KR102606844B1 - Semiconductor resist composition and method of forming patterns using the composition - Google Patents

Abstract

It relates to a composition for a semiconductor photoresist containing an organometallic compound represented by the following formula (1), an organometallic compound represented by the following formula (2), and a solvent, and a pattern forming method using the same.
[Formula 1]

[Formula 2]

The specific details of Chemical Formula 1 and Chemical Formula 2 are the same as defined in the specification.

Description

Composition for semiconductor photoresist and method of forming a pattern using the same {SEMICONDUCTOR RESIST 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 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.

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. It showed impressive performance when used (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%.

In order to overcome the disadvantages of the chemically amplified (CA) 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 known to be less sensitive to stochastic effects, resulting in less line edge roughness and fewer defects. .

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 having excellent etch resistance, sensitivity, resolution, and pattern formation properties.

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, an organometallic compound represented by Formula 2 below, and a solvent.

[Formula 1]

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. C6 to C30 aryl group, ethylene oxide group, or propylene oxide group, or a combination thereof,

X, Y, and Z are each independently -OR ¹ or -OC(=O)R ² ,

Wherein R ¹ 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 ² 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.

[Formula 2]

In Formula 2,

X' is -OR ³ or -OC(=O)R ⁴ ,

R ³ 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 ⁴ 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.

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 ringed C6 to C20 aryl group, an ethylene oxide group, a propylene oxide group, or a combination thereof,

Wherein R ¹ and R ³ are each independently 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, or a substituted or unsubstituted C2 to C8 It may be an alkynyl group, a substituted or unsubstituted C6 to C20 aryl group, or a combination thereof,

R ² and R ⁴ are each independently 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, or a substituted or unsubstituted C2 It may be a C8 to C8 alkynyl group, a substituted or unsubstituted C6 to C20 aryl 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 It may be a phenyl 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 ¹ and R ³ 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. It may be a sil 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 ² and R ⁴ are each independently hydrogen, methyl group, ethyl group, propyl group, butyl group, isopropyl group, tert-butyl group, 2,2-dimethylpropyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, It may be a 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.

The compound represented by Formula 1 may be a compound represented by Formula 3, a compound represented by Formula 4, a compound represented by Formula 5, a compound represented by Formula 6, or a combination thereof.

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

In Formulas 3 to 6,

R is as defined in Formula 1 above,

R ^a , R ^b , R ^c , R ⁱ , R ^k , and R ^l are each independently as defined for R ¹ in Formula 1 above,

R ^d , R ^e , R ^f , R ^g , R ^h , and R ^j are each independently as defined for R ² in Formula 1 above.

The composition for semiconductor photoresist may include the organometallic compound represented by Formula 1 and the organometallic compound represented by Formula 2 in a weight ratio of 20:1 to 1:1.

The composition for semiconductor photoresist contains 0.01 to 30% by weight of the organometallic compound represented by Formula 1 and 0.01 to 15% by weight of the organometallic compound represented by Formula 2, based on 100% by weight of the composition for semiconductor photoresist. It can be included.

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, 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.

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 layer.

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

The composition for semiconductor photoresists according to one embodiment has relatively improved etch resistance, sensitivity, and resolution, and has excellent pattern formation properties. Therefore, when used, the composition has excellent sensitivity and does not collapse the pattern even if it has a high aspect ratio. A photoresist pattern can be provided.

1 to 5 are cross-sectional views illustrating a method of forming a pattern using a composition for a semiconductor photo resist 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 arbitrarily shown for convenience of explanation, so this description is not necessarily limited to what is shown.

In the drawing, the thickness is enlarged to clearly express various layers and regions. 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.

In this specification, unless otherwise defined, “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 and a solvent, and the organometallic compound consists of a compound represented by the following formulas (1) and (2).

[Formula 1]

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. C6 to C30 aryl group, ethylene oxide group, propylene oxide group, or a combination thereof,

X, Y, and Z are each independently -OR ¹ or -OC(=O)R ² ,

Wherein R ¹ 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 ² 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.

[Formula 2]

In Formula 2,

X' is -OR ³ or -OC(=O)R ⁴ ,

R ³ 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 ⁴ 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 organotin copolymer containing the organometallic compound represented by Formula 1 and Formula 2 is represented by Formula 1 in which one R group and three -OR ¹ or -OC(=O)R ² are substituted on the tin atom. It can be produced by copolymerizing an organometallic compound and an organometallic compound represented by Formula 2 in which four tin atoms are substituted with -OR ¹ or -OC(=O)R ² .

