Semiconductor photoresist composition, method for forming pattern using the composition, and photoresist film

Abstract

Disclosed are a semiconductor photoresist composition, a method for forming or providing a pattern using the semiconductor photoresist composition, and a photoresist film manufactured in the method for forming the pattern, the semiconductor photoresist composition comprises: an organometallic compound having two radiation-sensitive functional groups and three hydrolyzable ligands and comprising a pentavalent metal; and a solvent.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority to and the benefit of Korean Patent Application No. 10-2024-0037805, filed on March 19, 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, a method of forming or providing a pattern using the semiconductor photoresist composition, and a photoresist film manufactured in the method of forming a pattern. Background Art

[0004] Extreme ultraviolet (EUV) lithography has attracted attention as a fundamental technology for manufacturing next-generation semiconductor devices (e.g., semiconductor chips). EUV lithography is a patterning technology that uses EUV radiation with a wavelength of 13.5 nanometers as an exposure light source. EUV lithography enables the formation of fine patterns (e.g., less than or equal to 20 nanometers) during the exposure process in the manufacturing of semiconductor devices (e.g., semiconductor chips).

[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 insufficient specifications of chemically amplified (CA) photoresists for next-generation devices, including 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-specific photoresists limits resolution of small feature sizes in electron-beam (e-beam) lithography. Chemically amplified (CA) photoresists are designed for high sensitivity. However, their sensitivity may be reduced because their elemental composition reduces the photoresist's light absorption at a wavelength of 13.5 nm, and CA photoresists may experience more difficulty with EUV exposure.

[0007] CA photoresists may experience difficulty with small feature sizes due to roughness issues, and line edge roughness (LER) of CA photoresists may experimentally increase because photospeed may decrease due in part to the nature of the acid-catalyzed process. Due to these undesirable drawbacks and issues with CA photoresists, the semiconductor industry needs or demands 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. Inorganic photosensitive compositions are primarily or mostly used for negative-tone patterning due to their resistance to removal by developing compositions due to chemical modification via a non-chemical amplification mechanism. Inorganic compositions include inorganic elements with higher EUV absorptivity than hydrocarbons. 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 relatively few undesirable 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 double-layer configurations for extreme ultraviolet (deep ultraviolet), X-ray and electron beam light sources. Improved performance was obtained when a cationic hafnium metal oxide sulfate (HfSOx) material and a peroxy complexing agent were used to image a 15 nm half-pitch (HP) by projection EUV exposure. The system exhibits high performance of non-CA photoresists and has a practical photosensitivity close to that required for EUV photoresists. However, hafnium metal oxide sulfate materials including peroxy complexing agents have some practical disadvantages. First, these materials are coated in a corrosive sulfuric acid / hydrogen peroxide mixture and have insufficient shelf life stability. Second, it is challenging to change the material structure as a composite mixture to improve performance. Third, development should be carried out in a high concentration of 25 wt% tetramethylammonium hydroxide (TMAH) solution and / or the like.

[0011] To address these issues, research has focused on developing molecules containing tin (Sn) with excellent or moderate extreme ultraviolet (EUV) absorption. In organotin polymers, the alkyl ligands in these tin-containing molecules dissociate through light absorption or the generation of secondary electrons. The dissociated alkyl ligands then crosslink with adjacent chains via oxygen bonds, enabling negative patterning that is resistant to removal by organic developers. While such organotin polymers exhibit greatly improved sensitivity while maintaining adequate resolution and line-edge roughness, patterning properties require further improvement for commercial viability. Summary of the Invention

[0012] One or more aspects of embodiments of the present disclosure relate to semiconductor photoresist compositions that can minimize or reduce undesirable patterning defects and process delay effects.

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

[0014] One or more aspects of embodiments of the present disclosure relate to a photoresist film manufactured by a method of forming or providing a pattern.

[0015] 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.

[0016] A semiconductor photoresist composition according to one or more embodiments may include an organometallic compound having two radiation-sensitive functional groups and three hydrolyzable ligands and including a pentavalent metal, and a solvent.

[0017] A method of forming or providing a pattern according to one or more embodiments may include providing an etch target layer on a substrate, coating a semiconductor photoresist composition on the etch target layer to provide a photoresist layer, exposing and developing the photoresist layer to provide a photoresist film having a photoresist pattern, and etching the etch target layer using the photoresist pattern as an etch mask.

[0018] The photoresist film according to one or more embodiments may be manufactured by the method of forming or providing a pattern described in one or more embodiments of the present disclosure.

[0019] The semiconductor photoresist composition according to one or more embodiments may significantly reduce reactivity with moisture after exposure (eg, chemical reactivity between the semiconductor photoresist composition and moisture), thereby alleviating or reducing deviations due to process delays. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] 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.

[0021] Figure 1A-1E Each is a cross-sectional view illustrating a method of forming or providing a pattern using a semiconductor photoresist composition according to one or more embodiments.

[0022] Description of Reference Numerals

[0023] 100: substrate

[0024] 102: Film

[0025] 104: Resist base

[0026] 106: Photoresist layer

[0027] 106a: Unexposed area

[0028] 106b: Exposure area

[0029] 108: Photoresist pattern

[0030] 112: Organic layer pattern

[0031] 110: Patterned mask

[0032] 114: Thin film pattern DETAILED DESCRIPTION

[0033] 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, in order to clarify the present disclosure, functions or structures that are generally understood by those skilled in the art may not be described.

[0034] In order to clearly illustrate the embodiments of the present disclosure, certain descriptions and relationships may be omitted, and throughout the present disclosure, substantially the same or similar configuration elements or arrangement elements may be denoted by substantially the same reference numerals. In addition, since the size and thickness of each configuration or arrangement 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.

[0035] As used herein, "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.

[0036] It will be further understood that the terms "include", "comprising" 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.

[0037] As used herein, the singular forms "a," "an," and "the" are intended to include the plural forms unless the context clearly indicates otherwise. In addition, the use of "may" when describing embodiments of the present disclosure refers to "one or more embodiments of the present disclosure."

[0038] In the context of the present disclosure, unless defined otherwise, the term "use" may be considered synonymous with the term "utilize."

[0039] As used herein, 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 one 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 (e.g., limitations of the measurement system). For example, "about" can mean within one or more standard deviations of the stated value, or within ±30%, 20%, 10%, or 5% of the stated value.

[0040] Any numerical range described herein is intended to include all subranges of substantially 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 the minimum value 1.0 and the maximum value 10.0 (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 expressly state any subranges contained within the range expressly stated herein.

