Semiconductor photoresist composition and method for forming pattern using the same

Abstract

Disclosed are a semiconductor photoresist composition and a method for forming or providing a pattern using the same. The semiconductor photoresist composition may include a first organometallic compound represented by Chemical Formula 1, a second organometallic compound represented by Chemical Formula 2, and a solvent.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority to and the benefit of Korean Patent Application No. 10-2024-0039349, filed on March 21, 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 or providing a pattern using the semiconductor photoresist composition. Background Art

[0004] Extreme ultraviolet (EUV) lithography has attracted widespread attention as a fundamental technology for manufacturing next-generation semiconductor devices (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 or provision of fine patterns (e.g., less than or equal to 20 nanometers) during the exposure process during 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 performed at spatial resolutions of 16 nm or less. Efforts have been or are underway to meet the resolution, speed, and feature roughness (also known as line edge roughness, or LER) specifications of chemically amplified (CA) photoresists for next-generation devices, which are insufficient.

[0006] Intrinsic image blurring caused by acid-catalyzed reactions in polymer-based photoresists limits resolution of small features, a phenomenon found in electron beam (e-beam) lithography. Chemically amplified (CA) photoresists are designed for high sensitivity. However, their elemental composition reduces the photoresist's absorption of light at 13.5 nm, potentially reducing sensitivity. Furthermore, CA photoresists may experience increased difficulty with EUV exposure.

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

[0008] To overcome the shortcomings of chemically amplified (CA) organic photosensitive compositions, inorganic photosensitive compositions have been investigated. These compositions are primarily or predominantly used for negative-tone patterning and are resistant to removal by developing compositions due to chemical modification via a non-chemical amplification mechanism. Inorganic compositions contain inorganic elements with higher EUV absorptivity than hydrocarbons, ensuring sensitivity through a non-chemical amplification mechanism. They are also less susceptible to stochastic effects, resulting in low line-edge roughness and a relatively low number of defects.

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

[0010] These materials are effective for large-pitch patterning of bilayer configurations with extreme ultraviolet (deep ultraviolet), X-ray, and electron beam sources. x ) materials together with a peroxide complexing agent obtained improved performance when imaged at 15 nm half-pitch (HP) by projection EUV exposure. The system exhibits high performance of non-CA photoresists and has practical photosensitivity close to the requirements of EUV photoresists. However, hafnium metal oxide sulfate materials including peroxide complexing agents have some practical disadvantages. First, these materials are coated in a mixture of corrosive sulfuric acid / hydrogen peroxide 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) that exhibit excellent or moderate extreme ultraviolet (EUV) absorption. In the case of organotin polymers (ITPs) containing tin, alkyl ligands dissociate through light absorption or generated secondary electrons. The dissociated alkyl ligands then crosslink with adjacent chains via oxygen bonds, enabling negative-tone patterning that cannot be removed by organic developers. While such ITPs exhibit greatly improved sensitivity while maintaining the desired resolution and line-edge roughness, further improvement in patterning properties is required for commercial viability. Summary of the Invention

[0012] One or more aspects of the embodiments of the present disclosure relate to semiconductor photoresist compositions having excellent or appropriate coating properties and / or line edge roughness (LER).

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

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

[0015] The semiconductor photoresist composition according to one or more embodiments may include a first organometallic compound represented by Chemical Formula 1, a second organometallic compound represented by Chemical Formula 2, and a solvent.

[0016] Chemical formula 1

[0017]

[0018] Chemical formula 2

[0019]

[0020] In Chemical Formula 1 and Chemical Formula 2,

[0021] R 1 and R 2 may be each independently a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, or -L a -OR a (where L a may be a single bond (eg, a single covalent bond) or a substituted or unsubstituted C1 to C20 alkylene group, and R a may be a substituted or unsubstituted C1 to C20 alkyl group),

[0022] X 1 To X 3 Can be independently selected from alkoxy or aryloxy (-OR b , where R b 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, a substituted or unsubstituted C7 to C30 aralkyl group, or a combination thereof), and a carboxyl group (—O(CO)R c , where R cmay 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, substituted or unsubstituted C7 to C30 aralkyl, or a combination thereof, and

