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

Abstract

To provide a semiconductor photoresist composition and pattern formation method that improve coating properties and bridge defect resistance while maintaining excellent sensitivity characteristics. [Solution] The semiconductor photoresist composition comprises an organometallic compound, an alcohol compound substituted with at least one halogen, an alcohol compound without halogen substitution, and a solvent. The pattern formation method using the semiconductor photoresist composition comprises 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.

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 EUV lithography requires the development of compatible photoresists that can be performed with a spatial resolution of 16 nm or less. Currently, chemically amplified (CA) photoresists are being developed and efforts are being made to meet the specifications for resolution, photospeed, surface roughness, and line edge roughness (LER) for next-generation devices.

[0004] The intrinsic image blur caused by acid-catalyzed reactions in polymer photoresists limits resolution at small feature sizes, a fact long known in electron beam lithography. While CA photoresists are designed for high sensitivity, their typical elemental makeup reduces the photoresist's absorbance at a wavelength of 13.5 nm, consequently decreasing sensitivity and sometimes creating further difficulties under EUV exposure.

[0005] CA photoresists also experience difficulties due to roughness issues in small form factors, and experiments have shown that 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 mentioned 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. They are also known to be sensitive with less probabilistic variability (stochastic effect), resulting in fewer LERs and defects.

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

[0008] These materials are deep ultraviolet, X-ray, and electron beam sources and have been effective in patterning large shapes in bilayer configurations. More recently, the use of cationic hafnium metal oxide sulfate (HfSOx) materials with peroxo-complexing agents to image 15 nm half-pitch (HP) by projection EUV lithography has shown impressive performance (see, for example, Patent Document 2 or Non-Patent Document 2). This system exhibits the best performance of non-CA photoresists and has a photospeed that approaches the requirements for a viable EUV photoresist. However, hafnium metal oxide sulfate materials with peroxo-complexing agents have several practical drawbacks. Firstly, the material is coated with a highly corrosive sulfuric acid / hydrogen peroxide mixture and has poor shelf-life stability. Secondly, it is a composite mixture and its composition is not easily modified for performance improvement. Thirdly, it must be developed with extremely high concentrations of TMAH (tetramethylammonium hydroxide) solution, such as 25 wt%.

[0009] In recent years, active research has been conducted on tin-containing molecules, as it has become known that they exhibit outstanding absorption of extreme ultraviolet light. In the case of organotin polymers, one such example, the alkyl ligand is dissociated by light absorption or the secondary electrons generated by it, and negative tone patterning is possible through crosslinking via oxo bonds with surrounding chains, which prevents removal by organic developers. While such organotin polymers have shown a dramatic improvement in sensitivity while maintaining resolution and LER, further improvements in the aforementioned patterning properties are necessary for commercialization. [Prior art documents] [Patent Documents]

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

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

[0012] One embodiment of the present invention provides a semiconductor photoresist composition with improved coating properties and bridge defect resistance while maintaining excellent sensitivity characteristics.

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

[0014] A semiconductor photoresist composition according to one embodiment of the present invention comprises an organometallic compound, an alcohol compound substituted with at least one halogen, an alcohol compound without halogen substitution, and a solvent.

[0015] A pattern formation method according to another embodiment of the present invention includes the steps of: forming an etching target film on a substrate; applying the above-described semiconductor photoresist composition on the etching target film to form a photoresist film; patterning the photoresist film to form a photoresist pattern; and etching the etching target film using the photoresist pattern as an etching mask. [Effects of the Invention]

[0016] By using a semiconductor photoresist composition according to one embodiment of the present invention, surface roughness can be improved through improved sensitivity and coating properties, thereby providing a photoresist pattern with excellent LER and pattern line width. [Brief explanation of the drawing]

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

[0018] Embodiments of the present invention will be described in detail below with reference to the attached drawings. However, in order to clarify the gist of this description, descriptions of functions or configurations that are already publicly known will be omitted.

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

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

[0021] In this document, "substituted" means that the hydrogen atom is replaced by deuterium, halogen group, hydroxyl group, carboxyl group, thiol group, cyano group, nitro group, -NRR' (where R and R' are independently hydrogen, a substituted or unsubstituted saturated or unsaturated aliphatic hydrocarbon group having 1 to 30 carbon atoms, a substituted or unsubstituted saturated or unsaturated alicyclic hydrocarbon group having 3 to 30 carbon atoms, or a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 carbon atoms), -SiRR'R'' (where R, R', and R'' are independently hydrogen, a substituted or 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.

