Composition for semiconductor photoresist and method for forming patterns using the same

Abstract

The present invention provides a semiconductor photoresist composition with excellent sensitivity and LER characteristics, as well as a pattern formation method utilizing the semiconductor photoresist composition. [Solution] The present invention relates to a semiconductor photoresist composition comprising an organometallic compound; a (meth)acrylate polymer containing at least one metal having a valency of 2 to 6; and a solvent, and a pattern formation method utilizing the same.

Description

[Technical Field]

[0001] This document relates to a semiconductor photoresist composition and a pattern formation method using the same. [Background technology]

[0002] EUV (extreme ultraviolet) lithography is attracting attention as one of the key technologies for manufacturing next-generation semiconductor devices. EUV lithography is a pattern formation technique that uses EUV light with a wavelength of 13.5 nm as the exposure light source. It has been demonstrated that EUV lithography can form extremely fine patterns (for example, less than 20 nm) in the exposure process of semiconductor device manufacturing.

[0003] The realization of extreme ultraviolet (EUV) lithography requires the development of compatible photoresists that can achieve spatial resolutions of 16 nm or less. Currently, traditional chemically amplified (CA) photoresists are striving to meet the specifications for resolution, photospeed, feature roughness, and line edge roughness (LER) for next-generation devices.

[0004] The intrinsic image blur caused by acid-catalyzed reactions in these polymer-type photoresists limits resolution at small feature sizes, a fact long known in electron beam lithography. Chemically amplified (CA) photoresists are designed for high sensitivity, but their typical elemental makeup lowers the absorbance of the photoresist at a wavelength of 13.5 nm, resulting in reduced sensitivity, which can make them even more challenging, partly under EUV exposure.

[0005] Furthermore, CA photoresists can suffer from roughness issues with small peach size, and experiments have shown that line edge roughness (LER) increases as the photospeed decreases, partly due to the nature of the acid-catalyzed process. Due to the shortcomings and problems of CA photoresists, the semiconductor industry is seeking new types of high-performance photoresists.

[0006] To overcome the shortcomings of the chemically amplified organic photosensitive compositions described above, inorganic photosensitive compositions have been studied. Inorganic photosensitive compositions are mainly used for negative tone patterning that is resistant to removal by developer compositions through chemical modification via a non-scientific amplification mechanism. Inorganic compositions contain inorganic elements that have a higher EUV absorption rate compared to hydrocarbons, and are known to ensure sensitivity even with a non-scientific amplification mechanism, have low sensitivity to the stochastic effect, and have fewer line edge roughness and defects.

[0007] Inorganic photoresists based on tungsten and tungsten peroxopolyacids mixed with niobium, titanium, and / or tantalum have been reported for use as radiation-sensitive materials for patterning (US5061599; H. Okamoto, T. Iwayanagi, K. Mochiji, H. Umezaki, T. Kudo, Applied Physics Letters, 49(5), 298-300, 1986).

[0008] These materials, being deep UV, X-ray, and electron beam sources, were effective in patterning large pitchers in bilayer configurations. More recently, projection EUV lithography has shown impressive performance when using cationic hafnium metal oxide sulfate (HfSOx) materials with a peroxo complexing agent to image 15 nm half-pitch (HP) (US2011-0045406; JKStowers, A.Telecky, M.Kocsis, BLClark, DAKEszler, A.Grenville, CNAnderson, PPNaulleau, Proc.SPIE, 7969, 796915, 2011). This system demonstrates the best performance of non-CA photoresists and has a light speed that approaches the requirements for a viable EUV photoresist. However, hafnium metal oxide sulfate materials containing peroxo complexing agents have several practical drawbacks. Firstly, these materials are coated with a highly corrosive sulfuric acid / hydrogen peroxide mixture, resulting in poor shelf-life stability. Secondly, structural modifications to improve performance are not easy as they are composite mixtures. Thirdly, they must be developed with extremely high concentrations of TMAH (tetramethylammonium hydroxide) solution, such as 25 wt%.

[0009] In recent years, tin-containing molecules have been found to exhibit excellent absorption of extreme ultraviolet light, and active research is being conducted on them. In the case of organotin polymers, one such example, alkyl ligands dissociate due to light absorption or the secondary electrons generated by this absorption, and crosslinking with surrounding chains via iodine bonds enables negative tone patterning that is not removed by organic developers. While such organotin polymers have shown a dramatic improvement in sensitivity while maintaining resolution and line edge roughness, further improvements to the aforementioned patterning properties are necessary for commercialization. [Overview of the project] [Problems that the invention aims to solve]

[0010] One embodiment provides a semiconductor photoresist composition with excellent sensitivity and LER characteristics.

[0011] Other embodiments provide a pattern formation method using the semiconductor photoresist composition described above. The semiconductor photoresist composition according to one embodiment comprises an organometallic compound, an acrylate polymer containing at least one of a monomer derived from the monomer represented by the following chemical formula 1 and a monomer derived from the monomer represented by the following chemical formula 2, and a solvent. [ka]

[0012] In the aforementioned chemical formulas 1 and 2, R 1 is hydrogen, or a substituted or unsubstituted C1-C10 alkyl group. M 1 and M 2 These are, independently, metals with valencies of 2 to 6. L 1 These are single bonds, -C(O)O-, substituted or unsubstituted C1-C10 alkylene groups, substituted or unsubstituted C6-C20 arylene groups, or combinations thereof. R 6 and R 7is each independently a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C6-C20 aryl group, OR b or OC(=O)R c (where R b and R c are each independently a substituted or unsubstituted C1-C10 alkyl group), n1 is an integer from 1 to 5, n2 is an integer from 0 to 4, when n1 and n2 are each 2 or more, each R 6 and R 7 are the same as or different from each other.

[0013] The pattern formation method according to another embodiment includes a step of forming an etching target film on a substrate, a step of applying the above-described composition for semiconductor photoresist on the etching target film to form a photoresist film, a step of patterning the photoresist film to form a photoresist pattern, and a step of etching the etching target film using the photoresist pattern as an etching mask.

[0014] A pattern formed using the composition for semiconductor photoresist according to one embodiment can have excellent sensitivity and LER characteristics.

Brief Description of the Drawings

[0015] [Figure 1] It is a cross-sectional view for explaining a pattern formation method using the composition for semiconductor photoresist according to one embodiment.

Embodiments for Carrying Out the Invention

[0016] The embodiments of the present invention will be described in detail below with reference to the attached drawings. However, in order to clarify the gist of this description, explanations of functions or configurations that have already been made public will be omitted.

[0017] To clearly explain this description, unnecessary explanatory parts have been omitted, and the same or similar reference numerals are used throughout the specification for identical or similar components. Furthermore, the dimensions and thicknesses of each component shown in the drawings are provided arbitrarily for explanatory purposes and are not necessarily limited to those depicted in the drawings.

