Semiconductor photoresist composition and method of forming patterns using the composition

Abstract

To solve the following problem that: an organotin polymer having excellent absorption of extreme ultraviolet rays has shown greatly improved sensitivity while maintaining resolution and line edge roughness, but additional improvement of patterning characteristics is required for commercial availability.SOLUTION: A semiconductor photoresist composition comprising a Sn-containing organometallic compound, a carboxylic acid compound substituted with an O-containing heterocycle, and a solvent.SELECTED DRAWING: Figure 1

Description

[Technical Field]

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

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

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

[0004] Intrinsic image blur due to acid-catalyzed reactions in these polymeric photoresists limits resolution at small feature sizes, a well-known fact in electron beam (e-beam) lithography. Chemically amplified (CA) photoresists are designed for high sensitivity, but their typical elemental makeup reduces the photoresist's absorbance at 13.5 nm wavelengths, reducing sensitivity and presenting additional challenges under EUV exposure.

[0005] Additionally, when using CA photoresists, difficulties can be experienced with roughness issues at small feature sizes, and it has been demonstrated that line edge roughness (LER) increases due in part to reduced photospeed, which is due in part to the nature of the acid-catalyzed process. Due to the shortcomings and problems of CA photoresists, the semiconductor industry is calling for a new type of high-performance photoresist.

[0006] To overcome the drawbacks of chemically amplified organic photosensitive compositions, inorganic photosensitive compositions have been developed. Inorganic photosensitive compositions primarily utilize negative-tone patterning, which is resistant to removal by developer compositions due to chemical modification using a non-chemically amplified mechanism. Inorganic compositions contain inorganic elements with higher EUV absorption than hydrocarbons, ensuring high sensitivity even with a non-chemically amplified mechanism. They are also known to produce fewer line edge roughness and fewer defects due to their high sensitivity and reduced stochastic effect.

[0007] Inorganic photoresists based on peroxopolyacids of tungsten mixed with tungsten, niobium, titanium, and / or tantalum have been reported as radiation-sensitive materials for patterning (US Pat. No. 5,061,599; H. Okamoto, T. Iwayanagi, K. Mochiji, H. Umezaki, T. Kudo, Applied Physics Letters, 49(5), 298-300, 1986).

[0008] These materials have been effective for patterning large features in bilayer configurations with deep UV, x-ray, and electron beam sources. More recently, impressive performance has been demonstrated when using cationic hafnium metal oxide sulfate (HfSOx) materials with peroxocomplexing agents to image 15 nm half-pitch (HP) patterns with projection EUV exposure (US 2011-0045406; J.K. Stowers, A. Telecky, M. Kocsis, B.L. Clark, D.A. Keszler, A. Grenville, C.N. Anderson, P.P. Naulleau, Proc. SPIE, 7969, 796915, 2011). This system exhibits the best performance of any non-CA photoresist and has photospeeds approaching the requirements for a viable EUV photoresist. However, hafnium metal oxide sulfate materials with peroxo complexing agents have several practical drawbacks. First, these materials are coated with a highly corrosive sulfuric acid / hydrogen peroxide mixture, resulting in poor shelf-life stability. Second, because they are complex mixtures, it is difficult to modify their structure to improve performance. Third, they must be developed using extremely high-concentration solutions, such as 25 wt% TMAH (tetramethylammonium hydroxide).

[0009] Recently, active research has been conducted on tin-containing molecules, which are known to have excellent absorption of extreme ultraviolet rays. In the case of organotin polymers, one such polymer, alkyl ligands are dissociated by light absorption or the secondary electrons generated by the absorption, and crosslinking with surrounding chains through oxo bonds enables negative-tone patterning that is resistant to removal by organic developers. These organotin polymers have shown dramatic improvements in sensitivity while maintaining resolution and line edge roughness, but further improvements in patterning properties are required for commercialization. Summary of the Invention [Problem to be solved by the invention]

[0010] An embodiment of the present invention provides a composition for semiconductor photoresist that has excellent sensitivity and line edge roughness (LER) characteristics and has improved sensitivity.

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

[0012] A semiconductor photoresist composition according to one embodiment of the present invention comprises a Sn-containing organometallic compound, a carboxylic acid compound substituted with an oxygen-containing heterocycle, and a solvent.

[0013] A pattern forming method according to another embodiment of the present invention includes the steps of forming a layer to be etched on a substrate, applying the above-described semiconductor photoresist composition on the layer to be etched to form a photoresist layer, patterning the photoresist layer to form a photoresist pattern, and etching the layer to be etched using the photoresist pattern as an etching mask. [Effects of the Invention]

[0014] The semiconductor photoresist composition according to one embodiment of the present invention can achieve excellent sensitivity and excellent LER characteristics. [Brief explanation of the drawings]

[0015] [Figure 1] 1A to 1C are cross-sectional views illustrating a method for forming a pattern using a semiconductor photoresist composition according to an embodiment. DETAILED DESCRIPTION OF THE INVENTION

[0016] Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. However, in the description, descriptions of functions or configurations that are already known will be omitted in order to clarify the gist of the description.