[0023] X 4 To X 6 Each independently selected from an amino group, an alkylamine group or a dialkylamine group (-NR d R e , where R d and R e 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 C7 to C30 aralkyl group, or a combination thereof), an amido group (-NR f (COR g ), where R f and R g 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 C7 to C30 aralkyl group, or a combination thereof), an amidinate group (-NR h C(NR i )R j , where R h 、R i and R j each independently represents 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 C7 to C30 aralkyl group, or a combination thereof), an alkylthio group, or an arylthio group (-SR k , where R kmay 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, or a combination thereof), a thiocarboxyl group (-S(CO)R l , where R l may be hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C7 to C30 aralkyl group, or a combination thereof), a phosphite group (-OP(O)OR m R n , where R m and R n 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 C7 to C30 aralkyl group, or a combination thereof), and a sulfonate group (-OS(O)2R o , where R o 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, substituted or unsubstituted C7 to C30 aralkyl, or a combination thereof.

[0024] According to one or more embodiments, a method of forming or providing a pattern may include forming or providing an etching target layer on a substrate, coating a semiconductor photoresist composition on the etching target layer to form or provide a photoresist layer, patterning the photoresist layer to form or provide a photoresist pattern, and etching the etching target layer using the photoresist pattern as an etching mask.

[0025] The semiconductor photoresist composition according to one or more embodiments may provide a photoresist pattern having excellent or appropriate coating properties and line edge roughness. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] The above and other aspects and features of certain embodiments of the present disclosure will become more apparent from the following description taken in conjunction with the accompanying drawings, in which:

[0027] 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.

[0028] Description of Reference Numerals

[0029] 100:Semiconductor substrate / substrate

[0030] 102:Film

[0031] 104: resist bottom layer

[0032] 106: Photoresist layer

[0033] 106a: Unexposed area

[0034] 106b: Exposed area

[0035] 108: Photoresist pattern

[0036] 110: Patterned mask

[0037] 112: organic layer pattern

[0038] 114: Thin film pattern DETAILED DESCRIPTION

[0039] 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.

[0040] In order to clearly illustrate the embodiments of the present disclosure, some descriptions and relationships may be omitted, and substantially the same or similar configuration elements may be designated by the same reference numerals throughout the present disclosure. 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.

[0041] As used herein, the terms "and / or" and "or" may include any and all combinations of one or more of the listed items. Expressions such as "at least one of," when preceding a list of elements, modify the entire list of elements rather than the individual elements of the list.

[0042] It will be further understood that the terms "comprising", "including" or "having" used in this disclosure specify the presence of the features, integers, steps, operations, elements and / or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components and / or groups thereof. The " / " used hereinafter may be interpreted as "and" or "or" as appropriate.

[0043] As used herein, the singular forms "a," "an," and "the" are intended to include the plural forms as well, 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."

[0044] In the context of the present disclosure, unless defined otherwise, the terms "use," "using," and "used" may be considered synonymous with the terms "utilize," "utilizing," and "utilized," respectively.

[0045] As used herein, the term "about" or similar terms are used as terms of approximation rather than terms of degree, and are intended to account for 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 the errors associated with the measurement of the particular quantity (i.e., the limitations of the measurement system). For example, "about" may mean within one or more standard deviations, or within ±30%, 20%, 10%, or 5% of the stated value.

[0046] Any numerical range described herein is intended to include all subranges of substantially the same numerical precision contained within the described range. For example, a range of "1.0 to 10.0" is intended to include all subranges between (and including) the described minimum value of 1.0 and the described maximum value of 10.0, i.e., having a minimum value equal to or greater than 1.0 and a maximum value equal to or less than 10.0, such as, for example, 2.4 to 7.6. Any maximum numerical limit described herein is intended to include all lower numerical limits contained therein, and any minimum numerical limit described in this specification is intended to include all higher numerical limits contained therein. Therefore, the applicant reserves the right to amend this specification (including the claims) to explicitly describe any subranges contained within the range explicitly described herein.

[0047] 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 should be understood that if (for example, when) an element such as a layer, film, region, or substrate is referred to as being "on" another element, it 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 not be intervening elements.

[0048] As used herein, "substituted" refers to hydrogen atoms replaced by deuterium, halogen, carboxyl, hydroxyl, thiol, cyano, nitro, -NRR' (wherein, R and R' are each independently hydrogen, substituted or unsubstituted C1 to C30 saturated or unsaturated aliphatic hydrocarbon groups, substituted or unsubstituted C3 to C30 saturated or unsaturated alicyclic hydrocarbon groups, or substituted or unsubstituted C6 to C30 aromatic hydrocarbon groups), -SiRR'R" (wherein, R, R' and R" are each independently The alkyl radicals may be independently substituted with 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 the hydrogen atom remains.

