# Patent

## Title
Resist protective film-forming composition and patterning process

## Abstract

A pattern is printed by forming a photoresist layer on a wafer, forming a protective film thereon, exposure, and development. The protective film is formed from a composition comprising a copolymer comprising recurring units derived from a styrene, indene, benzofuran or benzothiophene monomer having 1,1,1,3,3,3-hexafluoro-2-propanol, and recurring units derived from a styrene, vinylnaphthalene, indene, benzofuran, benzothiophene, stilbene, styrylnaphthalene or dinaphthylethylene monomer and an ether solvent.

## Background
CROSS-REFERENCE TO RELATED APPLICATION
This non-provisional application claims priority under 35 U.S.C. §119(a) on Patent Application No. 2012-202464 filed in Japan on Sep. 14, 2012, the entire contents of which are hereby incorporated by reference.
TECHNICAL FIELD
This invention relates to a composition for forming a resist protective film for use in the micropatterning step in the fabrication of semiconductor devices, and a pattern forming process using the same.
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 a light source with a shorter wavelength.
Resist materials adapted for KrF excimer laser (248 nm) started use on the 0.3 μm process and entered the mass production phase on the 0.13 μm rule. A wavelength change-over from KrF to shorter wavelength ArF excimer laser (193 nm) is expected to enable miniaturization of the design rule to below 0.13 μm. Since commonly used novolak resins and polyvinylphenol resins have very strong absorption in proximity to 193 nm, they cannot be used as the base resin for resists. To ensure transparency and dry etching resistance, acrylic resins and alicyclic (typically cycloolefin) resins are investigated, leading to mass-scale production of devices by the ArF lithography.
For the next 45-nm node devices which required an advancement to reduce the wavelength of exposure light, the F2 lithography of 157 nm wavelength became a candidate. However, for the reasons that the projection lens uses a large amount of expensive CaF2 single crystal, the scanner thus becomes expensive, hard pellicles are introduced due to the extremely low durability of soft pellicles, the optical system must be accordingly altered, and the etch resistance of resist is low; the F2 lithography was postponed and instead, the early introduction of ArF immersion lithography was advocated. This enables mass-scale production of 45-nm node devices. For the mass-scale production of 32-nm node devices, the double patterning process utilizing sidewall spacer technology is used although the process suffers from complexity and length.
For the fabrication of 32-nm node and subsequent devices, the EUV lithography using an exposure wavelength of 13.5 nm which is shorter than the conventional lasers by one order of magnitude and thus featuring improved resolution is expected rather than the double patterning process with noticeable costs. Efforts are focused on the EUV lithography.
In the EUV lithography, a low laser power and light attenuation by reflecting mirror lead to a reduced quantity of light. Then light with a low intensity reaches the wafer surface. It is urgently demanded to develop a high-sensitivity resist material in order to gain a throughput despite a low light quantity. However, a trade-off relationship of sensitivity is pointed out that the sensitivity of resist material can be increased at the sacrifice of resolution and edge roughness (LER, LWR).
EUV resist materials are susceptible to environmental impacts because of their high sensitivity. In general, an amine quencher is added to chemically amplified resist materials for rendering the resist materials unsusceptible to contamination with airborne amine. The amount of amine quencher added to the EUV resist materials is only a fraction as compared with the ArF and other lithography resist materials. As a result, the EUV resist materials tend to take a T-top profile under the influence of amine from the resist surface.
For shutting off environmental impacts, it is effective to form a protective film on top of the resist film. Application of a protective film was effective for the chemically amplified resist materials of the early stage based on a t-BOC-protected polyhydroxystyrene and free of an amine quencher, used in the KrF excimer laser lithography. Also at the initial stage of the ArF immersion lithography, a protective film was applied to prevent the acid generator from leaching out in water and thus inhibit the profile from becoming T-topped. Patent Document 1 discloses a protective film material based on a homopolymer of styrene having 1,1,1,3,3,3-hexafluoro-2-propanol or a copolymer thereof with methacrylate.
With respect to the EUV lithography, it was also proposed to form a protective film on top of the resist film (see Patent Documents 2 to 4 and Non-Patent Document 1). The protective film thus formed is effective for improving environmental resistance and reducing the outgassing from the resist film.
EUV laser sources of the discharge-produced plasma (DPP) or laser-produced plasma (LPP) method emit not only light of wavelength 13.5 nm available for pattern formation, but also broad light (though weak) of wavelength 140 to 300 nm, known as out-of-band (OOB) light. The broad light has a low intensity, but a wide span of wavelength and is not negligible as energy quantity. The EUV microstepper is loaded with a Zr filter for cutting off OOB light, but the quantity of light is reduced thereby. The EUV scanner may not be loaded with the filter because a reduction of light quantity is not permissible for the goal of enhancing the throughput.
There is a need for a resist material which is sensitive to EUV, but not to OOB light. For such resist materials, the cation structure of sulfonium salt PAG is important. Patent Document 5 (JP-A 2011-138107, paragraph [0052] describes a polymer-bound acid generator having a high sensitivity to EUV light, but a low sensitivity to OOB light. Non-Patent Document 1 describes the superiority of a protective film which is formed on top of the resist layer for cutting off OOB light.
As the resist protective film, a number of materials have been proposed in the ArF immersion lithography application. Among others, Patent Document 6 discloses a protective film material comprising recurring units of hexafluoroalcohol-containing styrene although it is considered practically unacceptable because of very high absorption at wavelength 193 nm.
In connection with a protective film for use in the immersion lithography, it is pointed out in Patent Document 7 that the solvent for the coating of a protective film dissolves the resist film surface to invite intermixing between the protective film and the resist film, resulting in a thickness loss of the resist pattern after development. The film thickness loss becomes outstanding particularly when alcohol solvents are used. Ether solvents are effective for preventing a film thickness loss. Polymers that are dissolvable in ether solvents include polymers containing hexafluoroalcohol (HFA) as described in Patent Document 5. However, since fluorine atoms have strong absorption to EUV light, a resist film on which a protective film is formed using a HFA-containing polymer undesirably exhibits a low sensitivity on patterning.
CITATION LIST
Patent Document 1: JP-A 2006-053300
Patent Document 2: JP-A 2006-058739 (WO 2006112306)
Patent Document 3: JP 4716047
Patent Document 4: JP-A 2008-065304
Patent Document 5: JP-A 2011-138107
Patent Document 6: JP-A 2005-352384 (US 7316886)
Patent Document 7: JP 4771083 (US 20070122741)
Non-Patent Document 1: Proc. SPIE Vol. 7969, p796916-1 (2011)
SUMMARY OF INVENTION
An object of the invention is to provide a resist protective film-forming composition which is effective for mitigating the environmental impact on a resist film, cutting off OOB light, reducing a film thickness loss of the resist pattern, avoiding bridges between pattern features, allowing the resist film to exhibit a high sensitivity, and suppressing outgassing from the resist film. Another object is to provide a pattern forming process using the same.
The inventors have found that a protective film formed on a resist film as defined below is effective for mitigating the environmental impact on the resist film, absorbing OOB light, reducing a film thickness loss of the resist pattern, and avoiding bridges between pattern features. The protective film is made soluble in alkaline developer so that it can be stripped off at the same time as development of the resist film. Thus the process is simple as compared with the protective film of solvent stripping type, and the concomitant increase of the process cost is minimized.
It is reported that at wavelength 13.5 nm, hydrogen, carbon, silicon and sulfur atoms have low absorption and oxygen and fluorine atoms have high absorption. The fluoropolymer described in Patent Document 2 possesses noticeable absorption at wavelength 13.5 nm. If the resist protective film is absorptive, the sensitivity of the resist film is shifted to the lower side. In the EUV lithography with a low laser power, the low sensitivity of the resist film is a problem. Then the resist protective film must be highly transparent. Also since the aforementioned fluoropolymer does not dissolve in alkaline developer, a stripping cup specialized for the protective film must be separately used prior to development. As such, the process is complicated. Since a protective film which can be stripped at the same time as development of the resist film is desirable, the design of protective film material needs to incorporate an alkali-soluble group into the material. The protective film defined herein meets these requirements.
Suitable alkali-soluble groups include carboxyl, phenol, sulfo, and hexafluoroalcohol groups. From the standpoint of transparency, the use of a hexafluoroalcohol group as the alkali-soluble group in the protective film is undesirable because the hexafluoroalcohol group having as many as six fluorine atoms possesses strong absorption. Nevertheless, the hexafluoroalcohol-containing polymers are advantageous in that they are soluble in ether solvents that cause little or no damages to the resist film.
It is reported that polyhydroxystyrene-based resist materials have a high acid generation efficiency upon EUV exposure. The EUV exposure brings about energy transfer from phenol group to the acid generator to exert a sensitizing effect, leading to enhanced sensitivity. Therefore, polyhydroxystyrene-based resist materials are investigated for the purpose of enhancing the sensitivity of resist film.
JP 4425776 proposes a resist material based on a polymer having an acid generator (PAG) bound to its backbone. On use of a sulfonium or iodonium salt acid generator whose sulfonic acid is bound to the backbone, the distance of acid diffusion is shortened, thereby minimizing image blur due to acid diffusion. This is advantageous in forming fine size patterns. One shortcoming of the resist film having PAG bound thereto is a low sensitivity. The sensitivity may be enhanced by copolymerizing hydroxystyrene having a phenol group or the like. However, copolymerization of a monomer having a phenol group capable of enhancing an alkaline dissolution rate is not desirable because a thickness loss of the resist pattern can occur. There is a need for a resist protective film-forming composition which allows the resist film to exhibit a high sensitivity and minimizes the thickness loss of the resist pattern as developed.
In one aspect, the invention provides a resist protective film-forming composition which is used in a lithography pattern forming process comprising the steps of forming a photoresist layer on a wafer, forming a protective film thereon, exposure, and development. The resist protective film-forming composition comprises a copolymer comprising recurring units (p) derived from at least one monomer selected from the group consisting of a styrene, indene, benzofuran and benzothiophene having 1,1,1,3,3,3-hexafluoro-2-propanol, and recurring units (q1), (q2), (q3) or (q4) derived from at least one monomer selected from the group consisting of a styrene, vinylnaphthalene, indene, benzofuran, benzothiophene, stilbene, styrylnaphthalene, and dinaphthylethylene, as represented by the general formula (1), as a base resin.