[0041] In the accompanying drawings, the thickness of layers, films, panels, regions, and / or the like may be exaggerated for clarity. In the accompanying drawings, the thickness of portions of layers or regions and / or the like 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 may be directly on the other element, or intervening elements may be present. If (for example, when) an element is referred to as being "directly on" another element, there may be no intervening elements.

[0042] As used herein, "substituted" refers to the replacement of a hydrogen atom by 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 "each independently represents 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), 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 a hydrogen atom remains.

[0043] As used herein, if (e.g., when) no further definition is provided, "alkyl" refers to a straight or branched aliphatic hydrocarbon group. The alkyl group may be a "saturated alkyl group" that does not contain any double or triple bonds.

[0044] 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.

[0045] As used herein, if (eg, when) no definition is otherwise provided, "cycloalkyl" refers to a monovalent cyclic aliphatic hydrocarbon group.

[0046] 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.

[0047] As used herein, "aliphatic unsaturated organic group" refers to a hydrocarbon group containing double bonds, triple bonds or a combination thereof between carbon atoms in the molecule.

[0048] The aliphatic unsaturated organic group may be a C2 to C8 aliphatic unsaturated organic group. For example, the aliphatic unsaturated organic group may 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 may 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.

[0049] 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 or fused-ring polycyclic functional groups (eg, rings that share adjacent pairs of carbon atoms).

[0050] 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.

[0051] As used herein, unless otherwise defined, "alkenyl" refers to an aliphatically unsaturated alkenyl group that is a straight or branched aliphatic hydrocarbon group containing at least one double bond.

[0052] As used herein, unless otherwise defined, "alkynyl" refers to an aliphatically unsaturated alkynyl group that is a straight or branched aliphatic hydrocarbon group containing at least one triple bond.

[0053] Semiconductor photoresist compositions according to one or more embodiments are disclosed below.

[0054] A semiconductor photoresist composition according to one or more embodiments may include an organometallic compound having two radiation-sensitive functional groups and three hydrolyzable ligands and including a pentavalent metal, and a solvent.

[0055] According to one or more embodiments of the present disclosure, the organometallic compound may have two radiation-sensitive functional groups and three hydrolyzable ligands per metal atom, thereby forming a stable cluster that is spherical (e.g., substantially spherical) in structure. Furthermore, the radiation-sensitive functional groups may provide a shielding effect. As a result, post-exposure reactivity with moisture (e.g., the chemical reactivity between the semiconductor photoresist composition and moisture) may be significantly reduced or minimized, thereby alleviating or reducing deviations caused by process delays.

[0056] The pentavalent metal may be selected from arsenic (As), antimony (Sb), and bismuth (Bi).

[0057] In one or more embodiments, the pentavalent metal may be Sb.

[0058] The hydrolyzable ligand may be selected from the following: 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(CO)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), alkylamino, or dialkylamino (—NR c R d , where R c and R d 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 amide group (-NR e (CORf ), 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 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 alkylthio group, or an arylthio group (-SR j , where R j The alkyl radicals may be 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 thiocarboxyl (-S(CO)R k , where R k The alkyl radical 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).

[0059] As an example, the organometallic compound may be represented by Chemical Formula 1.

[0060] Chemical formula 1

[0061]

[0062] In Chemical Formula 1,

[0063] M 1 Can be selected from As, Sb and Bi,

[0064] R 1 and R 2may be each independently 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, and

[0065] X 1 To X 3 Can be independently selected from the following: 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(CO)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), alkylamino, or dialkylamino (—NR c R d , where R c and R d may each independently 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 amide group (-NR e (COR 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), amidino (-NR g C(NR h )R i , where R g 、R h and R imay 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, or an arylthio group (-SR j , where R j The alkyl radicals may be 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 thiocarboxyl (-S(CO)R k , where R k The alkyl radical 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).

[0066] As an example, X 1 To X 3 Can be independently selected from the following: alkoxy or aryloxy (-OR a , where R a may be a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C3 to C10 cycloalkyl group, a substituted or unsubstituted C2 to C10 alkenyl group, a substituted or unsubstituted C2 to C10 alkynyl group, a substituted or unsubstituted C6 to C20 aryl group, or a combination thereof), a carboxyl group (-O(CO)R b , where R b The alkyl group may be hydrogen, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C3 to C10 cycloalkyl, substituted or unsubstituted C2 to C10 alkenyl, substituted or unsubstituted C2 to C10 alkynyl, substituted or unsubstituted C6 to C20 aryl, or a combination thereof), alkylamino, or dialkylamino (-NR c R d , where R c and R d may be each independently hydrogen, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C3 to C10 cycloalkyl, substituted or unsubstituted C2 to C10 alkenyl, substituted or unsubstituted C2 to C10 alkynyl, substituted or unsubstituted C6 to C30 aryl, or a combination thereof), an amide group (-NR e (COR f ), where R e and R fmay be each independently hydrogen, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C3 to C10 cycloalkyl, substituted or unsubstituted C2 to C10 alkenyl, substituted or unsubstituted C2 to C10 alkynyl, substituted or unsubstituted C6 to C20 aryl, or a combination thereof), amidino (-NR g C(NR h )R i , where R g 、R h and R i may each independently be hydrogen, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C3 to C10 cycloalkyl, substituted or unsubstituted C2 to C10 alkenyl, substituted or unsubstituted C2 to C10 alkynyl, substituted or unsubstituted C6 to C20 aryl, or a combination thereof), alkylthio, or arylthio (-SR j , where R j The alkyl radicals may be substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C3 to C10 cycloalkyl, substituted or unsubstituted C2 to C10 alkenyl, substituted or unsubstituted C2 to C10 alkynyl, substituted or unsubstituted C6 to C20 aryl, or a combination thereof) and thiocarboxyl (-S(CO)R k , where R k The alkyl radical may be hydrogen, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C3 to C10 cycloalkyl, substituted or unsubstituted C2 to C10 alkenyl, substituted or unsubstituted C2 to C10 alkynyl, substituted or unsubstituted C6 to C20 aryl, or a combination thereof).

[0067] For example, X 1 To X 3 Can be independently selected from the following: alkoxy or aryloxy (-OR a , where R a may be a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C3 to C10 cycloalkyl group, a substituted or unsubstituted C2 to C10 alkenyl group, a substituted or unsubstituted C2 to C10 alkynyl group, a substituted or unsubstituted C6 to C20 aryl group, or a combination thereof), a carboxyl group (-O(CO)R b , where R b The alkyl radicals may be hydrogen, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C3 to C10 cycloalkyl, substituted or unsubstituted C2 to C10 alkenyl, substituted or unsubstituted C2 to C10 alkynyl, substituted or unsubstituted C6 to C20 aryl, or a combination thereof, and amide (-NR e (COR f ), where R e and Rf and (the alkyl radicals) may each independently be hydrogen, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C3 to C10 cycloalkyl, substituted or unsubstituted C2 to C10 alkenyl, substituted or unsubstituted C2 to C10 alkynyl, substituted or unsubstituted C6 to C20 aryl, or a combination thereof.

