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, a compound represented by Chemical Formula 1, and a solvent.

Description

[0001] Cross-reference to related applications

[0002] This application claims priority to and the benefit of Korean Patent Application No. 10-2024-0022099, filed on February 15, 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 is gaining attention as a technology for manufacturing next-generation semiconductor devices. EUV lithography is a patterning technique that uses EUV radiation with a wavelength of 13.5 nanometers as an exposure light source. EUV lithography enables the formation of extremely fine patterns (e.g., less than or equal to 20 nanometers) during the exposure process in semiconductor device manufacturing.

[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 made to meet the insufficient 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 photoresists, depending on the polymer type or species, has long been known to limit resolution at small feature sizes in electron-beam (e-beam) lithography. CA photoresists are designed for high sensitivity. However, their elemental composition reduces the photoresist's light absorption at a wavelength of 13.5 nm, potentially reducing their sensitivity. CA photoresists may also encounter additional difficulties with EUV exposure.

[0007] CA photoresists can have difficulty with small feature sizes due to roughness issues, and experimentally, the line edge roughness (LER) of CA photoresists increases because the photospeed is reduced due in part to the nature of the acid catalyst process. Due to these shortcomings and problems with CA photoresists, the semiconductor industry needs or desires a new type of high-performance photoresist.

[0008] To overcome the shortcomings of chemically amplified (CA) organic photosensitive compositions, inorganic photosensitive compositions have been investigated. These compositions have been used for negative tone patterning, demonstrating resistance to removal by developer compositions through chemical modification, a non-chemical amplification mechanism. Inorganic compositions contain inorganic elements with higher EUV absorptivity than hydrocarbons. Therefore, they can ensure sensitivity through a non-chemical amplification mechanism and are potentially less sensitive to stochastic effects, resulting in low line-edge roughness and a reduced number of defects.

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

[0010] These materials are effective for large-pitch patterning of bilayer configurations using extreme ultraviolet (DUV), X-ray, and electron beam sources. Relatively high performance was achieved when a cationic hafnium metal oxide sulfate (HfSOx) material was used in conjunction with a peroxide complexing agent to image a 15nm half-pitch (HP) via projection EUV exposure. This system exhibited high performance for non-CA photoresists and had practical photospeeds approaching those required for EUV photoresists. However, hafnium metal oxide sulfate 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, structural changes to improve performance as a composite mixture are not easy to make. Third, development should be performed in a very concentrated 25 wt% tetramethylammonium hydroxide (TMAH) solution and / or the like.

[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 organotin polymers therein, 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 tone 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, further improvement of patterning properties is still needed for commercial availability. Summary of the Invention

[0012] One or more aspects of embodiments of the present disclosure are directed to a semiconductor photoresist composition having excellent sensitivity (or appropriate sensitivity) and storage stability (or appropriate storage stability).

[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] A semiconductor photoresist composition according to one or more embodiments of the present disclosure includes a tin (Sn)-containing organic metal compound; a compound represented by Chemical Formula 1; and a solvent.

[0015] Chemical formula 1

[0016]

[0017] In Chemical Formula 1,

[0018] X 1 It can be P(=O)R 4 or S(=O)2,

[0019] R 1 to R 4 may each 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 C1 to C20 alkoxy group, or a substituted or unsubstituted C6 to C30 aryloxy group, R 1 and R 2 can exist independently or can be linked to form a ring, and

[0020] From R 3 and R 4 At least one selected therefrom may be a fluorine-containing group.

[0021] A method of forming a pattern according to one or more embodiments of the present disclosure may include providing 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.

[0022] The semiconductor photoresist composition according to one or more embodiments of the present disclosure may achieve excellent sensitivity (or appropriate sensitivity) and storage stability (or appropriate storage stability). BRIEF DESCRIPTION OF THE DRAWINGS

[0023] The drawings, together with the specification, illustrate embodiments of the presently disclosed subject matter, and, together with the description, serve to explain principles of the embodiments of the presently disclosed subject matter.

[0024] 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 of the present disclosure.

[0025] Explanation of Figure Numbers

[0026] 100: substrate;

[0027] 102: Film;

[0028] 104: resist bottom layer;

[0029] 106: photoresist layer;

[0030] 106a: unexposed area;

[0031] 106b: exposure area;

[0032] 108: photoresist pattern;

[0033] 110: patterned mask;

[0034] 112: organic layer pattern;

[0035] 114: Thin film pattern. DETAILED DESCRIPTION

[0036] Hereinafter, one or more 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, functions or structures that are generally understood by those skilled in the art may not be described in order to clarify the present disclosure.

