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, as well as a pattern formation method using the above composition, by reducing the influence of variables during pattern formation and improving CD (critical dimension) stability. [Solution] The present invention relates to a semiconductor photoresist composition comprising an organometallic compound, a compound containing one or more nitro groups and one or more hydroxyl groups, and a solvent, and a pattern formation method utilizing the same.

Description

[Technical Field]

[0001] The present invention relates to a semiconductor photoresist composition and a pattern formation method utilizing 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. EUV lithography has been demonstrated to be able to 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 polymeric photoresists limits resolution at small feature sizes, a fact long known in e-beam lithography. Chemically amplified (CA) photoresists are designed for high sensitivity, but their typical elemental makeup reduces the absorbance of the photoresist at a wavelength of 13.5 nm, and as a result, they may experience additional difficulties under EUV exposure, in part because of the reduced sensitivity.

[0005] CA photoresists may also experience difficulties due to roughness issues at small feature sizes, and experimentally, it has been shown that line edge roughness (LER) increases as photospeed decreases, in part due to the nature of the acid catalysis process. Due to the drawbacks and problems of CA photoresists, there is a need in the semiconductor industry for new types of high-performance photoresists.

[0006] To overcome the shortcomings of the chemically amplified organic-based photosensitive compositions described above, inorganic-based photosensitive compositions have been studied. In the case of inorganic-based photosensitive compositions, they are mainly used for negative tone patterning that has resistance to removal by a developer composition through chemical modification by a non-chemically amplified mechanism. In the case of inorganic-based compositions, they contain inorganic elements that have a higher EUV absorption rate compared to hydrocarbons, and it is known that they can ensure sensitivity even with a non-chemically amplified mechanism and are less sensitive to the stochastic effect, resulting in fewer line edge roughness and defects.

[0007] Inorganic photoresists based on tungsten and peroxopolyacids of tungsten mixed with niobium, titanium, and / or tantalum have been reported for 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 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 a peroxo complexing agent to image a 15 nm half-pitch (HP) by projection EUV lithography (US2011-0045406; JKStowers, A.Telecky, M.Kocsis, BLClark, DAKeszler, A.Grenville, CNAnderson, PPNaulleau, Proc.SPIE, 7969, 796915, 2011). This system exhibits 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, they are complex mixtures, making structural modifications for performance improvement difficult. Thirdly, they must be developed with extremely high concentrations of TMAH (tetramethylammonium hydroxide) solution, such as 25 wt%, or similar.

[0009] Recently, there has been active research into tin-containing molecules, as they are known to exhibit outstanding absorption of extreme ultraviolet light. In the case of organotin polymers, one such polymer, 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. Such organotin polymers have shown a dramatic improvement in sensitivity while maintaining resolution and line edge roughness, but further improvements in the aforementioned patterning properties are necessary for commercialization. [Overview of the project] [Problems that the invention aims to solve]

[0010] 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.

[0011] Another embodiment of the present invention provides a pattern formation method using the semiconductor photoresist composition described above. [Means for solving the problem]

[0012] A composition for semiconductor photoresists according to one embodiment of the present invention comprises an organometallic compound, a compound containing one or more nitro groups and one or more hydroxyl groups, and a solvent. [Effects of the Invention]

[0013] 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]

[0014] [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]

[0015] 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, descriptions of functions or configurations that are already publicly known will be omitted.

[0016] 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.

[0017] 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.

[0018] 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 unsubstituted This means that the group is substituted with 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, an 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.

[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 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.

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

[0022] 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, or a cycloalkyl group having 3 to 6 carbon atoms. For example, the cycloalkyl group may be, but is not limited to, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, or a cyclohexyl group.

[0023] 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.

[0024] 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 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 one to three of the heteroatoms.

[0025] 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.

[0026] 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.

[0027] A semiconductor photoresist composition according to one embodiment will be described below.

[0028] A composition for semiconductor photoresists according to one embodiment of the present invention may include an organometallic compound, a compound comprising one or more nitro groups and one or more hydroxyl groups, and a solvent.

[0029] 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.

[0030] In this process, the patterning of the metal oxide is affected by various variables such as temperature, solvent, concentration, catalyst, and atmospheric conditions, and in particular, the smaller the pattern size, the greater the relative influence. 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 is greater compared to existing photoresists.

[0031] 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.

[0032] Therefore, in this invention, we aimed to develop a photoresist composition that can suppress the deformation phenomenon of pattern width caused by NOx by introducing a compound containing one or more nitro groups and one or more hydroxyl groups to reduce the reactivity of the central metal in the organometallic compound to radicals, and stabilizing the generated radicals to reduce their reactivity.

