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

Abstract

This invention provides a semiconductor photoresist composition with excellent resolution characteristics and pattern adhesion by reducing the influence of variables during pattern formation and improving CD (critical dimension) stability. Alternatively, it provides a pattern formation method using this semiconductor photoresist composition. [Solution] The present invention provides a semiconductor photoresist composition comprising an organometallic compound, a halogen and an aromatic ring compound containing an electron-withdrawing group (EWG) other than a halogen, and a solvent, and a pattern formation method utilizing the same.

Description

Technical Field

[0001] The present invention relates to a composition for a semiconductor photoresist and a pattern forming method using the same.

Background Art

[0002] As one of the elemental technologies for manufacturing next-generation semiconductor devices, EUV (extreme ultraviolet light) lithography has attracted attention. EUV lithography is a pattern forming technology that uses EUV light with a wavelength of 13.5 nm as an exposure light source. According to EUV lithography, it has been demonstrated that extremely fine patterns (for example, 20 nm or less) can be formed in the exposure process of the semiconductor device manufacturing process.

[0003] The realization of extreme ultraviolet (EUV) lithography requires the development of compatible photoresists that can be performed with spatial resolutions of 16 nm or less. Currently, traditional chemically amplified (CA) photoresists are striving to meet the specifications for resolution, photospeed, and feature roughness, line edge roughness (or 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, while designed for high sensitivity, can sometimes experience further difficulties, partly under EUV exposure, because their typical elemental makeup reduces the photoresist absorbance at a wavelength of 13.5 nm, resulting in reduced sensitivity.

[0005] CA photoresists also sometimes experience difficulties due to roughness issues with small feature sizes, and experiments have shown that line edge roughness (LER) increases due to a decrease in photospeed, partly due to the nature of the acid-catalyzed process. Due to the shortcomings and problems of CA photoresists, the semiconductor industry has a demand for 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, where chemical modification via a non-chemical amplification mechanism makes them resistant to removal by developer compositions. 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-chemical amplification mechanism, and are less sensitive to the stochastic effect, resulting in less line edge roughness and fewer defects.

[0007] Inorganic photoresists based on tungsten and peroxopolyacids of tungsten mixed with niobium, titanium, and / or tantalum have been reported for use as radiation-sensitive materials for patterning (Patent Document 1, Non-Patent Document 1).

[0008] These materials are deep UV, X-ray, and electron beam sources and have been effective in patterning large features in bilayer configurations. More recently, impressive performance has been demonstrated when using cationic hafnium metal oxide sulfate (HfSOx) materials with peroxo complexing agents to image a 15 nm half-pitch (HP) by projection EUV exposure (Patent Document 2, Non-Patent Document 2). This system exhibits the best performance of non-CA photoresists and has a photosensitivity that approaches the requirements for a viable EUV photoresist. However, hafnium metal oxide sulfate materials with peroxo complexing agents have several practical drawbacks. Firstly, this material is coated with a highly corrosive sulfuric acid / hydrogen peroxide mixture, resulting in poor shelf-life stability. Secondly, it is a complex mixture, making structural modifications for performance improvement difficult. Thirdly, it must be developed with an extremely high concentration of TMAH (tetramethylammonium hydroxide) solution, such as 25 wt%.

[0009] Recently, there has been active research into tin-containing molecules, as they have been found to exhibit outstanding absorption of extreme ultraviolet light. In the case of organotin polymers, one such example, the alkyl ligand is dissociated by light absorption or the secondary electrons generated by it, and negative tone patterning is possible through crosslinking via oxo bonds with surrounding chains, preventing removal by organic developers. While such organotin polymers have shown a dramatic improvement in sensitivity while maintaining resolution and line edge roughness, further improvements in patterning properties are necessary for commercialization. [Prior art documents] [Patent Documents]

[0010] [Patent Document 1] U.S. Patent No. 5061599 [Patent Document 2] U.S. Patent Application Publication No. 2011 / 0045406 [Non-patent literature]

[0011] [Non-Patent Document 1] H. Okamoto, T. Iwayanagi, K. Mochiji, H. Umezaki, T. Kudo, Applied Physics Letters, 49(5), 298-300, 1986 [Non-Patent Document 2] JKStowers,A.Telecky,M.Kocsis,BLClark,DAKeszler,A.Grenville,CNAnderson,PPNaulleau,Proc.SPIE,7969,796915,2011 [Overview of the project] [Problems that the invention aims to solve]

[0012] One embodiment of the present invention provides a semiconductor photoresist composition with excellent resolution characteristics and pattern adhesion by reducing the influence of variables during pattern formation and improving CD (critical dimension) stability.

[0013] Another embodiment of the present invention provides a pattern formation method utilizing the semiconductor photoresist composition. [Means for solving the problem]

[0014] A semiconductor photoresist composition according to one embodiment of the present invention comprises an organometallic compound, a halogen, an aromatic ring compound containing an electron-withdrawing group (EWG) other than a halogen, and a solvent.

