KR102586099B1 - Semiconductor photoresist composition and method of forming patterns using the composition - Google Patents

Abstract

The present invention relates to a composition for a semiconductor photoresist containing an organometallic compound represented by Formula 1 below, a radically reactive compound represented by Formula 2 or Formula 3 below, and a solvent, and a method of forming a pattern using the same.
[Formula 1]
R _n M _m X _l Y _k
[Formula 2]

[Formula 3]

Specific details of Chemical Formulas 1 to 3 are the same as defined in the specification.

Description

Composition for semiconductor photoresist and method of forming a pattern using the same {SEMICONDUCTOR PHOTORESIST COMPOSITION AND METHOD OF FORMING PATTERNS USING THE COMPOSITION}

This disclosure relates to a composition for semiconductor photoresist and a method of forming a pattern using the same.

As one of the essential technologies for manufacturing next-generation semiconductor devices, EUV (extreme ultraviolet light) lithography is attracting attention. EUV lithography is a pattern formation technology that uses EUV light with a wavelength of 13.5 nm as an exposure light source. It has been demonstrated that EUV lithography can form extremely fine patterns (for example, 20 nm or less) in the exposure process of the semiconductor device manufacturing process.

Implementation of extreme ultraviolet (EUV) lithography requires the development of compatible photoresists that can perform at spatial resolutions of 16 nm or less. Currently, traditional chemically amplified (CA) photoresists have poor performance in resolution, photospeed, and feature roughness, or line edge roughness (LER), for next-generation devices. We are working hard to meet specifications.

Intrinsic image blur due to the acid catalyzed reactions that occur in these polymer photoresists limits resolution at small feature sizes, which limits the resolution of e-beam This has been known for a long time in lithography. Chemically amplified (CA) photoresists are designed for high sensitivity, but their typical elemental makeup lowers the photoresist's absorbance at a wavelength of 13.5 nm, thereby reducing sensitivity, in part. may experience more difficulties under EUV exposure.

CA photoresists can also suffer from roughness issues at small feature sizes and, due in part to the nature of acid-catalyzed processes, line edge roughness (LER) decreases as photospeed decreases. Experiments have shown that increases. Due to the drawbacks and problems of CA photoresists, there is a need in the semiconductor industry for new types of high performance photoresists.

In order to overcome the disadvantages of the chemically amplified organic photosensitive composition described above, inorganic photosensitive compositions have been studied. In the case of inorganic photosensitive compositions, they are mainly used for negative tone patterning that is resistant to removal by a developer composition due to chemical modification through a non-chemical amplification mechanism. In the case of inorganic compositions, they contain inorganic elements with a higher EUV absorption rate than hydrocarbons, so sensitivity can be secured even through non-chemical amplification mechanisms, and they are less sensitive to stochastic effects, so they are known to have less line edge roughness and fewer defects. .

Inorganic photoresists based on tungsten and peroxopolyacids of tungsten mixed with niobium, titanium, and/or tantalum are radiation sensitive materials for patterning. It has been reported for (US5061599,; H. Okamoto, T. Iwayanagi, K. Mochiji, H. Umezaki, T. Kudo, Applied Physics Letters, 49(5), 298-300, 1986).

These materials have been effective in patterning large features in a bilayer configuration with deep UV, x-ray, and electron beam sources. More recently, cationic hafnium metal oxide sulfate (HfSOx) material was used with a peroxo complexing agent to image 15 nm half-pitch (HP) by projection EUV lithography. showed impressive performance when using (US2011-0045406,; J. K. Stowers, A. Telecky, M. Kocsis, B. L. Clark, D. A. Keszler, A. Grenville, C. N. Anderson, P. P. Naulleau, Proc. SPIE, 7969, 796915, 2011 ). This system demonstrated the best performance of non-CA photoresist, with optical velocities approaching the requirements for a viable EUV photoresist. However, hafnium metal oxide sulfate materials with peroxo complexing agents have some practical drawbacks. First, these materials are coated in a highly corrosive sulfuric acid/hydrogen peroxide mixture and have poor shelf-life stability. Second, as it is a complex mixture, it is not easy to change the structure to improve performance. Third, it must be developed in an extremely high concentration of TMAH (tetramethylammonium hydroxide) solution, such as about 25 wt%.

Recently, active research has been conducted as it has become known that molecules containing tin have excellent absorption of extreme ultraviolet rays. In the case of organotin polymer, which is one of them, the alkyl ligand is dissociated due to light absorption or secondary electrons generated thereby, and negative tone patterning that is not removed by organic developer is possible through crosslinking through oxo bonds with surrounding chains. Such organotin polymers have shown dramatic improvement in sensitivity while maintaining resolution and line edge roughness, but additional improvement in patterning characteristics is required for commercialization.

One embodiment provides a composition for a semiconductor photoresist with excellent resolution and sensitivity characteristics.

Another embodiment provides a method of forming a pattern using the composition for semiconductor photoresist.

A composition for a semiconductor photoresist according to one embodiment includes an organometallic compound represented by Formula 1 below, a radically reactive compound represented by Formula 2 or Formula 3 below, and a solvent.

[Formula 1]

R _n M _m X _l Y _k

In Formula 1,

R is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 aliphatic unsaturated organic group containing one or more double bonds or triple bonds, or a substituted or unsubstituted C2 to C20 aliphatic unsaturated organic group. A C6 to C30 aryl group, a substituted or unsubstituted C4 to C30 heteroaryl group, a carbonyl group, an ethylene oxide group, a propylene oxide group, or a combination thereof,

M is tin (Sn) or antimony (Sb),

X is sulfur (S), selenium (Se), or tellerium (Te),

Y is -OR ^a or -OC(=O)R ^b ,

Wherein R ^a is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, substituted or unsubstituted. A ringed C6 to C30 aryl group, or a combination thereof,

R ^b is hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, substituted or An unsubstituted C6 to C30 aryl group, or a combination thereof,

The n, m, l and k are each independently integers from 1 to 20.

[Formula 2]

[Formula 3]

In Formula 2 and Formula 3,

R ¹ and R ² are each independently a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, or a substituted or unsubstituted C2 to C20 aliphatic unsaturated group containing one or more double bonds or triple bonds. An organic group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof,

R ³ is a substituted or unsubstituted divalent C1 to C20 saturated aliphatic hydrocarbon group, a substituted or unsubstituted divalent C3 to C20 saturated alicyclic hydrocarbon group, or a substituted or unsubstituted 2 containing at least one double bond or triple bond. It is a valent C2 to C20 unsaturated aliphatic hydrocarbon group, a substituted or unsubstituted divalent C6 to C20 aromatic hydrocarbon group, a divalent ethylene oxide group, a divalent propylene oxide group, or a combination thereof.