[0017] In order to clarify the present description, parts unnecessary for the description have been omitted, and the same or similar components have been given the same reference numerals throughout the specification. Furthermore, the size and thickness of each component shown in the drawings are arbitrarily shown for the convenience of explanation, and the present description is not necessarily limited to those shown in the drawings.

[0018] In the drawings, thicknesses of multiple layers and regions are exaggerated to clearly show them. Also, for ease of explanation, the thicknesses of some layers and regions are exaggerated in the drawings. When a layer, film, region, plate, or other portion is said to be "on" another portion, this does not only mean that it is "directly on" that other portion, but also includes the case where there is another portion between them.

[0019] In this description, "substituted" means that a hydrogen atom is substituted with deuterium, halogen, a hydroxy group, a carboxyl group, a thiol group, a cyano group, a nitro group, -NRR' (wherein R and R' are each 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'' (wherein R, R', and R'' are each independently hydrogen, a substituted or unsubstituted "Unsubstituted" means substituted with a group selected from the group consisting of a saturated or unsaturated aliphatic hydrocarbon group having 1 to 30 carbon atoms, a substituted or unsubstituted saturated or unsaturated alicyclic hydrocarbon group having 3 to 30 carbon atoms, or a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 carbon atoms, an alkyl group having 1 to 30 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkylsilyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, 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 atoms are not substituted with other substituents and remain as hydrogen atoms.

[0020] Unless otherwise defined, the term "alkyl group" used herein refers to a straight-chain or branched-chain aliphatic hydrocarbon group. 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, a tert-butyl group, or a 2,2-dimethylpropyl group.

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

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

[0024] As used herein, "aliphatically unsaturated organic group" refers to a hydrocarbon group containing bonds between carbon atoms in the molecule that are double bonds, triple bonds, or a combination thereof.

[0025] The aliphatic unsaturated organic group may be an aliphatic unsaturated organic group having 2 to 8 carbon atoms. For example, the aliphatic unsaturated organic group may be an aliphatic unsaturated organic group having 2 to 7 carbon atoms, an aliphatic unsaturated organic group having 2 to 6 carbon atoms, an aliphatic unsaturated organic group having 2 to 5 carbon atoms, or an aliphatic unsaturated organic group having 2 to 4 carbon atoms. For example, the aliphatic unsaturated organic group having 2 to 4 carbon atoms may be a vinyl group, an ethynyl group, an allyl group, a 1-propenyl group, a 1-methyl-1-propenyl group, a 2-propenyl group, a 2-methyl-2-propenyl group, a 1-propynyl group, a 1-methyl-1-propynyl group, a 2-propynyl group, a 2-methyl-2-propynyl group, a 1-butenyl group, a 2-butenyl group, a 3-butenyl group, a 1-butynyl group, a 2-butynyl group, or a 3-butynyl group.

[0026] As used herein, "aryl group" refers to a cyclic substituent in which all elements have p-orbitals and these p-orbitals form conjugation, including monocyclic or fused-ring polycyclic (i.e., rings that share adjacent pairs of carbon atoms) functional groups.

[0027] As used herein, the term "heteroaryl group" refers to a substituent containing at least one heteroatom selected from the group consisting of N, O, S, P, and Si within an aryl group. Two or more heteroaryl groups may be directly linked via a sigma bond, or, if the heteroaryl group contains two or more rings, the two or more rings may be fused to each other. If the heteroaryl group is a fused ring, each ring may contain 1 to 3 heteroatoms.

[0028] As used herein, unless otherwise defined, the term "alkenyl group" refers to a straight-chain or branched-chain aliphatic hydrocarbon group and an aliphatic unsaturated alkenyl group containing one or more double bonds.

[0029] As used herein, unless otherwise defined, the term "alkynyl group" refers to a straight-chain or branched-chain aliphatic hydrocarbon group and an aliphatic unsaturated alkynyl group containing one or more triple bonds.

[0030] Hereinafter, a semiconductor photoresist composition according to one embodiment will be described.

[0031] A composition for semiconductor photoresist according to one embodiment of the present invention may include a Sn-containing organometallic compound, a carboxylic acid compound substituted with an oxygen-containing heterocycle, and a solvent.

[0032] The semiconductor photoresist composition contains a carboxylic acid compound substituted with an oxygen (O)-containing heterocycle, thereby improving sensitivity and LER and achieving excellent resolution.

[0033] The carboxylic acid compound substituted with an oxygen-containing heterocycle is represented by the following chemical formula 1.