[0015] Another embodiment of the present invention provides a pattern formation method comprising the steps of: forming an etching target film on a substrate; applying the above-described 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. [Effects of the Invention]

[0016] A pattern formed using a semiconductor photoresist composition according to one embodiment of the present invention can achieve excellent resolution due to improved CD stability. [Brief explanation of the drawing]

[0017] [Figure 1] This is a cross-sectional view illustrating a pattern formation method using a semiconductor photoresist composition according to one embodiment. [Modes for carrying out the invention]

[0018] 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 are already publicly known will be omitted.

[0019] To clearly explain this description, unnecessary explanatory parts have been omitted, and the same or similar components are denoted by the same reference numerals throughout the specification. Furthermore, the dimensions and thicknesses of each component shown in the drawings are arbitrarily shown for explanatory purposes, and this description is not necessarily limited to those shown.

[0020] In the drawings, the thicknesses were enlarged to clearly represent multiple layers and regions. Furthermore, for explanatory purposes, the thicknesses of some layers and regions were exaggerated in the drawings. When a layer, film, region, plate, or other part is said to be "on top of" another part, this includes not only cases where it is "directly on top" of another part, but also cases where there is another part in between.

[0021] In this document, "substituted" means that the hydrogen atom is replaced by deuterium, halogen group, hydroxyl group, carboxyl group, thiol group, cyano group, nitro group, -NRR' (where R and R' are independently hydrogen, a substituted or unsubstituted saturated or unsaturated aliphatic hydrocarbon group having 1 to 30 carbon atoms, a substituted or unsubstituted saturated or unsaturated alicyclic hydrocarbon group having 3 to 30 carbon atoms, or a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 carbon atoms), -SiRR'R'' (where R, R', and R'' are independently hydrogen, a substituted or This means that the group is substituted with an unsubstituted saturated or unsaturated aliphatic hydrocarbon group having 1 to 30 carbon atoms, a substituted or unsubstituted saturated or unsaturated alicyclic hydrocarbon group having 3 to 30 carbon atoms, or a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 carbon atoms), an alkyl group having 1 to 30 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkylsilyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, a ring-forming aryl group having 6 to 30 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a sulfide group having 1 to 20 carbon atoms, or a combination thereof. "Unsubstituted" means that the hydrogen atom is not substituted by another substituent and remains as a hydrogen atom.

[0022] 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.

[0023] The alkyl group may be an alkyl group having 1 to 8 carbon atoms. For example, the alkyl group may be an alkyl group having 1 to 7 carbon atoms, an alkyl group having 1 to 6 carbon atoms, or an alkyl group having 1 to 5 carbon atoms. For example, the alkyl group having 1 to 5 carbon atoms 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.

[0024] In this document, "cycloalkyl group" refers to a monovalent cyclic aliphatic saturated hydrocarbon group unless otherwise defined.

[0025] The cycloalkyl group may be a cycloalkyl group having 3 to 8 carbon atoms, for example, a cycloalkyl group having 3 to 7 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, a cycloalkyl group having 3 to 5 carbon atoms, or a cycloalkyl group having 3 to 4 carbon atoms. For example, the cycloalkyl group may be a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, or a cyclohexyl group, but is not limited to these.

[0026] In this specification, “aryl group” means 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-ring polycyclic (i.e., rings sharing adjacent pairs of carbon atoms) functional groups.

[0027] In this specification, 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 through sigma bonds, or, if a 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 heteroatoms.

[0028] In this specification, "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.

[0029] In this specification, "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.

[0030] A semiconductor photoresist composition according to one embodiment will be described below.

[0031] A semiconductor photoresist composition according to one embodiment of the present invention may contain an organometallic compound, a linear carboxylic acid compound, a cyclic carboxylic acid compound represented by chemical formula 1, and a solvent.

[0032] A pattern formation method using a semiconductor photoresist composition containing an organometallic compound comprises the following steps: the photoresist composition is applied onto a film to be etched, thereby coating the film with the organometallic compound or its cluster molecules; and the organic matter in the photoresist composition is removed and the metal oxide is patterned through a first baking step, an exposure step, a second baking step, and a development step.

[0033] In this process, the patterning of metal oxides is affected by a variety of variables, including temperature, solvent, concentration, catalyst, and atmospheric conditions. In particular, the smaller the pattern size, the greater the relative influence of these variables. Typically, in the case of patterns formed by photoresist compositions containing organometallic compounds, the size is very small, ranging from a few nanometers to tens of nanometers, and the influence of process conditions on pattern formation becomes greater compared to existing photoresists.

[0034] In particular, it is known that pattern formation using photoresist compositions containing organometallic compounds is affected by the concentration of nitrogen oxides (NOx) in the atmosphere. NOx is highly reactive among substances present in the atmosphere and can react with moisture in the atmosphere, sunlight, etc., to cause phenomena such as smog. When the NOx concentration exceeds a certain level, problems have been observed where the pattern width and other parameters observed after development differ from the target values.