Herein R1 is hydrogen, hydroxyl, a straight, branched or cyclic C1-C10 alkyl, alkoxy, acyloxy, cyano, nitro, amino group or halogen atom, m is 1 or 2; R2 and R3 each are hydrogen, or R2 and R3, taken together, may be methylene, —O— or —S— to form a ring; R4 to R8 are each independently hydrogen, hydroxyl, a straight, branched or cyclic C1-C10 alkyl, alkoxy, acyloxy, C2-C6 alkenyl, C6-C10 aryl, cyano, nitro, amino, trifluoromethyl, ester group, or halogen atom; X1 is methylene, —O— or —S—; X2 and X3 each are phenylene or naphthylene; n is an integer of 1 to 5, 0.1≦p<1.0, 0≦q1≦0.9, 0≦q2≦0.9, 0≦q3≦0.9, 0≦q4≦0.9, and 0<q1+q2+q3+q4≦0.9.

Preferably, the protective film-forming composition is soluble in an alkaline developer.
In a preferred embodiment, the protective film-forming composition may further comprise an ether solvent selected from the group consisting of diisopropyl ether, diisobutyl ether, diisopentyl ether, di-n-pentyl ether, methyl cyclopentyl ether, methyl cyclohexyl ether, di-n-butyl ether, di-sec-butyl ether, diisopentyl ether, di-sec-pentyl ether, di-tert-amyl ether, and di-n-hexyl ether.
More preferably, the solvent is a mixture of the ether solvent with an alcohol solvent. The alcohol solvent is selected from the group consisting of 1-butyl alcohol, 2-butyl alcohol, isobutyl alcohol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, tert-amyl alcohol, neopentyl alcohol, 2-methyl-1-butanol, 3-methyl-1-butanol, 3-methyl-3-pentanol, cyclopentanol, 1-hexanol, 2-hexanol, 3-hexanol, 2,3-dimethyl-2-butanol, 3,3-dimethyl-1-butanol, 3,3-dimethyl-2-butanol, 2-ethyl-1-butanol, 2-methyl-1-pentanol, 2-methyl-2-pentanol, 2-methyl-3-pentanol, 3-methyl-1-pentanol, 3-methyl-2-pentanol, 3-methyl-3-pentanol, 4-methyl-1-pentanol, 4-methyl-2-pentanol, 4-methyl-3-pentanol, cyclopentanol, and cyclohexanol.
Specifically, the protective film-forming composition may further comprise a solvent containing at least 50% by weight of an ether solvent based on the total solvent weight, the ether solvent being selected from the group consisting of diisopropyl ether, diisobutyl ether, diisopentyl ether, di-n-pentyl ether, methyl cyclopentyl ether, methyl cyclohexyl ether, di-n-butyl ether, di-sec-butyl ether, diisopentyl ether, di-sec-pentyl ether, di-tert-amyl ether, and di-n-hexyl ether.
In a second aspect, the invention provides a lithography pattern forming process comprising the steps of forming a photoresist layer on a wafer, forming a protective film thereon, exposure, and development, the protective film being formed from the resist protective film-forming composition defined above.
In a third aspect, the invention provides a pattern forming process comprising the steps of forming a photoresist layer on a wafer, forming a protective film thereon, and exposure in vacuum, the protective film being formed from the resist protective film-forming composition defined above.
Preferably, the exposure step uses radiation having a wavelength of 3 to 15 nm or electron beam. Also preferably, the development step following exposure includes applying an alkaline developer to develop the photoresist layer and strip off the protective film simultaneously.
In a further aspect, the invention provides a pattern forming process comprising the steps of forming a photoresist layer on a wafer, forming a protective film thereon, and exposure in vacuum, the protective film being formed from the resist protective film-forming composition defined above. The photoresist layer is formed from a resist composition comprising a polymer comprising recurring units (a1) and/or (a2) having a carboxyl group and/or phenolic hydroxyl group whose hydrogen is substituted by an acid labile group, as represented by the general formula (2) and having a weight average molecular weight of 1,000 to 500,000, as a base resin.




Herein R9 and R11 each are hydrogen or methyl, R10 and R12 each are an acid labile group, Y1 is a single bond, a C1-C12 linking group having an ester, lactone ring, phenylene or naphthylene moiety, phenylene group or naphthylene group, Y2 is a single bond, ester or amide group, 0≦a1≦0.9, 0≦a2≦a2≦0.9, and 0<a1+a2<1.0.

Preferably, the polymer in the resist composition has copolymerized with the recurring units (a1) and/or (a2), recurring units of at least one type selected from recurring units (b1) to (b3) of sulfonium salt, as represented by the general formula (3).




Herein R020, R024, and R028 each are hydrogen or methyl, R021 is a single bond, phenylene, —O—R033—, or —C(═O)—Y—R033—, Y is oxygen or NH, R033 is a straight, branched or cyclic C1-C6 alkylene group, alkenylene group or phenylene group, which may contain a carbonyl (—CO—), ester (—COO—), ether (—O—), or hydroxyl moiety, R022, R023, R025, R026, R027, R029, R030, and R031 are each independently a straight, branched or cyclic C1-C12 alkyl group which may contain a carbonyl, ester or ether moiety, a C6-C12 aryl group, a C7-C20 aralkyl group, or a thiophenyl group, A1 is a single bond, -A0-C(═O)—O—, -A0-O— or -A0-O—C(═O)—, A0 is a straight, branched or cyclic C1-C12 alkylene group which may contain a carbonyl, ester or ether moiety, A2 is hydrogen, CF3 or carbonyl group, Z1 is a single bond, methylene, ethylene, phenylene, fluorinated phenylene, —O—R032—, or —C(═O)—Z2—R032, Z2 is oxygen or NH, R032 is a straight, branched or cyclic C1-C6 alkylene, phenylene, fluorinated phenylene, trifluoromethyl-substituted phenylene or alkenylene group, which may contain a carbonyl, ester, ether or hydroxyl moiety, M− is a non-nucleophilic counter ion, 0≦b1≦0.5, 0≦b2≦0.5, 0≦b3≦0.5, and 0<b1+b2+b3≦0.5.

Advantageous Effects of Invention
The resist protective film-forming composition, when applied onto the resist film, prevents the resist pattern from being T-topped due to contamination with airborne amine and exerts a sensitizing effect on the resist film for enhancing the sensitivity of the resist film. At the same time, the protective film restrains outgassing from the resist film during exposure in vacuum. When the protective film-forming composition is formulated soluble in alkaline developer, the protective film can be stripped off at the same time as development of the resist film. Furthermore, since the protective film-forming composition does not dissolve the resist film or form an intermix layer, the resist shape after development is not at all changed. The protective film has the additional effect of absorbing OOB light having a wavelength of 140 to 300 nm emitted by the EUV laser, thereby preventing the resist film from becoming sensitive to the OOB light. Although the polymer in the protective film-forming composition has a hexafluoroalcohol group having EUV-absorbable fluorine atoms as an alkali-soluble group, it has an aromatic group having a high proportion of EUV-unabsorbable carbon atoms at the same time. For this reason, a lowering of sensitivity due to absorption of fluorine atoms is minimized. The inclusion of a hexafluoroalcohol group eliminates any damages to the photoresist film, prevents formation of any intermixing layer between the protective film and the photoresist film, and minimizes a film thickness loss of the resist pattern after development.
DESCRIPTION OF PREFERRED EMBODIMENTS
The terms “a” and “an” herein do not denote a limitation of quantity, but rather denote the presence of at least one of the referenced item. “Optional” or “optionally” means that the subsequently described event or circumstance may or may not occur, and that the description includes instances where the event occurs and instances where it does not. As used herein, the notation (Cn-Cm) means a group containing from n to m carbon atoms per group.
The abbreviations and acronyms have the following meaning.
Mw: weight average molecular weight
Mn: number average molecular weight
Mw/Mn: molecular weight distribution or dispersity
GPC: gel permeation chromatography
PEB: post-exposure baking
PAG: photoacid generator
LER: line edge roughness
LWR: line width roughness
Protective Film-Forming Composition
The resist protective film-forming composition comprises as a base resin a polymer comprising recurring units (p) derived from at least one hydrocarbon monomer selected from among a styrene, indene, benzofuran and benzothiophene having 1,1,1,3,3,3-hexafluoro-2-propanol for alkaline solubility. The recurring units (p) are represented by the following general formula.