[0037] In order to clearly illustrate the embodiments of the present disclosure, some descriptions and relationships may be omitted, and throughout the present disclosure, the same (or substantially the same) or similar configuration elements may be represented by the same (or substantially the same) reference numerals. In addition, since the size and thickness of each configuration shown in the drawings may be arbitrarily displayed for better understanding and ease of description, the embodiments of the present disclosure are not necessarily limited thereto.

[0038] In the drawings, the thickness of layers, films, panels, regions, etc. may be exaggerated for clarity. In the drawings, the thickness of some layers or regions, etc. may be exaggerated for clarity. It will 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 also be present.

[0039] As used herein, "substituted" refers to hydrogen atoms replaced by deuterium, halogen, hydroxyl, thiol, cyano, nitro, -NRR' (wherein, R and R' can each independently be 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" can each independently be The term "unsubstituted" refers to a group consisting of a C1 to C30 alkyl group, a C1 to C30 saturated or unsaturated aliphatic hydrocarbon group, a C3 to C30 saturated or unsaturated alicyclic hydrocarbon group, or a C6 to C30 aromatic hydrocarbon group, a C1 to C30 alkyl group, a C1 to C10 haloalkyl group, a C1 to C10 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 a combination thereof. "Unsubstituted" means that a hydrogen atom is not replaced by another substituent and the hydrogen atom remains.

[0040] As used herein, if (for example, when) no definition is provided otherwise, "alkyl" may refer 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.

[0041] 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.

[0042] As used herein, if (eg, when) no definition is otherwise provided, "cycloalkyl" may refer to a monovalent cyclic aliphatic hydrocarbon group.

[0043] The cycloalkyl group may be a C3 to C8 cycloalkyl group, a C3 to C7 cycloalkyl group, or a C3 to C6 cycloalkyl group. For example, the cycloalkyl group may be a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, or a cyclohexyl group, but is not limited thereto.

[0044] As used herein, "aliphatic unsaturated organic group" refers to a hydrocarbon group containing bonds between carbon atoms in the molecule which may be double bonds, triple bonds, or a combination thereof.

[0045] 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.

[0046] As used herein, "aryl" refers to a cyclic substituent in which all atoms have p orbitals and these p orbitals are conjugated, and can include monocyclic functional groups, polycyclic functional groups, or fused ring (eg, rings that share adjacent pairs of carbon atoms) functional groups.

[0047] 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.

[0048] 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.

[0049] As used herein, unless otherwise defined, "alkynyl" refers to an aliphatically unsaturated alkynyl group containing at least one triple bond as a straight or branched aliphatic hydrocarbon radical.

[0050] Semiconductor photoresist compositions according to one or more embodiments of the present disclosure are described below.

[0051] A semiconductor photoresist composition according to one or more embodiments of the present disclosure may include a tin (Sn)-containing organic metal compound, a compound represented by Chemical Formula 1, and a solvent.

[0052] Chemical formula 1

[0053]

[0054] In Chemical Formula 1,

[0055] X 1 It can be P(=O)R 4 or S(=O)2,

[0056] R1 to R 4 may each 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 C1 to C20 alkoxy group, or a substituted or unsubstituted C6 to C30 aryloxy group, R 1 and R 2 can exist independently or can be linked to form a ring, and

[0057] From R 3 and R 4 At least one selected therefrom may be a fluorine-containing group.

[0058] The semiconductor photoresist composition may include a compound having a structure in which a fluorine-containing phosphate and an imide are linked through oxygen, thereby providing a photoresist composition having increased sensitivity (or appropriate sensitivity) to extreme ultraviolet light and improved storage stability (or appropriate storage stability).

[0059] In some embodiments, a compound having a structure in which a fluorine-containing phosphate or sulfate and an imide are linked by oxygen may not be ionic and therefore have relatively higher stability than ionic compounds. In some embodiments, if (for example, when) exposed to light, the phosphate or sulfate and imide moieties separate (for example, dissociate or decompose) to produce an acid, which may help improve sensitivity by changing the solubility of the photosensitive material in the developer with only a small amount of energy. By including fluorine, it may have a relatively high efficiency in absorbing light energy, and since the phosphate or sulfate is stable in an ionic state, it can easily dissociate even with a small amount of energy.

[0060] In some embodiments, R 1 and R 2 The connection to form a ring can be represented by Chemical Formula 1-1.

[0061] Chemical formula 1-1

[0062]

[0063] In Chemical Formula 1-1,

[0064] X 1 It can be P(=O)R 4 or S(=O)2,

[0065] R 3 and R 4may each 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 C1 to C20 alkoxy group, or a substituted or unsubstituted C6 to C30 aryloxy group,

[0066] From R 3 and R 4 At least one selected from may be a fluorine-containing group, and

[0067] R 5 to R 8 and 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, a substituted or unsubstituted C1 to C20 alkoxy group, or a substituted or unsubstituted C6 to C30 aryloxy group.

