KR102015690B1 - Shrink material and pattern forming process - Google Patents

Abstract

The invention provides a shrink material comprising a specific polymer and a solvent containing an anti-loss solvent. A resist composition comprising a base resin and an acid generator is applied onto a substrate to form a resist film, exposed, and developed in an organic solvent developer to form a negative resist pattern, a shrink material is applied onto the pattern, and an extra shoe The pattern is formed by removing the link material with an organic solvent to reduce the size of the holes and / or slits in the pattern.

Description

Shrinking material and pattern formation method {SHRINK MATERIAL AND PATTERN FORMING PROCESS}

Cross Reference to Related Applications

The regular application is 35 U.S.C. Patent applications 2014-248080 and 2015-077690, filed in Japan on December 8, 2014 and April 6, 2015, under §119 (a), with priority claims, the entire disclosures of which are 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.

Recently, efforts to reduce pattern rules have been rapidly progressed to meet the demand for high integration and operating speed of LSI, and photolithography has been used as a general purpose technology. Photolithography has inherent limitations in resolution determined by the wavelength of the light source. One example of a micropatterning approach that goes beyond the resolution limits is a combination of ArF excimer laser immersion lithography and double patterning. A typical example of double patterning involves forming a pattern by exposure, transferring the pattern to a hard mask on the substrate by etching, performing a second exposure at the half-pitch shifted position, and etching the hard mask. Lito-etch-litto-etch (LELE) process. This process has the problem of mismatch between two exposure 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 a film on the opposite side of the hard mask feature, and doubling the pattern size leaving the sidewalls of the film. The SADP process requires only one exposure and alleviates the problem of overlay error. In order to simplify the process, a variant of the SADP process has also been proposed which forms a silicon oxide film on the side of the resist pattern feature after development rather than the sidewall of the hard mask feature. Since the SADP process succeeded in reducing the pitch of the line pattern by 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 in the chip as a whole is incomplete. A known method of hole pattern reduction is the RELACS ^® method described in Patent Document 1. This method seeks to reduce the size of the hole pattern by applying a resist pattern after development to a water-soluble material containing a crosslinking agent, baking the coating to form a crosslinked layer on the resist surface to thicken the resist pattern. Patent document 2 describes a shrink material comprising an amino-containing polymer or polyamine, which is bonded to the resist surface by a neutralization reaction with carboxyl groups on the resist surface to thicken the resist film. In addition, Non-Patent Document 1 proposes to reduce the hole pattern by using the direct magnetic arrangement (DSA) of the block copolymer.

Shrinks by the Relax ^® method cause problems because the crosslinking agent becomes active as an acid catalyst in the resist, and when the acid diffusion is uneven, the size of the hole after the shrinking becomes uneven. In the shrink method based on the neutralization and adhesion of the amino polymer, since the pattern is thickened by directly reflecting the unevenness of the resist surface, the dimensional variation of the resist pattern after development and the dimensional variation after shrinkage are the same. The shrink method using the DSA action of the block copolymer has the advantage of including an increase in the amount of shrink and a minimum dimensional change after the shrink, with some problems. When so-called DSA is applied to holes of different sizes, no shrinkage can be caused for holes of sizes that cause contradictions in the arrangement of the block copolymers. When the DSA is applied to the trench pattern, shape deformation such as a plurality of hole patterns is formed, for example, becomes a problem.

There is a need for a shrink material that can shrink the hole pattern without changing the shape of the resist pattern, and can improve the dimensional variation 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 proposed an alkali aqueous solution treatment type shrink material applied to the positive tone resist pattern produced by alkali development. With regard to the shrink of hole patterns having a narrow pitch, such a shrink material did not obtain a sufficient amount of shrink and did not reduce the dimensional variation.

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

In order to obtain a shrink material capable of effectively shrinking the resist pattern after development, the inventors have formed a resist film based on an acid generator and a base resin having an acid labile group-substituted carboxyl group, Thereby forming a negative tone resist pattern, applying a resist pattern with a shrink material comprising a specific polymer and a solvent containing an anti-loss solvent, firing, and removing the excess shrink material with an organic solvent in the resist pattern. It has been found that the size of the holes and / or slits of 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 Formulas 1a and 1b, and an anti-vanishing agent which prevents the development of the resist pattern after development. Provided is a shrink material comprising a solvent containing:

<Formula 1a>

<Formula 1b>

In the above formula, A is a single bond or a C ₁ -C ₁₀ alkylene group which may contain etheric oxygen atoms in the middle of the chain; R ¹ is hydrogen, fluorine, methyl or trifluoromethyl; Each R ² is 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 An alkyl group or 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 optionally substituted Monovalent aromatic ring-containing groups; Z combines with a carbon atom to form a C ₅ -C ₁₅ alicyclic 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 hydrogen or a hydroxyl or alkoxy moiety, and at least one of R ^x and R ^y is cyclic C _{A 5-} C ₁₅ alkyl group; f is an integer of 1-3, s is an integer of 0-2, a is (5 + 2s-f), and m is 0 or 1.

The polymer preferably further comprises a repeating unit having the formula

<Formula 2>

In the above formula, B is a single bond or a C ₁ -C ₁₀ alkylene group which may contain etheric oxygen atoms in the middle of the chain; R ¹ is as defined above; Each R ³ is 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 An alkyl group or optionally halo-substituted, linear, branched or cyclic, C ₁ -C ₆ alkoxy group; g is an integer of 0-3, t is an integer of 0-2, b is (5 + 2t-g), and n is 0 or 1.

The polymer preferably further comprises repeating units having the formula

<Formula 3>

In the above formula, C is a single bond or a C ₁ -C ₁₀ alkylene group which may contain etheric oxygen atoms in the middle of the chain; R ¹ is as defined above; Each R ⁴ is 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 An alkyl group or 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) divalent hydrocarbon group which may contain an ethereal oxygen atom, a carbonyl moiety or a carbonyloxy moiety in the middle of the chain 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 be bonded to D to form a ring with the carbon atom to which they are attached; r is 0 or 1, h is an integer of 1-3, u is an integer of 0-2, c is (5 + 2u-h), v is 1 or 2.

The polymer preferably further comprises at least one repeating unit selected from units having the formulas (4) and (5):

<Formula 4>

<Formula 5>

In the above formula, R ⁵ and R ⁶ 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 groups or optionally halo-substituted, linear, branched or cyclic, C ₁ -C ₆ alkoxy groups; 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 one or more repeating units selected from units having the formulas (A) to (E):

<Formula A>

<Formula B>

<Formula C>

<Formula D>

<Formula E>

In the above formula, 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 substituted by —O— or —C (═O) — And; 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, k ^1B is an integer of 1 to 4.

The polymer preferably further comprises repeating units having the formula (F):

<Formula F>

In the above formula, R ¹⁰¹ is hydrogen or methyl; X is a single bond, -C (= 0)-, -C (= 0) -O- or -C (= 0) -NH-; R ¹⁰² is a single bond or a linear, branched or cyclic C ₁ -C ₁₀ alkylene group which may contain an ether, ester, carbonyl moiety, -N = or -S-, or a phenylene or naphthylene group Is; 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 are bonded together to form an ether bond together with the nitrogen atom to which they are attached; Optionally form a containing ring, or one of R ¹⁰³ and R ¹⁰⁴ may combine with R ¹⁰² to form a ring 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):

<Formula 9>

In the above formula, 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 C ₆ -C ₂₀ monovalent aromatic ring-containing group, Some or all of the carbon-bonded hydrogen atoms may be substituted by fluorine, lactone ring-containing moieties, lactam ring-containing moieties or hydroxyl moieties, wherein the ether, ester or carbonyl moiety is a carbon-carbon bond And M ⁺ is a sulfonium, iodonium or ammonium cation.

The shrink material may further comprise a salt having Formula 10:

<Formula 10>

In the above formula, R ¹² is a linear, branched or cyclic C ₁ -C ₃₅ monovalent hydrocarbon group which may contain oxygen atoms, and some or all of the carbon-bonded hydrogen atoms may be substituted by fluorine, Provided that the hydrogen atom bonded to the carbon atom in the α-position relative to sulfonic acid is not substituted by fluorine and M ⁺ is a sulfonium, iodonium or ammonium cation.

In a preferred embodiment, the shrink material comprises primary, secondary and tertiary aliphatic amines, mixed amines, aromatic amines, heterocyclic amines, nitrogen-containing compounds with carboxyl groups, nitrogen-containing compounds with sulfonyl groups, It may further comprise 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 anti-loss solvent 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 anti-loss solvent is one or more solvents selected from the group consisting of:

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 Latex, isobutyl valerate, tert-butyl valerate, pentyl valerate, isopentyl valerate, ethyl isovalerate, propyl isovalerate, isopropyl isovalerate, butyl isovalerate, isobutyl isovalerate, tert -Butyl isovalerate, isopentyl isovalerate, ethyl 2-methylvalerate, butyl 2-methylvalerate, ethyl pivalate, propyl pivalate, isopropyl pivalate, butyl pivalate, tert-butyl pivalate, ethyl Pentenoate, propyl pentenoate, isopropyl pentenoate, butyl Tenoate, tert-butyl pentenoate, propyl crotonate, isopropyl crotonate, butyl crotonate, tert-butyl crotonate, butyl propionate, isobutyl propionate, tert-butyl propionate Benzyl propionate, ethyl hexanoate, allyl hexanoate, propyl butyrate, butyl butyrate, isobutyl butyrate, 3-methylbutyl butyrate, tert-butyl butyrate, ethyl 2-methylbutyrate, isopropyl 2-methylbutyrate, Methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, phenyl acetate, benzyl acetate, methyl phenyl acetate, benzyl formate, phenylethyl formate, methyl 3-phenylpropionate, ethyl phenylacetate and 2-phenyl Ester solvents of 7 to 16 carbon atoms, including ethyl acetate,

2-octanone, 3-octanone, 4-octanone, 2-nonanone, 3-nonanone, 4-nonanone, 5-nonanone, diisobutyl ketone, ethylcyclohexanone, ethylacetophenone, ethyl ketone solvents of 8 to 16 carbon atoms, including n-butyl ketone, di-n-butyl ketone and diisobutyl ketone, and

1-butanol, 2-butanol, isobutyl alcohol, t-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, t-pentyl alcohol, neopentyl alcohol, 2-methyl-1-butanol, 3 -Methyl-1-butanol, 3-methyl-3-pentanol, cyclopentanol, 1-hexanol, 2-hexanol, 3-hexanol, 2,3-dimethyl-2-butanol, 3,3-dimethyl -1-butanol, 3,3-dimethyl-2-butanol, 2,2-diethyl-1-butanol, 2-methyl-1-pentanol, 2-methyl-2-pentanol, 2-methyl-3- Pentanol, 3-methyl-1-pentanol, 3-methyl-2-pentanol, 3-methyl-3-pentanol, 4-methyl-1-pentanol, 4-methyl-2-pentanol, 4- Alcohol solvent of 4 to 10 carbon atoms, including methyl-3-pentanol, cyclohexanol and 1-octanol.