[0068] For example, R 1 and R 2 and each independently may be a substituted or unsubstituted methyl group, a substituted or unsubstituted ethyl group, a substituted or unsubstituted propyl group, a substituted or unsubstituted butyl group, a substituted or unsubstituted isopropyl group, a substituted or unsubstituted tert-butyl group, a substituted or unsubstituted 2,2-dimethylpropyl group, a substituted or unsubstituted tert-amyl group, a substituted or unsubstituted vinyl group, a substituted or unsubstituted propenyl group, a substituted or unsubstituted butenyl group, a substituted or unsubstituted ethynyl group, a substituted or unsubstituted propynyl group, a substituted or unsubstituted butynyl group, a substituted or unsubstituted benzyl group, a substituted or unsubstituted methoxy group, a substituted or unsubstituted ethoxy group, a substituted or unsubstituted propoxy group, or a combination thereof.

[0069] R a may be substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted propyl, substituted or unsubstituted butyl, substituted or unsubstituted isopropyl, substituted or unsubstituted tert-butyl, substituted or unsubstituted tert-amyl, substituted or unsubstituted 2,2-dimethylpropyl, substituted or unsubstituted cyclopropyl, substituted or unsubstituted cyclobutyl, substituted or unsubstituted cyclopentyl, substituted or unsubstituted cyclohexyl, substituted or unsubstituted vinyl, substituted or unsubstituted propenyl, substituted or unsubstituted butenyl, substituted or unsubstituted ethynyl, substituted or unsubstituted propynyl, substituted or unsubstituted butynyl, substituted or unsubstituted phenyl, substituted or unsubstituted tolyl, substituted or unsubstituted xylyl, substituted or unsubstituted benzyl, or a combination thereof, and

[0070] R b 、R c 、R d 、R e 、R f 、R g 、R h 、R i 、R j and R kand each independently may be hydrogen, substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted propyl, substituted or unsubstituted butyl, substituted or unsubstituted isopropyl, substituted or unsubstituted tert-butyl, substituted or unsubstituted tert-amyl, substituted or unsubstituted 2,2-dimethylpropyl, substituted or unsubstituted cyclopropyl, substituted or unsubstituted cyclobutyl, substituted or unsubstituted cyclopentyl, substituted or unsubstituted cyclohexyl, substituted or unsubstituted vinyl, substituted or unsubstituted propenyl, substituted or unsubstituted butenyl, substituted or unsubstituted ethynyl, substituted or unsubstituted propynyl, substituted or unsubstituted butynyl, substituted or unsubstituted phenyl, substituted or unsubstituted tolyl, substituted or unsubstituted xylyl, substituted or unsubstituted benzyl, or a combination thereof.

[0071] In one or more embodiments, the semiconductor photoresist composition may further include at least one selected from the group consisting of an organometallic compound represented by Chemical Formula 2 and an organometallic compound represented by Chemical Formula 3.

[0072] Chemical formula 2 Chemical formula 3

[0073]

[0074] In Chemical Formula 2 and Chemical Formula 3,

[0075] M 2 Can be selected from As, Sb and Bi,

[0076] M 3 Can be selected from tin (Sn), lead (Pb) and titanium (Ti),

[0077] R 3 and R 4 may be independently selected from the following: 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, and

[0078] X 4 To X 10 Can be independently selected from the following: 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), a carboxyl group (-O(CO)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), alkylamino, or dialkylamino (—NR c R d , where R c and R d may each independently 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 amide group (-NR e (COR 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), amidino (-NR g C(NR h )R i , where R g 、R h and R i 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, or an arylthio group (-SR j , where R j The alkyl radicals may be 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 thiocarboxyl (-S(CO)R k , where R kThe alkyl radical 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).

[0079] For example, the organometallic compound represented by Chemical Formula 1:at least one organometallic compound selected from the group consisting of the organometallic compound represented by Chemical Formula 2 and the organometallic compound represented by Chemical Formula 3 may be in a weight ratio of about 11:1 to about 1:11.

[0080] For example, the organometallic compound represented by Chemical Formula 1: at least one organometallic compound selected from the organometallic compound represented by Chemical Formula 2 and the organometallic compound represented by Chemical Formula 3 may be in a weight ratio of about 5:1 to about 1:5, or a weight ratio of about 2:1 to about 1:2.

[0081] For example, M 2 It may be antimony.

[0082] For example, M 3 It may be tin.

[0083] The organometallic compound represented by Chemical Formula 1 may strongly absorb extreme ultraviolet light of 13.5 nm and may have excellent or appropriate sensitivity to high-energy light.

[0084] In the semiconductor photoresist composition according to one or more embodiments, the amount of the organometallic compound represented by Chemical Formula 1 may be from about 0.5 wt % to about 30 wt %, for example, from about 1 wt % to about 30 wt %, from about 1 wt % to about 25 wt %, for example, from about 1 wt % to about 20 wt %, for example, from about 1 wt % to about 15 wt %, for example, from about 1 wt % to about 10 wt %, for example, from about 1 wt % to about 5 wt %, but the embodiments of the present disclosure are not limited thereto. If (for example, when) the amount of the organometallic compound represented by Chemical Formula 1 is within the above range, the storage stability and etching resistance of the semiconductor photoresist composition can be improved or enhanced (for example, to achieve appropriate storage stability and etching resistance of the semiconductor photoresist composition), and the resolution characteristics can be improved or enhanced (for example, to achieve appropriate resolution characteristics).

[0085] Since the semiconductor photoresist composition according to one or more embodiments of the present disclosure may include the organometallic compound according to one or more embodiments, a semiconductor photoresist composition having excellent or appropriate sensitivity and pattern forming properties may be provided.

[0086] The solvent in the semiconductor photoresist composition according to one or more embodiments may be an organic solvent, and may be, for example, an aromatic compound (e.g., xylene, toluene and / or the like), an alcohol (e.g., 4-methyl-2-pentenol, 4-methyl-2-propanol, 1-butanol, methanol, isopropanol, 1-propanol and / or the like), an ether (e.g., anisole, tetrahydrofuran and / or the like), an ester (n-butyl acetate, propylene glycol monomethyl ether acetate, ethyl acetate, ethyl lactate and / or the like), a ketone (e.g., methyl ethyl ketone, 2-heptanone and / or the like), or a mixture thereof, but the embodiments of the present disclosure are not limited thereto.

