KR20200049069A - Photosensitive composition and pattern formed using the composition - Google Patents

Abstract

The present invention relates to a photosensitive composition capable of securing the uniformity of a pattern, comprising a polymer (A), and to a pattern comprising the photosensitive composition or a cured product thereof.

Description

Photosensitive composition and pattern formed using the composition {PHOTOSENSITIVE COMPOSITION AND PATTERN FORMED USING THE COMPOSITION}

The present invention relates to a photosensitive composition and a photoresist pattern formed using the composition.

The high integration of semiconductors has progressed with the development of photolithography technology that is unmatched by other patterning techniques in terms of performance, reliability, and human and physical infrastructure. In particular, as the photoresist of a shorter light source and a photochemical reaction corresponding thereto are applied, the integration of the device is rapidly increased due to the development of KrF excimer laser (248 nm) and ArF laser (193 nm) lithography technology to which a high sensitivity chemically amplified photoresist is applied Has been increasing.

Through various attempts to change the composition of the photosensitive composition, sensitivity, resolution, and roughness of line width have been improved. Among them, various photoactive compounds for use in photosensitive compositions have been proposed. In particular, custom photoacid generators (PAGs) that control acid diffusion and improve miscibility with polymers are very important for high resolution lithography. For example, if the photoacid generator is not uniformly distributed in the resist film, defects such as T-topping, foot formation, and notching may occur in the imaged photoresist film.

The structure of the photoacid generator plays an important role in the overall performance of the photoresist by affecting the interaction of the photoacid generator with other photoresist compositions. This interaction has an important effect on the diffusion of the acid produced by irradiation of light. Research into photoacid generators with specific structural, chemical and physical properties to improve acid diffusion properties and better compatibility with other photoresist compositions is ongoing.

PCT / KR2010 / 007678

The present invention is a photosensitive composition capable of securing the uniformity of the pattern by improving the line width roughness (LWR) of the photoresist pattern; And it provides a pattern comprising the photosensitive composition or a cured product thereof.

In order to solve the above problem, the present applicant has included a polymer (A) comprising a photo-acid generator and a main chain composed of a norbornene ring in a photosensitive composition. In one embodiment, the photosensitive composition comprises a polymer (A), the polymer (A) is a structural unit represented by the following formula 1a; And a structural unit represented by the following Chemical Formula 1b.

[Formula 1a]

[Formula 1b]

In the formulas 1a and 1b,

M1 is an organic cation, M2 is an organic anion,

Y1 is a straight-chain or branched alkylene group; A divalent saturated hydrocarbon ring group; A divalent aromatic hydrocarbon group; A divalent saturated heterocyclic group; A divalent aromatic heterocyclic group; A divalent ring group in which two or more rings are condensed among a saturated hydrocarbon ring, an aromatic hydrocarbon, a saturated heterocycle, and an aromatic heterocycle; -O-; -C (= O)-; -C (= O) O-; -C (= O) N (R19)-; -N (R19)-; -S-; -S (= O)-; -S (= O) _2- ; And -S (= O) ₂ O-, or any one group selected from the group consisting of two or more groups selected from the group, and R19 is hydrogen; heavy hydrogen; Alkyl groups; Saturated hydrocarbon ring group; Or an aromatic hydrocarbon group, two or more R19 are the same as or different from each other,

Y2 and R1 to R3 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Halogen group; Nitrile group; Alkyl groups; Saturated hydrocarbon ring group; Aromatic hydrocarbon groups; Saturated heterocyclic group; Aromatic heterocyclic group; A ring group in which two or more rings of a saturated hydrocarbon ring, aromatic hydrocarbon, saturated heterocycle, and aromatic heterocycle are condensed; -OR; -OC (= O) R; -C (= O) R; -C (= O) OR; -C (= O) NR ₂ ; -NR ₂ ; -SR; -S (= O) R; -S (= O) ₂ R; And -S (= O) ₂ OR is a group selected from the group consisting of two or more groups selected from the group, and R is hydrogen; heavy hydrogen; Alkyl groups; Saturated hydrocarbon ring group; Aromatic hydrocarbon groups; Saturated heterocyclic group; Aromatic heterocyclic group; Or a saturated hydrocarbon ring, an aromatic hydrocarbon, a saturated heterocycle, and an aromatic heterocycle are two or more rings condensed ring groups, and two or more Rs are the same or different from each other,

R1 to R3, Y1 and Y2 are each independently deuterium; Halogen group; Hydroxy group; Oxo group (= O); Or it may be further substituted with an alkyl group.

Another exemplary embodiment of the present specification provides a pattern including the above-mentioned claim photosensitive composition or a cured product thereof.

The pattern formed from the photosensitive composition of the present invention is excellent in optimal exposure amount and / or variation in line width (LWR).

The photosensitive composition of the present invention can be used to realize a fine pattern for semiconductors.

Before describing an exemplary embodiment of the present invention, first, some terms in the specification are clarified.

Also, as used herein, “comprise” and / or “comprising” specifies the shapes, numbers, steps, actions, elements, elements and / or the presence of these groups. And does not exclude the presence or addition of one or more other shapes, numbers, actions, elements, elements and / or groups.

In this specification, the weight average molecular weight is a standard polystyrene equivalent weight average molecular weight measured by gel permeation chromatography (GPC).

In one embodiment, the weight average molecular weight can be measured by the following method using a gel permeation chromatography (GPC, Waters, Inc. Waters707). A sample is prepared by dissolving 0.2 mg of the compound to be measured in 10 mg of tetrahydrofuran. After introducing tetrahydrofuran into the mobile phase at a flow rate of 1 ml / min, the weight average molecular weight is measured at 35 ° C using a detector (RI and PAD Detector).

는 다른 단위 또는 치환기와 연결되는 부위를 나타낸 것이다.In this specification,

Indicates a site connected to another unit or substituent.

In the present specification, the organic group means a monovalent compound composed of carbon, hydrogen, and a nonmetallic element (oxygen, nitrogen, chlorine, etc.). The organic group includes all non-cyclic compounds, compounds that form rings, heterocyclic compounds, and the like.

Hereinafter, some embodiments of the present invention will be described in detail. However, the spirit and scope of the present invention are not limited to the specific embodiments of the present invention described below, and include all of various conversions, equivalents, and substitutes.

The polymer (A) according to an exemplary embodiment of the present invention is a chemically amplified compound for electron beam or extreme ultraviolet.

In the present invention, upon exposure to the coating layer formed of the photosensitive composition, the polymer (A) of the portion irradiated with light decomposes and changes to a property that is easily dissolved in a developer. A pattern can be formed by removing the area exposed by the exposure process with a developer.

An exemplary embodiment of the present specification is a photosensitive composition comprising a polymer (A), wherein the polymer (A) is a structural unit represented by the following formula 1a; And it provides a photosensitive composition comprising a structural unit represented by the formula (1b).

[Formula 1a]

[Formula 1b]

In the formulas 1a and 1b,

M1 is an organic cation, M2 is an organic anion,

Y1 is a straight-chain or branched alkylene group; A divalent saturated hydrocarbon ring group; A divalent aromatic hydrocarbon group; A divalent saturated heterocyclic group; A divalent aromatic heterocyclic group; A divalent ring group in which two or more rings are condensed among a saturated hydrocarbon ring, an aromatic hydrocarbon, a saturated heterocycle, and an aromatic heterocycle; -O-; -C (= O)-; -C (= O) O-; -C (= O) N (R19)-; -N (R19)-; -S-; -S (= O)-; -S (= O) _2- ; And -S (= O) ₂ O-, or any one group selected from the group consisting of two or more groups selected from the group, and R19 is hydrogen; heavy hydrogen; Alkyl groups; Saturated hydrocarbon ring group; Or an aromatic hydrocarbon group, two or more R19 are the same as or different from each other,

Y2 and R1 to R3 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Halogen group; Nitrile group; Alkyl groups; Saturated hydrocarbon ring group; Aromatic hydrocarbon groups; Saturated heterocyclic group; Aromatic heterocyclic group; A ring group in which two or more rings of a saturated hydrocarbon ring, aromatic hydrocarbon, saturated heterocycle, and aromatic heterocycle are condensed; -OR; -OC (= O) R; -C (= O) R; -C (= O) OR; -C (= O) NR ₂ ; -NR ₂ ; -SR; -S (= O) R; -S (= O) ₂ R; And -S (= O) ₂ OR is a group selected from the group consisting of two or more groups selected from the group, and R is hydrogen; heavy hydrogen; Alkyl groups; Saturated hydrocarbon ring group; Aromatic hydrocarbon groups; Saturated heterocyclic group; Aromatic heterocyclic group; Or a saturated hydrocarbon ring, an aromatic hydrocarbon, a saturated heterocycle, and an aromatic heterocycle are two or more rings condensed ring groups, and two or more Rs are the same or different from each other,

R1 to R3, Y1 and Y2 are each independently deuterium; Halogen group; Hydroxy group; Oxo group (= O); Or it may be further substituted with an alkyl group.

In one embodiment, the polymer (A) may be a Random (irregular), Alternating (alternating) or Block (block) polymer.

In the present specification, a halogen group includes a fluoro group, bromo group, and iodine group.

In the present specification, the straight chain alkylene group is -CH _2- ; -(CH ₂ ) _2- ; -(CH ₂ ) ₃ -and the like, but is not limited thereto.

In the present specification, the branched alkylene group is -CH (CH ₃ )-; -C (CH ₃ ) _2- ; -C (CH ₃ ) (CH ₂ CH ₃ )-; -CH ₂ CH (CH ₃ ) It may mean CH _2- , but is not limited thereto.

In the present specification, a saturated hydrocarbon ring group means a monovalent group in which one hydrogen is removed from a monocyclic or polycyclic saturated hydrocarbon ring.

The monocyclic saturated hydrocarbon ring means cycloalkane. The cycloalkane may be cyclopropane, cyclobutane, cyclopentane, cyclohexane, and the like, but is not limited thereto.

The polycyclic saturated hydrocarbon ring is a bicyclo-type cycloalkane; Or a spiro-type cycloalkane. The bicyclo-type alkane includes fused cycloalkane; And bridged cycloalkane.