[0035] Therefore, in this invention, by introducing an aromatic ring compound having an electron-withdrawing group (EWG) other than halogen, it is possible to increase sensitivity to extreme ultraviolet light and improve pattern roughness. At the same time, by further introducing a halogen to the aromatic ring compound and coordinating it to the central metal of the organometallic compound, the reactivity of the central metal to radicals is reduced, and the generated radicals are stabilized and their reactivity is reduced, thereby developing a photoresist composition that can suppress the deformation phenomenon of pattern width caused by NOx.

[0036] Aromatic ring compounds containing halogens and electron-withdrawing groups other than halogens are represented by the following chemical formula 1. [Chemical formula 1] [ka] In chemical formula 1, Z is a halogen, EWG is an electron-withdrawing group, A is a substituted or unsubstituted aromatic ring with 6 to 20 carbon atoms. n1 and m1 are each independent integers greater than or equal to 1. n1 + m1 is an integer less than or equal to the valence of A.

[0037] A can be a divalent, trivalent, or tetravalent group depending on the number of linked substituents, allowing for a variety of variations.

[0038] For example, A may be a substituted or unsubstituted benzene ring, a substituted or unsubstituted naphthalene ring, a substituted or unsubstituted anthracene ring, a substituted or unsubstituted phenanthrene ring, a substituted or unsubstituted pyrene ring, a substituted or unsubstituted triphenylene ring, or a combination thereof.

[0039] For example, Z may be at least one selected from fluorine, chlorine, and iodine.

[0040] Electron-withdrawing groups are groups that draw electron density from atoms adjacent to themselves through resonance effects, inductive effects, hyperconjugation effects, or a combination thereof, and include weak electron-withdrawing groups such as halogens; intermediate electron-withdrawing groups such as aldehyde groups, carbonyl-containing groups, carboxyl groups, ester groups, or amide groups; or strong electron-withdrawing groups such as trihalide groups, cyano groups, sulfonyl groups, sulfonic acid bases, or nitro groups.

[0041] As an example, the electron-withdrawing group may be a cyano group, a cyano-containing group, a nitro group, an amino group, an ammonium group, an amidino group, a C1-C10 alkylamino group, a C6-C20 arylamino group, a C7-C20 arylalkylamino group, a C1-C10 carboxyl group, an ester group, a C1-C10 alkyl group substituted with a carbonyl group, a C2-C10 heteroalkyl group substituted with a carbonyl group, a ring-forming C6-C14 aryl group substituted with a carbonyl group, a ring-forming C2-C10 heteroaryl group substituted with a carbonyl group, an amide group, a sulfonyl group, a sulfonic acid base, or a ring-forming C2-C30 N-containing heteroaryl group.

[0042] As a specific example, the electron-withdrawing group may be a cyano group, nitro group, amino group, ammonium group, alkylamino group having 1 to 6 carbon atoms, arylamino group having 6 to 12 carbon atoms, arylalkylamino group having 7 to 12 carbon atoms, or a sulfonic acid base.

[0043] In one embodiment, chemical formula 1 is represented by either chemical formula 1-1 or chemical formula 1-3 below. [Chemical formula 1-1] [ka] [Chemical formula 1-2] [ka] [Chemical formula 1-3] [ka] In chemical formulas 1-1 to 1-3, Z is a halogen, EWG is an electron-withdrawing group, R 1 ~R 4 Each of these is independently a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, a nitro group, a substituted or unsubstituted C1-C30 amino group, a substituted or unsubstituted C1-C10 alkyl group, or a substituted or unsubstituted ring-forming C6-C20 aryl group.

[0044] In one embodiment, R 1 ~R 4 Each of these may independently be hydrogen, a halogen, a hydroxyl group, a substituted or unsubstituted C1-C10 alkyl group, or a substituted or unsubstituted ring-forming C6-C20 aryl group.

[0045] In one specific embodiment, R 1 ~R 4 Each of these may independently be hydrogen, a halogen, a hydroxyl group, a substituted or unsubstituted C1-C5 alkyl group, or a substituted or unsubstituted ring-forming C6-C12 aryl group.

[0046] For example, R 1 ~R 4 Each of these may independently be hydrogen, halogen, hydroxyl group, substituted or unsubstituted methyl group, substituted or unsubstituted ethyl group, substituted or unsubstituted propyl group, substituted or unsubstituted iso-propyl group, substituted or unsubstituted butyl group, substituted or unsubstituted sec-butyl group, substituted or unsubstituted iso-butyl group, substituted or unsubstituted tert-butyl group, substituted or unsubstituted phenyl group, or a combination thereof.

[0047] For example, aromatic ring compounds containing halogens and non-halogen electron-withdrawing groups are selected from the compounds listed in Group 1 below. [Group 1] [Chem.]

[0048] An aromatic ring compound containing a halogen and an electron-withdrawing group other than halogen may be contained in an amount of 0.01 to 25% by weight based on 100% by weight of the composition for semiconductor photoresist.