[0087] In one or more embodiments, the semiconductor photoresist composition may further include a resin in addition to the organometallic compound and the solvent according to one or more embodiments.

[0088] The resin may be a phenolic resin comprising at least one aromatic moiety selected from the moieties listed in Group 2.

[0089] Group 2

[0090]

[0091] The resin may have a weight average molecular weight of about 500 g / mole to about 20,000 g / mole.

[0092] 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 (eg, based on 100 wt % of the total amount of the semiconductor photoresist composition).

[0093] If (eg, when) the resin is within the above content (eg, amount) range, it may have excellent or appropriate etching resistance and heat resistance.

[0094] In one or more embodiments, the semiconductor photoresist composition according to one or more embodiments may include the organometallic compound, solvent, and resin described in one or more embodiments of the present disclosure. However, the semiconductor photoresist composition according to one or more embodiments may further include additives in one or more embodiments.

[0095] For example, it may further include at least one additional additive selected from alcohol compounds, thiol compounds, carboxylic acid compounds, and phosphoric acid compounds.

[0096] For example, examples of the additional additive may include ethanethiol, succinic acid, ethane phosphate, and / or the like, but embodiments of the present disclosure are not limited thereto.

[0097] The amount of the additional additive may be about 0.01 to about 1 wt % based on the total amount of the semiconductor photoresist composition (eg, based on 100 wt % of the total amount of the semiconductor photoresist composition).

[0098] For example, the amount of the additional additive may be about 0.01 to about 1 wt %, or about 0.01 to about 0.5 wt % based on the total amount of the semiconductor photoresist composition (eg, based on 100 wt % of the total amount of the semiconductor photoresist composition).

[0099] In one or more embodiments, other additives may be included, such as surfactants, crosslinkers, levelers, organic acids, quenchers, or combinations thereof. The semiconductor photoresist composition may further include other additives selected from surfactants, crosslinkers, levelers, organic acids, quenchers, or combinations thereof.

[0100] The surfactant may include, for example, alkylbenzene sulfonate, alkylpyridinium salt, polyethylene glycol, quaternary ammonium salt, or a combination thereof, but embodiments of the present disclosure are not limited thereto.

[0101] 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 the embodiments of the present disclosure are not limited thereto. The crosslinking agent may be a crosslinking agent having at least two crosslinking-forming substituents, for example, compounds such as methoxymethylated biuret, butoxymethylated biuret, methoxymethylated melamine, butoxymethylated melamine, methoxymethylated benzoguanidine, butoxymethylated benzoguanidine, 4-hydroxybutyl acrylate, acrylic acid, urethane acrylate, acrylic acid methacrylate, 1,4-butanediol diglycidyl ether, glycidol, 1,2-cyclohexanedicarboxylic acid diglycidyl ester, trimethylolpropane triglycidyl ether, 1,3-bis(glycidylpropyl)tetramethyldisiloxane, methoxymethylated urea, butoxymethylated urea, methoxymethylated thiourea, and / or the like.

[0102] The leveling agent may be used to improve or enhance coating flatness during the printing process (eg, to achieve appropriate coating flatness), and may be a commercially available or commonly available leveling agent.

[0103] The organic acid may include p-toluenesulfonic acid, benzenesulfonic acid, p-dodecylbenzenesulfonic acid, 1,4-naphthalenedisulfonic 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 the embodiments of the present disclosure are not limited thereto.

[0104] The quencher can be diphenyl(p-tolyl)amine, methyldiphenylamine, triphenylamine, phenylenediamine, naphthylamine, diaminonaphthalene, or a combination thereof.

[0105] According to one or more embodiments, the amounts of these other additives used can be controlled based on the desired or appropriate properties.

[0106] In one or more embodiments, the semiconductor photoresist composition may further include a silane coupling agent as an adhesion enhancer to improve or enhance the close contact force with the substrate (for example, to improve or enhance the 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 the like; or 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, p-phenylyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane; trimethoxy[3-(phenylamino)propyl]silane, and / or the like, but the embodiments of the present disclosure are not limited thereto.

[0107] The semiconductor photoresist composition can form or provide a pattern with a high aspect ratio without collapse. In one or more embodiments, in order to form or provide 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, for example, about 5 nanometers to about 20 nanometers, or for example, about 5 nanometers to about 10 nanometers width (e.g., line width), the semiconductor photoresist composition can be used for a photoresist process using light with a wavelength ranging from 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, the semiconductor photoresist composition according to one or more embodiments can be used to realize extreme ultraviolet lithography using an EUV light source with a wavelength of about 13.5 nanometers.

[0108] According to one or more embodiments, a method for forming or providing a pattern using the semiconductor photoresist composition described in one or more embodiments of the present disclosure may be provided. For example, the pattern produced may be a photoresist pattern.

[0109] A method of forming or providing a pattern according to one or more embodiments may include providing an etch target layer on a substrate, coating a semiconductor photoresist composition on the etch target layer to provide a photoresist layer, exposing and developing the photoresist layer to provide a photoresist film having a photoresist pattern, and etching the etch target layer using the photoresist pattern as an etch mask.

[0110] The following are for reference Figure 1A-1EMethods of forming or providing patterns using semiconductor photoresist compositions are described. Figure 1A-1E Each is a cross-sectional view for explaining a method of forming or providing a pattern using a semiconductor photoresist composition according to one or more embodiments.

[0111] refer to Figure 1A , an object for etching (e.g., an etching target layer or an etching target layer) may be prepared. The object for etching may be a thin film 102 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 washed to remove undesirable impurities (e.g., undesirable residues) and / or 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.

[0112] Subsequently, a resist base layer composition forming or providing the resist base layer 104 may be spin-coated on the surface of the washing film 102. However, one or more embodiments of the present disclosure are not limited thereto, and one or more suitable coating methods may be used, for example, spray coating, dip coating, doctor blade coating, printing methods such as inkjet printing and screen printing, and / or the like.

[0113] 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.

[0114] The applied composition may then be dried and baked to form or provide a resist bottom layer 104 on the thin film 102. The baking may be performed at about 100°C to about 500°C, for example, about 100°C to about 300°C.

[0115] The resist bottom layer 104 may be formed or provided between the substrate 100 and the photoresist layer 106, thereby preventing or reducing non-uniformity (e.g., substantial non-uniformity) in the photoresist line width and improving pattern formation if (e.g., when) radiation reflected from the interface between the substrate 100 and the photoresist layer 106 or an interlayer hard mask is scattered to unintended photoresist areas.

[0116] refer to Figure 1B The photoresist layer 106 may be formed or provided by coating a semiconductor photoresist composition on the resist base layer 104. The photoresist layer 106 may be obtained by coating a semiconductor photoresist composition according to one or more embodiments on the thin film 102 that may be formed or provided on the substrate 100 and then curing it through heat treatment.