The fused cycloalkane means a fused ring of a cycloalkane that shares a pair of adjacent carbon atoms with each other. The bridged cycloalkane refers to a saturated hydrocarbon ring in which two non-adjacent carbons in the ring are directly bonded or connected to each other with an alkylene group. The spiro-linked cycloalkane means a saturated hydrocarbon ring connected while sharing one carbon atom.

The polycyclic saturated hydrocarbon ring is, for example, adamantane (adamantane); Norbornane; Tricyclodecane; Bicyclo [3.1.1] heptein; Decalin; Octahydro-1H-4,7-methanoindene; Octahydro-1H-4,7-ethanoindene; Bicyclo [3.1.0] hexane; Bicyclo [2.2.1] heptane; Bicyclo [3.2.0] heptane; Bicyclo [3.1.1] heptane; Bicyclo [4.1.0] heptane; Bicyclo [3.2.1] octane; Bicyclo [2.2.2] octane; Bicyclo [4.2.0] octane; Bicyclo [3.2.2] nonane; Bicyclo [4.4.0] decane; Spiro [4.3] octane; Spiro [5.2] octane; Spiro [5.4] decane (spiro [5.4] decane), and the like, but is not limited thereto.

In the present specification, the aromatic hydrocarbon may be benzene, naphthalene, anthracene, tetracene, triphenylene, phenanthrene, and the like, but is not limited thereto.

In the present specification, a saturated heterocyclic ring means a ring in which one or more carbons are substituted with S, O, N or Si in the saturated hydrocarbon ring.

In the present specification, an aromatic heterocycle means a ring composed of two or more elements with aromaticity.

In one embodiment, Y1 is a straight-chain or branched alkylene group; A divalent saturated hydrocarbon ring group; A divalent aromatic hydrocarbon group; A divalent ring group in which a saturated hydrocarbon ring and an aromatic hydrocarbon are condensed; -O-; -S-; -C (= O)-; -C (= O) O-; And -C (= O) NH- is a group selected from the group consisting of two or more groups selected from the group.

In one embodiment, Y1 is a straight-chain or branched alkylene group; -O-; And -S- is a group selected from the group consisting of two or more groups selected from the group.

If the miscibility and compatibility of the resin and photoacid generator contained in the composition is not good, the photoacid generator may not be uniformly distributed in the photosensitive film. If there is a difference in the content of the photoacid generator in each part, a difference occurs in the amount of acid generated in each part during exposure, and the amount of the resin dissolved in the developer in each part also varies. In this case, the variation (LWR) of the pattern width of the photoresist pattern becomes large, making it difficult to control the fine pattern.

On the other hand, the polymer (A) of the present invention has a group that generates an acid upon irradiation with light (a photoacid generator) to a polymer of a single molecule or a norbornene derivative containing norbornene, so that the photoacid generator is uniformly distributed in the photosensitive composition. Can be. Accordingly, there is no compatibility problem between the resin and the photoacid generator, and thus the variation in pattern width (LWR) is improved.

In one embodiment, the polymer (A) is a structural unit represented by the formula (1a); And a copolymer in which structural units represented by Chemical Formula 1b are irregularly arranged in a line. In this case, the main chain of the polymer (A) consists of a norbornene ring. In the present specification, the main chain of the polymer means a stem molecular chain forming a skeleton of the polymer.

When the main chain of the polymer (A) is composed of a norbornene ring, the glass transition temperature (Tg) is higher than that of the compound whose main chain is composed of an alkylene group. The lower the glass transition temperature (Tg) of the compound, the greater the fluidity of the resin during heat treatment after exposure, which is advantageous for acid diffusion, but the faster the acid diffusion, the greater the variation in pattern width when forming a fine pattern. If the glass transition temperature of the resin and the photo-acid generator is made high, diffusion of the acid generated from the photo-acid generator during exposure is not large, so that a fine pattern with a relatively uniform pattern width can be realized.

In the present specification, the glass transition temperature can be measured by differential scanning calorimetry (DSC). In one embodiment, the glass transition temperature can be measured using DSC3 of Melttler.

In one embodiment, the weight average molecular weight of the polymer (A) is 3,000 g / mol to 15,000 g / mol. When the weight average molecular weight of the compound of Formula 1 is less than 3,000 g / mol, cracks may occur in the photosensitive film, and when it exceeds 15,000 g / mol, sensitivity may decrease and a foot phenomenon may occur.

In one embodiment, the weight average molecular weight of the polymer (A) is 15,000 g / mol or less; 12,000 g / mol or less; 9,000 g / mol or less; Or 7,000 g / mol or less.

In one embodiment, the structural unit represented by the formula (1a) is included in 80 to 99.9 mol% of the total structural unit contained in the polymer (A).

In one embodiment, the structural unit represented by Formula 1b is included in 0.1 mol% to 20 mol% compared to the total structural unit included in the polymer (A).

In one embodiment, when the structural unit represented by Chemical Formula 1b is included in an amount exceeding the above range, the resolution of the pattern may be lowered.

In one embodiment, the formula 1b is represented by the following formula 1c.

[Formula 1c]

In Chemical Formula 1c,

The definitions of R1, M1, M2 and Y2 are as defined in Formula 1b,

L1 and L2 are the same as or different from each other, and each independently a linear or branched alkylene group; A divalent saturated hydrocarbon ring group; A divalent aromatic hydrocarbon group; A divalent saturated heterocyclic group; A divalent aromatic heterocyclic group; A divalent ring group in which two or more rings are condensed among a saturated hydrocarbon ring, an aromatic hydrocarbon, a saturated heterocycle, and an aromatic heterocycle; -O-; -C (= O)-; -C (= O) O-; -C (= O) N (R19)-; -N (R19)-; -S-; -S (= O)-; -S (= O) _2- ; And -S (= O) ₂ O-, or any one group selected from the group consisting of two or more groups selected from the group, and R19 is hydrogen; heavy hydrogen; Alkyl groups; Saturated hydrocarbon ring group; Or an aromatic hydrocarbon group, two or more R19 are the same as or different from each other,

L1 and L2 are the same as or different from each other, and each independently deuterium; Halogen group; Hydroxy group; Oxo group (= O); Or it may be further substituted with an alkyl group,

n1 is an integer of 0 or more, and when n1 is 2 or more, L1 is the same or different from each other,

n2 is an integer of 0 or more, and when n2 is 2 or more, L2 is the same or different from each other,

R4 and R5 are the same as or different from each other, and each independently the same as the definition of R1,

b1 is 0 or 1, b2 is 0 or 1, and the sum of b1 and b2 is 1.

In one embodiment, L1 and L2 are the same as or different from each other, and each independently a straight-chain or branched alkylene group; A divalent saturated hydrocarbon ring group; A divalent aromatic hydrocarbon group; A divalent ring group in which a saturated hydrocarbon ring and an aromatic hydrocarbon are condensed; -O-; -C (= O)-; -C (= O) O-; And -C (= O) N (R19)-is any one group selected from the group consisting of, or two or more groups selected from the group are connected groups, R19 is hydrogen; heavy hydrogen; Alkyl groups; Saturated hydrocarbon ring group; Or an aromatic hydrocarbon group, two or more R19 are the same as or different from each other.

In one embodiment, L1 is a straight or branched alkylene group; A divalent saturated hydrocarbon ring group; -O-; And -C (= O)-, or a group selected from the group, or two or more groups selected from the group, wherein L1 is deuterium; Halogen group; Hydroxy group; Oxo group (= O); Or it may be further substituted with an alkyl group.

In one embodiment, L1 is a methylene group; And -O- is a group selected from the group consisting of two or more groups selected from the group.

In one embodiment, the n1 is 1 to 10; 1 to 8; 1 to 6; Or an integer from 1 to 4.

In one embodiment, L2 is a straight or branched alkylene group; A divalent saturated hydrocarbon ring group; And a divalent aromatic hydrocarbon group, or two or more groups selected from the group, wherein L2 is deuterium; Halogen group; Hydroxy group; Oxo group (= O); Or it may be further substituted with an aliphatic hydrocarbon group.

In one embodiment, L2 is a phenylene group.

In one embodiment, the n2 is 1 to 10; 1 to 8; 1 to 6; Or an integer from 1 to 4.

In one embodiment, R1 is hydrogen.

In one embodiment, R2 is hydrogen.

In one embodiment, R3 is represented by Formula 4 below.

[Formula 4]

In Chemical Formula 4,

R10 is a straight-chain or branched alkyl group; Saturated hydrocarbon ring group; Aromatic hydrocarbon groups; Saturated heterocyclic group; Aromatic heterocyclic group; A ring group in which two or more rings of a saturated hydrocarbon ring, aromatic hydrocarbon, saturated heterocycle, and aromatic heterocycle are condensed; -OR '; -OC (= O) R '; -C (= O) R '; -C (= O) OR '; -C (= O) NR '₂; -NR '₂; -SR '; -S (= O) R '; -S (= O) ₂ R '; And -S (= O) ₂ OR 'is a group selected from the group consisting of two or more groups selected from the group, and R' is hydrogen; heavy hydrogen; Alkyl groups; Saturated hydrocarbon ring group; Aromatic hydrocarbon groups; Saturated heterocyclic group; Aromatic heterocyclic group; Or two or more rings of a saturated hydrocarbon ring, aromatic hydrocarbon, saturated heterocycle, and aromatic heterocycle are condensed, and two or more R 'are the same as or different from each other, and R10 may be further substituted with an oxo group.

In one embodiment, R10 is a straight or branched chain alkyl group; Saturated hydrocarbon ring group; Aromatic hydrocarbon groups; Saturated heterocyclic group; Aromatic heterocyclic group; A ring group in which two or more rings of a saturated hydrocarbon ring, aromatic hydrocarbon, saturated heterocycle, and aromatic heterocycle are condensed; -OR '; -OC (= O) R '; -C (= O) R '; And -C (= O) OR 'is a group selected from the group consisting of two or more groups selected from the group, and R' is hydrogen; heavy hydrogen; Alkyl groups; Saturated hydrocarbon ring group; Aromatic hydrocarbon groups; Or a saturated hydrocarbon ring, two or more R 'is the same as or different from each other, R10 may be further substituted with an oxo group.