[0033] The compound comprising one or more nitro groups and one or more hydroxyl groups may have a chain-like or cyclic structure, and may be one or more compounds selected from the group consisting of saturated or unsaturated aliphatic compounds comprising one or more nitro groups and one or more hydroxyl groups, aromatic ring compounds comprising one or more nitro groups and one or more hydroxyl groups, and heterocyclic compounds comprising one or more nitro groups and one or more hydroxyl groups.

[0034] The compound containing one or more nitro groups and one or more hydroxyl groups may be a compound represented by the following chemical formula 1: [ka]

[0035] In the above chemical formula 1, A is a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, a substituted or unsubstituted alkenylene group having 2 to 10 carbon atoms, a substituted or unsubstituted alkynylene group having 2 to 10 carbon atoms, a substituted or unsubstituted heteroalkylene group having 1 to 10 carbon atoms, a substituted or unsubstituted heteroalkenylene group having 2 to 10 carbon atoms, or a substituted or unsubstituted heteroalkylynylene group having 2 to 10 carbon atoms, and is one or more selected from the group consisting of substituted or unsubstituted cycloalkanes having 3 to 20 carbon atoms, substituted or unsubstituted cycloalkenes having 3 to 20 carbon atoms, substituted or unsubstituted aromatic rings having 6 to 20 carbon atoms, and substituted or unsubstituted heteroaromatic rings having 3 to 20 carbon atoms, and n and m are each independently integers of 1 or more, and n+m is an integer less than or equal to the bond valency of A.

[0036] In the above chemical formula 1, A is, for example, one or more selected from the group consisting of substituted or unsubstituted alkylene groups having 1 to 10 carbon atoms, substituted or unsubstituted alkenylene groups having 2 to 10 carbon atoms, substituted or unsubstituted alkylylene groups having 2 to 10 carbon atoms, substituted or unsubstituted heteroalkylene groups having 1 to 10 carbon atoms, substituted or unsubstituted cycloalkanes having 3 to 20 carbon atoms, substituted or unsubstituted cycloalkenes having 3 to 20 carbon atoms, substituted or unsubstituted aromatic rings having 6 to 20 carbon atoms, and substituted or unsubstituted heteroaromatic rings having 3 to 20 carbon atoms. For example, A may be one or more selected from the group consisting of substituted or unsubstituted alkylene groups having 1 to 10 carbon atoms, substituted or unsubstituted aromatic rings having 6 to 20 carbon atoms, and substituted or unsubstituted heteroaromatic rings having 3 to 20 carbon atoms. Furthermore, for example, it may be one or more selected from the group consisting of substituted or unsubstituted alkylene groups having 1 to 5 carbon atoms, substituted or unsubstituted aromatic rings having 6 to 10 carbon atoms, and substituted or unsubstituted heteroaromatic rings having 3 to 10 carbon atoms, for example, one or more selected from the group consisting of substituted or unsubstituted methylene groups, substituted or unsubstituted ethylene groups, substituted or unsubstituted propylene groups, substituted or unsubstituted benzenes, and substituted or unsubstituted quinolines.

[0037] The compound comprising one or more nitro groups and one or more hydroxyl groups may be one or more compounds selected from the compounds listed in Group 1 below: [ka]

[0038] The compound containing one or more nitro groups and one or more hydroxyl groups may be present in an amount of 0.01 to 5 parts by weight based on 100 parts by weight of the organometallic compound. When the compound containing one or more nitro groups and one or more hydroxyl groups is included within the above content range, it is possible to achieve the effect of maintaining pattern formation while suppressing the influence of NOx.

[0039] The compound comprising one or more nitro groups and one or more hydroxyl groups may be present in an amount of 0.001 to 10% by weight relative to 100% by weight of the semiconductor photoresist composition. When the compound comprising one or more nitro groups and one or more hydroxyl groups is included within the above content range, it is possible to achieve the effect of maintaining pattern formation while suppressing the effects of NOx.

[0040] The compound comprising one or more nitro groups and one or more hydroxyl groups according to one embodiment may be included in an amount of 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 semiconductor photoresist composition.

[0041] The organometallic compound may be included in an amount of 0.5% to 30% by weight relative to 100% by weight of the semiconductor photoresist composition. By including the organometallic compound within the above content range in the semiconductor photoresist composition according to one embodiment, the sensitivity of the photoresist can be improved.

[0042] In one embodiment of a semiconductor photoresist composition, the organometallic compound may be contained in an amount of 0.5% to 30% by weight, for example, 1% to 30% by weight, 1% to 25% by weight, for example, 1% to 20% by weight, for example, 1% to 15% by weight, for example, 1% to 10% by weight, for example, 1% to 5% by weight, based on 100% by weight of the semiconductor photoresist composition.