[0018] In the drawings, thicknesses are shown enlarged to clearly represent various layers and regions. Furthermore, in the drawings, the thicknesses of some layers and regions are shown exaggeratedly for ease of explanation. When a part such as a layer, film, region, or plate is said to be "on top of" or "on" another part, this includes not only when it is "directly on top of" another part, but also when there is yet another part in between. In this description, "substituted" means that a hydrogen atom is replaced by deuterium, a halogen group, a hydroxyl group, a carboxyl group, a thiol group, a cyano group, a nitro group, -NRR' (where R and R' are, independently, hydrogen, a substituted or unsubstituted C1-C30 saturated or unsaturated aliphatic hydrocarbon group, a substituted or unsubstituted C3-C30 saturated or unsaturated alicyclic hydrocarbon group, or a substituted or unsubstituted C6-C30 aromatic hydrocarbon group), -SiRR'R'' (where R, R', and R'' are, independently, This means that the hydrogen atom is substituted with hydrogen, a substituted or unsubstituted C1-C30 saturated or unsaturated aliphatic hydrocarbon group, a substituted or unsubstituted C3-C30 saturated or unsaturated alicyclic hydrocarbon group, or a substituted or unsubstituted C6-C30 aromatic hydrocarbon group, a C1-C30 alkyl group, a C1-C10 haloalkyl group, a C1-C10 alkylsilyl group, a C3-C30 cycloalkyl group, a C6-C30 aryl group, a C1-C20 alkoxy group, a C1-C20 sulfide group, or a combination thereof. "Unsubstituted" means that the hydrogen atom remains a hydrogen atom without being substituted by another substituent.

[0019] In this specification, "alkyl(alkyl) group" means a linear or branched aliphatic hydrocarbon group unless otherwise defined. The alkyl group may be a "saturated alkyl group" that does not contain any double or triple bonds.

[0020] The alkyl group may be a C1-C8 alkyl group. For example, the alkyl group may be a C1-C7 alkyl group, a C1-C6 alkyl group, or a C1-C5 alkyl group. For example, the C1-C5 alkyl group may be a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, or a tert-butyl group or a 2,2-dimethylpropyl group.

[0021] In this document, unless otherwise specified, "cycloalkyl group" refers to a monovalent cyclic aliphatic saturated hydrocarbon group.

[0022] The cycloalkyl group may be a C3-C8 cycloalkyl group, for example, a C3-C7 cycloalkyl group, a C3-C6 cycloalkyl group, a C3-C5 cycloalkyl group, or a C3-C4 cycloalkyl group. For example, the cycloalkyl group may be a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, or a cyclohexyl group, and is not limited to these.

[0023] In this description, "aliphatic unsaturated organic group" means a hydrocarbon group in which the bonds between carbon atoms in the molecule are double bonds, triple bonds, or combinations thereof.

[0024] The aliphatic unsaturated organic group may be a C2-C8 aliphatic unsaturated organic group. For example, the aliphatic unsaturated organic group may be a C2-C7 aliphatic unsaturated organic group, a C2-C6 aliphatic unsaturated organic group, a C2-C5 aliphatic unsaturated organic group, or a C2-C4 aliphatic unsaturated organic group. For example, the C2-C4 aliphatic unsaturated organic group may be a vinyl group, an ethynyl group, an allyl group, a 1-profenyl group, a 1-methyl-1-profenyl group, a 2-profenyl group, a 2-methyl-2-profenyl group, a 1-propynyl group, a 1-methyl-1-propynyl group, a 2-propynyl group, a 2-methyl-2-propynyl group, a 1-butenyl group, a 2-butenyl group, a 3-butenyl group, a 1-butynyl group, a 2-butynyl group, or a 3-butynyl group.

[0025] In this description, "aryl group" refers to a substituent in which all elements of the cyclic substituent have p-orbitals, and these p-orbitals form a conjugation, and includes monocyclic or fused polycyclic (i.e., rings sharing adjacent pairs of carbon atoms) functional groups.

[0026] In this description, a "heteroaryl group" means an aryl group containing at least one heteroatom selected from the group consisting of N, O, S, P, and Si. Two or more heteroaryl groups can be directly linked by sigma bonds, or, if the heteroaryl group contains two or more rings, the two or more rings can be fused together. If the heteroaryl group is a fused ring, each ring may contain 1 to 3 of the heteroatoms.

[0027] In this document, "alkenyl group" means an aliphatic unsaturated alkenyl group, which is a linear or branched aliphatic hydrocarbon group containing one or more double bonds, unless otherwise defined. In this document, "alkynyl group" means an aliphatic unsaturated alkynyl group, which is a linear or branched aliphatic hydrocarbon group containing one or more triple bonds, unless otherwise defined.

[0028] In this text, "meth(acrylic)" means "acrylic" and / or "methacrylic," and "(meth)acrylate" means "acrylate" and / or "methacrylate."

[0029] A semiconductor photoresist composition according to one embodiment will be described below.

[0030] A semiconductor photoresist composition according to one embodiment of the present invention may include an organometallic compound, a (meth)acrylate polymer comprising at least one of a monomer derived from the monomer represented by the following chemical formula 1 and a monomer derived from the monomer represented by the following chemical formula 2, and a solvent. [ka]

[0031] In the aforementioned chemical formulas 1 and 2, R 1 is hydrogen, or a substituted or unsubstituted C1-C10 alkyl group. M 1 and M 2 These are, independently, metals with valencies of 2 to 6. L 1 These are single bonds, -C(O)O-, substituted or unsubstituted C1-C10 alkylene groups, substituted or unsubstituted C6-C20 arylene groups, or combinations thereof. R 6 and R 7Each of these is independently a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C6-C20 aryl group, OR b Or OC(=O)R c (Here, R b and R c (Each of these is independently a substituted or unsubstituted C1-C10 alkyl group.) n1 is an integer between 1 and 5. n2 is an integer between 0 and 4. If n1 and n2 are each 2 or greater, then each R 6 and R 7 They are either identical or different from one another.

[0032] The (meth)acrylate polymer contained in the aforementioned semiconductor photoresist composition can improve sensitivity and LER by introducing a metal element with high EUV absorption rate into the polymer, thereby reducing photon shot noise in the photoresist pattern.

[0033] As an example, the aforementioned M 1 n1 is Sn, Sb, or Te, and n1 may be an integer from 1 to 3.

[0034] As an example, the aforementioned M 2 n2 is either Sn or Sb, and n2 may be an integer of 1 or 2.

[0035] As a specific example, the aforementioned M 1 and M 2 These are Sn, where n1 may be an integer of 3 and n2 may be an integer of 2.

[0036] For example, the monomers represented by chemical formulas 1 and 2 may be selected from the groups listed in Group I below. [ka]

[0037] In one embodiment, the (meth)acrylate polymer may contain at least one of the structural units derived from the monomer represented by chemical formula 1 and the structural unit derived from the monomer represented by chemical formula 2 in an amount of 50 to 100 mol%.

[0038] On the other hand, the (meth)acrylate polymer may further contain structural units derived from monomers containing ethylenically unsaturated groups.

[0039] The aforementioned "monomer containing an ethylenically unsaturated group" refers to a molecule having one or more carbon-carbon double bonds and capable of insertion-add polymerization.

[0040] The monomer containing the ethylenically unsaturated group may be, for example, an alkyl (meth)acrylate monomer; or it may be a (meth)acrylate monomer containing one or more functional groups selected from a hydroxyl group, an amino group, a carboxyl group, a sulfonamide group, a hexafluoroisopropyl alcohol group [-C(CF3)2OH], an anhydride, a lactone group, an ester group, an ether group, an allylamine group, a pyrrolidone group, and combinations thereof.