In one embodiment, R10 is deuterium; Halogen group; Hydroxy group; Alkoxy groups; Aryloxy group; Haloalkyl group; Alkyl groups; Oxo group (= O); Or a saturated hydrocarbon ring group unsubstituted or substituted with an alkyl group.

In one embodiment, b1 is 1.

In one embodiment, b2 is 1.

In one embodiment, the M1 is represented by any one of the following formulas a-1 to a-3.

In the above formulas a-1 to a-3,

는 Y1과 연결되는 부위를 나타내며,

Represents a site connected to Y1,

R11 to R14 are the same as or different from each other, and each independently a linear or branched alkyl group; Saturated hydrocarbon ring group; Aromatic hydrocarbon groups; Saturated heterocyclic group; Aromatic heterocyclic group; Or a saturated hydrocarbon ring, an aromatic hydrocarbon, a saturated heterocyclic ring, or an aromatic heterocyclic ring group having two or more rings condensed,

R11 to R14 are the same as or different from each other, and each independently deuterium; Halogen group; Hydroxy group; Alkoxy groups; Oxo group (= O); Or it may be further substituted with an alkyl group,

c1 is an integer of 0 or more, and when c1 is 2 or more, R13 is the same or different from each other,

c2 is an integer from 1 to 10.

는 L2와 연결되는 부위를 나타낸다.In one embodiment, M1 of Formula 1c is represented by any one of Formulas a-1 to A-3, in this case

Indicates a site connected to L2.

In one embodiment, the R11 to R14 are the same as or different from each other, and each independently a methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hex Real group, heptyl group, octyl group, benzylmethyl group, phenylethyl group, 2-oxopropyl group, 2-cyclopentyl-1-oxoethyl group, 2-cyclohexyl-1-oxoethyl group, 2- (4-methylcyclohexyl)- Alkyl groups such as 1-oxoethyl group, 2-phenyl-1-oxoethyl group, 2- (1-naphthyl) -1-oxoethyl group, and 2- (2-naphthyl) -1-oxoethyl group; Cyclopentyl group, cyclohexyl group, cycloheptyl group, cycloprotyl group, 2-methylcyclohexyl group, 3-methylcyclohexyl group, norbornyl group, adamantanyl group, 2-oxocyclopentyl group, 2-oxocyclohex Saturated hydrocarbon ring groups such as an actual group; Phenyl group, naphthyl group, p-methoxyphenyl group, m-methoxyphenyl group, o-methoxyphenyl group, ethoxyphenyl group, p-tert-butoxyphenyl group, m-tert-butoxyphenyl group, 2-methylphenyl group, 3- Methylphenyl group, 4-methylphenyl group, ethylphenyl group, 4-tert-butylphenyl group, 4-butylphenyl group, dimethylphenyl group, methylnaphthyl group, ethyl naphthyl group, methoxynaphthyl group, ethoxynaphthyl group, dimethylnaphthyl group, diethyl Aromatic hydrocarbons such as naphthyl group, dimethoxynaphthyl group, and diethoxynaphthyl group.

In one embodiment, the R11 to R14 are the same as or different from each other, and each independently hydrogen; Or it is a C6-C30 aromatic hydrocarbon group.

In one embodiment, the R11 to R14 are the same as or different from each other, and each independently hydrogen; Or a phenyl group.

In one embodiment, c2 is an integer from 1 to 3.

In one embodiment, the M2-Y2 is represented by the following formula (10).

[Formula 10]

In Chemical Formula 10,

R15 is a halogen group, R16 is a halogen group,

a10 is an integer from 1 to 5, and when a10 is 2 or more, -C (R15) (R16)-is the same as or different from each other,

L11 and L12 are the same as or different from each other, and each independently a single bond; Straight-chain or branched alkylene groups; A divalent saturated hydrocarbon ring group; A divalent aromatic hydrocarbon group; A divalent saturated heterocyclic group; A divalent aromatic heterocyclic group; A divalent ring group in which two or more rings are condensed among a saturated hydrocarbon ring, an aromatic hydrocarbon, a saturated heterocycle, and an aromatic heterocycle; -O-; -C (= O)-; -C (= O) O-; -C (= O) N (R19)-; -N (R19)-; -S-; -S (= O)-; -S (= O) _2- ; And -S (= O) ₂ O-, or any one group selected from the group consisting of two or more groups selected from the group, and R19 is hydrogen; heavy hydrogen; Alkyl groups; Saturated hydrocarbon ring group; Or an aromatic hydrocarbon group, two or more R19 are the same as or different from each other,

R17 is a saturated hydrocarbon ring group,

L11, L12 and R17 are the same as or different from each other, and each independently deuterium; Halogen group; Hydroxy group; Oxo group (= O); Or it may be further substituted with an alkyl group.

In one embodiment, R15 is a fluoro group.

In one embodiment, R16 is a fluoro group.

In one embodiment, a10 is 1 or 2.

In one embodiment, L11 is a single bond.

In one embodiment, L12 is a straight chain alkylene group.

In one embodiment, L12 is C1-C15; C1-C10; C1-C6; Or it is a C1-C4 linear alkylene group.

In one embodiment, R17 is an adamantanyl group unsubstituted or substituted with a hydroxy group.

In one embodiment, the polymer (A) may further include other photoacid generators.

In one embodiment, the photoacid generator is a sulfonium salt; Iodonium salt; Diazonium salt; Phosphonium salt; Pyridinium salt; Halogen-containing compounds; Sulfone compounds; Sulfonate ester compounds; Quinone diazide compounds; And it may be one or two or more selected from the group consisting of diazomethane compounds, but is not limited thereto.

The sulfonium salts include, for example, diphenyl (4-phenylthiophenyl) sulfonium hexafluoroantimonate, 4,4'-bis [diphenylsulfonylolphenyl sulfide bishexafluoroantimonate and these Combination of triphenylsulfonium nonafluorobutanesulfonate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium pyrenesulfonate, triphenylsulfonium dodecylbenzenesulfonate, triphenylsulfonium p- Toluenesulfonate, triphenylsulfonium benzenesulfonate, triphenylsulfonium 10-camposulfonate, triphenylsulfonium octanesulfonate, triphenylsulfonium 2-trifluoromethylbenzenesulfonate, triphenylsulfonium hexafluor Loantimonate, and the like, but is not limited thereto.

The iodonium salt is, for example, diphenyl iodonium trifluoromethane sulfonate, diphenyl iodonium pyrene sulfonate, diphenyl iodonium dodecylbenzenesulfonate, diphenyl iodonium p-toluene Sulfonate, diphenyliodonium benzenesulfonate, diphenyliodonium 10-camposulfonate, diphenyliodonium octanesulfonate, diphenyliodonium 2-trifluoromethylbenzenesulfonate, bis (4 -t-butylphenyl) iodonium nonafluorobutane sulfonate, and the like, but is not limited thereto.

The diazonium salt may be, for example, phenyldiazonium hexafluorophosphate, phenyldiazonium hexafluoroantimonate, phenyldiazonium tetrafluoroborate, phenyldiazonium tetrakis (pentafluorophenyl) borate, etc. , But is not limited to this.

The phosphonium salt is, for example, triphenylphosphonium chloride, triphenylphosphonium bromide, tri (p-methoxyphenyl) phosphonium tetrafluoroborate, tri (p-methoxyphenyl) phosphonium hexafluorophos Phonate, tri (p-ethoxyphenyl) phosphonium tetrafluoroborate, benzyltriphenylphosphonium hexafluoroantimonate, and the like, but is not limited thereto.

The pyridinium salt is, for example, 1-benzyl-2-cyanopyridinium hexafluorophosphate, 1-benzyl-2-cyanopyridinium hexafluoroantimonate, 1-benzyl-2-cyanopyri Dinium tetrafluoroborate, 1-benzyl-2-cyanopyridinium tetrakis (pentafluorophenyl) borate, 1- (naphthylmethyl) -2-cyanopyridinium hexafluorophosphate, 1- (naphthyl Methyl) -2-cyanopyridinium hexafluoroantimonate, and the like, but is not limited thereto.

Halogen-containing compounds include haloalkyl group-containing hydrocarbon compounds and haloalkyl group-containing heterocyclic compounds. Halogen-containing compounds are, for example, phenyl-bis (trichloromethyl) -s-triadine, 4-methoxyphenyl-bis (trichloromethyl) -s-triadine and 1-naphthyl-bis (trichloromethyl) ) -s-triadine, such as (poly) trichloromethyl-s-triadine and 1,1-bis (4-chlorophenyl) -2,2,2-trichloroethane, but is not limited thereto.

Sulfone compounds include, for example, β-ketosulfone and β-sulfonylsulfone and their α-diazo compounds. Specific examples of sulfone compounds include phenacylphenylsulfone, mesitylphenacylsulfone, bis (phenylsulfonyl) methane, 1,1-bis (phenylsulfonyl) cyclobutane, and 1,1-bis (phenylsulfonyl) cyclopentane , 1,1-bis (phenylsulfonyl) cyclohexane and 4-trisphenacylsulfone, and the like, but is not limited thereto.

Sulfonic acid esters compounds include alkylsulfonate esters, haloalkyl sulfonate esters, aryl sulfonate esters and amino sulfonates. The sulfonate ester compound may be, for example, benzoin tosylate, pyrogallol tristrifluoromethanesulfonate, pyrogallol trisnonafluorobutanesulfonate, pyrogallol methanesulfonate triester, and the like, but is not limited thereto.

The diazomethane compound is, for example, bis (trifluoromethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (phenylsulfonyl) diazomethane, bis (p-toluene sulfide) Phonyl) diazomethane, methylsulfonyl-p-toluenesulfonyldiazomethane, 1-cyclohexylsulfonyl-1- (1,1-dimethylethylsulfonyl) diazomethane and bis (1,1-dimethylethyl Sulfonyl) diazomethane, and the like, but is not limited thereto.

The quinone diazide compound is, for example, sulfonic acid esters of quinone diazide derivatives such as 1,2-benzoquinone diazide-4-sulfonic acid ester and 1,2-naphthoquinone diazide-4-sulfonic acid ester. ; 1,2-benzoquinone-2-diazide-4-sulfonic acid chloride, 1,2-naphthoquinone-2-diazide-4-sulfonic acid chloride, 1,2-naphthoquinone-diazide-5- Sulfonic acid chloride, 1,2-naphthoquinone-1-diazide-6-sulfonic acid chloride, and the like, but is not limited thereto.

