KR20160069497A - Shrink material and pattern forming process - Google Patents

Abstract

The present invention provides a shrink material comprising a specific polymer and an anti-loss solvent. A resist film is formed by applying a resist composition including a base resin and an acid generating agent, on a substrate, the resist film is exposed, a negative resist pattern is formed by being developed in an organic solvent developer, a shrink material is applied onto the pattern, and the pattern is formed by reducing a size of a hole and/or a slit inside the pattern after removing an extra shrink material using an organic solvent.

Description

[0001] SHRINK MATERIAL AND PATTERN FORMING PROCESS [0002]

Cross-reference to related application

This standard application is filed at 35 U.S.C. Priority is claimed on patent applications Nos. 2014-248080 and 2015-077690, filed in Japan on December 8, 2014 and April 6, 2015, under §119 (a), the entire contents of which are incorporated herein by reference Incorporated herein by reference.

Technical field

The present invention relates to a shrink material for reducing the size of a feature in a resist pattern and a pattern forming method using the shrink material.

In recent years, efforts to reduce the pattern rule in order to meet the demand for high integration and operation speed of the LSI have been rapidly advancing, and photolithography has been used as a general purpose technology. Photolithography has inherent limitations in the resolution obtained by the wavelength of the light source. An example of a micropatterning approach that goes beyond the limits of resolution is the combination of ArF excimer laser immersion lithography and double patterning. A typical example of double patterning is to form the pattern by exposure, transfer the pattern to the hard mask on the substrate by etching, perform the second exposure at the half-pitch shifted position, and etch the hard mask Etch-litho-etch (LELE) process. This process has the problem of mismatch between two exposures or overlay errors. Another example of double patterning is a self-aligned double patterning (SADP) process that includes transferring a resist pattern to a hard mask, growing the film on the opposite side of the hard mask feature, and leaving the side walls of the film to double the pattern size. The SADP process requires only one exposure and alleviates the problem of overlay error. To simplify the process, a variant of the SADP process is also proposed, which forms a silicon oxide film on the surface of the resist pattern features after development rather than the sidewalls of the hardmask feature. Since the SADP process has succeeded in reducing the pitch of the line pattern in half, the pitch can be reduced to 1/4 by repeating the SADP process twice.

In addition to reducing the line pattern, it is also necessary to reduce the hole pattern. If the hole pattern is not reduced, the reduction on the entire chip is incomplete. By the known methods of the hole pattern is reduced and a method mozzarella Lax ^® (RELACS) described in Patent Document 1. In this method, after development, the resist pattern is coated with a water-soluble material containing a crosslinking agent, and the coating is baked to form a crosslinked layer on the resist surface to thicken the resist pattern to reduce the size of the hole pattern. Patent Document 2 discloses a shrink material comprising an amino-containing polymer or a polyamine, which binds to the surface of a resist by a neutralization reaction with a carboxyl group on the surface of the resist to thicken the resist film. Also, in Non-Patent Document 1, it has been proposed to reduce the hole pattern by using direct magnetic alignment (DSA) of a block copolymer.

Shrink by mozzarella Lax ^® method is the crosslinking agent has the activity as an acid catalyst in the resist, and if the acid diffusion unevenness is a problem, because non-uniform, the size of holes and then shrink. In the shrinking method based on neutralization and attachment of an amino polymer, since the pattern is thickened by directly reflecting the unevenness of the resist surface, the dimensional fluctuation of the resist pattern after development and the fluctuation of dimension after shrink is the same. The shrink process using the DSA action of the block copolymer has the advantage of including an increase in shrink amount and a minimum dimensional variation after shrink, except for some problems. When the so-called DSA is applied to holes of different sizes, shrinking can not be induced in holes having a size which causes contradictions in the arrangement of block copolymers. When the DSA is applied to the trench pattern, for example, shape distortion such as formation of a plurality of hole patterns becomes a problem.

There is a demand for a shrink material which can shrink the hole pattern without changing the shape of the resist pattern and can improve dimensional fluctuation and edge roughness (LWR) of the resist pattern after development.

Patent Document 1: JP-A H10-073927 (USP 6579657) Patent Document 2: JP-A 2008-275995 (US 20100119717) Patent Document 3: JP-A 2007-293294

Non-Patent Document 1: Proc. SPIE Vol. 8323 p83230W-1 (2012)

As discussed above, the resist pattern of the above crosslinking or neutralizing reaction-application method of mozzarella Lax ^® material of the intermediate-mounted does not cause a pattern modification, did not reduce a dimensional fluctuation of a resist pattern. Patent Document 3 proposes an alkaline aqueous solution type shrink material applied to a positive tone resist pattern produced by an alkali development. With respect to a shoe link with a narrow pitch of holes, such a shrink material has obtained sufficient shrinkage amount and has not been able to reduce the dimensional variation.

An object of the present invention is to provide a shrink material capable of shrinking a hole size while improving dimensional fluctuation upon application to a hole resist pattern after development; And a pattern forming method using the same.

In order to obtain a shrink material capable of effectively shrinking a resist pattern after development, the present inventors have found that a resist film based on a base resin having an acid labile group-substituted carboxyl group and an acid generator is formed and exposed to an organic solvent Thereby forming a negative tone resist pattern, applying a resist pattern to a shrink material containing a specific polymer and a solvent containing a dissipation-inhibiting solvent, firing the material, and removing the excess shrink material with an organic solvent, The size of the hole and / or the slit of the substrate can be shrunk in a controlled manner.

In one embodiment, the present invention provides a polymer comprising at least one repeating unit selected from units having the following general formula (1a) and (1b), and an anti-vanishing agent that prevents the resist pattern from being lost after development A shrink material comprising a solvent comprising:

<Formula 1a>

&Lt; EMI ID =

In the above formulas, A is a single bond or a C ₁ -C ₁₀ alkylene group which may contain an etheric oxygen atom in the middle of the chain; R &lt; ¹ &gt; is hydrogen, fluorine, methyl or trifluoromethyl; R ² are each independently hydrogen, halogen, optionally halo-substituted, linear, branched or cyclic, C ₂ -C ₈ acyloxy group, optionally halo-substituted, linear, branched or cyclic, C ₁ -C ₆ Alkyl group or an optionally halo-substituted, linear, branched or cyclic, C ₁ -C ₆ alkoxy group; L is hydrogen, a linear, branched or cyclic, C ₁ -C ₁₀ monovalent aliphatic hydrocarbon group which may contain an etheric oxygen atom, a carbonyl moiety or a carbonyloxy moiety in the middle of the chain or an optionally substituted A monovalent aromatic ring-containing group; Z is combined with the carbon atom form a C ₅ -C ₁₅ alicyclic, and; R ^x and R ^y are each independently a linear, branched or cyclic C ₁ -C ₁₅ alkyl group which may be substituted with a hydroxyl or alkoxy moiety, and at least one of R ^x and R ^y is a cyclic C ₅ -C ₁₅ alkyl group; f is an integer of 1 to 3, s is an integer of 0 to 2, a is (5 + 2s-f), and m is 0 or 1.

The polymer preferably further comprises a repeating unit having the formula (2): &lt; EMI ID =

(2)

In the above formulas, B is a single bond or a C ₁ -C ₁₀ alkylene group which may contain an etheric oxygen atom in the middle of the chain; R ¹ is as defined above; R ³ is independently hydrogen, halogen, optionally halo-each-substituted, linear, branched or cyclic, C ₂ -C ₈ acyloxy group, optionally halo-substituted, linear, branched or cyclic, C ₁ -C ₆ Alkyl group or an optionally halo-substituted, linear, branched or cyclic, C ₁ -C ₆ alkoxy group; g is an integer of 0 to 3, t is an integer of 0 to 2, b is (5 + 2t-g), and n is 0 or 1.

The polymer preferably further comprises a repeating unit having the following formula (3): &lt; EMI ID =

(3)

In the above formulas, C is a single bond or a C ₁ -C ₁₀ alkylene group which may contain an etheric oxygen atom in the middle of the chain; R ¹ is as defined above; R ⁴ are each independently hydrogen, halogen, optionally halo-substituted, linear, branched or cyclic, C ₂ -C ₈ acyloxy group, optionally halo-substituted, linear, branched or cyclic, C ₁ -C ₆ Alkyl group or an optionally halo-substituted, linear, branched or cyclic, C ₁ -C ₆ alkoxy group; D is a single bond or a linear, branched or cyclic C ₁ -C ₁₀ (v + 1) hydrocarbon group which may contain an etheric oxygen atom, a carbonyl moiety or a carbonyloxy moiety in the middle of the chain And some or all of the carbon-bonded hydrogen atoms may be replaced by fluorine; Rf ¹ and Rf ² are each independently a C ₁ -C ₆ alkyl group containing one or more fluorine atoms and Rf ¹ may combine with D to form a ring together with the carbon atoms to which they are attached; r is 0 or 1, h is an integer of 1 to 3, u is an integer of 0 to 2, c is (5 + 2u-h), and v is 1 or 2.

The polymer preferably further comprises at least one repeating unit selected from the following units represented by the following general formulas (4) and (5)

&Lt; Formula 4 >

&Lt; Formula 5 >

R ⁵ and R ⁶ are each independently selected from the group consisting of hydrogen, halogen, optionally halo-substituted, linear, branched or cyclic, C ₂ -C ₈ acyloxy, optionally halo-substituted, linear, A C ₁ -C ₆ alkyl group or an optionally halo-substituted, linear, branched or cyclic, C ₁ -C ₆ alkoxy group; i and j are each independently an integer of 0 to 2, d is (6-i), and e is (4-j).

The polymer preferably further comprises at least one repeating unit selected from the following units represented by the following formulas (A) to (E)

&Lt; Formula (A)

&Lt; Formula B >

&Lt; EMI ID =

<Formula D>

(E)

In the above formulas, R ¹ is as defined above; X ^A is an acid labile group; X ^B and X ^C are each independently a single bond or a linear or branched C ₁ -C ₄ divalent hydrocarbon group; X ^D is a linear, branched, or cyclic, C ₁ -C ₁₆ divalent to pentavalent aliphatic hydrocarbon group, and any component -CH ₂ - may be replaced by -O- or -C (= O) - ; X ^E is an acid labile group; Y ^A is a substituent having a lactone, sultone or carbonate structure; Z ^A is hydrogen, a C ₁ -C ₃₀ fluoroalkyl group or a C ₁ -C ₁₅ fluoroalcohol-containing substituent; k ^1A is an integer of 1 to 3, and k ^1B is an integer of 1 to 4.

The polymer preferably further comprises a repeating unit having the following formula (F): &lt; RTI ID = 0.0 &gt;

<Formula F>

In the above formula, R &lt; ¹⁰¹ &gt; is hydrogen or methyl; X is a single bond, -C (= O) -, -C (= O) -O- or -C (= O) -NH-; R ¹⁰² is a single bond or a linear, branched or cyclic C ₁ -C ₁₀ alkylene group which may contain an ether, an ester, a carbonyl moiety, -N = or -S-, or a phenylene or naphthylene group ; R ¹⁰³ and R ¹⁰⁴ are each independently hydrogen, a linear or branched C ₁ -C ₄ alkyl group or an acid labile group, or R ¹⁰³ and R ¹⁰⁴ may bond together to form an ether bond together with the nitrogen atom to which they are bonded. Or one of R ¹⁰³ and R ¹⁰⁴ may combine with R ¹⁰² to form a ring together with the nitrogen atom to which they are attached; k ^1C is 1 or 2;

The shrink material may further comprise a salt having the formula (9): &lt; EMI ID =

&Lt; Formula 9 >

In the above formulas, R ¹¹ is a linear, branched or cyclic C ₁ -C ₂₀ alkyl group, a linear, branched or cyclic C ₂ -C ₂₀ alkenyl group or a C ₆ -C ₂₀ monovalent aromatic ring- Some or all of the carbon-bonded hydrogen atoms may be replaced by fluorine, a lactone ring-containing moiety, a lactam ring-containing moiety or a hydroxyl moiety, and the ether, ester or carbonyl moiety may be substituted by a carbon- And M ⁺ is a sulfonium, iodonium or ammonium cation.

The shrink material may further comprise a salt having the formula (10): &lt; EMI ID =

&Lt; Formula 10 >

In the above formula, R ¹² is a linear, branched or cyclic C ₁ -C ₃₅ monovalent hydrocarbon group which may contain an oxygen atom, and some or all of the carbon-bonded hydrogen atoms may be substituted by fluorine, The hydrogen atom bonded to the carbon atom at the? -Position to the monosulfonic acid is not substituted by fluorine, and M ⁺ is a sulfonium, iodonium or ammonium cation.

In a preferred embodiment, the shrink material is selected from the group consisting of primary, secondary and tertiary aliphatic amines, mixed amines, aromatic amines, heterocyclic amines, nitrogen-containing compounds having carboxyl groups, nitrogen- At least one basic compound selected from the group consisting of a nitrogen-containing compound having a hydroxyl group, a nitrogen-containing compound having a hydroxyphenyl group, an alcoholic nitrogen-containing compound, an amide derivative, an imide derivative and a carbamate have.

The dissolution-inhibiting agent is preferably an ester solvent of 7 to 16 carbon atoms, a ketone solvent of 8 to 16 carbon atoms, or an alcohol solvent of 4 to 10 carbon atoms.