[0022] In this specification, "alkyl (alkyl) group" means a linear or branched aliphatic hydrocarbon group unless otherwise defined. The alkyl group may be a "saturated alkyl group" that does not contain any double or triple bonds.

[0023] The alkyl group may be an alkyl group having 1 to 8 carbon atoms. For example, the alkyl group may be an alkyl group having 1 to 7 carbon atoms, an alkyl group having 1 to 6 carbon atoms, or an alkyl group having 1 to 5 carbon atoms. For example, the alkyl group having 1 to 5 carbon atoms may be a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, or a tert-butyl group or a 2,2-dimethylpropyl group.

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

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

[0026] In this specification, “aryl group” means a substituent in which all elements of the cyclic substituent have p-orbitals, and these p-orbitals are conjugated, and includes monocyclic or fused-ring polycyclic (i.e., rings sharing adjacent pairs of carbon atoms) functional groups.

[0027] In this specification, a "heteroaryl group" means an aryl group containing at least one heteroatom selected from the group consisting of N, O, S, P, and Si. Two or more heteroaryl groups can be directly linked through sigma bonds, or, if 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.

[0028] In this specification, "alkenyl group" means an aliphatic unsaturated alkenyl group, which is a linear or branched aliphatic hydrocarbon group containing one or more double bonds, unless otherwise defined.

[0029] In this specification, "alkynyl group" means an aliphatic unsaturated alkynyl group, which is a linear or branched aliphatic hydrocarbon group containing one or more triple bonds, unless otherwise defined.

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

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

[0032] The semiconductor photoresist composition comprises an organometallic compound, two alcohol compounds, and a solvent. In particular, by including both an alcohol compound substituted with at least one halogen and an alcohol compound without a halogen, the sensitivity to extreme ultraviolet light and the roughness of the pattern formed using this composition are increased.

[0033] The alcohol compound substituted with at least one halogen is represented by the following chemical formula 1.

[0034] [Chemical formula 1] [ka]

[0035] In the aforementioned chemical formula 1, Z is a halogen, A is 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 alkynylene groups having 2 to 10 carbon atoms, substituted or unsubstituted cycloalkanes having 3 to 20 carbon atoms, substituted or unsubstituted cycloalkenes having 3 to 20 carbon atoms, and substituted or unsubstituted aromatic rings having 6 to 20 carbon atoms. n1 and m1 are each independent integers greater than or equal to 1. n1 + m1 is an integer less than or equal to the bond valence of A.

[0036] The A may be a divalent, trivalent, or tetravalent group depending on the number of linked substituents, and various modifications are possible.

[0037] As an example, A 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 alkenylene groups having 2 to 5 carbon atoms, substituted or unsubstituted alkynylene groups having 2 to 5 carbon atoms, substituted or unsubstituted cycloalkanes having 3 to 10 carbon atoms, and substituted or unsubstituted aromatic rings having 6 to 12 carbon atoms.

[0038] As a specific example, A 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 cycloalkanes having 3 to 10 carbon atoms, and substituted or unsubstituted aromatic rings having 6 to 12 carbon atoms.

[0039] For example, A may be one or more selected from the group consisting of substituted or unsubstituted methylene groups, substituted or unsubstituted ethylene groups, substituted or unsubstituted propylene groups, and substituted or unsubstituted benzenes.

[0040] For example, Z may be at least one selected from fluorine, chlorine, and iodine.

[0041] For example, Z may be at least one selected from fluorine and iodine.

[0042] In one embodiment, the chemical formula 1 is represented by any one of the following chemical formulas 1-1 to 1-4.

[0043] [Chemical formula 1-1] [ka]

[0044] [Chemical formula 1-2] [ka]

[0045] [Chemical formula 1-3] [ka]

[0046] [Chemical formula 1-4] [ka]

[0047] In the aforementioned chemical formulas 1-1 to 1-4, Z is a halogen, R 1 ~R 8 Each of these is independently a hydrogen atom, a halogen, a hydroxyl group, an amino group, a nitro group, a substituted or unsubstituted C1-C30 amine group, a substituted or unsubstituted C1-C10 alkyl group, or a substituted or unsubstituted C6-C20 aryl group. n is one of the integers between 1 and 10.