In one embodiment, the photosensitive composition may not include a separate photoacid generator other than the polymer (A). The photoacid generator is a compound that generates an acid when irradiated with actinic rays or radiation. In one embodiment, when the photosensitive composition includes only the polymer (A) as a photoacid generator, the variation in pattern width (LWR) of the pattern may be further reduced.

In one embodiment, the polymer (A) is included in 100 parts by weight compared to 100 parts by weight of a photoacid generator (a compound that generates an acid upon light irradiation) contained in the photosensitive composition.

The photosensitive composition may further include a polymer (B) comprising a structural unit containing a hydroxyl group to improve sensitivity control and pattern profile.

In one embodiment, the weight ratio of the polymer (A) and the polymer (B) included in the photosensitive composition is 8: 2 to 4: 6; Or 7: 3 to 5: 5. When the content of the polymer (B) is less than the above range, a residual film may remain on the substrate after developing the photoresist layer. It can be broken.

In one embodiment, the structural unit containing the hydroxy group is a structural unit represented by the following formula c-1.

In Chemical Formula c-1, R61 is hydrogen; Or an alkyl group.

In one embodiment, R61 is hydrogen; Or a methyl group.

In one embodiment, the OH group of Chemical Formula c-1 is bonded to the para position of benzene.

In one embodiment, the polymer (B) is a structural unit having a hydroxyl group protected by an acid-decomposable group; And a structural unit having a carboxyl group protected by an acid-decomposable group.

In the present specification, an acid-labile group means a group in which a bond is removed by an acid.

The structural unit having a hydroxyl group protected with an acid-decomposable group can be decomposed to a hydroxy group under acid conditions, and a structural unit having a carboxyl group protected with an acid-decomposable group can be decomposed to carboxylic acid under acid conditions.

In addition, the photosensitive composition of the present invention, by including the polymer (B), it is easy to adjust the sensitivity can finely adjust the pattern shape.

In one embodiment, the structural unit having a hydroxyl group protected by the acid-decomposable group is a structural unit represented by the following formula d-1, and the structural unit having a carboxyl group protected by the acid-decomposable group is represented by the following formula d-2 It is a structural unit.

In the above formulas d-1 and d-2,

R21 and R22 are the same as or different from each other, and each independently -Si (R24) (R25) (R26); A substituted or unsubstituted ring group containing lactone; A substituted or unsubstituted ring group containing sulfone; -C (R27) (R28) O (R29); -(CH ₂ ) _n C (= O) O (R30); -C (R31) (R32) (R33); A substituted or unsubstituted aliphatic ring group; Or a substituted or unsubstituted aromatic ring group,

R24 to R33 are the same as or different from each other, and each independently deuterium; Nitrile group; -N (R42) (R43); -C (= O) (R44); -C (= O) O (R45); A substituted or unsubstituted alkyl group; A substituted or unsubstituted aliphatic ring group; And a group selected from the group consisting of substituted or unsubstituted aromatic ring groups, or a group in which two or more groups selected from the group are connected, and R42 to R45 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted alkyl group; A substituted or unsubstituted aliphatic hydrocarbon group; Or a substituted or unsubstituted aromatic hydrocarbon group,

n is an integer from 0 to 6,

R20 and R23 are the same as or different from each other, and each independently hydrogen; Or an alkyl group.

In one embodiment, in the definition of the substituents of the formulas d-1 and d-2, 'substituted or unsubstituted' deuterium; Nitrile group; -O (R46); Oxo group (= O); -N (R47) (R48); -C (= O) (R49); -C (= O) O (R50); Alkyl groups; Aliphatic ring group; And it is any one group selected from the group consisting of an aromatic ring group, or two or more groups selected from the group are connected, R46 to R50 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Alkyl groups; Aliphatic hydrocarbon groups; Or an aromatic hydrocarbon group.

In one embodiment, the carbon number of the alkyl group of R21 and R22 is 1 to 30; 1 to 20; Or 1 to 10.

In one embodiment, the aliphatic ring group of R21 and R22 is an aliphatic hydrocarbon ring group; Or it may be an aliphatic heterocyclic group containing S, O or N. The aliphatic ring group is monocyclic; Or polycyclic. The polycyclic ring is bicyclo; Or as a spy, include a structured form.

In the present specification, the aliphatic ring group is an aliphatic hydrocarbon ring group; And aliphatic heterocyclic groups. The aliphatic hydrocarbon ring group includes a saturated hydrocarbon ring group and an unsaturated hydrocarbon ring group. The unsaturated hydrocarbon ring group means a group in which some single bonds of a cycloalkyl group, a bicyclo type cycloalkyl group, and a spiro type cycloalkyl group are replaced by an unsaturated bond. The aliphatic heterocyclic group means a group in which some carbons of the aliphatic hydrocarbon ring group are substituted with O, S, Se or N.

In one embodiment, the R24 to R33 are the same as or different from each other, and each independently a methyl group, ethyl group, n-propyl group, isopropyl group, tert-butyl group, cyclopentyl group; Cyclohexyl group; Bicyclo [2.2.1] heptein; Tricyclo [2.2.1.0 ^2,6 ] heptane; Adamantane; Tetracyclo [3.2.0.0 ^2,7 .0 ^4,6 ] heptane; Octahydro-1H-indene; Octahydro-1H-4,7-methanoindene; Decahydro-1,4-methanonaphthalene; Decahydro-1,4: 5,8-dimethanonaphthalene, and the like, but are not limited thereto.

In one embodiment, the-(CH ₂ ) _n C (= O) O (R30) is tert-butoxycarbonyl group, tert-butoxycarbonylmethyl group, tert-amyloxycarbonyl group, tert-amyloxycarbonylmethyl group , 1,1-diethylpropyloxycarbonyl group, 1,1-diethylpropyloxycarbonylmethyl group, 1-ethylcyclopentyloxycarbonyl group, 1-ethylcyclopentyloxycarbonylmethyl group, 1-ethyl-2-cyclopentenyl It may be an oxycarbonyl group, 1-ethyl-2-cyclopentenyloxycarbonylmethyl group, 1-ethoxyethoxycarbonylmethyl group, 2-tetrahydropyranyloxycarbonylmethyl group, 2-tetrahydroprenyloxycarbonylmethyl group However, it is not limited thereto.

In one embodiment, the aliphatic ring group of R21 and R22 is a cyclopentyl group; Cyclohexyl group; Bicyclo [2.2.1] heptanyl group; Tricyclo [2.2.1.0 ^2,6 ] heptanyl group; Adamantane; Tetracyclo [3.2.0.0 ^2,7 .0 ^4,6 ] heptanyl group; Octahydro-1H-indenyl group; Octahydro-1H-4,7-methanoindenyl group; Decahydro-1,4-methanonaphthyl group; Decahydro-1,4: 5,8-dimethanonaphthyl group, and the like, but is not limited thereto.

In the present specification, the aromatic ring group is an aromatic hydrocarbon group; Or it may be an aromatic heterocycle containing O, N, Se or S. The aromatic hydrocarbon group may be, for example, a phenyl group, a biphenyl group, a terphenyl group, a stilbenyl group, a naphthyl group, anthracenyl group, phenanthrenyl group, pyrenyl group, perylenyl group, chrysenyl group, fluorenyl group, and the like. It is not limited. The aromatic heterocyclic group is, for example, a thiophenyl group, furanyl group, pyrrolyl group, imidazolyl group, thiazolyl group, oxazolyl group, oxadiazolyl group, triazolyl group, pyridinyl group, bipyridinyl group, pyrimidyl group , Triazinyl group, acridinyl group, pyridazinyl group, pyrazinyl group, quinolinyl group, quinazolinyl group, quinoxalinyl group, phthalazinyl group, pyridopyrimidinyl group, pyridopyrazinyl group, pyrazinopira group Genyl group, isoquinolinyl group, indolyl group, carbazolyl group, benzoxazolyl group, benzimidazolyl group, benzothiazolyl group, benzocarbazolyl group, dibenzocarbazolyl group, benzothiophenyl group, dibenzothiophenyl group , Benzofuranyl group, dibenzofuranyl group; Benzosilol group; Dibenzosilol group; A phenanthrolinyl group, a thiazolyl group, an isooxazolyl group, an oxadiazolyl group, a thiadiazolyl group, a benzothiazolyl group, a phenothiazinyl group, a phenoxazinyl group, and the like, but is not limited thereto.

In the present specification, lactone means a cyclic ester, and may be 5 to 7 membered rings. The ring containing the lactone includes a ring in which another ring is condensed in the form of a bicyclo structure or a spy structure on the lactone. In one embodiment, the ring containing the lactone is dihydrofuran-2 (3H) -one; Tetrahydro-2H-pyran-2-one; 6-oxabicyclo [3.2.1] octan-7-one; Hexahydro-2H-3,5-methanocyclopenta [b] furan-2-one; Tetrahydro-2,6-methanofuro [3,2-b] furan-5 (2H) -one; Hexahydro-3,6-methanobenzofuran-2 (3H) -one; Hexahydrobenzofuran-2 (3H) -one; Hexahydro-4,7-methanobenzofuran-2 (3H) -one; 2-oxabicyclo [2.2.2] -octan-3-one; 4-octatricyclo [4.3.0.0 ^3,8 ] nonan-5-one; 2-oxaspiro [4.5] decane-1-one; Dihydro-2'H-spiro [bicyclo [2.2.1] heptan-2,3'-furan] 2'-one; Tetrahydrofuro [3,2-b] furan-2 (5H) -one; Tetrahydro-2H-cyclopenta [b] furan-2-one; 4- ^oxatricyclo [4.3.1.1 ^3,8 ] undecan-5-one, and the like, but is not limited thereto.

In the present specification, sulfone means a cyclic sulfonic acid ester, and may be 5 to 7 membered rings. The ring containing the sulfone includes a ring in which another ring is condensed in the form of a bicyclo structure or a spy structure in the sulfone. In one embodiment, the ring containing the sulfone is hexahydro-3,5-methanocyclopenta [c] [1,2] oxaol 1,1-dioxide; 1,2-oxathiolane 2,2-dioxide (1,2-oxathiolane 2,2-dioxide); 1,2-oxacyane 2,2-dioxide (1,2-oxathiane 2,2-dioxide), and the like, but is not limited thereto.