[0043] The organometallic compound may be an organotin compound containing at least one of an organooxy group and an organocarbonyloxy group.

[0044] The aforementioned organometallic compound is represented by the following chemical formula 2. [ka]

[0045] In the aforementioned chemical formula 2, R 1is selected from 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 carbon atoms, and a substituted or unsubstituted arylalkyl group having 7 to 30 carbon atoms, R 2 ~R 4 are each independently 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 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 carbon atoms, or a combination thereof), a carboxyl group or an acyloxy 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 carbon atoms, or a combination thereof), an alkylamide or a dialkylamide (-NR d R e , where 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 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 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 an acylthio 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 2 ~R 4 At least one of them is an alkoxy and an aryloxy (-OR b Here, R b (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), a carboxyl group, or an acyloxy group (-O(CO)R c , R c (where 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 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), 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 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 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 acylthio groups (-S(CO)R l , R l (The group 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.)

[0046] The aforementioned R 2 ~R 4 At least one of them is an alkoxy and an aryloxy (-OR b Here, R b(wherein C1-C20 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), and a carboxyl group or acyloxy group (-O(CO)R c , R c (The group 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.)

[0047] 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.

[0048] 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.

[0049] The aforementioned R 1 This is selected from 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, and substituted or unsubstituted C7-C20 arylalkyl groups. 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 C6-C20 aryl groups, or combinations thereof. R c This can 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.

[0050] The aforementioned R 1 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, 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 group 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.

[0051] Furthermore, the Sn-containing organometallic compound is represented by the following chemical formula 3 or chemical formula 4. [ka] In the aforementioned chemical formula 3, R 5 is a hydrocarbyl group having 1 to 31 carbon atoms, where 0 <z≦2であり、0<(z+x)≦4であり;

[0052] [ka] In the above chemical formula 4, R 6 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 aforementioned a, b, c, and d are each independent integers between 1 and 20.

[0053] A semiconductor resist composition according to one embodiment may further contain a resin in addition to the organometallic compound, the compound comprising one or more nitro groups and one or more hydroxyl groups, and the solvent.

[0054] The aforementioned resin may be a phenolic resin containing at least one of the aromatic molecules listed in Group 2 below. [ka]

[0055] The aforementioned resin may have a weight-average molecular weight of 500 g / mol to 20,000 g / mol.

[0056] On the other hand, the semiconductor photoresist composition preferably comprises the organometallic compound described above, a compound containing one or more nitro groups and one or more hydroxyl groups, a solvent, and a resin.

[0057] 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.

[0058] The semiconductor photoresist compositions according to the embodiments described above may optionally further contain additives. Examples of such additives include surfactants, crosslinking agents, leveling agents, organic acids, quenchers, or combinations thereof.

[0059] The surfactant may be, but is not limited to, alkylbenzene sulfonates, alkylpyridinium salts, polyethylene glycol, quaternary ammonium salts, or combinations thereof.

[0060] 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.

[0061] Leveling agents are used to improve coating flatness during printing, and commercially available, known leveling agents can be used.

[0062] Organic acids may include, but are 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 combinations thereof.

[0063] The quencher may be diphenyl(p-tolyl)amine, methyldiphenylamine, triphenylamine, phenylenediamine, naphthylamine, diaminonaphthalene, or a combination thereof.

[0064] The amount of these additives used can be easily adjusted according to the desired physical properties, and they can also be omitted.

[0065] Furthermore, the semiconductor photoresist composition may be further enhanced with a silane coupling agent as an adhesion enhancer to improve adhesion to the substrate (for example, to improve the adhesion strength 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-acryloxypropyltrimethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane; or carbon-carbon unsaturated bond-containing silane compounds such as trimethoxy[3-(phenylamino)propyl]silane.

[0066] 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 a photoresist process using light with wavelengths of 5 nm to 1080 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 40 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 fine patterns with widths of 5 nm to 80 nm, such as fine patterns with widths of 5 nm to 70 nm, such fine patterns with widths of 5 nm to 50 nm, such fine patterns with widths of 5 nm to 40 nm, such fine patterns with widths of 5 nm to 30 nm, and such fine patterns with widths 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.

[0067] On the other hand, according to another embodiment, a method for forming a pattern using the semiconductor photoresist composition can be provided. For example, the manufactured pattern may be a photoresist pattern.

[0068] A pattern formation method according to one embodiment includes the steps of forming an etching target film on a substrate, applying the 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.