R is a substituted or unsubstituted C1 to C8 alkyl group, a substituted or unsubstituted C3 to C8 cycloalkyl group, a substituted or unsubstituted C2 to C8 aliphatic unsaturated organic group containing one or more double bonds or triple bonds, substituted or unsubstituted. It is a substituted C6 to C20 aryl group, a substituted or unsubstituted C4 to C20 heteroaryl group, a carbonyl group, an ethylene oxide group, a propylene oxide group, or a combination thereof,

R ^a is a substituted or unsubstituted C1 to C8 alkyl group, a substituted or unsubstituted C3 to C8 cycloalkyl group, a substituted or unsubstituted C2 to C8 alkenyl group, a substituted or unsubstituted C2 to C8 alkynyl group, substituted or unsubstituted. A ringed C6 to C20 aryl group, or a combination thereof,

R ^b is hydrogen, a substituted or unsubstituted C1 to C8 alkyl group, a substituted or unsubstituted C3 to C8 cycloalkyl group, a substituted or unsubstituted C2 to C8 alkenyl group, a substituted or unsubstituted C2 to C8 alkynyl group, or a substituted or unsubstituted C2 to C8 alkenyl group. Alternatively, it may be an unsubstituted C6 to C20 aryl group, or a combination thereof.

R ¹ and R ² are each independently a substituted or unsubstituted C1 to C8 alkyl group, a substituted or unsubstituted C3 to C8 cycloalkyl group, or a substituted or unsubstituted C2 to C8 aliphatic group containing one or more double bonds or triple bonds. An unsaturated organic group, a substituted or unsubstituted C6 to C20 aryl group, or a combination thereof,

R ³ is a substituted or unsubstituted divalent C1 to C8 saturated aliphatic hydrocarbon group, a substituted or unsubstituted divalent C3 to C6 saturated or unsaturated alicyclic hydrocarbon group, or a substituted group containing 1 or 2 double or triple bonds. Alternatively, it may be an unsubstituted divalent C2 to C8 unsaturated aliphatic hydrocarbon group, a substituted or unsubstituted C6 to C10 arylene group, a divalent ethylene oxide group, a divalent propylene oxide group, or a combination thereof.

The R is methyl group, ethyl group, propyl group, butyl group, isopropyl group, tert-butyl group, 2,2-dimethylpropyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, ethenyl group, prop Phenyl group, butenyl group, ethynyl group, propynyl group, butynyl group, phenyl group, tolyl group, xylene group, benzyl group, formyl group, acetyl group, propanoyl group, butanoyl group, pentanoyl group, ethylene oxide group, propylene oxide group, or a combination thereof,

R ^a is an ethyl group, propyl group, butyl group, isopropyl group, tert-butyl group, 2,2-dimethylpropyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, ethenyl group, propenyl group. , butenyl group, ethynyl group, propynyl group, butynyl group, phenyl group, tolyl group, xylene group, benzyl group, or a combination thereof,

R ^b is hydrogen, ethyl group, propyl group, butyl group, isopropyl group, tert-butyl group, 2,2-dimethylpropyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, ethenyl group, It may be a propenyl group, butenyl group, ethynyl group, propynyl group, butynyl group, phenyl group, tolyl group, xylene group, benzyl group, or a combination thereof.

R ¹ and R ² are each independently methyl, ethyl, propyl, butyl, isopropyl, tert-butyl, 2,2-dimethylpropyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclo Hexyl group, ethenyl group, propenyl group, butenyl group, ethynyl group, propynyl group, butynyl group, phenyl group, tolyl group, xylene group, benzyl group, ethylene oxide group, propylene oxide group, or a combination thereof,

R ³ is methylene group, ethylene group, propylene group, butylene group, cyclobutylene group, cyclopentylene group, cyclohexylene group, ethenylene group, propenylene group, ethynylene group, propynylene group, phenylene group, or It could be a combination of these.

The organometallic compound represented by Formula 1 may include an M-X-M bond.

The radical reactive compound represented by Formula 2 or Formula 3 may include a compound represented by Formula 4 to Formula 6 below, or a combination thereof.

[Formula 4]

[Formula 5]

[Formula 6]

The organometallic compound represented by Formula 1 and the radical reactive compound represented by Formula 2 or Formula 3 may be included in a weight ratio of 50:1 to 1:1.

The composition for semiconductor photoresist includes 1 to 30% by weight of an organometallic compound represented by Formula 1 and 0.01 to 15% by weight of a radical reactive compound represented by Formula 2 or Formula 3, based on the total mass of the composition for semiconductor photoresist. It may include weight percent.

The composition for semiconductor photoresist may further include additives such as a surfactant, a cross-linking agent, a leveling agent, or a combination thereof.

A pattern forming method according to another embodiment includes forming a film to be etched on a substrate, forming a photoresist film by applying the composition for a semiconductor photoresist described above on the film to be etched, patterning the photoresist film to form a photoresist pattern. It includes forming and etching the etch target layer using the photoresist pattern as an etch mask.

The step of forming the photoresist pattern may use light with a wavelength of 5 nm to 150 nm.

The pattern forming method may further include providing a resist underlayer formed between the substrate and the photoresist film.

The photoresist pattern may have a width of 5 nm to 100 nm.

Since the composition for a semiconductor photoresist according to one embodiment has relatively excellent resolution and sensitivity, using it can provide a photoresist pattern that has excellent limiting resolution and does not collapse even if it has a high aspect ratio.

1 to 5 are cross-sectional views illustrating a method of forming a pattern using a composition for semiconductor photoresist according to an embodiment.

Hereinafter, embodiments of the present invention will be described in detail with reference to the attached drawings. However, in explaining this description, descriptions of already known functions or configurations will be omitted to make the gist of this description clear.

In order to clearly explain this description, parts that are not related to the description have been omitted, and identical or similar components are given the same reference numerals throughout the specification. In addition, the size and thickness of each component shown in the drawings are shown arbitrarily for convenience of explanation, so the present description is not necessarily limited to what is shown.

In the drawing, the thickness is enlarged to clearly express various layers and areas. Also, in the drawing, the thickness of some layers and regions is exaggerated for convenience of explanation. When a part of a layer, membrane, region, plate, etc. is said to be "on" or "on" another part, this includes not only being "directly above" the other part, but also cases where there is another part in between.

