23 A-1 (0.25) A-8 (0.25) L-1 (0.20) L-4 (0.30) 8,300 P24 A-1 (0.30) A-8 (0.15) L-1 (0.30) L-5 (0.25) 8,600

(67) TABLE-US-00002 TABLE 2 A-1 A-2 A-3 0 A-4 A-5 A-6 A-7 A-8 A-9 A-10 L-1 L-2 L-3 0 L-4 L-5 H-1
Preparation of Resist Composition

(68) A resist composition in solution form was prepared by dissolving a resin, acid generator, and quencher (or basic compound) in an organic solvent in accordance with the formulation (pbw) of Table 3, and filtering through a Teflon® filter with a pore size of 0.2 μm.

(69) Table 4 shows the structure of the acid generators (S-1 to 5) and basic compounds (Q-1 to 4). In Table 4, sulfonium salts S-1 and S-4 correspond to the sulfonium salts as essential component (B) in the inventive resist composition. In Table 3, resists R1 to R14 correspond to inventive resist compositions whereas resists R15 to R40 correspond to comparative resist compositions.

(70) TABLE-US-00003 TABLE 3 Acid Acid Basic Organic Organic Resin generator 1 generator 2 compound solvent 1 solvent 2 Resist (pbw) (pbw) (pbw) (pbw) (pbw) (pbw) R1 P1(80) S-1(5) S-4(5) — PGMEA(1,650) GBL(720) R2 P2(80) S-1(5) S-4(5) — PGMEA(1,650) GBL(720) R3 P3(80) S-1(5) S-4(5) — PGMEA(1,650) GBL(720) R4 P4(80) S-1(5) S-4(5) — PGMEA(1,650) GBL(720) R5 P5(80) S-1(5) S-4(5) — PGMEA(1,650) GBL(720) R6 P6(80) S-1(5) S-4(5) — PGMEA(1,650) GBL(720) R7 P7(80) S-1(5) S-4(5) — PGMEA(1,650) GBL(720) R8 P8(80) S-1(5) S-4(5) — PGMEA(1,650) GBL(720) R9 P9(80) S-1(5) S-4(5) — PGMEA(1,650) GBL(720) R10 P2(80) S-1(5) S-4(7) — PGMEA(1,650) GBL(720) R11 P2(80) S-1(5) S-4(10) — PGMEA(1,650) GBL(720) R12 P2(80) S-1(7) S-4(5) — PGMEA(1,650) GBL(720) R13 P2(80) S-1(10) S-4(5) — PGMEA(1,650) GBL(720) R14 P2(80) S-1(5) S-4(5) Q-3(0.5) PGMEA(1,650) GBL(720) R15 P2(80) S-2(5) S-4(5) — PGMEA(1,650) GBL(720) R16 P2(80) S-3(5) S-4(5) — PGMEA(1,650) GBL(720) R17 P2(80) S-5(10) — Q-1(1.0) PGMEA(1,650) GBL(720) R18 P2(80) S-1(10) — Q-1(1.0) PGMEA(1,650) GBL(720) R19 P2(80) S-1(10) — Q-2(1.0) PGMEA(1,650) GBL(720) R20 P2(80) S-1(10) — Q-3(1.0) PGMEA(1,650) GBL(720) R21 P10(80) S-1(5) S-4(5) — PGMEA(1,650) GBL(720) R22 P11(80) S-1(5) S-4(5) — PGMEA(1,650) GBL(720) R23 P12(80) S-1(5) S-4(5) — PGMEA(1,650) GBL(720) R24 P13(80) S-1(5) S-4(5) — PGMEA(1,650) GBL(720) R25 P14(80) S-1(5) S-4(5) — PGMEA(1,650) GBL(720) R26 P15(80) S-1(5) S-4(5) — PGMEA(1,650) GBL(720) R27 P16(80) S-1(5) S-4(5) — PGMEA(1,650) GBL(720) R28 P17(80) S-1(5) S-4(5) — PGMEA(1,650) GBL(720) R29 P18(80) S-1(5) S-4(5) — PGMEA(1,650) GBL(720) R30 P19(80) S-1(5) S-4(5) — PGMEA(1,650) GBL(720) R31 P20(80) S-1(5) S-4(5) — PGMEA(1,650) GBL(720) R32 P19(80) S-1(5) S-4(7) — PGMEA(1,650) GBL(720) R33 P19(80) S-1(5) S-4(10) — PGMEA(1,650) GBL(720) R34 P19(80) S-1(7) S-4(5) — PGMEA(1,650) GBL(720) R35 P19(80) S-1(10) S-4(5) — PGMEA(1,650) GBL(720) R36 P19(80) S-5(10) — Q-1(1.0) PGMEA(1,650) GBL(720) R37 P21(80) S-1(5) S-4(5) — PGMEA(1,650) GBL(720) R38 P22(80) S-1(5) S-4(5) — PGMEA(1,650) GBL(720) R39 P23(80) S-1(5) S-4(5) — PGMEA(1,650) GBL(720) R40 P24(80) S-1(5) S-4(5) Q-4(1.0) PGMEA(1,650) GBL(720)

(71) TABLE-US-00004 TABLE 4 S-1 S-2 S-3 S-4 S-5 Q-1 Q-2 0 Q-3 Q-4

(72) The solvents in Table 3 are identified below. PGMEA: propylene glycol monomethyl ether acetate GBL: γ-butyrolactone

(73) Preparation of Protective Film

(74) A top coat or protective film-forming material (TC-1, TC-2) was prepared by mixing a base polymer (TC polymer 1, 2) with an organic solvent in accordance with the following formulation, dissolving, and filtering through a Teflon® filter with a pore size of 0.2 μm. TC-1: Mixing Formulation

(75) TABLE-US-00005 TC polymer 1 100 pbw Organic solvent 1 2,600 pbw   Organic solvent 2 260 pbw TC-2: Mixing Formulation

(76) TABLE-US-00006 TC polymer 2 100 pbw Organic solvent 1 2,600 pbw   Organic solvent 2 260 pbw

(77) These components are identified below. The base polymers have the following structural formula.