[0069] 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 pattern formation method using the semiconductor photoresist composition according to the present invention.

[0070] Referring to Figure 1(a), first, the 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 explanation will only cover the case where the object to be etched is a thin film 102. The surface of the thin film 102 is cleaned to remove any contaminants remaining on the thin film 102. The thin film 102 may be, for example, a silicon nitride film, a polysilicon film, or a silicon oxide film.

[0071] 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, 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.

[0072] The above-mentioned resist underlayer coating step can be omitted, and the following description will focus on the case where the resist underlayer is coated.

[0073] 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 to 500°C, for example, at approximately 100°C to 300°C.

[0074] 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.

[0075] Referring to Figure 1(b), the semiconductor photoresist composition is coated onto the resist underlayer film 104 to form a photoresist film 106. The photoresist film 106 may be formed by coating the semiconductor photoresist composition onto a thin film 102 formed on the substrate 100 and then curing it by a heat treatment process.

[0076] 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.

[0077] Since the compositions for semiconductor photoresists have already been explained in detail, we will omit further explanation.

[0078] 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.

[0079] Referring to Figure 1(c), the photoresist film 106 is selectively exposed using a patterned mask 110.

[0080] As an example, examples of light that can be used in the exposure process include not only light such as the activation irradiation diagram i-line (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).

[0081] More specifically, the exposure light according to one embodiment may be light having a wavelength range of 5 nm to 150 nm, and may be light having a high energy wavelength such as EUV (Extreme UltraViolet; wavelength 13.5 nm) or E-Beam (electron beam).

[0082] 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.

[0083] Next, a second baking step is performed on the substrate 100. The second baking step can be performed at a temperature of approximately 90°C to approximately 200°C. By performing the second baking step, the exposed region 106b of the photoresist film 106 becomes less soluble in the developer.

[0084] Figure 1(d) shows a 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 and then removing the photoresist film 106a corresponding to the unexposed region using an organic solvent such as 2-heptanone.

[0085] 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.

[0086] 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.

[0087] As described 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 width of 5nm to 100nm 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.

[0088] 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.

[0089] Next, the photoresist pattern 108 is used as an etching mask to etch the resist underlayer film 104. 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.

[0090] 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.

[0091] 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.

[0092] 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]

[0093] 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.

[0094] Synthesis of organometallic compounds Synthesis Example 1 0.7 g of t-butylSnPh3 and 300 g of propionic acid were placed in a 250 ml two-necked round-bottom flask and heated under reflux for 24 hours. Unreacted propionic acid was removed under reduced pressure to obtain the compound represented by the following chemical formula 5. [ka]

[0095] 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. [ka]

[0096] (Manufacturing of semiconductor photoresist compositions) Examples 1-9 and Comparative Examples 1-2 The organometallic compounds represented by chemical formulas 5 and 6, obtained in Synthesis Example 1 and Synthesis Example 2, were dissolved in 3% by weight of Propylene glycol methyl ether acetate (PGMEA). Then, additives containing one or more nitro groups and one or more hydroxyl groups were added and dissolved in the solution in the weight ratio with respect to the organometallic compounds as shown in Table 1 below. The solution was then filtered through a 0.1 μm PTFE (polytetrafluoroethylene) syringe filter to produce semiconductor photoresist compositions according to the examples and comparative examples. The compositions were coated onto a silicon wafer to a thickness of 240 Å, and then a patterned film was produced through PAB, exposure, PEB, and development processes.

[0097] [Table 1]

[0098] C1: 2-Nitroethanol C2: 4-Nitrophenol C3: 8-Hydroxy-5-nitroquinoline C4: Nitroethane C5: 2-Pentanol

[0099] Evaluation: Evaluation of CD uniformity The semiconductor resist compositions according to Examples 1 to 8 and Comparative Examples 1 to 3 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.

[0100] Subsequently, a linear array with a width of 180 nm was projected onto a wafer coated with the photoresist composition using KrF light. Then, the resist and substrate were heated on a hot plate at 180°C for 180 seconds. The fired film was developed with PGMEA solvent to form a negative tone image. Finally, the process was completed by firing at 200°C for 180 seconds.

[0101] Using a CD-SEM, the CD value for each resist was measured both when there was no NOx in the atmosphere and when the NOx concentration was 0.015 ppm or higher. The degree of CD change (ΔCD(%)) is shown in Table 2 below. The NOx concentration was measured using a Sky2000-NOx detector (safe gas). The formula for calculating the degree of change is as follows. [formula] ΔCD%=((CD ≧0.015ppm NOx / CD w / o NOx )-1)×100

[0102] [Table 2]

[0103] The results in Table 2 show that the patterns formed using the semiconductor photoresist compositions of Examples 1-8 exhibited a smaller degree of CD change in response to NOx concentration changes compared to Comparative Examples 1-3, indicating superior resistance to NOx influence.