[0117] For example, forming a pattern using a 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 it to form or provide the photoresist layer 106 .

[0118] The photoresist layer may partially include at least one selected from the moieties represented by Chemical Formula 4-1 to Chemical Formula 4-5.

[0119] Chemical formula 4-1

[0120]

[0121] Chemical formula 4-2

[0122]

[0123] Chemical formula 4-3

[0124]

[0125] Chemical formula 4-4

[0126]

[0127] Chemical formula 4-5

[0128]

[0129] In Chemical Formula 4-1 to Chemical Formula 4-5,

[0130] M 1 and M 2 Can be selected independently from As, Sb and Bi,

[0131] M 3 Can be selected from Sn, Pb and Ti, and

[0132] R 1 to R 4 Each may be independently 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.

[0133] The semiconductor photoresist composition has been described in more detail and will not be repeated here.

[0134] 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 about 80°C to about 120°C.

[0135] refer to Figure 1C , the photoresist layer 106 may be selectively exposed using a patterned mask 110 .

[0136] For example, exposure can use activating radiation with a high-energy wavelength, such as EUV (extreme ultraviolet; wavelength of about 13.5 nanometers), E-Beam (electron beam) and / or the like, and light with 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.

[0137] For example, light used for exposure according to one or more embodiments may have a wavelength of about 5 nm to about 150 nm and / or a high energy wavelength, such as EUV (extreme ultraviolet; wavelength 13.5 nm), E-Beam (electron beam), and / or the like.

[0138] By forming or providing a polymer resulting from a cross-linking reaction, such as a condensation reaction between organometallic compounds, the exposed region 106 b of the photoresist layer 106 may have a different solubility from the unexposed region 106 a of the photoresist layer 106 .

[0139] 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.

[0140] 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 or provide 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.

[0141] According to one or more embodiments, the developer used in the method for forming or providing a pattern according to one or more embodiments may be an organic solvent. The organic solvent used in the method for forming or providing a pattern according to one or more embodiments may be, for example, ketones such as methyl ethyl ketone, acetone, cyclohexanone, 2-heptanone, and / or the like; alcohols such as 4-methyl-2-propanol, 1-butanol, isopropanol, 1-propanol, methanol, and / or the like; esters such as propylene glycol monomethyl ether acetate, ethyl acetate, ethyl lactate, n-butyl acetate, butyrolactone, and / or the like; aromatic compounds such as benzene, xylene, toluene, and / or the like; or combinations thereof.

[0142] However, the photoresist pattern according to one or more embodiments is not necessarily limited to a negative image, but may form or provide a positive image. Here, the developer for forming or providing the positive image may be a quaternary ammonium hydroxide composition, such as tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, or a combination thereof.

[0143] According to one or more embodiments, exposure to light having high energy, such as EUV (extreme ultraviolet; wavelength 13.5 nm), E-Beam (electron beam), and / or the like, and light having a short 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), and / or the like, may provide a photoresist pattern 108 having a width of approximately 5 nm to approximately 100 nm. For example, the photoresist pattern 108 may 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, approximately 5 nm to approximately 20 nm, or approximately 5 nm to approximately 10 nm.

[0144] In one or more 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, for example, less than or equal to about 30 nanometers, for example, less than or equal to about 20 nanometers, or for example, less than or equal to about 10 nanometers), and a line edge roughness less than or equal to about 5 nanometers, less than or equal to about 3 nanometers, less than or equal to about 2 nanometers, or less than or equal to about 1 nanometer.

[0145] According to one or more embodiments, a photoresist film manufactured by the method of forming or providing a pattern described in one or more embodiments may be provided.

[0146] Subsequently, the photoresist pattern 108 on the photoresist film can be used as an etching mask to etch the resist bottom layer 104. Through this etching process, an organic layer pattern 112 can be formed. The organic layer pattern 112 can also have a width (eg, line width) corresponding to the photoresist pattern 108.

[0147] refer to 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 or provided as a thin film pattern 114.

[0148] 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 a mixed gas thereof.

[0149] In the exposure process, the thin film pattern 114 formed or provided by the photoresist pattern 108 formed or provided using the exposure process performed using the EUV light source may have a width (e.g., line width) corresponding to 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 or provided by the photoresist pattern 108 formed or provided using the exposure process performed using the EUV light source may have a width (e.g., line 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, for example, a width (e.g., line width) less than or equal to about 20 nanometers, like the photoresist pattern 108.

[0150] Hereinafter, the subject matter of the present disclosure will be described in more detail by way of examples of preparing semiconductor photoresist compositions according to one or more embodiments of the present disclosure. However, the present disclosure is not technically limited to the following examples.

[0151] Synthesis of organometallic compounds

[0152] Synthesis Example 1: Synthesis of Compound P-1 (Diphenylantimony Trichloride)

[0153] 10.0 g (28.3 mmol) of triphenyl antimony and 3.23 g (14.2 mmol) of antimony trichloride were added to a 250 ml single-necked round-bottom flask, then stirred in a 70°C oil bath and reacted at room temperature (25 ± 3°C) for 2 days. Subsequently, 100 ml of dichloromethane (DCM) was added to the resulting reactant to completely dissolve it, and then 42.5 ml (42.5 mmol) of a 1M thionyl chloride DCM solution was slowly added dropwise. After the resulting mixture was stirred for 24 hours, 80 ml of DCM was added thereto and allowed to stand in a refrigerator at -20°C to obtain 8.3 g of crystals.

[0154] Synthesis Example 2: Synthesis of Compound P-2 (Diphenyl Antimony Tripropionate)

[0155] 2.09 g (5.47 mmol) of the compound (diphenylantimony trichloride) in Synthesis Example 1 was dissolved in 100 ml of toluene, and then an excess of propionic acid and 2.02 g (18.0 mmol) of potassium propionate were added in sequence. After purging with nitrogen (e.g., nitrogen or N2), the resulting mixture was refluxed in an oil bath at 110°C with stirring for one day.

[0156] Subsequently, after removing the solvent and propionic acid under reduced pressure at 80° C., the resulting residue was dissolved in 50 ml of dichloromethane and then filtered. The resulting filtrate was treated under nitrogen to remove dichloromethane, to obtain 2.7 g of a light yellow solid.

