Semiconductor photoresist composition and method of forming pattern using the same

Abstract

Disclosed are a semiconductor photoresist composition and a method of forming a pattern using the same. The semiconductor photoresist composition may include: a tin (Sn)-containing organometallic compound; comprising at least two keto groups; an aromatic ring compound substituted with at least one selected from the group consisting of-OH,-SH, and-NR13R14, wherein R13 and R14 may each independently be hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C20 aryl group; and a solvent.

Description

[0001] Cross-reference to related applications

[0002] This application claims priority to and the benefit of Korean Patent Application No. 10-2024-0022896, filed on February 16, 2024, in the Korean Intellectual Property Office, the disclosure of which is incorporated herein by reference in its entirety. Technical Field

[0003] One or more embodiments of the present disclosure relate to a semiconductor photoresist composition and a method of forming a pattern using the semiconductor photoresist composition. Background Art

[0004] Extreme ultraviolet (EUV) lithography has attracted widespread attention as a fundamental technology for manufacturing next-generation semiconductor devices. In other words, EUV lithography has garnered significant attention as a key technology for the production of next-generation semiconductor devices. EUV lithography is a pattern-forming technology that uses EUV radiation with a wavelength of 13.5 nanometers as an exposure light source. According to EUV lithography, during the manufacturing process of semiconductor devices (e.g., semiconductor chips), extremely fine patterns (e.g., less than or equal to 20 nanometers) can be formed during the exposure process.

[0005] Extreme ultraviolet (EUV) lithography is enabled by the development of compatible photoresists that can be processed at spatial resolutions of 16 nm or less. Efforts have been or are underway to meet the suboptimal specifications of chemically amplified (CA) photoresists for next-generation devices, such as resolution, speed, and feature roughness (also known as line edge roughness, or LER).

[0006] Intrinsic image blurring caused by acid-catalyzed reactions in polymer-based or type-based photoresists limits resolution of small features, a situation that has long existed in electron-beam (e-beam) lithography. Chemically amplified (CA) photoresists are designed for high sensitivity. However, their typical elemental composition reduces the photoresist's light absorption at a wavelength of 13.5 nm, potentially reducing their sensitivity. Furthermore, CA photoresists may encounter more difficulties with EUV exposure.

[0007] Furthermore, CA photoresists may experience difficulty with small feature sizes due to roughness issues, and the line edge roughness (LER) of CA photoresists may increase in experiments because the photospeed may be partially reduced due to the nature of the acid catalyst process. Therefore, due to these defects and problems of CA photoresists, the semiconductor industry needs or requires a new type of high-performance photoresist.

[0008] To overcome the shortcomings of chemically amplified (CA) organic photosensitive compositions, inorganic photosensitive compositions have been studied. These compositions are primarily or primarily used for negative tone patterning, resisting removal by developer compositions through chemical modification via a non-chemical amplification mechanism. Inorganic compositions contain inorganic elements with higher EUV absorptivity than hydrocarbon groups. Therefore, they can ensure sensitivity through a non-chemical amplification mechanism and may be less sensitive to stochastic effects, resulting in low line edge roughness and fewer defects.

[0009] Inorganic photoresists based on tungsten peroxypolyacids mixed with tungsten, niobium, titanium, and / or tantalum have been reported as radiation-sensitive materials for patterning.

[0010] These materials are effective for large-pitch patterning of bilayer configurations with extreme ultraviolet (DUV), X-ray, and electron beam sources. Improved performance was achieved when using a cationic hafnium metal oxide sulfate (HfSOx) material with a peroxide complexing agent to image a 15nm half-pitch (HP) via projection EUV exposure. The system exhibited high performance for non-CA photoresists and had practical photospeeds approaching those required for EUV photoresists. However, HfSOx materials containing peroxide complexing agents have several practical drawbacks. First, these materials are coated in a corrosive sulfuric acid / hydrogen peroxide mixture and have insufficient shelf life stability. Second, varying the material structure as a composite mixture to improve performance is challenging. Third, development should be performed in a very concentrated 25 wt% tetramethylammonium hydroxide (TMAH) solution and / or similar solutions.

[0011] To address these issues, research has focused on developing molecules containing tin (Sn) that have excellent or moderate absorption of extreme ultraviolet light. In the case of organotin polymers in tin-containing molecules, the alkyl ligands dissociate through light absorption or the generation of secondary electrons. The dissociated alkyl ligands then crosslink with adjacent chains through oxo bonds, thereby achieving negative patterning that cannot be removed by organic developers. Although such organotin polymers exhibit greatly improved sensitivity and maintain the required resolution and line edge roughness, the patterning characteristics need further improvement for commercial viability. Summary of the Invention

[0012] One or more aspects of embodiments of the present disclosure are directed to a semiconductor photoresist composition having reduced pattern line width variation and particle defects according to oxynitride concentration and improved sensitivity.

[0013] One or more aspects of the embodiments of the present disclosure relate to a method of forming a pattern using the semiconductor photoresist composition.

[0014] Additional aspects will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the presented embodiments of the disclosure.

[0015] The semiconductor photoresist composition according to one or more embodiments of the present disclosure may include a tin (Sn)-containing organic metal compound, a compound including at least two ketone groups, a molecule selected from -OH, -SH and -NR 13 R 14 At least one substituted aromatic ring compound (wherein R 13 and R 14 and (each independently) hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C20 aryl group, and a solvent.

[0016] A method of forming a pattern according to one or more embodiments of the present disclosure may include forming an etch target layer on a substrate, coating a semiconductor photoresist composition on the etch target layer to form a photoresist layer, patterning the photoresist layer to form a photoresist pattern, and etching the etch target layer using the photoresist pattern as an etch mask.

[0017] The semiconductor photoresist composition according to one or more embodiments of the present disclosure may enable formation of clear patterns by reducing pattern line width variations and particle defects depending on oxynitride concentration and improving sensitivity. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] Figure 1A-1E is a cross-sectional view for explaining a method of forming a pattern using a semiconductor photoresist composition according to one or more embodiments of the present disclosure.

[0019] Explanation of Figure Numbers

[0020] 100: substrate;

[0021] 102: Film;

[0022] 104: resist bottom layer;

[0023] 106: photoresist layer;

[0024] 106a: unexposed area;

[0025] 106b: exposure area;

[0026] 108: photoresist pattern;

[0027] 110: patterned mask;

[0028] 112: organic layer pattern;

[0029] 114: Thin film pattern. DETAILED DESCRIPTION

[0030] The present disclosure can be modified in many alternative forms, and therefore specific embodiments will be illustrated in the drawings and described in more detail. However, it should be understood that there is no intention to limit the present disclosure to the particular forms disclosed, but rather to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the present disclosure.

[0031] Hereinafter, embodiments of the present disclosure will be described in more detail with reference to the accompanying drawings. In the following description of the present disclosure, well-known appropriate functions or structures will not be described in order to clarify the present disclosure.