In this description, “substitution” means that the hydrogen atom is deuterium, halogen group, hydroxy group, cyano group, nitro group, -NRR' (where R and R' are each independently hydrogen, substituted or unsubstituted C1 to C30 saturated or an unsaturated aliphatic hydrocarbon group, a substituted or unsubstituted C3 to C30 saturated or unsaturated alicyclic hydrocarbon group, or a substituted or unsubstituted C6 to C30 aromatic hydrocarbon group), -SiRR'R" (where R, R', and R” are each independently hydrogen, a substituted or unsubstituted C1 to C30 saturated or unsaturated aliphatic hydrocarbon group, a substituted or unsubstituted C3 to C30 saturated or unsaturated alicyclic hydrocarbon group, or a substituted or unsubstituted C6 to C30 saturated or unsaturated aliphatic hydrocarbon group. C30 aromatic hydrocarbon group), C1 to C30 alkyl group, C1 to C10 haloalkyl group, C1 to C10 alkylsilyl group, C3 to C30 cycloalkyl group, C6 to C30 aryl group, C1 to C20 alkoxy group, or a combination thereof. means that “Unsubstituted” means that a hydrogen atom remains a hydrogen atom without being substituted with another substituent.

In this specification, “alkyl group” means a straight-chain or branched-chain aliphatic hydrocarbon group, unless otherwise defined. The alkyl group may be a “saturated alkyl group” that does not contain any double or triple bonds.

The alkyl group may be a C1 to C8 alkyl group. For example, the alkyl group may be a C1 to C7 alkyl group, a C1 to C6 alkyl group, a C1 to C5 alkyl group, or a C1 to C4 alkyl group. For example, the C1 to C4 alkyl group may be methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, or tert-butyl or 2,2-dimethylpropyl.

In this description, unless otherwise defined, “cycloalkyl group” refers to a monovalent cyclic aliphatic saturated hydrocarbon group.

The cycloalkyl group may be a C3 to C8 cycloalkyl group, for example, a C3 to C7 cycloalkyl group, a C3 to C6 cycloalkyl group, a C3 to C5 cycloalkyl group, or a C3 to C4 cycloalkyl group. For example, the cycloalkyl group may be a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, or a cyclohexyl group, but is not limited thereto.

As used herein, “aliphatic unsaturated organic group” means a hydrocarbon group containing a bond between carbon atoms in the molecule that is a double bond, triple bond, or a combination thereof.

The aliphatic unsaturated organic group may be a C2 to C8 aliphatic unsaturated organic group. For example, the aliphatic unsaturated organic group may be a C2 to C7 aliphatic unsaturated organic group, a C2 to C6 aliphatic unsaturated organic group, a C2 to C5 aliphatic unsaturated organic group, or a C2 to C4 aliphatic unsaturated organic group. For example, C2 to C4 aliphatic unsaturated organic groups include vinyl group, ethynyl group, allyl group, 1-propenyl group, 1-methyl-1-propenyl group, 2-propenyl group, 2-methyl-2-propenyl group, 1- Propinenyl group, 1-methyl-1propynyl group, 2-propynyl group, 2-methyl-2-propynyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1-butynyl group, 2 -It may be a butynyl group or a 3-butynyl group.

In this specification, “aryl group” refers to a substituent in which all elements of a cyclic substituent have p-orbitals, and these p-orbitals form conjugation, and are monocyclic or fused. Contains ring polycyclic (i.e. rings splitting adjacent pairs of carbon atoms) functional groups.

As used herein, unless otherwise defined, “alkenyl group” refers to a straight-chain or branched aliphatic hydrocarbon group and an aliphatic unsaturated alkenyl group containing one or more double bonds. do.

As used herein, unless otherwise defined, the term “alkynyl group” refers to a straight-chain or branched aliphatic hydrocarbon group and an aliphatic unsaturated alkynyl group containing one or more triple bonds. do.

Hereinafter, a composition for a semiconductor photoresist according to an embodiment will be described.

A composition for a semiconductor photoresist according to an embodiment of the present invention includes an organometallic compound, a radically reactive compound, and a solvent, wherein the organometallic compound is represented by the following formula (1), and the radically reactive compound is represented by the following formula (2) or It is represented by formula 3.

[Formula 1]

R _n M _m X _l Y _k

In Formula 1,

R is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 aliphatic unsaturated organic group containing one or more double bonds or triple bonds, or a substituted or unsubstituted C2 to C20 aliphatic unsaturated organic group. A C6 to C30 aryl group, a substituted or unsubstituted C4 to C30 heteroaryl group, a carbonyl group, an ethylene oxide group, a propylene oxide group, or a combination thereof,

M is tin (Sn) or antimony (Sb),

X is sulfur (S), selenium (Se), or tellerium (Te),

Y is -OR ^a or -OC(=O)R ^b ,

Wherein R ^a is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, substituted or unsubstituted. A ringed C6 to C30 aryl group, or a combination thereof,

R ^b is hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, substituted or An unsubstituted C6 to C30 aryl group, or a combination thereof,

The n, m, l and k are independently integers from 1 to 20.

[Formula 2]

[Formula 3]

In Formula 2 and Formula 3,

R ¹ and R ² are each independently a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, or a substituted or unsubstituted C2 to C20 aliphatic unsaturated group containing one or more double bonds or triple bonds. An organic group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof,

R ³ is a substituted or unsubstituted divalent C1 to C20 saturated aliphatic hydrocarbon group, a substituted or unsubstituted divalent C3 to C20 saturated alicyclic hydrocarbon group, or a substituted or unsubstituted 2 containing at least one double bond or triple bond. It is a valent C2 to C20 unsaturated aliphatic hydrocarbon group, a substituted or unsubstituted divalent C6 to C20 aromatic hydrocarbon group, a divalent ethylene oxide group, a divalent propylene oxide group, or a combination thereof.

The organometallic compound represented by Formula 1 shows the form of a cluster formed by the atoms represented by R, M,

M is tin (Sn) or antimony (Sb), X is sulfur (S), selenium (Se), or tellerium (Te), and Y is -OR ^a or -OC(=O)R ^b . You can.

The tin or antimony strongly absorbs extreme ultraviolet light at 13.5 nm, so an organometallic compound containing it may have excellent sensitivity to light with high energy. Accordingly, the organometallic compound according to one embodiment is a conventional It can exhibit superior stability and sensitivity compared to organic and/or inorganic resists.

remind R in Formula 1 can impart photosensitivity to the compound represented by Formula 1, and as R is bonded to tin or antimony to form a Sn-R or Sb-R bond, it imparts solubility in organic solvents to organometallic compounds. can do.

The organometallic compound represented by Formula 1 may contain an X-M bond by essentially including sulfur (S), selenium (Se), or tellerium (Te) atoms represented by It can be included. The X-M bond may be any one of Sn-S, Sn-Se, Sn-Te, Sb-S, Sb-Se, and Sb-Te, and may include a combination of these at the same time. Since the strength of the bond between the In addition, since the bond between Therefore, the composition for semiconductor photoresist containing the organometallic compound containing the X-M bond is easy to handle, has improved storage stability and solubility characteristics, and can have excellent sensitivity.

Meanwhile, the compound represented by Formula 1 contains Y as a ligand connected to a tin or antimony element, and Y may be -OR ^a or -OC(=O)R ^b . When the organometallic compound includes -OR ^a or -OC(=O)R ^b as a ligand, a pattern formed using a semiconductor photoresist composition containing it may exhibit excellent limiting resolution.

