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

Abstract

One embodiment of the present invention provides a semiconductor photoresist composition that exhibits excellent sensitivity, reduces the influence of variables during pattern formation, and improves pattern stability. [Solution] The present invention relates to a semiconductor photoresist composition comprising an organometallic compound represented by the following chemical formula 1 and a solvent, and a pattern formation method utilizing the same. JPEG2026137659000021.jpg42170 The definition of Chemical Formula 1 is as described in the specification.

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 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, thereby decreasing 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 by non-chemical amplification mechanisms results in resistance to removal by developer compositions. Inorganic compositions contain inorganic elements that have a higher EUV absorption rate compared to hydrocarbons, ensuring sensitivity even with non-chemical amplification mechanisms, 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 use as radiation-sensitive materials for patterning (US5061599; H.Okamoto, T.Iwayanagi, K.Mochiji, H.Umezaki, T.Kudo, Applied Physics Letters, 49(5), 298-300, 1986).

[0008] These materials 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) solutions, such as 25 wt%.

[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 that exhibits excellent sensitivity, reduces the influence of variables during pattern formation, and improves pattern 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 semiconductor photoresist composition according to one embodiment of the present invention comprises an organometallic compound represented by the following chemical formula 1; and a solvent: [ka]

[0013] In the above chemical formula 1, Z 1 It is a group containing at least one boron element, X 1 ~X 3 These are independently alkoxy and aryloxy (-OR) b , here R bis 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 where 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 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 amidinato (-NR h C(NR i )R j where R h R i and R jEach of these is independently hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof), alkylthio and arylthio (-SR k , here R k (which is a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof) or a thiocarboxyl group (-S(CO)R l , R l (These are hydrogen, substituted or unsubstituted C1-C20 alkyl groups, substituted or unsubstituted C3-C20 cycloalkyl groups, substituted or unsubstituted C2-C20 alkenyl groups, substituted or unsubstituted C2-C20 alkynyl groups, substituted or unsubstituted C6-C30 aryl groups, or combinations thereof.) [Effects of the Invention]

[0014] A semiconductor photoresist composition according to one embodiment of the present invention exhibits excellent sensitivity, storage stability, and coating properties, enabling precise control of small-sized patterns and achieving superior resolution. [Brief explanation of the drawing]

[0015] [Figure 1A] This is a cross-sectional view illustrating a pattern formation method using a semiconductor photoresist composition according to one embodiment. [Figure 1B] This is a cross-sectional view illustrating a pattern formation method using a semiconductor photoresist composition according to one embodiment. [Figure 1C]This is a cross-sectional view illustrating a pattern formation method using a semiconductor photoresist composition according to one embodiment. [Figure 1D] This is a cross-sectional view illustrating a pattern formation method using a semiconductor photoresist composition according to one embodiment. [Figure 1E] 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]

[0016] 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.

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

[0018] 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.

[0019] 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.

[0020] 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.

[0021] 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.

[0022] In this document, "cycloalkyl group" refers to a monovalent cyclic aliphatic saturated hydrocarbon group unless otherwise defined.

[0023] 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 a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, or a cyclohexyl group, but is not limited to these.

[0024] 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.

[0025] 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.

[0026] 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.

[0027] 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.

[0028] A semiconductor photoresist composition according to one embodiment will be described below.

[0029] A semiconductor photoresist composition according to one embodiment comprises an organometallic compound represented by the following chemical formula 1, and a solvent: [ka]

[0030] In the above chemical formula 1, Z 1 It is a group containing at least one boron element, X 1 ~X 3 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 C6-C30 aryl group, a substituted or unsubstituted C7-C30 arylalkyl group, an alkoxy, and an aryloxy (-OR) group. 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 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 a thiocarboxyl group (-S(CO)R l , R l(These are hydrogen, substituted or unsubstituted C1-C20 alkyl groups, substituted or unsubstituted C3-C20 cycloalkyl groups, substituted or unsubstituted C2-C20 alkenyl groups, substituted or unsubstituted C2-C20 alkynyl groups, substituted or unsubstituted C6-C30 aryl groups, or combinations thereof.) X 1 ~X 3 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 thiocarboxyl 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.)