[0104] 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]

[0105] 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; Compounds comprising one or more nitro groups and one or more hydroxyl groups; and A composition for semiconductor photoresists, comprising a solvent.

2. The semiconductor photoresist composition according to claim 1, wherein the compound comprising one or more nitro groups and one or more hydroxyl groups is one or more compounds selected from the group consisting of saturated or unsaturated aliphatic compounds comprising one or more nitro groups and one or more hydroxyl groups, aromatic ring compounds comprising one or more nitro groups and one or more hydroxyl groups, and heterocyclic compounds comprising one or more nitro groups and one or more hydroxyl groups.

3. The semiconductor photoresist composition according to claim 1, wherein the compound comprising one or more nitro groups and one or more hydroxyl groups is a compound represented by the following chemical formula 1: 【Chemistry 1】 In the aforementioned chemical formula 1, A is a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, a substituted or unsubstituted alkenylene group having 2 to 10 carbon atoms, a substituted or unsubstituted alkylene group having 2 to 10 carbon atoms, a substituted or unsubstituted heteroalkylene group having 1 to 10 carbon atoms, a substituted or unsubstituted heteroalkenylene group having 2 to 10 carbon atoms, or a substituted or unsubstituted heteroalkylene group having 2 to 10 carbon atoms, and is one or more selected from the group consisting of a substituted or unsubstituted cycloalkane having 3 to 20 carbon atoms, a substituted or unsubstituted cycloalkene having 3 to 20 carbon atoms, a substituted or unsubstituted aromatic ring having 6 to 20 carbon atoms, and a substituted or unsubstituted heteroaromatic ring having 3 to 20 carbon atoms. n and m are independent integers greater than or equal to 1. n+m is an integer less than or equal to the bond valency of A.

4. The semiconductor photoresist composition according to claim 3, wherein A in the chemical formula 1 is one or more selected from the group consisting of a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, a substituted or unsubstituted aromatic ring having 6 to 20 carbon atoms, and a substituted or unsubstituted heteroaromatic ring having 3 to 20 carbon atoms.

5. The semiconductor photoresist composition according to claim 1, wherein the compound comprising one or more nitro groups and one or more hydroxyl groups is one or more compounds selected from the compounds listed in Group 1 below: 【Chemistry 2】

6. The semiconductor photoresist composition according to claim 1, wherein the compound comprising one or more nitro groups and one or more hydroxyl groups is contained in an amount of 0.01 to 5 parts by weight based on 100 parts by weight of the organometallic compound.

7. The semiconductor photoresist composition according to claim 1, wherein the compound comprising one or more nitro groups and one or more hydroxyl groups is included in an amount of 0.001% to 10% by weight based on 100% by weight of the semiconductor photoresist composition.

8. 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.

9. 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.

10. 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.

11. The organometallic compound is represented by the following chemical formula 2, and is the semiconductor photoresist composition according to claim 1: 【Transformation 3】 In the aforementioned chemical formula 2, R １ 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 C7-C30 arylalkyl groups. R ２ to R ４ are each independently 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 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 carbon atoms, or a combination thereof), a carboxyl group or an acyloxy 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 carbon atoms, or a combination thereof), an alkylamide or a dialkylamide ( -NR ｄ R ｅ , where R ｄ and R ｅ are each independently 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 carbon atoms, or a combination thereof), an amidato ( -NR ｆ (COR ｇ ), where 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 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 an acylthio 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 ２ ~R ４ 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, or acyloxy 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 C6-C30 aryl groups, or combinations thereof), alkylamides or dialkylamides (-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 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 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) and an acylthio 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 C6-C30 aryl group, or a combination thereof.)

12. The aforementioned R ２ ~R ４ 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 C6-C30 aryl group, or a combination thereof), and a carboxyl group or acyloxy group (-O(CO)R ｃ , R ｃ The semiconductor photoresist composition according to claim 11, 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.

13. The aforementioned R １ This is selected from 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, and substituted or unsubstituted C7-C20 arylalkyl groups. 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 12, 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.

14. 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: 【Chemistry 4】 In the aforementioned chemical formula 3, R ５ is a hydrocarbyl group having 1 to 31 carbon atoms, where 0 < z ≤ 2 and 0 < (z + x) ≤ 4; 【Transformation 5】 In the aforementioned chemical formula 4, R ６ 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.

15. 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 14 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.

Images