In addition, the organic ligand of -OR ^a or -OC(=O)R ^b can determine the solubility of the compound represented by Formula 1 in a solvent.

R is a substituted or unsubstituted C1 to C8 alkyl group, a substituted or unsubstituted C3 to C8 cycloalkyl group, a substituted or unsubstituted C2 to C8 aliphatic unsaturated organic group containing one or more double bonds or triple bonds, substituted or unsubstituted. It may be a substituted C6 to C20 aryl group, a substituted or unsubstituted C4 to C20 heteroaryl group, a carbonyl group, an ethylene oxide group, a propylene oxide group, or a combination thereof, for example, a methyl group, an ethyl group, a propyl group. , butyl group, isopropyl group, tert-butyl group, 2,2-dimethylpropyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, ethenyl group, propenyl group, butenyl group, ethynyl group, pro It may be a pinyl group, butynyl group, phenyl group, tolyl group, xylene group, benzyl group, formyl group, acetyl group, propanoyl group, butanoyl group, pentanoyl group, ethylene oxide group, propylene oxide group, or a combination thereof.

R ^a is a substituted or unsubstituted C1 to C8 alkyl group, a substituted or unsubstituted C3 to C8 cycloalkyl group, a substituted or unsubstituted C2 to C8 alkenyl group, a substituted or unsubstituted C2 to C8 alkynyl group, substituted or unsubstituted. It may be a ringed C6 to C20 aryl group, or a combination thereof, for example, an ethyl group, propyl group, butyl group, isopropyl group, tert-butyl group, 2,2-dimethylpropyl group, cyclopropyl group, It may be a cyclobutyl group, cyclopentyl group, cyclohexyl group, ethenyl group, propenyl group, butenyl group, ethynyl group, propynyl group, butynyl group, phenyl group, tolyl group, xylene group, benzyl group, or a combination thereof.

R ^b is hydrogen, a substituted or unsubstituted C1 to C8 alkyl group, a substituted or unsubstituted C3 to C8 cycloalkyl group, a substituted or unsubstituted C2 to C8 alkenyl group, a substituted or unsubstituted C2 to C8 alkynyl group, or a substituted or unsubstituted C2 to C8 alkenyl group. Or it may be an unsubstituted C6 to C20 aryl group, or a combination thereof, for example, hydrogen, ethyl group, propyl group, butyl group, isopropyl group, tert-butyl group, 2,2-dimethylpropyl group, Cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, ethenyl group, propenyl group, butenyl group, ethynyl group, propynyl group, butynyl group, phenyl group, tolyl group, xylene group, benzyl group, or a combination thereof. You can.

A composition for a semiconductor photoresist according to one embodiment includes a radically reactive compound represented by Formula 2 or Formula 3 below.

[Formula 2]

[Formula 3]

In Formula 2 and Formula 3,

R ¹ and R ² are each independently a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, or a substituted or unsubstituted C2 to C20 aliphatic unsaturated group containing one or more double bonds or triple bonds. An organic group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof,

R ³ is a substituted or unsubstituted divalent C1 to C20 saturated aliphatic hydrocarbon group, a substituted or unsubstituted divalent C3 to C20 saturated alicyclic hydrocarbon group, or a substituted or unsubstituted 2 containing at least one double bond or triple bond. It is a valent C2 to C20 unsaturated aliphatic hydrocarbon group, a substituted or unsubstituted divalent C6 to C20 aromatic hydrocarbon group, a divalent ethylene oxide group, a divalent propylene oxide group, or a combination thereof.

When the composition for semiconductor photoresist includes a compound represented by Formula 2 or Formula 3 as a radical reactive compound, pattern formation properties such as resolution, sensitivity, and line edge roughness (LER) characteristics of the composition for semiconductor photoresist Characteristics can be improved.

R ¹ and R ² are each independently a substituted or unsubstituted C1 to C8 alkyl group, a substituted or unsubstituted C3 to C8 cycloalkyl group, or a substituted or unsubstituted C2 to C8 aliphatic group containing one or more double bonds or triple bonds. It may be an unsaturated organic group, a substituted or unsubstituted C6 to C20 aryl group, or a combination thereof, for example, methyl group, ethyl group, propyl group, butyl group, isopropyl group, tert-butyl group, 2,2- Dimethylpropyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, ethenyl group, propenyl group, butenyl group, ethynyl group, propynyl group, butynyl group, phenyl group, tolyl group, xylene group, benzyl group, It may be an ethylene oxide group, a propylene oxide group, or a combination thereof.

R ³ is a substituted or unsubstituted divalent C1 to C8 saturated aliphatic hydrocarbon group, a substituted or unsubstituted divalent C3 to C6 saturated or unsaturated alicyclic hydrocarbon group, or a substituted group containing 1 or 2 double or triple bonds. Or it may be an unsubstituted divalent C2 to C8 unsaturated aliphatic hydrocarbon group, a substituted or unsubstituted C6 to C10 arylene group, a divalent ethylene oxide group, a divalent propylene oxide group, or a combination thereof, for example, a methylene group. , ethylene group, propylene group, butylene group, cyclobutylene group, cyclopentylene group, cyclohexylene group, ethenylene group, propenylene group, ethynylene group, propynylene group, phenylene group, or a combination thereof. .

The radical reactive compound represented by Formula 2 or Formula 3 may include a compound represented by Formula 4 to Formula 6 below, or a combination thereof.

[Formula 4]

[Formula 5]

[Formula 6]

The organometallic compound represented by Formula 1 and the radically reactive compound represented by Formula 2 or Formula 3 may be included in the composition for a semiconductor photoresist at a weight ratio of 50:1 to 1:1, for example, 40:1. 1 to 1:1, such as 35:1 to 1:1, such as 30:1 to 1:1, such as 25:1 to 1:1, such as 20:1 to 1:1. 1:1, for example 18:1 to 1:1, for example 15:1 to 1:1, for example 12:1 to 1:1, for example 10:1 to 1: 1, for example 8:1 to 1:1, for example 5:1 to 1:1, for example 3:1 to 1:1, for example 2:1 to 1:1 may be included, but is not limited to these. When the weight ratio of the organometallic compound represented by Formula 1 and the radical reactive compound represented by Formula 2 or Formula 3 satisfies the above range, a composition for semiconductor photoresists having excellent sensitivity can be provided.

The composition for a semiconductor photoresist contains 1 to 30% by weight of an organometallic compound represented by Formula 1 and 0.01 to 0.01 to 30% by weight of a radically reactive compound represented by Formula 2 or Formula 3, based on 100% by weight of the composition for semiconductor photoresists. It may contain 15% by weight, for example, 1 to 20% by weight of the organometallic compound represented by Formula 1, and 0.1 to 10% by weight of the radical reactive compound represented by Formula 2 or Formula 3. For example, it may include 1 to 10% by weight of the organometallic compound represented by Formula 1 and 0.1 to 5% by weight of the radical reactive compound represented by Formula 2 or Formula 3, and is limited thereto. It doesn't work.