Specifically, the dissolution-inhibiting solvent is at least one solvent selected from the group consisting of:

But are not limited to, pentyl acetate, isopentyl acetate, 2-methylbutyl acetate, hexyl acetate, 2-ethylhexyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, hexyl formate, ethyl valerate, propyl valerate, Isobutyl valerate, tert-butyl valerate, pentyl valerate, isopentyl valerate, ethyl isovalerate, propyl isovalerate, isopropyl isovalerate, butyl isovalerate, isobutyl isovalerate, tert Butyl-2-methylvalerate, ethyl 2-methylvalerate, ethyl pivalate, propyl pivalate, isopropyl pivalate, butyl pivalate, tert-butyl pivalate, ethyl Pentenoate, propylpentanoate, isopropylpentenoate, butyl Propyl crotonate, isopropyl crotonate, butyl crotonate, tert-butyl crotonate, butyl propionate, isobutyl propionate, tert-butyl propionate , Ethyl benzoate, ethyl benzoate, benzyl propionate, ethyl hexanoate, allyl hexanoate, propyl butyrate, butyl butyrate, isobutyl butyrate, 3-methylbutyl butyrate, Methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, phenylacetate, benzyl acetate, methyl phenylacetate, benzyl formate, phenyl ethyl formate, methyl 3-phenyl propionate, ethyl phenylacetate, An ester solvent of 7 to 16 carbon atoms including ethyl acetate,

2-butanone, 2-octanone, 3-octanone, 4-octanone, 2-nonanone, 3-nonanone, 4-nonanone, 5-nonanone, diisobutyl ketone, ethylcyclohexanone, a ketone solvent of 8 to 16 carbon atoms including n-butyl ketone, di-n-butyl ketone and diisobutyl ketone, and

Propanol, 3-pentanol, t-pentyl alcohol, neopentyl alcohol, 2-methyl-1-butanol, 3-butanol, 3-butanol, Butanol, 3-methyl-3-pentanol, cyclopentanol, 1-hexanol, 2-hexanol, 3-hexanol, Butanol, 2-methyl-1-butanol, 2-methyl-2-pentanol, Pentanol, 4-methyl-1-pentanol, 4-methyl-2-pentanol, 4- Alcohol solvents of 4 to 10 carbon atoms, including methyl-3-pentanol, cyclohexanol and 1-octanol.

Preferably, the solvent comprises a dissolution-inhibiting solvent and an additional solvent, and the further solvent is selected from the group consisting of 2-octanone, 2-nonanone, 2-heptanone, 3-heptanone, Propyl acetate, butyl acetate, isobutyl acetate, pentyl acetate, isopentyl acetate, butenyl acetate, propyl formate, butyl &lt; RTI ID = 0.0 & Methyl formate, ethyl crotonate, methyl propionate, ethyl propionate, ethyl 3-ethoxypropionate, isobutyl formate, isopentyl formate, methyl valerate, methyl pentenoate, methyl crotonate, ethyl crotonate, Propyl lactate, butyl lactate, isobutyl lactate, pentyl lactate, isopentyl lactate, methyl 2-hydroxyisobutyrate, methyl 2-hydroxyisobutyrate, Methyl benzoate, ethyl benzoate, phenyl acetate, benzyl acetate, methyl phenylacetate, benzyl formate, phenyl ethyl formate, methyl 3-phenyl propionate, benzyl propionate, ethyl phenyl Acetate and 2-phenyl ethyl acetate.

In another embodiment, the present invention provides a resist composition comprising a resist composition comprising a base resin comprising a repeating unit having an acid labile group-substituted carboxyl group, an acid generator, and an organic solvent on a substrate and prefiring to form a resist film ; Exposing the resist film to high-energy radiation, and firing the film; Developing the exposed resist film in an organic solvent-based developer to form a negative resist pattern; Applying a shrink material as defined herein to a negative resist pattern and firing; And removing the excess shrink material with an organic solvent.

Typically, the base resin in the resist composition comprises a repeating unit (a) having an acid labile group-substituted carboxyl group represented by the following formula (11)

&Lt; Formula 11 >

Wherein R ²¹ is hydrogen or methyl, R ²² is an acid labile group, Z is a single bond or -C (= O) -OR ²³ - and R ²³ is an ether or ester linkage to a carbon- A linear, branched or cyclic C ₁ -C ₁₀ alkylene group or naphthylene group which may be interposed.

In the pattern formation method, the developer is at least one compound selected from the group consisting of 2-octanone, 2-nonanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-hexanone, 3-hexanone, diisobutylketone, Isobutyl acetate, butenyl acetate, propyl formate, butyl formate, isobutyl formate, pentyl formate, isopentyl acetate, isopentyl acetate, butenyl acetate, propyl formate, butyl formate, isobutyl acetate, butyl acetate, isobutyl acetate, Methyl formate, ethyl crotonate, methyl propionate, ethyl propionate, ethyl 3-ethoxypropionate, methyl lactate, ethyl lactate, propyl lactate, ethyl lactate, Butyl lactate, isobutyl lactate, pentyl lactate, isopentyl lactate, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, methyl benzoate, Ethyl benzoate, phenyl benzoate, phenyl acetate, benzyl acetate, methyl phenylacetate, benzyl formate, phenyl ethyl formate, methyl 3-phenyl propionate, benzyl propionate, ethyl phenylacetate and 2-phenyl ethyl acetate At least one organic solvent.

Preferably, the step of removing the excess shrink material is carried out in the presence of a solvent selected from the group consisting of propyl acetate, butyl acetate, isobutyl acetate, butenyl acetate, pentyl acetate, isopentyl acetate, 2- methylbutyl acetate, hexyl acetate, But are not limited to, cyclohexyl acetate, methylcyclohexyl acetate, propyl formate, butyl formate, isobutyl formate, pentyl formate, isopentyl formate, hexyl formate, methyl valerate, ethyl valerate, propyl valerate, Isobutyl valerate, isobutyl valerate, isobutyl valerate, isobutyl valerate, isopentyl valerate, ethyl isovalerate, propyl isovalerate, isopropyl isovalerate, butyl isovalerate, isobutyl iso Valerate, tert-butyl isovalerate , Ethyl 2-methylvalerate, ethyl 2-methylvalerate, methyl crotonate, ethyl crotonate, propyl crotonate, isopropyl crotonate, butyl crotonate, tert-butyl Methyl propionate, ethyl propionate, ethyl pentenoate, propyl pentenoate, isopropyl pentenoate, butyl pentenoate, tert-butyl pentenoate, methyl lactate, ethyl lactate, Propyl lactate, butyl lactate, isobutyl lactate, pentyl lactate, isopentyl lactate, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, ethyl pivalate, propyl pivalate, isopropyl pivalate , Butyl pivalate, tert-butyl pivalate, butyl propionate, isobutyl propionate, tert-butyl propionate, benzyl propionate Propyl butyrate, isobutyl butyrate, 3-methylbutyl butyrate, tert-butyl butyrate, ethyl 2-methyl butyrate, isopropyl propyl propionate, ethyl propionate, ethyl propionate, ethyl hexanoate, Methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, phenylacetate, benzyl acetate, methyl phenylacetate, benzyl formate, phenyl ethyl formate, methyl 3-phenyl propionate, ethyl phenyl Acetate, 2-phenylethylacetate, 2-heptanone, 3-heptanone, 4-heptanone, 2-hexanone, 3-hexanone, Ethyl n-butyl ketone, di-n-butyl acrylate, ethyl n-butyl acrylate, ethyl n-butyl methacrylate, Ketone, diisobutyl ketone, 1-butane Butanol, isobutyl alcohol, t-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, t-pentyl alcohol, neopentyl alcohol, Butanol, 3-methyl-3-pentanol, cyclopentanol, 1-hexanol, 2-hexanol, 3-hexanol, Butanol, 3,3-dimethyl-2-butanol, 2,2-diethyl-1-butanol, Pentanol, 4-methyl-1-pentanol, 4-methyl-2-pentanol, 4-methyl- At least one organic solvent selected from the group consisting of 3-pentanol, cyclohexanol and 1-octanol is used.

Typically, the high-energy radiation is an i-ray with a wavelength of 364 nm, a KrF excimer laser with a wavelength of 248 nm, an ArF excimer laser with a wavelength of 193 nm, or EUV or EB with a wavelength of 13.5 nm.

Forming a resist film based on a base resin having an acid labile group-substituted carboxyl group and an acid generator, treating it with an exposure and an organic solvent to form a negative tone resist pattern, and subjecting the shrink material of the present invention to a resist pattern The method including applying has succeeded in reducing the size of holes and / or slits in the resist pattern in a controlled manner.

Figures 1 (a) to 1 (f) show cross sections of steps of a patterning or shrink process according to the invention; 1 (a) shows a resist film formed on a substrate; 1 (b) shows a resist film during exposure; 1 (c) shows the pattern formation after PEB and the development of the resist film; Figure 1 (d) shows the shrink material applied over the resist pattern; Fig. 1 (e) shows a resist pattern having shrunk space by removing the excess shrink material after firing; Figure 1 (f) shows a dry etch of the substrate through a shrunk pattern as a mask.

The terms " a " and "an" herein do not denote a limitation of the quantity, but rather indicate the presence of one or more of the items mentioned. "Optional" or "optionally" means that the subsequently described example or circumstance may or may not occur, and that the description includes instances where the instance or circumstance occurs and instances where it does not. As used herein, the notation (C _n -C _m ) means a group containing n to m carbon atoms per group. As used herein, the term "membrane" is used interchangeably with "application" or "layer".

Abbreviations and acronyms have the following meanings.

EB: electron beam

Mw: weight average molecular weight

Mn: number average molecular weight

Mw / Mn: molecular weight distribution or dispersion degree

GPC: gel permeation chromatography

PEB: post-exposure baking

PAG: photoacid generator

In the formula, Me represents methyl; Ac is acetyl; And the broken line represents valence bonding.

Shrink material

The present invention provides a shrink material comprising a polymer and a solvent containing a dissolution-preventing solvent to prevent the resist pattern from being lost after development. The polymer is defined as comprising at least one repeating unit selected from the units having the general formulas (1a) and (1b). It is noted that such polymers are often referred to as "polymers for shrinking materials ".

<Formula 1a>

&Lt; EMI ID =

In the above formulas (1a) and (1b), "A" is a single bond or a C ₁ -C ₁₀ alkylene group which may contain an etheric oxygen atom in the middle of the chain. Suitable alkylene groups include methylene, ethylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, cyclopentylene, cyclohexylene, and structural isomers thereof having a branched or cyclic structure. In particular, A is preferably a single bond, methylene, ethylene, propylene or trimethylene. When A is a group containing an etheric oxygen atom, in the case of m = 1 in the general formula (1), the etheric oxygen atom may be contained at any position except between the alpha and beta position and the carbon with respect to the ester oxygen. In the case of m = 0, the etheric oxygen atom is the atom bonded to the main chain, and the second etheric oxygen atom can be included at any position except between the alpha and beta -position to the etheric oxygen atom .

In formulas (1a) and (1b), R ¹ is hydrogen, fluorine, methyl or trifluoromethyl. R ² are each independently hydrogen, halogen, optionally halo-substituted, linear, branched or cyclic, C ₂ -C ₈ acyloxy group, optionally halo-substituted, linear, branched or cyclic, C ₁ -C ₆ Alkyl group or an optionally halo-substituted, linear, branched or cyclic, C ₁ -C ₆ alkoxy group.

Examples of the halogen include fluorine, chlorine, bromine and iodine. Suitable acyloxy groups include acetoxy, propionyloxy, butyryloxy, pivaloyloxy and cyclohexylcarbonyloxy. Suitable alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, s-butyl, t-butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, decanyl, undecyl, Norbornyl, and adamantyl. Suitable alkoxy groups include methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, s-butoxy, t-butoxy, pentyloxy, hexyloxy, cyclopentyloxy, cyclohexyloxy, 1- 1-cyclopentyloxy, 1-methyl-1-cyclohexyloxy and 1-ethyl-1-cyclohexyloxy.

In formulas (1a) and (1b), L is hydrogen, a linear, branched, or cyclic, C ₁ -C ₁₀ 1 alkyl group which may contain an etheric oxygen atom, a carbonyl moiety or a carbonyloxy moiety at the mid- An aliphatic hydrocarbon group or an optionally substituted monovalent aromatic ring-containing group. Suitable monovalent aliphatic hydrocarbon groups are linear, branched, or cyclic alkyl, alkenyl, and alkynyl groups. Suitable alkyl groups include those exemplified above except that they have 1 to 10 carbon atoms. Suitable alkenyl groups include but are not limited to vinyl, allyl, propenyl, cyclopropenyl, butenyl, cyclobutenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, methylcyclohexenyl, Decyl, dimethylcyclohexenyl, and cyclooctenyl. Suitable alkynyl groups include ethynyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl and octynyl. Suitable monovalent aromatic ring-containing groups include phenyl, naphthyl, phenanthryl, anthryl, pyrenyl, biphenylyl, acenaphthenyl and fluorenyl. Preferably, L is hydrogen, methyl, ethyl, propyl, isopropyl, cyclopentyl, cyclohexyl, adamantyl, methylcarbonyl or phenyl.