[0034] [ka]

[0035] In chemical formula 1, A1 is an oxygen-containing heterocycle; L 1 is a single bond, a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, a substituted or unsubstituted alkenylene group having 2 to 10 carbon atoms, a substituted or unsubstituted alkynylene group having 2 to 10 carbon atoms, or a substituted or unsubstituted arylene group having 6 to 20 carbon atoms.

[0036] The oxygen-containing heterocycle may be substituted or unsubstituted furan, substituted or unsubstituted tetrahydrofuran, substituted or unsubstituted pyran, substituted or unsubstituted dihydropyran, substituted or unsubstituted maleic anhydride, substituted or unsubstituted succinic anhydride, substituted or unsubstituted butyrolactone, or a combination thereof.

[0037] As an example, the carboxylic acid compound substituted with an oxygen-containing heterocycle is represented by any one of the following chemical formulas 1-1 to 1-7.

[0038] [ka]

[0039] In chemical formulas 1-1 to 1-7, R 1 ~R 6 are each independently a hydrogen atom, a halogen atom, a hydroxy group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof; L 1 represents a single bond, a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, a substituted or unsubstituted alkenylene group having 2 to 10 carbon atoms, a substituted or unsubstituted alkynylene group having 2 to 10 carbon atoms, or a substituted or unsubstituted arylene group having 6 to 20 carbon atoms, m1 and m3 each independently represent an integer from 1 to 7; m2 is an integer from 1 to 5; m4 and m5 each independently represent an integer of 1 to 3; m6 is 1.

[0040] When m1 is 2 or more, each R 1 may be the same or different from each other.

[0041] When m2 is 2 or more, each R 2 may be the same or different from each other.

[0042] If m3 is 2 or more, each R 3 may be the same or different from each other.

[0043] If m4 is 2 or more, each R 4 may be the same or different from each other.

[0044] If m5 is 2 or more, each R 5 may be the same or different from each other.

[0045] If m6 is 2 or more, each R 6 may be the same or different from each other.

[0046] As a specific example, the carboxylic acid compound substituted with an oxygen-containing heterocycle may be one selected from the compounds listed in Group 1 below.

[0047] [ka]

[0048] The carboxylic acid compound substituted with an oxygen-containing heterocycle is contained in an amount of 0.001 to 10% by weight relative to 100% by weight of the semiconductor photoresist composition.

[0049] For example, the carboxylic acid compound substituted with an oxygen-containing heterocycle is contained in an amount of 0.01 to 10 wt %, 0.01 to 5 wt %, 0.05 to 5 wt %, or 0.1 to 5 wt % relative to 100 wt % of the semiconductor photoresist composition.

[0050] The Sn-containing organometallic compound is contained in an amount of 0.5% by weight to 30% by weight relative to 100% by weight of the semiconductor photoresist composition.

[0051] The composition for semiconductor photoresist according to one embodiment contains the Sn-containing organometallic compound and the carboxylic acid compound substituted with an oxygen-containing heterocycle in the above content ranges, thereby improving the sensitivity of the photoresist.

[0052] A semiconductor photoresist composition according to one embodiment may contain a Sn-containing organometallic compound and a carboxylic acid compound substituted with an oxygen-containing heterocycle in a weight ratio of 99:1 to 60:40 (Sn-containing organometallic compound:carboxylic acid compound substituted with an oxygen-containing heterocycle, the same applies below). For example, the semiconductor photoresist composition may contain a Sn-containing organometallic compound and a carboxylic acid compound substituted with an oxygen-containing heterocycle in a weight ratio of 90:10 to 60:40.

[0053] When the weight ratio of the Sn-containing organometallic compound to the carboxylic acid compound satisfies the above range, a semiconductor photoresist composition having excellent sensitivity can be provided.

[0054] The Sn-containing organometallic compound may contain at least one of an organic oxy group and an organic carbonyloxy group.

[0055] The organometallic compound is represented by the following chemical formula 2.

[0056] [ka]

[0057] In chemical formula 2,

[0058] R 9 is selected from a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and a substituted or unsubstituted arylalkyl group having 6 to 30 carbon atoms.

[0059] R 10 ~R 12 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 6 to 30 carbon atoms, an alkoxy group, or an aryloxy group (-OR a , where R a 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 b , R b 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 alkylamido group or a dialkylamido group (-NR c R d , where R c and R dare 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 group (-NR e (COR f ), where R e and R f 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 group (-NR g C(NR h )R i , where R g , R h and R i 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 alkylthio group, or an arylthio group (-SR j , where R j 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), or a thiocarboxyl group ((-SCO)R k , R kis 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).

[0060] R 10 ~R 12 At least one of the groups is an alkoxy group or an aryloxy group (-OR a , where R a 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 b , R b 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 alkylamido group, or a dialkylamido group (-NR c R d , where R c and R d 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 group (-NR e (COR f ), where R e and R fare 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 group (-NR g C(NR h )R i , where R g , R h and R i 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 alkylthio group, or an arylthio group (-SR j , where R j 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), and a thiocarboxyl group (-S(CO)R k , R k is selected from 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).