The composition for a semiconductor photoresist according to one embodiment includes the organometallic compound represented by Formula 1 and the radical reactive compound represented by Formula 2 or Formula 3 within the above content range, thereby providing coating, etc. when forming a photoresist from the composition. The process can be facilitated and the sensitivity of the photoresist can be improved.

The solvent included in the semiconductor resist composition according to one embodiment may be an organic solvent, for example, aromatic compounds (e.g., xylene, toluene), alcohols (e.g., 4-methyl-2-pentanol) , 4-methyl-2-propanol, 1-butanol, methanol, isopropyl alcohol, 1-propanol), ethers (e.g., anisole, tetrahydrofuran), esters (n-butyl acetate, propylene glycol mono) It may include, but is not limited to, methyl ether acetate, ethyl acetate, ethyl lactate), ketones (e.g., methyl ethyl ketone, 2-heptanone), and mixtures thereof.

The composition for a semiconductor resist according to one embodiment may further include a resin in addition to the above-described organometallic compound and solvent.

The resin may be a phenolic resin containing at least one aromatic moiety listed in Group 1 below.

[Group 1]

The resin may have a weight average molecular weight of 500 to 20,000.

The resin may be included in an amount of 0.1% by weight to 50% by weight based on the total content of the semiconductor resist composition.

When the resin is contained within the above content range, it can have excellent etching resistance and heat resistance.

Additionally, the composition for semiconductor resist according to one embodiment may further include additives in some cases. Examples of the additives include surfactants, cross-linking agents, leveling agents, organic acids, quenchers, or combinations thereof.

The surfactant may be, for example, an alkylbenzenesulfonic acid salt, an alkylpyridinium salt, polyethylene glycol, a quaternary ammonium salt, or a combination thereof, but is not limited thereto.

The cross-linking agent may include, for example, a melamine-based cross-linking agent, a substituted urea-based cross-linking agent, an acrylic-based cross-linking agent, an epoxy-based cross-linking agent, or a polymer-based cross-linking agent, but is not limited thereto. A crosslinking agent having at least two crosslinking substituents, for example, methoxymethylated glycoluryl, butoxymethylated glycoluryl, methoxymethylated melamine, butoxymethylated melamine, methoxymethylated benzoguanamine, butoxymethylated benzoguanamine. , 4-hydroxybutyl acrylate, acrylic acid, urethane acrylate, acrylic methacrylate, 1,4-butanediol diclicidyl ether, glycidol, diglycidyl 1,2-cyclohexane dicrboxylate, Compounds such as trimethylpropane triglycidyl ether, 1,3-bis(glycidoxypropyl_)tetramethyldisiloxane, methoxymethylated urea, butoxymethylated urea, or methoxymethylated thiourea can be used.

The leveling agent is intended to improve coating flatness during printing, and known leveling agents available commercially can be used.

Organic acids include p-toluenesulfonic acid, benzenesulfonic acid, p-dodecylbenzenesulfonic acid, 1,4-naphthalenedisulfonic acid, methanesulfonic acid, sulfonium fluoride salt, malonic acid, citric acid, propionic acid, methacrylic acid, oxalic acid, It may be lactic acid, glycolic acid, succinic acid, or a combination thereof, but is not limited thereto.

The quencher may be diphenyl (p-tryl) amine, methyl diphenyl amine, triphenyl amine, phenylenediamine, naphthylamine, diaminonaphthalene, or a combination thereof.

The amount of these additives used can be easily adjusted depending on the desired physical properties, and may be omitted.

In addition, the composition for semiconductor resist may further use a silane coupling agent as an additive as an adhesion promoter to improve adhesion to the substrate (for example, to improve the adhesion of the composition for semiconductor resist to the substrate). The silane coupling agent is, for example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyl trichlorosilane, vinyltris(β-methoxyethoxy)silane; or 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, p-styryl trimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldi. ethoxysilane; Silane compounds containing carbon-carbon unsaturated bonds such as trimethoxy[3-(phenylamino)propyl]silane may be used, but are not limited thereto.

The composition for semiconductor photoresist may not cause pattern collapse even if a pattern having a high aspect ratio is formed. Therefore, for example, a micropattern with a width of 5 nm to 100 nm, for example, a micropattern with a width of 5 nm to 80 nm, for example, a micropattern with a width of 5 nm to 70 nm, e.g. A micropattern with a width of 5 nm to 50 nm, for example, a micropattern with a width of 5 nm to 40 nm, for example, a micropattern with a width of 5 nm to 30 nm, for example, a micropattern with a width of 5 nm to 20 nm. To form a pattern, a photoresist process using light with a wavelength of 5 nm to 150 nm, e.g., a photoresist process using light with a wavelength of 5 nm to 100 nm, e.g., a photoresist process using light with a wavelength of 5 nm to 80 nm. A resist process, for example a photoresist process using light with a wavelength of 5 nm to 50 nm, for example a photoresist process using light with a wavelength of 5 nm to 30 nm, for example a photoresist process using light with a wavelength of 5 nm to 20 nm. It can be used in the photoresist process. Therefore, by using the composition for semiconductor photoresist according to one embodiment, extreme ultraviolet lithography using an EUV light source with a wavelength of about 13.5 nm can be implemented.

Meanwhile, according to another embodiment, a method of forming a pattern using the above-described composition for semiconductor photoresist may be provided. As an example, the manufactured pattern may be a photoresist pattern.

Another pattern forming method in one embodiment includes forming a film to be etched on a substrate, forming a photoresist film by applying the composition for a semiconductor photoresist described above on the film to be etched, and patterning the photoresist film to form a photoresist pattern. It includes forming and etching the etch target layer using the photoresist pattern as an etch mask.

Hereinafter, a method of forming a pattern using the above-described composition for semiconductor photoresist will be described with reference to FIGS. 1 to 5. 1 to 5 are cross-sectional views illustrating a method of forming a pattern using a composition for semiconductor photoresist according to the present invention.

Referring to Figure 1, first, an object to be etched is prepared. An example of the object to be etched may be the thin film 102 formed on the semiconductor substrate 100. Hereinafter, only the case where the etching object is the thin film 102 will be described. The surface of the thin film 102 is cleaned to remove contaminants remaining on the thin film 102. The thin film 102 may be, for example, a silicon nitride film, a polysilicon film, or a silicon oxide film.

Next, a composition for forming a resist underlayer film 104 is coated on the surface of the cleaned thin film 102 using a spin coating method. However, one embodiment is not necessarily limited to this, and various known coating methods such as spray coating, dip coating, knife edge coating, and printing methods such as inkjet printing and screen printing may be used.