[0068] For example, the fluorine-containing group can be a C1 to C20 alkyl group substituted with at least one fluorine, a C3 to C20 cycloalkyl group substituted with at least one fluorine, a C2 to C20 alkenyl group substituted with at least one fluorine, a C2 to C20 alkynyl group substituted with at least one fluorine, a C6 to C30 aryl group substituted with at least one fluorine, a C1 to C20 alkoxy group substituted with at least one fluorine, or a C6 to C30 aryloxy group substituted with at least one fluorine. As used herein, "at least one fluorine" can mean "at least one fluorine atom".

[0069] In some embodiments, the fluorine-containing group may include a C1 to C10 alkyl group substituted with at least one fluorine, a C3 to C10 cycloalkyl group substituted with at least one fluorine, a C2 to C10 alkenyl group substituted with at least one fluorine, a C2 to C10 alkynyl group substituted with at least one fluorine, a C6 to C12 aryl group substituted with at least one fluorine, a C1 to C10 alkoxy group substituted with at least one fluorine, or a C6 to C12 aryloxy group substituted with at least one fluorine.

[0070] For example, the fluorine-containing group may be substituted with at least two fluorine atoms or at least three fluorine atoms (eg, at least two fluorine atoms or at least three fluorine atoms). In some embodiments, the fluorine-containing group may be a trifluoromethyl group, but is not limited thereto.

[0071] In some embodiments, the compound represented by Chemical Formula 1 may be (eg, selected from) one of the compounds listed in Group 1.

[0072] Group 1

[0073]

[0074] The compound represented by Chemical Formula 1 may be included in the semiconductor photoresist composition in an amount of about 0.01 wt % to about 10 wt % based on 100 wt % of the semiconductor photoresist composition. In some embodiments, the compound represented by Chemical Formula 1 may be included in an amount of about 0.01 wt % to about 10 wt % based on 100 wt % of the semiconductor photoresist composition.

[0075] For example, based on 100 wt % of the semiconductor photoresist composition, the compound represented by Chemical Formula 1 can be included in the semiconductor photoresist composition in an amount of about 0.01 wt % to about 5 wt % or about 0.05 wt % to about 5 wt %. In some embodiments, based on 100 wt % of the semiconductor photoresist composition, the amount of the compound represented by Chemical Formula 1 can be about 0.01 wt % to about 5 wt % or about 0.05 wt % to about 5 wt %.

[0076] The tin-containing organometallic compound can be included in the semiconductor photoresist composition in an amount of about 0.5 wt % to about 30 wt % based on 100 wt % of the semiconductor photoresist composition. In some embodiments, the tin-containing organometallic compound can be included in an amount of about 0.5 wt % to about 30 wt % based on 100 wt % of the semiconductor photoresist composition.

[0077] The semiconductor photoresist composition according to one or more embodiments of the present disclosure may improve the sensitivity of the photoresist by including the tin-containing organometallic compound and the compound represented by Chemical Formula 1 within the content range described in one or more embodiments of the present disclosure.

[0078] The semiconductor photoresist composition according to one or more embodiments of the present disclosure may include a tin-containing organometallic compound and a compound represented by Chemical Formula 1 in a weight ratio of about 99.9:0.1 to about 80:20. In some embodiments, the weight ratio of the tin-containing organometallic compound to the compound represented by Chemical Formula 1 may be about 99.9:0.1 to about 80:20. For example, the semiconductor photoresist composition may include a tin-containing organometallic compound and a compound represented by Chemical Formula 1 in a weight ratio of about 95:5 to about 85:15. In some embodiments, the weight ratio of the tin-containing organometallic compound to the compound represented by Chemical Formula 1 may be about 95:5 to about 85:15.

[0079] If (for example, when) the weight ratio of the tin-containing organometallic compound to the compound represented by Chemical Formula 1 satisfies the range described in one or more embodiments of the present disclosure, a semiconductor photoresist composition having excellent or appropriate sensitivity may be provided.

[0080] The tin-containing organometallic compound may include an organooxy group and / or an organocarbonyloxy group.

[0081] The tin-containing organometallic compound can be represented by Chemical Formula 2.