In formula (I), Z is bonded to the carbon atom to form a C ₅ -C ₁₅ aliphatic ring group. Suitable aliphatic ring groups include, but are not limited to,

In formula (1b), R ^x and R ^y are each independently a hydrogen, a linear, branched or cyclic, C ₁ -C ₁₅ alkyl group which may be substituted by a hydroxyl or alkoxy moiety, and one of R ^x and R ^y Or more are cyclic C ₅ -C ₁₅ alkyl groups. Preferably, R ^x and R ^y are selected from the group consisting of methyl, ethyl, propyl, butyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, adamantyl, norbornyl and the above groups substituted with a hydroxyl or alkoxy moiety .

In formulas (1a) and (1b), f is an integer of 1 to 3, s is an integer of 0 to 2, a is (5 + 2s-f), and m is 0 or 1.

Of the repeating units of the formulas (1a) and (1b), the repeating units of the following formulas (1a ') and (1b'

<Formula 1a '

&Lt; Formula 1b &

In the above formula, R ¹ , R ^x , R ^y , L and f are as defined above.

Preferable examples of the repeating units of the formulas (1a) and (1b) are given below, but are not limited thereto:

Preferably, the polymer for shrinking material further comprises a repeating unit of formula (2) and / or (3) to provide sufficient adhesion to the resist pattern and adhesion to the substrate. The recurring units of the following formula (2) or (3) are suitable columns for favorably promoting the insolubilization reaction to cause the polymer to be insolubilized in the shrinkage material peeling liquid as a result of the removal of acid labile groups in the recurring units of formula Allow vibration. Particularly, the repeating unit represented by the formula (2) is more preferable.

(2)

(3)

In formula (2), B is a single bond or a C ₁ -C ₁₀ alkylene group which may contain an etheric oxygen atom in the middle of the chain. Suitable alkylene groups are as exemplified above for "A &quot;.

In formula (2), R ¹ is as defined above. R ³ is independently hydrogen, halogen, optionally halo-each-substituted, linear, branched or cyclic, C ₂ -C ₈ acyloxy group, optionally halo-substituted, linear, branched or cyclic, C ₁ -C ₆ Alkyl group or an optionally halo-substituted, linear, branched or cyclic, C ₁ -C ₆ alkoxy group. Examples of acyloxy, alkyl and alkoxy groups are as exemplified above for R &lt; ² &gt;.

G is an integer of 0 to 3, t is an integer of 0 to 2, b is (5 + 2t-g), and n is 0 or 1. Here, g represents the number of hydroxyl groups bonded to the aromatic ring. It is preferable that g is 1 or more so as to obtain a sufficient amount of shrink to provide a high activity for the insolubilization reaction in which the polymer is insolubilized in the release liquid as a result of the removal of the acid labile group in the repeating units of the formulas (Ia) and . The unit of formula (2) wherein g is 1 or more is more preferably 50 mol% or more of the unit of formula (2). The unit of formula (2) wherein g = 0 is effective for controlling the dissolution rate and for controlling the thermal vibration of the polymer, but may not be included depending on the specific design.

In the repeating unit of formula (2), the repeating unit of formula (2) wherein g is 1 or more, n is 0, and B is a single bond, that is, the aromatic ring is directly bonded to the polymer main chain, A unit derived from a monomer having a 1-substituted or unsubstituted vinyl group bonded to a substituted aromatic ring, usually a hydroxystyrene unit. Suitable units include those derived from 3-hydroxystyrene, 4-hydroxystyrene, 5-hydroxy-2-vinylnaphthalene and 6-hydroxy-2-vinylnaphthalene. As indicated by the following formula (2 '), units derived from 3-hydroxystyrene or 4-hydroxystyrene are preferred.

&Lt; Formula (2) &gt;

In the above formula, R ¹ is as defined above, and k is an integer of 1 to 3.

In the repeating unit of formula (2), the repeating unit of formula (2) having a linker-containing repeating unit, i.e., n = 1, that is, an ester linker, is a unit derived from a carbonyl-substituted vinyl monomer, typically (meth) acrylate .

In the repeating unit represented by formula (2) having a linker (-CO-O-B-) derived from (meth) acrylate, preferred examples of the unit in which g is 1 or more are shown below, but are not limited thereto.

In the repeating unit of formula (2), the unit wherein g = 0 is a unit derived from the above compound having an aromatic ring substituted with styrene, vinyl naphthalene, vinyl anthracene and halogen, acyloxy, alkyl, alkoxy or similar moieties. g is 0 and the unit having a linker (-CO-OB-) derived from (meth) acrylate has g of 1 or more, the hydroxyl group is removed, the hydrogen of the hydroxyl group is substituted by an acyl or alkyl group Lt; / RTI &gt; units.

In Formula (3), C is a single bond or a C ₁ -C ₁₀ alkylene group which may contain an etheric oxygen atom in the middle of the chain. Suitable alkylene groups are as exemplified above for "A &quot;.

In formula (3), R ¹ is as defined above. R ⁴ are each independently hydrogen, halogen, optionally halo-substituted, linear, branched or cyclic, C ₂ -C ₈ acyloxy group, optionally halo-substituted, linear, branched or cyclic, C ₁ -C ₆ Alkyl group or an optionally halo-substituted, linear, branched or cyclic, C ₁ -C ₆ alkoxy group. Examples of acyloxy, alkyl and alkoxy groups are as exemplified above for R &lt; ² &gt;.

In formula (3), D is a linear, branched or cyclic C ₁ -C ₁₀ (v + 1) bond, which may contain a bond or an etheric oxygen atom, a carbonyl moiety or a carbonyloxy moiety at the mid- ) Is a hydrocarbon group, and some or all of the carbon-bonded hydrogen atoms may be substituted by fluorine. Preferred hydrocarbon groups are aliphatic hydrocarbon groups, examples of which are the same as illustrated above for the monovalent aliphatic hydrocarbon group of L, where "v"

In Formula (3), Rf ¹ and Rf ² each independently represent a C ₁ -C ₆ alkyl group containing one or more fluorine atoms. Rf &lt; ¹ &gt; may combine with D to form a ring with the carbon atoms to which they are attached. Suitable alkyl groups containing one or more fluorine atoms include monofluoromethyl, difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, 1,1,2,2,2-pentafluoro Trifluoromethyl, ethyl, 2,2,2-trifluoro-1- (trifluoromethyl) ethyl, perfluoroisopropyl, heptafluoropropyl, 2,2,3,3-tetrafluoropropyl, 2,2 , 3,3,3-pentafluoropropyl, 3,3,3-trifluoro-2- (trifluoromethyl) propyl, nonafluorobutyl, 1H, 1H, 5H-octafluoropentyl, 1H, 1H, 2H-nonafluoropentyl, perfluoropentyl, perfluoropentyl, 1H, 1H-4-trifluoromethylperfluoropentyl, perfluorohexyl, 4-pentafluoroethylperfluorocyclohexyl, 2H-perfluorohexyl and perfluorocyclohexyl.

In Formula (3), h is an integer of 1 to 3, u is an integer of 0 to 2, and c is (5 + 2u-h).

In formula (3), r is 0 or 1. When r = 1, an aromatic ring is interposed between the polymer main chain and a hydroxyl group bonded to the carbon adjacent to the carbon substituted by the fluorine-containing group. In such a case, v representing the number of substituents in D is 1 or 2. When D is not a single bond, D has one or two hydroxyl groups, each of which is bonded to a carbon adjacent to the carbon substituted by the fluorine-containing group, i.e., v is 1 or 2.

When r = 0, h is 1, C is a single bond, but D is not a single bond. In this case, D is bonded to the polymer backbone by a carbonyloxy group. In this case, D also has one or two hydroxyl groups, each bonded to a carbon adjacent to the carbon substituted by the fluorine-containing group.

Preferable examples of the repeating unit having the formula (3) are shown below, but are not limited thereto.

The units of formula (2) or (3) may be used alone or in combination (i.e., one or more)

The polymer for shrinking material may further comprise at least one repeating unit selected from the following units represented by the following general formulas (4) and (5) as a main structural unit. In this embodiment, in addition to the etch resistance inherent in the aromatic rings, the polymer may have another advantage of imparting a dry etch resistance to the shrunk resist pattern by bonding the annular structure to the backbone.

&Lt; Formula 4 >

&Lt; Formula 5 >

R ⁵ and R ⁶ are each independently selected from the group consisting of hydrogen, halogen, optionally halo-substituted, linear, branched or cyclic, C ₂ -C ₈ acyloxy, optionally halo-substituted, linear, Cyclic, C ₁ -C ₆ alkyl group or optionally halo-substituted, linear, branched or cyclic, C ₁ -C ₆ alkoxy group. Examples of acyloxy, alkyl and alkoxy groups are as exemplified above for R &lt; ² &gt;.

In the formulas (4) and (5), i and j are each independently an integer of 0 to 2, d is (6-i), and e is (4-j).

The units of formula (4) or (5) may be used alone or in combination of two or more.

When the unit of the formula (4) or the unit of the formula (5) in which i or j is 1 or more is selected, in order to improve the etching resistance of the polymer with respect to other repeating units of the polymer, And is effective for achieving a desired effect.

&Lt; Formula 4 &

&Lt; Formula 5 &

The polymer for shrinking material may further comprise at least one repeating unit selected from the units having the following general formulas (A) to (E). These units can be used as an auxiliary unit by which the polymer can impart adhesion to the resist pattern or to control the solubility of the polymer in the solvent.

&Lt; Formula (A)

&Lt; Formula B >

&Lt; EMI ID =

<Formula D>

(E)

In the above formula, R &lt; ¹ &gt; is as defined above. X ^A is an acid labile group. X ^B and X ^C are each independently a single bond or a linear or branched C ₁ -C ₄ divalent hydrocarbon group. X ^D is a linear, branched, or cyclic, C ₁ -C ₁₆ divalent to pentavalent aliphatic hydrocarbon group, and any component -CH ₂ - may be replaced by -O- or -C (= O) - have. X ^E is an acid labile group. Y ^A is a substituent having a lactone, sultone or carbonate structure. Z ^A is hydrogen, a C ₁ -C ₃₀ fluoroalkyl group or a C ₁ -C ₁₅ fluoroalcohol-containing substituent, k ^1A is an integer of 1 to 3, and k ^1B is an integer of 1 to 4.

The repeating unit of formula (A) decomposes under the action of an acid to form a carboxylic acid. Such units may be incorporated to control the solubility of the polymer for shrinking materials in organic solvents. The acid labile group represented by X ^A can be selected from various groups mentioned above. Examples of acid labile groups include groups of the following formulas L1 to L4, tertiary alkyl groups of 4 to 20 carbon atoms, preferably 4 to 15 carbon atoms, each alkyl moiety having 1 to 6 carbon atoms And an oxoalkyl group having 4 to 20 carbon atoms.

&Lt; Formula (L1)

&Lt; Formula (L2)

<Formula L3>

&Lt; Formula L4 &

In the above formulas, R ^L01 and R ^L02 are each independently hydrogen or a linear, branched or cyclic alkyl group of 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms. R ^L03 is a monovalent hydrocarbon group of 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms, which may contain heteroatoms such as oxygen, and examples thereof include linear, branched or cyclic alkyl groups, some hydrogen A substituted form of the alkyl group substituted by a valence hydroxyl, alkoxy, oxo, amino, alkylamino, and the like, and a similar group separated by an etheric oxygen atom. R ^L04 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, 4 to 20 carbon atoms Lt; 1 &gt; R ^L05 is an optionally substituted, linear, branched or cyclic C ₁ -C ₁₀ alkyl group or an optionally substituted C ₆ -C ₂₀ aryl group. R ^L06 is an optionally substituted, linear, branched or cyclic C ₁ -C ₁₀ alkyl group or an optionally substituted C ₆ -C ₂₀ aryl group. R ^L07 to R ^L16 independently represent hydrogen or an optionally substituted monovalent hydrocarbon group of 1 to 15 carbon atoms. The letter x is an integer from 0 to 6, y is 0 or 1, z is 0, 1, 2 or 3, and 2y + z is 2 or 3.

In formula (L1), examples of R ^L01 and R ^L02 include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert- butyl, cyclopentyl, cyclohexyl, Adamantyl.

Examples of monovalent hydrocarbon groups represented by R ^L03 include, but are not limited to, those exemplified above for the alkyl groups represented by R ^L01 and R ^L02 . Examples of substituted alkyl groups represented by R ^L03 are as set forth below:

A pair of R ^L01 and R ^L02 , R ^L01 and R ^L03, or R ^L02 and R ^L03 may bond together to form a ring together with the carbon and oxygen atoms to which they are bonded. Each ring-forming R ^L01 , R ^L02 and R ^L03 is a linear or branched alkylene group of from 1 to 18 carbon atoms, preferably from 1 to 10 carbon atoms when they form a ring.

In Formula L2, an exemplary tertiary alkyl group of R ^L04 is tert-butyl, tert-pentyl, 1,1-diethylpropyl, 2-cyclopentylpropan-2-yl, 2-cyclohexylpropan- 2-yl) propane-2-yl, 1-ethylcyclopentyl, 1-butylcyclopentyl, 2-ethylcyclopentyl, Cyclopentenyl, 1-ethyl-2-cyclohexenyl, 2-methyl-2-adamantyl and 2-ethyl-2-adamantyl Til. 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.