[0049] As used herein, if (e.g., when) no further definition is provided, "alkyl" refers to a linear or branched aliphatic hydrocarbon group. The alkyl group may be a "saturated alkyl group" that does not contain any double or triple bonds.

[0050] The alkyl group may be a C1 to C10 alkyl group. For example, the alkyl group may be a C1 to C8 alkyl group, 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.

[0051] As used herein, if (eg, when) no definition is otherwise provided, "cycloalkyl" refers to a monovalent cyclic aliphatic hydrocarbon group.

[0052] The cycloalkyl group may be a C3 to C10 cycloalkyl group, for example, 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 the embodiments of the present disclosure are not limited thereto.

[0053] As used herein, "aryl" refers to a substituent in which all atoms in the cyclic substituent have p orbitals and these p orbitals are conjugated, and can include monocyclic or fused-ring polycyclic (eg, rings that share adjacent pairs of carbon atoms) functional groups.

[0054] 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.

[0055] As used herein, unless otherwise defined, "alkynyl" refers to an aliphatically unsaturated alkynyl group that is a straight or branched aliphatic hydrocarbon radical containing at least one triple bond.

[0056] In the chemical formulae described herein, t-Bu refers to tert-butyl.

[0057] Semiconductor photoresist compositions according to one or more embodiments are described below.

[0058] The semiconductor photoresist composition according to one or more embodiments may include a first organometallic compound represented by Chemical Formula 1, a second organometallic compound represented by Chemical Formula 2, and a solvent.

[0059] Chemical formula 1

[0060]

[0061] Chemical formula 2

[0062]

[0063] In Chemical Formula 1 and Chemical Formula 2,

[0064] R 1 and R 2 may be each independently a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, or -L a -OR a (where L a may be a single bond (eg, a single covalent bond) or a substituted or unsubstituted C1 to C20 alkylene group, and R a may be a substituted or unsubstituted C1 to C20 alkyl group),

[0065] X 1 To X 3 Can be independently selected from alkoxy or aryloxy (-OR b , where R b 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, a substituted or unsubstituted C7 to C30 aralkyl group, or a combination thereof), and a carboxyl group (—O(CO)R c , where R c 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, substituted or unsubstituted C7 to C30 aralkyl, or a combination thereof, and

[0066] X 4 To X 6 can be independently selected from amino, alkylamino or dialkylamino (-NR d R e , where R d and R e and (-NR ) are 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, a substituted or unsubstituted C7 to C30 aralkyl group, or a combination thereof. f (COR g ), where R f and R g and (-NR ) 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 C7 to C30 aralkyl group, or a combination thereof), an amidino group (-NR h C(NR i )R j , where R h 、R i and R j and (-SR 100, -SR 100) each independently represent 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 C7 to C30 aralkyl group, or a combination thereof), an alkylthio group, or an arylthio group (-SR 100). 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, a substituted or unsubstituted C7 to C30 aralkyl group, or a combination thereof), a thiocarboxyl group (-S(CO)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, substituted or unsubstituted C7 to C30 aralkyl, or a combination thereof), a phosphite group (-OP(O)ORm R n , where R m and R n 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 C7 to C30 aralkyl group, or a combination thereof), and a sulfonic acid group (-OS(O)2R o , where R o 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, substituted or unsubstituted C7 to C30 aralkyl, or a combination thereof.

[0067] In a composition in which two or more types or kinds of organotin compounds having different ligands are mixed, the degree of disorder of the entire composition system may increase, and the surface roughness after spin coating may be improved or enhanced.

[0068] The first organometallic compound can be an organometallic compound with a highly reactive ligand and can improve or enhance sensitivity (e.g., to provide suitable sensitivity) by promoting the curing of exposed areas, and if (e.g., when) mixed with a second organometallic compound, can inhibit the curing of unexposed areas, thereby improving the bridge margin, and can reduce crystallinity by introducing one or more suitable ligands, thereby achieving excellent or suitable coating performance and LER.