The compounds represented by Formula 1 and Formula 2 are organotin compounds, and tin strongly absorbs extreme ultraviolet light at 13.5 nm and may have excellent sensitivity to high-energy light, and the R in Formula 1 can impart photosensitivity to the compound represented by Formula 1, and as R is bonded to tin to form a Sn-R bond, it can impart solubility in organic solvents to the organotin compound. In addition, -OR ³ or -OC(=O)R ⁴ X, Y, and Z of Formula 1 and X' of Formula 2 can determine the solubility of the two compounds in the solvent.

With respect to R of Formula 1, the organotin copolymer having the structural units represented by Formula 1 and Formula 2 formed by copolymerization of the above compounds is R from the Sn-R bond when exposed to extreme ultraviolet rays. As the functional group dissociates, radicals are generated, The radicals generated in this way form additional -Sn-O-Sn- bonds to initiate a condensation polymerization reaction between the organotin copolymers, thereby forming a semiconductor photo resist from the composition according to one embodiment.

In the organometallic compound represented by Formula 1, the substituent represented by R is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted group containing one or more double bonds or triple bonds, or It may be an unsubstituted C2 to C20 aliphatic unsaturated organic group, a substituted or unsubstituted C6 to C30 aryl group, an ethylene oxide group, a propylene oxide group, or a combination thereof.

In addition to the substituent R, the compound represented by Formula 1 further includes three organic ligands X, Y, and Z, which are each hydrolyzed to form Sn-O bonds. In addition, the compound represented by Formula 2 contains four X' substituents that are hydrolyzed to form a Sn-O bond with a tin element. The X, Y ^{, Z} and Sn-O-Sn bonds are formed between organotin compounds, thereby forming an organotin copolymer containing the organometallic compound represented by Formula 1 and the organometallic compound represented by Formula 2.

The composition for a semiconductor photoresist according to an embodiment of the present invention simultaneously contains an organometallic compound represented by Formula 1 and an organometallic compound represented by Formula 2, so that the organometallic compound represented by Formula 1 or Formula 2 It is possible to provide a photoresist composition having superior sensitivity compared to a semiconductor photoresist composition that contains only the organometallic compound represented by .

By appropriately adjusting the ratio of the organometallic compound represented by Formula 1 and the organometallic compound represented by Formula 2 in the copolymer, the degree to which the ligand represented by R is dissociated from the copolymer can be controlled, and accordingly, the The degree of cross-linking through oxo bonds with surrounding chains is controlled by radicals generated when the ligand dissociates, and as a result, it is possible to provide a semiconductor photoresist with excellent sensitivity, low line edge roughness, and excellent resolution. That is, by including both the organometallic compound represented by Formula 1 and the organometallic compound represented by Formula 2, it is possible to provide a semiconductor photo resist with excellent sensitivity, line edge roughness, and resolution.

The R is, for example, 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 oil containing one or more double bonds or triple bonds. It may be a substituted or unsubstituted C6 to C20 aryl group, ethylene oxide group, propylene oxide 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, ethylene oxide group, propylene oxide group, or a combination thereof.

For example, R ¹ and R ³ are each independently 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, It may be a substituted or unsubstituted C2 to C8 alkynyl 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, tol It may be a lyl group, a xylene group, a benzyl group, or a combination thereof.

For example, R ² and R ⁴ are each independently 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, or a substituted or unsubstituted C2 to C8 alkenyl group. Or it may be an unsubstituted C2 to C8 alkynyl group, a substituted or unsubstituted C6 to C20 aryl group, or a combination thereof, for example, hydrogen, 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, It may be a tolyl group, a xylene group, a benzyl group, or a combination thereof.

The compound represented by Formula 1 may include a compound represented by Formula 3, a compound represented by Formula 4, a compound represented by Formula 5, a compound represented by Formula 6, or a combination thereof.

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

In Formulas 3 to 6,

R is as defined in Formula 1 above,

R ^a , R ^b , R ^c , R ⁱ , R ^k , and R ^l are each independently the same as defined for R ¹ in Formula 1 above,

R ^d , R ^e , R ^f , R ^g , R ^h , and R ^j are each independently the same as defined for R ² in Formula 1 above.