Examples of the alkyl group of R ^L05 in formula (L3) include linear, branched or cyclic alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, n-hexyl, cyclopentyl, cyclohexyl and bicyclo [2.2.1] heptyl and some hydrogen atoms are replaced by hydroxyl, alkoxy, carboxyl, alkoxycarbonyl, oxo, amino, alkylamino, cyano, Thio, sulfo and the like, or a substituted form of the above-mentioned group substituted by a methylene moiety by an oxygen or sulfur atom. Examples of the aryl group of R ^L05 include phenyl, methylphenyl, naphthyl, anthryl, phenanthryl and pyrenyl.

In formula L4, for example, the alkyl and aryl group of R ^L06 are the same as exemplified with respect to R ^L05. Exemplary C ₁ -C ₁₅ monovalent hydrocarbon radicals of R ^L07 to R ^L16 include linear, branched or cyclic alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, N-octyl, n-nonyl, n-decyl, cyclopentyl, cyclohexyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylbutyl, cyclohexylmethyl, cyclohexylethyl and cyclo Hexylbutyl and substituted forms of these groups in which some hydrogen atoms are replaced by hydroxyl, alkoxy, carboxyl, alkoxycarbonyl, oxo, amino, alkylamino, cyano, mercapto, alkylthio, . Alternatively, two of R ^L07 through R ^L16 may combine together to form a ring with the carbon atom (s) to which they are attached (e.g., a pair of R ^L07 and R ^L08 , R ^L07 and R ^L09 , R ^L08 and R ^L10 , R ^L09 and R ^L10 , R ^L11 and R ^L12 or R ^L13 and R ^L14 form a ring. Each of R ^L07 to R ^L16 represents a C ₁ -C ₁₅ divalent hydrocarbon group, and in the case where an alkylene forms a ring, an example thereof is as exemplified above for a monovalent hydrocarbon group in which one hydrogen atom is removed. Two of R ^L07 to R ^L16 attached to adjacent carbon atoms may be directly bonded together to form a double bond (for example, a pair of R ^L07 and R ^L09 , R ^L09 and R ^L15 , or R ^L13 and R ^L15 ).

In the acid labile group of formula (L1), the linear or branched form is exemplified by, but not limited to,

In the acid labile group of formula (L1), cyclic groups include, for example, tetrahydrofuran-2-yl, 2-methyltetrahydrofuran-2-yl, tetrahydropyran-2-yl and 2-methyltetrahydropyran- to be.

Examples of the acid labile group of the formula L2 include tert-butoxycarbonyl, tert-butoxycarbonylmethyl, tert-pentyloxycarbonyl, tert-pentyloxycarbonylmethyl, 1,1-diethylpropyloxycarbonyl, 1-ethylcyclopentyloxycarbonyl, 1-ethylcyclopentenyloxycarbonyl, 1-ethyl-2-cyclopentyloxycarbonyl, 1- Cyclopentenyloxycarbonylmethyl, 1-ethoxyethoxycarbonylmethyl, 2-tetrahydropyranyloxycarbonylmethyl and 2-tetrahydrofuranyloxycarbonylmethyl can be mentioned.

Examples of the acid labile group of the formula L3 include 1-methylcyclopentyl, 1-ethylcyclopentyl, 1-n-propylcyclopentyl, 1-isopropylcyclopentyl, 1-n-butylcyclopentyl, Cyclopentyl, 1-cyclohexylcyclopentyl, 1- (4-methoxy-n-butyl) cyclopentyl, 1- (bicyclo [2.2.1] heptan- 1-cyclopentene-3-yl, 3-ethyl-1-cyclopentene-2-yl, cyclopentyl, 3-yl, 3-methyl-1-cyclohexen-3-yl and 3-ethyl-1-cyclohexen-3-yl.

In the acid labile group of the formula (L4), these groups of the following formulas (L4-1) to (L4-4) are preferred.

<Formula L4-1>

<Formula L4-2>

<Formula L4-3>

<Chemical Formula L4-4>

In the formulas (L4-1) to (L4-4), the broken line indicates a bonding site and a direction. R ^L41 are each independently a monovalent hydrocarbon group, typically a linear, branched or cyclic C ₁ -C ₁₀ alkyl group such as methyl, ethyl, propyl, isopropyl, n-butyl, sec- Pentyl, tert-pentyl, n-hexyl, cyclopentyl and cyclohexyl.

In the case of formulas L4-1 to L4-4, enantiomers and diastereomers may exist. Each of formulas (L4-1) to (L4-4) collectively represents all said stereoisomers. When X ^A is an acid labile group of the formula L 4, a plurality of stereoisomers may be included.

For example, the formula (L4-3) represents one or two mixtures selected from the groups having the following formulas (L4-3-1) and (L4-3-2).

<Formula L4-3-1>

<Formula L4-3-2>

Note that R ^L41 is as defined above.

Similarly, the formula (L4-4) represents a mixture of one or more selected from groups having the following formulas (L4-4-1) to (L4-4-4).

<Formula L4-4-1>

<Chemical Formula L4-4-2>

<Formula L4-4-3>

<Chemical Formula L4-4-4>

Note that R ^L41 is as defined above.

Each of formulas (L4-1) to (L4-4), (L4-3-1) and (L4-3-2) and (L4-4-1) to (L4-4-4) collectively mean an enantiomer thereof and an enantiomer Lt; / RTI &gt;

In the above formulas L4-1 to L4-4, L4-3-1 and L4-3-2 and L4-4-1 to L4-4-4, the bonding direction is bicyclo [2.2.1] Is on the exo side with respect to the heptane ring and ensures a high reactivity to the acid catalytic desorption reaction (see JP-A 2000-336121). In the preparation of these monomers having a tertiary exo-alkyl group of the bicyclo [2.2.1] heptane structure as a substituent, it is preferred that in the preparation of these monomers having an endo-alkyl group as represented by the following general formulas L4-1-endo to L4-4- May contain monomers. For excellent reactivity, an exo ratio of at least 50 mol% is preferred, and an exo ratio of at least 80 mol% is more preferred.

&Lt; General Formula L4-1-Endo &

&Lt; Formula L4-2-Endo &

&Lt; Formula L4-3-Endo &

<L4-4-Endo>

Note that R ^L41 is as defined above.

Examples of acid labile groups of formula L4 are given below.

Examples of tertiary C ₄ -C ₂₀ alkyl groups represented by X ^A , trialkylsilyl groups wherein each alkyl moiety has 1 to 6 carbon atoms and C ₄ -C ₂₀ oxoalkyl groups include those exemplified for R ^L04 Same as.

Examples of repeating units having the formula (A) are shown below, but are not limited thereto. R ¹ is as defined above.

Examples of repeating units having the formula B are shown below, but are not limited thereto. R ¹ is as defined above.

Examples of repeating units having the formula C are given below, but are not limited thereto. R ¹ is as defined above.

Examples of repeating units having the formula D are shown below, but are not limited thereto. R ¹ is as defined above.

The polymer containing the repeating unit of the formula (E) decomposes under the action of an acid to form a hydroxyl group, so that its solubility in various solvents can be changed. In the formula (E), the acid labile group X ^E can be selected from the various groups mentioned above. Examples of the acid labile group X ^E is the formula L1 through tertiary alkyl group, each alkyl moiety of 1 to 6 carbons in the group of formula L4, 4 to 20 carbon atoms, such as the acid labile group X ^A above Trialkylsilyl groups with atoms and oxoalkyl groups with 4 to 20 carbon atoms.

Examples of repeating units having the formula (E) are shown below, but are not limited thereto. R ¹ is as defined above.

In the repeating units of the formulas (A) to (E), the units of the formulas (A) to (C) are preferable because the polymer can easily adjust the solvent solubility and adhesiveness.

The polymer for shrinking material may further comprise a repeating unit represented by the following formula (F). The unit of formula (F) can induce a neutralization reaction with a carboxyl group present on the surface of the resist pattern film to which the shrink material is applied. As a result, the polymer for the shrink material is attached to the surface of the resist film, which shows increased adhesion.

<Formula F>

In the above formula, R &lt; ¹⁰¹ &gt; is hydrogen or methyl. X is a single bond, -C (= O) -, -C (= O) -O- or -C (= O) -NH-. R ¹⁰² is a single bond or a linear, branched or cyclic C ₁ -C ₁₀ alkylene group which may contain an ether, an ester, a carbonyl moiety, -N = or -S-, or a phenylene or naphthylene group to be. R ¹⁰³ and R ¹⁰⁴ are each independently hydrogen, a linear or branched C ₁ -C ₄ alkyl group or an acid labile group, or R ¹⁰³ and R ¹⁰⁴ may bond together to form an ether bond together with the nitrogen atom to which they are bonded. Or one of R ¹⁰³ and R ¹⁰⁴ may combine with R ¹⁰² to form a ring together with the nitrogen atom to which they are attached; k ^1C is 1 or 2;

The repeating unit of formula (F) can be derived from a monomer having the following formula:

&Lt; Chemical Formula Fa &

In the above formulas, R ¹⁰¹ to R ¹⁰⁴ , X and k ^1C are as defined above.

Examples of monomers having the formula Fa are shown below, but are not limited thereto.

In the above formulas, R ¹⁰¹ to R ¹⁰⁴ are as defined above.

Polymers for shrinking materials may be used alone or in combination. When the polymer is used alone, it is designed by selecting a repeating unit having a desired function, and determining the composition ratio of the repeating units so as to provide appropriate shrink and dimension uniformity to the shrink material mixed therewith.

Polymers for shrinking materials can be produced by combining appropriate monomers and copolymerizing them, while combining protection and deprotection reactions, if required in a standard manner. The copolymerization reaction is preferably a radical polymerization, but is not limited thereto.

In the shrink material polymer, the repeating units of the general formula (I) and / or the general formula (Ib) are preferably incorporated in an amount of 5 mol% or more, more preferably 10 mol% or more, based on the total repeating units.

The repeating unit represented by the formula (2) is preferably incorporated in an amount of 0 to 90 mol% based on the total repeating units. In the case of sufficient adhesion to the resist pattern and substrate adhesion, the amount of the unit of formula (2) is more preferably 5 to 85 mol%, still more preferably 10 to 80 mol%.

The repeating unit represented by the general formula (3) is preferably mixed in an amount of 0 to 90 mol% based on the total repeating units. In the case of sufficient adhesion to the resist pattern and substrate adhesion, the amount of the unit of the formula (3) is more preferably 5 to 85 mol%, still more preferably 10 to 80 mol%.

The repeating unit represented by the formula (4) or (5) is preferably incorporated in an amount of 0 to 30 mol% based on the total repeating units. In the case of a larger etching resistance, the amount of the units of the formula (4) or (5) is more preferably 5 to 30 mol%, still more preferably 5 to 20 mol%.

The repeating units of the formulas (A) to (E) are preferably incorporated in an amount of 0 to 30 mol% based on the total repeating units. For greater substrate adhesion and solubility control, the amount of units of formulas (A) to (E) is more preferably 1 to 30 mol%, even more preferably 5 to 20 mol%.

The repeating unit of the formula (F) is preferably incorporated in an amount of 0 to 30 mol% based on the total repeating units. For greater adhesion, the amount of units of formula (F) is more preferably from 1 to 30 mol%, even more preferably from 1 to 20 mol%.

In the shrink material polymer, it is preferable that the repeating unit selected from the repeating units represented by formulas (1a) and / or (1b) and the repeating units represented by formulas (2), (4) and (5) Thereby ensuring that the shrink material having properties is compounded. More preferably, the repeating unit represented by the formula (1a) and / or the repeating unit represented by the formula (1b) and the repeating unit represented by the formula (2), the formula (4) and the formula (5) correspond to not less than 70 mol%, more preferably not less than 85 mol% do.

When the total constitutional unit of the polymer for shrinking material is a repeating unit selected from the repeating units of the formulas (1a) and / or (1b) and the units of the formulas (2), (4) and (5), high etching resistance and high resolution are utilized It is possible. In the polymers for shrinking materials, repeating units other than the repeating units of the general formulas (1a), (1b), (2), (4) and (5) may be incorporated. For example, a (meth) acrylate unit protected with a normal acid labile group and / or a (meth) acrylate unit having an adherent group such as a lactone structure can be used. The characteristics of the shrink material film can be fine-tuned by incorporating the repeating unit, although additional repeating units are optional.

The polymer for a shrink material preferably has a weight average molecular weight (Mw) measured by GPC using a tetrahydrofuran solvent on a polystyrene standard material of preferably 1,000 to 500,000, more preferably 2,000 to 100,000, still more preferably 2,000 To 20,000. If Mw is too low, the acid diffusion distance can be extended, and the shrink can be increased, making it uncontrollable. When the Mw is too high, the solubility in the peeling liquid solvent may be lowered, leaving a scum in the space at the end of the stripping step, resulting in a footing phenomenon.

When a polymer has a broad molecular weight distribution or a degree of dispersion (Mw / Mn) indicating the presence of low molecular weight and high molecular weight polymer fractions, foreign matter is left on the pattern and there is a possibility that the pattern profile is deteriorated. The finer the pattern rule, the stronger the influence of molecular weight and dispersion. Therefore, in order to provide a shrink material suitable for micropatterning with small feature sizes, the multicomponent copolymer, i.e. the polymer for shrink material, should have a narrow dispersion (Mw / Mn) of 1.0 to 2.0, in particular 1.0 to 1.5 .

It is acceptable to use a blend of two or more polymers having different composition ratios, molecular weights, or dispersions.