Herein R1 is hydrogen, hydroxyl, a straight, branched or cyclic C1-C10 alkyl group, alkoxy group, acyloxy group, cyano group, nitro group, amino group or halogen atom, m is 1 or 2, R2 and R3 each are hydrogen, or R2 and R3, taken together, may be methylene, —O— or —S— to form a ring.

The inclusion of 1,1,1,3,3,3-hexafluoro-2-propanol group improves the solubility of a polymer in ether solvents which cause no damages to the photoresist film. Suitable monomers from which the recurring units (p) are derived include styrene derivatives, indene derivatives (see JP-A 2003-096007), benzofuran derivatives, and benzothiophene derivatives, as exemplified below.







The 1,1,1,3,3,3-hexafluoro-2-propanol (HFA) group has the drawback that the sensitivity of a resist film is reduced due to the high absorption of EUV by fluorine atoms. To mitigate the drawback, preferably recurring units having a HFA group are derived from styrene or indene having little absorption to EUV, or copolymerized with a monomer having an aromatic group containing more hydrocarbon. Suitable recurring units resulting from copolymerization of a monomer having a hydrocarbon-rich aromatic group include recurring units (q1) to (q4) derived from a monomer selected from among a styrene, vinylnaphthalene, indene, benzofuran, benzothiophene, stilbene, styrylnaphthalene, and dinaphthylethylene, as represented by the general formula (1).




Herein R1, R2, R3, and m are as defined above. R4 to R8 are each independently hydrogen, hydroxyl, a straight, branched or cyclic C1-C10 alkyl group, alkoxy group, acyloxy group, C2-C6 alkenyl group, C6-C10 aryl group, cyano group, nitro group, amino group, trifluoromethyl group, ester group (—OCOR0 wherein R0 is C1-C6 alkyl), or halogen atom. X1 is methylene, —O— or —S—. X2 and X3 each are phenylene or naphthylene, n is an integer of 1 to 5, 0.1≦p<1.0, 0≦q1≦0.9, 0≦q2≦0.9, 0≦q3≦0.9, 0≦q4≦0.9, and 0<q1+q2+q3+q4≦0.9.

Examples of the monomer from which recurring units (q1) are derived are shown below.










Examples of the monomer from which recurring units (q2) are derived are shown below.










Examples of the monomer from which recurring units (q3) are derived are shown below.










Examples of the monomer from which recurring units (q4) are derived are shown below.







While the copolymer for the protective film is characterized by comprising recurring units (p) and (q1) to (q4), recurring units (r) having a carboxyl or sulfo group may be copolymerized therein for improving the alkaline solubility of the protective film, as described in JP-A 2008-065304.
Although recurring units (p) derived from at least one monomer selected from among a styrene, indene, benzofuran and benzothiophene having a 1,1,1,3,3,3-hexafluoro-2-propanol group (simply, hexafluoroalcohol group) may be incorporated in a molar fraction of 1 (p=1), it is preferred that the recurring units (p) be copolymerized with recurring units (q1) to (q4) of other monomers and recurring units (r) having a carboxyl or sulfo group in a copolymerization ratio in the range:

    0.1≦p<1.0, 0≦q1≦0.9, 0≦q2≦0.9, 0≦q3≦0.9, 0≦q4≦0.9, 0<q1+q2+q3+q4≦0.9, and 0≦r≦0.6;
    preferably 0.2≦p<1.0, 0≦q1≦0.8, 0≦q2≦0.8, 0≦q3≦0.8, 0≦q4≦0.8, 0<q1+q2+q3+q4≦0.8, and 0≦r≦0.5; and
    more preferably 0.3≦p<1.0, 0≦q1≦0.7, 0≦q2≦0.7, 0≦q3≦0.7, 0≦q4≦0.7, 0<q1+q2+q3+q4≦0.7, and 0≦r≦0.4.


The polymer comprising recurring units (p) derived from a monomer selected from a styrene, indene, benzofuran and benzothiophene having 1,1,1,3,3,3-hexafluoro-2-propanol should preferably have a weight average molecular weight (Mw) in the range of 1,000 to 10,000, as measured by GPC versus polystyrene standards. A polymer with a Mw in excess of 10,000 may be less soluble in solvents and alkaline developers. A polymer with a Mw of less than 1,000 may allow for intermixing with the resist film, leading to a film thickness loss of the resist pattern after development.
The polymer for the protective film is generally synthesized by radical copolymerization initiated with such a radical as 2,2′-azobisisobutyronitrile (AIBN) or ion polymerization (anionic polymerization) in the presence of an alkyl lithium or similar catalyst. Such polymerization may be carried out by the standard procedure.
Suitable radical polymerization initiators include, but are not limited to, azo compounds such as

    2,2′-azobis(4-methoxy-2,4-dimethylvaleronitrile),
    2,2′-azobis(2,4-dimethylvaleronitrile),
    2,2′-azobisisobutyronitrile (AIBN),
    2,2′-azobis(2,4,4-trimethylpentane),

peroxides such as tert-butyl peroxypivalate, lauroyl peroxide, benzoyl peroxide, and tert-butyl peroxylaurate. Suitable water-soluble initiators are persulfates such as potassium persulfate. Also useful are redox initiators which are obtained by combining a peroxide such as potassium persulfate or hydrogen peroxide with a reducing agent such as sodium sulfite. The amount of the initiator used may vary with its type, polymerization conditions or the like. Typically the initiator is used in an amount of 0.001 to 5%, preferably 0.01 to 2% by weight based on the total weight of monomers.



For the polymerization reaction, a solvent may be used. Any solvents may be used as long as they do not retard polymerization reaction. Suitable solvents include esters such as ethyl acetate and n-butyl acetate, ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, aliphatic or aromatic hydrocarbons such as toluene, xylene and cyclohexane, alcohols such as isopropyl alcohol and ethylene glycol monomethyl ether, and ether solvents such as diethyl ether, dioxane and tetrahydrofuran. These solvents may be used alone or in admixture. A well-known molecular weight modifier such as dodecyl mercaptan may be used together.
For the polymerization reaction, the reaction temperature may vary with the type of initiator or the boiling point of solvent. The temperature is typically 20 to 200° C., preferably 50 to 140° C. The reactor used herein is not particularly limited.
From the polymer solution or dispersion thus obtained, the organic solvent or water as the reaction medium may be removed by any well-known means, for example, by reprecipitation and filtration, or heat distillation in vacuum.
The protective film-forming composition is generally formulated by dissolving the copolymer in a solvent. The solvent used herein is not particularly limited as long as it does not dissolve the photoresist film. Examples of the solvent in which the resist film can be dissolved include ketones such as cyclohexanone and methyl-2-n-amyl ketone, alcohols such as 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, and 1-ethoxy-2-propanol; ethers such as propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, and diethylene glycol dimethyl ether; and 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. These solvents should not be used herein.
Examples of the solvent which does not dissolve the photoresist film and which can be preferably used herein include ether solvents such as diisopropyl ether, diisobutyl ether, diisopentyl ether, di-n-pentyl ether, methyl cyclopentyl ether, methyl cyclohexyl ether, di-n-butyl ether, di-sec-butyl ether, diisopentyl ether, di-sec-pentyl ether, di-tert-amyl ether, and di-n-hexyl ether.
Mixtures of the ether solvents with higher alcohols of 4 or more carbon atoms are also useful. Suitable higher alcohols of 4 or more carbon atoms include 1-butyl alcohol, 2-butyl alcohol, isobutyl alcohol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, tert-amyl alcohol, neopentyl alcohol, 2-methyl-1-butanol, 3-methyl-1-butanol, 3-methyl-3-pentanol, cyclopentanol, 1-hexanol, 2-hexanol, 3-hexanol, 2,3-dimethyl-2-butanol, 3,3-dimethyl-1-butanol, 3,3-dimethyl-2-butanol, 2-ethyl-1-butanol, 2-methyl-1-pentanol, 2-methyl-2-pentanol, 2-methyl-3-pentanol, 3-methyl-1-pentanol, 3-methyl-2-pentanol, 3-methyl-3-pentanol, 4-methyl-1-pentanol, 4-methyl-2-pentanol, 4-methyl-3-pentanol, cyclopentanol, and cyclohexanol.
With the higher alcohol of 4 or more carbon atoms, an aromatic solvent may be blended for preventing intermixing with the resist film. Suitable aromatic solvents include toluene, xylene, mesitylene, ethylbenzene, propylbenzene, butylbenzene, tert-butylbenzene, and anisole.
Preferably the ether solvent accounts for at least 50% by weight, more preferably at least 60% by weight based on the total weight of the solvent mixture.
The solvent (or solvent mixture) is preferably used in an amount of 100 to 30,000 parts, more preferably 200 to 20,000 parts by weight per 100 parts by weight of the base resin.
An acid generator may be added to the protective film-forming composition. Typical of the acid generator used herein is a compound capable of generating an acid in response to actinic light or radiation, known as photoacid generator (PAG). The PAG is any compound capable of generating an acid upon exposure to high-energy radiation. Suitable PAGs include sulfonium salts, iodonium salts, sulfonyldiazomethane, N-sulfonyloxyimide, and oxime-O-sulfonate acid generators. The acid generators may be used alone or in admixture of two or more. Exemplary acid generators are described in U.S. Pat. No. 7,537,880 (JP-A 2008-111103, paragraphs [0122] to [0142]). The addition of PAG to the protective film-forming composition is effective for minimizing bridge defects between resist pattern features after development.
The PAG is preferably used in an amount of 0.1 to 10 parts, more preferably 1 to 5 parts by weight per 100 parts by weight of the base resin.
An amine quencher may also be added to the protective film-forming composition. Exemplary amine quenchers are described in JP-A 2008-111103, paragraphs [0146] to [0164], for example. The addition of the amine quencher is effective for rendering the resist pattern after development more rectangular. A combination of an acid generator with an amine quencher is effective for reducing the LWR of the resist pattern. The amine quencher is preferably used in an amount of 0.01 to 10 parts, more preferably 0.02 to 8 parts by weight per 100 parts by weight of the base resin.
A surfactant may be added to the protective film-forming composition. Exemplary surfactants are described in JP-A 2008-111103, paragraphs [0165] to [0166]. The surfactant is preferably used in an amount of 0.0001 to 10 parts, more preferably 0.001 to 5 parts by weight per 100 parts by weight of the base resin.
Resist Composition
The photoresist composition used in the pattern forming process of the invention is typically a chemically amplified positive resist composition. The resist composition used herein comprises a polymer comprising recurring units (a1) and/or (a2) having a carboxyl group and phenolic hydroxyl group whose hydrogen is substituted by an acid labile group, respectively, as represented by the general formula (2).