[0157] Synthesis Example 3: Synthesis of Compound P-3 (Monophenylantimony Tetrachloride)

[0158] 5.0 g (14.2 mmol) of triphenylantimony and 6.46 g (28.4 mmol) of antimony trichloride were added to a 250 ml single-necked round-bottom flask, stirred in a 70°C oil bath, and then reacted at room temperature for 2 days. Subsequently, 120 ml of dichloromethane (DCM) was added to the resulting reaction mixture to completely dissolve it, and then 42.5 ml (42.5 mmol) of a 1M thionyl chloride DCM solution was slowly added dropwise. After the resulting mixture was stirred for 24 hours, 100 ml of DCM was added thereto, and then allowed to stand in a refrigerator at -20°C for one day to obtain 6.2 g of crystals.

[0159] Synthesis Example 4: Synthesis of Compound P-4 (Monophenylantimony Tetrapropionate)

[0160] 2.00 g (5.87 mmol) of the compound of Synthesis Example 3 (monophenyl antimony tetrachloride) was dissolved in 100 ml of toluene, followed by the addition of excess propionic acid and 2.11 g (18.8 mmol) of potassium propionate. The resulting mixture was purged with nitrogen (e.g., nitrogen or N2) and refluxed in a 110°C oil bath for one day. Subsequently, after removing the solvent and propionic acid at 80°C under low pressure, the resulting residue was dissolved in 50 ml of dichloromethane and then filtered. The resulting filtrate was treated under nitrogen to remove dichloromethane to obtain 2.1 g of a light yellow solid.

[0161] Synthesis Example 5: Synthesis of Compound P-5 (Tripropionate Monophenyltin)

[0162] 3.0 g (7.02 mmol) of tetraphenyltin and 5.49 g (21.1 mmol) of tin tetrachloride were added to a 250 ml single-necked round-bottom flask, followed by stirring in an 80°C oil bath and reacting at room temperature for 2 days. Subsequently, 20.8 g (281 mmol) of propionic acid was added, followed by stirring under reflux at 130°C for 1 day. The solvent and propionic acid were then removed at 100°C under reduced pressure to obtain 11.3 g of a viscous light yellow liquid.

[0163] Synthesis Example 6: Synthesis of Compound P-6 (Dibenzylphenylantimony)

[0164] 5.0 g (14.2 mmol) of triphenylantimony and 6.46 g (28.4 mmol) of antimony trichloride were added to a 250 ml single-necked round-bottom flask, followed by stirring in a 70°C oil bath and reacting at room temperature for 2 days. Subsequently, the resultant was dissolved in 40 ml of anhydrous tetrahydrofuran (THF), and 85.2 ml (85.2 mmol) of a 1M benzylmagnesium chloride THF solution was slowly added dropwise at 0°C. The resulting mixture was then stirred at room temperature for one day and treated under reduced pressure to remove THF, yielding 15.1 g of a solid.

[0165] Synthesis Example 7: Synthesis of Compound P-7 (Dibenzylantimony Trichloride)

[0166] In a 100 ml single-necked round-bottom flask, 5.0 g (12.2 mmol) of dibenzylphenylantimony of Synthesis Example 6 was dissolved in 30 ml of dichloromethane, and 6.1 ml (12.2 mmol) of HCl 2M diethyl ether solution was slowly added dropwise at -78°C. Subsequently, the resulting mixture was stirred at room temperature for one day, and 12.2 ml (12.2 mmol) of thionyl chloride 1M dichloromethane solution was slowly added dropwise. The mixture was stirred for 24 hours, 80 ml of dichloromethane was added, and then allowed to stand in a refrigerator at -20°C for one day to obtain 4.3 g of crystals.

[0167] Synthesis Example 8: Synthesis of Compound P-8 (Dibenzylantimony Tripropionate)

[0168] A pale yellow solid (dibenzylantimony tripropionate) was obtained in substantially the same manner as in Synthesis Example 2, except that dibenzylantimony trichloride of Synthesis Example 7 was used instead of diphenylantimony trichloride of Synthesis Example 1.

[0169] Synthesis Example 9: Synthesis of Compound P-9 (Benzyldiphenylantimony)

[0170] 10.0 g (28.4 mmol) of triphenylantimony and 3.23 g (14.2 mmol) of antimony trichloride were added to a 250 ml single-necked round-bottom flask, followed by stirring in a 70°C oil bath, and then reacted at room temperature for 2 days. Subsequently, the resultant was dissolved in 40 ml of anhydrous tetrahydrofuran (THF), and 42.6 ml (42.6 mmol) of a 1M THF solution of benzylmagnesium chloride was slowly added dropwise at 0°C. The resulting mixture was then stirred at room temperature for one day and treated under reduced pressure to remove THF, yielding 12.7 g of a solid.

[0171] Synthesis Example 10: Synthesis of Compound P-10 (Monobenzylantimony Tetrachloride)

[0172] In a 100 ml single-necked round-bottom flask, 4.65 g (12.2 mmol) of benzyldiphenylantimony of Synthesis Example 9 was dissolved in 30 ml of dichloromethane, and 6.1 ml (12.2 mmol) of HCl 2M diethyl ether solution was slowly added dropwise at -78°C. Subsequently, the resulting mixture was stirred at room temperature for one day, and 12.2 ml (12.2 mmol) of thionyl chloride 1M dichloromethane solution was slowly added dropwise. After the mixture was stirred for 24 hours, 80 ml of dichloromethane was added, and then the mixture was allowed to stand in a refrigerator at -20°C for one day to obtain 3.1 g of crystals.

[0173] Synthesis Example 11: Synthesis of Compound P-11 (Monobenzylantimony Tetrapropionate)

[0174] A pale yellow solid (monobenzyl antimony tetrapropionate) was obtained in substantially the same manner as in Synthesis Example 4, except that monobenzyl antimony tetrachloride of Synthesis Example 10 was used instead of monophenyl antimony tetrachloride of Synthesis Example 3, with a yield of 65%.

[0175] Synthesis Example 12: Synthesis of Compound P-12 (Tripropoxydiphenylantimony)

[0176] 2.09 g (5.47 mmol) of the compound of Synthesis Example 1 (diphenylantimony trichloride) was dissolved in 100 ml of anhydrous ether, and 1.35 g (16.4 mmol) of sodium propoxide was slowly added dropwise at 0° C. Subsequently, the resulting mixture was stirred at room temperature for one day.

[0177] Then, after removing the solvent under reduced pressure at 50°C, the resulting residue was dissolved in 50 ml of dichloromethane, followed by filtration. The resulting filtrate was treated under nitrogen to remove dichloromethane, to obtain 2.3 g of a pale yellow solid.

[0178] Preparation of semiconductor photoresist compositions

[0179] Examples 1 to 17 and Comparative Examples 1 to 5

[0180] The organometallic compounds obtained in Synthesis Examples 1 to 12 having the compositions shown in Table 1 were dissolved in xylene at a concentration of 3 wt %, and then filtered through a 0.1 μm polytetrafluoroethylene (PTFE) syringe filter to prepare semiconductor photoresist compositions.