In one embodiment, the R21 and R22 are the same as or different from each other, and each independently a trimethylsilyl (TMS) group; Triethylsilyl (TES) group; t-butyldimethylsilyl group; t-butyl diphenyl silyl group; Triisopropylsilyl (TIPS) group; Tetrahydropyranyl (THP) groups; Tetrahydrofuranyl (THF) groups; p-methoxybenzyl methyl group; o-nitrobenzyl methyl group; p-nitrobenzyl methyl group; Adamantanyl group; -COCH ₃ ; -COC (CH ₃ ) ₃ ; -COCH (CH ₃ ) ₂ ; Or -CO (C ₆ H ₅ ); C1-C10 alkyl group; C3-C12 aliphatic cyclic group; Or it may be an aromatic ring group of C6-C30, but is not limited thereto.

In one embodiment, R20 and R23 are the same as or different from each other, and each independently hydrogen; Or it is a C1-C10 alkyl group.

In one embodiment, R20 and R23 are the same as or different from each other, and each independently hydrogen; Or a methyl group.

In one embodiment, the polymer (B) is a structural unit represented by the formula d-1 or d-2; It is a random polymer of the structural unit represented by the formula (c-1).

In one embodiment, the polymer (B) is a structural unit represented by the formula d-1 or d-2; The structural unit represented by Chemical Formula c-1 is a polymer arranged irregularly in a line.

In one embodiment, the polymer (B) is a polymer in which structural units represented by the formulas c-1, d-1 and d-2 are irregularly arranged in a linear manner at a molar ratio of e1: e2: e3. In one embodiment, the e1: e2 + e3 is 9: 1 to 5: 5; Or 8: 2 to 6: 4.

In one embodiment, the polymer (B) is a polymer in which structural units represented by the formulas c-1 and d-1 are irregularly arranged in a linear manner at a molar ratio of f1: f2. In one embodiment, the f1: f2 is 9: 1 to 5: 5; Or 8: 2 to 6: 4.

In one embodiment, the polymer (B) is a polymer in which the structural units represented by the formulas c-1 and d-2 are arranged irregularly in a line at a molar ratio of g1: g2. In one embodiment, the g1: g2 is 9: 1 to 5: 5; Or 8: 2 to 6: 4.

In the polymer (B), if the proportion of the structural unit containing a group protected by an acid-decomposable group is less than the above range, the sensitivity of the polymer (B) may be low and the pattern shape may not be uniform. The phenomenon may occur up to a portion other than the desired pattern shape, and the shape of the pattern may be damaged.

In one embodiment, the structural unit represented by Chemical Formula d-1 may be any one selected from the following structural units, but is not limited thereto.

In one embodiment, the structural unit represented by Chemical Formula d-2 may be any one selected from the following structural units, but is not limited thereto.

In one embodiment, the weight average molecular weight of the polymer (B) is 3,000 g / mol or more and 15,000 g / mol or less; 3,500 g / mol or more and 10,000 g / mol or less; Or 4,000 g / mol or more and 7,000 g / mol or less. If the molecular weight of the polymer (B) is less than the above range, cracks may occur in the formed photosensitive film, and if it exceeds the above range, sensitivity may deteriorate and a foot phenomenon may occur.

In one embodiment, the photosensitive composition further comprises an acid diffusion inhibitor.

As the acid diffusion inhibitor, a compound capable of suppressing the diffusion rate of the acid generated from the polymer (A) is suitable, and in one embodiment, a basic compound may be used as the acid diffusion inhibitor. The diffusion rate of the acid in the photosensitive film is suppressed by the combination of the acid diffusion inhibitor to improve the resolution, to suppress the change in sensitivity after exposure, or to reduce the dependence on the substrate or the environment to improve exposure margin and pattern profile.

In one embodiment of the present specification, the acid diffusion inhibitor is an aliphatic, aromatic or heterocyclic amine; A nitrogen-containing compound containing a carboxyl group, sulfonyl group, hydroxy group or carbamate group; Amide derivatives; And it may include one or two or more selected from the group consisting of imide derivatives, but is not limited thereto.

The aliphatic amine can be a mono-, di- or tri- aliphatic amine. The aliphatic amine is ammonia, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tert-butylamine, pentylamine, tert-amylamine, cyclo Pentylamine, hexylamine, cyclohexylamine, heptylamine, octylamine, nonylamine, decylamine, dodecylamine, tetraethylenepentamine, dimethylamine, diethylamine, methylenediamine, ethylenediamine, di-n-propylamine , Diisopropylamine, di-n-butylamine, diisobutylamine, di-sec-butylamine, dipentylamine, dicyclopentylamine, dihexylamine, dicyclohexylamine, diheptylamine, dioctylamine , Dinonylamine, didecylamine, didodecylamine, N, N-dimethylmethylenediamine, N, N-dimethylethylenediamine, N, N-dimethyltetraethylenepentamine, trimethylamine, triethylamine, tri-n- Propylamine, triisopropylamine, tri-n-butylamine, triisobutylamine, tri -sec-butylamine, tripentylamine, tricyclopentylamine, trihexylamine, tricyclohexylamine, triheptylamine, trioctylamine, trinonylamine, tridecylamine, tridodecylamine, tricetylamine, N , N, N ', N'-tetramethylmethylenediamine, N, N, N', N'-tetramethylethylenediamine, N, N, N ', N'-tetramethyltetraethylenepentamine, etc. It is not limited.

Specific examples of the aromatic amine and heterocyclic amine include aniline, N-methylaniline, N-ethylaniline, N-propylaniline, N, N-dimethylaniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, and ethyl Aniline, propylaniline, trimethylaniline, 2-nitroaniline, 3-nitroaniline, 4-nitroaniline, 2,4-dinitroaniline, 2,6-dinitroaniline, 3,5-dinitroaniline, N, N -Aniline derivatives such as dimethyltoluidine; Diphenyl (p-tolyl) amine; Methyldiphenylamine; Triphenylamine; Phenylenediamine; Naphthylamine; Diaminonaphthalene; Pyrrole derivatives such as pyrrole, 1-methylpyrrole, 2,4-dimethylpyrrole, 2,5-dimethylpyrrole and N-methylpyrrole; Oxazole derivatives such as oxazole and isooxazole; Thiazole derivatives such as thiazole and isothiazole; Imidazole derivatives such as imidazole, 4-methylimidazole and 4-methyl-2-phenylimidazole; Pyrazole derivatives; Furazane derivatives; Pyrroline derivatives such as pyrroline and 2-methyl-1-pyrrole; Pyrrolidine derivatives such as pyrrolidine, N-methylpyrrolidine, pyrrolidinone, and N-methylpyrrolidone; Imidazoline derivatives; Imidazolidine derivatives; Pyridine, methylpyridine, ethylpyridine, propylpyridine, butylpyridine, (1-butylpentyl) pyridine, dimethylpyridine, trimethylpyridine, triethylpyridine, phenylpyridine, 3-methyl-2-phenylpyridine, 4-tert-butylpyridine , Diphenylpyridine, benzylpyridine, methoxypyridine, butoxypyridine, dimethoxypyridine, 4-pyrrolidinopyridine, 1-methyl-4-phenylpyridine, 2- (1-ethylpropyl) pyridine, aminopyridine, dimethyl Pyridine derivatives such as aminopyridine; Pyridazine derivatives; Pyrimidine derivatives; Pyrazine derivatives; Pyrazoline derivatives; Pyrazolidine derivatives; Piperidine derivatives; Piperazine derivatives; Morpholine derivatives; Indole derivatives; Isoindole derivatives; 1H-indazole derivatives; Indoline derivatives; Quinoline derivatives such as quinoline and 3-quinolinecarbonitrile; Isoquinoline derivatives; Cynolin derivatives; Quinazoline derivatives; Quinoxaline derivatives; Phthalazine derivatives; Purine derivatives; Pteridine derivatives; Carbazole derivatives; Phenanthridine derivatives; Acridine derivatives; Phenazine derivatives; 1,10-phenanthroline derivatives; Adenine derivatives; Adenosine derivatives; Guanine derivatives; Guanosine derivatives; Uracil derivatives; Uridine derivatives, and the like.

Tridine derivatives; Acridine derivatives; Phenazine derivatives; 1,10-phenanthroline derivatives; Adenine derivatives; Adenosine derivatives; Guanine derivatives; Guanosine derivatives; Uracil derivatives; Uridine derivatives, and the like.

The nitrogen-containing compound having the carboxyl group is aminobenzoic acid, indolecarboxylic acid, amino acid derivatives (for example, nicotinic acid, alanine, arginine, aspartic acid, glutamic acid, glycine, histidine, isoleucine, glycylleucine, leucine, methionine, phenylalanine, threonine , Lysine, 3-aminopyrazine-2-carboxylic acid, methoxyalanine) and the like.

The nitrogen-containing compound having a sulfonyl group may be 3-pyridinesulfonic acid, p-toluenesulfonic acid pyridinium, or the like.

The nitrogen-containing compound having a hydroxy group is a nitrogen-containing compound having a hydroxyphenyl group, 2-hydroxypyridine, aminocresol, 2,4-quinolinediol, 3-indolemethanol hydrate, monoethanolamine as an alcoholic nitrogen-containing compound, Diethanolamine, triethanolamine, N-ethyldiethanolamine, N, N-diethylethanolamine, triisopropanolamine, 2,2'-iminodiethanol, 2-aminoethanol, 3-amino-1-propanol, 4 -Amino-1-butanol, 4- (2-hydroxyethyl) morpholine, 2- (2-hydroxyethyl) pyridine, 1- (2-hydroxyethyl) piperazine, 1- [2- (2- Hydroxyethoxy) ethyl] piperazin, piperidineethanol, 1- (2-hydroxyethyl) pyrrolidine, 1- (2-hydroxyethyl) -2-pyrrolidinone, 3-piperidino- 1,2-propanediol, 3-pyrrolidino-1,2-propanediol, 8-hydroxyurolidine, 3-quinuclidinol, 3-tropanol, 1-methyl-2-pyrrolidineethanol, 1-aziridine Ethanol, such as N- (2- hydroxyethyl) phthalimide, N- (2- hydroxyethyl) iso-nicotinamide and the like.