In formula (2), R9 and R11 are each independently hydrogen or methyl. R10 and R12 each are an acid labile group. Y1 is a single bond, a C1-C12 linking group having at least one ester, lactone ring, phenylene or naphthylene moiety, a phenylene group or a naphthylene group. Y2 is a single bond, an ester group or an amide group, 0≦a1≦0.9, 0≦a2≦a2≦0.9, and 0<a1+a2<1.0.

Of the recurring units in the polymer serving as base resin in the resist composition, the recurring units (a1) having an acid labile group in formula (2) are recurring units having a carboxyl group, typically (meth)acrylate, in which the hydrogen of its hydroxyl moiety is substituted by an acid labile group. Suitable monomers from which the recurring units (a1) are derived are illustrated below.













Herein R9 and R10 are as defined above.

The recurring units (a2) having an acid labile group in formula (2) are recurring units having a phenolic hydroxyl group, typically hydroxystyrene or hydroxyphenyl(meth)acrylate, in which the hydrogen of its hydroxyl moiety is substituted by an acid labile group. Suitable monomers from which the recurring units (a2) are derived are illustrated below.




Herein R11 and R12 are as defined above.

The acid labile groups represented by R10 and R12 in formula (2) may be selected from a variety of such groups. The acid labile groups may be the same or different and preferably include groups of the following formulae (A-1) to (A-3).




In formula (A-1), R30 is a tertiary alkyl group of 4 to 20 carbon atoms, preferably 4 to 15 carbon atoms, a trialkylsilyl group in which each alkyl moiety has 1 to 6 carbon atoms, an oxoalkyl group of 4 to 20 carbon atoms, or a group of formula (A-3). Exemplary tertiary alkyl groups are tert-butyl, tert-amyl, 1,1-diethylpropyl, 1-ethylcyclopentyl, 1-butylcyclopentyl, 1-ethylcyclohexyl, 1-butylcyclohexyl, 1-ethyl-2-cyclopentenyl, 1-ethyl-2-cyclohexenyl, and 2-methyl-2-adamantyl. Exemplary trialkylsilyl groups are trimethylsilyl, triethylsilyl, and dimethyl-tert-butylsilyl. Exemplary oxoalkyl groups are 3-oxocyclohexyl, 4-methyl-2-oxooxan-4-yl, and 5-methyl-2-oxooxolan-5-yl. Letter k is an integer of 0 to 6.
In formula (A-2), R31 and R32 are hydrogen or straight, branched or cyclic alkyl groups of 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms. Exemplary alkyl groups include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, cyclopentyl, cyclohexyl, 2-ethylhexyl, and n-octyl. R33 is a monovalent hydrocarbon group of 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms, which may contain a heteroatom such as oxygen, examples of which include straight, branched or cyclic alkyl groups and substituted forms of such alkyl groups in which some hydrogen atoms are replaced by hydroxyl, alkoxy, oxo, amino, alkylamino or the like. Illustrative examples of the substituted alkyl groups are shown below.




A pair of R31 and R32, R31 and R33, or R32 and R33 may bond together to form a ring with the carbon and oxygen atoms to which they are attached. Each of R31, R32 and R33 is a straight or branched alkylene group of 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms when they form a ring, while the ring preferably has 3 to 10 carbon atoms, more preferably 4 to 10 carbon atoms.
Examples of the acid labile groups of formula (A-1) include tert-butoxycarbonyl, tert-butoxycarbonylmethyl, tert-amyloxycarbonyl, tert-amyloxycarbonylmethyl,

    1,1-diethylpropyloxycarbonyl,
    1,1-diethylpropyloxycarbonylmethyl,
    1-ethylcyclopentyloxycarbonyl,
    1-ethylcyclopentyloxycarbonylmethyl,
    1-ethyl-2-cyclopentenyloxycarbonyl,
    1-ethyl-2-cyclopentenyloxycarbonylmethyl,
    1-ethoxyethoxycarbonylmethyl,
    2-tetrahydropyranyloxycarbonylmethyl, and
    2-tetrahydrofuranyloxycarbonylmethyl groups.


Also included are substituent groups having the formulae (A-1)-1 to (A-1)-10.







Herein R37 is each independently a straight, branched or cyclic C1-C10 alkyl group or C6-C20 aryl group. R38 is hydrogen or a straight, branched or cyclic C1-C10 alkyl group. R39 is each independently a straight, branched or cyclic C2-C10 alkyl group or C6-C20 aryl group. The subscript k is an integer of 0 to 6.
Of the acid labile groups of formula (A-2), the straight and branched ones are exemplified by the following groups having formulae (A-2)-1 to (A-2)-69.






















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




Herein R40 and R41 each are hydrogen or a straight, branched or cyclic C1-C8 alkyl group, or R40 and R41, taken together, may form a ring with the carbon atom to which they are attached, and R40 and R41 are straight or branched C1-C8 alkylene groups when they form a ring. R42 is a straight, branched or cyclic C1-C10 alkylene group. Each of b1 and d1 is 0 or an integer of 1 to 10, preferably 0 or an integer of 1 to 5, and c1 is an integer of 1 to 7. “A” is a (c1+1)-valent aliphatic or alicyclic saturated hydrocarbon group, aromatic hydrocarbon group or heterocyclic group having 1 to 50 carbon atoms, which may be separated by a heteroatom or in which some hydrogen atoms attached to carbon atoms may be substituted by hydroxyl, carboxyl, carbonyl radicals 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 contain a heteroatom or in which some hydrogen atoms attached to carbon atoms may be substituted by hydroxyl, carboxyl, acyl radicals or halogen atoms. The subscript c1 is preferably an integer of 1 to 3.
The crosslinking acetal groups of formulae (A-2a) and (A-2b) are exemplified by the following formulae (A-2)-70 through (A-2)-77.




In formula (A-3), R34, R35 and R36 each are a monovalent hydrocarbon group, typically a straight, branched or cyclic C1-C20 alkyl group, straight, branched or cyclic C2-C20 alkenyl group or aryl group, which may contain a heteroatom such as oxygen, sulfur, nitrogen or fluorine. A pair of R34 and R35, R34 and R36, or R35 and R36 may bond together to form a C3-C20 aliphatic ring with the carbon atom to which they are attached.
Exemplary tertiary alkyl groups of formula (A-3) include tert-butyl, triethylcarbyl, 1-ethylnorbornyl, 1-methylcyclohexyl, 1-ethylcyclopentyl, 2-(2-methyl)adamantyl, 2-(2-ethyl)adamantyl, and tert-amyl.
Other exemplary tertiary alkyl groups include those of the following formulae (A-3)-1 to (A-3)-18.