[0181] Table 1

[0182]

[0183] Evaluation 1: Evaluation of sensitivity and line edge roughness (LER)

[0184] Each photoresist composition of the examples and comparative examples was spin-coated at 1500 rpm for 30 seconds, coated on a 200 mm circular silicon wafer with hexamethyldisilane (HMDS) deposited on the surface, and baked at 110°C for 60 seconds (after coating, baking (post-coating bake, PAB) was performed and allowed to stand at room temperature (23±2°C) for 30 seconds).

[0185] Subsequently, a linear array of 50 circular pads with a diameter of 500 microns was projected onto a wafer coated with a composition for photoresist using extreme ultraviolet light (Lawrence Berkeley National Laboratory Micro Exposure Tool, MET). The pad exposure time was adjusted to ensure that an increasing dose of extreme ultraviolet light was applied to each pad.

[0186] Then, after exposure, the resist and substrate were baked on a hot plate at 160°C for 120 seconds. The baked film was developed with propylene glycol methyl 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.

[0187] The residual resist thickness of the exposed pads was measured using an ellipsometer. The remaining thickness was measured for each exposure dose and plotted as a function of exposure dose to measure Eop (optimum energy). Sensitivity was evaluated according to the following criteria, and the results are shown in Table 2.

[0188] In one or more embodiments, line edge roughness (LER) of a line and space (line&space) pattern is measured using an electron microscope.

[0189] These results were evaluated according to the following criteria and are shown in Table 2.

[0190] Sensitivity assessment criteria

[0191] -A: The relative value of Eop relative to Comparative Example 1 is less than 50%

[0192] -B: Relative value of Eop relative to Comparative Example 1 is greater than or equal to 50% and less than 100%

[0193] -C: relative value of Eop relative to Comparative Example 1 is greater than or equal to 100%

[0194] Evaluation criteria for line edge roughness (LER)

[0195] -A: less than or equal to 4 nanometers

[0196] -B: greater than 4 nm and less than or equal to 7 nm

[0197] -C: larger than 7 nanometers

[0198] Evaluation 2: Evaluation of process delay stability

[0199] After the process was completed, a line / space CD pattern was formed or provided on the patterned wafer. The wafer was then transferred to a CD-SEM measurement system (GC-9380, Hitachi) to measure the CD (critical dimension) of the mask pattern's 14nm half-pitch area. The minimum CD value of the line-to-line distance, or space CD, was also measured. The CD dimensional change rate calculated according to Equation 1 was measured according to the following criteria, and the results are shown in Table 2. The measurement error was ±1.0nm.

[0200] Equation 1

[0201] ΔCD: CD without delay after exposure - CD with 30 minutes delay after exposure

[0202] Evaluation Criteria

[0203] -AA: ΔCD less than 3%

[0204] -A: ΔCD greater than or equal to 3% and less than 5%

[0205] -B: ΔCD greater than or equal to 5% and less than 10%

[0206] -C: ΔCD greater than or equal to 10%

[0207] Table 2

[0208] Sensitivity LER Process delay stability Example 1 B C A Example 2 B B AA Example 3 B B A Example 4 A B B Example 5 B B A Example 6 B B B Example 7 A B A Example 8 A A A Example 9 A B A Example 10 A B B Example 11 A B A Example 12 B B A Example 13 B B AA Example 14 A A A Example 15 A B A Example 16 A B A Example 17 A B A Comparative Example 1 C B C Comparative Example 2 B C C Comparative Example 3 B B C Comparative Example 4 A C C Comparative Example 5 C - -

[0209] As can be seen from the results in Table 2, the patterns provided or formed using the semiconductor photoresist compositions according to Examples 1 to 17 exhibit superior sensitivity and / or line edge roughness and stability characteristics to process delay compared to Comparative Examples 1 to 5.

[0210] Hereinafter, certain embodiments of the present disclosure have been described and illustrated. However, it should be apparent to those skilled in the art that the present disclosure is not limited to the described embodiments 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 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: an organometallic compound having two radiation-sensitive functional groups and three hydrolyzable ligands and including a pentavalent metal; as well as solvent.

2. The semiconductor photoresist composition according to claim 1, wherein the pentavalent metal is one selected from arsenic, antimony, and bismuth.

3. The semiconductor photoresist composition according to claim 1, wherein: The hydrolyzable ligand is selected from the following: 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; -O(CO)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 Represents an alkylamino or dialkylamino 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 (COR 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(CO)R k Represents a thiocarboxyl group, 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.

4. The semiconductor photoresist composition according to claim 1, wherein: The organometallic compound is represented by Chemical Formula 1: Chemical formula 1 Wherein, in Chemical Formula 1, M 1 Select from As, Sb and Bi, R 1 and R 2 are each independently 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, and X 1 To X 3 Each independently selected from the following: by -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; -O(CO)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 Represents an alkylamino or dialkylamino 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 (COR 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 is represented by -S(CO)R k Represents a thiocarboxyl group, 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.

5. The semiconductor photoresist composition according to claim 4, wherein: X 1 To X 3 Each independently selected from the following: by -OR a Represents an alkoxy or aryloxy group, wherein R a is a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C3 to C10 cycloalkyl group, a substituted or unsubstituted C2 to C10 alkenyl group, a substituted or unsubstituted C2 to C10 alkynyl group, a substituted or unsubstituted C6 to C20 aryl group, or a combination thereof; -O(CO)R b Represents a carboxyl group, where R b is hydrogen, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C3 to C10 cycloalkyl, substituted or unsubstituted C2 to C10 alkenyl, substituted or unsubstituted C2 to C10 alkynyl, substituted or unsubstituted C6 to C20 aryl, or a combination thereof; (-NR c R d Represents an alkylamino or dialkylamino group, wherein R c and R d are each independently hydrogen, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C3 to C10 cycloalkyl, substituted or unsubstituted C2 to C10 alkenyl, substituted or unsubstituted C2 to C10 alkynyl, substituted or unsubstituted C6 to C30 aryl, or a combination thereof; -NR e (COR f ) represents an amide group, wherein R e and R f are each independently hydrogen, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C3 to C10 cycloalkyl, substituted or unsubstituted C2 to C10 alkenyl, substituted or unsubstituted C2 to C10 alkynyl, substituted or unsubstituted C6 to C20 aryl, or a combination thereof; 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 C10 alkyl, substituted or unsubstituted C3 to C10 cycloalkyl, substituted or unsubstituted C2 to C10 alkenyl, substituted or unsubstituted C2 to C10 alkynyl, substituted or unsubstituted C6 to C20 aryl, or a combination thereof; -SR j represents an alkylthio or arylthio group, wherein R j is a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C3 to C10 cycloalkyl group, a substituted or unsubstituted C2 to C10 alkenyl group, a substituted or unsubstituted C2 to C10 alkynyl group, a substituted or unsubstituted C6 to C20 aryl group, or a combination thereof; and is represented by -S(CO)R k Represents a thiocarboxyl group, wherein R k is hydrogen, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C2-C10 alkenyl, substituted or unsubstituted C2-C10 alkynyl, substituted or unsubstituted C6-C20 aryl, or a combination thereof.