[0069] As an example, R 1 and R 2 may be each independently a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C2 to C10 alkenyl group, a substituted or unsubstituted C2 to C10 alkynyl group, or -L a -OR a (where L a may be a single bond (eg, a single covalent bond) or a substituted or unsubstituted C1 to C20 alkylene group, and R a may be a substituted or unsubstituted C1 to C20 alkyl group),

[0070] X 1 To X 3 can be independently selected from alkoxy or aryloxy (-OR b , where R bmay 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, a substituted or unsubstituted C7 to C20 aralkyl group, or a combination thereof), and a carboxyl group (-O(CO)R c , where R c may be selected from 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, substituted or unsubstituted C7 to C20 aralkyl, or a combination thereof, and

[0071] X 4 To X 6 can be independently selected from amino, alkylamino or dialkylamino (-NR d R e , where R d and R e may each independently be hydrogen, 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, a substituted or unsubstituted C7 to C20 aralkyl group, or a combination thereof), an amide group (-NR f (COR g ), where R f and R g and (-NR ) may each independently be hydrogen, 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, a substituted or unsubstituted C7 to C20 aralkyl group, or a combination thereof), or an amidino group (-NR h C(NR i )R j , where R h , R i and R j and (-SR 10, -SR 10) may each independently be hydrogen, 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, a substituted or unsubstituted C7 to C20 aralkyl group, or a combination thereof), an alkylthio group, or an arylthio group (-SR k , where Rk 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, a substituted or unsubstituted C7 to C20 aralkyl group, or a combination thereof), a thiocarboxyl group (-S(CO)R l , where R l 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, substituted or unsubstituted C7 to C20 aralkyl, or a combination thereof), a phosphite group (-OP(O)OR m R n , where R m and R n may each independently be hydrogen, 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, a substituted or unsubstituted C7 to C20 aralkyl group, or a combination thereof), and a sulfonic acid group (-OS(O)2R o , where R o The alkyl radical may be selected from 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, substituted or unsubstituted C7 to C20 aralkyl, or a combination thereof.

[0072] 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.

[0073] Rb 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

[0074] R c , R d , R e , R f , R g , R h , R i , R j , R k , R l , R m , R n , and R o and 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.

[0075] For example, X 4 to X 6 can be independently selected from amino, alkylamino or dialkylamino (-NR d R e , where R d and R emay 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 C7 to C30 aralkyl group, or a combination thereof), an amide group (-NR f (COR g ), where R f and R g and (-S(CO)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, substituted or unsubstituted C7 to C30 aralkyl, or a combination thereof), a phosphite group (-OP(O)OR m R n , where R m and R n 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 C7 to C30 aralkyl group, or a combination thereof), and a sulfonic acid group (-OS(O)2R o , where R o 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, substituted or unsubstituted C7 to C30 aralkyl, or a combination thereof.

[0076] In one or more embodiments, the first organometallic compound and the second organometallic compound may be included in a weight ratio of about 90:10 to about 40:60.

[0077] For example, the first organometallic compound and the second organometallic compound may be included in a weight ratio of about 80:20 to about 40:60, eg, about 70:30 to about 40:60.

[0078] The first organometallic compound can be selected from the compounds listed in Group 1.

[0079] Group 1

[0080]

[0081] The second organometallic compound can be selected from the compounds listed in Group 2.

[0082] Group 2

[0083]

[0084] The organometallic compound can strongly absorb extreme ultraviolet light at 13.5 nanometers and may have excellent or appropriate sensitivity to high-energy light.

[0085] In the semiconductor photoresist composition according to one or more embodiments, the first and second organometallic compounds may be included in an amount of about 1 wt % to about 30 wt %, for example, about 1 wt % to about 25 wt %, for example, about 1 wt % to about 20 wt %, for example, about 1 wt % to about 15 wt %, for example, about 1 wt % to about 10 wt %, or for example, about 1 wt % to about 5 wt %, based on 100 wt % of the semiconductor photoresist composition. If (for example, when) the organometallic compounds are included in an amount within the above range, the storage stability and / or etching resistance of the composition for the semiconductor photoresist may be improved or enhanced, and the resolution characteristics may be improved or enhanced.

[0086] Since the semiconductor photoresist composition according to one or more embodiments may include the first and second organometallic compounds as described in one or more embodiments, a semiconductor photoresist composition having excellent or appropriate sensitivity and / or pattern forming performance may be provided.