[0082] Chemical formula 2

[0083]

[0084] In Chemical Formula 2,

[0085] R 9 may be selected from substituted or unsubstituted C1 to C20 alkyl groups, substituted or unsubstituted C3 to C20 cycloalkyl groups, substituted or unsubstituted C2 to C20 alkenyl groups, substituted or unsubstituted C2 to C20 alkynyl groups, substituted or unsubstituted C6 to C30 aryl groups, and substituted or unsubstituted C7 to C30 aralkyl groups,

[0086] R 10 to R 12 Each 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 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), a carboxyl group (-O(C=O)R b , where R b The alkyl group 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 a combination thereof), an alkylamide group, or a dialkylamide group (-NR c R d , where R c and R d may be each independently 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), an amide group (-NR e (C=OR f ), where R e and Rf may be 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), an amidino group (-NR g C(NR h )R i , where R g 、R h and R i The thio 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), an alkylthio group, and an arylthio group (-SR k , where R k 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), or a thiocarboxyl group (-S(C=O)R l , where R l 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 a combination thereof, and

[0087] R 10 to R 12 At least one of them can be selected from alkoxy or aryloxy (-OR a , where R a 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), a carboxyl group (-O(C=O)R b , where R b The alkyl group 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 a combination thereof), an alkylamide group, or a dialkylamide group (-NR c R d, where R c and R d may be each independently 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), an amide group (-NR e (C=OR f ), where R e and R f may be 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), an amidino group (-NR g C(NR h )R i , where R g 、R h and R i The thio 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), an alkylthio group, and an arylthio group (-SR k , where R k 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), and a thiocarboxyl group (-S(C=O)R l , where R l The alkyl radical may 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 a combination thereof.

[0088] In some embodiments, R 10 to R 12 At least one of them can be selected from alkoxy or aryloxy (-OR a , where R amay 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), and a carboxyl group (-O(C=O)R b , where R b The alkyl radical may 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 a combination thereof.

[0089] In some embodiments, the compound represented by Chemical Formula 2 may include -OR a or -OC(=O)R b As a ligand, a pattern formed using a semiconductor photoresist composition containing the compound can exhibit excellent or appropriate limiting resolution.

[0090] In some embodiments, -OR a or -OC(=O)R b The ligand may determine the solubility of the compound represented by Chemical Formula 2 in a solvent.

[0091] R 9 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 a combination thereof,

[0092] 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 a combination thereof, and

[0093] 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 a combination thereof.

[0094] R 9can 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 a combination thereof,

[0095] R a can 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, and

[0096] R b can 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.

[0097] In some embodiments, the organotin compound can be represented by Chemical Formula 3 or Chemical Formula 4.

[0098] Chemical Formula 3

[0099] R 13 z SnO (2-(z / 2)-(x / 2)) (OH) x

[0100] In Chemical Formula 3,

[0101] R 13 can be a C1-C31 hydrocarbon group, 0 < z ≤ 2, and 0 < (z + x) ≤ 4;

[0102] Chemical Formula 4

[0103] R 14 n Sn m X l Y k

[0104] wherein, in Chemical Formula 4,

[0105] R 14 can 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,

[0106] X can be sulfur (S), selenium (Se) or tellurium (Te),

[0107] Y can be -OR m or -OC(=O)R n ,

[0108] where R m 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,

[0109] R n 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 a combination thereof, and

[0110] n, m, l and k may each independently be an integer from 1 to 20.

[0111] The solvent of the semiconductor photoresist composition according to one or more embodiments of the present disclosure may be an organic solvent, for example, an aromatic compound (such as xylene, toluene, etc.), an alcohol (such as 4-methyl-2-pentanol, 4-methyl-2-propanol, 1-butanol, methanol, isopropanol, 1-propanol), an ether (such as anisole, tetrahydrofuran), an ester (n-butyrate, propylene glycol monomethyl ether acetate (PGMEA), ethyl acetate, ethyl acetate), a ketone (such as methyl ethyl ketone, 2-heptanone), or a mixture thereof, but is not limited thereto.

[0112] The semiconductor photoresist composition according to one or more embodiments of the present disclosure may further include a resin in addition to the tin-containing organometallic compound, the compound represented by Chemical Formula 1, and the solvent as described in one or more embodiments of the present disclosure.

[0113] The resin may be a phenolic resin comprising at least one Group 2 aromatic moiety.

[0114] Group 2

[0115]

[0116] The resin may have a weight average molecular weight of about 500 g / mol to about 20,000 g / mol.

[0117] The resin may be included in an amount of about 0.1 wt % to about 50 wt % based on the total amount of the semiconductor photoresist composition. The resin may be included in an amount of about 0.1 wt % to about 50 wt % based on the total amount of the semiconductor photoresist composition.

[0118] If (for example, when) the resin is included in the content range described in one or more embodiments of the present disclosure, it may have excellent or appropriate etching resistance and heat resistance.