In addition to the polymers defined above, the shrink material includes a solvent containing a dissipation-inhibiting solvent that prevents the resist pattern from being lost after development. The elimination-preventing agent may be an ether solvent of 6 to 12 carbon atoms, a hydrocarbon solvent of 6 to 12 carbon atoms, an ester solvent of 7 to 16 carbon atoms, a ketone solvent of 8 to 16 carbon atoms, Alcohol solvents of carbon atoms and water. If the dissolution-inhibiting solvent corresponds to not less than 50% by weight of the total solvent, another solvent may be contained so that the resist pattern disappears after development.

Although a number of water shroud materials have already been proposed, it is difficult to quickly apply to large diameter wafers because of the high surface tension of water. In particular, problems arise in the case of fine hole patterns formed by negative phenomena. When the holes are filled with the shrink material by spin coating, the high surface tension water solvent prevents the shrink material from being buried from the hole to the bottom. On the contrary, when the shrink material dissolved in an organic solvent whose surface tension is lower than that of water is applied, the ability to fill or fill the hole bottom is improved. In addition, the organic solvent used in the shrink material dissolves the polymer for shrink material.

As the solvent used for the shrink material, a high solvent for the polymer for the shrink material makes it possible to use an ester solvent of 7 to 16 carbon atoms, a ketone solvent of 8 to 16 carbon atoms and an alcohol solvent of 4 to 10 carbon atoms desirable.

Examples of ester solvents of 7 to 16 carbon atoms include pentyl acetate, isopentyl acetate, 2-methylbutyl acetate, hexyl acetate, 2-ethylhexyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, hexyl formate, ethyl valerate , Propyl valerate, isopropyl valerate, butyl valerate, isobutyl valerate, tert-butyl valerate, pentyl valerate, isopentyl valerate, ethyl isovalerate, propyl isovalerate, isopropyl isovalerate, Butyl isobarylate, isobutyl isovalerate, tert-butyl isovalerate, isopentyl isovalerate, ethyl 2-methyl valerate, butyl 2-methyl valerate, ethyl pivalate, propyl pivalate, isopropyl pivalate , Butyl pivalate, tert-butyl pivalate, ethyl pentenoate, pro Butylpentanoate, isopropylpentanoate, butylpentanoate, tert-butylpentanoate, propyl crotonate, isopropyl crotonate, butyl crotonate, tert-butyl crotonate, butyl propionate Butyl propionate, tert-butyl propionate, benzyl propionate, ethyl hexanoate, allyl hexanoate, propyl butyrate, butyl butyrate, isobutyl butyrate, 3-methylbutyl butyrate, Methyl benzoate, ethyl benzoate, butyl benzoate, butyl benzoate, phenylacetate, benzyl acetate, methyl phenylacetate, benzyl formate, phenyl ethyl formate, methyl 3 -Phenyl propionate, ethyl phenylacetate and 2-phenyl ethyl acetate.

Examples of the ketone solvent having 8 to 16 carbon atoms include 2-octanone, 3-octanone, 4-octanone, 2-nonanone, 3-nonanone, 4-nonanone, Ketone, ethylcyclohexanone, ethylacetophenone, ethyl n-butyl ketone, di-n-butyl ketone and diisobutyl ketone.

Examples of alcohol solvents of 4 to 10 carbon atoms include 1-butanol, 2-butanol, isobutyl alcohol, t-butyl alcohol, 1-pentanol, 2-pentanol, Butanol, 3-methyl-3-pentanol, cyclopentanol, 1-hexanol, 2-hexanol, 2-methyl-1-butanol, Dimethyl-2-butanol, 3,3-dimethyl-1-butanol, 3,3-dimethyl-2-butanol, 2,2- Pentanol, 3-methyl-1-pentanol, 3-methyl-2-pentanol, 3-methyl- , 4-methyl-2-pentanol, 4-methyl-3-pentanol, cyclohexanol and 1-octanol. These solvents may be used alone or in combination.

Any C ₈ -C ₁₂ ether, C ₆ -C ₁₂ alkane, alkene, alkyne, and aromatic solvents may be blended with dissolution-inhibiting solvents to prevent mixing of the shrink material and the resist pattern.

Suitable ether compounds of 8 to 12 carbon atoms include di-n-butyl ether, diisobutyl ether, di-sec-butyl ether, di-n-pentyl ether, diisopentyl ether, Di-tert-pentyl ether and di-n-hexyl ether. Suitable alkanes of 6 to 12 carbon atoms include but are not limited to hexane, heptane, octane, nonane, decane, undecane, dodecane, methylcyclopentane, dimethylcyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, cycloheptane, Octane and cyclononane. Suitable alkenes of 6 to 12 carbon atoms include hexene, heptene, octene, cyclohexene, methylcyclohexene, dimethylcyclohexene, cycloheptene and cyclooctene. Suitable alkynes of 6 to 12 carbon atoms include hexyne, heptyne and octyne. Suitable aromatic solvents include toluene, xylene, ethylbenzene, isopropylbenzene, tert-butylbenzene, mesitylene and anisole. The solvents may be used alone or in combination.

In addition to the dissipation-inhibiting solvent, the shrink material may contain additional solvents. The additional solvent may be selected from the group consisting of 2-octanone, 2-nonanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-hexanone, 3-hexanone, diisobutyl ketone, methylcyclohexanone, Butene acetate, propyl formate, butyl formate, isobutyl formate, pentyl formate, isopentyl formate, methyl ethyl ketone, methyl isobutyl acetate, isobutyl acetate, Methyl propionate, ethyl propionate, ethyl 3-ethoxypropionate, methyl lactate, ethyl lactate, propyl lactate, butyl propionate, ethyl propionate, Butyl lactate, isobutyl lactate, pentyl lactate, isopentyl lactate, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, methyl benzoate, ethyl benzoate , Phenyl acetate, benzyl acetate, methyl phenylacetate, benzyl formate, phenyl ethyl formate, methyl 3-phenyl propionate, benzyl propionate, ethyl phenylacetate and 2-phenyl ethyl acetate. If an additional solvent is used, it is preferably blended in an amount less than 50% by weight of the total solvent.

In the shrink material, the solvent is preferably used in an amount of 100 to 100,000 parts by weight, more preferably 200 to 50,000 parts by weight, per 100 parts by weight of the polymer.

Salts, basic compounds and surfactants may be added to the shrinkage material, if desired. Salts that may be added are typically selected from sulfonium salts and iodonium salts and ammonium salts that are typically added to the resist composition. The basic compound that may be added may be selected from basic compounds that are ordinarily added to the resist composition, for example, primary, secondary and tertiary aliphatic amines, mixed amines, aromatic amines, heterocyclic amines, A nitrogen-containing compound having a hydroxyl group, a nitrogen-containing compound having a hydroxyl group, a nitrogen-containing compound having a hydroxyphenyl group, an alcoholic nitrogen-containing compound, an amide derivative, There is a bar mate. The addition of a salt or a basic compound suppresses the diffusion of excess acid from the resist film and is effective for controlling the amount of shrink. Surfactants that may be added may be selected from surfactants conventionally added to the resist composition.

As the salt, a carboxylic acid salt having the formula (9) is preferable.

&Lt; Formula 9 >

In the above formulas, R ¹¹ is a linear, branched or cyclic C ₁ -C ₂₀ alkyl group, a linear, branched or cyclic C ₂ -C ₂₀ alkenyl group or a C ₆ -C ₂₀ monovalent aromatic ring- Some or all of the carbon-bonded hydrogen atoms may be replaced by fluorine, a lactone ring-containing moiety, a lactam ring-containing moiety or a hydroxyl moiety, and the ether, ester or carbonyl moiety may be substituted by a carbon- As shown in FIG. M ⁺ is a sulfonium, iodonium or ammonium cation.

Examples of alkyl groups, alkenyl groups and monovalent aromatic ring-containing groups are as described above.

Preferred sulfonium, iodonium and ammonium cations have the following general formula (P1) to (P3). The carboxylic acid salt having the cation can be added to effectively control acid diffusion:

<Formula P1>

&Lt; Formula (P2)

<Formula P3>

In the above formulas, each of R ¹⁰¹ to R ¹⁰⁹ independently represents a linear, branched or cyclic C ₁ -C ₁₂ alkyl or oxoalkyl group, a linear, branched or cyclic C ₂ -C ₁₂ alkenyl or oxoalkenyl group, C _A C ₆ -C ₂₀ monovalent aromatic ring-containing group or a C ₇ -C ₁₂ aralkyl or aryloxoalkyl group, and some or all of the hydrogen atoms may be substituted by halogen, alkyl, alkoxy, and the like. A pair of R ¹⁰¹ and R ¹⁰² , or R ¹⁰⁶ and R ¹⁰⁷ may bond together to form a ring together with the sulfur or nitrogen atom to which they are attached. When they form a ring, they together form a C ₁ -C ₁₀ alkylene or arylene group, and the ring may contain an ether, an ester, a sultone or an amino moiety.

Examples of the alkyl group, the alkenyl group and the monovalent aromatic ring-containing group are as described above. Suitable oxoalkyl and oxoalkenyl groups include the abovementioned alkyl and alkenyl groups in which the oxomo moiety is bonded to a carbon atom. Suitable aralkyl groups include benzyl, 1-phenylethyl and 2-phenylethyl. Suitable aryloxoalkyl groups include 2-aryl-2-oxo, including 2-phenyl-2-oxoethyl, 2- (1-naphthyl) -2-oxoethyl and 2- Ethyl group.

Preferable examples of the anion of the carboxylic acid salt include the carboxylic acid anion described in JP 3991462 and the following, but are not limited thereto:

Preferable examples of the cation of the carboxylic acid salt include, but are not limited to, the following:

The sulfonate salt having the following formula (10) is also preferable as a salt.

&Lt; Formula 10 >

In the above formula, M &lt; ^{+ &gt;} is as defined above. R ¹² is a linear, branched, or cyclic C ₁ -C ₃₅ monovalent hydrocarbon group that may contain an oxygen atom, and some or all of the carbon-bonded hydrogen atoms may be replaced by fluorine, The hydrogen atom bonded to the carbon atom at the? -position is not substituted by fluorine.

In the sulfonic acid salt having the formula (10), it is preferable to have the following formula (10 '):

<Formula 10 '

Wherein M ⁺ is as defined above, R ¹¹⁰ and R ¹¹¹ are each independently hydrogen or trifluoromethyl,

In the shrink material, the salt is preferably used in an amount of 0 to 50 parts by weight, more preferably 0.1 to 20 parts by weight, per 100 parts by weight of the polymer.

Exemplary basic compounds include primary, secondary and tertiary amine compounds as described in JP-A 2008-111103 paragraphs [0146] to [0164] (USP 7,537,880), specifically hydroxyl, ether, ester, lactone , Amine compounds having a cyano or sulfonate group, and compounds having a carbamate group as described in JP 3790649. Particularly, a tertiary amine compound, specifically, an amine compound having a hydroxyl group, an ether group, an ester group or a lactone ring and a compound having a carbamate group are preferable.

In the shrink material, the basic compound is preferably used in an amount of 0 to 30 parts by weight, more preferably 0.1 to 20 parts by weight, per 100 parts by weight of the polymer.

Suitable surfactants include those described in paragraphs [0165] to [0166] of JP-A 2008-111103. The surfactant is preferably used in an amount of 0 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, per 100 parts by weight of the polymer for shrinking material.

Resist composition

The resist composition used in the pattern forming method of the present invention is defined as including a base resin, an acid generator (or a compound generating an acid in response to high-energy radiation), and an organic solvent. Optionally, the resist composition further comprises a basic compound, a dissolution regulator, a surfactant, acetylenic alcohol and other additives.

The base resin used herein is defined as comprising a repeating unit (a) having an acid labile group-substituted carboxyl group, preferably represented by the following formula (11).

&Lt; Formula 11 >

In the above formula, R ²¹ is hydrogen or methyl. R ²² is an acid labile group. Z is a single bond or -C (= O) -OR ²³ -, and R ²³ is a linear, branched or cyclic C ₁ -C ₁₀ alkylene group in which the ether or ester bond may intervene in the carbon- Naphthylene group.

Suitable alkylene groups are as exemplified above. Suitable acid labile groups are those described in paragraphs [0039] to [0044] (USP 9,017,918) of JP-A 2014-088557.

The base resin may further include a repeating unit (b) having an adhesive group selected from hydroxyl, lactone ring, ether, ester, carbonyl and cyano groups so as to improve the substrate adhesion and prevent the pattern from collapsing. The base resin includes repeating units (c) derived from indene, acenaphthylene, chromone, coumarin and norbornadiene derivatives as described in paragraph [0085] of JP-A 2012-037867; (D) derived from styrene, vinyl naphthalene, vinyl anthracene, vinyl pyrene and methylene indane derivatives as described in paragraph [0088]; (E) derived from an onium salt having a polymerizable olefin and which functions as an acid generator as described in the paragraphs [0089] to [0091].