[0032] In order to clearly illustrate the present disclosure, descriptions and relationships may not be provided here, and the same or similar configuration elements are designated by the same reference numerals throughout the disclosure. In addition, since the size and thickness of each configuration shown in the drawings are arbitrarily shown for better understanding and ease of description, the embodiments of the present disclosure are not necessarily limited thereto.

[0033] In the accompanying drawings, the thickness of layers, films, panels, regions, and / or the like may be exaggerated to improve clarity. In the accompanying drawings, the thickness of portions of layers or regions and / or the like may be exaggerated to improve clarity. It should be understood that if (for example, when) an element, such as a layer, film, region, or substrate, is referred to as being "on" another element, it can be directly on the other element, or intervening elements may be present. In contrast, when an element is referred to as being "directly on" another element, there are no intervening elements.

[0034] As used herein, "substituted" refers to the replacement of a hydrogen atom with deuterium, halogen, carboxyl, hydroxyl, thiol, cyano, nitro, -NRR' (wherein R and R' are each independently hydrogen, a substituted or unsubstituted C1 to C30 saturated or unsaturated aliphatic hydrocarbon group, a substituted or unsubstituted C3 to C30 saturated or unsaturated alicyclic hydrocarbon group, or a substituted or unsubstituted C6 to C30 aromatic hydrocarbon group), -SiRR'R" (wherein R, R' and R" are each independently hydrogen, a substituted or unsubstituted C1 to C30 saturated or unsaturated alicyclic hydrocarbon group, or a substituted or unsubstituted C6 to C30 aromatic hydrocarbon group), The term "substituted" refers to a C1 to C30 alkyl group (e.g., a C1 to C10 alkyl group, a C1 to C20 alkylsilyl group, a C3 to C30 cycloalkyl group, a C6 to C30 aryl group, a C1 to C20 alkoxy group, a C1 to C20 sulfide group, or any suitable combination thereof. "Unsubstituted" means that a hydrogen atom is not replaced with another substituent and the hydrogen atom remains.

[0035] As used herein, if (for example, when) no other definition is provided, "alkyl" refers to a straight-chain or branched aliphatic hydrocarbon group. The alkyl group may be a "saturated alkyl group" that does not contain any double or triple bonds.

[0036] The alkyl group may be a C1 to C8 alkyl group. For example, the alkyl group may be a C1 to C7 alkyl group, a C1 to C6 alkyl group, or a C1 to C5 alkyl group. For example, the C1 to C5 alkyl group 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.

[0037] As used herein, if (eg, when) no definition is otherwise provided, "cycloalkyl" refers to a monovalent cyclic aliphatic hydrocarbon group.

[0038] The cycloalkyl group may be a C3 to C8 cycloalkyl group, for example, a C3 to C7 cycloalkyl group, a C3 to C6 cycloalkyl group, a C3 to C5 cycloalkyl group, or a C3 to C4 cycloalkyl group. For example, the cycloalkyl group may be a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, or a cyclohexyl group, but the embodiments of the present disclosure are not limited thereto.

[0039] As used herein, the "aliphatic unsaturated organic group" refers to a hydrocarbon group containing a double bond, a triple bond, or (for example, any appropriate) combinations thereof between carbon atoms in the molecule.

[0040] The aliphatic unsaturated organic group can be a C2 to C8 aliphatic unsaturated organic group.For example, the aliphatic unsaturated organic group can be a C2 to C7 aliphatic unsaturated organic group, a C2 to C6 aliphatic unsaturated organic group, a C2 to C5 aliphatic unsaturated organic group or a C2 to C4 aliphatic unsaturated organic group.For example, the C2 to C4 aliphatic unsaturated organic group can be vinyl, ethynyl, allyl, 1-propenyl, 1-methyl-1-propenyl, 2-propenyl, 2-methyl-2-propenyl, 1-propynyl, 1-methyl-1-propynyl, 2-propynyl, 2-methyl-2-propynyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-butynyl, 2-butynyl or 3-butynyl.

[0041] As used herein, "aryl" refers to a cyclic substituent in which all atoms have p orbitals and these p orbitals are conjugated, and may include monocyclic functional groups, polycyclic functional groups, or fused ring (eg, rings sharing adjacent pairs of carbon atoms) functional groups.

[0042] As used herein, "heteroaryl" may refer to an aryl group containing at least one heteroatom selected from nitrogen (N), oxygen (O), sulfur (S), phosphorus (P), and silicon (Si). Two or more heteroaryl groups may be directly linked by a sigma bond, or if (e.g., when) the heteroaryl group contains two or more rings, the two or more rings may be fused. If (e.g., when) the heteroaryl group is a fused ring, each ring may contain one to three heteroatoms.

[0043] As used herein, unless otherwise defined, "alkenyl" refers to an aliphatically unsaturated alkenyl group containing at least one double bond as a straight-chain or branched aliphatic hydrocarbon group.

[0044] As used herein, unless otherwise defined, "alkynyl" refers to an aliphatic unsaturated alkynyl group containing at least one triple bond as a straight-chain or branched aliphatic hydrocarbon group.

[0045] Semiconductor photoresist compositions according to one or more embodiments of the present disclosure are described below.

[0046] The semiconductor photoresist composition according to one or more embodiments may include a tin (Sn)-containing organic metal compound; a compound including at least two ketone groups; a compound selected from -OH, -SH, and -NR 13 R 14 At least one substituted aromatic ring compound (wherein R 13 and R 14 and (each independently may be hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C20 aryl group); and a solvent.

[0047] In the semiconductor photoresist composition, by including a compound including at least two ketone groups that functions as or is used as a scavenger, line width variation rate can be minimized or reduced, and

[0048] In one or more embodiments, by comprising a hydrocarbon selected from -OH, -SH and -NR 13 R 14 At least one substituted aromatic ring compound (wherein R 13 and R 14 and (each independently may be hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C20 aryl group), defects, sensitivity, and LER may be improved due to solvent stabilization, thereby obtaining excellent or appropriate resolution.

[0049] For example, the weight ratio of the aromatic ring compound to the compound including at least two ketone groups may be about 1:1 to about 1:10.

[0050] For example, the weight ratio of the aromatic ring compound to the compound including at least two ketone groups may be about 1:1 to about 1:10, about 1:2 to about 1:10, or about 1:2 to about 1:9.

[0051] The compound including at least two keto groups may be represented by Chemical Formula 1 or Chemical Formula 2.

[0052] Chemical formula 1

[0053]

[0054] Chemical formula 2

[0055]

[0056] In Chemical Formula 1 and Chemical Formula 2,

[0057] R 1 to R 6 may each independently be hydrogen, halogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, or (for example, any suitable) combination thereof,

[0058] L 1 To L 3 may each independently be a single bond, a carbonyl group, a substituted or unsubstituted C1 to C20 alkylene group, or a combination thereof (eg, any suitable combination),

[0059] n1 and n2 can each independently be an integer from 0 to 2, and

[0060] n1+n2 may be greater than or equal to 1.