[0041] The alkyl (meth)acrylate monomer may be, for example, one or more of methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, dodecyl (meth)acrylate, isobornyl (meth)acrylate, lauryl (meth)acrylate, or mixtures thereof.

[0042] Examples of the hydroxyl group-containing (meth)acrylate monomers include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 1,4-cyclohexanedimethanol mono(meth)acrylate, 1-chloro-2-hydroxypropyl (meth)acrylate, diethylene glycol mono(meth)acrylate, 1,6-hexanediol mono(meth)acrylate, and penta-ethyl (meth)acrylate. This may include one or more of the following: thritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, neopentyl glycol mono(meth)acrylate, trimethylol propanedi(meth)acrylate, trimethylol ethanedi(meth)acrylate, 2-hydroxy-3-phenyloxypropyl(meth)acrylate, 4-hydroxycyclopentyl(meth)acrylate, 4-hydroxycyclohexyl(meth)acrylate, cyclohexanedimethanol mono(meth)acrylate, or mixtures thereof.

[0043] The amino group-containing (meth)acrylate monomer may be, for example, one or more of the following: N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, N,N-dibutylaminoethyl (meth)acrylate, 2-(2-dimethylaminoethyl(methyl)amino)ethyl (meth)acrylate, 2-(2-dimethylaminoethyloxy)ethyl (meth)acrylate, 2-(diisopropylamino)ethyl (meth)acrylate, 2-morpholinoethyl (meth)acrylate, 2-1-(piperidyl)ethyl (meth)acrylate, 2-(N-ethylanilino)ethyl (meth)acrylate, 2-imidazole-1-ylethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylamide, or mixtures thereof.

[0044] The (meth)acrylate polymer may be a homopolymer or copolymer having multiple different structural units, for example, two, three, four or more different structural units.

[0045] As a specific example, the (meth)acrylate polymer may be one selected from the polymers listed in Group 1 below.

[0046] [ka] [ka]

[0047] The (meth)acrylate polymer may be included in an amount of 0.001 to 10% by weight per 100% by weight of the semiconductor photoresist composition.

[0048] For example, the (meth)acrylate polymer may be included in an amount of 0.01 to 10% by weight, 0.01 to 5% by weight, 0.05 to 5% by weight, or 0.1 to 5% by weight based on 100% by weight of the semiconductor photoresist composition.

[0049] The organometallic compound may be included in an amount of 0.5% to 30% by weight based on 100% by weight of the semiconductor photoresist composition.

[0050] A semiconductor photoresist composition according to one embodiment can improve the sensitivity of a photoresist by containing the organometallic compound and the (meth)acrylate polymer within the specified content range.

[0051] A semiconductor photoresist composition according to one embodiment may contain the organometallic compound and the (meth)acrylate polymer in a weight ratio of 99:1 to 60:40. For example, a semiconductor photoresist composition may contain the organometallic compound and the (meth)acrylate polymer in a weight ratio of 90:10 to 60:40.

[0052] When the weight ratio of the organometallic compound to the aforementioned (meth)acrylate polymer satisfies the above range, a semiconductor photoresist composition with excellent sensitivity can be provided.

[0053] The organometallic compound may also be an organotin compound containing at least one of an organooxy group and an organocarbonyloxy group.

[0054] The aforementioned organometallic compound is represented by the following chemical formula 3. [ka]

[0055] In the aforementioned chemical formula 3, R 9 This is selected from substituted or unsubstituted C1-C20 alkyl groups, substituted or unsubstituted C3-C20 cycloalkyl groups, substituted or unsubstituted C2-C20 alkenyl groups, substituted or unsubstituted C2-C20 alkynyl groups, substituted or unsubstituted C6-C30 aryl groups, and substituted or unsubstituted C6-C30 arylalkyl groups. R 10 ~R 12 These are, independently, substituted or unsubstituted C1-C20 alkyl groups, substituted or unsubstituted C3-C20 cycloalkyl groups, substituted or unsubstituted C2-C20 alkenyl groups, substituted or unsubstituted C2-C20 alkynyl groups, substituted or unsubstituted C6-C30 aryl groups, substituted or unsubstituted C6-C30 arylalkyl groups, alkoxy and aryloxy (-OR) b , here R b (which are substituted or unsubstituted C1-C20 alkyl groups, substituted or unsubstituted C3-C20 cycloalkyl groups, substituted or unsubstituted C2-C20 alkenyl groups, substituted or unsubstituted C2-C20 alkynyl groups, substituted or unsubstituted C6-C30 aryl groups, or combinations thereof), carboxyl groups (-O(CO)R c , R c(which is hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof), alkylamide or dialkylamide (-NR d R e , here R d and R e Each of these is independently hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof), amidato (-NR f (COR g ), here R f and R g Each of these is independently hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof), amidinato (-NR h C(NR i )R j , here R h , R i and R j Each of these is independently hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof), alkylthio and arylthio (-SR k , here R k(which is a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof), or a thiocarboxyl group (-S(CO)R l , R l (These are hydrogen, substituted or unsubstituted C1-C20 alkyl groups, substituted or unsubstituted C3-C20 cycloalkyl groups, substituted or unsubstituted C2-C20 alkenyl groups, substituted or unsubstituted C2-C20 alkynyl groups, substituted or unsubstituted C6-C30 aryl groups, or combinations thereof.) R 10 ~R 12 At least one of them is an alkoxy and an aryloxy (-OR b , here R b (which are substituted or unsubstituted C1-C20 alkyl groups, substituted or unsubstituted C3-C20 cycloalkyl groups, substituted or unsubstituted C2-C20 alkenyl groups, substituted or unsubstituted C2-C20 alkynyl groups, substituted or unsubstituted C6-C30 aryl groups, or combinations thereof), carboxyl groups (-O(CO)R c , R c (which is hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof), alkylamide or dialkylamide (-NR d R e , here R d and R e Each of these is independently hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof), amidato (-NR f (COR g ), here Rf and R g Each of these is independently hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof), amidinato (-NR g C(NR h )R i , here R h , R i and R j Each of these is independently hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof), alkylthio and arylthio (-SR) k , here R k (which are substituted or unsubstituted C1-C20 alkyl groups, substituted or unsubstituted C3-C20 cycloalkyl groups, substituted or unsubstituted C2-C20 alkenyl groups, substituted or unsubstituted C2-C20 alkynyl groups, substituted or unsubstituted C6-C30 aryl groups, or combinations thereof), and thiocarboxyl groups (-S(CO)R l , R l (is selected from hydrogen, substituted or unsubstituted C1-C20 alkyl groups, substituted or unsubstituted C3-C20 cycloalkyl groups, substituted or unsubstituted C2-C20 alkenyl groups, substituted or unsubstituted C2-C20 alkynyl groups, substituted or unsubstituted C6-C30 aryl groups, or a combination thereof).

[0056] The aforementioned R 10 ~R 12 At least one of them is an alkoxy and an aryloxy (-OR b , here R a(which are substituted or unsubstituted C1-C20 alkyl groups, substituted or unsubstituted C3-C20 cycloalkyl groups, substituted or unsubstituted C2-C20 alkenyl groups, substituted or unsubstituted C2-C20 alkynyl groups, substituted or unsubstituted C6-C30 aryl groups, or combinations thereof), and carboxyl groups (-O(CO)R c , R c (is selected from hydrogen, substituted or unsubstituted C1-C20 alkyl groups, substituted or unsubstituted C3-C20 cycloalkyl groups, substituted or unsubstituted C2-C20 alkenyl groups, substituted or unsubstituted C2-C20 alkynyl groups, substituted or unsubstituted C6-C30 aryl groups, or a combination thereof).