Herein R43 is each independently a straight, branched or cyclic C1-C8 alkyl group or C6-C20 aryl group, typically phenyl, R44 and R46 each are hydrogen or a straight, branched or cyclic C1-C20 alkyl group, and R45 is a C6-C20 aryl group, typically phenyl.
The polymer may be crosslinked within the molecule or between molecules with groups having R47 which is a di- or multi-valent alkylene or arylene group, as shown by the following formulae (A-3)-19 and (A-3)-20.




Herein R43 is as defined above, R47 is a straight, branched or cyclic C1-C20 alkylene group or arylene group, typically phenylene, which may contain a heteroatom such as oxygen, sulfur or nitrogen, and e1 is an integer of 1 to 3.
Of acid labile groups of formula (A-3), recurring units of (meth)acrylate having an exo-form structure represented by the formula (A-3)-21 are preferred as the recurring unit (a1).




Herein, R9 and a1 are as defined above; Rc3 is a straight, branched or cyclic C1-C8 alkyl group or an optionally substituted C6-C20 aryl group; Rc4 to Rc9, Rc12 and Rc13 are each independently hydrogen or a monovalent C1-C15 hydrocarbon group which may contain a heteroatom; and Rc10 and Rc13 are hydrogen or a monovalent C1-C15 hydrocarbon group which may contain a heteroatom. Alternatively, a pair of Rc4 and Rc5, Rc6 and Rc8, Rc6 and Rc9, Rc7 and Rc9, Rc7 and Rc13, Rc8 and Rc12, Rc10 and Rc11, or Rc11 and Rc12, taken together, may form a ring, and in that event, each ring-forming Rc is a divalent C1-C15 hydrocarbon group which may contain a heteroatom. Also, a pair of Rc4 and Rc13, Rc10 and Rc13, or Rc6 and Rc8 which are attached to vicinal carbon atoms may bond together directly to form a double bond. The formula also represents an enantiomer.

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







Also included in the acid labile groups of formula (A-3) are acid labile groups of (meth)acrylate having furandiyl, tetrahydrofurandiyl or oxanorbornanediyl in recurring units (a1) represented by the following formula (A-3)-22.




Herein, R9 and a1 are as defined above; Rc14 and Rc15 are each independently a monovalent, straight, branched or cyclic C1-C10 hydrocarbon group, or Rc14 and Rc15, taken together, may form an aliphatic hydrocarbon ring with the carbon atom to which they are attached. Rc16 is a divalent group selected from furandiyl, tetrahydrofurandiyl and oxanorbornanediyl. Rc17 is hydrogen or a monovalent, straight, branched or cyclic C1-C10 hydrocarbon group which may contain a heteroatom.

Examples of the monomers from which the recurring units substituted with acid labile groups having furandiyl, tetrahydrofurandiyl and oxanorbornanediyl are derived are shown below. Note that Me is methyl and Ac is acetyl.






















Also included in the acid labile group R10 in recurring units (a1) are groups having the general formula (A-3)-23.




Herein, R23-1 is hydrogen, a C1-C4 alkyl, alkoxy, alkanoyl or alkoxycarbonyl group, C6-C10 aryl group, halogen atom or cyano group, and m23 is an integer of 1 to 4.

Examples of the monomer from which the recurring units (a1) having an acid labile group of formula (A-3)-23 substituted thereon are derived are shown below.







Also included in the acid labile group R10 in recurring units (a1) are groups having the general formula (A-3)-24.




Herein, R24-1 and R24-2 each are hydrogen, a C1-C4 alkyl, alkoxy, alkanoyl or alkoxycarbonyl group, hydroxy group, C6-C10 aryl group, halogen atom or cyano group. R is hydrogen, a straight, branched or cyclic C1-C12 alkyl group, C2-C12 alkenyl group, C2-C12 alkynyl, or C6-C10 aryl group, which may have an oxygen or sulfur atom. R24-3, R24-4, R24-5 and R24-6 each are hydrogen, or a pair of R24-3 and R24-4, R24-4 and R24-5, or R24-5 and R24-6 may bond together to form a benzene ring. The subscripts m24 and n24 each are an integer of 1 to 4.

Examples of the monomer from which the recurring units (a1) having an acid labile group of formula (A-3)-24 substituted thereon are derived are shown below.

























Also included in the acid labile group R10 in recurring units (a1) are groups having the general formula (A-3)-25.




Herein, R25-1 is each independently hydrogen or a straight, branched or cyclic C1-C6 alkyl group; when m25 is not less than 2, groups R25-2 may bond together to form a C2-C8 non-aromatic ring. The circle stands for a link selected from ethylene, propylene, butylene and pentylene with the carbon atoms CA and CB. R25-2 is a C1-C4 alkyl group, alkoxy group, alkanoyl group, alkoxycarbonyl group, hydroxyl group, nitro group, C6-C10 aryl group, halogen atom, or cyano group. R has the same meaning as R in formula (A-3)-24. When the circle stands for ethylene or propylene, it is excluded that R25-1 be hydrogen. The subscripts m25 and n25 each are an integer of 1 to 4.

Examples of the monomer from which the recurring units (a1) having an acid labile group of formula (A-3)-25 substituted thereon are derived are shown below.








































Also included in the acid labile group R10 in recurring units (a1) are groups having the general formula (A-3)-26.




Herein, R26-1 and R26-2 each are hydrogen, a C1-C4 alkyl group, alkoxy group, alkanoyl group, alkoxycarbonyl group, hydroxyl group, nitro group, C6-C10 aryl group, halogen atom, or cyano group. R has the same meaning as R in formula (A-3)-24. The subscripts m26 and n26 each are an integer of 1 to 4.

Examples of the monomer from which the recurring units (a1) having an acid labile group of formula (A-3)-26 substituted thereon are derived are shown below.



















Also included in the acid labile group R10 in recurring units (a1) are groups having the general formula (A-3)-27.




Herein, R27-1 and R27-2 each are hydrogen, a C2-C4 alkyl group, alkoxy group, alkanoyl group, alkoxycarbonyl group, hydroxyl group, C6-C10 aryl group, halogen atom, or cyano group. R has the same meaning as R in formula (A-3)-24. J is methylene, ethylene, vinylene, or —CH2—S—. The subscripts m27 and n27 each are an integer of 1 to 4.

Examples of the monomer from which the recurring units (a1) having an acid labile group of formula (A-3)-27 substituted thereon are derived are shown below.

























Also included in the acid labile group R10 in recurring units (a1) are groups having the general formula (A-3)-28.




Herein, R28-1 and R28-2 each are hydrogen, a C1-C4 alkyl group, alkoxy group, alkanoyl group, alkoxycarbonyl group, hydroxyl group, C6-C10 aryl group, halogen atom, or cyano group. R has the same meaning as R in formula (A-3)-24. K is carbonyl, ether, sulfide, —S(═O)— or —S(═O)2—. The subscripts m28 and n28 each are an integer of 1 to 4.

Examples of the monomer from which the recurring units (a1) having an acid labile group of formula (A-3)-28 substituted thereon are derived are shown below.





































The polymer in the resist composition should preferably have further copolymerized therein recurring units of at least one type selected from recurring units (b1) to (b3) of sulfonium salt as represented by the general formula (3). A resist composition based on such a polymer having an acid generator bound to its backbone has the advantage that it forms a pattern with minimized edge roughness (LWR) after development.




Herein R020, R024 and R028 each are hydrogen or methyl. R021 is a single bond, phenylene, —O—R033—, or —C(═O)—Y—R033— wherein Y is oxygen or NH and R033 is a straight, branched or cyclic C1-C6 alkylene group, alkenylene group or phenylene group, which may contain a carbonyl (—CO—), ester (—COO—), ether (—O—) or hydroxyl moiety. R022, R023, R025, R026, R027, R029, R030, and R031 are each independently a straight, branched or cyclic C1-C12 alkyl group which may contain a carbonyl, ester or ether moiety, or a C6-C12 aryl group, C7-C20 aralkyl group, or thiophenyl group.

    A1 is a single bond, -A0-C(═O)—O—, -A0-O— or -A0-O—C(═O)—, wherein A0 is a straight, branched or cyclic C1-C12 alkylene group which may contain a carbonyl, ester or ether moiety.
    A2 is hydrogen, CF3 or carbonyl group. Z1 is a single bond, methylene, ethylene, phenylene, fluorinated phenylene, —O—R032—, or —C(═O)—Z2—R032— wherein Z2 is oxygen or NH and R032 is a straight, branched or cyclic C1-C6 alkylene, phenylene, fluorinated phenylene, trifluoromethyl-substituted phenylene or alkenylene group, which may contain a carbonyl, ester, ether or hydroxyl moiety. M− is a non-nucleophilic counter ion, and b1, b2 and b3 are in the range: 0≦b1≦0.5, 0≦b2≦0.5, 0≦b3≦0.5, and 0≦b1+b2+b3≦0.5.