[0031] A pattern formation method using a semiconductor photoresist composition containing an organometallic compound comprises the steps of applying the photoresist composition onto a film to be etched so that the organometallic compound or its cluster molecules within the photoresist composition are coated onto the film to be etched, and then removing the organic matter within the photoresist composition and patterning the metal oxide through a first baking step, an exposure step, a second baking step, and a development step.

[0032] In this process, the patterning of the metal oxide is affected by various variables such as temperature, solvent, concentration, catalyst, and atmospheric conditions, and this effect is relatively greater as the pattern size decreases. 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.

[0033] In particular, it is known that the pattern formation process 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 atmospheric moisture, sunlight, etc., to cause phenomena such as smog. However, 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.

[0034] Therefore, in the present invention, by including a boron atom in the organometallic compound as described above, the boron atom reacts with radicals derived from nitrogen oxides, thereby suppressing unwanted radical reactions. In other words, when using a semiconductor photoresist composition according to one embodiment for pattern formation, the reaction with nitrogen oxides in the atmosphere is suppressed in the exposure region during the exposure process, and the reaction with radicals that diffuse unnecessarily in the non-exposure region is suppressed, thereby reducing defects and residues generated in the pattern, and thus improving the pattern profile, such as increasing the uniformity of the pattern.

[0035] Z in Chemical Formula 1 1 can be a group represented by the following Chemical Formula 2:

Chemical Structure

[0036] In Chemical Formula 2, L is a single bond or a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, and R 1 and R 2 are each independently hydrogen, deuterium, halogen, 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 20 carbon atoms, or the R 1 and R 2 [ are selectively linked to form a ring, and * is the linking point with Sn in Chemical Formula 1.

[0037] R in Chemical Formula 2 1 and R 2 are each independently hydrogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, or R 1 and R 2 can be selectively linked to form a ring. For example, the R 1 and R 2 are each independently hydrogen, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, or the R 1 and R 2 can be linked to each other to form a ring.

[0038] When R 1 and R 2 in Chemical Formula 2 are linked to form a ring, R 1 and R 2is selectively linked and can form a substituted or unsubstituted heterocyclic ring having 2 to 20 carbon atoms. For example, R 1 and R 2 are selectively linked and can form a substituted or unsubstituted heterocyclic ring having 2 to 10 carbon atoms. For example, Chemical Formula 2 is represented by the following Chemical Formula 2-1:

Chemical Formula

[0039] In Chemical Formula 2-1, L 21 is a single bond or a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, and R 21 to R 24 are each independently hydrogen, deuterium, halogen, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a combination thereof, and * is the linking point with Sn in Chemical Formula 1.

[0040] In one embodiment, in the definition of X 1 to X 3 in Chemical Formula 1, R b is a substituted or unsubstituted methyl group, a substituted or unsubstituted ethyl group, a substituted or unsubstituted propyl group, a substituted or unsubstituted butyl group, a substituted or unsubstituted isopropyl group, a substituted or unsubstituted tert-butyl group, a substituted or unsubstituted tert-pentyl group, a substituted or unsubstituted 2,2-dimethylpropyl group, a substituted or unsubstituted cyclopropyl group, a substituted or unsubstituted cyclobutyl group, a substituted or unsubstituted cyclopentyl group, a substituted or unsubstituted cyclohexyl group, a substituted or unsubstituted ethenyl group, a substituted or unsubstituted propenyl group, a substituted or unsubstituted butenyl group, a substituted or unsubstituted ethynyl group, a substituted or unsubstituted propynyl group, a substituted or unsubstituted butynyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted tolyl group, a substituted or unsubstituted xylene group, a substituted or unsubstituted benzyl group, or a combination thereof,<\ The R c , R d , R e , R f , Rg , R h , R i , R j , R k , and R l Each of these can independently be hydrogen, a substituted or unsubstituted methyl group, a substituted or unsubstituted ethyl group, a substituted or unsubstituted propyl group, a substituted or unsubstituted butyl group, a substituted or unsubstituted isopropyl group, a substituted or unsubstituted tert-butyl group, a substituted or unsubstituted tert-pentyl group, a substituted or unsubstituted 2,2-dimethylpropyl group, a substituted or unsubstituted cyclopropyl group, a substituted or unsubstituted cyclobutyl group, a substituted or unsubstituted cyclopentyl group, a substituted or unsubstituted cyclohexyl group, a substituted or unsubstituted ethenyl group, a substituted or unsubstituted propenyl group, a substituted or unsubstituted butenyl group, a substituted or unsubstituted ethynyl group, a substituted or unsubstituted propynyl group, a substituted or unsubstituted butynyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted tolyl group, a substituted or unsubstituted xylene group, a substituted or unsubstituted benzyl group, or a combination thereof.