[0061] R 10 ~R 12 At least one of the groups is an alkoxy group or an aryloxy group (-OR a , where R ais 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), and a carboxyl group (-O(CO)R b , R b is selected from 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).

[0062] On the other hand, the compound represented by formula 2 has -OR as a ligand. a or -OC(=O)R b By including the compound (I), a pattern formed using a semiconductor photoresist composition containing the compound can exhibit excellent limit resolution.

[0063] Also, -OR a or -OC(=O)R b The ligand can determine the solubility of the compound represented by formula 2 in a solvent.

[0064] R 9 may be a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 8 carbon atoms, a substituted or unsubstituted aliphatic unsaturated organic group having 2 to 8 carbon atoms and containing one or more double bonds or triple bonds, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a substituted or unsubstituted heteroaryl group having 4 to 20 carbon atoms, a carbonyl group, an ethoxy group, a propoxy group, or a combination thereof.

[0065] R amay be a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 8 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 8 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 8 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or a combination thereof.

[0066] R b may be hydrogen, a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 8 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 8 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 8 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or a combination thereof.

[0067] R 9 may be a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, a tert-butyl group, a 2,2-dimethylpropyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, an ethenyl group, a propenyl group, a butenyl group, an ethynyl group, a propanyl group, a butynyl group, a phenyl group, a tolyl group, a xylene group, a benzyl group, a formyl group, an acetyl group, a propanoyl group, a butanoyl group, a pentanoyl group, an ethoxy group, a propoxy group, or a combination thereof.

[0068] R a may be 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 propanyl group, a butynyl group, a phenyl group, a tolyl group, a xylene group, a benzyl group, or a combination thereof.

[0069] R bmay be hydrogen, ethyl, propyl, butyl, isopropyl, tert-butyl, 2,2-dimethylpropyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, ethenyl, propenyl, butenyl, ethynyl, propanyl, butynyl, phenyl, tolyl, xylene, benzyl, or a combination thereof.

[0070] The Sn-containing organometallic compound is represented by the following chemical formula 3 or 4.

[0071] [Chemical formula 3] R 12 z SnO (2-(z / 2)-(x / 2)) (OH) x

[0072] In chemical formula 3, R 12 is a hydrocarbyl group having 1 to 31 carbon atoms, and 0 <z≦2であり、0<(z+x)≦4である。

[0073] [Chemical formula 4] R 13 a1 Sn b1 X c1 Y d1

[0074] In chemical formula 4, R 13 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 l or -OC(=O)R m and R lis 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; R m 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; a1, b1, c1 and d1 each independently represent an integer of 1 to 20.

[0075] The solvent contained in the semiconductor photoresist composition according to one embodiment is an organic solvent, and examples thereof may include, but are not limited to, aromatic compounds (e.g., xylene, toluene), alcohols (e.g., 4-methyl-2-pentanol, 4-methyl-2-propanol, 1-butanol, methanol, isopropyl alcohol, 1-propanol), ethers (e.g., anisole, tetrahydrofuran), esters (n-butyl acetate, propylene glycol monomethyl ether acetate, ethyl acetate, ethyl lactate), ketones (e.g., methyl ethyl ketone, 2-heptanone), and mixtures thereof.

[0076] The semiconductor resist composition according to an embodiment may further include a resin in addition to the Sn-containing organometallic compound, the carboxylic acid compound substituted with an oxygen-containing heterocycle, and the solvent.

[0077] The resin may be a phenolic resin containing at least one aromatic moiety listed in Group 2 below.

[0078] [ka]

[0079] The resin may have a weight average molecular weight of 500 to 20,000.

[0080] The resin may be contained in an amount of 0.1% by weight to 50% by weight based on the total content of the semiconductor photoresist composition.

[0081] When the resin is contained within the above content range, excellent etching resistance and heat resistance can be achieved.

[0082] The semiconductor photoresist composition preferably comprises the above-mentioned Sn-containing organometallic compound, a carboxylic acid compound, a solvent, and a resin.

[0083] The semiconductor photoresist composition according to the above-described embodiment may further include an additive, such as a surfactant, a crosslinking agent, a leveling agent, an organic acid, a quencher, or a combination thereof.

[0084] The surfactant may be, for example, but not limited to, alkylbenzene sulfonate, alkylpyridinium salt, polyethylene glycol, quaternary ammonium salt, or a combination thereof.

[0085] 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, and polymer-based crosslinking agents. Examples of crosslinking agents having at least two crosslink-forming substituents that can be used include methoxymethylated glycoluril, butoxymethylated glycoluril, 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-cyclohexanedicarboxylate, trimethylpropane triglycidyl ether, 1,3-bis(glycidoxypropyl)tetramethyldisiloxane, methoxymethylated urea, butoxymethylated urea, and methoxymethylated thiourea.