A composition for a semiconductor photoresist according to an embodiment of the present invention includes a compound having a substituent linked to three oxygen atoms each on a tin atom, as shown in Formula 1 or Formula 3 to Formula 6, and Formula 2 As shown, a photoresist pattern is provided that includes a compound having four substituents connected to an oxygen atom on a tin atom and an organometallic copolymer obtained by copolymerizing these compounds. This photoresist is relatively Etch resistance, sensitivity, and resolution are improved, and pattern formation is excellent, so the pattern does not collapse even with a high aspect ratio.

The organometallic compound represented by Formula 1 and the organometallic compound represented by Formula 2 may be included in the composition for semiconductor photoresist at a weight ratio of 20:1 to 1:1, for example, 18:1 to 1:1. 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, it may include, but is not limited to, 5:1 to 1:1, for example, 3:1 to 1:1, for example, 2:1 to 1:1. When the weight ratio of the organometallic compound represented by Formula 1 and the organometallic compound represented by Formula 2 satisfies the above range, a composition for a semiconductor photoresist having excellent sensitivity can be provided.

The composition for semiconductor photoresist contains 0.01 to 30% by weight of the organometallic compound represented by Formula 1 and 0.01 to 15% by weight of the organometallic compound represented by Formula 2, based on 100% by weight of the composition for semiconductor photoresist. It may include, for example, 0.1 to 20% by weight of the organometallic compound represented by Formula 1 and 0.1 to 10% by weight of the organometallic compound represented by Formula 2, for example, It may include 0.1 to 10% by weight of the organometallic compound represented by Formula 1 and 0.1 to 5% by weight of the organometallic compound represented by Formula 2, but is not limited thereto.

The semiconductor photoresist composition according to one embodiment includes the organometallic compound represented by Formula 1 and the organometallic compound represented by Formula 2 within the above content range, thereby facilitating processes such as coating when forming a photoresist from the composition. This can be done 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.

In one embodiment, the semiconductor resist composition 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.

Meanwhile, the composition for semiconductor resist according to one embodiment is preferably composed of the above-described organometallic compound, solvent, and resin. However, the composition for semiconductor resist according to the above-described embodiment may further include additives in some cases. Examples of the additives include surfactants, cross-linking agents, leveling agents, 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 crosslinking agent may include, for example, a melamine-based crosslinking agent, a substituted urea-based crosslinking agent, or a polymer-based crosslinking 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. Compounds such as 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.

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 photo resist 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 resist described above on the film to be etched, and patterning the photoresist film to form a photoresist pattern. 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 semiconductor resist composition 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 resist 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, at 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 FIG. 2, the photoresist film 106 is formed by coating the above-described semiconductor resist composition on the resist underlayer film 104. The photoresist film 106 may be formed by coating the above-described semiconductor resist 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 resist composition is a process of 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. and drying the applied semiconductor resist composition to form a photoresist film 106.

Since the composition for semiconductor resist 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 106b of the photoresist film 106 has a different solubility from the unexposed area 106a of the photoresist film 106 as a polymer is formed through a crosslinking reaction such as condensation between organometallic compounds. .

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 106b 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 106a corresponding to the unexposed area using a developer. Specifically, the photoresist film 106a 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, 10 nm to 50 nm, 10 nm to 40 nm, 10 nm. It may be formed to have a width of from 30 nm to 10 nm to 20 nm thick.

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, 25 nm or less, and about 10 nm or less, It may have a pitch with a line width roughness of about 5 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 photo resist pattern 108. For example, the thin film pattern 114 formed by an exposure process performed using an EUV light source has a thickness of 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 60 nm to 60 nm, 10 nm to 50 nm, 10 nm to 40 nm, 10 nm to 30 nm, or 10 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

Dissolve 20 g (51.9 mmol) of Ph ₃ SnCl in 70 ml of THF in a 250 mL two-necked round bottom flask, and lower the temperature to 0°C in an ice bath. Afterwards, butyl magnesium chloride (BuMgCl) 1M THF solution (62.3 mmol) was slowly added dropwise. After the dropwise addition is completed, the mixture is stirred at room temperature for 12 hours to obtain a compound represented by the following formula (7) with a yield of 85%.

[Formula 7]

Synthesis Example 2

It was synthesized in the same manner as in Synthesis Example 1, except that isopropyl magnesium chloride (iPrMgCl) 2M THF solution (62.3 mmol) was used instead of butyl magnesium chloride (BuMgCl) 1M THF solution, and is represented by the following formula 8. The compound was obtained with a yield of 88%.