Preferably, the solvent contains an anti-loss solvent and an additional solvent, and the additional solvent is 2-octanone, 2-nonanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-hexa. Paddy, 3-hexanone, diisobutyl ketone, methylcyclohexanone, acetophenone, methylacetophenone, propyl acetate, butyl acetate, isobutyl acetate, pentyl acetate, isopentyl acetate, butenyl acetate, propyl formate, butyl Formate, isobutyl formate, pentyl formate, isopentyl formate, methyl valerate, methyl pentenoate, methyl crotonate, ethyl crotonate, methyl propionate, ethyl propionate, ethyl 3-e Oxypropionate, methyl lactate, ethyl lactate, 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, phenylethyl formate, methyl 3-phenylpropionate, benzyl propionate, ethyl phenyl Acetate and 2-phenylethyl acetate.

In another embodiment, the present invention is applied to a substrate by applying a resist composition comprising a base resin, an acid generator and an organic solvent comprising a repeating unit having an acid labile group-substituted carboxyl group, and pre-fired to form a resist film Making; Exposing the resist film to high-energy radiation and firing the film; Developing the exposed resist film in an organic solvent developer to form a negative resist pattern; Applying a shrink material as defined herein to the 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):

<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 an ether or ester bond to the carbon-carbon bond Linear, branched or cyclic C ₁ -C ₁₀ alkylene groups or naphthylene groups which may be interrupted.

In the pattern formation method, the developer is 2-octanone, 2-nonanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-hexanone, 3-hexanone, diisobutyl ketone, methylcyclo Hexanon, acetophenone, methylacetophenone, propyl acetate, butyl acetate, isobutyl acetate, pentyl acetate, isopentyl acetate, butenyl acetate, propyl formate, butyl formate, isobutyl formate, pentyl formate, isopentyl Formate, methyl valerate, methyl pentenoate, methyl crotonate, ethyl crotonate, methyl propionate, ethyl propionate, ethyl 3-ethoxypropionate, methyl lactate, ethyl lactate, propyl Lactate, butyl lactate, isobutyl lactate, pentyl lactate, isopentyl lactate, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, methyl benzoate, Methyl benzoate, phenyl acetate, benzyl acetate, methyl phenylacetate, benzyl formate, phenylethyl formate, methyl 3-phenylpropionate, benzyl propionate, ethyl phenylacetate and 2-phenylethyl acetate At least one organic solvent.

Preferably, the step of removing excess shrink material is propyl acetate, butyl acetate, isobutyl acetate, butenyl acetate, pentyl acetate, isopentyl acetate, 2-methylbutyl acetate, hexyl acetate, 2-ethylhexyl acetate, Cyclohexyl acetate, methylcyclohexyl acetate, propyl formate, butyl formate, isobutyl formate, pentyl formate, isopentyl formate, hexyl formate, methyl valerate, ethyl valerate, propyl valerate, isopropyl valerate Rate, Butyl valerate, isobutyl valerate, tert-butyl valerate, pentyl valerate, isopentyl valerate, ethyl isovalerate, propyl isovalerate, isopropyl isovalerate, butyl isovalerate, isobutyl iso Valerate, tert-butyl isovalerate , Isopentyl 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, 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 Nitrate, ethyl 3-ethoxypropionate, ethyl hexanoate, allyl hexanoate, propyl butyrate, butyl butyrate, isobutyl butyrate, 3-methylbutyl butyrate, tert-butyl butyrate, ethyl 2-methylbutyrate, isopropyl 2-methylbutyrate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, phenyl acetate, benzyl acetate, methyl phenylacetate, benzyl formate, phenylethyl formate, methyl 3-phenylpropionate, ethyl phenyl Acetate, 2-phenylethyl acetate, 2-heptanone, 3-heptanone, 4-heptanone, 2-hexanone, 3-hexanone, 2-octanone, 3-octanone, 4-octanone, 2- Nonanone, 3-nonanone, 4-nonanone, 5-nonanone, methylcyclohexanone, ethylcyclohexanone, acetophenone, methylacetophenone, ethylacetophenone, ethyl n-butyl ketone, di-n-butyl Ketone, diisobutyl ketone, 1-butane Ol, 2-butanol, isobutyl alcohol, t-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, t-pentyl alcohol, neopentyl alcohol, 2-methyl-1-butanol, 3-methyl -1-butanol, 3-methyl-3-pentanol, cyclopentanol, 1-hexanol, 2-hexanol, 3-hexanol, 2,3-dimethyl-2-butanol, 3,3-dimethyl-1 -Butanol, 3,3-dimethyl-2-butanol, 2,2-diethyl-1-butanol, 2-methyl-1-pentanol, 2-methyl-2-pentanol, 2-methyl-3-pentanol , 3-methyl-1-pentanol, 3-methyl-2-pentanol, 3-methyl-3-pentanol, 4-methyl-1-pentanol, 4-methyl-2-pentanol, 4-methyl- 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 i-ray with wavelength 364 nm, KrF excimer laser with wavelength 248 nm, ArF excimer laser with wavelength 193 nm, EUV with wavelength 13.5 nm or EB.

Forming a resist film based on an acid labile group-based resin having an acid labile group-substituted carboxyl group and an acid generator, which is subjected to exposure and organic solvent development to form a negative tone resist pattern, and the shrink material of the present invention is applied to the resist pattern. Methods involving application have succeeded in reducing the size of the holes and / or slits in the resist pattern in a controlled manner.

1 (a) to 1 (f) show cross sections of the steps of the pattern forming or shrink method according to the present invention; 1 (a) shows a resist film formed over 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; 1 (d) shows a shrink material applied over the resist pattern; FIG. 1 (e) shows a resist pattern having a shrunk space after firing, after removing excess shrunk material; 1 (f) shows the dry etching of the substrate through the shrunk pattern as a mask.

The terms "a" and "an" herein do not indicate a limitation of quantity, but rather indicate the presence of one or more of the items mentioned. “Any” or “optionally” means that a case or situation described later may or may not occur, and that description includes cases where and when cases and situations do not occur. 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

GPC: Gel Permeation Chromatography

PEB: Post Exposure Baking

PAG: Mine Generator

In the formula, Me represents methyl; Ac is acetyl; And dashed lines represent valence bonds.

Shrink material

The present invention provides a shrink material comprising a polymer and a solvent containing an anti-loss solvent which prevents the resist pattern from developing after development. A polymer is defined to include one or more repeating units selected from units having Formula 1a and Formula 1b. Note that such polymers are often referred to as “polymers for shrink materials”.

<Formula 1a>

<Formula 1b>

In Formulas 1a and 1b, “A” is a C ₁ -C ₁₀ alkylene group which may contain an etheric oxygen atom in the middle of a single bond or chain. Suitable alkylene groups include methylene, ethylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, cyclopentylene, cyclohexylene and structural isomers thereof having branched or cyclic structures. In particular, A is preferably a single bond, methylene, ethylene, propylene or trimethylene. When A is a group containing an etheric oxygen atom, in case of m = 1 in the general formula (1), the etheric oxygen atom may be included at any position except between carbon at the α and β-positions relative to the ester oxygen. In the case of m = 0, the etheric oxygen atom becomes an atom bonded to the main chain, and the second etheric oxygen atom may be included at any position except between carbon at the α and β-positions relative to the ether oxygen atom. .

In Formula 1a and Formula 1b, R ¹ is hydrogen, fluorine, methyl or trifluoromethyl. Each R ² is 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 optionally halo-substituted, linear, branched or cyclic, C ₁ -C ₆ alkoxy group.

Examples of halogens 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, dodec Yarns, norbornyl and adamantyl. Suitable alkoxy groups include methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, s-butoxy, t-butoxy, pentyloxy, hexyloxy, cyclopentyloxy, cyclohexyloxy, 1- Methyl-1-cyclopentyloxy, 1-ethyl-1-cyclopentyloxy, 1-methyl-1-cyclohexyloxy, and 1-ethyl-1-cyclohexyloxy.

In Formula 1a and Formula 1b, L is hydrogen, a linear, branched or cyclic, C ₁ -C ₁₀ monovalent which may contain an ethereal oxygen atom, a carbonyl moiety or a carbonyloxy moiety in the middle position of the chain Aliphatic hydrocarbon groups or optionally substituted monovalent aromatic ring-containing groups. Suitable monovalent aliphatic hydrocarbon groups are linear, branched or cyclic alkyl, alkenyl and alkynyl groups. Suitable alkyl groups include the groups exemplified above except those having from 1 to 10 carbon atoms. Suitable alkenyl groups include vinyl, allyl, propenyl, cyclopropenyl, butenyl, cyclobutenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, methylcyclohexenyl, ox Tenyl, dimethylcyclohexenyl and cyclooctenyl. Suitable alkynyl groups include ethynyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl and octinyl. Suitable monovalent aromatic ring-containing groups include phenyl, naphthyl, phenanthryl, anthryl, pyrenyl, biphenylyl, acenaphthenyl and fluorenyl. Preferably, L includes hydrogen, methyl, ethyl, propyl, isopropyl, cyclopentyl, cyclohexyl, adamantyl, methylcarbonyl or phenyl.