[0061] As an example, the aromatic ring compound may include a compound selected from -OH, -SH and -NR 13 R 14 At least one substituted phenyl group; selected from -OH, -SH and -NR 13 R 14 At least one substituted naphthyl group; selected from -OH, -SH and -NR 13 R 14 At least one substituted anthracene group; selected from -OH, -SH and -NR 13 R 14 At least one substituted phenanthrenyl; or selected from -OH, -SH and -NR 13 R 14 at least one substituted triphenylene group, and

[0062] R 13 and R 14 Each independently may be hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C20 aryl group.

[0063] For example, the aromatic ring compound can be selected from -OH, -SH and -NR 13 R 14 (where R 13 and R 14 and (the substituted or unsubstituted C1 to C10 alkyl groups) may be each independently substituted by at least two of hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C20 aryl group.

[0064] In one or more embodiments, the aromatic ring compound may be substituted with at least two -OH groups.

[0065] In another example, the aromatic ring compound may be substituted with at least two -SH groups.

[0066] In one or more embodiments, the aromatic ring compound may be formed by at least two -NR 13 R 14 Substitute (where R 13 and R 14 and (each independently represents hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C20 aryl group).

[0067] For example, the compound including at least two ketone groups may be any one selected from the group consisting of pentane-2,4-dione, 2,3-butanedione, 3-methyl-2,4-pentanedione, and 2,2,6,6-tetramethyl-3,5-heptanedione.

[0068] For example, the aromatic ring compound may be any one selected from 1,4-hydroquinone, 1,2-benzenediol, 1,3-benzenediol, benzene-1,2-dithiol, 1,4-phenylenediamine, 4-aminobenzene-1-thiol, 3-aminobenzene-1-thiol, and 2-aminobenzene-1-thiol.

[0069] The compound including at least two ketone groups and the aromatic ring compound may each be present in an amount of about 0.001 wt % to about 10 wt % based on 100 wt % of the semiconductor photoresist composition.

[0070] For example, the compound including at least two ketone groups and the aromatic ring compound may each be present in an amount of about 0.005 wt % to about 10 wt %, about 0.01 wt % to about 10 wt %, or about 0.1 wt % to about 5 wt %, based on 100 wt % of the semiconductor photoresist composition.

[0071] The tin-containing organometallic compound may be present in an amount of about 0.5 wt % to about 30 wt % based on 100 wt % of the semiconductor photoresist composition.

[0072] The semiconductor photoresist composition according to one or more embodiments of the present disclosure may include a tin-containing organic metal compound, a compound including at least two ketone groups, and an aromatic ring compound within the above-mentioned content (e.g., amount) range, thereby improving the sensitivity and solubility of the photoresist and reducing the line width variation rate depending on the atmospheric environment.

[0073] In the semiconductor photoresist composition according to one or more embodiments, the weight ratio of the tin-containing organometallic compound: the compound including at least two ketone groups, and the aromatic ring compound may be (i.e., the weight ratio of the tin-containing organometallic compound to the compound including at least two ketone groups and the aromatic ring compound may be) about 90:10 to about 50:50. For example, the semiconductor photoresist composition may include the tin-containing organometallic compound: the compound including at least two ketone groups, and the aromatic ring compound in a weight ratio of about 90:10 to about 60:40.

[0074] If (for example, when) the weight ratio 1) of 1) the tin-containing organometallic compound to 2) a) the compound including at least two ketone groups and 2) b) the aromatic ring compound satisfies the above range, a semiconductor photoresist composition having excellent or appropriate sensitivity can be provided.

[0075] The tin-containing organometallic compound may include at least one of an organooxy group and an organocarbonyloxy group.

[0076] The organometallic compound can be represented by Chemical Formula 3.

[0077] Chemical formula 3

[0078]

[0079] In Chemical Formula 3,

[0080] R 7 The group may be selected from substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, and substituted or unsubstituted C7 to C30 aralkyl,

[0081] R 8 to R 10Each of the above groups may independently be a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C7 to C30 aralkyl group, an alkoxy group or an aryloxy group (-OR a , where R a It may be a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, or any suitable combination thereof), a carboxyl group (-O(C=O)R b , where R b It may be hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, or any suitable combination thereof), an alkylamide group, or a dialkylamide group (-NR c R d , where R c and R d may each independently be hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof (e.g., any appropriate combination), an amide group (-NR e (C=OR f ), where R e and R f may each independently be hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof (e.g., any appropriate combination), an amidino group (-NR g C(NR h )R i , where R g 、R h and R iThe alkyl groups may each independently be hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof (e.g., any appropriate combination), an alkylthio group, or an arylthio group (-SR j , where R j It may be a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, or any suitable combination thereof, or a thiocarbonyl group (-S(C=O)R k , where R k may be hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, or any suitable combination thereof, and

[0082] R 8 to R 10 At least one of them can be selected from alkoxy or aryloxy (-OR a , where R a It may be a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, or any suitable combination thereof), a carboxyl group (-O(C=O)R b , where R b It may be hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, or any suitable combination thereof), an alkylamide group, or a dialkylamide group (-NR c R d , where R c and R d may each independently be hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof (e.g., any appropriate combination), an amide group (-NR e(C=OR f ), where R e and R f may each independently be hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof (e.g., any appropriate combination), an amidino group (-NR g C(NR h )R i , where R g 、R h and R i The alkyl groups may each independently be hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof (e.g., any appropriate combination), an alkylthio group, or an arylthio group (-SR j , where R j It may be a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, or any suitable combination thereof, or a thiocarbonyl group (-S(C=O)R k , R k It can be selected from hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, or any appropriate combination thereof.

[0083] R 8 to R 10 At least one of (eg, selected from) may be an alkoxy group or an aryloxy group (-OR a , where R a It may be a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof (e.g., any appropriate combination), or a carboxyl group (-O(C=O)R b , where R bIt may be hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, or (e.g., any appropriate) combination thereof.

[0084] In one or more embodiments, the compound represented by Chemical Formula 4 may include -OR a or -OC(=O)R b As a ligand, the compound can be used to allow a pattern formed using a semiconductor photoresist composition containing the compound to exhibit excellent or appropriate limiting resolution.

[0085] In one or more embodiments, OR a or -OC(=O)R b The ligand may determine the solubility of the compound represented by Chemical Formula 4 in a solvent.

[0086] R 7 It may be a substituted or unsubstituted C1 to C8 alkyl group, a substituted or unsubstituted C3 to C8 cycloalkyl group, a substituted or unsubstituted C2 to C8 aliphatic unsaturated organic group including one or more double bonds or triple bonds, a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C4 to C20 heteroaryl group, a carbonyl group, an ethoxy group, a propoxy group, or any suitable combination thereof,

[0087] R a may be a substituted or unsubstituted C1 to C8 alkyl group, a substituted or unsubstituted C3 to C8 cycloalkyl group, a substituted or unsubstituted C2 to C8 alkenyl group, a substituted or unsubstituted C2 to C8 alkynyl group, a substituted or unsubstituted C6 to C20 aryl group, or any suitable combination thereof, and

[0088] R b It may be hydrogen, substituted or unsubstituted C1 to C8 alkyl, substituted or unsubstituted C3 to C8 cycloalkyl, substituted or unsubstituted C2 to C8 alkenyl, substituted or unsubstituted C2 to C8 alkynyl, substituted or unsubstituted C6 to C20 aryl, or any suitable combination thereof.