As the amide derivative, formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, propionamide, benzamide and the like can be used.

Amide derivatives are formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, N, N-diethylacetamide, propionamide, benz Amide, N, N-bis (2-hydroxyethyl) pivalamide, tetrabutylmalonamide, and the like.

The imide derivative may be phthalimide, succinimide, maleimide, or the like.

In one embodiment, the acid diffusion inhibitor is tert-pentyl-4-hydroxypiperidine-1-carboxylate.

In one embodiment, the acid diffusion inhibitor is 0.1 to 2 parts by weight relative to 100 parts by weight of the polymer (A); It is preferably included in the photosensitive composition in 0.1 to 1 part by weight.

In one embodiment, the photosensitive composition further comprises a solvent.

Specifically as the solvent, γ-butyrolactone, 1,3-dimethylimidazolidinone, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, toluene , Xylene, tetramethylbenzene, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl Ether, propylene glycol monoethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether, ethyl acetate, butyl acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, Dipropylene glycol monomethyl ether acetate, ethanol, propanol, ethylene glycol, propyl Propylene glycol, carbitol, N, N-diethylacetamide, dimethylformamide (DMF), diethylformamide (DEF), N, N-dimethylacetamide (DMAc), N-methylpyrrolidone (NMP) , N-ethylpyrrolidone (NEP), 1,3-dimethyl-2-imidazolidinone, N, N-dimethylmethoxyacetamide, dimethylsulfoxide, pyridine, dimethylsulfone, hexamethylphosphoamide, tetra Methylurea, N-methylcaractam, tetrahydrofuran, m-dioxane, P-dioxane, 1,2-dimethoxyethane, bis (2-methoxyethyl) ether, 1,2-bis (2- Any one selected from the group consisting of methoxyethoxy) ethane, bis [2- (2-methoxyethoxy)] ether and mixtures thereof can be used.

In one embodiment, the photosensitive composition may further include at least one additive selected from the group consisting of a dissolution rate modifier, a sensitizer, an adhesion promoter, a plasticizer, a filler, a leveling agent, and a surfactant.

The additive may be used in a range of 0.1 to 10 parts by weight based on 100 parts by weight of the polymer (A).

Specifically, as the adhesion promoter, vinyl trimethoxysilane, vinyl triethoxysilane, vinyl tris (2-methoxyethoxy) -silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-ethoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, or 3- Mercaptopropyl trimethoxysilane and the like can be used, and one type alone or two or more types can be used in combination.

The surfactant may be used without particular limitation as long as it can be used in the photosensitive composition, and among them, it may be preferable to use a fluorine-based surfactant or a silicone-based surfactant.

In one embodiment, the polymer (A) may be formed by polymerizing norbornene derivatives containing M1 and M2 and norbornene derivatives not containing M1 and M2. However, the present invention is not limited thereto, and may be formed by polymerizing a norbornene derivative not containing M1 and M2 to form a polymer having a main chain composed of a norbornene ring, and then reacting with a compound containing M1 and M2.

One embodiment of the present specification provides a pattern formed using the photosensitive composition. In one embodiment, the pattern includes the polymer (A) or a cured product thereof.

In one embodiment, a method of forming a pattern using the photosensitive composition includes: (1) forming a photosensitive film on a substrate using the photosensitive composition; (2) selectively exposing the photosensitive film; And (3) developing the exposed photosensitive film.

The step (1) of forming a photosensitive film may include applying a photosensitive composition onto a substrate; And drying the coating (soft baked; SOB).

In one embodiment, as a method of applying the photosensitive composition, a spin coater, a bar coater, a blade coater, a curtain coater, a screen printing machine, a coating method, a spray coater method, or the like may be used, but the photosensitive composition may be used. Any method that can be applied can be used without limitation.

In the step of drying the coating (soft bake), the coating may be dried at 90 ° C to 120 ° C for 1 second to 10 minutes. The drying method may be, for example, an oven, a hot plate, vacuum drying, etc., but is not limited thereto. After the drying step, the solvent is removed from the photosensitive composition, thereby increasing the adhesion between the substrate and the photosensitive film.

The step of (2) selectively exposing the photosensitive film is a step of aligning the mask on the photoresist layer and then exposing the area of the photosensitive film that is not covered by the mask to light. The mask may be in contact with the photosensitive film, or may be aligned at a predetermined distance from the photosensitive film. In the exposure process, examples of the light source irradiated by the light irradiation means include electromagnetic light, ultraviolet light, visible light, electron beam, X-ray, and laser light. Further, as a method of irradiating the light source, a known means such as a high pressure mercury lamp, xenon lamp, carbon arc lamp, halogen lamp, cold cathode tube for copier, LED, semiconductor laser, etc. can be used.

The step of selectively exposing the photosensitive film (2) may further include heating a post-exposure bake (PEB) after the exposure. By heating the exposed photosensitive film, it is possible to rearrange the components in the photosensitive composition, thereby reducing the standing wave of the photosensitive film. In addition, the heating (PEB) helps diffusion of the acid generated during exposure, and facilitates deprotecting of the acid-decomposable group included in the polymer (B).

The heating (post-exposure bake) may be a photosensitive film at 110 ℃ to 130 ℃ conditions of 1 second to 10 minutes, but is not limited as long as it is above the temperature to dry the coating (soft bake).

In one embodiment, the photosensitive composition is coated on a silicon substrate and heated at 120 ° C. for 60 seconds to form a 56 nm thick photosensitive film, exposed under ArF ultraviolet light using a photo mask (pattern width 16 nm), and the exposed substrate Is heated at 110 ° C. for 90 seconds, developed in a 2.38 wt% tetramethylammonium hydroxide (TMAH) solution, and the exposure amount capable of forming a 32 nm line pattern is the optimal exposure amount (Eop), the optimum of the photosensitive composition The exposure amount is 75 mJ / cm ² or less; 73 mJ / cm ² or less; Or 70 mJ / cm ² or less.

The step (3) of developing the exposed photosensitive film is a step of removing the unexposed portion of the photosensitive film by dipping it in a developer. As the developing method, a conventionally known developing method of a photosensitive film, for example, a rotating spray method, a paddle method, an immersion method with ultrasonic treatment, and the like can be used, but is not limited thereto.

As the developing solution, for example, a basic aqueous solution such as hydroxide, carbonate, hydrogen carbonate, or quaternary ammonium salt of ammonia water may be used as an alkali metal or alkaline earth metal. Of these, an aqueous ammonia quaternary ammonium solution such as an aqueous tetramethyl ammonium solution is particularly preferred.

The step (3) of developing the exposed photosensitive film may further include drying the developed pattern after developing the exposed photosensitive film. After development, the pattern can be formed by drying under air or nitrogen atmosphere.

The step of developing (3) the exposed photosensitive film may further include post-baking the pattern after drying the pattern. The above step may be further performed to increase the adhesive strength and corrosion resistance of the semiconductor substrate and the photosensitive film. The heating may be performed under conditions of 1 second to 30 minutes at 120 ° C to 150 ° C using an oven, a hot plate, or the like. When it is necessary to significantly increase the etch resistance of the photosensitive film, the photosensitive film may be heated for 1 to 30 minutes (deep UV hardening) while dipping deep UV at a high temperature of 120 ° C to 190 ° C.

In one embodiment, the thickness of the pattern is 100 nm or less.

In one embodiment, the photosensitive composition may be used to form a fine pattern of less than 10 nm by using extreme ultraviolet (EUV) or electron beam (E-beam) as a light source.

In one embodiment, the pattern may be in the form of a line.

In one embodiment, the pattern is coated on a silicon substrate with a photosensitive composition and baked at 120 ° C. for 60 seconds to form a thin film, and exposed under ArF ultraviolet light using a photo mask (pattern width 16 nm). ), Then bake for 90 seconds at a temperature of 110 ° C., and the line width roughness when developing in a 2.38 wt% tetramethylammonium hydroxide (TMAH) solution is 10.5 nm or less. ; Or 10.2 nm or less.

In one embodiment, when the photosensitive composition does not include a separate photoacid generator, the variation in the pattern width is 9 nm or less; 8.7 nm or less; 8.4 nm or less; Or 8.2 nm or less.

The photosensitive composition according to an exemplary embodiment of the present specification may be used in all lithography processes that require a fine pattern, and may be used in semiconductors or in the manufacture of all other electronic devices. In one embodiment, the photosensitive composition can be used in an EUV lithography process.

In one embodiment of the present invention, the method for forming a pattern of the photoresist layer can be used in a semiconductor circuit manufacturing process. In one embodiment, the semiconductor circuit manufacturing process comprises (4) etching the region of the semiconductor substrate not covered by the photoresist layer in the pattern forming process and ashing the photoresist layer from the semiconductor substrate. It may be performed by a method further comprising a step.

The step of etching the area of the substrate not covered by the photosensitive film (4) is etching a substrate area other than the pattern of the photosensitive film. In one embodiment, the substrate may be a semiconductor substrate. The step of removing the photosensitive film from the substrate may be performed by using a known method, for example, by heating the wafer in a low pressure state using a reaction chamber and then injecting a plasma containing an oxygen group or oxygen ions.

In one embodiment, the photosensitive composition is a photosensitive composition for manufacturing a semiconductor circuit. In one embodiment, a circuit pattern may be formed on a semiconductor such as a silicon wafer using the photosensitive composition.

In addition, the photosensitive composition, the photoresist layer, or the photoresist pattern may be used without limitation in the field of devices such as devices used in semiconductor post-processing.

The embodiments according to the present invention are for more detailed description of the present invention, and may be modified in various forms other than those described below, and the scope of the present invention is limited to the embodiments described below. It is not intended.

Synthesis Example 1 (Preparation of compounds a1, a2, b1 and b2)

Preparation of compound a1

A solution of 57.6 g (0.3 mol) of methyl 2,2-difluoro-2- (fluorosulfonyl) acetate in 57.6 g of water was cooled to 0 ° C., and then 28 g of a 50% sodium hydroxide solution was slowly dropped. Knocked. The solution is heated to 100 ° C. for 3 hours, and cooled to room temperature when the reaction is complete. Neutralized with 34.5 g of 37% hydrochloric acid and concentrated to give sodium 1,1-difluoro-2-methoxy-2-oxoethanesulfonate.