[0057] On the other hand, the compound represented by chemical formula 3 has -OR as a ligand. b Or -OC(=O)R c By including this, patterns formed using a semiconductor photoresist composition containing it can exhibit excellent limiting resolution.

[0058] Also, -OR b Or -OC(=O)R c The ligand can determine the solubility of the compound represented by chemical formula 3 in a solvent.

[0059] The aforementioned R 9 These are substituted or unsubstituted C1-C8 alkyl groups, substituted or unsubstituted C3-C8 cycloalkyl groups, substituted or unsubstituted C2-C8 aliphatic unsaturated organic groups containing one or more double or triple bonds, substituted or unsubstituted C6-C20 aryl groups, substituted or unsubstituted C4-C20 heteroaryl groups, carbonyl groups, ethoxy groups, propoxy groups, or combinations thereof. R b These are substituted or unsubstituted C1-C8 alkyl groups, substituted or unsubstituted C3-C8 cycloalkyl groups, substituted or unsubstituted C2-C8 alkenyl groups, substituted or unsubstituted C2-C8 alkynyl groups, substituted or unsubstituted C6-C20 aryl groups, or combinations thereof. Rc may be hydrogen, a substituted or unsubstituted C1-C8 alkyl group, a substituted or unsubstituted C3-C8 cycloalkyl group, a substituted or unsubstituted C2-C8 alkenyl group, a substituted or unsubstituted C2-C8 alkynyl group, a substituted or unsubstituted C6-C20 aryl group, or a combination thereof.

[0060] Said R 9 is a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, a tert-butyl group, a 2,2-dimethylpropyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, an ethenyl group, a propenyl group, a butenyl group, an ethynyl group, a propynyl group, a butynyl group, a phenyl group, a tolyl group, a xylene group, a benzyl group, a formyl group, an acetyl group, a propanoyl group, a butanoyl group, a pentanoyl group, an ethoxy group, a propoxy group, or a combination thereof, <0000�42>R b is an ethyl group, a propyl group, a butyl group, an isopropyl group, a tert-butyl group, a 2,2-dimethylpropyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, an ethenyl group, a propenyl group, a butenyl group, an ethynyl group, a propynyl group, a butynyl group, a phenyl group, a tolyl group, a xylene group, a benzyl group, or a combination thereof, R c may be hydrogen, an ethyl group, a propyl group, a butyl group, an isopropyl group, a tert-butyl group, a 2,2-dimethylpropyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, an ethenyl group, a propenyl group, a butenyl group, an ethynyl group, a propynyl group, a butynyl group, a phenyl group, a tolyl group, a xylene group, a benzyl group, or a combination thereof.

[0061] Further, the Sn-containing organometallic compound is represented by the following Chemical Formula 4 or Chemical Formula 5. [[ID=2l]]

Chemical Formula

[0062] The solvent contained in the semiconductor photoresist composition according to one embodiment may be an organic solvent and may include, but is not limited to, 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 monomethyl ether acetate, ethyl acetate, ethyl lactate), ketones (e.g., methyl ethyl ketone, 2-heptanone), and mixtures thereof.

[0063] In addition to the organometallic compound, (meth)acrylate polymer, and solvent, the semiconductor resist composition according to one embodiment may further contain a resin.

[0064] The aforementioned resin may be a phenolic resin containing at least one of the aromatic molecules listed in Group 2 below.

[0065] [ka]

[0066] The resin may have a weight-average molecular weight of 500 to 20,000.

[0067] The resin may be included in an amount of 0.1% to 50% by weight relative to the total content of the semiconductor photoresist composition.

[0068] When the aforementioned resin is included within the aforementioned content range, it can have excellent etching resistance and heat resistance.

[0069] On the other hand, the semiconductor photoresist composition preferably consists of the aforementioned organometallic compound, (meth)acrylate polymer, solvent, and resin.

[0070] The semiconductor photoresist composition according to the above-described embodiment may further contain additives. Examples of such additives include surfactants, crosslinking agents, leveling agents, organic acids, quenchers, or combinations thereof.

[0071] The surfactants may include, but are not limited to, alkylbenzene sulfonates, alkylpyridinium salts, polyethylene glycols, quaternary ammonium salts, or combinations thereof.

[0072] Examples of crosslinking agents include, but are not limited to, melamine-based crosslinking agents, substituted urea-based crosslinking agents, acrylic-based crosslinking agents, epoxy-based crosslinking agents, or polymer-based crosslinking agents. Examples of crosslinking agents having at least two crosslinking substituents include compounds such as methoxymethylated glycolyl, butoxymethylated glycolyl, methoxymethylated melamine, butoxymethylated melamine, methoxymethylated benzoguanamine, butoxymethylated benzoguanamine, 4-hydroxybutyl acrylate, acrylic acid, urethane acrylate, acrylic methacrylate, 1,4-butanediol diglycidyl ether, glycidol, diglycidyl 1,2-cyclohexanecarboxylate, trimethylpropane triglycidyl ether, 1,3-bis(glycidoxypropyl)tetramethyldisiloxane, methoxymethylated urea, butoxymethylated urea, or methoxymethylated thiourea.

[0073] Leveling agents are used to improve the flatness of the coating during printing, and commercially available, known leveling agents can be used.

[0074] The organic acid may be, but is not limited to, p-toluenesulfonic acid, benzenesulfonic acid, p-dodecylbenzenesulfonic acid, 1,4-naphthalenedisulfonic acid, methanesulfonic acid, fluorinated sulfonium salts, malonic acid, citric acid, propionic acid, methacrylic acid, oxalic acid, lactic acid, glycolic acid, succinic acid, or a combination thereof.

[0075] The quencher may be diphenyl(p-tolyl)amine, methyldiphenylamine, triphenylamine, phenylenediamine, naphthylamine, diaminonaphthalene, or a combination thereof.

[0076] The amount of these additives used can be easily adjusted according to the desired physical properties, and may even be omitted.

[0077] Furthermore, the semiconductor photoresist composition may further use a silane coupling agent as an adhesive enhancer to improve adhesion to the substrate (for example, to improve the adhesion of the semiconductor photoresist composition to the substrate). The silane coupling agent may be, but is not limited to, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltris(β-methoxyethoxy)silane; or 3-methacryloxypropyltrimethoxysilane, 3-acryloxpropyltrimethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane; or carbon-carbon unsaturated bond-containing silane compounds such as trimethoxy[3-(phenylamino)propyl]silane.

[0078] The semiconductor photoresist composition may not exhibit pattern distortion even when forming patterns with a high aspect ratio. Therefore, it can be used in photoresist processes using light with wavelengths of 5 nm to 150 nm, photoresist processes using light with wavelengths of 5 nm to 100 nm, photoresist processes using light with wavelengths of 5 nm to 80 nm, photoresist processes using light with wavelengths of 5 nm to 50 nm, photoresist processes using light with wavelengths of 5 nm to 30 nm, and photoresist processes using light with wavelengths of 5 nm to 20 nm to form fine patterns with widths of 5 nm to 100 nm, 5 nm to 80 nm, 5 nm to 50 nm, 5 nm to 40 nm, 5 nm to 30 nm, and 5 nm to 20 nm. Therefore, by using a semiconductor photoresist composition according to one embodiment, extreme ultraviolet lithography using an EUV light source with a wavelength of approximately 13.5 nm can be realized.