[0041] X in the above chemical formula 1 1 ~X 3 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.)

[0042] For example, the 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 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.

[0043] The organometallic compound is one or more compounds selected from the following group 1.

[0044] [ka]

[0045] 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, and is not limited to these amounts. When the organometallic compound is contained in an amount within the above range, the storage stability and etching resistance of the semiconductor photoresist composition are improved, and the resolution characteristics are improved.

[0046] By including the organometallic compound in the above-mentioned content range in a semiconductor photoresist composition according to one embodiment, the sensitivity of the photoresist can be further enhanced and the pattern formation properties can be further improved.

[0047] 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, 2-methyl-1-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.

[0048] In one embodiment, the semiconductor photoresist composition may further contain a resin in addition to the organometallic compound and the solvent.

[0049] The aforementioned resin may be a phenolic resin containing at least one of the aromatic molecules listed in Group 2 below.

[0050] [ka]

[0051] The aforementioned resin may have a weight-average molecular weight of 500 g / mol to 20,000 g / mol.

[0052] 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. When the resin is included within the above content range, it can have excellent etching resistance and heat resistance.

[0053] On the other hand, a semiconductor photoresist composition according to one embodiment is preferably composed of the organometallic compound, solvent, and resin described above. The semiconductor photoresist composition according to the above embodiment may optionally further contain additives. Examples of such additives include surfactants, crosslinking agents, leveling agents, organic acids, quenchers, or combinations thereof.

[0054] The surfactants may include, but are not limited to, alkylbenzene sulfonates, alkylpyridinium salts, polyethylene glycol, quaternary ammonium salts, or combinations thereof.

[0055] 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.

[0056] Leveling agents are used to improve coating flatness during printing, and commercially available, known leveling agents can be used.

[0057] 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.

[0058] The quencher may be diphenyl(p-tolyl)amine, methyldiphenylamine, triphenylamine, phenylenediamine, naphthylamine, diaminonaphthalene, or a combination thereof.

[0059] The amount of these additives used can be easily adjusted according to the desired physical properties, and they can also be omitted.

[0060] 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.

[0061] 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 100 nm, such as 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 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, 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 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.

[0062] 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.

[0063] 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.

[0064] The following describes a method for forming a pattern using the semiconductor photoresist composition described above, with reference to Figures 1A to 1E. Figures 1A to 1E are cross-sectional views illustrating a pattern formation method using the semiconductor photoresist composition according to the present invention.

[0065] Referring to Figure 1A, first, the object to be etched is prepared. 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. 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.

[0066] 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.

[0067] 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.

[0068] 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.

[0069] 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.

[0070] Referring to Figure 1B, 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.

[0071] 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.

[0072] Since the compositions for semiconductor photoresists have already been explained in detail, we will omit further explanation.

[0073] 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.

[0074] Referring to Figure 1C, the photoresist film 106 is selectively exposed using a patterned mask 110.

[0075] 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).

[0076] More specifically, the exposure light in one embodiment may be light having a wavelength range of 5 nm to 150 nm, or it may be light having a high energy wavelength such as EUV (Extreme UltraViolet; wavelength 13.5 nm) or E-Beam (electron beam).

[0077] 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.

[0078] 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.

[0079] Figure 1D 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.

[0080] 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 2-methyl-1-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.

[0081] 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.

[0082] 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 thickness width of 5nm to 100nm. For example, the photoresist pattern 108 can be formed with thicknesses 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.

[0083] 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.

[0084] 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.

[0085] Referring to Figure 1E, 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.

[0086] 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.

[0087] 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.