[0049] For example, an aromatic ring compound containing a halogen and an electron-withdrawing group other than halogen may be contained in an amount of 0.01 to 20% by weight, 0.01 to 10% by weight, 0.02 to 10% by weight, 0.03 to 10% by weight, or 0.05 to 10% by weight based on 100% by weight of the composition for semiconductor photoresist.

[0050] The organometallic compound may be contained in an amount of 0.5 to 30% by weight based on 100% by weight of the composition for semiconductor photoresist.

[0051] By including an aromatic ring compound containing a halogen and an electron-withdrawing group other than halogen in the composition for semiconductor photoresist according to one embodiment within the above content range, the sensitivity of the photoresist can be improved.

[0052] The organometallic compound may be an organotin compound containing at least one of an organic oxy group and an organic carbonyloxy group.

[0053] For example, the organometallic compound is represented by the following Chemical Formula 2. [Chemical Formula 2] [Chem.] In Chemical Formula 2, R 5This 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 ring-forming C6-C30 aryl groups, and substituted or unsubstituted C7-C30 arylalkyl groups. R 6 ~R 8 Each of these independently comprises 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 ring-forming C6-C30 aryl group, a substituted or unsubstituted C7-C30 arylalkyl group, an alkoxy, and an aryloxy (-OR) group. 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 ring-forming C6-C30 aryl groups, or combinations thereof), carboxyl groups (-O(CO)R c , R c (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 ring-forming C6-C30 aryl groups, or combinations thereof), alkylamides or dialkylamides or arylamides or diarylamides (-NR d R e Here, R d and R eEach of these 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 ring-forming C6-C30 aryl group, or a combination thereof), amidato (-NR f (COR g ), here R f and R g Each of these 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 ring-forming 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 ring-forming 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 ring-forming 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 ring-forming C6-C30 aryl groups, or combinations thereof.) R 6 ~R 8 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 ring-forming C6-C30 aryl groups, or combinations thereof), carboxyl groups (-O(CO)R c , R c (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 ring-forming C6-C30 aryl groups, or combinations thereof), alkylamides or dialkylamides or arylamides or diarylamides (-NR d R e Here, R d and R e Each of these 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 ring-forming C6-C30 aryl group, or a combination thereof), amidato (-NR f (COR g ), here R f and R gEach of these 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 ring-forming 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 ring-forming 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 ring-forming C6-C30 aryl groups, or combinations thereof) and thiocarboxyl groups (-S(CO)R l , R l (The carbon atom 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 ring-forming C6-C30 aryl group, or a combination thereof.)

[0054] R 6 ~R 8 At least one of them is an alkoxy and an aryloxy (-OR b Here, R b(wherein 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 ring-forming C6-C30 aryl group, or a combination thereof), and a carboxyl group (-O(CO)R c , R c (The carbon atom 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 ring-forming C6-C30 aryl group, or a combination thereof.)

[0055] On the other hand, the compound represented by chemical formula 2 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.

[0056] Also, -OR b Or -OC(=O)R c The ligand can determine the solubility of the compound represented by chemical formula 2 in a solvent.

[0057] R 5 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 ring-forming C6-C20 aryl groups, substituted or unsubstituted ring-forming C4-C20 heteroaryl groups, carbonyl groups, ethoxy groups, propoxy groups, or combinations thereof. R bThese 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 ring-forming C6-C20 aryl groups, or combinations thereof. R c This 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 ring-forming C6-C20 aryl group, or a combination thereof.

[0058] R 5 These are methyl group, ethyl group, propyl group, butyl group, isopropyl group, tert-butyl group, 2,2-dimethylpropyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, ethenyl group, propenyl group, butenyl group, ethynyl group, propynyl group, butynyl group, phenyl group, tolyl group, xylene group, benzyl group, formyl group, acetyl group, propanoyl group, butanoyl group, pentanoyl group, ethoxy group, propoxy group, or combinations thereof. R b These are ethyl group, propyl group, butyl group, isopropyl group, tert-butyl group, 2,2-dimethylpropyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, ethenyl group, propenyl group, butenyl group, ethynyl group, propynyl group, butynyl group, phenyl group, tolyl group, xylene group, benzyl group, or combinations thereof. R c This may be hydrogen, ethyl group, propyl group, butyl group, isopropyl group, tert-butyl group, 2,2-dimethylpropyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, ethenyl group, propenyl group, butenyl group, ethynyl group, propynyl group, butynyl group, phenyl group, tolyl group, xylene group, benzyl group, or a combination thereof.

[0059] Furthermore, organometallic compounds are represented by chemical formula 3 or chemical formula 4 below. [Chemical formula 3] R 9 z SnO (2-(z / 2)-(x / 2)) (OH) x In chemical formula 3, R 9 is a hydrocarbyl group having 1 to 31 carbon atoms, where 0 <z≦2であり、0<(z+x)≦4であり; [Chemical formula 4] R 10 a Sn b X c Y d In chemical formula 4, R 10 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 ring-forming C6-C30 aryl groups, substituted or unsubstituted ring-forming 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, 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 ring-forming C6-C30 aryl groups, or combinations thereof. R nThese 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 ring-forming C6-C30 aryl groups, or combinations thereof. a, b, c, and d are each independent integers between 1 and 20.