[0089] R 7 The alkyl radical may be methyl, ethyl, propyl, butyl, isopropyl, tert-butyl, 2,2-dimethylpropyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, vinyl, propenyl, butenyl, ethynyl, propynyl, butynyl, phenyl, tolyl, xylyl, benzyl, formyl, acetyl, propionyl, butyryl, valeryl, ethoxy, propoxy, or any suitable combination thereof,

[0090] R a may be ethyl, propyl, butyl, isopropyl, tert-butyl, 2,2-dimethylpropyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, vinyl, propenyl, butenyl, ethynyl, propynyl, butynyl, phenyl, tolyl, xylyl, benzyl, or a combination thereof (e.g., any suitable combination), and

[0091] R b may be hydrogen, ethyl, propyl, butyl, isopropyl, tert-butyl, 2,2-dimethylpropyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, vinyl, propenyl, butenyl, ethynyl, propynyl, butynyl, phenyl, tolyl, xylyl, benzyl, or a combination thereof (e.g., any suitable combination).

[0092] In one or more embodiments, the organotin compound may be represented by Chemical Formula 4 or Chemical Formula 5.

[0093] Chemical Formula 4

[0094] R 11 z SnO (2-(z / 2)-(x / 2)) (OH) x

[0095] In Chemical Formula 4,

[0096] R 11 may be a C1-C31 hydrocarbon group, 0 < z ≤ 2, and 0 < (z + x) ≤ 4;

[0097] Chemical Formula 5

[0098] R 12 a1 Sn b1 X c1 Y d1

[0099] In Chemical Formula 5,

[0100] R 12 may be a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 aliphatic unsaturated organic group containing one or more double bonds or triple bonds, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C4-C30 heteroaryl group, a carbonyl group, an epoxyethyl group, an epoxypropyl group, or a combination thereof (e.g., any suitable combination),

[0101] X may be sulfur (S), selenium (Se), or tellurium (Te),

[0102] Y may be -OR l or -OC(=O)Rm ,

[0103] where R l It may be a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, or any suitable combination thereof,

[0104] R m may be hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, or any suitable combination thereof, and

[0105] a1, b1, c1, and d1 may each independently be an integer of 1 to 20.

[0106] The solvent of the semiconductor photoresist composition according to one or more embodiments may be an organic solvent, and may be, for example, one or more selected from aromatic compounds (e.g., xylene, toluene and / or the like), alcohols (e.g., 4-methyl-2-pentanol, 4-methyl-2-propanol, 1-butanol, methanol, isopropanol, 1-propanol and / or the like), ethers (e.g., anisole, tetrahydrofuran and / or the like), esters (e.g., n-butyrate, propylene glycol monomethyl ether acetate, ethyl acetate, ethyl lactate and / or the like), ketones (e.g., methyl ethyl ketone, 2-heptanone and / or the like) and / or mixtures thereof, but the embodiments of the present disclosure are not limited thereto.

[0107] According to one or more embodiments, the semiconductor photoresist composition includes the above-mentioned tin-containing organic metal compound, a compound including at least two ketone groups, a molecule selected from -OH, -SH and -NR 13 R 14 At least one substituted aromatic ring compound (wherein R 13 and R 14 The alkyl group (which may be independently hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C20 aryl group) and a solvent may further include a resin.

[0108] The resin may be a phenolic resin comprising at least one aromatic moiety selected from the moieties listed in Group 1.

[0109] Group 1

[0110]

[0111] The resin may have a weight average molecular weight of about 500 g / mol to about 20,000 g / mol.

[0112] The amount of the resin may be about 0.1 wt % to about 50 wt % based on the total amount of the semiconductor photoresist composition.

[0113] If (eg, when) the resin is within the above content (eg, amount) range, it may have excellent or appropriate etching resistance and heat resistance.

[0114] In contrast, the semiconductor photoresist composition according to one or more embodiments may include (e.g., consist of) the above-mentioned tin-containing organometallic compound, a compound including at least two ketone groups, a molecule selected from -OH, -SH and -NR 13 R 14 At least one substituted aromatic ring compound (wherein R 13 and R 14 which may each independently be hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C20 aryl group), a solvent, and a resin.

[0115] However, the semiconductor photoresist composition according to the above embodiment may further include additives as needed or desired. Examples of the additives may include surfactants, crosslinking agents, leveling agents, organic acids, quenchers, or any suitable combination thereof.

[0116] The surfactant may include, for example, alkylbenzene sulfonate, alkylpyridinium salt, polyethylene glycol, quaternary ammonium salt, or (eg, any appropriate) combination thereof, but embodiments of the present disclosure are not limited thereto.

[0117] The cross-linking agent may be, for example, a melamine-based cross-linking agent, a substituted urea-based cross-linking agent, an acrylic cross-linking agent, an epoxy-based cross-linking agent, or a polymer-based cross-linking agent, but embodiments of the present disclosure are not limited thereto. It may be a cross-linking agent having at least two cross-linking substituents, for example, a compound such as methoxymethylated biuret, butoxymethylated biuret, methoxymethylated melamine, butoxymethylated melamine, methoxymethylated benzoguanidine, butoxymethylated benzoguanidine, 4-hydroxybutyl acrylate, acrylic acid, urethane acrylate, methyl acrylate, 1,4-butanediol diglycidyl ether, glycidol, 1,2-cyclohexanedicarboxylic acid diglycidyl ester, trimethylolpropane triglycidyl ether, 1,3-bis(glycidyloxypropyl)tetramethyldisiloxane, methoxymethylated urea, butoxymethylated urea, methoxymethylated thiourea, and / or the like.

[0118] A leveling agent may be used to improve the flatness of the coating during the printing process and may be a suitable leveling agent available on the market.

[0119] The organic acid may include p-toluenesulfonic acid, benzenesulfonic acid, p-dodecylbenzenesulfonic acid, 1,4-naphthalene disulfonic acid, methanesulfonic acid, sulfonium fluoride, malonic acid, citric acid, propionic acid, methacrylic acid, oxalic acid, lactic acid, glycolic acid, succinic acid, or a combination thereof (e.g., any appropriate combination), but the embodiments of the present disclosure are not limited thereto.

[0120] The quencher can be diphenyl(p-tolyl)amine, methyldiphenylamine, triphenylamine, phenylenediamine, naphthylamine, diaminonaphthalene, or (eg, any suitable) combination thereof.

[0121] The amount of additives used can be controlled or selected according to desired or appropriate properties.