[0079] On the other hand, according to another embodiment, a method for forming a pattern using the semiconductor photoresist composition described above can be provided. For example, the manufactured pattern may be a photoresist pattern.

[0080] Another pattern formation method according to one embodiment includes the steps of forming an etching target film on a substrate, applying the aforementioned semiconductor photoresist composition on the etching target film to form a photoresist film, patterning the photoresist film to form a photoresist pattern, and etching the etching target film using the photoresist pattern as an etching mask.

[0081] The following describes a method for forming a pattern using the semiconductor photoresist composition described above, with reference to Figure 1. Figure 1 is a cross-sectional view illustrating a method for forming a pattern using the semiconductor photoresist composition according to the present invention. Referring to Figure 1(a), first, an object to be etched is prepared. An example of the object to be etched is a thin film 102 formed on a semiconductor substrate 100. The following description will only cover the case where the object to be etched is a thin film 102. To remove contaminants remaining on the thin film 102, the surface of the thin film 102 is cleaned. The thin film 102 may be, for example, a silicon nitride film, a polysilicon film, or a silicon oxide film.

[0082] Next, a resist underlayer forming composition for forming a resist underlayer 104 is coated onto the surface of the cleaned thin film 102 using a spin coating method. However, this 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, can also be used.

[0083] The above-mentioned resist underlayer coating process may be omitted, and the following description will focus on the case where the resist underlayer is coated.

[0084] Subsequently, drying and baking processes are performed to form a resist underlayer film 104 on the thin film 102. The baking process is carried out at approximately 100 to 500°C, for example, at approximately 100°C to 300°C.

[0085] The resist underlayer 104 is formed between the substrate 100 and the photoresist film 106. When irradiation lines reflected from the interface between the substrate 100 and the photoresist film 106 or from the interlayer hard mask scatter into unintended photoresist regions, this prevents non-uniformity of the photoresist linewidth and interference with pattern formation.

[0086] Referring to Figure 1(b), the above-mentioned semiconductor photoresist composition is coated onto the resist underlayer film 104 to form a photoresist film 106. The photoresist film 106 may also be formed by coating the above-mentioned semiconductor photoresist composition onto a thin film 102 formed on the substrate 100 and then curing it through a heat treatment process.

[0087] More specifically, the step of forming a pattern using a semiconductor photoresist composition may include the steps of applying the above-described semiconductor photoresist composition onto a substrate 100 on which a thin film 102 is formed by spin coating, slit coating, inkjet printing, etc., and drying the applied semiconductor photoresist composition to form a photoresist film 106.

[0088] Since the compositions for semiconductor photoresists have already been explained in detail, we will omit any redundant explanations.

[0089] Next, a first baking step is performed in which the substrate 100 on which the photoresist film 106 is formed is heated. The first baking step can be performed at a temperature of approximately 80°C to approximately 120°C.

[0090] Referring to Figure 1(c), the photoresist film 106 is selectively exposed using a patterned mask 110.

[0091] For example, examples of light that can be used in the exposure process include not only short-wavelength light such as the activation irradiation line i-line (wavelength 365 nm), KrF excimer laser (wavelength 248 nm), and ArF excimer laser (wavelength 193 nm), but also high-energy wavelength light such as EUV (Extreme UltraViolet; wavelength 13.5 nm) and E-Beam (electron beam).

[0092] More specifically, the exposure light according to one embodiment may be short-wavelength light having a wavelength range of 5 nm to 150 nm, or it may be light having a high-energy wavelength such as EUV (Extreme UltraViolet; wavelength 13.5 nm) or E-Beam (electron beam).

[0093] The exposed region 106b of the photoresist film 106 forms a polymer through crosslinking reactions such as condensation between organometallic compounds, thereby acquiring different solubility from the unexposed region 106a of the photoresist film 106.

[0094] Next, a second baking process is performed on the substrate 100. The second baking process can be carried out at a temperature of approximately 90°C to approximately 200°C. By performing the second baking process, the exposed region 106b of the photoresist film 106 becomes less soluble in the developer.

[0095] Figure 1(d) shows a photoresist pattern 108 formed by dissolving and removing the photoresist film 106a in the unexposed region using a developer. Specifically, the photoresist pattern 108 in the negative tone image is completed by dissolving and then removing the photoresist film 106a in the unexposed region using an organic solvent such as 2-heptanone.

[0096] As mentioned 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; alcohols such as 4-methyl-2-propanol, 1-butanol, isopropanol, 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 combinations thereof.

[0097] 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, examples of developers that can be used to form a positive tone image include quaternary ammonium hydroxide compositions such as tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, or combinations thereof.

[0098] As mentioned above, the photoresist pattern 108 formed by exposure with light having wavelengths such as i-line (wavelength 365nm), KrF excimer laser (wavelength 248nm), and ArF excimer laser (wavelength 193nm), as well as high-energy light such as EUV (Extreme UltraViolet; wavelength 13.5nm) and E-Beam (electron beam), can have a thickness width of 5nm to 100nm. For example, the photoresist pattern 108 may be formed with thickness widths of 5nm to 90nm, 5nm to 80nm, 5nm to 70nm, 5nm to 60nm, 5nm to 50nm, 5nm to 40nm, 5nm to 30nm, and 5nm to 20nm.

[0099] On the other hand, the photoresist pattern 108 can have 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 a pitch having a line width roughness of about 10 nm or less, about 5 nm or less, about 3 nm or less, or about 2 nm or less.

[0100] Next, the photoresist pattern 108 is used as an etching mask to etch the resist underlayer film 104. The organic film pattern 112 is formed by the etching process described above. The formed organic film pattern 112 may also have a width corresponding to the photoresist pattern 108.

[0101] Referring to Figure 1(e), the photoresist pattern 108 is applied as an etching mask to etch the exposed thin film 102. As a result, the thin film is formed as a thin film pattern 114.

[0102] The thin film 102 can be etched, for example, by dry etching using an etching gas, and the etching gas can be, for example, CHF3, CF4, Cl2, BCl3, or a mixture thereof.

[0103] In the previously performed exposure process, the thin film pattern 114 formed using the photoresist pattern 108 formed by the exposure process using an EUV light source can have a width corresponding to the photoresist pattern 108. For example, it can have a width of 5 nm to 100 nm, similar to the photoresist pattern 108. For example, the thin film pattern 114 formed by the exposure process using an EUV light source can have a width of 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 to 30 nm, or 5 nm to 20 nm, similar to the photoresist pattern 108, and more specifically, it can be formed with a width of 20 nm or less. [Examples]

[0104] The present invention will be described in more detail below through the examples of the manufacturing of the semiconductor photoresist composition described above. However, the technical features of the present invention are not limited by the following examples.

[0105] Synthesis of organometallic compounds Synthesis Example 1 Place 340.7g of t-butylSnPh and 300g of propionic acid in a 250ml two-necked round-bottom flask and heat under reflux for 24 hours.