[0060] 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.

[0061] A semiconductor resist composition according to one embodiment may further contain a resin in addition to an organometallic compound, an aromatic ring compound containing a halogen and an electron-withdrawing group other than a halogen, and a solvent.

[0062] The resin may be a phenolic resin containing at least one aromatic molecule listed in Group 2 below. [Group 2] [ka]

[0063] The resin may have a weight-average molecular weight of 500 to 20,000.

[0064] 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.

[0065] When the resin is included within the above-mentioned content range, it can have excellent etching resistance and heat resistance.

[0066] On the other hand, the semiconductor photoresist composition preferably consists of an organometallic compound, an aromatic ring compound containing a halogen and an electron-withdrawing group other than a halogen, a solvent, and a resin.

[0067] The semiconductor photoresist compositions according to the embodiments described above may optionally further contain additives. Examples of additives include surfactants, crosslinking agents, leveling agents, organic acids, quenchers, or combinations thereof.

[0068] The surfactant may be, but is not limited to, alkylbenzene sulfonates, alkylpyridinium salts, polyethylene glycol, quaternary ammonium salts, or combinations thereof.

[0069] 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-cyclohexane dicarboxylate, trimethylpropane triglycidyl ether, 1,3-bis(glycidoxypropyl)tetramethyldisiloxane, methoxymethylated urea, butoxymethylated urea, or methoxymethylated thiourea.

[0070] Leveling agents are used to improve coating flatness during printing, and commercially available, known leveling agents can be used.

[0071] The organic acid may be, but is not limited to, p-toluenesulfonic acid, benzenesulfonic acid, p-dodecylbenzenesulfonic acid, 1,4-naphthalenedisulfonic acid, methanesulfonic acid, sulfonium fluoride salts, malonic acid, citric acid, propionic acid, methacrylic acid, oxalic acid, lactic acid, glycolic acid, succinic acid, or a combination thereof.

[0072] The quencher may be diphenyl(p-tolyl)amine, methyldiphenylamine, triphenylamine, phenylenediamine, naphthylamine, diaminonaphthalene, or a combination thereof.

[0073] The amount of these additives used can be easily adjusted according to the desired physical properties, and they can also be omitted.

[0074] Furthermore, to improve the adhesion to the substrate (for example, to improve the adhesion strength of the semiconductor photoresist composition to the substrate), a silane coupling agent may be added as an adhesion enhancer to the semiconductor photoresist composition. Examples of silane coupling agents include, but are not limited to, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltris(β-methoxyethoxy)silane; or 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane; and carbon-carbon unsaturated bond-containing silane compounds such as trimethoxy[3-(phenylamino)propyl]silane.

[0075] The semiconductor photoresist composition may not experience pattern collapse 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, such as, for example, a photoresist process using light with wavelengths of 5 nm to 100 nm, such as a photoresist process using light with wavelengths of 5 nm to 80 nm, such as a photoresist process using light with wavelengths of 5 nm to 80 nm, such as a photoresist process using light with wavelengths of 5 nm to 50 nm, such as a photoresist process using light with wavelengths of 5 nm to 30 nm, and such as a photoresist process using light with wavelengths of 5 nm to 20 nm, in order to form fine patterns with widths of 5 nm to 100 nm, such as a photoresist process using light with wavelengths of 5 nm to 80 nm, such as a photoresist process using light with wavelengths of 5 nm to 50 nm, such as a photoresist process using light with wavelengths of 5 nm to 30 nm, and such as a photoresist process using light with wavelengths of 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.

[0076] On the other hand, according to another embodiment, a method for forming a pattern using a semiconductor photoresist composition can be provided. For example, the manufactured pattern may be a photoresist pattern.

[0077] A pattern formation method according to one embodiment includes the steps of forming an etching target film on a substrate, applying a 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.

[0078] The following describes a method for forming a pattern using a semiconductor photoresist composition with reference to Figure 1. Figure 1 is a cross-sectional view illustrating a pattern formation method using the semiconductor photoresist composition according to the present invention.

[0079] Referring to Figure 1(a), first prepare the object to be etched. An example of the object to be etched may be a thin film 102 formed on a semiconductor substrate 100. The following explanation will only cover the case where the object to be etched is a thin film 102. Clean the surface of the thin film 102 to remove any contaminants remaining on it. The thin film 102 may be, for example, a silicon nitride film, a polysilicon film, or a silicon oxide film.

[0080] Next, a resist underlayer forming composition for forming a resist underlayer 104 on the surface of the cleaned thin film 102 is coated using a spin coating method. However, one embodiment is not necessarily limited thereto, 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.