[0087] The solvent included 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-pentanol, 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-butyrate, 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.

[0088] In one or more embodiments, the semiconductor photoresist composition may further include a resin in addition to the first organometallic compound, the second organometallic compound, and the solvent as described in one or more embodiments.

[0089] The resin may be a phenolic resin comprising at least one aromatic moiety selected from those listed in Group 3.

[0090] Group 3

[0091]

[0092] The resin may have a weight average molecular weight (M) of about 500 g / mol to about 20,000 g / mol. w ).

[0093] 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 (eg, based on 100 wt % of the semiconductor photoresist composition).

[0094] If (eg, when) the resin is included in the above-mentioned content (eg, amount) range, it may have excellent or appropriate etching resistance and / or heat resistance.

[0095] In one or more embodiments, the semiconductor photoresist composition according to one or more embodiments can be composed of or include the first organometallic compound, the second organometallic compound, the solvent, and the resin as described in one or more embodiments. However, the semiconductor photoresist composition according to one or more embodiments can further include additives as needed or desired. Examples of additives can be surfactants, cross-linking agents, leveling agents, organic acids, quenchers, or combinations thereof.

[0096] 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.

[0097] The cross-linking agent may be, for example, a melamine-based cross-linking agent, a substituted urea-based cross-linking agent, an acrylic-based cross-linking agent, an epoxy-based cross-linking agent, or a polymer-based cross-linking agent, but the embodiments of the present disclosure are not limited thereto. It may be a cross-linking agent having at least two cross-linking-forming substituents, for example, a compound such as methoxymethylated glycoluril, butoxymethylated biuret, methoxymethylated melamine, butoxymethylated melamine, methoxymethylated benzoguanamine, butoxymethylated benzoguanamine, 4-hydroxybutyl acrylate, acrylic acid, urethane acrylate, methyl acrylate, 1,4-butanediol diglycidyl ether, glycidol, diglycidyl 1,2-cyclohexane dicarboxylate, trimethylpropane triglycidyl ether, 1,3-bis(glycidyloxypropyl)tetramethyldisiloxane, methoxymethylated urea, butoxymethylated urea, methoxymethylated thiourea and / or the like.

[0098] The leveling agent may be used to improve or enhance coating smoothness during the printing process, and may be a commercially available or commonly available leveling agent.

[0099] 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.

[0100] The quencher can be diphenyl(p-tolyl)amine, methyldiphenylamine, triphenylamine, phenylenediamine, naphthylamine, diaminonaphthalene, or a combination thereof.

[0101] The quencher can be diphenyl(p-tolyl)amine, methyldiphenylamine, triphenylamine, phenylenediamine, naphthylamine, diaminonaphthalene, or a combination thereof.

[0102] The amount of additives used can be controlled according to the desired properties.

[0103] 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; or 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, p-phenylenyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane; trimethoxy[3-(phenylamino)propyl]silane, and / or the like, but the embodiments of the present disclosure are not limited thereto.

[0104] 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 a width (e.g., line width) of, for example, about 5 nanometers to about 100 nanometers, such as about 5 nanometers to about 80 nanometers, such as about 5 nanometers to about 70 nanometers, such as about 5 nanometers to about 50 nanometers, such as about 5 nanometers to about 40 nanometers, such as about 5 nanometers to about 30 nanometers, such as about 5 nanometers to about 20 nanometers, or such as about 5 nanometers to about 10 nanometers, the semiconductor photoresist composition can be used for a photolithography process using light with a wavelength in the range of about 5 nanometers to about 150 nanometers, such as 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 implement extreme ultraviolet lithography using an EUV light source with a wavelength of about 13.5 nanometers.

[0105] 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 may be provided. For example, the pattern may be a photoresist pattern.

[0106] The method of forming or providing a pattern according to one or more embodiments may include forming or providing an etching target layer on a substrate, coating a semiconductor photoresist composition on the etching target layer to form or provide a photoresist layer, patterning the photoresist layer to form or provide a photoresist pattern, and etching the etching target layer using the photoresist pattern as an etching mask.

[0107] Below, we will refer to Figures 1A to 1E Methods of forming or providing patterns using semiconductor photoresist compositions are described. Figures 1A to 1EEach of them 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.