[0119] In some embodiments, the semiconductor photoresist composition according to one or more embodiments of the present disclosure may be composed of the tin-containing organometallic compound described in one or more embodiments of the present disclosure, the compound represented by Chemical Formula 1, a solvent, and a resin.

[0120] However, the semiconductor photoresist composition according to one or more embodiments of the present disclosure may further include additives as needed or desired. Examples of the additives may include surfactants, crosslinking agents, leveling agents, organic acids, quenchers, or combinations thereof.

[0121] The surfactant may include, for example, alkylbenzene sulfonate, alkylpyridinium salt, polyethylene glycol, quaternary ammonium salt, or a combination thereof, but is not limited thereto.

[0122] The crosslinking agent may be, for example, a melamine-based crosslinking agent, a substituted urea-based crosslinking agent, an acrylic crosslinking agent, an epoxy-based crosslinking agent, or a polymer-based crosslinking agent, but is not limited thereto. It may be a crosslinking agent having at least two crosslinking-forming 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.

[0123] The leveling agent may be used to improve the flatness of the coating during the printing process, and may be a commonly used or commonly available leveling agent.

[0124] 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, but is not limited thereto.

[0125] The quencher can be diphenyl(p-tolyl)amine, methyldiphenylamine, triphenylamine, phenylenediamine, naphthylamine, diaminonaphthalene, or a combination thereof.

[0126] In some embodiments, an acid compound may be mixed into the semiconductor photoresist composition according to one or more embodiments of the present disclosure.

[0127] The amount of additives used can be controlled according to appropriate or desired properties.

[0128] In some embodiments, the semiconductor photoresist composition may further include a silane coupling agent as an adhesion enhancer to improve close contact with the substrate (e.g., to improve adhesion of the semiconductor photoresist composition to the substrate). The silane coupling agent may be, for example, a silane compound containing a carbon-carbon unsaturated bond, such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltris(β-methoxyethoxy)silane and / or 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, p-phenylyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, trimethoxy[3-(phenylamino)propyl]silane and / or the like, but is not limited thereto.

[0129] The semiconductor photoresist composition can form a pattern with a high aspect ratio and no collapse. In some embodiments, in order to form a fine pattern with a width of, 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, the semiconductor photoresist composition can be used for a photolithography process using light with 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 some embodiments, the semiconductor photoresist composition according to one or more embodiments of the present disclosure can be used to realize extreme ultraviolet lithography using an EUV light source with a wavelength of about 13.5 nanometers.

[0130] According to one or more embodiments of the present disclosure, a method for forming a pattern using the semiconductor photoresist composition described in one or more embodiments of the present disclosure is provided. For example, the pattern formed can be a photoresist pattern.

[0131] A method for forming a pattern according to one or more embodiments of the present disclosure may include providing (e.g., forming) an etching target layer on a substrate, coating a semiconductor photoresist composition on the etching target layer to form a photoresist layer, patterning the photoresist layer to form a photoresist pattern, and etching the etching target layer using the photoresist pattern as an etching mask.

[0132] 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 of the present disclosure.

[0133] Reference Figure 1A An object for etching may be prepared. The object for etching may be a thin film 102 formed on a semiconductor substrate 100. Hereinafter, the object for etching may be defined as the thin film 102. The surface of the thin film 102 may be cleaned to remove impurities and the like remaining thereon. The thin film 102 may be, for example, a silicon nitride layer, a polysilicon layer, and / or a silicon oxide layer.

[0134] Subsequently, a resist base layer composition for forming the resist base layer 104 may be spin-coated on the surface of the washed thin film 102. However, the present disclosure is not limited thereto, and other suitable coating methods commonly used or commonly available, 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.

[0135] The coating process of the resist base layer will not be described repeatedly below, and the process including coating the resist base layer may be described below.

[0136] 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).

[0137] The resist bottom layer 104 may be formed between the substrate 100 and the photoresist layer 106, thereby preventing (or reducing or causing) non-uniformity (e.g., substantial non-uniformity) in the photoresist line width and pattern forming capability when light reflected from the interface between the substrate 100 and the photoresist layer 106 and / or the hard mask between the layers is scattered into unintended photoresist areas.

[0138] Reference Figure 1B, a photoresist layer 106 can be formed by coating a semiconductor photoresist composition on the resist bottom layer 104. The photoresist layer 106 can be obtained by coating a semiconductor photoresist composition according to one or more embodiments of the present disclosure on the thin film 102 formed on the substrate 100 and then curing it through heat treatment.

[0139] For example, forming a pattern using the semiconductor photoresist composition may include coating the semiconductor resist composition on the substrate 100 having the thin film 102 by spin coating, slit coating, inkjet printing, and / or the like, and then drying it to form the photoresist layer 106 .