[0081] The resist underlayer coating step can be omitted, and the following section describes the case where the resist underlayer is coated.

[0082] Subsequently, a drying and baking process is performed to form a resist underlayer film 104 on the thin film 102. The baking process is carried out at approximately 100°C to 500°C, for example, at approximately 100°C to 300°C.

[0083] The resist underlayer 104 is formed between the substrate 100 and the photoresist film 106. This prevents the scattering of irradiation lines reflected from the interface between the substrate 100 and the photoresist film 106 or from the interlayer hard mask into unintended photoresist regions, thereby preventing non-uniformity of the photoresist linewidth and interference with pattern formation.

[0084] Referring to Figure 1(b), a photoresist film 106 is formed by coating a semiconductor photoresist composition onto the resist underlayer film 104. The photoresist film 106 may also be formed by coating a thin film 102 formed on the substrate 100 with a semiconductor photoresist composition and then curing it by a heat treatment process.

[0085] More specifically, the step of forming a pattern using a semiconductor photoresist composition may include the steps of applying the 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.

[0086] Since the compositions for semiconductor photoresists have already been explained in detail, we will omit further explanation.

[0087] Next, a first baking step is performed to heat the substrate 100 on which the photoresist film 106 is formed. The first baking step can be performed at a temperature of approximately 80°C to approximately 120°C.

[0088] Referring to Figure 1(c), the photoresist film 106 is selectively exposed using a patterned mask 110.

[0089] As an example, examples of light that can be used in the exposure process include not only light with wavelengths such as the i-line activation irradiation diagram (wavelength 365 nm), KrF excimer laser (wavelength 248 nm), and ArF excimer laser (wavelength 193 nm), but also light with high energy wavelengths such as EUV (Extreme UltraViolet; wavelength 13.5 nm) and E-Beam (electron beam).

[0090] More specifically, the exposure light according to one embodiment may be light having a wavelength range of 5 nm to 150 nm, and may also be light having a high energy wavelength such as EUV (Extreme UltraViolet; wavelength 13.5 nm) or E-Beam (electron beam).

[0091] The exposed region 106b in the photoresist film 106 forms a polymer through crosslinking reactions such as condensation between organometallic compounds, resulting in a solubility different from that of the unexposed region 106a of the photoresist film 106.

[0092] 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 200°C. By performing the second baking process, the exposed region 106b of the photoresist film 106 becomes less soluble in the developer.

[0093] Figure 1(d) shows the photoresist pattern 108 formed by dissolving and removing the photoresist film 106a corresponding to the unexposed region using a developer. Specifically, the photoresist pattern 108 corresponding to the negative tone image is completed by dissolving the photoresist film 106a corresponding to the unexposed region using an organic solvent such as 2-heptanone and then removing it.

[0094] As described above, the developer used in the pattern formation method according to one embodiment may be an organic solvent. Examples of organic solvents used in the pattern formation 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.

[0095] However, the photoresist pattern according to one embodiment is not necessarily limited to being formed as a negative tone image, but can also 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.

[0096] As described above, the photoresist pattern 108 formed by exposure with light such as i-line (wavelength 365nm), KrF excimer laser (wavelength 248nm), 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 width of 5nm to 100nm in thickness. For example, the photoresist pattern 108 can be formed with 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.

[0097] On the other hand, the photoresist pattern 108 can have a half-pitch of approximately 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 approximately 10 nm or less, approximately 5 nm or less, approximately 3 nm or less, or approximately 2 nm or less.

[0098] Next, the resist underlayer film 104 is etched using the photoresist pattern 108 as an etching mask. This etching process forms an organic film pattern 112. The formed organic film pattern 112 can also have a width corresponding to the photoresist pattern 108.

[0099] 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 with the thin film pattern 114.

[0100] The thin film 102 can be etched, for example, by dry etching using an etching gas, which can be, for example, CHF3, CF4, Cl2, BCl3, or mixtures thereof.

[0101] The thin film pattern 114 formed using the photoresist pattern 108 formed by the exposure process using an EUV light source in the preceding exposure process 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 instance, the thin film pattern 114 formed by the exposure process using an EUV light source can have widths 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, and 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]

[0102] 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.

[0103] Synthesis of organometallic compounds Synthesis Example 1 340.7g of t-butylSnPh and 300g of propionic acid were placed in a 250ml two-necked round-bottom flask and heated under reflux for 24 hours.

[0104] The unreacted propionic acid was removed under reduced pressure to obtain the compound represented by the following chemical formula 5. [Chemical formula 5] [ka]

[0105] Synthesis Example 2 30 ml of anhydrous pentane was added to 10 g of t-AmylSnCl3, and the temperature was maintained at 0°C. Then, 7.4 g of diethylamine and 6.1 g of ethanol were added, and the mixture was stirred at room temperature for 1 hour. After the reaction was complete, the mixture was filtered, concentrated, and vacuum-dried to obtain the compound represented by the following chemical formula 6.