Examples of the monomer from which recurring units (b1) of sulfonium salt in formula (3) are derived are shown below.
















Herein, M− is a non-nucleophilic counter ion.

Examples of the non-nucleophilic counter ion M− include halide ions such as chloride and bromide ions; fluoroalkylsulfonate ions such as triflate, 1,1,1-trifluoroethanesulfonate, and nonafluorobutanesulfonate; arylsulfonate ions such as tosylate, benzenesulfonate, 4-fluorobenzenesulfonate, and 1,2,3,4,5-pentafluorobenzenesulfonate; alkylsulfonate ions such as mesylate and butanesulfonate; imidates such as bis(trifluoromethylsulfonyl)imide, bis(perfluoroethylsulfonyl)imide and bis(perfluorobutylsulfonyl)imide; and methidates such as tris(trifluoromethylsulfonyl)methide and tris(perfluoroethylsulfonyl)methide.
Also included are sulfonates having fluorine substituted at α-position as represented by the general formula (K-1) and sulfonates having fluorine substituted at α- and β-positions as represented by of the general formula (K-2).




In formula (K-1), R102 is hydrogen, or a straight, branched or cyclic C1-C20 alkyl group, C2-C20 alkenyl group, or C6-C20 aryl group, which may have an ether, ester, carbonyl moiety, lactone ring, or fluorine atom. In formula (K-2), R103 is hydrogen, or a straight, branched or cyclic C1-C30 alkyl or acyl group, C2-C20 alkenyl group, or C6-C20 aryl or aryloxy group, which may have an ether, ester, carbonyl moiety or lactone ring.

Examples of the monomer from which recurring units (b2) of sulfonium salt in formula (3) are derived are shown below.


































Examples of the monomer from which recurring units (b3) of sulfonium salt in formula (3) are derived are shown below.
















While the base resin in the resist composition used in the pattern forming process of the invention is a polymer characterized by comprising recurring units (a1) having a carboxyl group substituted with an acid labile group and/or recurring units (a2) having a phenolic hydroxyl group substituted with an acid labile group, and optionally recurring units (b1), (b2) or (b3) having an acid generator in the form of a sulfonium salt of sulfonic acid bound to the backbone, in the copolymerized form, it may have further copolymerized therein recurring units (c) having a phenolic hydroxyl group as an adhesive group.
Examples of the monomers from which the recurring units (c) having a phenolic hydroxyl group are derived are shown below.























































Other adhesive groups are also acceptable. For example, recurring units (d) having an adhesive group selected from among a hydroxyl group (other than phenolic hydroxyl), carboxyl group, lactone ring, carbonate group, thiocarbonate group, carbonyl group, cyclic acetal group, ether group, ester group, sulfonic acid ester group, cyano group, amide group, and —O—C(═O)-G- wherein G is sulfur or NH may be copolymerized.
Examples of the monomers from which the recurring units (d) are derived are shown below.






































































On use of a monomer having a hydroxyl group, prior to polymerization, the hydroxyl group may be replaced by an acetal group which is readily deprotected with an acid, such as ethoxyethoxy, and polymerization be followed by deprotection with weak acid and water. Alternatively, the hydroxyl group may be replaced by an acetyl, formyl, pivaloyl or similar group, and polymerization be followed by alkaline hydrolysis.
In a preferred embodiment, the polymer may have further copolymerized therein recurring units (e) of indene, benzofuran, benzothiophene, acenaphthylene, chromone, coumarin, and norbornadiene, or derivatives thereof, examples of which are shown below.




Besides the above recurring units, additional recurring units (f) may be copolymerized in the polymer, which include recurring units derived from styrene, vinylnaphthalene, vinylanthracene, vinylpyrene, methyleneindene, and the like.
In the copolymer for resist use, recurring units (a1), (a2), (b1), (b2), (b3), (c), (d), (e) and (f) may be incorporated in the following molar fraction:

    0≦a1<1.0, 0≦a2<1.0, 0<a1+a2<1.0,
    0≦b1≦0.5, 0≦b2≦0.5, 0≦b3≦0.5, 0<b1+b2+b3≦0.5,
    0≦c<1.0, 0≦d<1.0, 0≦e<1.0, 0≦f<1.0,

and 0.7≦a1+a2+b1+b2+b3+c+d≦1.0,

    preferably 0≦a1≦0.8, 0≦a2≦0.8, 0.1≦a1+a2≦0.8,
    0≦b1≦0.5, 0≦b2≦0.5, 0≦b3≦0.5, 0.02≦b1+b2+b3≦0.5,
    0≦c≦0.8, 0≦d≦0.8, 0≦e≦0.5, 0≦f≦0.5,

and 0.8≦a1+a2+b1+b2+b3+c+d≦1.0,and more preferably 

    0≦a1≦0.7, 0≦a2≦0.7, 0.1≦a1+a2≦0.7,
    0≦b1≦0.4, 0≦b2≦0.4, 0≦b3≦0.4, 0.02≦b1+b2+b3≦0.4,
    0≦c≦0.7, 0≦d≦0.7, 0≦e≦0.4, 0≦f≦0.4,
    and 0.85≦a1+a2+b1+b2+b3+c+d≦1.0.


It is noted that a1+a2+b1+b2+b3+c+d+e+f=1.0.
The polymer may be synthesized by dissolving selected ones of monomers corresponding to units (a1), (a2), (b1), (b2) and (b3) and optionally units (c), (d), (e) and (f) in an organic solvent, adding a radical polymerization initiator thereto, and effecting heat polymerization to form a copolymeric high-molecular-weight compound.
Examples of suitable organic solvents used for polymerization include toluene, benzene, tetrahydrofuran, diethyl ether and dioxane. Suitable polymerization initiators 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 2 to 100 hours, preferably 5 to 20 hours.
When hydroxystyrene or hydroxyvinylnaphthalene is copolymerized, an alternative method is possible. Specifically, acetoxystyrene or acetoxyvinylnaphthalene is used instead of hydroxystyrene or hydroxyvinylnaphthalene, and after polymerization, the acetoxy group is deprotected by alkaline hydrolysis as mentioned above, for thereby converting the relevant units to hydroxystyrene or hydroxyvinylnaphthalene units. For alkaline hydrolysis, a base such as aqueous ammonia or triethylamine may be used. The reaction temperature is −20° C. to 100° C., preferably 0° C. to 60° C., and the reaction time is 0.2 to 100 hours, preferably 0.5 to 20 hours.
The polymer serving as the base resin in the resist composition should have a weight average molecular weight (Mw) in the range of 1,000 to 500,000, and preferably 2,000 to 30,000, as measured by GPC versus polystyrene standards using tetrahydrofuran solvent. A polymer with a Mw of at least 1,000 may be fully heat resistant. A polymer with a Mw of up to 500,000 may not lose alkaline solubility or give rise to a footing phenomenon after pattern formation.
If a multi-component 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 polymer should preferably have a narrow dispersity (Mw/Mn) of 1.0 to 2.0, especially 1.0 to 1.5, in order to provide a resist composition suitable for micropatterning to a small feature size.
The polymer defined herein is suitable as a base resin in a positive resist composition. The positive resist composition is formulated by using the polymer as the base resin and combining it with an organic solvent, acid generator, dissolution regulator, basic compound, surfactant and the like in accordance with a particular purpose. This positive resist composition has a very high sensitivity because the dissolution rate in developer of the polymer in the exposed region is accelerated due to catalytic reaction. The resist film exhibits a high dissolution contrast and resolution, and has an exposure latitude, process adaptability, good pattern profile after exposure, better etching resistance, and minimal proximity bias due to restrained acid diffusion. Because of these advantages, the resist composition finds practical application and is best suited as the resist material for VLSI fabrication. Particularly when the acid generator is added to the resist composition so that it may be a chemically amplified positive one utilizing acid-catalyzed reaction, the composition becomes more useful due to a higher sensitivity and better properties.
Process
The lithography pattern forming process in a preferred embodiment involves at least the steps of forming a photoresist film on a substrate or wafer, forming a protective film thereon from the resist protective film-forming composition of the invention, exposure, and development in a developer.
First, a photoresist film is formed on a substrate. A typical film forming method is spin coating. If it is desirable to reduce the amount of the photoresist composition dispensed for spin coating, preferably the substrate is previously wetted with the resist solvent or a solvent miscible with the resist solvent before the resist composition is dispensed. See JP-A H09-246173, for example. The previous wetting assists in spreading of the photoresist composition solution over the substrate for thereby saving the amount of the photoresist composition dispensed for spin coating. The resist film preferably has a thickness of 10 to 500 nm, more preferably 20 to 300 nm.
Next, a resist protective film is formed on the photoresist film using the protective film-forming composition defined herein. A typical film forming method is spin coating. For spin coating of the protective film-forming composition, previous wetting as described for the photoresist film may be similarly utilized. That is, the surface of the photoresist film may be wetted before the protective film-forming composition is coated thereon. The resist protective film preferably has a thickness of 2 to 200 nm, more preferably 5 to 50 nm. The means of wetting the surface of the photoresist film include spin coating and vapor priming, with the spin coating technique being often employed. The solvent used for wetting is preferably selected from ether solvents which do not dissolve the resist film, optionally in admixture with higher alcohols or fluorinated solvents.
The protective film should preferably have an alkaline dissolution rate of at least 3 nm/s, more preferably at least 5 nm/s.
Once the resist film is coated with the protective film, it is exposed patternwise to radiation. In the exposure step, radiation having a wavelength of 3 to 15 nm or electron beam may be used. The exposure environment may be vacuum for both EUV and EB. Exposure is followed by optional PEB and development.
In the development step, the wafer is immersed in an alkaline developer for 3 to 300 seconds. The alkaline developer is typically a 2.38 wt % aqueous solution of tetramethylammonium hydroxide (TMAH). An aqueous solution of tetrabutylammonium hydroxide may also be used instead of the TMAH solution. In the development step using an alkaline developer, preferably the photoresist film is developed to form a resist pattern, and the protective film on the photoresist film is stripped off at the same time. Then stripping of the protective film can be carried out without adding a stripper unit to the existing system.
In addition to the foregoing steps, any of etching, resist removal, cleaning and other steps may be carried out.