[0048] In one embodiment, the R 1 ~R 8 Each of these may independently be hydrogen, a halogen, a hydroxyl group, a substituted or unsubstituted C1-C10 alkyl group, or a substituted or unsubstituted C6-C20 aryl group.

[0049] In one specific embodiment, the R 1 ~R 8 Each of these may independently be hydrogen, a halogen, a hydroxyl group, a substituted or unsubstituted C1-C5 alkyl group, or a substituted or unsubstituted C6-C12 aryl group.

[0050] For example, the R 1 ~R 8 Each of these may independently be hydrogen, halogen, hydroxyl group, substituted or unsubstituted methyl group, substituted or unsubstituted ethyl group, substituted or unsubstituted propyl group, substituted or unsubstituted iso-propyl group, substituted or unsubstituted butyl group, substituted or unsubstituted sec-butyl group, substituted or unsubstituted iso-butyl group, substituted or unsubstituted tert-butyl group, substituted or unsubstituted phenyl group, or a combination thereof.

[0051] For example, the alcohol compound in which at least one halogen is substituted can be selected from the compounds listed in Group 1 below.

[0052] [Group 1] [ka]

[0053] The alcohol compound in which the halogen is not substituted is represented by the following chemical formula 2.

[0054] [Chemical formula 2] [ka]

[0055] In the aforementioned chemical formula 2, B is 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 alkynylene groups having 2 to 10 carbon atoms, substituted or unsubstituted cycloalkanes having 3 to 20 carbon atoms, substituted or unsubstituted cycloalkenes having 3 to 20 carbon atoms, and substituted or unsubstituted aromatic rings having 6 to 20 carbon atoms. n2 and m2 are independently greater than or equal to 0. n² + m² is an integer greater than or equal to 1 and less than or equal to the bond valence of B. The substituents that are substituted do not include halogens.

[0056] For example, n2+m2 may be 1 or 2.

[0057] The aforementioned B can be a divalent, trivalent, or tetravalent group depending on the number of linked substituents, and various other modifications are possible.

[0058] As an example, B 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 alkenylene groups having 2 to 5 carbon atoms, substituted or unsubstituted alkynylene groups having 2 to 5 carbon atoms, substituted or unsubstituted cycloalkanes having 3 to 10 carbon atoms, and substituted or unsubstituted aromatic rings having 6 to 12 carbon atoms.

[0059] As a specific example, B 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 cycloalkanes having 3 to 10 carbon atoms, and substituted or unsubstituted aromatic rings having 6 to 12 carbon atoms.

[0060] For example, B may be one or more selected from the group consisting of substituted or unsubstituted methylene groups, substituted or unsubstituted ethylene groups, substituted or unsubstituted propylene groups, and substituted or unsubstituted benzenes.

[0061] In one embodiment, the chemical formula 2 is represented by the following chemical formula 2-1.

[0062] [Chemical Formula 2-1] [Chem.]

[0063] In the above Chemical Formula 2-1, R 9 ~R 13 are each independently hydrogen, a hydroxy group, an amino group, a nitro group, a substituted or unsubstituted amine group having 1 to 30 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, and n is one of the integers from 1 to 9.

[0064] In one embodiment, the above R 9 ~R 13 may each independently be hydrogen, a hydroxy group, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms.

[0065] In a specific embodiment, the above R 9 ~R 13 may each independently be hydrogen, a hydroxy group, a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms.

[0066] For example, the above R 9 ~R 13 may each independently be hydrogen, a hydroxy group, a substituted or unsubstituted methyl group, a substituted or unsubstituted ethyl group, a substituted or unsubstituted propyl group, a substituted or unsubstituted iso-propyl group, a substituted or unsubstituted butyl group, a substituted or unsubstituted sec-butyl group, a substituted or unsubstituted iso-butyl group, a substituted or unsubstituted tert-butyl group, a substituted or unsubstituted phenyl group, or a combination thereof.

[0067] For example, the unsubstituted halogen alcohol compound may be one selected from the compounds listed in Group 2 below.

[0068] [Group 2] [ka] .

[0069] The alcohol compound in which at least one halogen is substituted: The alcohol compound in which the halogen is not substituted may be present in a weight ratio of 15:1 to 1:15.