[0106] [Chemical formula 6] [ka]

[0107] Synthesis Example 3 10 g of dibutyltin dichloride was dissolved in 30 mL of ether, then 70 mL of 1 M sodium hydroxide (NaOH) aqueous solution was added, and the mixture was stirred for 1 hour. After stirring, the resulting solid was filtered, 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.

[0108] [Chemical formula 7] [ka]

[0109] (Manufacturing of semiconductor photoresist compositions) Examples 1-14 and Comparative Examples 1-4 The organometallic compounds represented by chemical formulas 5 to 7 obtained in Synthesis Examples 1 to 3, aromatic ring compounds A1 to A4 containing halogens and non-halogen EWGs, and at least one additive from trifluoroacetic acid were each dissolved in 3% by weight of Propylene glycol methyl ether acetate (PGMEA). After dissolving the additives in the weight ratios listed in Table 1 below, the mixture was filtered through a 0.1 μm PTFE (polytetrafluoroethylene) syringe filter to produce semiconductor photoresist compositions according to Examples 1 to 14 and Comparative Examples 1 to 4.

[0110] [Table 1]

[0111] [Aromatic ring compounds containing halogens and non-halogen EWGs] A1:1-iodo-4-nitrobenzene, A2:1-chloro-4-nitrobenzene, A3:4-iodobenzonitrile, A4:4-fluorobenzonitrile

[0112] Evaluation: CD uniformity and pattern adhesion evaluation The semiconductor resist compositions from Examples 1 to 14 and Comparative Examples 1 to 4 were spin-coated onto a 200 mm circular silicon wafer at 1500 rpm for 30 seconds, and then heated at 110°C for 60 seconds.

[0113] After that, a straight line array with a width of 180 nm was projected onto a wafer coated with a photoresist composition using KrF light. Then, the resist and the substrate were heated on a hot plate at a temperature of 180°C for 120 seconds. The baked film was developed with a PGMEA solvent to form a negative tone image. Finally, baking was performed at 200°C for 180 seconds to complete the process.

[0114] Using CD-SEM, when there is no NOx in the atmosphere and when the NOx concentration is 0.01 ppm or more, the CD values for each resist were measured respectively, and the CD change degree (ΔCD (%)) is shown in Table 2 below. The NOx concentration was measured using a Sky2000-NOx detector (Safe Gas). The formula for calculating the change degree is as follows. [Formula] ΔCD%=(CD ≧0.01ppm NOx / CD w / o NOx )

[0115] Also, for the pattern image formed by CD-SEM, if the pattern is partially separated or disappeared within a region of 15 μm × 15 μm, it is judged as "×", and if all are present, it is judged as "○", and the results are shown in Table 2 below.

Table 2

[0116] From the results in Table 2, it can be confirmed that the patterns formed using the semiconductor photoresist compositions according to Examples 1 to 14 are superior in resistance to NOx influence and pattern uniformity compared to Comparative Examples 1 to 4, and it can also be confirmed that the pattern adhesion is excellent.

[0117] Although specific embodiments of the present invention have been described and illustrated above, it is 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 can be said to fall within the scope of the claims of the present invention. [Explanation of symbols]

[0118] 100 circuit boards 102 Thin film 104 Resist underlayer 106 Photoresist film 106a Unexposed area 106b Exposed region 108 Photoresist Patterns 112 Organic film patterns 110 patterned masks 114 Thin Film Patterns

Claims

1. organometallic compounds, Aromatic ring compounds containing halogens and non-halogen electron-withdrawing groups, and A composition for semiconductor photoresists, comprising a solvent.

2. The aromatic ring compound containing the halogen and electron-withdrawing groups other than halogen is represented by the following chemical formula 1, according to the semiconductor photoresist composition of claim 1: [Chemical formula 1] 【Chemistry 1】 In the aforementioned chemical formula 1, Z is a halogen, EWG is an electron-withdrawing group, A is a substituted or unsubstituted aromatic ring with 6 to 20 carbon atoms. n1 and m1 are each independent integers greater than or equal to 1. n1 + m1 is an integer less than or equal to the valence of A.

3. The semiconductor photoresist composition according to claim 2, wherein A is a substituted or unsubstituted benzene ring, a substituted or unsubstituted naphthalene ring, a substituted or unsubstituted anthracene ring, a substituted or unsubstituted phenanthrene ring, a substituted or unsubstituted pyrene ring, a substituted or unsubstituted triphenylene ring, or a combination thereof.

4. The semiconductor photoresist composition according to claim 1, wherein the electron-withdrawing group is a cyano group, a cyano-containing group, a nitro group, an amino group, an ammonium group, an amidino group, a C1-C10 alkylamino group, a C6-C20 arylamino group, a C7-C20 arylalkylamino group, a C1-C10 carboxyl group, an ester group, a C1-C10 alkyl group substituted with a carbonyl group, a C2-C10 heteroalkyl group substituted with a carbonyl group, a ring-forming C6-C14 aryl group substituted with a carbonyl group, a ring-forming C2-C10 heteroaryl group substituted with a carbonyl group, an amide group, a sulfonyl group, a sulfonic acid base, or a ring-forming C2-C30 N-containing heteroaryl group.