In Formula 1a, Z combines with a carbon atom to form a C ₅ -C ₁₅ alicyclic group. Suitable alicyclic groups include, but are not limited to:

In Formula 1b, R ^x and R ^y are each independently a linear, branched or cyclic, C ₁ -C ₁₅ alkyl group which may be substituted with hydrogen or a hydroxyl or alkoxy moiety and one of R ^x and R ^y The above is a cyclic C ₅ -C ₁₅ alkyl group. Preferably, R ^x and R ^y are such groups substituted with methyl, ethyl, propyl, butyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, adamantyl, norbornyl, and hydroxyl or alkoxy moieties Is selected from.

In Formula 1a and Formula 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.

Among the repeating units of Formula 1a and Formula 1b, the repeating units of Formulas 1a 'and 1b' are preferred:

<Formula 1a '>

<Formula 1b '>

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

Preferred examples of repeating units of Formula 1a and Formula 1b are shown below, but not limited to:

Preferably, the polymer for shrink material further comprises repeating units of formula (2) and / or (3) to provide sufficient adhesion to the resist pattern and adhesion to the substrate. The repeating unit of formula (2) or formula (3) below has suitable heat of the polymer that advantageously promotes the insolubilization reaction that causes the polymer to be insolubilized in the shrink material stripper as a result of the removal of the acid labile groups in the repeating units of Formulas 1a and 1b. Allow vibration. In particular, the repeating unit of formula (2) is more preferred.

<Formula 2>

<Formula 3>

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

In formula (2), R ¹ is as defined above. Each R ³ is 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 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 ² .

In formula (2), g is an integer of 0 to 3, t is an integer of 0 to 2, b is (5 + 2t-g), n is 0 or 1. Where g represents the number of hydroxyl groups bonded to the aromatic ring. G is preferably at least 1 so that the polymer provides a high activity for the insolubilization reaction which is insolubilized in the stripping solution as a result of the removal of the acid labile groups in the repeating units of Formulas 1a and 1b to obtain a sufficient amount of shrinkage. . More preferably, the unit of formula (2) having g of 1 or more is 50 mol% or more of the unit of formula (2). Units of formula (2) with g = 0 are effective in controlling dissolution rate and thermal vibration of the polymer, but may not be included depending on the particular design.

In the repeating units of formula (2), when g is at least 1, n = 0 and B is a single bond, ie the repeating units of formula (2), ie, linker-free repeating units, in which the aromatic ring is directly bonded to the polymer backbone, are hydroxy Units derived from monomers having 1-substituted or unsubstituted vinyl groups bonded to substituted aromatic rings, typically hydroxystyrene units. Suitable units include those derived from 3-hydroxystyrene, 4-hydroxystyrene, 5-hydroxy-2-vinylnaphthalene and 6-hydroxy-2-vinylnaphthalene. As represented by the following formula (2 '), units derived from 3-hydroxystyrene or 4-hydroxystyrene are preferred.

<Formula 2 '>

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

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

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

In the repeating unit of formula (2), the unit with g = 0 is a unit derived from the above compound having an aromatic ring substituted with styrene, vinylnaphthalene, vinylanthracene and a halogen, acyloxy, alkyl, alkoxy or similar moiety. g = 0 and a unit having a linker (-CO-OB-) derived from (meth) acrylate, g is 1 or more, hydroxyl group is removed, and hydrogen of hydroxyl group is substituted by acyl or alkyl group Preferred examples of the units can be mentioned.

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

In formula (3), R ¹ is as defined above. Each R ⁴ is 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 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 ² .

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

In formula (3), Rf ¹ and Rf ² are each independently a C ₁ -C ₆ alkyl group containing at least one fluorine atom. Rf ¹ may be bonded to D to form a ring together with the carbon atom to which they are bonded. Suitable alkyl groups containing at least one fluorine atom include monofluoromethyl, difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, 1,1,2,2,2-pentafluoro Roethyl, 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-nonafluoropentyl, perfluoropentyl, 1H, 1H-4-trifluoromethylperfluoropentyl, perfluorohexyl, 4-pentafluoroethylperfluorocyclohexyl, 1H, 1H, 2H, 2H-perfluorohexyl and perfluorocyclohexyl.

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

In formula (3), r is 0 or 1. In the case of r = 1, an aromatic ring is interposed between the polymer backbone and the hydroxyl group bonded to the carbon adjacent to the carbon substituted with the fluorine-containing group. In this case, v representing the number of substituents in D is 1 or 2. If D is not a single bond, D has 1 or 2 hydroxyl groups bonded to the carbon adjacent to the carbon substituted with a fluorine-containing group, ie v is 1 or 2.

For r = 0, h is 1 and 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 also D has one or two hydroxyl groups each bonded to a carbon adjacent to the carbon substituted with a fluorine-containing group.

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

Units of formula (2) or formula (3) may be used alone or in combination (ie one or two or more),

The polymer for shrink material may further include at least one repeating unit selected from the units having the following formulas (4) and (5) as the main structural unit. In this embodiment, in addition to the benefits of etch resistance inherent to the aromatic ring, the polymer may have another benefit of bonding the cyclic structure to the backbone, giving dry etch resistance to the shrunk resist pattern.

<Formula 4>

<Formula 5>

In the above formula, R ⁵ and R ⁶ 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 groups or optionally halo-substituted, linear, branched or cyclic, C ₁ -C ₆ alkoxy groups. Examples of acyloxy, alkyl and alkoxy groups are as exemplified above for R ² .

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

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

When i or j is one or more units of formula (4) or (5), in order to improve the etching resistance of the polymer with respect to the other repeating units of the polymer, compounds from which the units of formula (4 ') or (5') are derived are obtained It is easy and effective to achieve the desired effect.

<Formula 4 '>

<Formula 5 '>

The polymer for shrink material may further comprise one or more repeating units selected from units having the formulas (A) to (E). These units can be used as auxiliary units to which the polymer can impart adhesion to a resist pattern or to control solubility of the polymer in a solvent.

<Formula A>

<Formula B>

<Formula C>

<Formula D>

<Formula E>

In the above formula, 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 substituted 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, k ^1B is an integer of 1 to 4.

The repeating unit of formula A decomposes under the action of an acid to produce a carboxylic acid. These units can be mixed to control the solubility of the polymer for shrink material in the organic solvent. The acid labile groups represented by X ^A can be selected from various such groups. Examples of acid labile groups include groups of the formulas L1 to L4, tertiary alkyl groups of 4 to 20 carbon atoms, preferably 4 to 15 carbon atoms, each alkyl moiety of 1 to 6 carbon atoms Trialkylsilyl group having and an oxoalkyl group of 4 to 20 carbon atoms.

<Formula L1>

<Formula L2>

<Formula L3>

<Formula L4>

In the formula, 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, examples being linear, branched or cyclic alkyl groups, some hydrogen Substituted forms of the above alkyl groups whose atoms are substituted by hydroxyl, alkoxy, oxo, amino, alkylamino and the like and analogous groups separated by etheric oxygen atoms are mentioned. R ^L04 is a tertiary alkyl group of 4 to 20 carbon atoms, preferably 4 to 15 carbon atoms, a trialkylsilyl group where each alkyl moiety has 1 to 6 carbon atoms, 4 to 20 carbon atoms Is an oxoalkyl group or a group of formula L1. 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 of 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), exemplary groups of R ^L01 and R ^L02 include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, cyclopentyl, cyclohexyl, 2-ethylhexyl, n-octyl and Adamantyl is mentioned.

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

A pair of R ^L01 and R ^L02 , R ^L01 and R ^L03 or R ^L02 and R ^L03 may be bonded 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 are linear or branched alkylene groups of 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms, when they form a ring.

In formula (L2), exemplary tertiary alkyl groups of R ^L04 are tert-butyl, tert-pentyl, 1,1-diethylpropyl, 2-cyclopentylpropan-2-yl, 2-cyclohexylpropan-2-yl, 2 -(Bicyclo [2.2.1] heptan-2-yl) propan-2-yl, 2- (adamantan-1-yl) propan-2-yl, 1-ethylcyclopentyl, 1-butylcyclopentyl, 1-ethylcyclohexyl, 1-butylcyclohexyl, 1-ethyl-2-cyclopentenyl, 1-ethyl-2-cyclohexenyl, 2-methyl-2-adamantyl and 2-ethyl-2-adamant 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-oxooxolalan-5-yl.

In formula (L3), examples of alkyl groups of R ^L05 include linear, branched or cyclic alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, tert-pentyl , n-hexyl, cyclopentyl, cyclohexyl and bicyclo [2.2.1] heptyl and some hydrogen atoms are hydroxyl, alkoxy, carboxyl, alkoxycarbonyl, oxo, amino, alkylamino, cyano, mercapto, alkyl Substituted forms of the group substituted by thio, sulfo and the like, or those in which the methylene moiety is substituted by oxygen or sulfur atom may be mentioned. Examples of the aryl group of R ^L05 include phenyl, methylphenyl, naphthyl, anthryl, phenanthryl and pyrenyl.

In formula (L4), examples of alkyl and aryl groups of R ^L06 are the same as those exemplified for R ^L05 . Exemplary C ₁ -C ₁₅ monovalent hydrocarbon groups of R ^L07 to R ^L16 include linear, branched or cyclic alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n -Pentyl, tert-pentyl, n-hexyl, 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 substituted by hydroxyl, alkoxy, carboxyl, alkoxycarbonyl, oxo, amino, alkylamino, cyano, mercapto, alkylthio, sulfo, and the like. . Alternatively, two of R ^L07 to R ^L16 may be joined together to form a ring having the carbon atom (s) to which they are attached (eg, 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 R ^L07 to R ^L16 represents a C ₁ -C ₁₅ divalent hydrocarbon group, typically when alkylene forms a ring, an example thereof is illustrated above for a monovalent hydrocarbon group with one hydrogen atom removed. Two of R ^L07 to R ^L16 attached to adjacent carbon atoms may be directly bonded together to form a double bond (eg, 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, linear or branched is exemplified by the following groups, but not limited thereto.