The resist underlayer coating process can be omitted, and the case of coating the resist underlayer film will be described below.

Afterwards, a drying and baking process is performed to form a resist underlayer film 104 on the thin film 102. The baking treatment may be performed at about 100 to about 500°C, for example, about 100°C to about 300°C.

The resist underlayer 104 is formed between the substrate 100 and the photoresist film 106, so that radiation reflected from the interface or interlayer hardmask of the substrate 100 and the photoresist film 106 is not intended. In the case of scattering into an unapplied photoresist area, non-uniformity of the photoresist linewidth and interference with pattern formation can be prevented.

Referring to Figure 2, the photoresist film 106 is formed by coating the above-described semiconductor photoresist composition on the resist underlayer film 104. The photoresist film 106 may be formed by coating the above-described semiconductor photoresist composition on the thin film 102 formed on the substrate 100 and then curing it through a heat treatment process.

More specifically, the step of forming a pattern using a semiconductor photoresist composition involves applying the above-described semiconductor resist composition to the substrate 100 on which the thin film 102 is formed by spin coating, slit coating, inkjet printing, etc. It may include a process of forming a photoresist film 106 by drying the applied semiconductor photoresist composition.

Since the composition for semiconductor photoresist has already been described in detail, redundant description will be omitted.

Next, a first baking process is performed to heat the substrate 100 on which the photoresist film 106 is formed. The first baking process may be performed at a temperature of about 80°C to about 120°C.

Referring to FIG. 3, the photoresist film 106 is selectively exposed.

For example, examples of light that can be used in the exposure process include light with a short wavelength such as activating radiation i-line (wavelength 365 nm), KrF excimer laser (wavelength 248 nm), and ArF excimer laser (wavelength 193 nm), as well as EUV (wavelength 193 nm). Examples include light with high energy wavelengths such as Extreme UltraViolet (wavelength 13.5 nm) and E-Beam (electron beam).

More specifically, the exposure light according to one embodiment may be short-wavelength light having a wavelength range of 5 nm to 150 nm, and may be light having a high-energy wavelength such as EUV (Extreme UltraViolet; wavelength 13.5 nm) or E-Beam (electron beam). You can.

The exposed area 106a of the photoresist film 106 forms a polymer through a crosslinking reaction such as condensation between organometallic compounds or between an organometallic compound and a radically reactive compound, thereby forming a polymer in the unexposed area 106a of the photoresist film 106. It has a different solubility from region 106b.

Next, a second baking process is performed on the substrate 100. The second baking process may be performed at a temperature of about 90°C to about 200°C. By performing the second baking process, the exposed area 106a of the photoresist film 106 becomes difficult to dissolve in the developer.

FIG. 4 shows a photoresist pattern 108 formed by dissolving and removing the photoresist film 106b corresponding to the unexposed area using a developer. Specifically, the photoresist film 106b corresponding to the unexposed area is dissolved and then removed using an organic solvent such as 2-heptanone, thereby forming a photoresist pattern corresponding to the negative tone image ( 108) is completed.

As described above, the developer used in the pattern forming method according to one embodiment may be an organic solvent. Examples of organic solvents used in the pattern forming method according to one embodiment include ketones such as methyl ethyl ketone, acetone, cyclohexanone, and 2-heptanone, 4-methyl-2-propanol, 1-butanol, isopropanol, Alcohols such as 1-propanol and methanol, esters such as propylene glycol monomethyl ether acetate, ethyl acetate, ethyl lactate, n-butyl acetate, and butyrolactone, aromatic compounds such as benzene, xylene, and toluene, or these A combination of .

However, the photoresist pattern according to one embodiment is not necessarily limited to being formed as a negative tone image, and may be formed to have a positive tone image. In this case, the developer that can be used to form a positive tone image is a quaternary ammonium hydroxide composition such as tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, or a combination thereof. I can hear it.

As previously explained, not only light with wavelengths such as i-line (wavelength 365 nm), KrF excimer laser (wavelength 248 nm), and ArF excimer laser (wavelength 193 nm), but also EUV (Extreme UltraViolet; wavelength 13.5 nm), The photoresist pattern 108 formed by exposure to high-energy light such as an E-Beam may have a width of 5 nm to 100 nm thick. For example, the photoresist pattern 108 is 5 nm to 90 nm, 5 nm to 80 nm, 5 nm to 70 nm, 5 nm to 60 nm, 5 nm to 50 nm, 5 nm to 40 nm, 5 nm. It can be formed to have a width of 30 nm to 5 nm and a thickness of 5 nm to 20 nm.

Meanwhile, the photoresist pattern 108 has a half-pitch of about 50 nm or less, for example, 40 nm or less, for example, 30 nm or less, for example, 20 nm or less, for example, 15 nm or less. And, it may have a pitch having a line width roughness of about 10 nm or less, about 5 nm or less, about 3 nm or less, and about 2 nm or less.

Next, the resist underlayer 104 is etched using the photoresist pattern 108 as an etch mask. The organic layer pattern 112 is formed through the etching process described above. The formed organic layer pattern 112 may also have a width corresponding to the photoresist pattern 108 .

Referring to FIG. 5, the photoresist pattern 108 is applied as an etch mask to etch the exposed thin film 102. As a result, the thin film is formed as a thin film pattern 114.

The etching of the thin film 102 may be performed, for example, by dry etching using an etching gas. The etching gas may be, for example, CHF ₃ , CF ₄ , Cl ₂ , BCl ₃ , or a mixture thereof.

In the previously performed exposure process, the thin film pattern 114 formed using the photoresist pattern 108 formed by the exposure process performed using an EUV light source may have a width corresponding to the photoresist pattern 108. . As an example, it may have a width of 5 nm to 100 nm, the same as the photoresist pattern 108. For example, the thin film pattern 114 formed by an exposure process performed using an EUV light source has 5 nm to 90 nm, 5 nm to 80 nm, 5 nm to 70 nm, 5 nm, like the photoresist pattern 108. It may have a width of 5 nm to 60 nm, 5 nm to 50 nm, 5 nm to 40 nm, 5 nm to 30 nm, or 5 nm to 20 nm, and more specifically, may have a width of 20 nm or less.

Hereinafter, the present invention will be described in more detail through examples related to the production of the above-described composition for semiconductor photoresist. However, the technical features of the present invention are not limited to the following examples.

Example

Synthesis Example 1: Synthesis of organometallic compounds

Add 0.353 g (1.00 mmol) of tert-butyltin triacetate ((CH ₃ ) ₃ CSn(OCMe) ₃ ) to 20 ml toluene solution. Afterwards, 0.179 g (1.00 mmol) of Bis(trimethylsilyl) sulfide ((CH ₃ ) ₃ Si) ₂ S) was added and stirred at room temperature for 48 hours. Next, 30 ml of n-hexane was added to obtain 0.41 g of Compound 1 as a colorless crystal.