[Formula 8]

Synthesis Example 3

A compound represented by the following formula 9 was synthesized in the same manner as in Synthesis Example 1, except that neopentyl magnesium chloride 1M THF solution (62.3 mmol) was used instead of butyl magnesium chloride (BuMgCl) 1M THF solution in Synthesis Example 1. Obtained with 76% yield.

[Formula 9]

Synthesis Example 4

The compound of Chemical Formula 7 (10 g, 24.6 mmol) of Synthesis Example 1 was dissolved in 50 mL of CH ₂ Cl ₂ , and 3 equivalents (73.7 mmol) of 2M HCl diethyl ether solution was slowly added dropwise at -78°C for 30 minutes. After stirring at room temperature for 12 hours, the solvent is concentrated and vacuum distilled to obtain a compound represented by the following formula (10) with a yield of 80%.

[Formula 10]

Synthesis Example 5

Except for using the compound of Chemical Formula 8 of Synthesis Example 2 instead of using the compound of Chemical Formula 7 of Synthesis Example 1, the compound of Chemical Formula 11 below was synthesized in the same manner as Synthesis Example 4, and 75% of the compound represented by Chemical Formula 11 below was used. Obtained by yield.

[Formula 11]

Synthesis Example 6

Except for using the compound of formula 9 in Synthesis Example 3 instead of using the compound of formula 7 in Synthesis Example 1, the compound of formula 12 below was synthesized in the same manner as in Synthesis Example 4, and 70% of the compound represented by formula 12 was used. Obtained by yield.

[Formula 12]

Synthesis Example 7

25 mL of acetic acid was slowly added dropwise to 10 g (25.6 mmol) of the compound of Chemical Formula 10 in Synthesis Example 4 at room temperature, and then heated to reflux for 12 hours. After raising the temperature to room temperature, acetic acid is vacuum distilled to obtain a compound represented by the following formula (13) in 90% yield.

[Formula 13]

Synthesis Example 8

25 mL of acrylic acid was slowly added dropwise to 10 g (25.4 mmol) of the compound of Chemical Formula 11 in Synthesis Example 5 at room temperature, and then heated to reflux at 80°C for 6 hours. After raising the temperature to room temperature, acrylic acid is vacuum distilled to obtain a compound represented by the following formula (14) in 50% yield.

[Formula 14]

Synthesis Example 9

25 mL of propionic acid was slowly added dropwise to 10 g (23.7 mmol) of the compound of Formula 12 in Synthesis Example 6 at room temperature, and then heated and refluxed at 110°C for 12 hours. After raising the temperature to room temperature, propionic acid is vacuum distilled to obtain a compound represented by the following formula (15) in 40% yield.

[Formula 15]

Synthesis Example 10

30 mL of anhydrous pentane was added to 10 g (35.4 mmol) of the compound of Chemical Formula 10 in Synthesis Example 4, and the temperature was lowered to 0°C. After slowly adding 7.8 g (106.3 mmol) of diethylamine dropwise, 7.9 g (106.3 mmol) of tert-butanol was added and stirred at room temperature for 1 hour. When the reaction is completed, it is filtered, concentrated, and vacuum dried to obtain a compound represented by the following formula (16) with a yield of 60%.

[Formula 16]

Synthesis Example 11

30 mL of anhydrous pentane was added to 10 g (37.3 mmol) of the compound of Chemical Formula 11 in Synthesis Example 5, and the temperature was lowered to 0°C. After slowly adding 8.2 g (111.9 mmol) of diethylamine dropwise, 6.7 g (111.9 mmol) of isopropanol was added and stirred at room temperature for 1 hour. When the reaction is completed, it is filtered, concentrated, and vacuum dried to obtain a compound represented by the following formula (17) with a yield of 65%.

[Formula 17]

Synthesis Example 12

30 mL of anhydrous pentane was added to 10 g (18.7 mmol) of the compound of Formula 12 in Synthesis Example 6, and the temperature was lowered to 0°C. After slowly adding 7.4 g (101.3 mmol) of diethylamine dropwise, 6.1 g (101.3 mmol) of ethanol was added and stirred at room temperature for 1 hour. When the reaction is completed, it is filtered, concentrated, and vacuum dried to obtain a compound represented by the following formula (18) with a yield of 60%.