[0106] The unreacted propionic acid is removed under reduced pressure to obtain the compound represented by the following chemical formula 5a. [ka]

[0107] Synthesis Example 2 Add 30 ml of anhydrous pentane to 10 g of t-AmylSnCl3, maintain the temperature at 0°C, then add 7.4 g of diethylamine and 6.1 g of ethaneol, and stir at room temperature for 1 hour. Once the reaction is complete, filter, concentrate, and vacuum dry to obtain the compound represented by the following chemical formula 6. [ka]

[0108] Synthesis Example 3 After dissolving 10 g of dibutyltin dichloride in 30 mL of ether, 70 mL of 1 M sodium hydroxide (NaOH) aqueous solution is added, and the mixture is stirred for 1 hour. After stirring, the resulting solid is filtered and washed three times with 25 mL of deionized water, and then dried under reduced pressure at 100°C to obtain an organometallic compound with a weight-average molecular weight of 1,500 represented by the following chemical formula 7. [ka]

[0109] Synthesis of (meth)acrylate polymers Synthesis Example 4 In a 250 mL 2-neck round-bottom flask, 20.82 g of Dibutyltin maleate (TCI), 1.00 g of Methyl methacrylate (SAMCHUN Chemical), 1.30 g of Hydroxy ethyl methacrylate (LGchem), 3.14 g of Dimethyl aminoethyl methacrylate (Sigma-Aldrich), and 132.70 g of Diisoamyl ether (DIAE) were added under a nitrogen atmosphere, and the flask was heated until the internal temperature reached 115°C. Once the internal temperature reached 115°C, 20.72 g of 33 wt% V-601 / DIAE solution (V-601) was added for 10 minutes, and after 6 hours, the reaction mixture was cooled to room temperature (25°C) to concentrate the reaction mixture to 50% solids. Approximately 270 g of heptane was added to the concentrated solution, and the resulting polymer was filtered. The filtered polymer is completely dissolved in 34 g of DIAE, followed by two steps of adding 270 g of heptane to induce precipitation. After complete drying, copolymer R1 (Mw=5,000) is finally obtained.

[0110] (In the following, w, x, y, and z represent mole percent.) [ka]

[0111] Synthesis Example 5 Copolymer R2 (Mw=5,000) was obtained by the same procedure as in Synthesis Example 4, except that 16.02 g of Trimethyltin styrene (TCI) was used instead of Dibutyltin maleate. [ka]

[0112] Synthesis Example 6 Copolymer R3 (Mw=5,000) was obtained by the same procedure as in Synthesis Example 4, except that 22.51 g of Tributyltin methacrylate (TCI) was used instead of Dibutyltin maleate. [ka]

[0113] Synthesis Example 7 Copolymer R4 (Mw=5,000) was obtained by carrying out the same procedure as in Synthesis Example 4, except that 22.27 g of Tributyltin vinyl (TCI) was used instead of Dibutyltin maleate. [ka]

[0114] Synthesis Example 8 Copolymer R5 (Mw=5,000) is obtained by carrying out the same procedure as in Synthesis Example 4, except that dimethyl aminoethyl methacrylate is not used. [ka]

[0115] Synthesis Example 9 Copolymer R6 (Mw=5,000) is obtained by carrying out the same procedure as in Synthesis Example 5, except that dimethyl aminoethyl methacrylate is not used. [ka]

[0116] Synthesis Example 10 Copolymer R7 (Mw=5,000) is obtained by carrying out the same procedure as in Synthesis Example 6, except that dimethyl aminoethyl methacrylate is not used. [ka]

[0117] Synthesis Example 11 In a 250 mL 2-neck round-bottom flask, 27.76 g of dibutyltin maleate (TCI), 2.00 g of methyl methacrylate (SAMCHUN Chemical), and 146.88 g of diisoamyl ether (DIAE) were added under a nitrogen atmosphere, and then the flask was heated until the internal temperature reached 115°C.

[0118] The subsequent steps are carried out in the same manner as in Synthesis Example 4 to obtain copolymer R8 (Mw=5,000). [ka]

[0119] Synthesis Example 12 In a 250 mL 2-neck round-bottom flask, 21.36 g of trimethyltin styrene (TCI), 2.00 g of methyl methacrylate (MMA, SAMCHUN Chemical), and 121.07 g of diisoamyl ether (DIAE) were added under a nitrogen atmosphere, and then the flask was heated until the internal temperature reached 115°C.

[0120] The subsequent steps are carried out in the same manner as in Synthesis Example 4 to obtain copolymer R9 (Mw=5,000). [ka]

[0121] Synthesis Example 13 In a 250 mL 2-neck round-bottom flask, 30.01 g of tributyltin methacrylate (TCI), 2.00 g of methyl methacrylate (MMA, SAMCHUN Chemical), and 155.88 g of diisoamyl ether (DIAE) were added under a nitrogen atmosphere, and then the flask was heated until the internal temperature reached 115°C.

[0122] The subsequent steps are carried out in the same manner as in Synthesis Example 4 to obtain copolymer R10 (Mw=5,000). [ka]

[0123] Synthesis Example 14 In a 250 mL 2-neck round-bottom flask, 34.7 g of dibutyltin maleate (TCI) and 166.43 g of diisoamyl ether (DIAE) were placed under a nitrogen atmosphere, and then the flask was heated until the internal temperature reached 115°C.

[0124] The subsequent steps are carried out in the same manner as in Synthesis Example 4 to obtain polymer R11 (Mw=5,000). [ka]

[0125] Synthesis Example 15 In a 250 mL 2-neck round-bottom flask, 26.7 g of trimethyltin styrene (TCI) and 134.42 g of diisoamyl ether (DIAE) were placed under a nitrogen atmosphere, and then the flask was heated until the internal temperature reached 115°C.

[0126] The subsequent steps are carried out in the same manner as in Synthesis Example 4 to obtain polymer R12 (Mw=5,000). [ka]

[0127] Synthesis Example 16 In a 250 mL 2-neck round-bottom flask, 37.51 g of tributyltin methacrylate (TCI) and 177.68 g of diisoamyl ether (DIAE) were placed under a nitrogen atmosphere, and then the flask was heated until the internal temperature reached 115°C.

[0128] The subsequent steps are carried out in the same manner as in Synthesis Example 4 to obtain polymer R13 (Mw=5,000). [ka]

[0129] Synthesis Example 17 Except for not using dibutyltin maleate, the synthesis is carried out in the same manner as in step 4 to obtain copolymer R14 (Mw=5,000). [ka]

[0130] Synthesis Example 18 In a 250 mL 2-neck round-bottom flask, 10.01 g of methyl methacrylate (SAMCHUN Chemical), 13.01 g of hydroxy ethyl methacrylate (LGchem), and 147.37 g of diisoamyl ether (DIAE) were added under a nitrogen atmosphere, and then the flask was heated until the internal temperature reached 115°C.

[0131] The subsequent steps are carried out in the same manner as in Synthesis Example 4 to obtain polymer R15 (Mw=5,000). [ka]

[0132] Synthesis Example 19 In a 250 mL 2-neck round-bottom flask, add 13.01 g of Hydroxy ethyl methacrylate (LGchem), 15.72 g of Dimethyl aminoethyl methacrylate (Sigma-Aldrich), and 132.70 g of Diisoamyl ether (DIAE) under a nitrogen atmosphere, then heat until the internal temperature reaches 115°C.