6. The semiconductor photoresist composition according to claim 5, wherein: X 1 To X 3 Each independently selected from the following: by -OR a Represents an alkoxy or aryloxy group, wherein R a is a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C3 to C10 cycloalkyl group, a substituted or unsubstituted C2 to C10 alkenyl group, a substituted or unsubstituted C2 to C10 alkynyl group, a substituted or unsubstituted C6 to C20 aryl group, or a combination thereof; (-O(CO)R b Represents a carboxyl group, where R b is hydrogen, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C3 to C10 cycloalkyl, substituted or unsubstituted C2 to C10 alkenyl, substituted or unsubstituted C2 to C10 alkynyl, substituted or unsubstituted C6 to C20 aryl, or a combination thereof; and -NR e (COR f ) represents an amide group, wherein R e and R f Each is independently hydrogen, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C3 to C10 cycloalkyl, substituted or unsubstituted C2 to C10 alkenyl, substituted or unsubstituted C2 to C10 alkynyl, substituted or unsubstituted C6 to C20 aryl, or a combination thereof.

7. The semiconductor photoresist composition according to claim 4, wherein: R 1 and R 2 each is independently substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted propyl, substituted or unsubstituted butyl, substituted or unsubstituted isopropyl, substituted or unsubstituted tert-butyl, substituted or unsubstituted 2,2-dimethylpropyl, substituted or unsubstituted tert-amyl, substituted or unsubstituted vinyl, substituted or unsubstituted propenyl, substituted or unsubstituted butenyl, substituted or unsubstituted ethynyl, substituted or unsubstituted propynyl, substituted or unsubstituted butynyl, substituted or unsubstituted benzyl, substituted or unsubstituted methoxy, substituted or unsubstituted ethoxy, substituted or unsubstituted propoxy, or a combination thereof, R a is substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted propyl, substituted or unsubstituted butyl, substituted or unsubstituted isopropyl, substituted or unsubstituted tert-butyl, substituted or unsubstituted tert-amyl, substituted or unsubstituted 2,2-dimethylpropyl, substituted or unsubstituted cyclopropyl, substituted or unsubstituted cyclobutyl, substituted or unsubstituted cyclopentyl, substituted or unsubstituted cyclohexyl, substituted or unsubstituted vinyl, substituted or unsubstituted propenyl, substituted or unsubstituted butenyl, substituted or unsubstituted ethynyl, substituted or unsubstituted propynyl, substituted or unsubstituted butynyl, substituted or unsubstituted phenyl, substituted or unsubstituted tolyl, substituted or unsubstituted xylyl, substituted or unsubstituted benzyl, or a combination thereof, and R b 、R c 、R d 、R e 、R f 、R g 、R h 、R i 、R j and R k each is independently hydrogen, substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted propyl, substituted or unsubstituted butyl, substituted or unsubstituted isopropyl, substituted or unsubstituted tert-butyl, substituted or unsubstituted tert-amyl, substituted or unsubstituted 2,2-dimethylpropyl, substituted or unsubstituted cyclopropyl, substituted or unsubstituted cyclobutyl, substituted or unsubstituted cyclopentyl, substituted or unsubstituted cyclohexyl, substituted or unsubstituted vinyl, substituted or unsubstituted propenyl, substituted or unsubstituted butenyl, substituted or unsubstituted ethynyl, substituted or unsubstituted propynyl, substituted or unsubstituted butynyl, substituted or unsubstituted phenyl, substituted or unsubstituted tolyl, substituted or unsubstituted xylyl, substituted or unsubstituted benzyl, or a combination thereof.

8. The semiconductor photoresist composition according to claim 1, wherein: The semiconductor photoresist composition further comprises at least one organometallic compound selected from the group consisting of an organometallic compound represented by Chemical Formula 2 and an organometallic compound represented by Chemical Formula 3: Chemical formula 2 Chemical formula 3 In Chemical Formula 2 and Chemical Formula 3, M 2 Select from As, Sb and Bi, M 3 Choose from tin, lead and titanium, R 3 and R 4 are each independently selected from the following: 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, and X 4 To X 10 Each independently selected from the following: by -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; -O(CO)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 Represents an alkylamino or dialkylamino 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 (COR 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, or -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 is represented by -S(CO)R k Represents a thiocarboxyl group, 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.

9. The semiconductor photoresist composition according to claim 8, wherein: The organometallic compound represented by Chemical Formula 1: at least one organometallic compound selected from the group consisting of the organometallic compound represented by Chemical Formula 2 and the organometallic compound represented by Chemical Formula 3 are in a weight ratio of 11:1 to 1:

11.

10. The semiconductor photoresist composition according to claim 1, wherein: The amount of the organometallic compound represented by Chemical Formula 1 is 0.5 wt % to 30 wt % based on 100 wt % of the semiconductor photoresist composition.

11. The semiconductor photoresist composition according to claim 1, wherein: The semiconductor photoresist composition further comprises at least one additive selected from alcohol compounds, thiol compounds, carboxylic acid compounds and phosphoric acid compounds.

12. The semiconductor photoresist composition according to claim 1, wherein: The semiconductor photoresist composition further comprises other additives selected from surfactants, crosslinking agents, leveling agents, organic acids, quenchers or combinations thereof.

13. A method for forming a pattern, comprising: providing an etching target layer on a substrate; applying the semiconductor photoresist composition according to claim 1 on the etching target layer to provide a photoresist layer; exposing and developing the photoresist layer to provide a photoresist film having a photoresist pattern; and The etch target layer is etched using the photoresist pattern as an etch mask.

14. The method according to claim 13, wherein The photoresist layer includes at least one selected from the groups represented by Chemical Formula 4-1 to Chemical Formula 4-5: Chemical formula 4-1 Chemical formula 4-2 Chemical formula 4-3 Chemical formula 4-4 Chemical formula 4-5 in, In Chemical Formula 4-1 to Chemical Formula 4-5, M 1 and M 2 each independently selected from arsenic, antimony, and bismuth, M 3 Choose from tin, lead, and titanium, and R 1 to R 4 Each is independently 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.

15. A photoresist film manufactured by the pattern forming method according to claim 13.

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