[0088] The semiconductor photoresist pattern formation method according to this embodiment may be carried out such that the rate of increase in the line width of the pattern formed under conditions containing nitrogen oxides is less than 10% compared to the line width of the pattern formed under conditions without nitrogen oxides. For example, the rate of increase in the line width of the pattern may be less than 10%, less than 9.9%, less than 9.8%, less than 9.7%, less than 9.6%, or less than 9.5%. Above, conditions without nitrogen oxides mean conditions in which nitrogen oxides are substantially absent or controlled at a technically negligible concentration (e.g., less than 1 ppb). Furthermore, under conditions containing nitrogen oxides, the concentration of nitrogen oxides may be based on the concentration of nitrogen oxides in the atmosphere, for example, conditions in which nitrogen oxides are present at a concentration of 0.001 ppm to 1.0 ppm.

[0089] The nitrogen oxide concentration conditions described above can be adjusted as needed within the range of 0.001 ppm to 1.0 ppm, and in one embodiment of the present invention, the nitrogen oxide-containing condition may be a concentration of 0.1 ppm.

[0090] The above rate of increase in line width can be measured by comparing the line widths of each pattern formed under the same process conditions, differing only in the presence or absence of nitrogen oxides. In one embodiment, even if nitrogen oxides are present in the atmosphere during the pattern formation process, the side reaction between the organometallic compound in the composition and nitrogen oxides is suppressed, thereby minimizing the unwanted increase in line width and the occurrence of pattern defects, and enabling the formation of a precise pattern.

[0091] A pattern formed using a semiconductor photoresist composition according to one embodiment may have a line width (CD, Critical Dimension) increase rate of less than 10% compared to a pattern formed under conditions containing nitrogen oxides (NOx). [Examples]

[0092] 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.

[0093] Synthesis of organometallic compounds Synthesis Example 1 [Chemical formula A synthesis method] 5 g of PhSn[(C6H4)PPh2] and 25 g of B(OH)2Br·SMe were dissolved in 50 mL of anhydrous benzene and stirred at room temperature for 3 hours. After the reaction was complete, the solvent was removed and the mixture was washed three times with n-hexane to obtain a yellow solid. 6 g of the yellow solid and 300 g of propionic acid were added 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 A-1.

[0094] [ka]

[0095] Synthesis Example 2 5 g of PhSn[(C6H4)PPh2] and 25 g of B(OMe)2Br·SMe were dissolved in 50 mL of anhydrous benzene and stirred at room temperature for 3 hours. After the reaction was complete, the solvent was removed and the mixture was washed three times with n-hexane to obtain a yellow solid. 6 g of the yellow solid was added to 50 mL of anhydrous pentane, and while maintaining the temperature at 0°C, 20 g of methyl isobutyl carbinol (MIBC) was added and the mixture was stirred at room temperature for 6 hours. After the reaction was complete, the mixture was filtered, concentrated, and vacuum-dried to obtain the compound represented by the following chemical formula A-2.

[0096] [ka]

[0097] Synthesis Example 3 The compound represented by chemical formula A-3 below was obtained by carrying out the same procedure as in Synthesis Example 2, except that XBr·SMe2 (wherein X is represented by chemical formula 3 below) was used instead of B(OMe)2Br·SMe2. [ka]

[0098] [ka]

[0099] Synthesis Example 4 The compound represented by the following chemical formula A-4 was obtained by carrying out the same procedure as in Synthesis Example 2, except that B(C2H4O2)Br·SMe2 was used instead of B(OMe)2Br·SMe2.

[0100] [ka]

[0101] Comparative Synthesis Example 1 0.7 g of t-ButylSnPh 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 B-1.

[0102] [ka]

[0103] Comparative Synthesis Example 2 The compound represented by the following chemical formula B-2 was obtained by carrying out the synthesis in the same manner as in Comparative Synthesis Example 1, except that t-AmylSnPh3 was used instead of t-ButylSnPh3.

[0104] [ka]

[0105] Comparative Synthesis Example 3 310 g of t-ButylSn(Dimethylamine) and 50 mL of anhydrous pentane were added to a 250 mL round-bottom flask. 20 g of MIBC was added while maintaining the temperature at 0°C, and the mixture was stirred at room temperature for 6 hours. After the reaction was complete, the mixture was filtered, concentrated, and vacuum-dried to obtain the compound represented by the following chemical formula B-3.

[0106] [ka]

[0107] Comparative Synthesis Example 4 The compound represented by the following chemical formula B-4 was obtained by carrying out the synthesis in the same manner as in Comparative Synthesis Example 3, except that t-AmylSn(Dimethylamine)3 was used instead of t-ButylSn(Dimethylamine)3.