[0140] The semiconductor photoresist composition has been described in more detail in one or more embodiments of the present disclosure and may not be described again below.

[0141] Subsequently, the substrate 100 having the photoresist layer 106 may be subjected to a first baking process. The first baking process may be performed at a temperature of about 80°C to about 120°C.

[0142] Reference Figure 1C , the photoresist layer 106 may be selectively exposed using a patterned mask 110 .

[0143] 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.

[0144] For example, exposure light according to one or more embodiments of the present disclosure may have short wavelengths ranging from about 5 nanometers to about 150 nanometers and high energy wavelengths, such as EUV (extreme ultraviolet; wavelength of about 13.5 nanometers), E-beam (electron beam) and / or the like.

[0145] 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 .

[0146] Subsequently, the substrate 100 may be subjected to a second baking 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.

[0147] exist Figure 1DIn the process, 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 (such as 2-heptanone and / or the like) to complete the photoresist pattern 108 corresponding to the negative image.

[0148] According to one or more embodiments of the present disclosure, the developer used in the method for forming a pattern according to one or more embodiments of the present disclosure may be an organic solvent. The organic solvent used in the method for forming a pattern according to one or more embodiments of the present disclosure 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 (PGMEA), 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 a combination thereof.

[0149] However, the photoresist pattern according to one or more embodiments of the present disclosure is not necessarily limited to a negative image, but can be formed to have a positive image. Here, the developer for forming the positive image can be a quaternary ammonium hydroxide composition, such as tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, or a combination thereof.

[0150] According to one or more embodiments of the present disclosure, exposure to light having high energy, such as extreme ultraviolet (EUV; wavelength of 13.5 nm), E-beam (electron beam), and light having a wavelength, such as i-line (wavelength of approximately 365 nm), KrF excimer laser (wavelength of approximately 248 nm), ArF excimer laser (wavelength of approximately 193 nm), can provide a photoresist pattern 108 having a width of about 5 nm to about 100 nm. For example, the photoresist pattern 108 may have a width of about 5 nm to about 90 nm, about 5 nm to about 80 nm, about 5 nm to about 70 nm, about 5 nm to about 60 nm, about 5 nm to about 50 nm, about 5 nm to about 40 nm, about 5 nm to about 30 nm, or about 5 nm to about 20 nm.

[0151] In some embodiments, the photoresist pattern 108 may have a pitch of half pitch 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 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.

[0152] 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.

[0153] Reference Figure 1E By 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.

[0154] The etching of the thin film 102 may be, for example, dry etching using an etching gas, and the etching gas may be, for example, CHF 3 , CF 4 , Cl 2 , BCl 3 and / or a mixed gas thereof.

[0155] During the exposure process, the width of the thin film pattern 114 formed using the photoresist pattern 108 may correspond to the width of the photoresist pattern 108 formed by the exposure process using an EUV light source. For example, the thin film pattern 114 may have a width of approximately 5 nanometers to approximately 100 nanometers, which may be equal to the width of the photoresist pattern 108. For example, the thin film pattern 114 formed using the photoresist pattern 108 formed by the exposure process using an EUV light source may have a width of approximately 5 nanometers to approximately 90 nanometers, approximately 5 nanometers to approximately 80 nanometers, approximately 5 nanometers to approximately 70 nanometers, approximately 5 nanometers to approximately 60 nanometers, approximately 5 nanometers to approximately 50 nanometers, approximately 5 nanometers to approximately 40 nanometers, approximately 5 nanometers to approximately 30 nanometers, or approximately 5 nanometers to approximately 20 nanometers. In some embodiments, the width is less than or equal to approximately 20 nanometers, which is similar to the width of the photoresist pattern 108.

[0156] Hereinafter, the subject matter of the present disclosure will be described in more detail by way of examples of preparing a semiconductor photoresist composition according to one or more embodiments of the present disclosure. However, the present disclosure is not technically limited to the following examples.

[0157] Synthesis Example 1

[0158] 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 heated under reflux for 24 hours.

[0159] By removing unreacted propionic acid under reduced pressure, the compound represented by Chemical Formula 5 was obtained.

[0160] Chemical formula 5

[0161]

[0162] Synthesis Example 2

[0163] 30 ml of anhydrous pentane was added to 10 g of t-amyltin trichloride (t-AmylSnCl3), and the temperature was maintained at 0°C. 7.4 g of diethylamine and 6.1 g of ethanol were then added, and stirred at room temperature for 1 hour. After the reaction was complete, the mixture was filtered, concentrated, and vacuum-dried to obtain the compound represented by Chemical Formula 6.