In the base resin, the repeating unit (a) is contained in an amount of more than 0 mol% to 100 mol%, preferably 1 mol% to 100 mol%, more preferably 20 to 90 mol%, based on the total repeating units Lt; / RTI &gt; The repeating unit (b) is incorporated in an amount of from 0 mol% to less than 100 mol%, preferably from 10 to 80 mol%, based on the total repeating units. The sum of the repeating units (a) and (b) is preferably 30 to 100 mol%. When the repeating units (c) to (e) are incorporated, the repeating unit (c) is preferably incorporated in an amount of 0 to 40 mol%, and the repeating unit (d) is incorporated in an amount of 0 to 20 mol% , The repeating unit (e) is incorporated in an amount of 0 to 30 mol%, and the sum of the repeating units (c) to (e) is 0 to 70 mol%.

The base resin should have a Mw of 1,000 to 500,000, more preferably 2,000 to 100,000, as measured by GPC for a polystyrene standard material. When the Mw is too low, the diffusion distance of the acid generated by the acid generator may be enlarged to degrade the resolution. If the Mw is too high, the solubility of the polymer in the developer may be reduced and the resolution may be deteriorated.

If the polymer has a broad molecular weight distribution or a degree of dispersion (Mw / Mn), this indicates the presence of low molecular weight and high molecular weight polymer fractions, so that the foreign matter remains on the pattern and there is a possibility that the pattern profile is damaged. As the pattern rule becomes finer, the influence of the molecular weight and the dispersion becomes stronger. Therefore, in order to provide a resist composition suitable for micropatterning to small feature sizes, it is preferred that the base resin should have a narrow dispersion (Mw / Mn) of 1.0 to 2.0, in particular 1.0 to 1.5.

A blend of two or more polymers having different composition ratios, molecular weights or dispersivities is acceptable as the base resin.

The resist composition contains an acid generator to function as a chemically amplified positive resist composition. The acid generator is a compound which is capable of generating an acid in response to an actinic ray or radiation ordinarily known as a photoacid generator (PAG). An appropriate amount of the PAG used is 0.5 to 30 parts by weight, more preferably 1 to 20 parts by weight, per 100 parts by weight of the base resin. PAGs are any compounds that can generate acids 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 combination of two or more. Examples of acids generated by PAG include sulfonic acid, imidic acid and methidic acid. Of these, fluorinated sulfonic acids at the? -Position are most commonly used. If the acid labile group is an acetal group that is susceptible to deprotection, fluorination at the? -Position is not always necessary. When the base resin has repeating units of an acid generator copolymerized therewith, the acid generator need not be added separately.

Examples of the organic solvent used in the present invention include ketones such as cyclohexanone and methyl-2-n-pentyl ketone; Alcohols such as 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol and 1-ethoxy-2-propanol; Ethers such as propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether and diethylene glycol dimethyl ether; Esters such as propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert Butyl acetate, tert-butyl propionate and propylene glycol mono-tert-butyl ether acetate; And lactones such as? -Butyrolactone and mixtures thereof. When an acid labile group in the form of an acetal is used, a high boiling alcohol solvent such as diethylene glycol, propylene glycol, glycerol, 1,4-butanediol or 1,3-butanediol may be added to accelerate the deprotection reaction of the acetal.

A suitable amount of the organic solvent is 100 to 10,000 parts by weight, preferably 300 to 8,000 parts by weight, per 100 parts by weight of the base resin.

Exemplary basic compounds include primary, secondary and tertiary amine compounds, specifically hydroxyl, ether, ester, lactone, cyano or the like as described in paragraphs [0146] to [0164] of JP-A 2008-111103 An amine compound having a sulfonate group and a compound having a carbamate group as described in JP 3790649 can be mentioned. Also, onium salts of unsulfonated sulfonic acids such as sulfonium salts, iodonium salts and ammonium salts in the? -Position as described in US 2008153030 (JP-A 2008-158339) and sulfonium salts such as those described in JP 3991462 and JP 4226803 Pseudo-onium salts of carboxylic acids can be used as quenchers. They can also be added to the shrink material.

When the acid labile group is a highly sensitive acetal group to the acid, the acid to remove the protecting group does not necessarily have to be fluorinated sulfonic acid, imidic acid or methidic acid at the? -Position. Even if a sulfonic acid which is not fluorinated at the? -position is used, a deprotection reaction may occur in some cases. Since the onium salt of sulfonic acid can not be used as a quencher in this case, it is preferred that the onium salt of imidacic be used singly.

An appropriate amount of the basic compound is 0.0001 to 30 parts by weight, preferably 0.001 to 20 parts by weight, per 100 parts by weight of the base resin.

Exemplary surfactants are described in paragraph [0165] - [0166] of JP-A 2008-111103. Exemplary dissolution regulators are described in paragraph [0155] - [0178] of JP-A 2008-122932 (US 2008090172), and exemplary acetylenic alcohols are described in paragraph [0182]. Surfactants, dissolution regulators and acetylenic alcohols may be used in any suitable amount depending on the purpose of their addition.

Further, a polymer additive may be added to improve water repellency on the surface of the resist film after spin coating. The water repellency improving agent can be used for liquid immersion lithography without using a topcoat. The water repellency improving agent has a specific structure having 1,1,1,3,3,3-hexafluoro-2-propanol residue and is described in JP-A 2007-297590 and JP-A 2008-111103. The water repellency improving agent added to the resist composition must be soluble in an organic solvent as a developer. The water repellency improving agent having a specific structure having a 1,1,1,3,3,3-hexafluoro-2-propanol residue has good solubility in a developer. A polymer in which an amino group or an amine salt is copolymerized as a repeating unit can act as a water repellent additive and is effective in preventing evaporation of an acid in PEB and preventing any hole pattern opening defect after development. An appropriate amount of the water repellency improving agent is 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight, per 100 parts by weight of the base resin.

Pattern formation method

In another embodiment, the resist composition is applied onto a substrate and pre-baked to form a resist film; Exposing the resist film to high-energy radiation, and firing the film; Developing the exposed resist film in an organic solvent-based developer to form a negative resist pattern; Applying a shrink material onto the negative resist pattern and firing; And removing the excess shrink material with an organic solvent.

1 (a) to 1 (f), a pattern shrinking method of the present invention is described. First, as shown in Fig. 1A, a chemically amplified positive resist composition is applied onto a substrate 20 on a substrate 10, and a resist film 30 is formed thereon. If necessary, a hard mask layer (not shown) may be interposed between the resist film 30 and the substrate 20 to be processed. The resist film 30 is exposed by a standard technique (Fig. 1 (b)), and PEB and organic solvent development are performed to form a negative resist pattern 30a (Fig. 1 (c)). The shrink material 40 is applied on the negative resist pattern 30a to apply the pattern as shown in Fig. 1 (d). The shrink material coating is baked, during which the heat serves to evaporate the solvent and to diffuse the acid from the resist pattern 30a to the shrink material coating 40. [ The use of an acid treats the polymer in the shrink material application as a deprotection reaction. Thereafter, the solvent is applied to remove the excess shrink material 40, leaving a shrink material film on the resist pattern 30a. This means that the resist pattern 30a is thickened and the width of the space in the resist pattern is shrunk as shown in Fig. 1 (e). When the shrunk pattern is used as a mask, the processed substrate 20 is dry-etched as shown in Fig. 1 (f).

The substrate 10 used herein is typically a silicon substrate. The substrate 20 (or the target film) 20 used in the present invention may be formed of a material such as SiO ₂ , SiN, SiON, SiOC, p-Si, α-Si, TiN, WSi, BPSG, SOG, Cr, CrO, CrON, MoSi, A dielectric film and an etching stopper film. The hard mask may be of SiO ₂ , SiN, SiON or p-Si. Often, a carbon film-like underlayer film or a silicon-containing interlayer film can be disposed instead of a hard mask, and an organic anti-reflective film can be interposed between the hard mask and the resist film.

The resist film 30 of the chemically amplified positive resist composition is formed directly on the substrate 20 on the substrate 10 by an intermediate intervening layer as described above or the like and the thickness of the resist film is preferably 10 to 1,000 Nm, more preferably 20 to 500 nm. Prior to exposure, the resist film is heated or prebaked at a temperature of 50 to 180 DEG C for preferably 10 to 300 seconds at 60 to 150 DEG C for 15 to 200 seconds, in particular.

Then, the resist film is exposed to high-energy radiation or EB having a wavelength of 400 nm or less. High-energy radiation is typically an i-ray with a wavelength of 364 nm, a KrF excimer laser with a wavelength of 248 nm, an ArF excimer laser with a wavelength of 193 nm or EUV with a wavelength of 13.5 nm. ArF 193-nm lithography is most preferred. The exposure can be carried out in a dry atmosphere, for example in an air or nitrogen stream or by immersion lithography in water. ArF liquid immersion lithography uses deionized water as a liquid immersion solvent or a liquid such as an alkane having a refractive index of at least 1 and highly transparent at an exposure wavelength. In the immersion lithography, the pre-baked resist film is exposed to light through a projection lens, and pure water or another liquid introduced between the resist film and the projection lens is injected. This allows the lens to be designed with a NA of 1.0 or greater, allowing the formation of finer feature size patterns. Immersion lithography is important for keeping ArF lithography as a finer node. In the case of liquid immersion lithography, rinsing (or post-immersion) may be carried out after exposure to remove water droplets remaining on the resist film, or it may be possible to prevent any elution from the resist film, In order to improve the wettability, a protective film can be applied on the resist film after the pre-baking. The resist protective film used in the immersion lithography is insoluble in water but can be obtained from a solution of a polymer having a 1,1,1,3,3,3-hexafluoro-2-propanol residue soluble in an alkali developer, Lt; / RTI &gt; carbon atoms, ethers of 8 to 12 carbon atoms, and mixtures thereof. After the formation of the resist film, deionized water rinsing (or post-immersion) may be performed to extract the acid generator or the like from the surface of the film or to clean the particles, or after rinsing to remove water droplets remaining on the resist film (Or post-immersion) may be performed.

The exposure is preferably performed at an irradiation dose of about 1 to 200 mJ / cm 2, more preferably about 10 to 100 mJ / cm 2. (PEB) on a hot plate at 50 to 150 ° C for 30 seconds to 5 minutes, preferably at 60 to 120 ° C for 30 seconds to 3 minutes.

Thereafter, the exposed resist film is developed for 0.1 to 3 minutes, preferably 0.5 to 2 minutes, by a conventional technique, such as an immersion, a puddle and a spraying technique, with a developer made of an organic solvent. In this manner, a negative resist pattern is formed on the substrate. The organic solvent used as the developer includes at least one organic solvent selected from the group consisting of 2-octanone, 2-nonanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-hexanone, 3-hexanone, diisobutylketone, Propyl acetate, isobutyl acetate, isopentyl acetate, propyl formate, butyl formate, isobutyl formate, pentyl formate, isopentyl acetate, isopentyl acetate, Methyl formate, ethyl crotonate, methyl propionate, ethyl propionate, ethyl 3-ethoxypropionate, methyl lactate, ethyl lactate, propyl lactate, ethyl lactate, Butyl lactate, isobutyl lactate, pentyl lactate, isopentyl lactate, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, methyl benzoate, Ethyl benzoate, phenyl acetate, benzyl acetate, methyl phenylacetate, benzyl formate, phenyl ethyl formate, methyl 3-phenyl propionate, benzyl propionate, ethyl phenylacetate and 2-phenyl ethyl acetate and mixtures thereof .

At the end of development, the resist film can be rinsed. As the rinsing liquid, a solvent which is compatible with the developer and does not dissolve the resist film is preferable. Suitable solvents include alcohols of 3 to 10 carbon atoms, ether compounds of 8 to 12 carbon atoms, alkanes of 6 to 12 carbon atoms, alkenes and alkynes, and aromatic solvents. Specific examples of suitable alcohols having 3 to 10 carbon atoms include n-propyl alcohol, isopropyl alcohol, 1-butyl alcohol, 2-butyl alcohol, isobutyl alcohol, tert-butyl alcohol, Butanol, 3-methyl-1-butanol, 3-methyl-3-pentanol, cyclopentanol, 1-hexanol, 1-pentanol, 2-butanol, 3-dimethyl-1-butanol, 3,3-dimethyl-2-butanol, Methyl-1-pentanol, 3-methyl-2-pentanol, 3-methyl-3-pentanol Pentanol, 4-methyl-3-pentanol, cyclohexanol and 1-octanol. Suitable alkanes of 6 to 12 carbon atoms include but are not limited to hexane, heptane, octane, nonane, decane, undecane, dodecane, methylcyclopentane, dimethylcyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, cycloheptane, Octane and cyclononane. Suitable alkenes of 6 to 12 carbon atoms include hexene, heptene, octene, cyclohexene, methylcyclohexene, dimethylcyclohexene, cycloheptene and cyclooctene. Suitable alkynes of 6 to 12 carbon atoms include hexyne, heptyne and octyne. Suitable ether compounds of 8 to 12 carbon atoms include di-n-butyl ether, diisobutyl ether, di-sec-butyl ether, di-n-pentyl ether, diisopentyl ether, Di-tert-pentyl ether and di-n-hexyl ether. Suitable aromatic solvents include toluene, xylene, ethylbenzene, isopropylbenzene, t-butylbenzene and mesitylene. The solvents may be used alone or in combination. After the rinsing liquid is applied, the substrate can be dried by spin drying and firing. However, rinsing is not essential. If the step of applying the developer to the substrate and then spin-drying the substrate is included, the rinsing step may be omitted.