[0133] The subsequent steps are carried out in the same manner as in Synthesis Example 4 to obtain polymer R16 (Mw=5,000). [ka]

[0134] Synthesis Example 20 In a 250 mL 2-neck round-bottom flask, 10.01 g of methyl methacrylate (SAMCHUN Chemical), 15.72 g of dimethyl aminoethyl methacrylate (Sigma-Aldrich), and 158.19 g of diisoamyl ether (DIAE) were added under a nitrogen atmosphere, and then the flask was heated until the internal temperature reached 115°C.

[0135] The subsequent steps are carried out in the same manner as in Synthesis Example 4 to obtain polymer R17 (Mw=5,000). [ka]

[0136] (Manufacturing of semiconductor photoresist compositions) Examples 1-25 and Comparative Examples 1-7 The organometallic compounds represented by chemical formulas 5 to 7 obtained in Synthesis Examples 1 to 3 and polymers R1 to R17 obtained in Synthesis Examples 4 to 20 are dissolved in Propylene glycol methyl ether acetate (PGMEA) at a concentration of 3 wt% in the weight ratios shown in Table 1 below, and filtered through a 0.1 μm PTFE (polytetrafluoroethylene) syringe filter to produce the semiconductor photoresist compositions according to Examples 1 to 25 and Comparative Examples 1 to 7.

[0137] [Table 1]

[0138] Evaluation: Sensitivity and Line Edge Roughness (LER) The photoresist compositions according to the above examples and comparative examples were spin-coated onto a 200 mm circular silicon wafer whose surface was deposited with HMDS at 1500 rpm for 30 seconds, then baked at 110°C for 60 seconds (post-apply bake, PAB), and left at room temperature (23±2°C) for 30 seconds.

[0139] Subsequently, a linear array of 50 circular pads with a diameter of 500 μm was projected onto a wafer coated with the photoresist composition using EUV light (Lawrence Berkeley National Laboratory Micro Exposure Tool, MET). The pad exposure time was adjusted to ensure that the increasing EUV dose was applied to each pad.

[0140] Subsequently, the resist and substrate were exposed on a hot plate at 160°C for 120 seconds and then fired. The fired film was developed with PGMEA solvent to form a negative tone image. Finally, the process was completed by hot plate firing at 150°C for 2 minutes.

[0141] The residual resist thickness of the exposed pads was measured using a polarization measurement method (Ellipsometer). The remaining thickness was measured for each exposure amount and graphed as a function of the exposure amount. Sensitivity was measured, and LER was measured from FE-SEM images. After that, sensitivity and line edge roughness were evaluated according to the following criteria, and the results are shown in Table 2.

[0142] [Sensitivity evaluation criteria] -A: 50mJ / cm 2 less than -B: 50mJ / cm 2 That's all. [LER Evaluation Criteria] -○: 2nm or less, -△: More than 2nm and less than 5nm, -×: More than 5nm

[0143] [Table 2]

[0144] The results in Table 2 confirm that the patterns formed using the semiconductor photoresist compositions of Examples 1 to 25 exhibit superior sensitivity, LER, and resolution characteristics compared to Comparative Examples 1 to 7.

[0145] Although specific embodiments of the present invention have been described and illustrated above, it will be obvious to those ordinary skill in the art that the present invention is not limited to the described embodiments and can be modified and transformed in various ways without departing from the spirit and scope of the invention. Therefore, such modifications or variations should not be understood individually from the technical spirit or viewpoint of the present invention, and the modified embodiments should be considered to fall within the scope of the claims of the present invention. [Explanation of Symbols]

[0146] 100...Substrate, 102...Thin film, 104...Resist underlayer film, 106...Photoresist film, 106a...Unexposed region, 106b...Exposed region, 108...Photoresist pattern, 112...Organic film pattern, 110...Patterned mask, 114...Thin film pattern.

Claims

1. Organometallic compounds; (Meth)acrylate polymers containing at least one metal having a valency of 2 to 6; and solvent A composition for semiconductor photoresists, comprising:

2. The semiconductor photoresist composition according to claim 1, wherein the (meth)acrylate polymer comprises at least one structural unit derived from the monomer represented by the following chemical formula 1 and structural unit derived from the monomer represented by the following chemical formula 2: 【Chemistry 1】 In the aforementioned chemical formulas 1 and 2, R １ is hydrogen, or a substituted or unsubstituted C1-C10 alkyl group, M １ and M ２ These are, independently, metals with valencies of 2 to 6. L １ These are single bonds, -C(O)O-, substituted or unsubstituted C1-C10 alkylene groups, substituted or unsubstituted C6-C20 arylene groups, or combinations thereof. R ６ and R ７ are each independently a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C6-C20 aryl group, OR ｂ or OC(=O)R ｃ (where R ｂ and R ｃ are each independently a substituted or unsubstituted C1-C10 alkyl group), n1 is an integer between 1 and 5. n² is an integer between 0 and 4. If n1 and n2 are each 2 or greater, then each R ６ and R ７ They are either identical or different from one another.

3. Said M １ is Sn, Sb, or Te, Said M ２ is Sn or Sb, The aforementioned n1 is an integer from 1 to 3, The semiconductor photoresist composition according to claim 2, wherein n2 is an integer of 1 or 2.

4. Said M １ and M ２ These are Sn, The above n1 is an integer of 3, The semiconductor photoresist composition according to claim 2, wherein n2 is an integer of 2.

5. The monomers represented by chemical formulas 1 and 2 are selected from the group listed in Group I below, according to claim 2, for use in semiconductor photoresists: 【Chemistry 2】

6. The semiconductor photoresist composition according to claim 2, wherein the (meth)acrylate polymer contains at least one of the structural units derived from the monomer represented by chemical formula 1 and the structural unit derived from the monomer represented by chemical formula 2 in an amount of 50 to 100 mol%.

7. The semiconductor photoresist composition according to claim 1, wherein the (meth)acrylate polymer further comprises at least one of an alkyl (meth)acrylate monomer, a hydroxyl group-containing (meth)acrylate monomer, an amino group-containing (meth)acrylate monomer, and a combination thereof.

8. The semiconductor photoresist composition according to claim 1, wherein the (meth)acrylate polymer is contained in an amount of 0.001 to 10% by weight based on 100% by weight of the semiconductor photoresist composition.

9. The semiconductor photoresist composition according to claim 1, wherein the organometallic compound is contained in an amount of 0.5% to 30% by weight based on 100% by weight of the semiconductor photoresist composition.

10. The semiconductor photoresist composition according to claim 1, further comprising an additive of a surfactant, a crosslinking agent, a leveling agent, an organic acid, an inhibitor (quencher), or a combination thereof.

11. The semiconductor photoresist composition according to claim 1, wherein the organometallic compound is an organotin compound containing at least one of an organic oxy group and an organic carbonyl oxy group.