[0086] The leveling agent is used to improve coating flatness during printing, and any known leveling agent that is commercially available can be used.

[0087] 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 combinations thereof.

[0088] The quencher may be diphenyl(p-tolyl)amine, methyldiphenylamine, triphenylamine, phenylenediamine, naphthylamine, diaminonaphthalene, or a combination thereof.

[0089] The amount of these other additives used can be easily adjusted depending on the desired physical properties, or the additives can be omitted.

[0090] The semiconductor photoresist composition may further contain a silane coupling agent as an additive to enhance adhesion to the substrate (e.g., to improve the adhesive strength of the semiconductor photoresist composition to the substrate). Examples of the silane coupling agent include, but are not limited to, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltris(β-methoxyethoxy)silane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, and silane compounds containing carbon-carbon unsaturated bonds, such as trimethoxy[3-(phenylamino)propyl]silane.

[0091] The semiconductor photoresist composition may form patterns with a high aspect ratio without causing pattern collapse. Therefore, for example, to form fine patterns having a width of 5 nm to 100 nm, 5 nm to 80 nm, 5 nm to 70 nm, 5 nm to 50 nm, 5 nm to 40 nm, 5 nm to 30 nm, or 5 nm to 20 nm, the composition can be used in photoresist processes using light with a wavelength of 5 nm to 150 nm, such as light with a wavelength of 5 nm to 100 nm, light with a wavelength of 5 nm to 80 nm, light with a wavelength of 5 nm to 50 nm, light with a wavelength of 5 nm to 30 nm, or light with a wavelength of 5 nm to 20 nm. Therefore, the semiconductor photoresist composition according to one embodiment can be used to achieve extreme ultraviolet lithography using an EUV light source with a wavelength of approximately 13.5 nm.

[0092] According to another embodiment, a method for forming a pattern using a semiconductor photoresist composition may be provided. For example, the pattern formed may be a photoresist pattern.

[0093] According to one embodiment, a method for forming a pattern includes forming a layer to be etched on a substrate, applying a semiconductor photoresist composition on the layer to be etched to form a photoresist layer, patterning the photoresist layer to form a photoresist pattern, and etching the layer to be etched using the photoresist pattern as an etching mask.

[0094] A method for forming a pattern using a semiconductor photoresist composition will now be described with reference to Figure 1. Figure 1 is a cross-sectional view illustrating a method for forming a pattern using a semiconductor photoresist composition according to the present invention.

[0095] Referring to FIG. 1(a), first, an 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 description will be limited to the case where the object to be etched is the thin film 102. The surface of the thin film 102 is cleaned to remove 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.

[0096] Next, a composition for forming a resist underlayer film is coated by spin coating on the surface of the cleaned thin film 102 to provide a resist underlayer film 104. However, the coating method is not limited thereto, and various known coating methods, such as spray coating, dip coating, knife edge coating, printing, inkjet printing, and screen printing, can also be used.

[0097] The resist underlayer film coating step can be omitted, and the following description will be given of the case where a resist underlayer film is coated.

[0098] Thereafter, drying and baking processes are performed to form a resist underlayer film 104 on the thin film 102. The baking process can be performed at about 100 to about 500°C, for example, about 100 to about 300°C.

[0099] The resist underlayer film 104 is formed between the substrate 100 and the photoresist film 106, and can prevent non-uniformity of the photoresist linewidth and deterioration of pattern formability when radiation reflected at the interface between the substrate 100 and the photoresist film 106 or an interlayer hard mask is scattered into unintended photoresist regions.

[0100] 1(b), a semiconductor photoresist composition is coated on the resist underlayer film 104 to form a photoresist film 106. The photoresist film 106 may be formed by coating the semiconductor photoresist composition on the thin film 102 formed on the substrate 100 and then curing it through a heat treatment process.

[0101] More specifically, the step of forming a pattern using the semiconductor photoresist composition may include a step of applying the semiconductor photoresist composition onto the substrate 100 on which the thin film 102 has been formed by a spin coating method, a slit coating method, an inkjet printing method, or the like, and a step of drying the applied semiconductor photoresist composition to form the photoresist film 106.

[0102] The semiconductor photoresist composition has already been explained in detail, so a duplicate explanation will be omitted.

[0103] Next, a first baking step is performed to heat the substrate 100 on which the photoresist film 106 is formed. The first baking step can be performed at a temperature of about 80°C to about 120°C.

[0104] Referring to FIG. 1( c ), the photoresist film 106 is selectively exposed to light using a patterned mask 110 .