[Formula 18]

Synthesis Example 13

After adding the compound of Formula 8 (10 g, 25.4 mmol) to a 100 mL round bottom flask, 25 ml of formic acid was slowly added dropwise at room temperature, and the mixture was heated and refluxed at 100°C for 24 hours. Afterwards, the temperature is lowered to room temperature and formic acid is vacuum distilled to obtain a compound represented by the following formula (19) with a yield of 90%.

[Formula 19]

Synthesis Example 14

After adding Ph ₄ Sn (20 g, 46.8 mmol) to a 100 mL round bottom flask, 50 ml of propionic acid was slowly added dropwise, and the mixture was heated and refluxed at 110°C for 26 hours. Afterwards, the temperature is lowered to room temperature, and propionic acid is vacuum distilled to obtain a compound represented by the following formula (20) with a yield of 95%.

[Formula 20]

Synthesis Example 15

After adding 154 mL of a 1M ethanol solution of sodium ethoxide to a 100 mL round bottom flask, 10 g (38.4 mmol) of SnCl ₄ was slowly added dropwise at 0°C. After raising the temperature to room temperature, stirring for 12 hours and vacuum distillation, the compound represented by the following formula (21) is obtained with a yield of 70%.

[Formula 21]

Examples 1 to 14

Compounds 13 to 19 obtained in Synthesis Examples 7 to 13 were each dissolved in xylene at a concentration of 2 wt%, and compounds 20 and 21 obtained in Synthesis Examples 14 and 15 were dissolved in Compound 13. to Compound 19 were dissolved in xylene at a concentration of 0.2 wt%, respectively, and then filtered through a 0.1㎛ PTFE (polytetrafluoroethylene) syringe filter to produce semiconductor photos according to Examples 1 to 14. A composition for resist is prepared. The specific combination of compounds constituting the composition for semiconductor photoresist is shown in Table 1 below.

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. On the treated substrate, the composition for semiconductor photoresist according to Examples 1 to 14 was spin-coated at 1500 rpm for 30 seconds, and baked at 100 ° C. for 120 seconds (post-apply bake, PAB) to form a photoresist. Forms a thin film.

The thickness of the film after coating and baking was measured using ellipsometry, and the measured thickness was about 25 nm.

Comparative Example 1

Except that only Compound 13 obtained in Synthesis Example 7 was used by dissolving it in xylene at a concentration of 2 wt%, the composition for semiconductor photoresist according to Comparative Example 1 and the composition containing the same were prepared in the same manner as in the above Example. A photoresist thin film was prepared. The thickness of the film after coating and baking was approximately 25 nm.

Comparative Example 2

A composition for a semiconductor photoresist according to Comparative Example 2 and a photoresist thin film containing the same were prepared in the same manner as Example 1, except that nBuSnOOH (TCI) was used instead of Compound 13 in Example 1. The thickness of the film after coating and baking was approximately 25 nm.

Organometallic compounds (A) Organometallic compounds (B) Example 1 Formula 13 Formula 20 Example 2 Formula 14 Formula 20 Example 3 Formula 15 Formula 20 Example 4 Formula 16 Formula 20 Example 5 Formula 17 Formula 20 Example 6 Formula 18 Formula 20 Example 7 Formula 19 Formula 20 Example 8 Formula 13 Formula 21 Example 9 Formula 14 Formula 21 Example 10 Formula 15 Formula 21 Example 11 Formula 16 Formula 21 Example 12 Formula 17 Formula 21 Example 13 Formula 18 Formula 21 Example 14 Formula 19 Formula 21 Comparative Example 1 Formula 13 - Comparative Example 2 nBuSnOOH (TCI) Formula 20

evaluation

The films according to Examples 1 to 14 and Comparative Examples 1 to 2 prepared by the coating method on a circular silicon wafer were polarized to form a line/space pattern of 12 to 100 nm by varying energy and focus. Exposure to ultraviolet rays. After exposure, it is fired at 180°C for 120 seconds, then dipped in a Petri dish containing 2-heptanone for 60 seconds, taken out, and washed with the same solvent for 10 seconds. Finally, after firing at 150°C for 5 minutes, pattern images are obtained by scanning electron microscopy (SEM). The highest resolution, optimal energy, and line edge roughness (LER) confirmed from the SEM images are shown in Table 2 below.