[0122] In one or more embodiments, the semiconductor photoresist composition may further include a silane coupling agent as an adhesion enhancer to improve the close contact force with the substrate (for example, to improve the adhesion of the semiconductor photoresist composition to the substrate). The silane coupling agent can be, for example, a silane compound containing a carbon-carbon unsaturated bond, such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltris(β-methoxyethoxy)silane, or 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, p-phenylyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, trimethoxy[3-(phenylamino)propyl]silane and / or the like, but embodiments of the present disclosure are not limited thereto.

[0123] Semiconductor photoresist compositions can form patterns with high aspect ratio and without collapse. In one or more embodiments, in order to form a fine pattern with, for example, about 5 nanometers to about 100 nanometers, for example, about 5 nanometers to about 80 nanometers, for example, about 5 nanometers to about 70 nanometers, for example, about 5 nanometers to about 50 nanometers, for example, about 5 nanometers to about 40 nanometers, for example, about 5 nanometers to about 30 nanometers, or for example, about 5 nanometers to about 20 nanometers width (for example, line width), semiconductor photoresist compositions can be used for the photolithography process using a wavelength range of about 5 nanometers to about 150 nanometers (for example, about 5 nanometers to about 100 nanometers, about 5 nanometers to about 80 nanometers, about 5 nanometers to about 50 nanometers, about 5 nanometers to about 30 nanometers, or about 5 nanometers to about 20 nanometers). In one or more embodiments, according to the semiconductor photoresist compositions of one or more embodiments, can be used for realizing extreme ultraviolet lithography using an EUV light source with a wavelength of about 13.5 nanometers.

[0124] According to one or more embodiments, a method for forming a pattern using the semiconductor photoresist composition is provided. For example, the pattern formed may be a photoresist pattern.

[0125] The method of forming a pattern according to one or more embodiments may include forming an etch target layer (e.g., an etch target layer) on a substrate, coating a semiconductor photoresist composition on the etch target layer to form a photoresist layer, patterning the photoresist layer to form a photoresist pattern, and etching the etch target layer using the photoresist pattern as an etch mask.

[0126] The following reference Figure 1A-1E Methods for forming patterns using semiconductor photoresist compositions are described. Figure 1A-1E is a cross-sectional view illustrating a method of forming a pattern using a semiconductor photoresist composition according to one or more embodiments.

[0127] Reference Figure 1A , a target for etching (e.g., an etching target layer or an etching target layer) may be prepared. The target for etching may be a thin film 102 formed on a semiconductor substrate 100. Hereinafter, the target for etching may be defined as the thin film 102. The surface of the thin film 102 may be cleaned to remove impurities and / or the like remaining thereon. The thin film 102 may be, for example, a silicon nitride layer, a polysilicon layer, or a silicon oxide layer.

[0128] Subsequently, a resist base layer composition for forming the resist base layer 104 may be spin-coated on the surface of the cleaned thin film 102. However, the embodiments of the present disclosure are not limited thereto, and one or more appropriate coating methods, such as spray coating, dip coating, doctor blade coating, printing methods (e.g., inkjet printing and / or screen printing), and / or the like, may be used.

[0129] The process of coating the resist base layer may not be provided, and the following description includes the process of coating the resist base layer.

[0130] The applied composition may then be dried and baked to form a resist bottom layer 104 on the thin film 102. The baking may be performed at a temperature of about 100°C to about 500°C (eg, about 100°C to about 300°C).

[0131] The resist bottom layer 104 can be formed between the substrate 100 and the photoresist layer 106, thereby preventing or reducing non-uniformity in the photoresist line width and patterning ability caused if (for example, when) light reflected from the interface between the substrate 100 and the photoresist layer 106 or the hard mask between the layers is scattered to unintended photoresist areas.

[0132] Reference Figure 1B , a photoresist layer 106 can be formed by coating a semiconductor photoresist composition on the resist base layer 104. The photoresist layer 106 can be obtained by coating the above-mentioned semiconductor photoresist composition on the thin film 102 formed on the substrate 100 and then curing it through heat treatment.

[0133] For example, forming a pattern using the semiconductor photoresist composition may include coating the semiconductor photoresist composition on the substrate 100 having the thin film 102 by spin coating, slit coating, inkjet printing, and / or the like, and then drying to form the photoresist layer 106 .

[0134] The semiconductor photoresist composition has been described in detail and will not be described again here.

[0135] Subsequently, the substrate 100 having the photoresist layer 106 may undergo a first baking (heat treatment) process. The first baking process may be performed at a temperature of about 80°C to about 120°C.

[0136] Reference Figure 1C , the photoresist layer 106 may be selectively exposed using a patterned mask 110 .

[0137] For example, exposure can use activating radiation including light having a high-energy wavelength, such as EUV (extreme ultraviolet; wavelength of about 13.5 nanometers), electron beam (E-Beam) and / or the like, as well as light having a short wavelength, such as i-line (wavelength of about 365 nanometers), KrF excimer laser (wavelength of about 248 nanometers), ArF excimer laser (wavelength of about 193 nanometers) and / or the like.

[0138] For example, the light or exposure beam used for exposure according to one or more embodiments may have a short wavelength and / or a high energy wavelength in the range of about 5 nanometers to about 150 nanometers, for example, may be EUV (extreme ultraviolet; wavelength 13.5 nanometers), and / or may be an electron beam (E-Beam), and / or similar light.

[0139] The exposed region 106 b of the photoresist layer 106 may form a polymer by utilizing a cross-linking reaction (eg, a condensation reaction between organic metal compounds) and thus have a different solubility from the unexposed region 106 a of the photoresist layer 106 .

[0140] Subsequently, the substrate 100 may undergo a second baking (heat treatment) process. The second baking process may be performed at a temperature of about 90° C. to about 200° C. Due to the second baking process, the exposed region 106 b of the photoresist layer 106 may become easily insoluble in a developer.

[0141] exist Figure 1D In the embodiment of the present invention, the unexposed regions 106a of the photoresist layer can be dissolved and removed using a developer to form a photoresist pattern 108. For example, the unexposed regions 106a of the photoresist layer can be dissolved and removed using an organic solvent (e.g., 2-heptanone and / or the like) to complete the photoresist pattern 108 corresponding to the negative image.

[0142] As described above, the developer used in the method for forming a pattern according to one or more embodiments may be an organic solvent. The organic solvent used in the method for forming a pattern according to one or more embodiments may be, for example, a ketone such as methyl ethyl ketone, acetone, cyclohexanone, 2-heptanone, and / or the like; an alcohol such as 4-methyl-2-propanol, 1-butanol, isopropanol, 1-propanol, methanol, and / or the like; an ester such as propylene glycol monomethyl ether acetate, ethyl acetate, ethyl lactate, n-butyl acetate, butyrolactone, and / or the like; an aromatic compound such as benzene, xylene, toluene, and / or the like, or (for example, any suitable) combination thereof.