5. The semiconductor photoresist composition according to claim 1, wherein the electron-withdrawing group is a cyano group, a nitro group, an amino group, an ammonium group, a C1-C6 alkylamino group, a C6-C12 arylamino group, a C7-C12 arylalkylamino group, or a sulfonic acid base.

6. The semiconductor photoresist composition according to claim 2, wherein the chemical formula 1 is represented by any one of the following chemical formulas 1-1 to 1-3: [Chemical formula 1-1] 【Chemistry 2】 [Chemical formula 1-2] 【Transformation 3】 [Chemical formula 1-3] 【Chemistry 4】 In the aforementioned chemical formulas 1-1 to 1-3, Z is a halogen, EWG is an electron-withdrawing group, R １ ~R ４ Each of these is independently a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, a nitro group, a substituted or unsubstituted C1-C30 amino group, a substituted or unsubstituted C1-C10 alkyl group, or a substituted or unsubstituted ring-forming C6-C20 aryl group.

7. The aromatic ring compound containing the halogen and electron-withdrawing groups other than halogen is one selected from the compounds listed in Group 1 below, according to claim 1, for semiconductor photoresist composition: [Group 1] 【Transformation 5】 。

8. The semiconductor photoresist composition according to claim 1, wherein the aromatic ring compound containing the halogen and electron-withdrawing groups other than halogen is contained in an amount of 0.01 to 25% 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 comprising 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 2, and is part of the semiconductor photoresist composition according to claim 1: [Chemical formula 2] 【Transformation 6】 In the aforementioned chemical formula 2, R ５ 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 ring-forming C6-C30 aryl groups, and substituted or unsubstituted C7-C30 arylalkyl groups. R ６ ~R ８ each independently represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 ring-forming carbon atoms, a substituted or unsubstituted arylalkyl group having 7 to 30 carbon atoms, alkoxy and aryloxy (—OR ｂ , where R ｂ is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 ring-forming carbon atoms, or a combination thereof), a carboxyl group (—O(CO)R ｃ , R ｃ is hydrogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 ring-forming carbon atoms, or a combination thereof), an alkylamide or dialkylamide or arylamide or diarylamide (—NR ｄ R ｅ , where R ｄ and R ｅ each independently represents hydrogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 ring-forming carbon atoms, or a combination thereof), an amidato (—NR ｆ (COR ｇ ), where 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 ring-forming 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 ring-forming 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 ring-forming 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 ring-forming C6-C30 aryl groups, or combinations thereof.) R ６ ~R ８ 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 ring-forming C6-C30 aryl groups, or combinations thereof), carboxyl groups (-O(CO)R ｃ , R ｃ (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 ring-forming C6-C30 aryl groups, or combinations thereof), alkylamide or dialkylamide or arylamide or diarylamide (-NR ｄ R ｅ Here, R ｄ and R ｅ Each of these 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 ring-forming 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 ring-forming 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 ring-forming 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 ring-forming C6-C30 aryl group, or a combination thereof) and a thiocarboxyl group (-S(CO)R ｌ , R ｌ (The carbon atom 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 ring-forming C6-C30 aryl group, or a combination thereof.)

13. The aforementioned R ６ ~R ８ At least one of them is an alkoxy and an aryloxy (-OR ｂ Here, R ｂ (wherein 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 ring-forming C6-C30 aryl group, or a combination thereof), and a carboxyl group (-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 ring-forming C6-C30 aryl group, or a combination thereof.

14. The aforementioned R ５ 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 ring-forming C6-C20 aryl groups, substituted or unsubstituted ring-forming 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 ring-forming 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 ring-forming C6-C20 aryl group, or a combination thereof.

15. The organometallic compound is represented by the following chemical formula 3 or chemical formula 4, and is part of the semiconductor photoresist composition according to claim 1: [Chemical formula 3] R ９ ｚ SnO （２－（ｚ／２）－（ｘ／２）） (OH) ｘ In the aforementioned chemical formula 3, R ９ is a hydrocarbyl group having 1 to 31 carbon atoms, where 0 < z ≤ 2 and 0 < (z + x) ≤ 4; [Chemical formula 4] R １０ ａ Sn ｂ X ｃ Y ｄ In the aforementioned chemical formula 4, R １０ 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 ring-forming C6-C30 aryl groups, substituted or unsubstituted ring-forming 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 ring-forming 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 ring-forming C6-C30 aryl groups, or combinations thereof. The terms a, b, c, and d are each independent integers between 1 and 20.

16. The steps include forming an etching target film on a substrate, The steps include applying the semiconductor photoresist composition according to any one of claims 1 to 15 onto the etchable film to form a photoresist film, The steps include: patterning the aforementioned photoresist film to form a photoresist pattern; 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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