After development, the shrink material of the invention preferably forms a shrink material coating having a thickness of from 1 to 150 nm, more preferably from 30 to 80 nm. The shrink material application is fired at a temperature of 40 to 180 DEG C for 5 to 300 seconds. Firing evaporates the solvent, inducing acid diffusion from the resist film to the shrink material and acid-assisted cleavage reaction to produce an olefin or bridged structure in the shrink material coating to induce polarity change, It acts to be insoluble in the organic solvent.

Finally, it is desirable to remove the excess shrink material using an organic solvent. Suitable organic solvents for use herein include propyl acetate, butyl acetate, isobutyl acetate, butenyl acetate, pentyl acetate, isopentyl acetate, 2-methylbutyl acetate, hexyl acetate, 2-ethylhexyl acetate, cyclohexyl acetate, But are not limited to, methyl cyclohexyl acetate, propyl formate, butyl formate, isobutyl formate, pentyl formate, isopentyl formate, hexyl formate, methyl valerate, ethyl valerate, propyl valerate, Isobutyl valerate, tert-butyl valerate, pentyl valerate, isopentyl valerate, ethyl isovalerate, propyl isovalerate, isopropyl isovalerate, butyl isovalerate, isobutyl isovalerate, tert - butyl isovalerate, isoprene Methyl 2-methylvalerate, ethyl 2-methylvalerate, methyl crotonate, ethyl crotonate, propyl crotonate, isopropyl crotonate, butyl crotonate, t-butyl crotonate Methyl propionate, ethyl propionate, methyl pentenoate, ethyl pentenoate, propyl pentenoate, isopropyl pentenoate, butyl pentenoate, t-butyl pentenoate, methyl lactate, ethyl lactate But are not limited to, ethyl acetate, propyl acetate, butyl acetate, propyl lactate, butyl lactate, isobutyl lactate, pentyl lactate, isopentyl lactate, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, Pivalate, butyl pivalate, tert-butyl pivalate, butyl propionate, isobutyl propionate, tert-butyl propionate, Ethyl butanoate, ethyl 2-methyl butyrate, ethyl 2-methyl butyrate, ethyl 2-methyl butyrate, ethyl 2-methyl propionate, Methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, phenylacetate, benzyl acetate, methyl phenylacetate, benzyl formate, phenyl ethyl formate, methyl 3-phenyl propionate, 2-heptanone, 4-heptanone, 2-hexanone, 3-hexanone, 2-octanone, 3-octanone, 4-octanone, 2-nonanone, 3-nonanone, 4-nonanone, 5-nonanone, methylcyclohexanone, ethylacetophenone, acetophenone, methyl acetophenone, ethylacetophenone, ethyl n-butyl ketone, Butyl ketone, diisobutyl ketone, 1- Butanol, isobutyl alcohol, t-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, t-pentyl alcohol, neopentyl alcohol, Butanol, 3-methyl-3-pentanol, cyclopentanol, 1-hexanol, 2-hexanol, 3-hexanol, Butanol, 3,3-dimethyl-2-butanol, 2,2-diethyl-1-butanol, Pentanol, 4-methyl-1-pentanol, 4-methyl-2-pentanol, 4-methyl- 3-pentanol, cyclohexanol and 1-octanol.

The organic solvent used for peeling the shrink material may be the same as the organic solvent used as the developer. This means that development of the resist film and removal of the shrink material can be performed using the same organic solvent. It is advantageous that only one nozzle is required.

A pattern formation method using a shrink material on application to a negative tone resist pattern formed by organic solvent development succeeded in reducing the size of holes and / or slits of the negative tone resist pattern in a controlled manner.

Example

Embodiments of the invention are given below by way of illustration and not limitation. The abbreviation "pbw" is parts by weight. For all polymers, Mw and Mn are determined by GPC for polystyrene standards.

[1] Synthesis of polymer

Synthetic example  One

Synthesis of Polymer 1

In a nitrogen atmosphere, 37.43 g of 4-acetoxystyrene, 5.85 g of acenaphthylene, 21.72 g of 4- (1-hydroxy-1-cyclopropyl) styrene, 7.08 g of dimethyl 2,2'-azobis (V-601, Wako Pure Chemical Industries, Ltd.) and 60 g of methyl ethyl ketone as a solvent were fed into a 200 ml dropping cylinder to form a monomer solution Respectively. A 500 ml flask under a nitrogen atmosphere was charged with 48 g of methyl ethyl ketone, which was heated at 80 &lt; 0 &gt; C. With stirring, the monomer solution was added dropwise to the flask over 4 hours. After completion of the dropwise addition, the polymerization solution was continuously stirred for 18 hours while maintaining its temperature at 80 캜. The polymerization solution was cooled to room temperature, where 1,000 g of hexane was added dropwise. The precipitated copolymer was collected by filtration and washed twice with 200 g of hexane. The copolymer was dissolved in a mixture of 126 g of tetrahydrofuran and 42 g of methanol in a 1 liter flask of nitrogen atmosphere, and 16.9 g of ethanolamine was added to the solution, which was stirred at 60 DEG C for 3 hours. The reaction solution was concentrated under reduced pressure. The concentrate was dissolved in a mixture of 300 g of ethyl acetate and 80 g of water. The solution was transferred to a separatory funnel, 8.5 g of acetic acid was added thereto, and then a separation operation was carried out. The lower layer was discarded. 80 g of water and 11.3 g of pyridine were added to the organic layer, and the separation work was carried out. The lower layer was discarded. 80 g of water was added to the organic layer, followed by washing with water and separation. Washing and separation operations were repeated 5 times. After separation, the organic layer was concentrated and dissolved in 140 g of acetone, at which time the acetone solution was added dropwise to 2,500 g of water. The crystallized precipitate was filtered, washed with water and suction filtrated for 2 hours. The filter cake was again dissolved in 150 g of acetone, at which time the acetone solution was added dropwise to 2,800 g of water. The crystallized precipitate was filtered, washed with water and dried to give 45.0 g of a white polymer. The polymer was analyzed by ¹³ C-NMR, ¹ H-NMR spectroscopy and GPC, and the results are shown below.

Hydroxystyrene: acenaphthylene: 4- (1-hydroxy-1-cyclopropyl) styrene = 60.0: 10.0: 30.0

Mw = 4,000

Mw / Mn = 1.66

Synthetic example  2 to 22 and comparison Synthetic example  1 to 3

Synthesis of Polymers 2 to 22 and Comparative Polymers 1 to 3

The polymers in the following Table 1 were produced by the same procedure as in Synthesis Example 1 except that the type and amount of monomers were changed. Table 1 below shows the ratio (molar ratio) of units incorporated into the polymer. Tables 2 to 5 below show the structures of the repeating units.

<Table 1>

<Table 2>

<Table 3>

<Table 4>

<Table 5>

Synthetic example  23, 24

Synthesis of Resist Polymer 1 and Water Repellent Polymer 1

The copolymerization reaction was carried out in a tetrahydrofuran solvent by combining appropriate monomers, crystallized from methanol, washed repeatedly with hexane, separated and dried to synthesize a polymer. A random copolymer represented by Resist Polymer 1 and water repellent Polymer 1 was obtained. The polymer was analyzed by ¹ H-NMR spectroscopy and GPC. The polymer is identified by its analytical data below.

Resist  Polymer 1

Mw = 7,500

Mw / Mn = 1.61

Water repellent polymer 1

Mw = 7,800

Mw / Mn = 1.55

[2] manufacture of shrink materials

Example  1 to 42 and Comparative Example  1 to 6

The synthesized polymers (Polymers 1 to 22 or Comparative Polymers 1 to 3), an onium salt, to a basic compound and a solvent mixture in accordance with the following recipe of Table 6 and Table 7, and the pore size is 0.2 ㎛ of Teflon (Teflon) ^® filter Lt; / RTI &gt; to yield a shrink material. The components listed in Table 6 and Table 7 below are identified as follows.

<Table 6>

<Table 7>

[3] Preparation of Resist Composition

(Resist polymer 1), an acid generator, a quencher and a water-repellent polymer were dissolved in a solvent, 100 ppm of a surfactant FC-4430 (3 M) was added thereto, and a pore size of 0.2 μm Filtered to form a resist composition in the form of a solution. In the following Table 8, PGMEA is propylene glycol monomethyl ether acetate, and PAG1 is identified below.

<Table 8>

[4] ArF lithography patterning test

A spin-on carbon film ODL-101 (Shin-Etsu Chemical Co., Ltd.) was deposited on the silicon wafer to a thickness of 180 nm and a silicon-containing spin-on hard mask SHB- A940 was deposited thereon to a thickness of 40 nm. The resist composition in Table 8 was spin-coated on the substrate for a three-layer process, and then fired on a hot plate at 100 占 폚 for 60 seconds to form a resist film having a thickness of 90 nm. Using a ArF excimer laser immersion lithography scanner NSR-610C (Nikon Corp., NA 1.30, σ 0.90 / 0.70, annular illumination), the resist film was irradiated through a 6% halftone phase shift mask Lt; / RTI &gt; After the exposure, the resist film was baked (PEB) at 90 DEG C for 60 seconds and then subjected to a puddle development in n-butyl acetate for 30 seconds to form a hole pattern having a hole size of 50 nm and a pitch of 150 nm.

The shrink material shown in Table 6 and Table 7 was applied onto the developed resist pattern to apply the pattern. The shrink material coatings were baked for 60 seconds at the temperatures shown in Tables 9 and 10 below. Then, puddle development was performed for 10 seconds in 4-methyl-2-pentanol to remove the excess shrink material. Both after development and after shrink treatment, the pattern was observed under CD-SEM (CG-4000, Hitachi, Ltd.) and the size of the hole was measured at a pitch of 150 nm. The results are shown in Tables 9 and 10 below.

<Table 9>

<Table 10>

While this invention has been illustrated and described as an embodiment, it is not intended to be limited to the details shown, since various changes and modifications may be made therein without departing in any way from the spirit of the invention. Thus, further modifications and equivalents of the invention disclosed herein may be made by those skilled in the art without further experimentation, and all such modifications and equivalents are intended to be within the scope of the present invention And is intended to be encompassed within the spirit and scope of the appended claims.

Japanese Patent Application Nos. 2014-248080 and 2015-077690 are incorporated herein by reference.

Although a few preferred embodiments have been described, many variations and modifications may be made in light of the above teachings. Therefore, the invention may be practiced otherwise than as specifically described without departing from the scope of the appended claims.

Claims (17)

A shrink material comprising a polymer containing at least one repeating unit selected from the following units represented by the following formulas (1a) and (1b), and a solvent containing a dissolution-inhibiting solvent for preventing the resist pattern from being lost after development:
<Formula 1a>

&Lt; EMI ID =

In the above formulas,
A is a single bond or a C ₁ -C ₁₀ alkylene group which may contain an etheric oxygen atom in the middle of the chain,
R &lt; ¹ &gt; is hydrogen, fluorine, methyl or trifluoromethyl,
R ² are each independently hydrogen, halogen, optionally halo-substituted, linear, branched or cyclic, C ₂ -C ₈ acyloxy group, optionally halo-substituted, linear, branched or cyclic, C ₁ -C ₆ Alkyl group or an optionally halo-substituted, linear, branched or cyclic, C ₁ -C ₆ alkoxy group,
L is hydrogen, a linear, branched or cyclic C ₁ -C ₁₀ monovalent aliphatic hydrocarbon group which may contain an etheric oxygen atom, a carbonyl moiety or a carbonyloxy moiety in the middle of the chain, or an optionally substituted 1 Is an aromatic ring-containing group,
Z is bonded to a carbon atom to form a C ₅ -C ₁₅ aliphatic ring group,
R ^x and R ^y are each independently a linear, branched or cyclic C ₁ -C ₁₅ alkyl group which may be substituted with a hydroxyl or alkoxy moiety, and at least one of R ^x and R ^y is a cyclic C The ₅ -C ₁₅ alkyl group,
f is an integer of 1 to 3, s is an integer of 0 to 2, a is (5 + 2s-f), and m is 0 or 1. The shrinkage material of claim 1, wherein the polymer further comprises a repeating unit having the formula:
(2)

In the above formulas,
B is a single bond or a C ₁ -C ₁₀ alkylene group which may contain an etheric oxygen atom in the middle of the chain,
R < ^{1 >} is as defined above,
R ³ is independently hydrogen, halogen, optionally halo-each-substituted, linear, branched or cyclic, C ₂ -C ₈ acyloxy group, optionally halo-substituted, linear, branched or cyclic, C ₁ -C ₆ Alkyl group or an optionally halo-substituted, linear, branched or cyclic, C ₁ -C ₆ alkoxy group,
g is an integer of 0 to 3, t is an integer of 0 to 2, b is (5 + 2t-g), and n is 0 or 1. The shrink material of claim 1, wherein the polymer further comprises a repeating unit having the following formula:
(3)