[0105] Examples of light that can be used in the exposure process include light with short wavelengths such as activation irradiation i-line (wavelength 365 nm), KrF excimer laser (wavelength 248 nm), and ArF excimer laser (wavelength 193 nm), as well as light with high-energy wavelengths such as EUV (Extreme UltraViolet; wavelength 13.5 nm) and E-Beam (electron beam).

[0106] More specifically, the exposure light in one embodiment may be short wavelength light having a wavelength range of 5 nm to 150 nm, or may be light having a high energy wavelength such as EUV (Extreme UltraViolet; wavelength 13.5 nm) or E-Beam (electron beam).

[0107] The exposed regions 106b in the photoresist film 106 have a different solubility from the unexposed regions 106a of the photoresist film 106 by forming a polymer through a crosslinking reaction such as condensation between organometallic compounds.

[0108] Next, a second baking step is performed on the substrate 100. The second baking step can be performed at a temperature of about 90° C. to about 200° C. By performing the second baking step, the exposed region 106b of the photoresist film 106 becomes less soluble in a developer.

[0109] 1(d) shows a photoresist pattern 108 formed by using a developer to dissolve and remove the unexposed regions 106a of the photoresist film 106. Specifically, the unexposed regions of the photoresist film 106 are dissolved and removed using an organic solvent such as 2-heptanone, thereby completing the photoresist pattern 108 corresponding to a negative tone image.

[0110] As described above, the developer used in the pattern formation method according to an embodiment may be an organic solvent. Examples of the organic solvent used in the pattern formation method according to an embodiment include ketones such as methyl ethyl ketone, acetone, cyclohexanone, and 2-heptanone, alcohols such as 4-methyl-2-propanol, 1-butanol, isopropanol, 1-propanol, and methanol, esters such as propylene glycol monomethyl ether acetate, ethyl acetate, ethyl lactate, n-butyl acetate, and butyrolactone, aromatic compounds such as benzene, xylene, and toluene, and combinations thereof.

[0111] However, the photoresist pattern according to an embodiment is not necessarily limited to being formed as a negative tone image, and may also be formed as 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.

[0112] As described above, the photoresist pattern 108 formed by exposure to light having a wavelength such as i-line (wavelength 365 nm), KrF excimer laser (wavelength 248 nm), or ArF excimer laser (wavelength 193 nm), as well as high-energy light such as EUV (Extreme UltraViolet; wavelength 13.5 nm) or E-Beam (electron beam), can have a thickness of 5 nm to 100 nm. For 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, or 5 nm to 20 nm.

[0113] On the other hand, the photoresist pattern 108 can have a pitch with a half-pitch of about 50 nm or less, e.g., 40 nm or less, 30 nm or less, 20 nm or less, 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.

[0114] Next, the resist underlayer film 104 is etched using the photoresist pattern as an etching mask, forming an organic layer pattern 112. The formed organic layer pattern 112 may also have a width corresponding to the photoresist pattern .

[0115] 1(e), the photoresist pattern 108 is applied as an etching mask to etch the exposed thin film 102. As a result, the thin film is shaped into a thin film pattern 114.

[0116] The thin film 102 can be etched by dry etching using an etching gas, such as CHF3, CF4, Cl2, BCl3, or a mixture thereof.

[0117] The thin film pattern 114 formed using the photoresist pattern 108 formed by the previous exposure process using an EUV light source may have a width corresponding to the photoresist pattern 108. For example, it may have a width of 5 nm to 100 nm, similar to the photoresist pattern 108. For example, the thin film pattern 114 formed by the exposure process using an EUV light source may 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, may have a width of 20 nm or less. [Example]

[0118] The present invention will be described in more detail below through examples of preparing the above-mentioned semiconductor photoresist composition, but the technical features of the present invention are not limited to the following examples.

[0119] (synthesis of organometallic compounds) Synthesis of organometallic compounds Synthesis Example 1 A 250 mL two-neck round-bottom flask was charged with 40.7 g of t-butyltriphenyltin and 300 g of propionic acid, and the resulting mixture was heated to reflux for 24 hours.

[0120] Unreacted propionic acid was removed under reduced pressure to obtain a compound represented by the following chemical formula 5.

[0121] [ka]

[0122] Synthesis Example 2 30 mL of anhydrous pentane was added to 10 g of t-amyltrichlorotin, and the temperature was maintained at 0°C. Then, 7.4 g of diethylamine and 6.1 g of ethanol were added and stirred at room temperature for 1 hour. After the reaction was completed, the mixture was filtered, the filtrate was concentrated, and the residue was dried in vacuo to obtain a compound represented by the following chemical formula 6.

[0123] [ka]

[0124] Synthesis Example 3 10 g of dibutyldichlorotin was dissolved in 30 mL of ether, and then 70 mL of 1 M aqueous sodium hydroxide (NaOH) was added. The resulting 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.