Resolution (nm) Energy (mJ/cm ² ) LER(nm) Example 1 15.0 53 2.5 Example 2 16.0 35 2.9 Example 3 15.1 48 2.5 Example 4 14.5 50 3.0 Example 5 15.6 48 3.0 Example 6 15.0 42 3.3 Example 7 15.6 35 3.0 Example 8 15.3 55 2.5 Example 9 15.8 35 3.0 Example 10 14.8 44 3.2 Example 11 15.5 52 2.5 Example 12 15.0 44 2.9 Example 13 14.3 37 3.6 Example 14 15.2 35 3.2 Comparative Example 1 18.5 75 4.6 Comparative Example 2 19.1 96 4.5

Referring to Table 2, the semiconductor photoresists according to Examples 1 to 14, which simultaneously include one of the compounds represented by Formulas 13 to 19 and one of the compounds represented by Formula 20 or Formula 21. It can be confirmed that the photoresist thin film using the composition exhibits excellent resolution, sensitivity, and line edge roughness (LER).

On the other hand, the photoresist thin film using the composition for semiconductor photoresist according to Comparative Example 1 containing only the compound represented by Formula 13 and Comparative Example 2 containing nBuSnOOH (TCI) and the compound represented by Formula 20 was prepared as described above. When compared to the example, it can be seen that the highest resolution, optimal energy, and line edge roughness (LER) evaluation are all measured at high values, and therefore, the resolution, sensitivity, and line edge roughness (LER) are all measured as high values compared to the example. You can confirm that it is not good.

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: Photoresist underlayer film 106: Photoresist film
106b: exposed area 106a: unexposed area
108: Photoresist pattern 112: Organic film pattern
114: thin film pattern

Claims (11)

A composition for a semiconductor photo resist comprising a first organometallic compound represented by the following formula (1), a second organometallic compound represented by the following formula (2), and a solvent:
[Formula 1]

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. C6 to C30 aryl group, ethylene oxide group, propylene oxide group, or a combination thereof,
X, Y, Z are each independently -OR ¹ or -OC(=O)R ² ,
Wherein R ¹ 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 ² 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;
[Formula 2]

In Formula 2,
X' is -OR ³ or -OC(=O)R ⁴ ,
R ³ 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 ⁴ 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 (provided that X, Y and Z in Formula 1 are each -OR ¹ , and X' in Formula 2 is each -OR Compositions containing a ³ -phosphorus second organometallic compound are excluded).
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. C6 to C20 aryl group, ethylene oxide group, propylene oxide group, or a combination thereof,
R ¹ and R ³ are each independently 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, or a substituted or unsubstituted C2 to C8 alkyl group. A nyl group, a substituted or unsubstituted C6 to C20 aryl group, or a combination thereof,
R ² and R ⁴ are each independently 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, or a substituted or unsubstituted C2 to C8 alkenyl group. A composition for a semiconductor photoresist comprising a C8 alkynyl group, a substituted or unsubstituted C6 to C20 aryl 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, ethylene oxide group, propylene oxide group, or a combination thereof,
R ¹ and R ³ 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, or a combination thereof,
R ² and R ⁴ are each independently hydrogen, methyl group, ethyl group, propyl group, butyl group, isopropyl group, tert-butyl group, 2,2-dimethylpropyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, A composition for a semiconductor photoresist comprising a 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.
In paragraph 1:
The first organometallic compound is a compound represented by the following Chemical Formula 3, a compound represented by the Chemical Formula 4, a compound represented by the Chemical Formula 5, a compound represented by the Chemical Formula 6, or a combination thereof. A composition for a semiconductor photo resist:
[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

In Formula 3, Formula 4, Formula 5, and Formula 6,
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. C6 to C30 aryl group, ethylene oxide group, propylene oxide group, or a combination thereof,
R ^a , R ^b , R ^c , R ⁱ , R ^k , and R ^l 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 A C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof,
R ^d , R ^e , R ^f , R ^g , R ^h , and R ^j are each independently hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, or a substituted or unsubstituted C1 to C20 cycloalkyl group. It is a C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof.
In paragraph 1:
A composition for a semiconductor photo resist comprising the first organometallic compound and the second organometallic compound in a weight ratio of 20:1 to 1:1.
In paragraph 1:
A composition for a semiconductor photoresist comprising 0.01 to 30% by weight of the first organometallic compound and 0.01 to 15% by weight of the second organometallic compound, based on 100% by weight of the composition for a semiconductor photoresist.
In paragraph 1:
The composition is a composition for a semiconductor photo resist further comprising an additive of 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 7 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 8:
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 8:
A pattern forming method further comprising providing a resist underlayer formed between the substrate and the photoresist film.
In paragraph 8:
The photoresist pattern has a width of 5 nm to 100 nm.