[0070] As an example, the alcohol compound with at least one halogen substituted: the alcohol compound without the halogen substituted may be present in a weight ratio of 10:1 to 1:15, 8:1 to 1:15, or 5:1 to 1:13.

[0071] The alcohol compound substituted with at least one halogen and the alcohol compound without halogen may be present in an amount of 0.01 to 20% by weight relative to 100% by weight of the semiconductor photoresist composition.

[0072] For example, the alcohol compound substituted with at least one halogen and the alcohol compound without the halogen may be included in amounts 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 per 100% by weight of the semiconductor photoresist composition.

[0073] The organometallic compound may be included in an amount of 0.5% to 30% by weight based on 100% by weight of the semiconductor photoresist composition.

[0074] A semiconductor photoresist composition according to one embodiment can improve the sensitivity of a photoresist by containing the alcohol compound with at least one halogen substituted and the alcohol compound without the halogen in the above-mentioned content range.

[0075] The organometallic compound may also be an organotin compound containing at least one of an organooxy group and an organocarbonyloxy group.

[0076] For example, the organometallic compound is represented by the following chemical formula 3.

[0077] [Chemical formula 3] [ka]

[0078] In the aforementioned chemical formula 3, R 14 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 15 ~R 17 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 (-O(CO)R c Here, 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 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 or arylthio (-SR k Here, R k(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), or a thiocarboxyl group (-S(CO)R l Here, 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 15 ~R 17 At least one of them is an alkoxy or aryloxy (-OR b Here, R b (where R 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 (-O(CO) where 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 g C(NR h )R i Here, R h , R i and R j Each of these is independently hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted 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 or arylthio (-SR k Here, R k (where R 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 thiocarboxyl group (-S(CO), where 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.)

[0079] The aforementioned R 15 ~R 17 At least one of them is an alkoxy or 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 (-O(CO)R c Here, 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.)

[0080] On the other hand, the compound represented by chemical formula 3 has -OR as a ligand. b Or -OC(=O)R c By including this, patterns formed using a semiconductor photoresist composition containing it can exhibit excellent limiting resolution.

[0081] Also, -OR b Or -OC(=O)R c The ligand can determine the solubility of the compound represented by chemical formula 3 in a solvent.

[0082] The aforementioned R 14These are substituted or unsubstituted C1-C8 alkyl groups, substituted or unsubstituted C3-C8 cycloalkyl groups, substituted or unsubstituted C2-C8 aliphatic unsaturated organic groups containing one or more double or triple bonds, substituted or unsubstituted C6-C20 aryl groups, substituted or unsubstituted C4-C20 heteroaryl groups, carbonyl groups, ethoxy groups, propoxy groups, or combinations thereof. R b These are substituted or unsubstituted C1-C8 alkyl groups, substituted or unsubstituted C3-C8 cycloalkyl groups, substituted or unsubstituted C2-C8 alkenyl groups, substituted or unsubstituted C2-C8 alkynyl groups, substituted or unsubstituted C6-C20 aryl groups, or combinations thereof. R c This may be hydrogen, a substituted or unsubstituted C1-C8 alkyl group, a substituted or unsubstituted C3-C8 cycloalkyl group, a substituted or unsubstituted C2-C8 alkenyl group, a substituted or unsubstituted C2-C8 alkynyl group, a substituted or unsubstituted C6-C20 aryl group, or a combination thereof.

[0083] The aforementioned R 14 These are methyl group, ethyl group, propyl group, butyl group, isopropyl group, tert-butyl group, 2,2-dimethylpropyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, ethenyl group, propenyl group, butenyl group, ethynyl group, propynyl group, butynyl group, phenyl group, tolyl group, xylene group, benzyl group, formyl group, acetyl group, propanoyl group, butanoyl group, pentanoyl group, ethoxy group, propoxy group, or combinations thereof. R b These are ethyl group, propyl group, butyl group, isopropyl group, tert-butyl group, 2,2-dimethylpropyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, ethenyl group, propenyl group, butenyl group, ethynyl group, propynyl group, butynyl group, phenyl group, tolyl group, xylene group, benzyl group, or combinations thereof. Rc It may be hydrogen, an ethyl group, a propyl group, a butyl group, an isopropyl group, a tert-butyl group, a 2,2-dimethylpropyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, an ethenyl group, a propenyl group, a butenyl group, an ethynyl group, a propynyl group, a butynyl group, a phenyl group, a tolyl group, a xylene group, a benzyl group, or a combination thereof.