[0125] [ka]

[0126] (Preparation of Semiconductor Photoresist Composition) Examples 1 to 18 and Comparative Examples 1 to 3 The Sn-containing organometallic compounds represented by Chemical Formulas 5 to 7 obtained in Synthesis Examples 1 to 3 and the carboxylic acid compounds represented by A1 to A5 below were dissolved in polypropylene glycol methyl ether acetate (PGMEA) at a concentration of 3 wt % in the weight ratios shown in Table 1 below, and the resulting solutions were filtered through a 0.1 μm PTFE (polytetrafluoroethylene) syringe filter to prepare semiconductor photoresist compositions according to Examples 1 to 18 and Comparative Examples 1 to 3.

[0127] [ka]

[0128] [Table 1]

[0129] Evaluation 1: Sensitivity and Line Edge Roughness (LER) evaluation The photoresist compositions of the Examples and Comparative Examples were each spin-coated at 1500 rpm for 30 seconds onto a 200 mm circular silicon wafer whose surface had been deposited with HMDS, baked at 110°C for 60 seconds (post-apply bake, PAB), and then left at room temperature (23±2°C) for 30 seconds.

[0130] Then, a linear array of 50 circular pads with a diameter of 500 μm was projected onto the wafer coated with the photoresist composition using an EUV exposure tool (Lawrence Berkeley National Laboratory Micro Exposure Tool, MET). The EUV dose was adjusted by adjusting the pad exposure time.

[0131] The resist and substrate were then baked on a hotplate at 160°C for 120 seconds. The baked film was developed with PGMEA to form a negative tone image. The process was then terminated by baking on a hotplate at 150°C for 2 minutes.

[0132] The remaining resist thickness of the exposed pad was measured using an ellipsometer. The remaining thickness was measured for each exposure dose and graphed as a function of exposure dose to measure sensitivity. LER was measured from FE-SEM images, and then sensitivity and line edge roughness were evaluated according to the following criteria. The results are shown in Tables 2 to 4.

[0133] [Sensitivity evaluation criteria] A: 50mJ / cm 2 less than B: 50 mJ / cm 2 End

[0134] [LER evaluation criteria] ○: 2nm or less △: More than 2nm but less than 5nm X: More than 5nm

[0135] Rating 2: Resolution (CD) rating A line / space CD pattern was formed on the patterned wafer, and then the patterned wafer was transferred to a CD-SEM measuring device (GC-9380, manufactured by Hitachi) to measure the CD (Critical Dimension) size of the part of the mask pattern where the half-pitch was 14 nm. The minimum value of the space CD, which is the spacing between lines, is shown in Tables 2 to 4.

[0136] [Table 2]

[0137] [Table 3]

[0138] [Table 4]

[0139] From the results in Tables 2 to 4, it can be seen that the patterns formed using the semiconductor photoresist compositions of Examples 1 to 18 exhibit superior sensitivity, LER, and resolution characteristics compared to Comparative Examples 1 to 3.

[0140] As described above, although specific embodiments of the present invention have been described and illustrated, the present invention is not limited to the described embodiments, and it is obvious to those skilled in the art that various modifications and variations can be made without departing from the spirit and scope of the present invention. Therefore, such modifications or variations should not be understood individually from the technical spirit and perspective 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]

[0141] 100: Substrate 102: Thin film 104: Resist underlayer film 106: Photoresist film 106a: Unexposed area 106b: Exposed area 108: Photoresist pattern 112: Organic film pattern 110: Patterned mask 114: Thin film pattern

Claims

1. Sn-containing organometallic compound, a carboxylic acid compound substituted with an oxygen-containing heterocycle, and A composition for semiconductor photoresist, comprising a solvent.

2. The carboxylic acid compound substituted with an oxygen-containing heterocycle is represented by the following chemical formula 1: 【Chemical 1】 In the above Chemical Formula 1, A1 is an oxygen-containing heterocycle; L １ is a single bond, a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, a substituted or unsubstituted alkenylene group having 2 to 10 carbon atoms, a substituted or unsubstituted alkynylene group having 2 to 10 carbon atoms, or a substituted or unsubstituted arylene group having 6 to 20 carbon atoms.

3. 2. The semiconductor photoresist composition according to claim 1, wherein the oxygen-containing heterocycle is substituted or unsubstituted furan, substituted or unsubstituted tetrahydrofuran, substituted or unsubstituted pyran, substituted or unsubstituted dihydropyran, substituted or unsubstituted maleic anhydride, substituted or unsubstituted succinic anhydride, substituted or unsubstituted butyrolactone, or a combination thereof.