EXAMPLE
Examples of the invention are given below by way of illustration and not by way of limitation. It is noted that Mw and Mn are determined by GPC versus polystyrene standards using tetrahydrofuran solvent.
The following polymers were used as the polymer comprising recurring units (p) derived from a styrene, indene, benzofuran or benzothiophene monomer having 1,1,1,3,3,3-hexafluoro-2-propanol for the protective film.










Resist protective topcoat solutions TC-1 to 19 and Comparative-TC-1 to 4 were prepared by mixing the polymer with an additive and a solvent in accordance with the formulation of Table 1. In the case of Comparative-TC-2, Comparative Protective Polymer 1 did not dissolve in a mixture of 4-methyl-2-pentanol and diisopentyl ether.










TABLE 1






Base resin
Additive
Solvent



(pbw)
(pbw)
(pbw)







TC-1
Protective Polymer 1(10)
—
diisopentyl ether(700)


TC-2
Protective Polymer 2(10)
—
diisopentyl ether(700)


TC-3
Protective Polymer 3(10)
—
diisopentyl ether(700)


TC-4
Protective Polymer 4(10)
—
diisopentyl ether(700)


TC-5
Protective Polymer 5(10)
—
diisopentyl ether(700)


TC-6
Protective Polymer 6(10)
—
diisopentyl ether(700)


TC-7
Protective Polymer 7(10)
—
diisopentyl ether(600)





di-n-butyl ether(200)


TC-8
Protective Polymer 8(10)
—
diisopentyl ether(700)


TC-9
Protective Polymer 9(10)
—
di-n-hexyl ether(400)





di-n-butyl ether(300)


TC-10
Protective Polymer 10(10)
—
diisopentyl ether(500)





xylene(200)


TC-11
Protective Polymer 11(10)
—
diisopentyl ether(700)


TC-12
Protective Polymer 1(10)
—
diisopentyl ether(600)





4-methyl-2-pentanol





(200)


TC-13
Protective Polymer 1(10)
—
diisopentyl ether(600)





2-methyl-1-butanol(200)


TC-14
Protective Polymer 1(10)
—
diisopentyl ether(600)





3-methyl-3-pentanol





(200)


TC-15
Protective Polymer 1(10)
—
diisopentyl ether(600)





2-methyl-2-pentanol





(200)


TC-16
Protective Polymer 1(10)
—
diisopentyl ether(600)





2-methyl-3-pentanol





(200)


TC-17
Protective Polymer 1(10)
—
diisopentyl ether(600)





3-methyl-2-pentanol





(200)


TC-18
Protective Polymer 1(10)
tri-n-
diisopentyl ether(700)




octylamine





(0.01)



TC-19
Protective Polymer 1(10)
1-
diisopentyl ether(700)




aminopyrene





(0.01)



Com-
Comparative
—
4-methy1-2-


parative-
Protective Polymer 1 (10)

pentanol(1,000)


TC-1





Com-
Comparative
—
4-methyl-2-pentanol


parative-
Protective Polymer 1 (10)

(100)


TC-2


diisopentyl ether(500)


Com-
Protective Polymer 1(10)
—
4-methyl-2-


parative-


pentanol(1,000)


TC-3





Com-
Comparative
—
diisopentyl ether(700)


parative-
Protective Polymer 2 (10)




TC-4









The resist protective topcoat solutions TC-1 to 19 and Comparative-TC-1, 3, 4 were spin coated onto silicon substrates and baked at 100° C. for 60 seconds to form protective films (TC-1 to 19 and Comparative-TC-1, 3, 4) having a thickness of 30 nm.
The silicon substrates covered with the protective films were developed in a 2.38 wt % TMAH aqueous solution for 30 seconds. After development, the thickness of the protective films was measured. The results are shown in Table 2. It was confirmed that after development, all the protective films were dissolved away.










TABLE 2







Resist protective film
Film thickness after development (nm)









TC-1
0



TC-2
0



TC-3
0



TC-4
0



TC-5
0



TC-6
0



TC-7
0



TC-8
0



TC-9
0



TC-10
0



TC-11
0



TC-12
0



TC-13
0



TC-14
0



TC-15
0



TC-16
0



TC-17
0



TC-18
0



TC-19
0



Comparative-TC-1
0



Comparative-TC-3
0



Comparative-TC-4
0










Examples and Comparative Examples
EUV Test
A positive resist composition was prepared by using the polymer synthesized by conventional radical polymerization, dissolving the polymer and other components in a solvent as shown in Table 3, and filtering through a filter having a pore size of 0.2 μm.
A silicon substrate of 8 inch diameter was coated with a silicon-containing SOG film of 35 nm thick (SHB-A940, Shin-Etsu Chemical Co., Ltd.). The positive resist composition was coated on the silicon substrate and prebaked on a hot plate at 105° C. for 60 seconds to form a resist film of 50 nm thick. The protective film solution was spin coated onto the resist film and prebaked on a hot plate at 100° C. for 60 seconds to form a protective film of 30 nm thick. The wafer was exposed using an EUV micro-stepper (NA 0.3, quadrupole illumination). As a simulation of OOB light irradiation, the wafer was exposed over the entire surface in a dose of 1 mJ/cm2 by means of an ArF excimer laser scanner. This was followed by PEB on a hot plate at 95° C. for 60 seconds and puddle development in a 2.38 wt % TMAH aqueous solution for 30 seconds, yielding a positive pattern. It is noted that Comparative Example 4 omitted formation of a protective film on the resist film, and Comparative Example 5 omitted formation of a protective film on the resist film and the ArF exposure simulating OOB. The results are shown in Table 4.



















TABLE 3






Polymer
PAG
Quencher
Surfactant
Solvent



(pbw)
(pbw)
(pbw)
(pbw)
(pbw)







Resist
Resist
—
Quencher
FC-4430
PGMEA(1,000)


com-
Polymer 1

(0.85)
(0.001)
PGME(500)


position 
(100)



cyclohexanone


1




(3,000)


Resist
Resist
—
Quencher
FC-4430
PGMEA(1,000)


com-
Polymer 2

(0.85)
(0.001)
PGME(500)


position 
(100)



cyclohexanone


2




(3,000)


Resist
Resist
PAG 1
Quencher
FC-4430
PGMEA(4,000)


com-
Polymer 3
(10.0)
(0.85)
(0.001)



position
(100)






3





PGMEA: propylene glycol monomethyl ether acetate


PGME: propylene glycol monomethyl ether


FC-4430: fluorochemical surfactant by 3M-Sumitomo Co., Ltd.


