[0143] However, the photoresist pattern according to one or more embodiments is not necessarily limited to a negative image, but can be formed to have a positive image. In one or more embodiments, the developer for forming the positive image can be a quaternary ammonium hydroxide composition, such as tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, or (e.g., any suitable) combination thereof.

[0144] In one or more embodiments, exposure to light having high energy, such as extreme ultraviolet (EUV; wavelength of 13.5 nm), E-beam (electron beam), or light having short wavelength, such as i-line (wavelength of approximately 365 nm), KrF excimer laser (wavelength of approximately 248 nm), or ArF excimer laser (wavelength of approximately 193 nm), can provide the photoresist pattern 108 having a width of approximately 5 nm to approximately 100 nm. For example, the photoresist pattern 108 can have a width of approximately 5 nm to approximately 90 nm, approximately 5 nm to approximately 80 nm, approximately 5 nm to approximately 70 nm, approximately 5 nm to approximately 60 nm, approximately 5 nm to approximately 50 nm, approximately 5 nm to approximately 40 nm, approximately 5 nm to approximately 30 nm, or approximately 5 nm to approximately 20 nm.

[0145] In one or more embodiments, the photoresist pattern 108 may have a pitch with a half pitch of less than or equal to about 50 nanometers (e.g., less than or equal to about 40 nanometers, e.g., less than or equal to about 30 nanometers, e.g., less than or equal to about 20 nanometers, or e.g., less than or equal to about 15 nanometers) and a line width roughness of less than or equal to about 10 nanometers, or less than or equal to about 5 nanometers, less than or equal to about 3 nanometers, or less than or equal to about 2 nanometers.

[0146] Subsequently, the resist bottom layer 104 may be etched using the photoresist pattern 108 as an etching mask. Through this etching process, an organic layer pattern 112 may be formed. The organic layer pattern 112 may also have a width corresponding to that of the photoresist pattern 108.

[0147] Reference Figure 1EBy using the photoresist pattern 108 as an etching mask, the exposed thin film 102 can be etched. As a result, the thin film can be formed into a thin film pattern 114.

[0148] The etching of the thin film 102 may be, for example, dry etching using an etching gas, which may be, for example, CHF 3 , CF 4 , Cl 2 , BCl 3 , or a (for example, any suitable) mixed gas thereof.

[0149] In the exposure process, the width of the thin film pattern 114 formed by using the photoresist pattern 108 formed by the exposure process using the EUV light source may correspond to the width of the photoresist pattern 108. For example, the thin film pattern 114 may have a width (e.g., line width) of about 5 nanometers to about 100 nanometers, which may be equal to the width of the photoresist pattern 108. For example, the thin film pattern 114 formed by using the photoresist pattern 108 formed by the exposure process using the EUV light source may have a width of about 5 nanometers to about 90 nanometers, about 5 nanometers to about 80 nanometers, about 5 nanometers to about 70 nanometers, about 5 nanometers to about 60 nanometers, about 5 nanometers to about 50 nanometers, about 5 nanometers to about 40 nanometers, about 5 nanometers to about 30 nanometers, or about 5 nanometers to about 20 nanometers, and, for example, have a width (e.g., line width) less than or equal to about 20 nanometers, like the width of the photoresist pattern 108.

[0150] Hereinafter, the present disclosure will be described in more detail by way of an example of preparing the above-mentioned semiconductor photoresist composition. However, the present disclosure is not technically limited to the following example.

[0151] Synthesis of organometallic compounds

[0152] Synthesis Example 1

[0153] 30 ml of anhydrous pentane was added to 10 g of tert-amyltin trichloride (t-AmylSnCl3) and the temperature was maintained at 0°C. 7.4 g of diethylamine and 6.1 g of ethanol were added thereto, followed by stirring at room temperature for 1 hour. When the reaction was complete, the resultant was filtered, concentrated, and vacuum-dried to obtain the compound represented by Chemical Formula 6.

[0154] Chemical formula 6

[0155]

[0156] Synthesis Example 2

[0157] 40.7 g of t-butyltriphenyltin (t-butylSnPh3) and 300 g of propionic acid were added to a 250 ml two-necked round-bottom flask, and then heated under reflux for 24 hours.

[0158] By removing unreacted propionic acid under reduced pressure, a compound represented by Chemical Formula 7 is obtained.

[0159] Chemical formula 7

[0160]

[0161] Synthesis Example 3

[0162] 10 g of dibutyltin chloride was dissolved in 30 ml of diethyl ether, and 70 ml of a 1 M sodium hydroxide (NaOH) aqueous solution was added, followed by stirring for 1 hour. After stirring, the resulting solid was filtered, washed three times with 25 ml of deionized water, and dried under reduced pressure at 100°C to obtain the organometallic compound represented by Chemical Formula 8, having a weight-average molecular weight of 1,500 g / mol.

[0163] Chemical formula 8

[0164]

[0165] Preparation of semiconductor photoresist compositions

[0166] Examples 1 to 10 and Comparative Examples 1 to 7

[0167] The organometallic compounds represented by Chemical Formulas 6 to 8 in Synthesis Examples 1 to 3 and the additives were dissolved in propylene glycol monomethyl ether acetate (PGMEA) at a concentration of 3 wt % in the weight ratios shown in Table 1, and then filtered through a 0.1 μm polytetrafluoroethylene (PTFE) syringe filter to prepare a semiconductor photoresist composition.

[0168] Table 1

[0169]

[0170] A1:1,4-Hydroquinone

[0171] A2: 1,2-benzenediolA3: 1,3-benzenediolA4: Benzene-1,2-dithiolA5: 1,4-phenylenediamine

[0172] B1: Pentane-2,4-dione

[0173] B2:2,3-Butanedione

[0174] C1:1,4-Benzoquinone

[0175] D1: Acetic acid

[0176] D2:1-Butanol

[0177] D3:2-Methyl-2-butanol

[0178] Evaluation 1: Sensitivity evaluation

[0179] Each photoresist composition according to the examples and comparative examples was spin-coated at 1500 rpm for 30 seconds on a 200 mm circular silicon wafer with hexamethyldisilazane (HMDS) deposited on the surface at room temperature (23±2° C.), and then baked at 110° C. for 60 seconds (post-coating baking (PAB)).

[0180] After that, EUV light is projected onto the wafer coated with the photoresist composition. Here, the exposure time of the pads is adjusted to ensure that each pad is applied with an increasing dose of EUV light.

[0181] After exposure, the resist and substrate were baked on a hot plate at 170°C for 60 seconds. The baked film was developed with a developer containing PGMEA solvent to form a negative image. Finally, the resulting film was baked again on a hot plate at 200°C for 60 seconds to complete the process.

[0182] Ellipsometers were used to measure the residual resist thickness of the exposed pads. The residual thickness was measured for each exposure dose and plotted as a function of exposure dose to measure sensitivity. The results are shown in Table 2.

[0183] The measurement error is ±2mJ.