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

Examples of acid labile groups of formula L2 include tert-butoxycarbonyl, tert-butoxycarbonylmethyl, tert-pentyloxycarbonyl, tert-pentyloxycarbonylmethyl, 1,1-diethylpropyloxycarbonyl, 1,1-diethylpropyloxycarbonylmethyl, 1-ethylcyclopentyloxycarbonyl, 1-ethylcyclopentyloxycarbonylmethyl, 1-ethyl-2-cyclopentenyloxycarbonyl, 1-ethyl-2- Cyclopentenyloxycarbonylmethyl, 1-ethoxyethoxycarbonylmethyl, 2-tetrahydropyranyloxycarbonylmethyl, and 2-tetrahydrofuranyloxycarbonylmethyl.

Examples of acid labile groups of formula L3 include 1-methylcyclopentyl, 1-ethylcyclopentyl, 1-n-propylcyclopentyl, 1-isopropylcyclopentyl, 1-n-butylcyclopentyl, 1-sec-butylcyclo Pentyl, 1-cyclohexylcyclopentyl, 1- (4-methoxy-n-butyl) cyclopentyl, 1- (bicyclo [2.2.1] heptan-2-yl) cyclopentyl, 1- (7-oxa Bicyclo [2.2.1] heptan-2-yl) cyclopentyl, 1-methylcyclohexyl, 1-ethylcyclohexyl, 3-methyl-1-cyclopenten-3-yl, 3-ethyl-1-cyclopentene- 3-yl, 3-methyl-1-cyclohexen-3-yl and 3-ethyl-1-cyclohexen-3-yl.

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

<Formula L4-1>

<Formula L4-2>

<Formula L4-3>

<Formula L4-4>

In the formulas L4-1 to L4-4, the dashed lines indicate the binding sites and directions. Each R ^L41 is 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-butyl, tert-butyl, n -Pentyl, tert-pentyl, n-hexyl, cyclopentyl and cyclohexyl.

For Formulas L4-1 to L4-4, enantiomers and diastereomers may be present. Each of formulas L4-1 to L4-4 collectively represents all such stereoisomers. When X ^A is an acid labile group of formula L4, a plurality of stereoisomers may be included.

For example, formula L4-3 represents one or a mixture of two selected from the groups having the 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, formula L4-4 represents one or a mixture of two or more selected from the groups having the formulas L4-4-1 to L4-4-4.

<Formula L4-4-1>

<Formula L4-4-2>

<Formula L4-4-3>

<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 is collectively an enantiomer and an enantiomer of Represents a mixture.

In Formulas L4-1 to L4-4, L4-3-1 and L4-3-2 and L4-4-1 to L4-4-4, the binding direction is bicyclo [2.2.1]. Note that it is on the exo side for the heptane ring and ensures high reactivity for acid catalyzed desorption reactions (see JP-A 2000-336121). In the preparation of these monomers having tertiary exo-alkyl groups of the bicyclo [2.2.1] heptane structure as substituents, they are substituted with an endo-alkyl group as shown by the following formulas L4-1-endo to formula L4-4-endo It may contain a monomer. For good reactivity, an exo ratio of at least 50 mol% is preferred, with an exo ratio of at least 80 mol% being more preferred.

<Formula L4-1- Endo>

<Formula L4-2-Endo>

<Formula L4-3-Endo>

<Formula L4-4-Endo>

Note that R ^L41 is as defined above.

Examples of examples of acid labile groups of formula L4 are shown below.

Examples of tertiary C ₄ -C ₂₀ alkyl groups represented by X ^A , trialkylsilyl groups where each alkyl moiety has 1 to 6 carbon atoms and C ₄ -C ₂₀ oxoalkyl group are illustrated for R ^L04 As shown.

Examples of examples of repeating units having Formula A are provided below, but are not limited to these. R ¹ is as defined above.

Examples of examples of repeating units having Formula B are provided below, but are not limited to these. R ¹ is as defined above.

Examples of examples of repeating units having Formula C are provided below, but are not limited to these. R ¹ is as defined above.

Examples of examples of repeating units having Formula D are provided below, but are not limited to these. R ¹ is as defined above.

Polymers comprising repeating units of formula E decompose under the action of an acid to produce hydroxyl groups, so that their solubility in various solvents can be altered. In the formula (E), the acid labile group X ^E can be selected from various such groups. Examples of acid labile groups X ^E include groups of formulas L1 to L4, tertiary alkyl groups of 4 to 20 carbon atoms, each alkyl moiety having from 1 to 6 carbons, such as the acid labile groups X ^A mentioned above Trialkylsilyl groups with atoms and oxoalkyl groups of 4 to 20 carbon atoms.

Examples of examples of repeating units having Formula E are provided below, but are not limited to these. 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 preferred because the polymer can easily adjust solvent solubility and adhesion.

The polymer for the shrink material may further comprise a repeating unit of formula (F). The unit of formula F can induce a neutralization reaction with carboxyl groups 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 adheres to the resist film surface, which shows increased adhesion.

<Formula F>

In the above formula, R ¹⁰¹ is hydrogen or methyl. X is a single bond, -C (= 0)-, -C (= 0) -O- or -C (= 0) -NH-. R ¹⁰² is a single bond or a linear, branched or cyclic C ₁ -C ₁₀ alkylene group which may contain an ether, ester, 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 are bonded together to form an ether bond together with the nitrogen atom to which they are attached; Optionally form a containing ring, or one of R ¹⁰³ and R ¹⁰⁴ may combine with R ¹⁰² to form a ring with the nitrogen atom to which they are attached; k ^1C is 1 or 2.

The repeating unit of formula F may be derived from monomers having the formula Fa:

<Formula Fa>

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

The polymer for the shrink material 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 unit so as to provide adequate shrinkage and dimensional uniformity to the blended shrink material therefrom.

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

In the shrink material polymer, the repeating units of formula 1a and / or formula 1b are preferably incorporated in an amount of at least 5 mol%, more preferably at least 10 mol%, based on the total repeating units.

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

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

The repeating unit of formula 4 or formula 5 is preferably incorporated in an amount of 0 to 30 mol% based on the total repeating unit. For greater etch resistance, the amount of units of formula 4 or formula 5 is more preferably 5 to 30 mol%, even more preferably 5 to 20 mol%.

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

In the shrink material polymer, the repeating unit of formula 1a and / or formula 1b and the repeating unit selected from formulas 2, 4 and 5 preferably correspond to at least 60 mol% based on the total repeating unit, which is desired This is because it is ensured to blend the shrink material having a property. More preferably, the repeating units of the formulas 1a and / or 1b and the repeating units of the formulas 2, 4 and 5 correspond to at least 70 mol%, even more preferably at least 85 mol% based on the total repeating units. do.

When the entire constituent unit of the polymer for the shrink material is a repeating unit of formula 1a and / or 1b and a repeating unit selected from units of formulas 2, 4 and 5, high etching resistance and high resolution are used in a compatible manner. It is possible. In the polymer for the shrink material, repeating units other than the repeating units of Formulas 1a, 1b, 2, 4 and 5 may be incorporated. For example, (meth) acrylate units protected by conventional acid labile groups and / or adhesive groups such as (meth) acrylate units having a lactone structure can be used. The characteristics of the shrink material film can be fine tuned by incorporating the repeating units, although additional repeating units are optional.

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

If the polymer has a wide molecular weight distribution or dispersion (Mw / Mn) indicating the presence of low and high molecular weight polymer fractions, foreign matter remains on the pattern and there is a possibility of deterioration of the pattern profile. 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 a small feature size, the multicomponent copolymer, ie the polymer for the shrink material, must have a narrow dispersion degree (Mw / Mn) of 1.0 to 2.0, in particular 1.0 to 1.5. It is preferable.

It is acceptable to use blends of two or more polymers that differ in composition ratio, molecular weight or degree of dispersion.

In addition to the polymers defined above, the shrink material comprises a solvent containing an anti-loss solvent which prevents the resist pattern from disappearing after development. Loss-proof solvents include ether solvents of 6 to 12 carbon atoms, hydrocarbon solvents of 6 to 12 carbon atoms, ester solvents of 7 to 16 carbon atoms, ketone solvents of 8 to 16 carbon atoms, and 4 to 10 Alcohol solvents and water of a carbon atom are mentioned. If the anti-loss solvent corresponds to 50% by weight or more of the total solvent, another solvent may be included that causes the resist pattern to disappear after development.

Although many aqueous shrink materials have already been proposed, it is difficult to quickly apply them to large diameter wafers because of the high surface tension of water. In particular, a problem occurs in the case of a fine hole pattern formed by a negative phenomenon. When the hole is filled with the shrink material by spin coating, the high surface tension water solvent prevents the shrink material from filling the hole into the floor. Conversely, when the shrink material dissolved in an organic solvent having a surface tension lower than water is applied, the ability to fill or fill the bottom of the hole is improved. In addition, the organic solvent used for the shrink material dissolves the polymer for the shrink material.