TABLE 4








Protective
Sensitivity
Pattern 





film
(mJ/cm2)
profile




















Ex-
1
Resist composition 1
TC-1
10.5
rectangular


ample
2
Resist composition 1
TC-2
11.5
rectangular



3
Resist composition 1
TC-3
10.5
rectangular



4
Resist composition 1
TC-4
10.3
rectangular



5
Resist composition 1
TC-5
10.4
rectangular



6
Resist composition 1
TC-6
10.2
rectangular



7
Resist composition 1
TC-7
10.3
rectangular



8
Resist composition 1
TC-8
10.9
rectangular



9
Resist composition 1
TC-9
10.4
rectangular



10
Resist composition 1
TC-10
10.7
rectangular



11
Resist composition 1
TC-11
10.9
rectangular



12
Resist composition 1
TC-12
10.9
rectangular



13
Resist composition 1
TC-13
10.9
rectangular



14
Resist composition 1
TC-14
10.9
rectangular



15
Resist composition 1
TC-15
10.9
rectangular



16
Resist composition 1
TC-16
10.3
rectangular



17
Resist composition 1
TC-17
10.5
rectangular



18
Resist composition 1
TC-18
10.9
rectangular



19
Resist composition 1
TC-19
10.9
rectangular



20
Resist composition 2
TC-1
10.4
rectangular



21
Resist composition 3
TC-1
10.4
rectangular


Com-
1
Resist composition 1
Comparative-
9.0
film 


parative


TC-1

thickness


Ex-




loss


ample
2
Resist composition 3
Comparative-
—
no film left





TC-1





3
Resist composition 3
Comparative-
—
no film left





TC-3





4
Resist composition 1
—
8.3
film 







thickness 







loss,







tapered



5
Resist composition 1
—
11.0
rectangular



6
Resist composition 1
Comparative-
12.0
rectangular





TC-4









Since the protective film-forming composition contains a large amount of ether solvent capable of preventing intermixing with the resist film, it causes few damages to the resist film and prevents intermixing between the resist film and the protective film. As a result, the resist pattern after development remains rectangular. Since the polymer comprising recurring units derived from a styrene, indene, benzofuran or benzothiophene monomer having 1,1,1,3,3,3-hexafluoro-2-propanol used in the protective film within the scope of the invention has a wide absorption band of wavelength 180 to 250 nm, a satisfactory OOB cutoff effect is exerted. In Comparative Example 1 where the protective polymer (Comparative-TC-1) was applied to a resist film based on acid labile group-substituted hydroxystyrene, the resist pattern after development showed a detrimental film thickness loss. In Comparative Example 6 where the resist protective film-forming composition (Comparative-TC-4) using a homopolymer of styrene having 1,1,1,3,3,3-hexafluoro-2-propanol was applied, the resist showed a drop of sensitivity due to the absorption of the protective film.
Japanese Patent Application No. 2012-202464 is incorporated herein by reference.
Although some preferred embodiments have been described, many modifications and variations may be made thereto in light of the above teachings. It is therefore to be understood that the invention may be practiced otherwise than as specifically described without departing from the scope of the appended claims.

## Claims

1. A resist protective film-forming composition which is used in a lithography pattern forming process comprising the steps of forming a photoresist layer on a wafer, forming a protective film thereon, exposure, and development,
said resist protective film-forming composition comprising a copolymer comprising recurring units (p) derived from at least one monomer selected from the group consisting of a styrene, indene, benzofuran and benzothiophene having 1,1,1,3,3,3-hexafluoro-2-propanol, and recurring units (q1), (q2), (q3) or (q4) derived from at least one monomer selected from the group consisting of a styrene, vinylnaphthalene, indene, benzofuran, benzothiophene, stilbene, styrylnaphthalene, and dinaphthylethylene, as represented by the general formula (1), as a base resin,





wherein R1 is hydrogen, hydroxyl, a straight, branched or cyclic C1-C10 alkyl, alkoxy, acyloxy, cyano, nitro, amino group or halogen atom, m is 1 or 2,
R2 and R3 each are hydrogen, or R2 and R3, taken together, may be methylene, —O— or —S— to form a ring,
R4 to R8 are each independently hydrogen, hydroxyl, a straight, branched or cyclic C1-C10 alkyl, alkoxy, acyloxy, C2-C6 alkenyl, C6-C10 aryl, cyano, nitro, amino, trifluoromethyl, ester group, or halogen atom,
X1 is methylene, —O— or —S—,
X2 and X3 each are phenylene or naphthylene,
n is an integer of 1 to 5, 0.1≦p<1.0, 0≦q1≦0.9, 0≦q2≦0.9, 0≦q3≦0.9, 0≦q4≦0.9, and 0<q1+q2+q3+q4≦0.9.

2. The protective film-forming composition of claim 1 which is soluble in an alkaline developer.

3. The protective film-forming composition of claim 1, further comprising an ether solvent selected from the group consisting of diisopropyl ether, diisobutyl ether, diisopentyl ether, di-n-pentyl ether, methyl cyclopentyl ether, methyl cyclohexyl ether, di-n-butyl ether, di-sec-butyl ether, diisopentyl ether, di-sec-pentyl ether, di-tert-amyl ether, and di-n-hexyl ether.

4. The protective film-forming composition of claim 3, further comprising an alcohol solvent in admixture with the ether solvent, said alcohol solvent being selected from the group consisting of 1-butyl alcohol, 2-butyl alcohol, isobutyl alcohol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, tert-amyl alcohol, neopentyl alcohol, 2-methyl-1-butanol, 3-methyl-1-butanol, 3-methyl-3-pentanol, cyclopentanol, 1-hexanol, 2-hexanol, 3-hexanol, 2,3-dimethyl-2-butanol, 3,3-dimethyl-1-butanol, 3,3-dimethyl-2-butanol, 2-ethyl-1-butanol, 2-methyl-1-pentanol, 2-methyl-2-pentanol, 2-methyl-3-pentanol, 3-methyl-1-pentanol, 3-methyl-2-pentanol, 3-methyl-3-pentanol, 4-methyl-1-pentanol, 4-methyl-2-pentanol, 4-methyl-3-pentanol, cyclopentanol, and cyclohexanol.

5. The protective film-forming composition of claim 1, further comprising a solvent containing at least 50% by weight of an ether solvent based on the total solvent weight, said ether solvent being selected from the group consisting of diisopropyl ether, diisobutyl ether, diisopentyl ether, di-n-pentyl ether, methyl cyclopentyl ether, methyl cyclohexyl ether, di-n-butyl ether, di-sec-butyl ether, diisopentyl ether, di-sec-pentyl ether, di-tert-amyl ether, and di-n-hexyl ether.

6. A lithography pattern forming process comprising the steps of forming a photoresist layer on a wafer, forming a protective film thereon, exposure, and development,
the protective film being formed from the resist protective film-forming composition of claim 1.

7. A pattern forming process comprising the steps of forming a photoresist layer on a wafer, forming a protective film thereon, and exposure in vacuum,
the protective film being formed from the resist protective film-forming composition of claim 1.

8. The process of claim 7 wherein the exposure step uses radiation having a wavelength of 3 to 15 nm or electron beam.

9. The process of claim 6, wherein the development step following exposure includes applying an alkaline developer to develop the photoresist layer and strip off the protective film simultaneously.

10. A pattern forming process comprising the steps of forming a photoresist layer on a wafer, forming a protective film thereon, and exposure in vacuum,
the protective film being formed from the resist protective film-forming composition of claim 1,
the photoresist layer being formed from a resist composition comprising a polymer comprising recurring units (a1) and/or (a2) having a carboxyl group and/or phenolic hydroxyl group whose hydrogen is substituted by an acid labile group, as represented by the general formula (2) and having a weight average molecular weight of 1,000 to 500,000, as a base resin,





wherein R9 and R11 each are hydrogen or methyl, R10 and R12 each are an acid labile group, Y1 is a single bond, a C1-C12 linking group having an ester, lactone ring, phenylene or naphthylene moiety, phenylene group or naphthylene group, Y2 is a single bond, ester or amide group, 0≦a1≦0.9, 0≦a2≦a2≦0.9, and 0<a1+a2<1.0.

11. The pattern forming process of claim 10 wherein the polymer in the resist composition has copolymerized with the recurring units (a1) and/or (a2), recurring units of at least one type selected from recurring units (b1) to (b3) of sulfonium salt, as represented by the general formula (3):




wherein R020, R024, and R028 each are hydrogen or methyl, R021 is a single bond, phenylene, —O—R033—, or —C(═O)—Y—R303—, Y is oxygen or NH, R033 is a straight, branched or cyclic C1-C6 alkylene group, alkenylene group or phenylene group, which may contain a carbonyl (—CO—), ester (—COO—), ether (—O—), or hydroxyl moiety, R022, R023, R025, R026, R027, R029, R030, and R031 are each independently a straight, branched or cyclic C1-C12 alkyl group which may contain a carbonyl, ester or ether moiety, a C6-C12 aryl group, a C7-C20 aralkyl group, or a thiophenyl group, A1 is a single bond, -A0-C(═O)—O—, -A0-O— or -A0-O—C(═O)—, A0 is a straight, branched or cyclic C1-C12 alkylene group which may contain a carbonyl, ester or ether moiety, A2 is hydrogen, CF3 or carbonyl group, Z1 is a single bond, methylene, ethylene, phenylene, fluorinated phenylene, —O—R032—, or —C(═O)—Z2—R032—, Z2 is oxygen or NH, R032 is a straight, branched or cyclic C1-C6 alkylene, phenylene, fluorinated phenylene, trifluoromethyl-ubstituted phenylene or alkenylene group, which may contain a carbonyl, ester, ether or hydroxyl moiety, M− is a non-nucleophilic counter ion, 0≦b1≦0.5, 0≦b2≦0.5, 0≦b3≦0.5, and 0<b1+b2+b3≦0.5.