[0084] Further, the organometallic compound is represented by the following Chemical Formula 4 or Chemical Formula 5.

[0085] [Chemical Formula 4] R 18 z SnO (2-(z / 2)-(x / 2)) (OH) x

[0086] In Chemical Formula 4, R 18 is a hydrocarbyl group having 1 to 31 carbon atoms, where 0 < z ≦ 2 and 0 < (z + x) ≦ 4.

[0087] [Chemical Formula 5] R 19 a Sn b X c Y d

[0088] In Chemical Formula 5, R 19 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 aliphatic unsaturated organic group having 2 to 20 carbon atoms and containing one or more double bonds or triple bonds, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 4 to 30 carbon atoms, a carbonyl group, an ethylene oxide group, a propylene oxide group, or a combination 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.

[0089] 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), or mixtures thereof.

[0090] A semiconductor resist composition according to one embodiment may further include a resin in addition to the organometallic compound, the alcohol compound substituted with at least one halogen, the alcohol compound without halogen substitution, and the solvent.

[0091] The aforementioned resin may be a phenolic resin containing at least one of the aromatic molecules listed in Group 3 below.

[0092] [Group 3] [ka]

[0093] The resin may have a weight-average molecular weight of 500 to 20,000.

[0094] 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.

[0095] When the aforementioned resin is included within the above-mentioned content range, it can have excellent etching resistance and heat resistance.

[0096] On the other hand, the semiconductor photoresist composition preferably comprises the organometallic compound, the alcohol compound substituted with at least one halogen, the alcohol compound without halogen substitution, a solvent, and a resin.

[0097] 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.

[0098] The surfactant may be, but is not limited to, alkylbenzene sulfonates, alkylpyridinium salts, polyethylene glycol, quaternary ammonium salts, or combinations thereof.

[0099] 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.

[0100] Leveling agents are used to improve coating flatness during printing, and commercially available, known leveling agents can be used.

[0101] The organic acid may be, but is not limited to, p-toluenesulfonic acid, benzenesulfonic acid, p-dodecylbenzenesulfonic acid, 1,4-naphthalenedisulfonic acid, methanesulfonic acid, sulfonium fluoride salts, malonic acid, citric acid, propionic acid, methacrylic acid, oxalic acid, lactic acid, glycolic acid, succinic acid, or a combination thereof.

[0102] The inhibitor may be diphenyl(p-tolyl)amine, methyldiphenylamine, triphenylamine, phenylenediamine, naphthylamine, diaminonaphthalene, or a combination thereof.

[0103] The amount of these additives used can be easily adjusted according to the desired physical properties, and they can also be omitted.

[0104] 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, a carbon-carbon unsaturated bond-containing silane compound such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltris(β-methoxyethoxy)silane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, or trimethoxy[3-(phenylamino)propyl]silane.

[0105] The semiconductor photoresist composition may not exhibit 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 80 nm, such as a photoresist process using light with wavelengths of 5 nm to 50 nm, such as a photoresist process using light with wavelengths of 5 nm to 30 nm, and such as a photoresist process using light with wavelengths of 5 nm to 20 nm, in order to form fine patterns with widths of 5 nm to 100 nm, such as a photoresist process using light with wavelengths of 5 nm to 80 nm, such as a photoresist process using light with wavelengths of 5 nm to 50 nm, such as a photoresist process using light with wavelengths of 5 nm to 30 nm, and such as a photoresist process using light with wavelengths of 5 nm to 20 nm. Therefore, by using the 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.

[0106] 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.

[0107] 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.

[0108] 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.

[0109] Referring to Figure 1(a), 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. Hereafter, the explanation will be based on the assumption that 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.

[0110] Next, a resist underlayer forming composition is applied to the surface of the cleaned thin film 102 using a spin coating method to provide a resist underlayer 104. However, the method is not necessarily limited to this, and various known coating methods, such as spray coating, dip coating, knife-edge coating, and printing methods, such as inkjet printing and screen printing, can also be used.

[0111] 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.

[0112] 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.

[0113] 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.

[0114] 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 also 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.

[0115] 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, or inkjet printing, and the steps of drying the applied semiconductor photoresist composition to form a photoresist film 106.

[0116] Since the compositions for semiconductor photoresists have already been explained in detail, we will omit any redundant explanations.