As the solvent used in the shrink material, due to the high dissolving power of the polymer for the shrink material, 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 are 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 isovalerate, isobutyl isovalerate, tert-butyl isovalerate, isopentyl isovalerate, ethyl 2-methylvalerate, butyl 2-methylvalerate, ethyl pivalate, propyl pivalate, isopropyl pivalate Butyl pivalate, tert-butyl pivalate, ethyl pentenoate, pro Phyllpentenoate, isopropyl pentenoate, butyl pentenoate, tert-butyl pentenoate, propyl crotonate, isopropyl crotonate, butyl crotonate, tert-butyl crotonate, butyl propionate Isobutyl propionate, tert-butyl propionate, benzyl propionate, ethyl hexanoate, allyl hexanoate, propyl butyrate, butyl butyrate, isobutyl butyrate, 3-methylbutyl butyrate, tert-butyl butyrate, Ethyl 2-methylbutyrate, isopropyl 2-methylbutyrate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, phenyl acetate, benzyl acetate, methyl phenylacetate, benzyl formate, phenylethyl formate, methyl 3 -Phenyl propionate, ethyl phenyl acetate and 2-phenylethyl acetate.

Examples of ketone solvents of 8 to 16 carbon atoms include 2-octanone, 3-octanone, 4-octanone, 2-nonanone, 3-nonanone, 4-nonanone, 5-nonanone, diisobutyl Ketones, 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, 3-pentanol, t-pentyl alcohol, neo Pentyl alcohol, 2-methyl-1-butanol, 3-methyl-1-butanol, 3-methyl-3-pentanol, cyclopentanol, 1-hexanol, 2-hexanol, 3-hexanol, 2,3 -Dimethyl-2-butanol, 3,3-dimethyl-1-butanol, 3,3-dimethyl-2-butanol, 2,2-diethyl-1-butanol, 2-methyl-1-pentanol, 2-methyl 2-pentanol, 2-methyl-3-pentanol, 3-methyl-1-pentanol, 3-methyl-2-pentanol, 3-methyl-3-pentanol, 4-methyl-1-pentanol , 4-methyl-2-pentanol, 4-methyl-3-pentanol, cyclohexanol, and 1-octanol. These solvents may be used alone or in combination.

To prevent mixing of the shrink material and resist pattern, any C ₈ -C ₁₂ ether, C ₆ -C ₁₂ alkanes, alkenes, alkynes and aromatic solvents may be blended with the anti-loss solvents.

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-sec-pentyl ether, Di-tert-pentyl ether and di-n-hexyl ether. Suitable alkanes of 6 to 12 carbon atoms include hexane, heptane, octane, nonane, decane, undecane, dodecane, methylcyclopentane, dimethylcyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, cycloheptane, cyclo 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 hexine, heptin and octin. Suitable aromatic solvents include toluene, xylene, ethylbenzene, isopropylbenzene, tert-butylbenzene, mesitylene and anisole. Solvents may be used alone or in combination.

In addition to the anti-loss solvents, the shrink material may contain additional solvents. Additional solvents are 2-octanone, 2-nonanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-hexanone, 3-hexanone, diisobutyl ketone, methylcyclohexanone, aceto Phenone, methylacetophenone, propyl acetate, butyl acetate, isobutyl acetate, pentyl acetate, isopentyl acetate, butenyl acetate, propyl formate, butyl formate, isobutyl formate, pentyl formate, isopentyl formate, methyl Valerate, methyl pentenoate, methyl crotonate, ethyl crotonate, methyl propionate, ethyl propionate, ethyl 3-ethoxypropionate, methyl lactate, ethyl lactate, propyl lactate, butyl Lactate, isobutyl lactate, pentyl lactate, isopentyl lactate, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, methyl benzoate, ethyl benzoate , Phenyl acetate, benzyl acetate, methyl phenylacetate, benzyl formate, phenylethyl formate, methyl 3-phenylpropionate, benzyl propionate, ethyl phenylacetate and 2-phenylethyl acetate. If an additional solvent is used it is preferably blended in an amount of less than 50% by weight of the total solvent.

In the shrink material, the solvent is used in an amount of preferably 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 shrink material as needed. Salts that can be added are typically selected from sulfonium salts and iodonium salts, and ammonium salts, which are typically added to resist compositions. The basic compound which may be added may be selected from basic compounds which are conventionally added to the resist composition, for example primary, secondary and tertiary aliphatic amines, mixed amines, aromatic amines, heterocyclic amines, carboxyl Nitrogen-containing compounds with groups, nitrogen-containing compounds with sulfonyl groups, nitrogen-containing compounds with hydroxyl groups, nitrogen-containing compounds with hydroxyphenyl groups, alcoholic nitrogen-containing compounds, amide derivatives, imide derivatives and carboxes There is a barmate. The addition of salts or basic compounds inhibits the diffusion of excess acid from the resist film and is effective to control the amount of shrink. The surfactant that may be added may be selected from surfactants that are typically added to the resist composition.

As the salt, carboxylic acid salts having the formula (9) are preferred.

<Formula 9>

In the above formula, 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 C ₆ -C ₂₀ monovalent aromatic ring-containing group, Some or all of the carbon-bonded hydrogen atoms may be substituted by fluorine, lactone ring-containing moieties, lactam ring-containing moieties or hydroxyl moieties, and ethers, esters or carbonyl moieties may be carbon-carbon bonds. May be intervened in 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 formulas P1 to P3. Acid diffusion with the cation can be added to effectively control acid diffusion:

<Formula P1>

<Formula P2>

<Formula P3>

In the above formula, R ¹⁰¹ to R ¹⁰⁹ are each independently 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 _6- C ₂₀ monovalent aromatic ring-containing group or C ₇ -C ₁₂ aralkyl or aryloxoalkyl group, and some or all of the hydrogen atoms may be substituted by halogen, alkyl, alkoxy or the like. A pair of R ¹⁰¹ and R ¹⁰² , or R ¹⁰⁶ and R ^107, may combine together to form a ring 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, which ring may contain ether, ester, sultone or amino moiety thereto.

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

Preferred examples of the anion of the carboxylic acid salts include, but are not limited to, the carboxylic acid anions described in JP 3991462 and those set forth below:

Preferred examples of the cation of the carboxylic acid salts include, but are not limited to:

Sulfonic acid salts having the formula (10) are also preferred as salts.

<Formula 10>

In the above formula, M ⁺ is as defined above. R ¹² is a linear, branched or cyclic C ₁ -C ₃₅ monovalent hydrocarbon group which may contain oxygen atoms, some or all of the carbon-bonded hydrogen atoms may be substituted by fluorine, provided that Hydrogen atoms bonded to carbon atoms in the α-position are not substituted by fluorine.

In sulfonic acid salts having the formula (10), those having the formula (10 ') are preferred:

<Formula 10 '>

In the above formula, M ⁺ is as defined above, R ¹¹⁰ and R ¹¹¹ are each independently hydrogen or trifluoromethyl, and l is an integer from 1 to 3.

In the shrink material, the salt is used in an amount of preferably 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 paragraphs [0146] to [0164] (USP 7,537,880) of JP-A 2008-111103, specifically hydroxyl, ether, ester, lactone And amine compounds having cyano or sulfonate groups and compounds having carbamate groups as described in JP 3790649. In particular, tertiary amine compounds, specifically, amine compounds having hydroxyl, ether, ester groups or lactone rings and compounds having carbamate groups are preferred.

In the shrink material, the basic compound is used in an amount of preferably 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 used in an amount of preferably 0 to 10 parts by weight, more preferably 0.1 to 5 parts by weight per 100 parts by weight of the polymer for the shrink material.

Resist composition

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

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

<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 —, R ²³ is a linear, branched or cyclic C ₁ -C ₁₀ alkylene group wherein an ether or ester bond may be interposed in a carbon-carbon bond, or 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 in order to improve substrate adhesion and prevent the pattern from collapsing. Base resins include repeating units (c) derived from indene, acenaphthylene, chromone, coumarin and norbornadiene derivatives as described in paragraph [0085] of JP-A 2012-037867; Repeating units (d) derived from styrene, vinylnaphthalene, vinylanthracene, vinylpyrene and methylene indan derivatives as described in paragraph [0088]; And / or a repeating unit (e) which functions as an acid generator as described in paragraphs [0089] to [0091] and which is derived from an onium salt having a polymerizable olefin.

In the base resin, the repeating unit (a) is in an amount of more than 0 mol% to 100 mol%, preferably 1 mol% to less than 100 mol%, more preferably 20 to 90 mol% based on the total repeat units. It is incorporated. 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 repeat units. The sum total of repeating units (a) and (b) becomes like this. Preferably it is 30-100 mol%. When the repeating units (c) to (e) are incorporated, preferably the repeating unit (c) is incorporated in an amount of 0 to 40 mol%, and the repeating unit (d) is incorporated in an amount of 0 to 20 mol% and , Repeating unit (e) is incorporated in an amount of 0 to 30 mol%, and the total of repeating units (c) to (e) is 0 to 70 mol%.

The base resin should preferably have a Mw measured by GPC for polystyrene standards, preferably in the range of 1,000 to 500,000, more preferably 2,000 to 100,000. If the Mw is too low, the diffusion distance of the acid generated by the acid generator may be extended to reduce resolution. If the Mw is too high, the solubility of the polymer in the developer may be reduced and the resolution may be lowered.

If the polymer has a broad molecular weight distribution or dispersion (Mw / Mn), this indicates the presence of low and high molecular weight polymer fractions, leaving foreign matter on the pattern and possibly damaging the pattern profile. The finer the pattern rule, the stronger the influence of molecular weight and dispersion. Therefore, in order to provide a resist composition suitable for micropatterning into small feature sizes, it is desirable for the base resin to have a narrow dispersion degree (Mw / Mn) of 1.0 to 2.0, in particular 1.0 to 1.5.

Blends of two or more polymers having different composition ratios, molecular weights or degrees of dispersion are acceptable as the base resin.

The resist composition contains an acid generator so that it can function as a chemically amplified positive resist composition. Acid generators are compounds that can generate acids in response to actinic radiation or radiation, commonly known as photoacid generators (PAG). Suitable amounts of PAG used are from 0.5 to 30 parts by weight, more preferably from 1 to 20 parts by weight, per 100 parts by weight of the base resin. PAG is any compound capable of generating an acid upon exposure to high-energy radiation. Suitable PAGs include sulfonium salts, iodonium salts, sulfonyldiazomethanes, N-sulfonyloxyimide and oxime-O-sulfonate acid generators. Acid generators may be used alone or in combination of two or more thereof. Examples of the acid generated by the PAG include sulfonic acid, imide acid and methic acid. Of these, sulfonic acids fluorinated at the α-position are most commonly used. If the acid labile group is an acetal group that is susceptible to deprotection, fluorination at the α-position is not always necessary. If the base resin has repeating units of acid generator copolymerized therewith, the acid generator need not be added separately.