Sodium 1,1-difluoro-2-methoxy-2-oxoethanesulfonate 42.4 g (0.2 mol), 1-adamantylmethanol 41.5 g (0.25 mol) and p-toluenesulfonic acid (p-TsOH) 51.6 g (0.3 mol) was dissolved in 140 g of dichloroethane and heated to 85 ° C. for 4 hours. The mixture was concentrated to remove dichloroethane, washed with 280 g of t-butyl methyl ether, and filtered. 100 g of acetonitrile was added to the obtained solid, stirred and filtered. The filtrate was concentrated to give the intermediate a1-1.

After dissolving 34.6 g (0.1 mol) of the intermediate a1-1 in 170 g of acetonitrile, 40.48 g (0.11 mol) of diphenyl (4-vinylphenyl) sulfonium bromide and 200 g of water were added and stirred for 15 hours. The concentrated solution was washed with t-butyl methyl ether and filtered to obtain compound a1 as a white solid. Nuclear magnetic resonance (NMR) data of compound a1 are as follows.

¹ H-NMR (500MHz, DMSO-D ₆ ): (ppm) 1.7 (m, 12H), 1.8 (m, 3H), 3.94 (s, 2H), 5.25 (d, 1H), 5.76 (d, 1H) , 6.72 (q, 1H), 7.36 (m, 14H)

Preparation of compound a2

Compound a2 was prepared by the same method as the preparation of compound a1, except that (4-merpentophenyl) diphenylsulfonium bromide was used instead of diphenyl (4-vinylphenyl) sulfonium bromide. Nuclear magnetic resonance (NMR) data of the compound a2 are as follows.

¹ H-NMR (500MHz, DMSO-D ₆ ): (ppm) 1.76 (m, 12H), 1.87 (m, 3H), 3.4 (s, 1H), 3.9 (s, 2H), 7.17 (d, 2H) , 7.35 (m, 12H)

Preparation of compound b1

Compound a1 62.2 g (0.1 mol), azobisisobutyronitrile 0.068 g (0.4 mmol) and bicyclo [2.2.1] -5-hepten-2-ylmethanethiol 12.6 g (0.09 mol) are propylene glycol Dissolve in 73.9 g of methyl ether acetate (solid content concentration 50 wt%). After heating to 65 ° C. for 1 hour, 73.9 g of a solvent was further added and then washed several times with water. Remove moisture with magnesium sulfate Concentration gave compound b1. Nuclear magnetic resonance (NMR) data of the compound b1 are as follows. ^It was confirmed that the reaction was terminated by confirming that H of the ethylene group between 5 and 7 ppm disappeared in ¹ H-NMR.

¹ H-NMR (500MHz, DMSO-D ₆ ): (ppm) 1.31 (m, 1H), 1.56 (m, 2H), 1.7 ~ 1.87 (m, 17H), 2.35 (m, 3H), 2.84 (m, 5H), 3.94 (s, 2H), 6.05 (m, 2H), 7.2 (d, 2H), 7.35 (m, 12H)

Preparation of compound b2

5- (vinyloxy) bicyclo [2.2.1] -2-heptene was used instead of bicyclo [2.2.1] -5-hepten-2-ylmethanethiol, and compound a2 was used instead of compound a1 Then, compound b2 was prepared by the same method as the preparation of compound b1. Nuclear magnetic resonance (NMR) data of the compound b2 are as follows. ^It was confirmed that the reaction was terminated by confirming that H of the ethylene group between 5 and 7 ppm disappeared in ¹ H-NMR.

¹ H-NMR (500MHz, DMSO-D ₆ ): (ppm) 1.51 (m, 2H), 1.7 ~ 1.87 (m, 17H), 2.38 (m, 1H), 2.84 (m, 1H), 2.96 (m, 2H), 3.34 (m, 1H), 3.77 (m, 4H), 5.98 (m, 1H), 6.23 (m, 1H), 7.33 (d, 2H), 7.35 (m, 12H)

Synthesis Example 2 (Preparation of compounds A1 to A3)

Preparation of compound A1

To the reaction flask, 2-methyladamantan-2-yl bicyclo [2.2.1] -5-heptene-2-carboxylate 17.2 g (0.06 mol), 3-hydroxyadamantan-1-ylbicyclo [2.2.1] -5-heptene-2-carboxylate 8.6 g (0.03 mol) and compound b1 7.5 g (0.01 mol) were added to anisole to a solid concentration of 33.3 wt% and stirred for 20 minutes under a nitrogen atmosphere. Did. A palladium catalyst solution was prepared by dissolving a palladium metal catalyst in anisole under an argon atmosphere. After the reaction solution was made at 65 ° C., the palladium catalyst solution was injected into the reaction solution with a syringe and stirred for 18 hours. After completion of the reaction, the reaction solution was diluted with anisole and then precipitated by adding it to excess hexane. The obtained solid was filtered and dried in an oven at 40 ° C. for 18 hours to obtain Compound A1. The weight average molecular weight of Compound A1 measured by gel permeation chromatography (GPC) was 4,700 g / mol. (m: n: o = 6: 3: 1)

Preparation of compound A2

Compound A2 was prepared by the same method as the preparation of Compound A1, except that Compound b2 was used instead of Compound b1. The weight average molecular weight of Compound A2 measured by gel permeation chromatography (GPC) was 4,500 g / mol.

Preparation of compound A3

Compound A3-1 was prepared by the same method as the preparation of Compound A1, except that bicyclo [2.2.1] -5-hepten-2-metalthiol was used instead of Compound b1. 23.6 g of Compound A3-1 obtained as a solid, 1.4 g of Compound a1, and 0.017 g (0.1 mmol) of azobisisobutyronitrile were dissolved in 25 g of propylene glycol methyl ether acetate (solid content concentration 50 wt%). The reaction was conducted for 1 hour by heating to 65 ° C., and 25 g of a solvent was further added, followed by washing with water several times. Moisture was removed with magnesium sulfate and concentrated to give compound A3. The weight average molecular weight of Compound A3 measured by gel permeation chromatography (GPC) was 4,300 g / mol.

Synthesis Example 3 (Preparation of compounds R1 and R2)

Preparation of compound R1

42 g (0.35 mol) of compound R1-1 and 37.2 g (0.15 mol) of compound R1-2 were added to 79.2 g of tetrahydrofuran in a reaction flask and stirred for 20 minutes under a nitrogen atmosphere. 0.48 g of azobisisobutyronitrile was dissolved in 2 g of tetrahydrofuran to prepare an initiator solution. After the reaction solution was made at 65 ° C., the initiator solution was added and stirred for 18 hours. After completion of the reaction, the reaction solution was diluted with tetrahydrofuran, and then precipitated in excess hexane. The obtained solid was filtered and dried in an oven at 30 ° C. for 18 hours to obtain compound R1. The weight average molecular weight of Compound R1 measured by gel permeation chromatography (GPC) was 6,700 g / mol. (r1: r2 = 7: 3)

Preparation of compound R2

To the reaction flask, 42.9 g (0.15 mol) of compound R2-1 and 28.8 g (0.1 mol) of compound R2-2 were added to 71.7 g of anisole and stirred for 20 minutes under a nitrogen atmosphere. A palladium catalyst solution was prepared by dissolving a palladium metal catalyst in anisole under an argon atmosphere. After the reaction solution was made at 65 ° C., the palladium catalyst solution was injected into the reaction solution with a syringe and stirred for 18 hours. After completion of the reaction, the reaction solution was diluted with anisole and then precipitated by adding it to excess hexane. The obtained solid was filtered and dried in an oven at 40 ° C. for 18 hours to obtain compound R2. The weight average molecular weight of Compound R2 measured by gel permeation chromatography (GPC) was 4,300 g / mol. (r3: r4 = 6: 4)

Example 1

100 parts by weight of the resin in which the compound R1 and the compound A1 are mixed in a weight ratio of 40:60 and 1 part by weight of N-tert-amyloxycarbonyl-4-hydroxypiperidine (acid diffusion inhibitor) in propylene glycol methyl ether acetate Put in to prepare a mixed solution having a solid content concentration of 4% by weight. The mixed solution was filtered through a 0.2 µm filter to prepare a photosensitive composition. After forming the antireflection film on the silicon wafer, the photosensitive composition was spin coated. Baking (SOB) was performed at 120 ° C for 60 seconds using a hot plate to form a photoresist layer.

The photoresist layer was patterned by irradiating ArF ultraviolet rays. For acid diffusion, baking was performed at 110 ° C. for 90 seconds (PEB), followed by development with a 2.38 wt% tetramethylammonium hydroxide (TMAH) aqueous solution for 60 seconds. The thickness of the prepared pattern was measured by a scanning electron microscope (SEM), and the thickness was 56 nm.

Example 2

A photoresist pattern was formed in the same manner as in Example 1, except that Compound A2 was used instead of Compound A1.

Example 3

A photoresist pattern was formed in the same manner as in Example 1, except that Compound A3 was used instead of Compound A1.

Comparative Example 1

R2 was used instead of Compound A1, and a photoresist pattern was formed in the same manner as in Example 1, except that 6 parts by weight of Compound D1 (photoacid generator; PAG) as compared to 100 parts by weight of the resin was further used in the mixed solution.

Comparative Example 2

A photoresist pattern was formed in the same manner as in Comparative Example 1, except that Compound D1 was used in an amount of 8 parts by weight compared to 100 parts by weight of the resin.

Example 4

A photoresist pattern was formed in the same manner as in Comparative Example 1, except that Compound A1 was used instead of Compound R2 and Compound D1 was used in an amount of 2 parts by weight compared to 100 parts by weight of the resin.

For the photoresist patterns formed in Experimental Examples 1 to 4 and Comparative Examples 1 to 2, LWR and dose were measured by the following method, and the results are shown in Table 1.

LWR measurement method

Using a scanning electron microscope (SEM), the difference between the widest part and the narrowest part of the line width of the line was measured to confirm the LWR (line width roughness) value. The smaller the LWR value, the more uniform the pattern. In the LWR evaluation column, LWR values of 9 nm or less were indicated by ○, 11 nm or less by △, and 11 nm or more by X.