[0117] 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.

[0118] Referring to Figure 1(c), the photoresist film 106 is selectively exposed using a patterned mask 110.

[0119] As an example, examples of light that can be used in the exposure process include not only light with wavelengths such as i-line (wavelength 365 nm), KrF excimer laser (wavelength 248 nm), and ArF excimer laser (wavelength 193 nm), but also light with high energy wavelengths such as EUV (wavelength 13.5 nm) or electron beam (E-Beam).

[0120] More specifically, the exposure light according to one embodiment may be light having a wavelength range of 5 nm to 150 nm, and may also be light having a high energy wavelength such as EUV or an electron beam.

[0121] 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.

[0122] 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.

[0123] 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.

[0124] 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, or toluene; or combinations thereof.

[0125] 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.

[0126] As described above, the photoresist pattern 108 formed by exposure with light such as i-line (wavelength 365 nm), KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), etc., and also with light having high energy such as EUV (wavelength 13.5 nm), electron beam (E-Beam), etc., can have a width with a thickness of 5 nm to 100 nm. As an example, the photoresist pattern 108 can be formed with a width of 5 nm to 90 nm, 5 nm to 80 nm, 5 nm to 70 nm, 5 nm to 60 nm, 5 nm to 50 nm, 5 nm to 40 nm, 5 nm to 30 nm, 5 nm to 20 nm.

[0127] On the other hand, the photoresist pattern 108 can have a pitch with 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 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.

[0128] Next, the resist underlayer film 104 is etched using the photoresist pattern 108 as an etching mask. In such an etching process, an organic film pattern 112 is formed. The formed organic film pattern 112 can also have a width corresponding to the photoresist pattern 108.

[0129] Referring to (e) of FIG. 1, the thin film 102 exposed by applying the photoresist pattern 108 as an etching mask is etched. As a result, the thin film is formed as a thin film pattern 114.

[0130] The etching of the thin film 102 can be performed, for example, by dry etching using an etching gas, and the etching gas can be, for example, CHF3, CF4, Cl2, BCl 3、 and a mixed gas of these can be used.

[0131] 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 a width of 5 nm to 90 nm, 5 nm to 80 nm, 5 nm to 70 nm, 5 nm to 60 nm, 5 nm to 50 nm, 5 nm to 40 nm, 5 nm to 30 nm, or 5 nm to 20 nm, similar to the photoresist pattern 108, and more specifically, it can be formed with a width of 20 nm or less.

[0132] 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.

[0133] <Synthesis of organometallic compounds> <Synthesis Example 1> 340.7g of t-butylSnPh and 300g of propionic acid were placed in a 250ml two-necked round-bottom flask and heated under reflux for 24 hours.

[0134] The unreacted propionic acid was removed under reduced pressure to obtain the compound represented by the following chemical formula 5.

[0135] [Chemical formula 5] [ka]

[0136] <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.

[0137] [Chemical formula 6] [ka]

[0138] <Synthesis Example 3> 10 g of dibutyltin dichloride was dissolved in 30 mL of ether, then 70 mL of 1 M sodium hydroxide aqueous solution was added and the mixture was stirred for 1 hour. After stirring, the resulting solid was filtered, washed three times with 25 mL of deionized water, and then dried under reduced pressure at 100°C to obtain an organometallic compound with a weight-average molecular weight of 1,500 represented by the following chemical formula 7.

[0139] [Chemical formula 7] [ka]

[0140] <Manufacturing of semiconductor photoresist compositions> <Examples 1-21 and Comparative Examples 1-3> The organometallic compounds represented by chemical formulas 5 to 7 obtained in Synthesis Examples 1 to 3 were each dissolved in propylene glycol methyl ether acetate (PGMEA) at a concentration of 3% by weight. Alcohol compounds A1 to A4, each substituted with at least one halogen, and unsubstituted alcohol compounds B1 and B2 were added and dissolved in the weight ratios shown in Table 1 below. The mixture was then filtered through a 0.1 μm PTFE (polytetrafluoroethylene) syringe filter to produce semiconductor photoresist compositions according to Examples 1 to 21 and Comparative Examples 1 to 3.