Synthesis Example 2: Synthesis of organometallic compounds

Add 0.353 g (1.00 mmol) of tert-butyltin triacetate ((CH ₃ ) ₃ CSn(OCMe) ₃ ) to 20 ml toluene solution. Afterwards, 0.226 g (1.00 mmol) of Bis(trimethylsilyl) selenide ((CH ₃ ) ₃ Si) ₂ Se) was added and stirred at room temperature for 48 hours. Next, 30 ml of n-hexane was added to obtain 0.44 g of colorless crystals of Compound 2.

Synthesis Example 3: Synthesis of organometallic compounds

Add 0.353g (1.00mmol) of tert-butyltin triacetate ((CH ₃ ) ₃ CSn(OCMe) ₃ ) to 20ml toluene solution. Afterwards, 0.274 g (1.00 mmol) of Bis(trimethylsilyl) selenide ((CH ₃ ) ₃ Si) ₂ Se) was added and stirred at room temperature for 48 hours. Next, 30 ml of n-hexane was added to obtain 0.46 g of colorless crystals of Compound 3.

Synthesis Example 4: Synthesis of organometallic compounds

Add 0.413 g (1.00 mmol) of di(tert-butyl)antimony triacetate ((CH ₃ ) ₃ CSb(OCMe) ₃ ) to 20 ml toluene solution. Afterwards, 0.179 g (1.00 mmol) of Bis(trimethylsilyl) sulfide ((CH ₃ ) ₃ Si) ₂ S) was added and stirred at room temperature for 48 hours. Next, 30 ml of n-hexane was added to obtain 0.44 g of colorless crystals of Compound 4.

Examples 1 to 6 and Comparative Example 1

Organometallic compounds of Compounds 1 to 4 obtained in Synthesis Examples 1 to 4, compounds represented by Formulas 4 to 6 as radical reactive compounds, and PGMEA (Propylene glycol methyl ether acetate) and PGME (Propylene glycol methyl ether) as solvents. ) were mixed in the weight ratio shown in Table 1 below and filtered through a 0.1㎛ PTFE (polytetrafluoroethylene) syringe filter to prepare compositions for semiconductor photoresists according to Examples 1 to 6.

In addition, the organometallic compound of Compound 1 according to Synthesis Example 1 and PGMEA (Propylene glycol methyl ether acetate) and PGME (Propylene glycol methyl ether) as solvents were mixed in the weight ratio shown in Table 1 below, and 0.1㎛ PTFE (polytetrafluoroethylene) Roethylene) was filtered using a syringe filter to prepare a composition for a semiconductor photoresist according to Comparative Example 1.

A 4-inch diameter circular silicon wafer with a native-oxide surface was used as a substrate for thin film coating, and the thin film was treated in a UV ozone cleaning system for 10 minutes prior to coating. The semiconductor photoresist compositions according to Examples 1 to 6 and Comparative Example 1 were spin-coated on the treated substrate at 1500 rpm for 30 seconds, and baked at 100°C for 60 seconds (post-apply bake, PAB). ) to form a photoresist thin film.

The thickness of the film after coating and baking was measured using ellipsometry, and the measured thickness was about 28 nm.

(Unit: weight%) Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative Example 1 organic metals
compound Compound 1 2.7 2.7 2.7 2.7 compound 2 2.7 Compound 3 2.7 Compound 4 2.7 radically reactive compounds Formula 4 0.3 Formula 5 0.3 0.3 0.3 0.3 Formula 6 0.3 PGMEA 50 50 50 50 50 50 50 PGME 47 47 47 47 47 47 47.3 total 100 100 100 100 100 100 100

evaluation

The films according to Examples 1 to 6 and Comparative Example 1 prepared by the above coating method on a circular silicon wafer were subjected to extreme ultraviolet rays (E-beam) at an acceleration voltage of 100 kV so that a nanowire pattern of 40 nm half-pitch was formed. expose to The exposed film was exposed to 160°C for 60 seconds, then dipped in a pedri dish containing 2-heptanone for 30 seconds, taken out, and washed with the same solvent for 10 seconds. Finally, after firing at 150°C for 180 seconds, a pattern image is obtained by FE-SEM (field emission scanning electron microscopy). After measuring the CD (Critical Dimension) size and line edge roughness (LER) of the formed line identified from the FE-SEM image, sensitivity and line edge roughness were evaluated according to the following criteria and are shown in Table 2.

※ Evaluation standard

(1) Sensitivity

The CD size measured at 1000 uC/cm ² energy was evaluated according to the following criteria, and the results are shown in Table 2.

- ◎: 40nm or more

- ○: 35nm or more and less than 40nm

- △: Less than 35nm

- X: Pattern not confirmed.

(2) Line Edge Roughness (LER)

- ○: 4nm or less

- △: More than 4nm and less than 7nm

- X: greater than 7nm

Sensitivity LER(nm) Example 1 ○ ○ Example 2 ◎ ○ Example 3 ○ △ Example 4 ◎ ○ Example 5 ◎ ○ Example 6 ○ △ Comparative Example 1 △ X

From the results in Table 2, the semiconductor photoresist compositions according to Examples 1 to 6 have higher sensitivity and line etch roughness (LER) than the semiconductor photoresist compositions according to Comparative Example 1 that do not contain a radical reactive compound. You can confirm its excellence.

Although specific embodiments of the present invention have been described and shown above, it is known in the art that the present invention is not limited to the described embodiments, and that various modifications and changes can be made without departing from the spirit and scope of the present invention. This is self-evident to those who have it. Accordingly, such modifications or variations should not be understood individually from the technical idea or viewpoint of the present invention, and the modified embodiments should be regarded as falling within the scope of the claims of the present invention.