[0164] Chemical formula 6

[0165]

[0166] Synthesis Example 3

[0167] 10 g of dibutyltin dichloride was dissolved in 30 ml of 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 an organometallic compound represented by Chemical Formula 7 having a weight-average molecular weight of 1,500 g / mol.

[0168] Chemical formula 7

[0169]

[0170] Synthesis Example 4

[0171] 10 g of N-hydroxysuccinimide was dissolved in 100 ml of dichloromethane, bis(trifluoromethyl)phosphinic chloride and 15 ml of triethylamine were added, and the mixture was stirred for 2 hours. The resulting solid was filtered and washed three times with 25 ml of deionized water, and then dried under reduced pressure. Thus, the compound represented by Chemical Formula 8 was obtained.

[0172] Chemical formula 8

[0173]

[0174] Synthesis Example 5

[0175] The compound represented by Chemical Formula 9 was obtained in substantially the same manner as in Synthesis Example 4, except that methyl-(trifluoromethyl)phosphonochloridate was used instead of bis(trifluoromethyl)phosphonochloridate.

[0176] Chemical formula 9

[0177]

[0178] Preparation of semiconductor photoresist compositions

[0179] Examples 1 to 9 and Comparative Examples 1 to 4

[0180] The compounds represented by Chemical Formulas 5 to 7 obtained according to Synthesis Examples 1 to 3, the compounds represented by Chemical Formulas 8 and 9 obtained according to Synthesis Examples 4 and 5, and the compounds represented by Chemical Formulas 10 and 11 were respectively dissolved in 4-methyl-2-pentanol at a concentration of 2 wt % in the weight ratios shown in Table 1, and then filtered with a 0.1 μm polytetrafluoroethylene (PTFE) syringe filter to prepare a semiconductor photoresist composition.

[0181] Chemical formula 10

[0182]

[0183] N-(Trifluoromethanesulfonyloxy)-5-norbornene-2,3-dicarboximide; TCI

[0184] Chemical formula 11

[0185]

[0186] Bis(4-tert-butylphenyl)iodoniumperfluoro-1-butanesulfonate; Sigma-Aldrich

[0187] Table 1

[0188]

[0189] Evaluation 1: Sensitivity evaluation

[0190] 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, baked at 110° C. for 60 seconds (post-coating bake (PAB)), and then allowed to stand at room temperature (23±2° C.) for 30 seconds.

[0191] Subsequently, a linear array of 50 circular pads with a diameter of 500 μm was projected onto a wafer coated with each photoresist composition using EUV light (Lawrence Berkeley National Laboratory Micro Exposure Tool (MET)). Here, the pad exposure time was adjusted to ensure that an increasing dose of EUV light was applied to each pad.

[0192] Then, after exposure, the resist and substrate were baked on a hot plate at 160°C for 120 seconds. The baked film was developed in propylene glycol monomethyl ether acetate (PGMEA) solvent to form a negative image. Finally, the obtained film was baked again on a hot plate at 150°C for 2 minutes to complete the process.

[0193] Ellipsometer was used to measure the residual resist thickness of the exposed pad. The residual thickness was measured for each exposure dose and plotted as a function of exposure dose to measure sensitivity. Sensitivity was evaluated according to the following criteria, and the results are shown in Table 2.

[0194] Evaluation Criteria

[0195] -A: less than 16mJ / cm 2

[0196] -B: greater than or equal to 16mJ / cm 2 And less than 20mJ / cm 2

[0197] -C: greater than or equal to 20mJ / cm 2

[0198] Evaluation 2: Storage stability evaluation

[0199] The photoresist compositions according to Examples and Comparative Examples were sealed in containers and stored in an oven at 40° C. After two weeks, whether the solutions remained transparent was visually evaluated. The results are shown in Table 2.

[0200] Evaluation Criteria

[0201] -○: The solution remains clear after 2 weeks

[0202] -X: The solution becomes turbid after 2 weeks

[0203] Table 2

[0204] Sensitivity Storage stability Example 1 B ○ Example 2 A ○ Example 3 A ○ Example 4 A ○ Example 5 A ○ Example 6 A ○ Example 7 A ○ Example 8 A ○ Example 9 A ○ Comparative Example 1 C ○ Comparative Example 2 C ○ Comparative Example 3 C ○ Comparative Example 4 A X

[0205] Referring to the results of Table 2, patterns formed using the semiconductor photoresist compositions of Examples 1 to 9, respectively, exhibited superior sensitivity and / or superior storage stability compared to patterns formed using the semiconductor photoresist compositions of Comparative Examples 1 to 4, respectively.