[0141] [Table 1]

[0142] [Alcohol compounds with halogen substitutions] A1:2-iodoethanol, A2:4-iodophenol, A3: 2-fluoroethanol, A4: 2-fluorophenol

[0143] [Alcohol compounds without halogen substitution] B1: Propanol, B2: Pinacol

[0144] <Evaluation 1: Surface Roughness (Rq) Evaluation> A photoresist composition was spin-coated onto a wafer at 1500 rpm for 60 seconds, and then baked at 110°C for 60 seconds to form a thin film. The surface roughness of the thin film was then measured using software (optical profiler) from images taken with an atomic force microscope (AFM) according to the following criteria, and the results are shown in Table 2.

[0145] [Surface roughness (Rq value) evaluation criteria] ○: 0.4 or less △: More than 0.4 but less than 0.7 ×: More than 0.7

[0146] <Evaluation 2: Sensitivity and LER characteristics evaluation> The photoresist compositions according to the examples and comparative examples were spin-coated onto a 200 mm circular silicon wafer whose surface was deposited with HMDS at 1500 rpm for 30 seconds, baked at 110°C for 60 seconds (post-apply bake, PAB), and then left at room temperature (23±2°C) for 30 seconds.

[0147] Subsequently, a linear array with a width of 50 nm was projected onto a wafer coated with the photoresist composition using EUV light (Lawrence Berkeley National Laboratory Micro Exposure Tool, MET). The pad exposure time was adjusted so that the increased EUV dose was applied to each pad.

[0148] Subsequently, the resist and substrate were exposed on a hot plate at 160°C for 120 seconds and then baked. The baked film was developed with PGMEA solvent to form a negative tone image. Finally, the process was completed by baking on a hot plate at 150°C for 2 minutes.

[0149] Using a CD-SEM, the resist linewidth in response to exposed dose (energy) changes was measured. The appropriate sensitivity to exposure was confirmed from the resist linewidth values ​​formed differently for each exposure dose, and the sensitivity and LER were evaluated according to the following criteria. The results are shown in Table 2.

[0150] [Sensitivity evaluation criteria] A: 33 mJ / cm 2 less than B: 33mJ / cm 2 More than 36mJ / cm 2 less than C: 36 mJ / cm² 2 More than 39mJ / cm 2 less than D: 40 mJ / cm 2 That's all.

[0151] [LER Evaluation Criteria] ◎: Less than 3nm ○: 3nm or more and less than 4nm △: 4nm or more and less than 5nm ×: 5nm or more

[0152] [Table 2]

[0153] The results in Table 2 confirm that the photoresist compositions for semiconductors produced in Examples 1 to 21 exhibit superior sensitivity and LER characteristics compared to Comparative Examples 1 to 3.

[0154] 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]

[0155] 100 circuit boards 102 Thin film 104 Resist underlayer 106 Photoresist film 106a Unexposed area 106b Exposed region 108 Photoresist Patterns 112 Organic film patterns 110 patterned masks 114 Thin Film Patterns

Claims

1. Organometallic compounds and, An alcohol compound in which at least one halogen is substituted, Alcohol compounds with unsubstituted halogens, A composition for semiconductor photoresists comprising a solvent.

2. The semiconductor photoresist composition according to claim 1, wherein the alcohol compound substituted with at least one halogen is represented by the following chemical formula 1. [Chemical formula 1] 【Chemistry 1】 (In the above chemical formula 1, Z is a halogen, A is 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 alkynylene groups having 2 to 10 carbon atoms, substituted or unsubstituted cycloalkanes having 3 to 20 carbon atoms, substituted or unsubstituted cycloalkenes having 3 to 20 carbon atoms, and substituted or unsubstituted aromatic rings having 6 to 20 carbon atoms. n1 and m1 are each independent integers greater than or equal to 1. n1 + m1 is an integer less than or equal to the bond valency of A.

3. The semiconductor photoresist composition according to claim 2, wherein the chemical formula 1 is represented by any one of the following chemical formulas 1-1 to 1-4. [Chemical formula 1-1] 【Chemistry 2】 [Chemical formula 1-2] 【Transformation 3】 [Chemical formula 1-3] 【Chemistry 4】 [Chemical formula 1-4] 【Transformation 5】 (Among the above chemical formulas 1-1 to 1-4, Z is a halogen, R １ ~R ８ Each of these is independently a hydrogen atom, a halogen, a hydroxyl group, an amino group, a nitro group, a substituted or unsubstituted C1-C30 amine group, a substituted or unsubstituted C1-C10 alkyl group, or a substituted or unsubstituted C6-C20 aryl group. n is one of the integers from 1 to 10.