100: substrate 102: thin film
104: resist underlayer film 106: photoresist film
106a: exposed area 106b: unexposed area
108: Photoresist pattern 112: Organic film pattern
114: thin film pattern

Claims (14)

A composition for a semiconductor photoresist comprising an organometallic compound represented by the following formula (1), a radical reactive compound represented by the following formula (2) or (3), and a solvent:
[Formula 1]
R _n M _m X _l Y _k
In Formula 1,
R is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 aliphatic unsaturated organic group containing one or more double bonds or triple bonds, or a substituted or unsubstituted C2 to C20 aliphatic unsaturated organic group. A C6 to C30 aryl group, a substituted or unsubstituted C4 to C30 heteroaryl group, a carbonyl group, an ethylene oxide group, a propylene oxide group, or a combination thereof,
M is tin (Sn) or antimony (Sb),
X is sulfur (S), selenium (Se), or tellerium (Te),
Y is -OR ^a or -OC(=O)R ^b ,
Wherein R ^a is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, substituted or unsubstituted. A ringed C6 to C30 aryl group, or a combination thereof,
R ^b is hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, substituted or An unsubstituted C6 to C30 aryl group, or a combination thereof,
where n, m, l and k are independently integers from 1 to 20;
[Formula 2]

[Formula 3]

In Formula 2 and Formula 3,
R ¹ and R ² are each independently a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, or a substituted or unsubstituted C2 to C20 aliphatic unsaturated group containing one or more double bonds or triple bonds. An organic group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof,
R ³ is a substituted or unsubstituted divalent C1 to C20 saturated aliphatic hydrocarbon group, a substituted or unsubstituted divalent C3 to C20 saturated alicyclic hydrocarbon group, or a substituted or unsubstituted 2 containing at least one double bond or triple bond. It is a valent C2 to C20 unsaturated aliphatic hydrocarbon group, a substituted or unsubstituted divalent C6 to C20 aromatic hydrocarbon group, a divalent ethylene oxide group, a divalent propylene oxide group, or a combination thereof.
In paragraph 1:
R is a substituted or unsubstituted C1 to C8 alkyl group, a substituted or unsubstituted C3 to C8 cycloalkyl group, a substituted or unsubstituted C2 to C8 aliphatic unsaturated organic group containing one or more double bonds or triple bonds, or a substituted or unsubstituted C2 to C8 aliphatic unsaturated organic group. A C6 to C20 aryl group, a substituted or unsubstituted C4 to C20 heteroaryl group, a carbonyl group, an ethylene oxide group, a propylene oxide group, or a combination thereof,
R ^a is a substituted or unsubstituted C1 to C8 alkyl group, a substituted or unsubstituted C3 to C8 cycloalkyl group, a substituted or unsubstituted C2 to C8 alkenyl group, a substituted or unsubstituted C2 to C8 alkynyl group, a substituted or unsubstituted an aryl group of C6 to C20, or a combination thereof,
R ^b is hydrogen, a substituted or unsubstituted C1 to C8 alkyl group, a substituted or unsubstituted C3 to C8 cycloalkyl group, a substituted or unsubstituted C2 to C8 alkenyl group, a substituted or unsubstituted C2 to C8 alkynyl group, substituted or A composition for a semiconductor photoresist comprising an unsubstituted C6 to C20 aryl group, or a combination thereof.
In paragraph 1:
R ¹ and R ² are each independently a substituted or unsubstituted C1 to C8 alkyl group, a substituted or unsubstituted C3 to C8 cycloalkyl group, or a substituted or unsubstituted C2 to C8 aliphatic unsaturated group containing one or more double bonds or triple bonds. An organic group, a substituted or unsubstituted C6 to C20 aryl group, or a combination thereof,
R ³ is a substituted or unsubstituted divalent C1 to C8 saturated aliphatic hydrocarbon group, a substituted or unsubstituted divalent C3 to C6 saturated or unsaturated alicyclic hydrocarbon group, a substitution containing 1 or 2 double or triple bonds, or A composition for a semiconductor photoresist comprising an unsubstituted divalent C2 to C8 unsaturated aliphatic hydrocarbon group, a substituted or unsubstituted C6 to C10 arylene group, a divalent ethylene oxide group, a divalent propylene oxide group, or a combination thereof.
In paragraph 1:
R is methyl group, ethyl group, propyl group, butyl group, isopropyl group, tert-butyl group, 2,2-dimethylpropyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, ethenyl group, propenyl group , butenyl group, ethynyl group, propynyl group, butynyl group, phenyl group, tolyl group, xylene group, benzyl group, formyl group, acetyl group, propanoyl group, butanoyl group, pentanoyl group, ethylene oxide group, propylene oxide group, or It is a combination of these,
R ^a is an ethyl group, propyl group, butyl group, isopropyl group, tert-butyl group, 2,2-dimethylpropyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, ethenyl group, propenyl group, butenyl group, ethynyl group, propynyl group, butynyl group, phenyl group, tolyl group, xylene group, benzyl group, or a combination thereof,
R ^b is hydrogen, ethyl group, propyl group, butyl group, isopropyl group, tert-butyl group, 2,2-dimethylpropyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, ethenyl group, prop A composition for a semiconductor photoresist comprising a phenyl group, butenyl group, ethynyl group, propynyl group, butynyl group, phenyl group, tolyl group, xylene group, benzyl group, or a combination thereof.
In paragraph 1:
R ¹ and R ² are each independently methyl group, ethyl group, propyl group, butyl group, isopropyl group, tert-butyl group, 2,2-dimethylpropyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group. Syl group, ethenyl group, propenyl group, butenyl group, ethynyl group, propynyl group, butynyl group, phenyl group, tolyl group, xylene group, benzyl group, ethylene oxide group, propylene oxide group, or a combination thereof,
R ³ is methylene group, ethylene group, propylene group, butylene group, cyclobutylene group, cyclopentylene group, cyclohexylene group, ethenylene group, propenylene group, ethynylene group, propynylene group, phenylene group, or these A composition for semiconductor photoresist that is a combination of.
In paragraph 1:
A composition for a semiconductor photoresist wherein the organometallic compound represented by Formula 1 contains an MXM bond.
In paragraph 1:
The radical reactive compound represented by Formula 2 or Formula 3 is a composition for semiconductor photoresist including a compound represented by Formula 4 to Formula 6 or a combination thereof:
[Formula 4]

[Formula 5]

[Formula 6]
.
In paragraph 1:
A composition for a semiconductor photoresist comprising an organometallic compound represented by Formula 1 and a radically reactive compound represented by Formula 2 or Formula 3 in a weight ratio of 50:1 to 1:1.
In paragraph 1:
Based on the total mass of the composition for semiconductor photoresist, a semiconductor comprising 1 to 30% by weight of an organometallic compound represented by Formula 1 and 0.01 to 15% by weight of a radical reactive compound represented by Formula 2 or Formula 3. Composition for photoresist.
In paragraph 1:
The composition for a semiconductor photoresist further includes an additive such as a surfactant, a cross-linking agent, a leveling agent, or a combination thereof.
Forming a film to be etched on a substrate;
forming a photoresist film by applying the composition for a semiconductor photoresist according to any one of claims 1 to 10 on the etching target film;
patterning the photoresist film to form a photoresist pattern; and
A pattern forming method comprising etching the etch target layer using the photoresist pattern as an etch mask.
In paragraph 11:
The step of forming the photoresist pattern is a pattern forming method using light with a wavelength of 5 nm to 150 nm.
In paragraph 11:
A pattern forming method further comprising providing a resist underlayer formed between the substrate and the photoresist film.
In paragraph 11:
The photoresist pattern is formed with a width of 5 nm to 100 nm.
law.