Examples of organic solvents used herein 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 γ-butyrolactone and mixtures thereof. When using an acid labile group in the acetal form, 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 acetal.

The 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 as described in paragraphs [0146] to [0164] of JP-A 2008-111103. Amine compounds having sulfonate groups and compounds having carbamate groups as described in JP 3790649. Also, onium salts of sulfonic acids that are not fluorinated at the α-position as described in US 2008153030 (JP-A 2008-158339), such as sulfonium salts, iodonium salts and ammonium salts and as described in JP 3991462 and JP 4226803 Analogous onium salts of carboxylic acids can be used as quenchers. They may also be added to the shrink material.

If the acid labile group is an acetal group that is very sensitive to acid, the acid to remove the protecting group does not necessarily need to be a fluorinated sulfonic acid, imide acid or meted acid at the α-position. Even using sulfonic acids that are not fluorinated at the α-position, deprotection reactions may occur in some cases. Since the onium salt of sulfonic acid cannot be used as a quencher in this case, the onium salt of imide acid is preferably used alone.

The suitable amount of basic compound is 0.0001-30 weight part, preferably 0.001-20 weight part per 100 weight part of base resin.

Exemplary surfactants are described in paragraphs [0165]-[0166] of JP-A 2008-111103. Exemplary dissolution control agents are described in paragraphs [0155]-[0178] of JP-A 2008-122932 (US 2008090172) and exemplary acetylene alcohols are described in paragraphs [0179]-[0182]. Surfactants, dissolution control agents and acetylene alcohols may be used in any suitable amount depending on the purpose of their addition.

In addition, a polymer additive can be added to improve the water repellency on the surface of the resist film after spin coating. Water repellency enhancers can be used for immersion lithography without topcoats. Water repellency enhancers have a specific structure with 1,1,1,3,3,3-hexafluoro-2-propanol residues and are described in JP-A 2007-297590 and JP-A 2008-111103. The water repellency enhancer added to the resist composition must be soluble in the organic solvent as a developer. The water repellent improver of a specific structure having a 1,1,1,3,3,3-hexafluoro-2-propanol residue has good solubility in a developer. Polymers in which amino groups or amine salts are copolymerized as repeating units can act as water repellent additives and are effective in preventing evaporation of acids in PEB and in preventing any hole pattern opening defects after development. A suitable amount of the water repellency enhancer 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

Another embodiment includes applying a resist composition onto 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 developer to form a negative resist pattern; Applying a shrink material over the negative resist pattern and firing; And removing the excess shrink material with an organic solvent.

Referring to Figures 1 (a) to 1 (f), a method of pattern shrinking of the present invention is described. First, as shown in Fig. 1 (a), a chemically amplified positive resist composition is applied on the substrate 20 on the substrate 10 to form a resist film 30 thereon. If necessary, a hard mask layer (not shown) may be interposed between the resist film 30 and the substrate to be processed 20. By the standard technique, the resist film 30 is exposed to light (FIG. 1 (b)), and PEB and organic solvent development are processed to form a negative resist pattern 30a (FIG. 1 (c)). As shown in Fig. 1 (d), the shrink material 40 is applied on the negative resist pattern 30a to apply the pattern. The shrinking material coating is fired, during which heat evaporates the solvent, and the acid functions to diffuse from the resist pattern 30a into the shrink material coating 40. The use of acid treats the polymer in the shrink material coating in a deprotection reaction. Thereafter, the solvent is applied to remove the excess shrink material 40 to leave a film of shrink material on the resist pattern 30a. This means that the resist pattern 30a was thickened so that the width of the space in the resist pattern was shrunk as shown in Fig. 1 (e). Using the shrunken pattern as a mask, the substrate 20 to be processed is dry etched as shown in Fig. 1 (f).

As used herein, the substrate 10 is generally a silicon substrate. The substrate to be processed (or target film) 20 used herein is SiO ₂ , SiN, SiON, SiOC, p-Si, α-Si, TiN, WSi, BPSG, SOG, Cr, CrO, CrON, MoSi, Low Dielectric films and etch stopper films. The hard mask may be of SiO ₂ , SiN, SiON or p-Si. Often, an underlayer film or silicon-containing interlayer in the form of a carbon film may be disposed in place of the hard mask, and an organic antireflective film may be inserted between the hard mask and the resist film.

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

The resist film is then exposed to high-energy radiation or EB with 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 an EUV with a wavelength of 13.5 nm. Most preferred is ArF 193-nm lithography. The exposure can be carried out in a drying atmosphere, for example in an air or nitrogen stream or by immersion lithography in water. ArF immersion lithography uses a liquid that is highly transparent to an exposure wavelength with a refractive index of 1 or more as deionized water or an alkane as the immersion solvent. In immersion lithography, the prefired resist film is exposed to light through the projection lens, and pure or another liquid introduced between the resist film and the projection lens is introduced. This allows the lens to be designed with a NA greater than 1.0, which allows for the formation of finer feature size patterns. Immersion lithography is important for extending ArF lithography to finer nodes. In the case of immersion lithography, post-exposure deionized water rinse (or post-immersion) may be performed to remove residual water droplets on the resist film, or prevent any elution from the resist film, and In order to improve water lubrication, a protective film may be applied onto the resist film after pre-firing. The resist protective film used for immersion lithography is 4 to 10 from a solution of a polymer having 1,1,1,3,3,3-hexafluoro-2-propanol moiety that is insoluble in water but soluble in alkaline developer. It is preferably formed in a solvent selected from alcohols of carbon atoms, ethers of 8 to 12 carbon atoms and mixtures thereof. After formation of the resist film, deionized water rinsing (or post-immersion) may be performed for extraction of acid generators or the like from the film surface or for washing the particles, or after exposure, rinsing to remove residual water droplets on the resist film. (Or post-immersion) may be carried out.

The exposure is preferably performed at a radiation dose of about 1 to 200 mJ / cm 2, more preferably about 10 to 100 mJ / cm 2. It is then calcined (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.

The exposed resist film is then developed with a developer made of organic solvent by conventional techniques such as immersion, poodle and spraying techniques for 0.1 to 3 minutes, preferably 0.5 to 2 minutes. In this way, a negative resist pattern is formed over the substrate. Organic solvents used as developers are 2-octanone, 2-nonanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-hexanone, 3-hexanone, diisobutyl ketone, methylcyclo Hexanon, acetophenone, methylacetophenone, propyl acetate, butyl acetate, isobutyl acetate, pentyl acetate, butenyl acetate, isopentyl acetate, propyl formate, butyl formate, isobutyl formate, pentyl formate, isopentyl Formate, methyl valerate, methyl pentenoate, methyl crotonate, ethyl crotonate, methyl propionate, ethyl propionate, ethyl 3-ethoxypropionate, methyl lactate, ethyl lactate, propyl Lactate, butyl lactate, isobutyl lactate, pentyl lactate, isopentyl lactate, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, methyl benzoate, Selected from ethyl benzoate, phenyl acetate, benzyl acetate, methyl phenylacetate, benzyl formate, phenylethyl formate, methyl 3-phenylpropionate, benzyl propionate, ethyl phenylacetate and 2-phenylethyl acetate and mixtures thereof It is desirable to be.

At the end of development, the resist film can be rinsed. As the rinse liquid, a solvent that is miscible 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, alkenes and alkynes of 6 to 12 carbon atoms, and aromatic solvents. Specifically, suitable alcohols of 3 to 10 carbon atoms include n-propyl alcohol, isopropyl alcohol, 1-butyl alcohol, 2-butyl alcohol, isobutyl alcohol, tert-butyl alcohol, 1-pentanol, 2-pentane Ol, 3-pentanol, tert-pentyl alcohol, neopentyl alcohol, 2-methyl-1-butanol, 3-methyl-1-butanol, 3-methyl-3-pentanol, cyclopentanol, 1-hexanol, 2-hexanol, 3-hexanol, 2,3-dimethyl-2-butanol, 3,3-dimethyl-1-butanol, 3,3-dimethyl-2-butanol, 2-ethyl-1-butanol, 2- Methyl-1-pentanol, 2-methyl-2-pentanol, 2-methyl-3-pentanol, 3-methyl-1-pentanol, 3-methyl-2-pentanol, 3-methyl-3-pentane Ol, 4-methyl-1-pentanol, 4-methyl-2-pentanol, 4-methyl-3-pentanol, cyclohexanol and 1-octanol. Suitable alkanes of 6 to 12 carbon atoms include hexane, heptane, octane, nonane, decane, undecane, dodecane, methylcyclopentane, dimethylcyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, cycloheptane, cyclo 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 hexine, heptin and octin. 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-sec-pentyl ether, Di-tert-pentyl ether and di-n-hexyl ether. Suitable aromatic solvents include toluene, xylene, ethylbenzene, isopropylbenzene, t-butylbenzene and mesitylene. Solvents may be used alone or in combination. After applying the rinse liquid, the substrate can be dried by spin drying and firing. However, rinsing is not essential. The rinsing step may be omitted if it comprises the step of spin drying the substrate after applying the developer thereto.

After development, the shrink material of the present invention preferably forms a shrink material coating having a thickness of 1 to 150 nm, more preferably 30 to 80 nm. The shrink material coating is baked at a temperature of 40 to 180 ° C. for 5 to 300 seconds. Firing evaporates the solvent, causing acid diffusion from the resist film to the shrink material and an acid-assisted desorption reaction to produce an olefin or crosslinked structure in the shrink material coating which induces a polarity change resulting in the shrink material coating being It acts to be insoluble in the organic solvent.