Dose measurement method

The exposure amount at which the line pattern formed by the pattern forming method has a 32 nm pitch is set as the optimal exposure amount (Eop, mJ / cm ² ), and the optimal exposure amount is expressed as a dose. Based on a 32nm pitch, 70mJ / cm ² or less ○, 90mJ / cm ² or less △, 90mJ / cm ² in excess was indicated by X.

Resin (wt%) PAG
(weight%) Dose
(mJ / cm ² ) Dose
evaluation LWR
(nm) LWR
evaluation Example 1 R1 (40) A1 (60) - 67 ○ 7.9 ○ Example 2 R1 (40) A2 (60) - 62 ○ 8.1 ○ Example 3 R1 (40) A3 (60) - 65 ○ 7.1 ○ Comparative Example 1 R1 (40) R2 (60) 6 98 X 12.2 X Comparative Example 2 R1 (40) R2 (60) 8 78 △ 11.3 X Example 4 R1 (40) A1 (60) 2 61 ○ 10.1 △

From Table 1, it can be confirmed that when the polymer (A) of the present invention is used, the optimal exposure amount of the photoresist pattern is excellent compared to the case where the compound containing no photoacid generator is used in the compound.

Claims (12)

A photosensitive composition comprising a polymer (A),
The polymer (A) is a structural unit represented by the following formula 1a; And a photosensitive composition comprising a structural unit represented by the formula (1b):
[Formula 1a]

[Formula 1b]

In the formulas 1a and 1b,
M1 is an organic cation, M2 is an organic anion,
Y1 is a straight-chain or branched alkylene group; A divalent saturated hydrocarbon ring group; A divalent aromatic hydrocarbon group; A divalent saturated heterocyclic group; A divalent aromatic heterocyclic group; A divalent ring group in which two or more rings are condensed among a saturated hydrocarbon ring, an aromatic hydrocarbon, a saturated heterocycle, and an aromatic heterocycle; -O-; -C (= O)-; -C (= O) O-; -C (= O) N (R19)-; -N (R19)-; -S-; -S (= O)-; -S (= O) _2- ; And -S (= O) ₂ O-, or any one group selected from the group consisting of two or more groups selected from the group, and R19 is hydrogen; heavy hydrogen; Alkyl groups; Saturated hydrocarbon ring group; Or an aromatic hydrocarbon group, two or more R19 are the same as or different from each other,
Y2 and R1 to R3 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Halogen group; Nitrile group; Alkyl groups; Saturated hydrocarbon ring group; Aromatic hydrocarbon groups; Saturated heterocyclic group; Aromatic heterocyclic group; A ring group in which two or more rings of a saturated hydrocarbon ring, aromatic hydrocarbon, saturated heterocycle, and aromatic heterocycle are condensed; -OR; -OC (= O) R; -C (= O) R; -C (= O) OR; -C (= O) NR ₂ ; -NR ₂ ; -SR; -S (= O) R; -S (= O) ₂ R; And -S (= O) ₂ OR is a group selected from the group consisting of two or more groups selected from the group, and R is hydrogen; heavy hydrogen; Alkyl groups; Saturated hydrocarbon ring group; Aromatic hydrocarbon groups; Saturated heterocyclic group; Aromatic heterocyclic group; Or a saturated hydrocarbon ring, an aromatic hydrocarbon, a saturated heterocycle, and an aromatic heterocycle are two or more rings condensed ring groups, and two or more Rs are the same or different from each other,
R1 to R3, Y1 and Y2 are each independently deuterium; Halogen group; Hydroxy group; Oxo group (= O); Or it may be further substituted with an alkyl group. The method according to claim 1, wherein the formula 1b is a photosensitive composition represented by the following formula 1c:
[Formula 1c]

In Chemical Formula 1c,
The definitions of R1, M1, M2 and Y2 are as defined in Formula 1b,
L1 and L2 are the same as or different from each other, and each independently a linear or branched alkylene group; A divalent saturated hydrocarbon ring group; A divalent aromatic hydrocarbon group; A divalent saturated heterocyclic group; A divalent aromatic heterocyclic group; A divalent ring group in which two or more rings are condensed among a saturated hydrocarbon ring, an aromatic hydrocarbon, a saturated heterocycle, and an aromatic heterocycle; -O-; -C (= O)-; -C (= O) O-; -C (= O) N (R19)-; -N (R19)-; -S-; -S (= O)-; -S (= O) _2- ; And -S (= O) ₂ O-, or any one group selected from the group consisting of two or more groups selected from the group, and R19 is hydrogen; heavy hydrogen; Alkyl groups; Saturated hydrocarbon ring group; Or an aromatic hydrocarbon group, two or more R19 are the same as or different from each other,
L1 and L2 are the same as or different from each other, and each independently deuterium; Halogen group; Hydroxy group; Oxo group (= O); Or it may be further substituted with an alkyl group,
n1 is an integer of 0 or more, and when n1 is 2 or more, L1 is the same or different from each other,
n2 is an integer of 0 or more, and when n2 is 2 or more, L2 is the same or different from each other,
R4 and R5 are the same as or different from each other, and each independently the same as the definition of R1,
b1 is 0 or 1, b2 is 0 or 1, and the sum of b1 and b2 is 1. The method according to claim 1, wherein the M1 is a photosensitive composition is represented by any one of the following formulas a-1 to formula a-3:

In the above formulas a-1 to a-3,

Represents a site connected to Y1,
R11 to R14 are the same as or different from each other, and each independently a linear or branched alkyl group; Saturated hydrocarbon ring group; Aromatic hydrocarbon groups; Saturated heterocyclic group; Aromatic heterocyclic group; Or a saturated hydrocarbon ring, an aromatic hydrocarbon, a saturated heterocyclic ring, or an aromatic heterocyclic ring group having two or more rings condensed,
R11 to R14 are the same as or different from each other, and each independently deuterium; Halogen group; Hydroxy group; Alkoxy groups; Oxo group (= O); Or it may be further substituted with an alkyl group,
c1 is an integer of 0 or more, and when c1 is 2 or more, R13 is the same or different from each other,
c2 is an integer from 1 to 10. The method according to claim 1, wherein M2-Y2 is a photosensitive composition represented by the following formula (10):
[Formula 10]

In Chemical Formula 10,
R15 is a halogen group, R16 is a halogen group,
a10 is an integer from 1 to 5, and when a10 is 2 or more, -C (R15) (R16)-is the same as or different from each other,
L11 and L12 are the same as or different from each other, and each independently a single bond; Straight-chain or branched alkylene groups; A divalent saturated hydrocarbon ring group; A divalent aromatic hydrocarbon group; A divalent saturated heterocyclic group; A divalent aromatic heterocyclic group; A divalent ring group in which two or more rings are condensed among a saturated hydrocarbon ring, an aromatic hydrocarbon, a saturated heterocycle, and an aromatic heterocycle; -O-; -C (= O)-; -C (= O) O-; -C (= O) N (R19)-; -N (R19)-; -S-; -S (= O)-; -S (= O) _2- ; And -S (= O) ₂ O-, or any one group selected from the group consisting of two or more groups selected from the group, and R19 is hydrogen; heavy hydrogen; Alkyl groups; Saturated hydrocarbon ring group; Or an aromatic hydrocarbon group, two or more R19 are the same as or different from each other,
R17 is a saturated hydrocarbon ring group,
L11, L12 and R17 are the same as or different from each other, and each independently deuterium; Halogen group; Hydroxy group; Oxo group (= O); Or it may be further substituted with an alkyl group. The method according to claim 1, The structural unit represented by the formula (1a) is included in 80 mol% to 99.9 mol% of the total structural unit included in the polymer (A), the structural unit represented by the formula (1b) is the polymer (A ) Is contained in 0.1 mol% to 20 mol% compared to the total structural unit included. The photosensitive composition according to claim 1, further comprising an acid diffusion inhibitor. The method according to claim 6, wherein the acid diffusion inhibitor is an aliphatic, aromatic or heterocyclic amine; A nitrogen-containing compound containing a carboxyl group, sulfonyl group, hydroxy group or carbamate group; Amide derivatives; And one or two or more selected from the group consisting of imide derivatives. The photosensitive composition according to claim 1, wherein the photosensitive composition comprises a polymer (B) comprising a structural unit containing a hydroxyl group. The method according to claim 8, wherein the structural unit comprising a hydroxy group is a photosensitive composition that is a structural unit represented by the following formula c-1:

In Chemical Formula c-1, R61 is hydrogen; Or an alkyl group. The method according to claim 8, wherein the polymer (B) is a structural unit having a hydroxyl group protected by an acid-decomposable group; And a structural unit having a carboxyl group protected by an acid-decomposable group. The method according to claim 10, The structural unit having a hydroxyl group protected by the acid-decomposable group is a structural unit represented by the following formula d-1, the structural unit having a carboxyl group protected by the acid-decomposable group is represented by the following formula d-2 Photosensitive composition which is a structural unit:

In the above formulas d-1 and d-2,
R21 and R22 are the same as or different from each other, and each independently -Si (R24) (R25) (R26); A substituted or unsubstituted ring group containing lactone; A substituted or unsubstituted ring group containing sulfone; -C (R27) (R28) O (R29); -(CH ₂ ) _n C (= O) O (R30); -C (R31) (R32) (R33); A substituted or unsubstituted aliphatic ring group; Or a substituted or unsubstituted aromatic ring group,
R24 to R33 are the same as or different from each other, and each independently deuterium; Nitrile group; -N (R42) (R43); -C (= O) (R44); -C (= O) O (R45); A substituted or unsubstituted alkyl group; A substituted or unsubstituted aliphatic ring group; And a group selected from the group consisting of substituted or unsubstituted aromatic ring groups, or a group in which two or more groups selected from the group are connected, and R42 to R45 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted alkyl group; A substituted or unsubstituted aliphatic hydrocarbon group; Or a substituted or unsubstituted aromatic hydrocarbon group,
n is an integer from 0 to 6,
R20 and R23 are the same as or different from each other, and each independently hydrogen; Or an alkyl group. A pattern comprising the photosensitive composition according to any one of claims 1 to 11 or a cured product thereof.