12. The organometallic compound is represented by the following chemical formula 3, and is the semiconductor photoresist composition according to claim 1: 【Transformation 3】 In the aforementioned chemical formula 3, R ９ These are selected from substituted or unsubstituted C1-C20 alkyl groups, substituted or unsubstituted C3-C20 cycloalkyl groups, substituted or unsubstituted C2-C20 alkenyl groups, substituted or unsubstituted C2-C20 alkynyl groups, substituted or unsubstituted C6-C30 aryl groups, and substituted or unsubstituted C6-C30 arylalkyl groups. R １０ ~R １２ These are, independently, substituted or unsubstituted C1-C20 alkyl groups, substituted or unsubstituted C3-C20 cycloalkyl groups, substituted or unsubstituted C2-C20 alkenyl groups, substituted or unsubstituted C2-C20 alkynyl groups, substituted or unsubstituted C6-C30 aryl groups, substituted or unsubstituted C6-C30 arylalkyl groups, alkoxy and aryloxy (-OR ｂ Here, R ｂ (These are substituted or unsubstituted C1-C20 alkyl groups, substituted or unsubstituted C3-C20 cycloalkyl groups, substituted or unsubstituted C2-C20 alkenyl groups, substituted or unsubstituted C2-C20 alkynyl groups, substituted or unsubstituted C6-C30 aryl groups, or combinations thereof), carboxyl groups (-O(CO)R ｃ , R ｃ (-NR) ｄ R ｅ Here, R ｄ and R ｅ Each is independently hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof), amidato (-NR ｆ (COR ｇ ), here R ｆ and R ｇ Each is independently a hydrogen atom, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof), amidinato (-NR ｈ C (NR ｉ ) R ｊ Here, R ｈ , R ｉ and R ｊ Each of these is independently hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof), alkylthio and arylthio (-SR ｋ Here, R ｋ (which is a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof), or a thiocarboxyl group (-S(CO)R ｌ , R ｌ (These are hydrogen, substituted or unsubstituted C1-C20 alkyl groups, substituted or unsubstituted C3-C20 cycloalkyl groups, substituted or unsubstituted C2-C20 alkenyl groups, substituted or unsubstituted C2-C20 alkynyl groups, substituted or unsubstituted C6-C30 aryl groups, or combinations thereof.) R １０ ~R １２ At least one of them is an alkoxy and an aryloxy (-OR ｂ Here, R ｂ (These are substituted or unsubstituted C1-C20 alkyl groups, substituted or unsubstituted C3-C20 cycloalkyl groups, substituted or unsubstituted C2-C20 alkenyl groups, substituted or unsubstituted C2-C20 alkynyl groups, substituted or unsubstituted C6-C30 aryl groups, or combinations thereof), carboxyl groups (-O(CO)R ｃ , R ｃ (-NR) ｄ R ｅ Here, R ｄ and R ｅ Each is independently hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof), amidato (-NR ｆ (COR ｇ ), here R ｆ and R ｇ Each is independently a hydrogen atom, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof), amidinato (-NR ｇ C (NR ｈ ) R ｉ Here, R ｈ , R ｉ and R ｊ Each of these is independently hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof), alkylthio and arylthio (-SR ｋ Here, R ｋ (which are substituted or unsubstituted C1-C20 alkyl groups, substituted or unsubstituted C3-C20 cycloalkyl groups, substituted or unsubstituted C2-C20 alkenyl groups, substituted or unsubstituted C2-C20 alkynyl groups, substituted or unsubstituted C6-C30 aryl groups, or combinations thereof), and thiocarboxyl groups (-S(CO)R ｌ , R ｌ (is selected from hydrogen, substituted or unsubstituted C1-C20 alkyl groups, substituted or unsubstituted C3-C20 cycloalkyl groups, substituted or unsubstituted C2-C20 alkenyl groups, substituted or unsubstituted C2-C20 alkynyl groups, substituted or unsubstituted C6-C30 aryl groups, or a combination thereof.)

13. The aforementioned R １０ ~R １２ At least one of them is an alkoxy and an aryloxy (-OR ｂ Here, R ａ (which are substituted or unsubstituted C1-C20 alkyl groups, substituted or unsubstituted C3-C20 cycloalkyl groups, substituted or unsubstituted C2-C20 alkenyl groups, substituted or unsubstituted C2-C20 alkynyl groups, substituted or unsubstituted C6-C30 aryl groups, or combinations thereof), and carboxyl groups (-O(CO)R ｃ , R ｃ The semiconductor photoresist composition according to claim 12, wherein is selected from hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof.

14. The aforementioned R ９ These are substituted or unsubstituted C1-C8 alkyl groups, substituted or unsubstituted C3-C8 cycloalkyl groups, substituted or unsubstituted C2-C8 aliphatic unsaturated organic groups containing one or more double or triple bonds, substituted or unsubstituted C6-C20 aryl groups, substituted or unsubstituted C4-C20 heteroaryl groups, carbonyl groups, ethoxy groups, propoxy groups, or combinations thereof. R ｂ These are substituted or unsubstituted C1-C8 alkyl groups, substituted or unsubstituted C3-C8 cycloalkyl groups, substituted or unsubstituted C2-C8 alkenyl groups, substituted or unsubstituted C2-C8 alkynyl groups, substituted or unsubstituted C6-C20 aryl groups, or combinations thereof. R ｃ The semiconductor photoresist composition according to claim 13, wherein is hydrogen, a substituted or unsubstituted C1-C8 alkyl group, a substituted or unsubstituted C3-C8 cycloalkyl group, a substituted or unsubstituted C2-C8 alkenyl group, a substituted or unsubstituted C2-C8 alkynyl group, a substituted or unsubstituted C6-C20 aryl group, or a combination thereof.

15. The organometallic compound is represented by the following chemical formula 4 or chemical formula 5, and is part of the semiconductor photoresist composition according to claim 1: 【Chemistry 4】 In the aforementioned chemical formula 4, R １３ is a C1-C31 hydrocarbyl group, where 0 < z ≤ 2 and 0 < (z + x) ≤ 4; 【Transformation 5】 In the aforementioned chemical formula 5, R １４ These are substituted or unsubstituted C1-C20 alkyl groups, substituted or unsubstituted C3-C20 cycloalkyl groups, substituted or unsubstituted C2-C20 aliphatic unsaturated organic groups containing one or more double or triple bonds, substituted or unsubstituted C6-C30 aryl groups, substituted or unsubstituted C4-C30 heteroaryl groups, carbonyl groups, ethylene oxide groups, propylene oxide groups, or combinations thereof. X is sulfur (S), selenium (Se), or tellurium (Te), Y is -OR ｍ or -OC(=O)R ｎ And, The aforementioned R ｍ These are substituted or unsubstituted C1-C20 alkyl groups, substituted or unsubstituted C3-C20 cycloalkyl groups, substituted or unsubstituted C2-C20 alkenyl groups, substituted or unsubstituted C2-C20 alkynyl groups, substituted or unsubstituted C6-C30 aryl groups, or combinations thereof. R ｎ These are hydrogen, substituted or unsubstituted C1-C20 alkyl groups, substituted or unsubstituted C3-C20 cycloalkyl groups, substituted or unsubstituted C2-C20 alkenyl groups, substituted or unsubstituted C2-C20 alkynyl groups, substituted or unsubstituted C6-C30 aryl groups, or combinations thereof. The terms a, b, c, and d are each independent integers between 1 and 20.

16. Steps include forming an etching target film on a substrate; A step of forming a photoresist film by applying the semiconductor photoresist composition according to any one of claims 1 to 15 onto the film to be etched; Steps of patterning the photoresist film to form a photoresist pattern; and A pattern formation method comprising the step of etching a film to be etched using the aforementioned photoresist pattern as an etching mask.

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