[0184] Evaluation 2: Evaluation of resolution (CD)

[0185] After the process was completed, a line / space CD pattern was formed on the patterned wafer and then transferred to a critical dimension scanning electron microscope (CD-SEM) measurement device (GC-9380, Hitachi) to measure the CD (critical dimension) size of the mask pattern's 14nm half-pitch area and the minimum value of the space CD (i.e., the distance between lines). The CD increase rate calculated according to Equation 1 is shown in Table 2. The measurement error was ±1.0nm.

[0186] Formula 1

[0187] ΔCD: NO in air x NO in air at high concentrations x CD at low concentration

[0188] Nitrogen oxides (NO x ) Concentration range: If the concentration of nitrogen oxides in the atmosphere is > 0.015 ppm, it is defined as high concentration. If the concentration of nitrogen oxides in the atmosphere is ≤ 0.015 ppm, it is defined as low concentration.

[0189] Evaluation 3: Evaluation of particle defects

[0190] Particle defects on patterned wafers after processing are analyzed using inspection equipment (AIT-FUSION, KLA). Scanning electron microscopy is used to observe, classify, and analyze contaminant particles and defects on patterned wafers. Particle defect management is managed by particle count, with an ND (Not Detected) level indicating no significant contaminant particles were observed.

[0191] Table 2

[0192]

[0193] As can be seen from the results in Table 2, the patterns formed using the semiconductor photoresist compositions of Examples 1 to 10 all exhibited excellent or appropriate sensitivity and LER, and excellent or appropriate resolution characteristics, with no increase in CD, compared to Comparative Examples 1 to 7.

[0194] In this disclosure, the terms "and / or" and "or" may include any and all combinations of one or more of the listed items. Expressions such as "at least one of" when preceding a list of elements modify the entire list of elements and do not modify the individual elements of the list.

[0195] It will be further understood that the terms "comprising", "including" or "having" used in this disclosure specify the presence of the features, integers, steps, operations, elements and / or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components and / or groups thereof. The " / " used hereinafter may be interpreted as "and" or "or" as appropriate.

[0196] As used in this disclosure, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise. In addition, "may" used in describing embodiments of the present disclosure refers to "one or more embodiments of the present disclosure."

[0197] In the context of the present disclosure, unless otherwise defined, the terms "use," "using," and "used" may be considered synonymous with the terms "utilize," "utilizing," and "utilized," respectively.

[0198] As used in this disclosure, the term "about" or similar terms are used as terms of approximation, rather than terms of degree, and are intended to take into account the inherent variations in measured or calculated values recognized by those of ordinary skill in the art. As used herein, "about" or "approximately" is inclusive of the stated value and means within an acceptable range of deviation for the particular value as determined by one of ordinary skill in the art, taking into account the measurement in question and errors associated with the measurement of the particular quantity (i.e., limitations of the measurement system). For example, "about" may mean within one or more standard deviations, or within ±30%, 20%, 10%, or 5% of the stated value.

[0199] Any numerical range described herein is intended to include all subranges of the same numerical precision contained within the range. For example, a range of "1.0 to 10.0" is intended to include all subranges between (and including) the minimum value 1.0 and the maximum value 10.0, i.e., a minimum value equal to or greater than 1.0 and a maximum value equal to or less than 10.0, such as 2.4 to 7.6. Any maximum numerical limit described herein is intended to include all lower numerical limits contained therein, and any minimum numerical limit described in this specification is intended to include all higher numerical limits contained therein. Therefore, the applicant reserves the right to amend this specification (including the claims) to explicitly state any subrange contained within the range explicitly described herein.

[0200] A person of ordinary skill in the art will understand, based on the entire content of this disclosure, that each appropriate feature of the various embodiments of the disclosure may be partially or completely combined with each other or with other features, and may be technically locked and operated with each other in various appropriate manners, and each embodiment may be implemented independently or in combination with each other in any appropriate manner, unless otherwise specified or implied.

[0201] The pattern forming device, semiconductor forming device and / or any other related device or component according to an embodiment of the present invention can be implemented using any appropriate hardware, firmware (e.g., application specific integrated circuit), software, or a combination of software, firmware, and hardware. For example, the various components of the device can be formed on an integrated circuit (IC) chip or on a separate IC chip. In addition, the various components of the device can be implemented on a flexible printed circuit film, a tape carrier package (TCP), a printed circuit board (PCB), or formed on a substrate. In addition, the various components of the device can be processes or threads running on one or more processors in one or more computing devices, executing computer program instructions and interacting with other system components to perform the various functions described herein. The computer program instructions are stored in a memory, which can be implemented in a computing device using a standard storage device (e.g., random access memory (RAM)). The computer program instructions can also be stored in other non-transient computer-readable media, such as a CD-ROM, a flash drive, or similar devices. Furthermore, those skilled in the art will recognize that the functionality of various computing devices may be combined or integrated into a single computing device, or that the functionality of a particular computing device may be distributed across one or more other computing devices without departing from the scope of the present disclosure.

[0202] Hereinafter, one or more embodiments of the present disclosure have been described and illustrated. However, it is obvious to those skilled in the art that the present disclosure is not limited to the one or more embodiments described, and that appropriate modifications and conversions may be made without departing from the spirit and scope of the present disclosure. In one or more embodiments, such modified or converted embodiments may not be understood separately from the technical ideas and aspects of the present disclosure, and the modified embodiments are within the scope of the claims of the present disclosure and their equivalents.

Claims

1. A semiconductor photoresist composition comprising: Tin (Sn)-containing organometallic compounds; Compounds comprising at least two keto groups; Aromatic ring compounds selected from -OH, -SH and -NR 13 R 14 At least one substitution, wherein R 13 and R 14 are each independently hydrogen, substituted or unsubstituted C1 to C10 alkyl, or substituted or unsubstituted C6 to C20 aryl; and solvent.

2. The semiconductor photoresist composition according to claim 1, wherein The weight ratio of the aromatic ring compound to the compound including at least two ketone groups is 1:1 to 1:

10.

3. The semiconductor photoresist composition according to claim 1, wherein The compound including at least two ketone groups is represented by Chemical Formula 1 or Chemical Formula 2: Chemical formula 1 Chemical formula 2 in, In Chemical Formula 1 and Chemical Formula 2, R 1 to R 6 are each independently hydrogen, halogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, or a combination thereof, L 1 To L 3 are each independently a single bond, a carbonyl group, a substituted or unsubstituted C1 to C20 alkylene group, or a combination thereof, n1 and n2 are each independently an integer from 0 to 2, and n1+n2 is greater than or equal to 1.

4. The semiconductor photoresist composition according to claim 1, wherein The aromatic ring compound includes a ring selected from -OH, -SH and -NR 13 R 14 At least one substituted phenyl group; selected from -OH, -SH and -NR 13 R 14 At least one substituted naphthyl group; selected from -OH, -SH and -NR 13 R 14 At least one substituted anthracene group; selected from -OH, -SH and -NR 13 R 14 At least one substituted phenanthrenyl; or selected from -OH, -SH and -NR 13 R 14 At least one substituted triphenylene, and R 13 and R 14 Each is independently hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C20 aryl group.