[0206] Hereinafter, certain embodiments have been described and illustrated. However, it may be apparent to those skilled in the art that the present disclosure is not limited to one or more embodiments of the present disclosure and may be appropriately modified and transformed without departing from the spirit and scope of the present disclosure. In some embodiments, such modified or transformed embodiments may not be understood separately from the technical ideas and aspects of one or more embodiments of the present disclosure, and the modified embodiments may be within the scope of the appended claims of the present disclosure and their equivalents.

Claims

1. A semiconductor photoresist composition comprising: Tin (Sn)-containing organometallic compounds; A compound represented by Chemical Formula 1; as well as Solvent: Chemical formula 1 Wherein, in Chemical Formula 1, X 1 P(=O)R 4 or S(=O)2, R 1 to R 4 are each 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 C1 to C20 alkoxy group, or a substituted or unsubstituted C6 to C30 aryloxy group, R 1 and R 2 Each exists independently or is connected to form a ring, and From R 3 and R 4 At least one selected therefrom is a fluorine-containing group.

2. The semiconductor photoresist composition according to claim 1, wherein: Chemical formula 1 is represented by Chemical formula 1-1: Chemical formula 1-1 In Chemical Formula 1-1, X 1 P(=O)R 4 or S(=O)2, R 3 and R 4 are each 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 C1 to C20 alkoxy group, or a substituted or unsubstituted C6 to C30 aryloxy group, From R 3 and R 4 At least one selected from is a fluorine-containing group, and R 5 to R 8 and each is 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, substituted or unsubstituted C1 to C20 alkoxy, or substituted or unsubstituted C6 to C30 aryloxy.

3. The semiconductor photoresist composition according to claim 1, wherein: The fluorine-containing group is a C1 to C20 alkyl group substituted by at least one fluorine, a C3 to C20 cycloalkyl group substituted by at least one fluorine, a C2 to C20 alkenyl group substituted by at least one fluorine, a C2 to C20 alkynyl group substituted by at least one fluorine, a C6 to C30 aryl group substituted by at least one fluorine, a C1 to C20 alkoxy group substituted by at least one fluorine, or a C6 to C30 aryloxy group substituted by at least one fluorine.

4. The semiconductor photoresist composition according to claim 1, wherein: The compound represented by Chemical Formula 1 is one selected from the compounds listed in Group 1: Group 1 Chemical formula 8 Chemical formula 9 Chemical formula 10 5. The semiconductor photoresist composition according to claim 1, wherein: The amount of the compound represented by Chemical Formula 1 is 0.01 wt % to 10 wt % based on 100 wt % of the semiconductor photoresist composition.

6. The semiconductor photoresist composition according to claim 1, wherein: The amount of the compound represented by Chemical Formula 1 is 0.05 wt % to 5 wt % based on 100 wt % of the semiconductor photoresist composition.

7. 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.

8. The semiconductor photoresist composition according to claim 1, wherein: A weight ratio of the tin-containing organometallic compound to the compound represented by Chemical Formula 1 is 99.9:0.1 to 80:

20.

9. The semiconductor photoresist composition according to claim 1, wherein: The semiconductor photoresist composition further includes an additive of a surfactant, a cross-linking agent, a leveler, an organic acid, a quencher, or a combination thereof.

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

11. The semiconductor photoresist composition according to claim 1, wherein: The tin-containing organometallic compound is represented by Chemical Formula 2: Chemical formula 2 Wherein, in Chemical Formula 2, R 9 is selected from 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, and a substituted or unsubstituted C7 to C30 aralkyl group, R 10 to R 12 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 k represents an alkylthio or arylthio group, wherein R k 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 -S(C=O)R l represents a thiocarbonyl group, wherein R l 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 10 to R 12 At least one selected from -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 k represents an alkylthio or arylthio group, wherein R k 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 is represented by -S(C=O)R l represents a thiocarbonyl group, wherein R l 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.

12. The semiconductor photoresist composition according to claim 11, wherein: R 9 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.

13. The semiconductor photoresist composition according to claim 1, wherein: The tin-containing organometallic compound is represented by Chemical Formula 3 or Chemical Formula 4: Chemical formula 3 R 13 z SnO (2-(z / 2)-(x / 2)) (OH) x Wherein, in Chemical Formula 3, R 13 is a C1 to C31 hydrocarbyl group, 0 < z ≤ 2, and 0 < (z + x) ≤ 4; Chemical formula 4 R 14 n Sn m X l Y k Wherein, in Chemical Formula 4, R 14 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 m or -OC(=O)R n , where R m 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 n 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 n, m, l and k are each independently an integer from 1 to 20.

14. A method for forming a pattern, comprising: providing an etching target layer on a substrate; applying the semiconductor photoresist composition according to any one of claims 1 to 13 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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