Finally, it is desirable to remove excess shrink material using an organic solvent. Suitable organic solvents that can be used herein include propyl acetate, butyl acetate, isobutyl acetate, butenyl acetate, pentyl acetate, isopentyl acetate, 2-methylbutyl acetate, hexyl acetate, 2-ethylhexyl acetate, cyclohexyl acetate, Methylcyclohexyl acetate, propyl formate, butyl formate, isobutyl formate, pentyl formate, isopentyl formate, hexyl formate, methyl valerate, ethyl valerate, propyl valerate, isopropyl valerate, butyl valerate Latex, isobutyl valerate, tert-butyl valerate, pentyl valerate, isopentyl valerate, ethyl isovalerate, propyl isovalerate, isopropyl isovalerate, butyl isovalerate, isobutyl isovalerate, tert -Butyl isovalerate, isopen Isovalerate, ethyl 2-methylvalerate, butyl 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 lac Tate, propyl lactate, butyl lactate, isobutyl lactate, pentyl lactate, isopentyl lactate, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, ethyl pivalate, propyl pivalate, isopropyl Fivalate, butyl pivalate, tert-butyl pivalate, butyl propionate, isobutyl propionate, tert-butyl propionate, benzylprop Lopionate, ethyl 3-ethoxypropionate, ethyl hexanoate, allyl hexanoate, propyl butyrate, butyl butyrate, isobutyl butyrate, 3-methylbutyl butyrate, tert-butyl butyrate, ethyl 2-methylbutyrate, Isopropyl 2-methylbutyrate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, phenyl acetate, benzyl acetate, methyl phenylacetate, benzyl formate, phenylethyl formate, methyl 3-phenylpropionate, Ethyl phenylacetate, 2-phenylethyl acetate, 2-heptanone, 3-heptanone, 4-heptanone, 2-hexanone, 3-hexanone, 2-octanone, 3-octanone, 4-octanone, 2-nonanone, 3-nonanone, 4-nonanone, 5-nonanone, methylcyclohexanone, ethylacetophenone, acetophenone, methylacetophenone, ethylacetophenone, ethyl n-butyl ketone, di-n- Butyl ketone, diisobutyl ketone, 1- Butanol, 2-butanol, isobutyl alcohol, t-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, t-pentyl alcohol, neopentyl alcohol, 2-methyl-1-butanol, 3-methyl -1-butanol, 3-methyl-3-pentanol, cyclopentanol, 1-hexanol, 2-hexanol, 3-hexanol, 2,3-dimethyl-2-butanol, 3,3-dimethyl-1 -Butanol, 3,3-dimethyl-2-butanol, 2,2-diethyl-1-butanol, 2-methyl-1-pentanol, 2-methyl-2-pentanol, 2-methyl-3-pentanol , 3-methyl-1-pentanol, 3-methyl-2-pentanol, 3-methyl-3-pentanol, 4-methyl-1-pentanol, 4-methyl-2-pentanol, 4-methyl- 3-pentanol, cyclohexanol, and 1-octanol are mentioned.

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

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

Example

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

[1] polymer synthesis

Synthesis Example  One

Synthesis of Polymer 1

In a nitrogen atmosphere, 37.43 g 4-acetoxystyrene, 5.85 g acenaphthylene, 21.72 g 4- (1-hydroxy-1-cyclopropyl) styrene, 7.08 g dimethyl 2,2'-azobis ( 2-methylpropionate) (V-601, Wako Pure Chemical Industries, Ltd.) and 60 g methyl ethyl ketone as a solvent were fed to a 200 ml dropping cylinder to form a monomer solution. It was. A 500 ml flask under nitrogen atmosphere was charged with 48 g of methyl ethyl ketone, which was heated at 80 ° C. While stirring, the monomer solution was added dropwise to the flask over 4 hours. After completion of the dropwise addition, the polymerization liquid was continuously stirred for 18 hours while maintaining its temperature at 80 ° C. The polymerization liquid was cooled to room temperature, at which time 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 tetrahydrofuran and 42 g methanol in a 1 L flask of nitrogen atmosphere and 16.9 g ethanolamine was added to the solution, which was stirred at 60 ° C. for 3 hours. The reaction solution was concentrated under reduced pressure. The concentrate was dissolved in a mixture of 300 g ethyl acetate and 80 g water. The solution was transferred to a separatory funnel and 8.5 g of acetic acid was added thereto followed by a separation operation. The lower layer was discarded. 80 g of water and 11.3 g of pyridine were added to the organic layer, and a separation operation was performed. The lower layer was discarded. 80 g of water was added to the organic layer, and water washing and separation operations were performed. Washing and separating operations were repeated five 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 off, washed with water and suction filtered 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 off, 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

Synthesis Example  2 to 22 and comparison Synthesis Example  1 to 3

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

The polymer in Table 1 was 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 structure of the repeating units.

TABLE 1

TABLE 2

TABLE 3

TABLE 4

TABLE 5

Synthesis Example  23, 24

Synthesis of Resist Polymer 1 and Water Repellent Polymer 1

The appropriate monomer was combined to copolymerize in a tetrahydrofuran solvent, crystallize from methanol, repeat washing with hexane, and separate and dry to synthesize a polymer. The random copolymer represented by the resist polymer 1 and the 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] production 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), onium salts, basic compounds and solvents are mixed according to the combinations of Tables 6 and 7 below, with a Teflon ^® filter with a pore size of 0.2 μm. Was filtered to produce a shrinking material. The components shown in Tables 6 and 7 below are identified as follows.

TABLE 6

TABLE 7

[3] preparation of resist composition

The polymer (resist polymer 1), acid generator, quencher and water repellent polymer were dissolved in the solvent according to the formulation of Table 8 below, 100 ppm of surfactant FC-4430 (3 m) was added thereto, and the pore size was 0.2 μm. Filtration through a phosphorous filter yielded a resist composition in solution form. In Table 8 below, 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 to a thickness of 180 nm on a silicon wafer, and the 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 onto a three-layer process substrate and then fired for 60 seconds on a hot plate at 100 ° C. to form a 90 nm thick resist film. Using an ArF excimer laser immersion lithography scanner NSR-610C (Nikon Corp., NA 1.30, s 0.90 / 0.70, annular illumination), the resist film is changed through a 6% halftone phase shift mask while varying the dose It exposed. After exposure, the resist film was baked (PEB) at 90 ° C. for 60 seconds and puddle developed for 30 seconds in n-butyl acetate to form a hole pattern with a hole size of 50 nm and a pitch of 150 nm.

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

TABLE 9

TABLE 10

While the invention has been illustrated and described in embodiments, it is not intended to be limited to the details given, as various modifications and substitutions may be made without departing from the spirit of the invention in any way. Thus, further modifications and equivalents of the invention disclosed herein can be made to those skilled in the art without further use of ordinary experiments, both of which modifications and equivalents are defined in the invention as defined by the following claims. It is believed to fall within the spirit and scope of the technology.

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

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

Claims (19)

A shrink material comprising a polymer comprising at least one repeating unit selected from units having Formulas 1a and 1b, and a solvent containing an anti-loss solvent that prevents the resist pattern from developing after development:
<Formula 1a>

<Formula 1b>

In the above formula,
A is a single bond or a C ₁ -C ₁₀ alkylene group which may contain etheric oxygen atoms in the middle of the chain,
R ¹ is hydrogen, fluorine, methyl or trifluoromethyl,
Each R ² is 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 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 or optionally substituted 1 which may contain an ethereal oxygen atom, a carbonyl moiety or a carbonyloxy moiety in the middle of the chain Is an aromatic ring-containing group,
Z is bonded to a carbon atom to form a C ₅ -C ₁₅ alicyclic 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 hydrogen or a hydroxyl or alkoxy moiety, and at least one of R ^x and R ^y is cyclic C _{A 5-} C ₁₅ alkyl group,
f is an integer of 1-3, s is an integer of 0-2, a is (5 + 2s-f), and m is 0 or 1. The shrink material of claim 1, wherein the polymer further comprises a repeating unit having Formula 2
<Formula 2>

In the above formula,
B is a single bond or a C ₁ -C ₁₀ alkylene group which may contain etheric oxygen atoms in the middle of the chain,
R ¹ is as defined above,
Each R ³ is 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 optionally halo-substituted, linear, branched or cyclic, C ₁ -C ₆ alkoxy group,
g is an integer of 0-3, t is an integer of 0-2, 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 formula
<Formula 3>

In the above formula,
C is a single bond or a C ₁ -C ₁₀ alkylene group which may contain etheric oxygen atoms in the middle of the chain,
R ¹ is as defined above,
Each R ⁴ is 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 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) divalent hydrocarbon group which may contain an ethereal oxygen atom, a carbonyl moiety or a carbonyloxy moiety in the middle of the chain Some or all of the carbon-bonded hydrogen atoms may be substituted by fluorine,
Rf ¹ and Rf ² are each independently a C ₁ -C ₆ alkyl group containing one or more fluorine atoms, Rf ¹ may be bonded to D to form a ring with the carbon atom to which they are attached,
r is 0 or 1, h is an integer of 1-3, u is an integer of 0-2, c is (5 + 2u-h), v is 1 or 2. The shrink material of claim 1, wherein the polymer further comprises one or more repeating units selected from units having Formulas 4 and 5:
<Formula 4>

<Formula 5>

In the above formula,
R ⁵ and R ⁶ 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 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 one or more repeating units selected from units having Formulas A-E:
<Formula A>

<Formula B>

<Formula C>

<Formula D>

<Formula E>

In the above formula,
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 which may be substituted by the component —CH ₂ — by —O— or —C (═O) —, X ^E is an acid Unstable 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, k ^1B is an integer of 1 to 4. The shrink material of claim 1, wherein the polymer further comprises a repeating unit having the formula (F):
<Formula F>