[0108] [ka]

[0109] (Manufacturing of semiconductor photoresist compositions) Examples 1-4 and Comparative Examples 1-4 The organometallic compounds obtained in Synthesis Examples 1-4 and the organometallic compounds obtained in Comparative Synthesis Examples 1-4 were each dissolved in 3 wt% PGMEA (propylene glycol monomethyl ether acetate), and filtered through a 0.1 μm PTFE syringe filter to produce semiconductor photoresist compositions according to the examples and comparative examples.

[0110] evaluation Each of the above semiconductor photoresist compositions was coated onto a silicon wafer to a thickness of 240 Å, and then a patterned film was manufactured by going through PAB, exposure, PEB, and development processes.

[0111] The photoresist compositions according to the above examples and comparative examples were spin-coated onto a 200 mm circular silicon wafer with a surface deposited with HMDS at 1500 rpm for 30 seconds, baked at 110°C for 60 seconds (post-apply bake, PAB), and then left at room temperature (23±2°C) for 30 seconds. Subsequently, a linear array with a width of 50 nm was projected onto the wafer coated with the photoresist composition using EUV light (Lawrence Berkeley National Laboratory Micro Exposure Tool, MET). The pad exposure time was adjusted so that the increasing EUV dose was applied to each pad.

[0112] Subsequently, the resist and substrate were exposed on a hot plate at 170°C for 60 seconds and then fired. The fired film was developed with PGMEA solvent to form a negative tone image. Finally, the process was completed by firing on a hot plate at 150°C for 60 seconds.

[0113] The line width and LER (Line edge roughness, in nm) of the pattern formed above were measured using SEM (Scanning electron microscopy) to check for the presence or absence of scum formation, and the results are shown in Table 1 below.

[0114] Furthermore, using Comparative Example 1 as a reference, we identified a nitrogen oxide (NOx) concentration (approximately 0.1 ppm) that increased the CD (Critical Dimension) by 15% at the same exposure dose, defining this as a high-concentration NOx environment. We then exposed photoresists with patterns formed in both the high-concentration NOx environment and the NOx-free environment, respectively, and measured the CD change range. The degree of improvement in the NOx effect was then evaluated based on the CD change range in the high-concentration NOx environment and the NOx-free environment according to the following criteria, and the results are shown in Table 1 below.

[0115] [NOx Impact Improvement Assessment Criteria] -○: Less than +5% -△: +5% or more but less than 10% -X:+10% or more

[0116] [Table 1]

[0117] Referring to Table 1 above, it was confirmed that the patterns formed using the semiconductor photoresist compositions of Examples 1 to 4 showed a smaller LER and a smaller CD change range due to NOx environmental differences compared to the patterns formed using the semiconductor photoresist compositions of Comparative Examples 1 to 4. Furthermore, no scum was generated in the patterns of the Examples, but scum was generated in the patterns of Comparative Examples 1, 2, and 4. It can be seen that the semiconductor photoresist composition of one embodiment has excellent pattern-forming properties and can reduce defects and residues generated in the patterns, and is therefore less affected by nitrogen oxides in the atmosphere.

[0118] Although specific embodiments of the present invention have been described and illustrated above, it will be obvious to those ordinary skill in the art that the present invention is not limited to the described embodiments and can be modified and transformed in various ways without departing from the spirit and scope of the invention. Accordingly, such modifications or variations should not be understood individually from the technical spirit or viewpoint of the present invention, and the modified embodiments fall within the scope of the claims of the present invention. [Explanation of Symbols]

[0119] 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 represented by the following chemical formula 1; and Compositions for semiconductor photoresists containing a solvent: 【Chemistry 1】 In the aforementioned chemical formula 1, Z １ It is a group containing at least one boron element, X １ ~X ３ are each independently 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 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 amidinato (-NR ｈ C(NR ｉ )R ｊ , where R ｈ , R ｉ and R ｊ Each of these is independently hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof), alkylthio and arylthio (-SR ｋ Here, R ｋ (which is a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof) or a thiocarboxyl group (-S(CO)R ｌ , R ｌ (These are hydrogen, 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.)