(78) ##STR00042## Organic Solvent 1: Isopentyl Alcohol Organic Solvent 2: 2-methyl-1-butanol

Examples 1 to 14 and Comparative Examples 1 to 26

(79) On a silicon substrate, an antireflective coating solution (ARC-29A by Nissan Chemical Industries, Ltd.) was coated and baked at 200° C. for 60 seconds to form an ARC of 100 nm thick. The resist solution (R1 to R40) was spin coated onto the ARC on the substrate and baked on a hot plate at 100° C. for 60 seconds to form a photoresist film of 100 nm thick.

(80) The protective film-forming material (TC-1, TC-2) was coated onto the resist film and baked at 100° C. for 60 seconds to form a protective film of 50 nm thick. Using an ArF excimer laser scanner (NSR-S610C by Nikon Corp., NA 1.30, σ 0.984, 4/5 annular illumination, cross pole (opening angle) 35°), 6% halftone phase shift mask), the resist film was subjected to immersion exposure and baked (PEB) for 60 seconds at the temperature shown in Tables 5 and 6. The resist film was developed in a 2.38 wt % aqueous solution of tetramethylammonium hydroxide for 60 seconds, forming a pattern.

(81) Resist evaluation was made on a grouped pattern of 50 nm line/100 nm pitch. On observation under an electron microscope, the optimum exposure dose (Eop) was defined as an exposure dose (mJ/cm.sup.2) which provided a line width of 45 nm. The pattern at the optimum dose was measured for roughness (LWR). While the focus was vertically shifted with the optimum dose fixed, the range (nm) of focus over which the grouped pattern could be resolved to a target size of 45 nm±10% (i.e., 41 nm to 50 nm) was determined and reported as DOF-1. A larger value of DOF-1 indicates a wider margin relative to a focal shift, i.e., better performance.

(82) Resist evaluation was also made on an isolated pattern of 160 nm line/1,760 nm pitch. While the focus was vertically shifted, the range (nm) of focus over which the isolated pattern could be resolved to a target size of 100 nm±10% (i.e., 90 nm to 110 nm) was determined and reported as DOF-2.

(83) Table 5 shows the test results (Examples 1 to 14) of the inventive resist compositions R1 to R14 in Table 3. Table 6 shows the test results (Comparative Examples 1 to 26) of the comparative resist compositions R15 to R40 in Table 3.

(84) TABLE-US-00007 TABLE 5 DOF-1 DOF-2 LWR Example Resist Protective film (nm) (nm) (nm) 1 R1 TC-1 160 60 3.5 2 R2 TC-1 180 80 3.2 3 R3 TC-1 240 100 3.0 4 R4 TC-1 200 80 3.3 5 R5 TC-1 200 60 2.8 6 R6 TC-1 200 70 3.3 7 R7 TC-1 220 60 2.8 8 R8 TC-1 200 80 3.2 9 R9 TC-1 200 70 3.0 10 R10 TC-1 200 100 3.0 11 R11 TC-1 180 100 2.9 12 R12 TC-1 200 100 3.1 13 R13 TC-2 200 100 3.0 14 R14 TC-1 200 90 3.3

(85) TABLE-US-00008 TABLE 6 Comparative DOF-1 DOF-2 LWR Example Resist Protective film (nm) (nm) (nm) 1 R15 TC-1 140 40 4.0 2 R16 TC-1 140 40 4.2 3 R17 TC-2 160 40 4.4 4 R18 TC-2 140 40 4.2 5 R19 TC-2 140 40 4.0 6 R20 TC-2 140 40 4.1 7 R21 TC-1 140 40 3.8 8 R22 TC-1 160 60 4.0 9 R23 TC-1 140 40 3.4 10 R24 TC-1 160 60 4.1 11 R25 TC-1 140 40 3.9 12 R26 TC-1 140 40 3.9 13 R27 TC-1 160 40 4.1 14 R28 TC-1 120 40 4.2 15 R29 TC-1 140 60 4.0 16 R30 TC-1 120 40 3.8 17 R31 TC-1 140 40 4.2 18 R32 TC-1 140 60 3.7 19 R33 TC-1 120 60 3.6 20 R34 TC-1 140 60 3.7 21 R35 TC-2 140 60 3.6 22 R36 TC-2 140 40 4.6 23 R37 TC-1 140 40 3.8 24 R38 TC-1 120 60 4.1 25 R39 TC-1 120 60 3.9 26 R40 TC-1 140 60 3.8

(86) As is evident from Tables 5 and 6, the positive resist compositions within the scope of the invention show substantial improvements in DOF and LWR.

(87) While the invention has been illustrated and described in typical embodiments, it is not intended to be limited to the details shown. Any modified embodiments having substantially the same features and achieving substantially the same results as the technical idea disclosed herein are within the spirit and scope of the invention.

(88) Japanese Patent Application No. 2015-094749 is incorporated herein by reference.

(89) 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.