4. The semiconductor photoresist composition according to claim 1, wherein the alcohol compound substituted with at least one halogen is selected from the compounds listed in Group 1 below. [Group 1] 【Transformation 6】

5. The semiconductor photoresist composition according to claim 1, wherein the unsubstituted halogen alcohol compound is represented by the following chemical formula 2. [Chemical formula 2] 【Transformation 7】 (In the above chemical formula 2, B is 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 alkynylene groups having 2 to 10 carbon atoms, substituted or unsubstituted cycloalkanes having 3 to 20 carbon atoms, substituted or unsubstituted cycloalkenes having 3 to 20 carbon atoms, and substituted or unsubstituted aromatic rings having 6 to 20 carbon atoms. n2 and m2 are each independently greater than or equal to 0. n² + m² is an integer greater than or equal to 1 and less than or equal to the bond valence of B. (Halogens are not included in the substituents that are substituted.)

6. The semiconductor photoresist composition according to claim 5, wherein the chemical formula 2 is represented by the following chemical formula 2-1. [Chemical formula 2-1] 【Transformation 8】 (In the above chemical formula 2-1, R ９ ~R １３ Each of these is independently a hydrogen atom, a hydroxyl group, an amino group, a nitro group, a substituted or unsubstituted C1-C30 amine group, a substituted or unsubstituted C1-C10 alkyl group, or a substituted or unsubstituted C6-C20 aryl group. n is one of the integers from 1 to 9.

7. The semiconductor photoresist composition according to claim 1, wherein the unsubstituted halogen alcohol compound is selected from the compounds listed in Group 2 below. [Group 2] 【Chemistry 9】

8. The semiconductor photoresist composition according to claim 1, wherein the alcohol compound substituted with at least one halogen and the alcohol compound not substituted with the halogen are contained in a weight ratio of 15:1 to 1:

15.

9. The semiconductor photoresist composition according to claim 1, wherein the alcohol compound substituted with at least one halogen and the alcohol compound not substituted with the halogen are contained in an amount of 0.01 to 20% by weight based on 100% by weight of the semiconductor photoresist composition.

10. 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.

11. 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.

12. 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.

13. The organometallic compound is represented by the following chemical formula 3, and the semiconductor photoresist composition is as described in claim 1. [Chemical formula 3] 【Chemistry 10】 (In the above chemical formula 3, R １４ 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 １５ to R １７ 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 (—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 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 hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof), amidinato (-NR ｈ C (NR ｉ ) R ｊ Here, R ｈ , R ｉ and R ｊ Each of these is independently hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof), alkylthio or arylthio (-SR ｋ Here, R ｋ (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), or a thiocarboxyl group (-S(CO)R ｌ Here, 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 １５ ~R １７ At least one of them is an alkoxy or aryloxy (-OR ｂ Here, R ｂ R 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 (-O(CO) where 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 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), amidat (-NR ｆ (COR ｇ ), here R ｆ and R ｇ Each of these is independently hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof), amidinato (-NR ｇ C (NR ｈ ) R ｉ Here, R ｈ , R ｉ and R ｊ Each of these is independently hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted 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 or arylthio (-SR ｋ Here, R ｋ (where R 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 thiocarboxyl group (-S(CO), where 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.)

14. The aforementioned R １５ ~R １７ At least one of them is an alkoxy or 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 (-O(CO)R ｃ Here, R ｃ The semiconductor photoresist composition according to claim 13, 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.

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

16. The semiconductor photoresist composition according to claim 1, wherein the organometallic compound is represented by the following chemical formula 4 or chemical formula 5. [Chemical formula 4] R １８ ｚ SnO （２－（ｚ／２）－（ｘ／２）） (OH) ｘ [Chemical formula 5] R １９ ａ Sn ｂ X ｃ Y ｄ (In the above chemical formula 4, R １８ is a hydrocarbyl group having 1 to 31 carbon atoms, where 0 < z ≤ 2 and 0 < (z + x) ≤ 4. In the aforementioned chemical formula 5, R １９ 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.)

17. 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 16 onto the etchable film to form a photoresist film; The steps include: patterning the aforementioned photoresist film to form a photoresist pattern; A pattern formation method comprising the step of etching a film to be etched using the aforementioned photoresist pattern as an etching mask.

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