In the above formulas,
C is a single bond or a C ₁ -C ₁₀ alkylene group which may contain an etheric oxygen atom in the middle of the chain,
R < ^{1 >} is as defined above,
R ⁴ are each independently hydrogen, halogen, optionally halo-substituted, linear, branched or cyclic, C ₂ -C ₈ acyloxy group, optionally halo-substituted, linear, branched or cyclic, C ₁ -C ₆ Alkyl group or an optionally halo-substituted, linear, branched or cyclic, C ₁ -C ₆ alkoxy group,
D is a single bond or a linear, branched or cyclic C ₁ -C ₁₀ (v + 1) hydrocarbon group which may contain an etheric oxygen atom, a carbonyl moiety or a carbonyloxy moiety in the middle of the chain And some or all of the carbon-bonded hydrogen atoms may be replaced by fluorine,
Rf ¹ and Rf ² are each independently a C ₁ -C ₆ alkyl group containing one or more fluorine atoms and Rf ¹ may bond with D to form a ring together with the carbon atoms to which they are attached,
r is 0 or 1, h is an integer of 1 to 3, u is an integer of 0 to 2, c is (5 + 2u-h), and v is 1 or 2. The shrink material according to claim 1, wherein the polymer further comprises at least one repeating unit selected from units having the following general formula (4) and general formula (5)
&Lt; Formula 4 >

&Lt; Formula 5 >

In the above formulas,
R ⁵ and R ⁶ are each independently selected from the group consisting of hydrogen, halogen, optionally halo-substituted, linear, branched or cyclic, C ₂ -C ₈ acyloxy, optionally halo-substituted, linear, branched or cyclic, C ₁ C ₁ -C ₆ alkyl group or optionally halo-substituted, linear, branched or cyclic, C ₁ -C ₆ alkoxy group, i and j are each independently an integer from 0 to 2, d is (6-i) , and e is (4-j). The shrink material of claim 1, wherein the polymer further comprises at least one repeating unit selected from units having the following general formulas (A) to (E):
&Lt; Formula (A)

&Lt; Formula B &gt;

&Lt; EMI ID =

<Formula D>

(E)

In the above formulas,
R ¹ is as defined above, X ^A is an acid labile group, X ^B and X ^C are each independently a single bond or a linear or branched C ₁ -C ₄ divalent hydrocarbon group, and X ^D is any Is a linear, branched or cyclic, C ₁ -C ₁₆ divalent to pentavalent aliphatic hydrocarbon group in which the -CH ₂ - moiety can be replaced by -O- or -C (= O) -, X ^E is an acid Y ^A is a substituent having a lactone, sultone or carbonate structure, Z ^A is hydrogen, a C ₁ -C ₃₀ fluoroalkyl group or a C ₁ -C ₁₅ fluoroalcohol-containing substituent, k ^1A Is an integer of 1 to 3, and k ^1B is an integer of 1 to 4. The shrinkage material of claim 1, wherein the polymer further comprises a repeating unit having the following formula:
<Formula F>

In the above formulas,
R ¹⁰¹ is hydrogen or methyl and X is a single bond, -C (= O) -, -C (= O) -O- or -C (= O) -NH- and R ¹⁰² is a single bond or an ether , A linear, branched or cyclic C ₁ -C ₁₀ alkylene group or a phenylene or naphthylene group which may contain an ester, a carbonyl moiety, -N = or -S-, R ¹⁰³ and R ¹⁰⁴ are Linear or branched C ₁ -C ₄ alkyl or acid labile group, or R ¹⁰³ and R ¹⁰⁴ , taken together, together with the nitrogen atom to which they are attached, form a ring optionally containing an ether linkage Or one of R ¹⁰³ and R ¹⁰⁴ may combine with R ¹⁰² to form a ring together with the nitrogen atom to which they are attached and k ^1C is 1 or 2. The shrink material of claim 1, further comprising a salt having the formula (9):
&Lt; Formula 9 >

In the above formulas,
R ¹¹ is a linear, branched or cyclic C ₁ -C ₂₀ alkyl group, a linear, branched or cyclic C ₂ -C ₂₀ alkenyl group or a C ₆ -C ₂₀ 1 aromatic ring-containing group, Some or all of the hydrogen atoms may be replaced by fluorine, a lactone ring-containing moiety, a lactam ring-containing moiety or a hydroxyl moiety, and an ether, ester or carbonyl moiety may be interposed at the carbon- And M ⁺ is a sulfonium, iodonium or ammonium cation. The shrink material of claim 1, further comprising a salt having the formula (10):
&Lt; Formula 10 >

In the above formulas,
R ¹² is a linear, branched, or cyclic C ₁ -C ₃₅ monovalent hydrocarbon group that may contain an oxygen atom, and some or all of the carbon-bonded hydrogen atoms may be replaced by fluorine, The hydrogen atom bonded to the carbon atom at the? -position is not substituted by fluorine, and M ⁺ is a sulfonium, iodonium or ammonium cation. The method according to claim 1, wherein the nitrogen-containing compound having a primary, secondary and tertiary aliphatic amine, mixed amine, aromatic amine, heterocyclic amine, carboxyl group, nitrogen-containing compound having a sulfonyl group, Further comprising at least one basic compound selected from the group consisting of a nitrogen-containing compound having a hydroxyl group, a nitrogen-containing compound having a hydroxyphenyl group, an alcoholic nitrogen-containing compound, an amide derivative, an imide derivative and a carbamate. The shrink material according to claim 1, wherein the dissolution inhibiting agent is an ester solvent of 7 to 16 carbon atoms, a ketone solvent of 8 to 16 carbon atoms or an alcohol solvent of 4 to 10 carbon atoms. 11. The composition of claim 10, wherein the dissolution-inhibiting solvent is
But are not limited to, pentyl acetate, isopentyl acetate, 2-methylbutyl acetate, hexyl acetate, 2-ethylhexyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, hexyl formate, ethyl valerate, propyl valerate, Isobutyl valerate, tert-butyl valerate, pentyl valerate, isopentyl valerate, ethyl isovalerate, propyl isovalerate, isopropyl isovalerate, butyl isovalerate, isobutyl isovalerate, tert Butyl-2-methylvalerate, ethyl 2-methylvalerate, ethyl pivalate, propyl pivalate, isopropyl pivalate, butyl pivalate, tert-butyl pivalate, ethyl Pentenoate, propylpentanoate, isopropylpentenoate, butyl Propyl crotonate, isopropyl crotonate, butyl crotonate, tert-butyl crotonate, butyl propionate, isobutyl propionate, tert-butyl propionate , Ethyl benzoate, ethyl benzoate, benzyl propionate, ethyl hexanoate, allyl hexanoate, propyl butyrate, butyl butyrate, isobutyl butyrate, 3-methylbutyl butyrate, Methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, phenylacetate, benzyl acetate, methyl phenylacetate, benzyl formate, phenyl ethyl formate, methyl 3-phenyl propionate, ethyl phenylacetate, An ester solvent of 7 to 16 carbon atoms including ethyl acetate,
2-butanone, 2-octanone, 3-octanone, 4-octanone, 2-nonanone, 3-nonanone, 4-nonanone, 5-nonanone, diisobutyl ketone, ethylcyclohexanone, ketone solvents of 8 to 16 carbon atoms, including n-butyl ketone, di-n-butyl ketone and diisobutyl ketone, and
Propanol, 3-pentanol, t-pentyl alcohol, neopentyl alcohol, 2-methyl-1-butanol, 3-butanol, 3-butanol, Butanol, 3-methyl-3-pentanol, cyclopentanol, 1-hexanol, 2-hexanol, 3-hexanol, Butanol, 2-methyl-1-butanol, 2-methyl-2-pentanol, Pentanol, 4-methyl-1-pentanol, 4-methyl-2-pentanol, 4- Alcohol solvents of 4 to 10 carbon atoms including methyl-3-pentanol, cyclohexanol and 1-octanol
&Lt; / RTI &gt; wherein the solvent is at least one solvent selected from the group consisting of: The method of claim 1, wherein the solvent comprises a dissolution-inhibiting solvent and an additional solvent, wherein the further solvent is selected from the group consisting of 2-octanone, 2-nonanone, 2-heptanone, 3- Propyl acetate, butyl acetate, isobutyl acetate, pentyl acetate, isopentyl acetate, butenyl acetate, propyl formate, propyl formate, propyl formate, propyl formate, Methyl formate, ethyl crotonate, methyl propionate, ethyl propionate, ethyl propionate, ethyl propionate, isobutyl formate, Propyl lactate, butyl lactate, isobutyl lactate, pentyl lactate, isopentyl lactate, methyl 2-hydroxyisobutyrate, methyl 2-hydroxyisobutyrate, Methyl 2-hydroxyisobutyrate, methyl benzoate, ethyl benzoate, phenylacetate, benzyl acetate, methyl phenylacetate, benzyl formate, phenyl ethyl formate, methyl 3-phenylpropionate, benzyl propionate, Ethyl phenyl acetate and 2-phenyl ethyl acetate. As a pattern forming method,
A resist composition comprising a base resin comprising a repeating unit having an acid labile group-substituted carboxyl group, an acid generator, and an organic solvent on a substrate,
Pre-baking to form a resist film,
Exposing the resist film to high-energy radiation,
Firing the membrane,
Developing the exposed resist film in an organic solvent type developer to form a negative resist pattern,
Applying the shrink material of claim 1 onto a negative resist pattern,
Firing step, and
Removing the excess shrink material with organic solvent
&Lt; / RTI &gt; 14. The pattern forming method according to claim 13, wherein the base resin in the resist composition comprises the repeating unit (a) having an acid labile group-substituted carboxyl group represented by the following formula (11)
&Lt; Formula 11 >

In the above formulas,
R ²¹ is hydrogen or methyl, R ²² is an acid labile group, Z is a single bond or -C (═O) -OR ²³ -, and R ²³ is a group in which an ether or ester bond can be interposed in the carbon- Linear, branched or cyclic C ₁ -C ₁₀ alkylene or naphthylene group. 14. The method according to claim 13, wherein the developer is selected from the group consisting of 2-octanone, 2-nonanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-hexanone, 3-hexanone, diisobutylketone, Isobutyl acetate, butenyl acetate, propyl formate, butyl formate, isobutyl formate, pentyl formate, isopentyl acetate, isopentyl acetate, butenyl acetate, propyl formate, butyl formate, isobutyl acetate, butyl acetate, isobutyl acetate, Methyl formate, ethyl crotonate, methyl propionate, ethyl propionate, ethyl 3-ethoxypropionate, methyl lactate, ethyl lactate, propyl lactate, ethyl lactate, Ethyl lactate, butyl lactate, isobutyl lactate, pentyl lactate, isopentyl lactate, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, methyl benzoate, ethyl One selected from the group consisting of benzoate, phenylacetate, benzyl acetate, methyl phenylacetate, benzyl formate, phenyl ethyl formate, methyl 3-phenyl propionate, benzyl propionate, ethyl phenylacetate and 2- Or more of the organic solvent. 14. The process of claim 13, wherein the step of removing the excess shrink material is carried out in a solvent selected from the group consisting of propyl acetate, butyl acetate, isobutyl acetate, butenyl acetate, pentyl acetate, isopentyl acetate, 2- methylbutyl acetate, hexyl acetate, , Cyclohexyl acetate, methyl cyclohexyl acetate, propyl formate, butyl formate, isobutyl formate, pentyl formate, isopentyl formate, hexyl formate, methyl valerate, ethyl valerate, propyl valerate, isopropyl Isobutyl valerate, isobutyl valerate, isobutyl valerate, isobutyl valerate, isopentyl valerate, ethyl isovalerate, propyl isovalerate, isopropyl isovalerate, butyl isovalerate, isobutyl valerate, isobutyl valerate, Isovalerate, tert-butyl isovalerate, Ethyl 2-methylvalerate, butyl 2-methylvalerate, methyl crotonate, ethyl crotonate, propyl crotonate, isopropyl crotonate, butyl crotonate, tert-butyl crotonate Methyl propionate, ethyl propionate, ethyl pentenoate, propyl pentenoate, isopropyl pentenoate, butyl pentenoate, tert-butyl pentenoate, methyl lactate, ethyl lactate, But are not limited to, lactate, butyl lactate, isobutyl lactate, pentyl lactate, isopentyl lactate, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, ethyl pivalate, propyl pivalate, Butyl pivalate, tert-butyl pivalate, butyl propionate, isobutyl propionate, tert-butyl propionate, benzyl propionate Propyl butyrate, isobutyl butyrate, 3-methylbutyl butyrate, tert-butyl butyrate, ethyl 2-methyl butyrate, isopropyl propyl propionate, ethyl propionate, ethyl propionate, ethyl hexanoate, Methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, phenylacetate, benzyl acetate, methyl phenylacetate, benzyl formate, phenyl ethyl formate, methyl 3-phenyl propionate, ethyl phenyl Acetate, 2-phenylethylacetate, 2-heptanone, 3-heptanone, 4-heptanone, 2-hexanone, 3-hexanone, Ethyl n-butyl ketone, di-n-butyl acrylate, ethyl n-butyl acrylate, ethyl n-butyl methacrylate, Ketone, diisobutyl ketone, 1-butanol Butanol, isobutyl alcohol, t-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, t-pentyl alcohol, neopentyl alcohol, Butanol, 3-methyl-3-pentanol, cyclopentanol, 1-hexanol, 2-hexanol, Butanol, 3,3-dimethyl-2-butanol, 2,2-diethyl-1-butanol, Methyl-1-pentanol, 4-methyl-2-pentanol, 4-methyl-3-pentanol, - at least one organic solvent selected from the group consisting of pentanol, cyclohexanol and 1-octanol is used. 14. The method according to claim 13, wherein the high-energy radiation is an i-ray with a wavelength of 364 nm, a KrF excimer laser with a wavelength of 248 nm, an ArF excimer laser with a wavelength of 193 nm, EUV or EB with a wavelength of 13.5 nm.

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