4. The carboxylic acid compound substituted with an oxygen-containing heterocycle is represented by any one of the following formulas 1-1 to 1-7: 【Chemistry 2】 In the chemical formulas 1-1 to 1-7, R １ ~R ６ each independently represents a hydrogen atom, a halogen atom, a hydroxy group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof; L １ represents a single bond, a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, a substituted or unsubstituted alkenylene group having 2 to 10 carbon atoms, a substituted or unsubstituted alkynylene group having 2 to 10 carbon atoms, or a substituted or unsubstituted arylene group having 6 to 20 carbon atoms, m1 and m3 are each independently an integer from 1 to 7; m2 is an integer from 1 to 5; m4 and m5 each independently represent an integer of 1 to 3; 2. The semiconductor photoresist composition according to claim 1, wherein m6 is 1.

5. 2. The semiconductor photoresist composition according to claim 1, wherein the carboxylic acid compound substituted with an oxygen-containing heterocycle is one selected from the compounds listed in Group 1 below. 【Chemistry 3】

6. 2. The semiconductor photoresist composition according to claim 1, wherein the carboxylic acid compound substituted with an oxygen-containing heterocycle is contained in an amount of 0.001 to 10 wt % relative to 100 wt % of the semiconductor photoresist composition.

7. 2. The semiconductor photoresist composition according to claim 1, wherein the carboxylic acid compound substituted with an oxygen-containing heterocycle is contained in an amount of 0.1 to 5 wt % relative to 100 wt % of the semiconductor photoresist composition.

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

9. 10. The semiconductor photoresist composition of claim 1, further comprising an additive selected from the group consisting of a surfactant, a crosslinking agent, a leveling agent, an organic acid, a quencher, and combinations thereof.

10. 2. The semiconductor photoresist composition according to claim 1, wherein the Sn-containing organometallic compound contains at least one of an organic oxy group and an organic carbonyl oxy group.

11. The Sn-containing organometallic compound is represented by the following chemical formula 2: 【Chemistry 4】 In the above Chemical Formula 2, R ９ is selected from a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and a substituted or unsubstituted arylalkyl group having 6 to 30 carbon atoms; R １０ ~R １２ 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 6 to 30 carbon atoms, an alkoxy group, or an aryloxy group (-OR ａ , where R ａ 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 ｂ , R ｂ 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 group or a dialkylamide group (—NR ｃ R ｄ , where R ｃ and R ｄ 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 group (—NR ｅ (COR ｆ ), where R ｅ and R ｆ 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 group (—NR ｇ C (NR ｈ ) R ｉ , where R ｇ , R ｈ and R ｉ 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 alkylthio group or an arylthio group (-SR ｊ , where R ｊ 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), or a thiocarboxyl group ((-SCO)R ｋ , R ｋ 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; R １０ ~R １２ At least one of the groups is an alkoxy group or an aryloxy group (—OR ａ , where R ａ 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 ｂ , R ｂ 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 group or a dialkylamide group (—NR ｃ R ｄ , where R ｃ and R ｄ 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 group (—NR ｅ (COR ｆ ), where R ｅ and R ｆ 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 group (—NR ｇ C (NR ｈ ) R ｉ , where R ｇ , R ｈ and R ｉ 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 alkylthio group or an arylthio group (-SR ｊ , where R ｊ 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), and a thiocarboxyl group (—S(CO)R ｋ , R ｋ is selected from the group consisting of 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.

12. The R １０ ~R １２ At least one of the groups is an alkoxy group or an aryloxy group (—OR ａ , where R ａ 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), and a carboxyl group (—O(CO)R ｂ , R ｂ is selected from the group consisting of 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.

13. The R ９ is a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 8 carbon atoms, a substituted or unsubstituted aliphatic unsaturated organic group having 2 to 8 carbon atoms and containing one or more double bonds or triple bonds, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a substituted or unsubstituted heteroaryl group having 4 to 20 carbon atoms, a carbonyl group, an ethoxy group, a propoxy group, or a combination thereof; R ａ is a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 8 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 8 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 8 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or a combination thereof; R ｂ is hydrogen, a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 8 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 8 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 8 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or a combination thereof.

14. The Sn-containing organometallic compound is represented by the following Chemical Formula 3 or Chemical Formula 4: [Chemical formula 3] R １２ ｚ SnO （２－（ｚ／２）－（ｘ／２）） (OH) ｘ In the above Chemical Formula 3, R １２ is a hydrocarbyl group having 1 to 31 carbon atoms, 0<z≦2, and 0<(z+x)≦4; [Chemical formula 4] R １３ ａ１ Sn ｂ１ X ｃ１ Y ｄ１ In the above Chemical Formula 4, R １３ 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 ｌ or -OC(=O)R ｍ and The R ｌ 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; R ｍ 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; 2. The semiconductor photoresist composition according to claim 1, wherein a1, b1, c1, and d1 each independently represent an integer of 1 to 20.

15. forming a film to be etched on a substrate; forming a photoresist film by applying the semiconductor photoresist composition according to any one of claims 1 to 14 onto the film to be etched; patterning the photoresist film to form a photoresist pattern; and etching the target layer using the photoresist pattern as an etching mask.

Images