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

In the above formula,
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 C ₆ -C ₂₀ monovalent aromatic ring-containing group, which is carbon-bonded Some or all of the hydrogen atoms may be substituted by fluorine, lactone ring-containing moieties, lactam ring-containing moieties or hydroxyl moieties, and ethers, esters or carbonyl moieties may be interrupted at the carbon-carbon bond And M ⁺ is a sulfonium, iodonium or ammonium cation. The shrink material of claim 1, further comprising a salt having Formula 10:
<Formula 10>

In the above formula,
R ¹² is a linear, branched or cyclic C ₁ -C ₃₅ monovalent hydrocarbon group which may contain oxygen atoms, some or all of the carbon-bonded hydrogen atoms may be substituted by fluorine, provided that Hydrogen atoms bonded to carbon atoms in the α-position are not substituted by fluorine and M ⁺ is a sulfonium, iodonium or ammonium cation. 2. A compound according to claim 1, wherein the primary, secondary and tertiary aliphatic amines, mixed amines, aromatic amines, heterocyclic amines, nitrogen-containing compounds with carboxyl groups, nitrogen-containing compounds with sulfonyl groups, hydroxyl groups A shrink material further comprising at least one basic compound selected from the group consisting of: nitrogen-containing compounds having, nitrogen-containing compounds having hydroxyphenyl groups, alcoholic nitrogen-containing compounds, amide derivatives, imide derivatives, and carbamates. The shrink material of claim 1, wherein the anti-loss solvent 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. The method of claim 10 wherein the anti-loss solvent is
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 Latex, isobutyl valerate, tert-butyl valerate, pentyl valerate, isopentyl valerate, ethyl isovalerate, propyl isovalerate, isopropyl isovalerate, butyl isovalerate, isobutyl isovalerate, tert -Butyl isovalerate, isopentyl isovalerate, ethyl 2-methylvalerate, butyl 2-methylvalerate, ethyl pivalate, propyl pivalate, isopropyl pivalate, butyl pivalate, tert-butyl pivalate, ethyl Pentenoate, propyl pentenoate, isopropyl pentenoate, butyl Tenoate, tert-butyl pentenoate, propyl crotonate, isopropyl crotonate, butyl crotonate, tert-butyl crotonate, butyl propionate, isobutyl propionate, tert-butyl propionate Benzyl propionate, ethyl hexanoate, allyl hexanoate, propyl butyrate, butyl butyrate, isobutyl butyrate, 3-methylbutyl butyrate, tert-butyl butyrate, ethyl 2-methylbutyrate, isopropyl 2-methylbutyrate, Methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, phenyl acetate, benzyl acetate, methyl phenyl acetate, benzyl formate, phenylethyl formate, methyl 3-phenylpropionate, ethyl phenylacetate and 2-phenyl Ester solvents of 7 to 16 carbon atoms, including ethyl acetate,
2-octanone, 3-octanone, 4-octanone, 2-nonanone, 3-nonanone, 4-nonanone, 5-nonanone, diisobutyl ketone, ethylcyclohexanone, ethylacetophenone, ethyl ketone solvents of 8 to 16 carbon atoms, including n-butyl ketone, di-n-butyl ketone and diisobutyl ketone, and
1-butanol, 2-butanol, isobutyl alcohol, t-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, t-pentyl alcohol, neopentyl alcohol, 2-methyl-1-butanol, 3 -Methyl-1-butanol, 3-methyl-3-pentanol, cyclopentanol, 1-hexanol, 2-hexanol, 3-hexanol, 2,3-dimethyl-2-butanol, 3,3-dimethyl -1-butanol, 3,3-dimethyl-2-butanol, 2,2-diethyl-1-butanol, 2-methyl-1-pentanol, 2-methyl-2-pentanol, 2-methyl-3- Pentanol, 3-methyl-1-pentanol, 3-methyl-2-pentanol, 3-methyl-3-pentanol, 4-methyl-1-pentanol, 4-methyl-2-pentanol, 4- Alcohol solvents of 4 to 10 carbon atoms, including methyl-3-pentanol, cyclohexanol and 1-octanol
Shrink material which is at least one solvent selected from the group consisting of: The method of claim 1, wherein the solvent contains an anti-loss solvent and an additional solvent, wherein the additional solvent is 2-octanone, 2-nonanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-hexanone, 3-hexanone, diisobutyl ketone, methylcyclohexanone, acetophenone, methylacetophenone, propyl acetate, butyl acetate, isobutyl acetate, pentyl acetate, isopentyl acetate, butenyl acetate, propyl fort Mate, butyl formate, isobutyl formate, pentyl formate, isopentyl formate, methyl valerate, methyl pentenoate, methyl crotonate, ethyl crotonate, methyl propionate, ethyl propionate, ethyl 3-ethoxypropionate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, isobutyl lactate, pentyl lactate, isopentyl lactate, methyl 2-hydroxyisobutyre Nitrate, ethyl 2-hydroxyisobutyrate, methyl benzoate, ethyl benzoate, phenyl acetate, benzyl acetate, methyl phenyl acetate, benzyl formate, phenylethyl formate, methyl 3-phenylpropionate, benzyl propionate, The shrink material selected from the group consisting of ethyl phenylacetate and 2-phenylethyl acetate. As a pattern formation method,
Applying to the substrate 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,
Pre-firing 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-based developer to form a negative resist pattern,
Applying the shrink material of claim 1 over the negative resist pattern,
Firing, and
Removing excess shrink material with organic solvent
Pattern forming method comprising a. The pattern forming method according to claim 13, wherein 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):
<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 an ether or ester bond that may be intervened in a carbon-carbon bond Linear, branched or cyclic C ₁ -C ₁₀ alkylene groups or naphthylene groups. The method of claim 13, wherein the developer is 2-octanone, 2-nonanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-hexanone, 3-hexanone, diisobutyl ketone, methylcyclo Hexanon, acetophenone, methylacetophenone, propyl acetate, butyl acetate, isobutyl acetate, pentyl acetate, isopentyl acetate, butenyl acetate, propyl formate, butyl formate, isobutyl formate, pentyl formate, isopentyl Formate, methyl valerate, methyl pentenoate, methyl crotonate, ethyl crotonate, methyl propionate, ethyl propionate, ethyl 3-ethoxypropionate, methyl lactate, ethyl lactate, propyl Lactate, butyl lactate, isobutyl lactate, pentyl lactate, isopentyl lactate, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, methyl benzoate, ethyl One selected from the group consisting of benzoate, phenyl acetate, benzyl acetate, methyl phenylacetate, benzyl formate, phenylethyl formate, methyl 3-phenylpropionate, benzyl propionate, ethyl phenylacetate and 2-phenylethyl acetate The pattern formation method containing the above organic solvent. The process of claim 13 wherein the step of removing the excess shrink material is propyl acetate, butyl acetate, isobutyl acetate, butenyl acetate, pentyl acetate, isopentyl acetate, 2-methylbutyl acetate, hexyl acetate, 2-ethylhexyl acetate , Cyclohexyl acetate, methylcyclohexyl acetate, propyl formate, butyl formate, isobutyl formate, pentyl formate, isopentyl formate, hexyl formate, methyl valerate, ethyl valerate, propyl valerate, isopropyl Valerate, butyl valerate, isobutyl valerate, tert-butyl valerate, pentyl valerate, isopentyl valerate, ethyl isovalerate, propyl isovalerate, isopropyl isovalerate, butyl isovalerate, isobutyl Isovalerate, tert-butyl isovalerate, Sorbent isovalerate, ethyl 2-methylvalerate, butyl 2-methylvalerate, methyl crotonate, ethyl crotonate, propyl crotonate, isopropyl crotonate, butyl crotonate, tert-butyl croton Tonate, 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 Yate, ethyl 3-ethoxypropionate, ethyl hexanoate, allyl hexanoate, propyl butyrate, butyl butyrate, isobutyl butyrate, 3-methylbutyl butyrate, tert-butyl butyrate, ethyl 2-methylbutyrate, isopropyl 2-methylbutyrate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, phenyl acetate, benzyl acetate, methyl phenylacetate, benzyl formate, phenylethyl formate, methyl 3-phenylpropionate, ethyl phenyl Acetate, 2-phenylethyl acetate, 2-heptanone, 3-heptanone, 4-heptanone, 2-hexanone, 3-hexanone, 2-octanone, 3-octanone, 4-octanone, 2- Nonanone, 3-nonanone, 4-nonanone, 5-nonanone, methylcyclohexanone, ethylcyclohexanone, acetophenone, methylacetophenone, ethylacetophenone, ethyl n-butyl ketone, di-n-butyl Ketones, diisobutyl ketones, 1-butanol , 2-butanol, isobutyl alcohol, t-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, t-pentyl alcohol, neopentyl alcohol, 2-methyl-1-butanol, 3-methyl- 1-butanol, 3-methyl-3-pentanol, cyclopentanol, 1-hexanol, 2-hexanol, 3-hexanol, 2,3-dimethyl-2-butanol, 3,3-dimethyl-1- Butanol, 3,3-dimethyl-2-butanol, 2,2-diethyl-1-butanol, 2-methyl-1-pentanol, 2-methyl-2-pentanol, 2-methyl-3-pentanol, 3-methyl-1-pentanol, 3-methyl-2-pentanol, 3-methyl-3-pentanol, 4-methyl-1-pentanol, 4-methyl-2-pentanol, 4-methyl-3 A pattern forming method using at least one organic solvent selected from the group consisting of pentanol, cyclohexanol and 1-octanol. The method of claim 13, wherein the high-energy radiation is i-ray with a wavelength of 364 nm, KrF excimer laser with a wavelength of 248 nm, ArF excimer laser with a wavelength of 193 nm, EUV or EB with a wavelength of 13.5 nm. The shrink material of claim 1, wherein Z is selected from the group represented by the following formula:

. The method of claim 1, wherein at least one of R ^x and R ^y is substituted with a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, an adamantyl group, a norbornyl group, and a hydroxyl group or an alkoxy group therein. Shrinking material selected from the group consisting of.

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