5. The semiconductor photoresist composition according to claim 1, wherein The aromatic ring compound is selected from -OH, -SH and -NR 13 R 14 At least two of them are substituted, wherein R 13 and R 14 Each is independently hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C20 aryl group.

6. The semiconductor photoresist composition according to claim 5, wherein The aromatic ring compound is substituted with at least two -OH groups.

7. The semiconductor photoresist composition according to claim 5, wherein The aromatic ring compound is substituted with at least two -SH groups.

8. The semiconductor photoresist composition according to claim 5, wherein The aromatic ring compound is connected with at least two -NR 13 R 14 Substituted, where R 13 and R 14 Each is independently hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C20 aryl group.

9. The semiconductor photoresist composition according to claim 1, wherein The compound including at least two ketone groups is any one selected from pentane-2,4-dione, 2,3-butanedione, 3-methyl-2,4-pentanedione and 2,2,6,6-tetramethyl-3,5-heptanedione.

10. The semiconductor photoresist composition according to claim 1, wherein The aromatic ring compound is any one selected from 1,4-hydroquinone, 1,2-benzenediol, 1,3-benzenediol, benzene-1,2-dithiol, 1,4-phenylenediamine, 4-aminobenzene-1-thiol, 3-aminobenzene-1-thiol and 2-aminobenzene-1-thiol.

11. The semiconductor photoresist composition according to claim 1, wherein The compound including at least two ketone groups and the aromatic ring compound are each present in an amount of 0.001 wt % to 10 wt % based on 100 wt % of the semiconductor photoresist composition.

12. The semiconductor photoresist composition according to claim 1, wherein The amount of the tin-containing organometallic compound is 0.5 wt % to 30 wt % based on 100 wt % of the semiconductor photoresist composition.

13. The semiconductor photoresist composition according to claim 1, wherein The weight ratio of the tin-containing organic metal compound to the compound including at least two ketone groups and the aromatic ring compound is 90:10 to 50:

50.

14. The semiconductor photoresist composition according to claim 1, wherein The semiconductor photoresist composition further includes an additive of a surfactant, a crosslinking agent, a planarizing agent, an organic acid, a quencher, or a combination thereof.

15. The semiconductor photoresist composition according to claim 1, wherein The tin-containing organometallic compound includes at least one of an organooxy group and an organocarbonyloxy group.

16. The semiconductor photoresist composition according to claim 1, wherein The tin-containing organometallic compound is represented by Chemical Formula 3: Chemical formula 3 in, In Chemical Formula 3, R 7 is selected from substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, and substituted or unsubstituted C7 to C30 aralkyl, R 8 to R 10 Each is independently a substituted or unsubstituted C1 to C20 alkyl group; a substituted or unsubstituted C3 to C20 cycloalkyl group; a substituted or unsubstituted C2 to C20 alkenyl group; a substituted or unsubstituted C2 to C20 alkynyl group; a substituted or unsubstituted C6 to C30 aryl group; a substituted or unsubstituted C7 to C30 aralkyl group; or a Represents an alkoxy or aryloxy group, wherein R a is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof; and -O(C=O)R b Represents a carboxyl group, where R b is hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, or a combination thereof; -NR c R d An alkylamide or dialkylamide group, wherein R c and R d are each independently hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, or a combination thereof; -NR e (C=OR f ) represents an amide group, wherein R e and R f are each independently hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, or a combination thereof; -NR g C(NR h )R i represents an amidine group, wherein R g 、R h and R i are each independently hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, or a combination thereof; -SR j represents an alkylthio or arylthio group, wherein R j is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof; and -S(C=O)R k or thiocarbonyl, wherein R k is hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, or a combination thereof, and R 8 to R 10 At least one of -OR a Represents an alkoxy or aryloxy group, wherein R a is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof; and -O(C=O)R b Represents a carboxyl group, where R b is hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, or a combination thereof; -NR c R d An alkylamide or dialkylamide group, wherein R c and R d are each independently hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, or a combination thereof; -NR e (C=OR f ) represents an amide group, wherein R e and R f are each independently hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, or a combination thereof; -NR g C(NR h )R i represents an amidine group, wherein R g 、R h and R i are each independently hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, or a combination thereof; -SR j represents an alkylthio or arylthio group, wherein R j is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof; and -S(C=O)R k or thiocarbonyl, wherein R k is hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, or a combination thereof.

17. The semiconductor photoresist composition according to claim 16, wherein R 8 to R 10 At least one of the -OR a Represents an alkoxy or aryloxy group, wherein R a is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof; or is represented by -O(C=O)R b Represents a carboxyl group, where R b is hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, or a combination thereof.

18. The semiconductor photoresist composition according to claim 16, wherein R 7 is a substituted or unsubstituted C1 to C8 alkyl group, a substituted or unsubstituted C3 to C8 cycloalkyl group, a substituted or unsubstituted C2 to C8 aliphatic unsaturated organic group containing one or more double bonds or triple bonds, a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C4 to C20 heteroaryl group, a carbonyl group, an ethoxy group, a propoxy group, or a combination thereof, R a is a substituted or unsubstituted C1 to C8 alkyl group, a substituted or unsubstituted C3 to C8 cycloalkyl group, a substituted or unsubstituted C2 to C8 alkenyl group, a substituted or unsubstituted C2 to C8 alkynyl group, a substituted or unsubstituted C6 to C20 aryl group, or a combination thereof, and R b is hydrogen, substituted or unsubstituted C1 to C8 alkyl, substituted or unsubstituted C3 to C8 cycloalkyl, substituted or unsubstituted C2 to C8 alkenyl, substituted or unsubstituted C2 to C8 alkynyl, substituted or unsubstituted C6 to C20 aryl, or a combination thereof.

19. The semiconductor photoresist composition according to claim 1, wherein The tin-containing organometallic compound is represented by Chemical Formula 4 or Chemical Formula 5: Chemical formula 4 R 11 z SnO (2-(z / 2)-(x / 2)) (OH) x in, In Chemical Formula 4, R 11 is a C1 to C31 hydrocarbon group, 0 <z≤2,0<(z+x)≤4; Chemical formula 5 R 12 a1 Sn b1 X c1 Y d1 Wherein, in Chemical Formula 5, R 12 is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 aliphatic unsaturated organic group containing one or more double bonds or triple bonds, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C4 to C30 heteroaryl group, 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 , where R l is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof, R m is hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, or a combination thereof, and a1, b1, c1 and d1 are each independently an integer of 1 to 20.

20. A method for forming a pattern, comprising: forming an etching target layer on a substrate; applying the semiconductor photoresist composition according to any one of claims 1 to 19 on the etching target layer to form a photoresist layer; patterning the photoresist layer to form a photoresist pattern; as well as The etch target layer is etched using the photoresist pattern as an etch mask.

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