2. Z in the aforementioned chemical formula 1 １ The semiconductor photoresist composition according to claim 1, wherein the group is represented by the following chemical formula 2: 【Chemistry 2】 In the aforementioned chemical formula 2, L is a single bond, or a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms. R １ and R ２ Each of these is independently hydrogen, deuterium, halogen, substituted or unsubstituted C1-C20 alkyl group, substituted or unsubstituted C3-C20 cycloalkyl group, substituted or unsubstituted C2-C20 alkenyl group, substituted or unsubstituted C2-C20 alkynyl group, substituted or unsubstituted C6-C20 aryl group, or the aforementioned R １ and R ２ They are selectively linked to form a ring, * indicates the linkage point with Sn in the above chemical formula 1.

3. R in the above chemical formula 2 １ and R ２ Each of these is independently a hydrogen atom, a substituted or unsubstituted C1-C20 alkyl group, or a substituted or unsubstituted C2-C20 alkenyl group, or R １ and R ２ The semiconductor photoresist composition according to claim 2, wherein the elements are selectively linked to form a ring.

4. R in the above chemical formula 2 １ and R ２ The semiconductor photoresist composition according to claim 2, wherein the elements are selectively linked to form a heterocycle having 2 to 20 carbon atoms, which may or may not be substituted.

5. The aforementioned R ｂ These are substituted or unsubstituted methyl groups, substituted or unsubstituted ethyl groups, substituted or unsubstituted propyl groups, substituted or unsubstituted butyl groups, substituted or unsubstituted isopropyl groups, substituted or unsubstituted tert-butyl groups, substituted or unsubstituted tert-pentyl groups, substituted or unsubstituted 2,2-dimethylpropyl groups, substituted or unsubstituted cyclopropyl groups, substituted or unsubstituted cyclobutyl groups, substituted or unsubstituted cyclopentyl groups, substituted or unsubstituted cyclohexyl groups, substituted or unsubstituted ethenyl groups, substituted or unsubstituted propenyl groups, substituted or unsubstituted butenyl groups, substituted or unsubstituted ethynyl groups, substituted or unsubstituted propynyl groups, substituted or unsubstituted butynyl groups, substituted or unsubstituted phenyl groups, substituted or unsubstituted tolyl groups, substituted or unsubstituted xylene groups, substituted or unsubstituted benzyl groups, or combinations thereof. The aforementioned R ｃ , R ｄ , R ｅ , R ｆ , R ｇ , R ｈ , R ｉ , R ｊ , R ｋ , and R ｌ The semiconductor photoresist composition according to claim 1, wherein each of them independently is hydrogen, a substituted or unsubstituted methyl group, a substituted or unsubstituted ethyl group, a substituted or unsubstituted propyl group, a substituted or unsubstituted butyl group, a substituted or unsubstituted isopropyl group, a substituted or unsubstituted tert-butyl group, a substituted or unsubstituted tert-pentyl group, a substituted or unsubstituted 2,2-dimethylpropyl group, a substituted or unsubstituted cyclopropyl group, a substituted or unsubstituted cyclobutyl group, a substituted or unsubstituted cyclopentyl group, a substituted or unsubstituted cyclohexyl group, a substituted or unsubstituted ethenyl group, a substituted or unsubstituted propenyl group, a substituted or unsubstituted butenyl group, a substituted or unsubstituted ethynyl group, a substituted or unsubstituted propynyl group, a substituted or unsubstituted butynyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted tolyl group, a substituted or unsubstituted xylene group, a substituted or unsubstituted benzyl group, or a combination thereof.

6. X in the aforementioned chemical formula 1 １ ~X ３ 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 1, 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.

7. The aforementioned 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 6, 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.

8. The semiconductor photoresist composition according to claim 1, wherein the organometallic compound is one or more compounds selected from the following group 1: 【Transformation 3】

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, or a combination thereof.

11. The steps include forming an etching target film on a substrate, The steps include applying the semiconductor photoresist composition described in claim 1 to 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.

12. The step of forming the aforementioned photoresist pattern is: The pattern forming method according to claim 11, wherein the method is performed such that the rate of increase in the line width of a photoresist pattern formed under conditions containing 0.1 ppm nitrogen oxides is less than 10% compared to the line width of a photoresist pattern formed under conditions not containing nitrogen oxides.

Images