[0108] Reference 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 cleaned to remove impurities and / or the like remaining thereon. The thin film 102 may be, for example, a silicon nitride layer, a polysilicon layer, and / or a silicon oxide layer.

[0109] Subsequently, a resist base layer composition for providing the resist base layer 104 may be spin-coated on the surface of the cleaned thin film 102. However, the embodiments of the present disclosure are not limited thereto, and one or more suitable coating methods, such as spray coating, dip coating, doctor blade coating, printing methods such as inkjet printing and screen printing, and / or the like, may be used.

[0110] The process of coating the resist primer layer may not be provided, and the process including coating the resist primer layer will be described below.

[0111] Then, the applied composition may be dried and baked (heat treated) to form or provide a resist bottom layer 104 on the thin film 102. The baking (heat treatment) may be performed at about 100°C to about 500°C, for example, about 100°C to about 300°C.

[0112] The resist bottom layer 104 may be located 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 pattern formation when radiation reflected from the interface between the substrate 100 and the photoresist layer 106 or the interlayer hard mask is scattered into unintended photoresist areas (e.g., when this occurs).

[0113] Reference Figure 1B The photoresist layer 106 can be formed or provided 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 on the thin film 102 formed or provided on the substrate 100 and then curing it through heat treatment.

[0114] For example, forming a pattern using a 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 to form or provide the photoresist layer 106 .

[0115] The composition of semiconductor photoresist has been described in detail and will not be repeated here.

[0116] Subsequently, the substrate 100 having the photoresist layer 106 may be subjected to a first baking (heat treatment) process. The first baking process may be performed at a temperature of about 80°C to about 120°C.

[0117] Reference Figure 1C , the photoresist layer 106 may be selectively exposed using a patterned mask 110 .

[0118] For example, exposure can use activation radiation of light with a high energy wavelength, such as EUV (extreme ultraviolet; wavelength of about 13.5 nanometers), electron beam (E-Beam) and / or similar light sources, as well as 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 similar light sources.

[0119] For example, the light or light beam used for exposure according to one or more embodiments may have a short wavelength in the range of about 5 nanometers to about 150 nanometers, and / or a high energy wavelength, such as EUV (extreme ultraviolet; wavelength 13.5 nanometers), electron beam (E-Beam), and / or similar light sources.

[0120] The exposed regions 106b of the photoresist layer 106 may have a different solubility than the unexposed regions 106a of the photoresist layer 106 by forming or providing a polymer resulting from a cross-linking reaction, such as a condensation between organometallic compounds (eg, a condensation reaction between organometallic compounds).

[0121] Subsequently, a second baking (heat treatment) process may be performed on the substrate 100. 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 to a developer.

[0122] exist Figure 1D In the process, the unexposed region 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 region 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 a negative tone image.

[0123] In 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.

[0124] However, the photoresist pattern according to one or more embodiments is not necessarily limited to a negative tone image, but can be formed or provided as a positive tone image. In one or more embodiments, the developer used to form or provide the positive tone image can be a quaternary ammonium hydroxide composition, such as tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, or a combination thereof.

[0125] In one or more embodiments, exposure to light or beams having high energy, such as EUV (extreme ultraviolet; wavelength 13.5 nm), electron beams (E-Beams), and / or similar light sources, and light having short wavelengths, such as i-line (wavelength of approximately 365 nm), KrF excimer lasers (wavelength of approximately 248 nm), ArF excimer lasers (wavelength of approximately 193 nm), and / or similar light sources, can provide a photoresist pattern 108 having a thickness or width of approximately 5 nm to approximately 100 nm. For example, the photoresist pattern 108 can have a thickness or 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.

[0126] In one or more embodiments, the photoresist pattern 108 may have a pitch having a half pitch less than or equal to about 50 nanometers, for example, 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 width 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.

[0127] Subsequently, the resist bottom layer 104 can be etched using the photoresist pattern 108 as an etching mask. Through this etching process, an organic layer pattern 112 can be formed or provided. The organic layer pattern 112 can also have a width (eg, line width) corresponding to the photoresist pattern 108.

[0128] 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 or provided as a thin film pattern 114.

[0129] 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.

[0130] During the exposure process, the thin film pattern 114 formed or provided using the photoresist pattern 108 formed or provided by 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 using the photoresist pattern 108 formed or provided by 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, which is similar to or substantially similar to the width of the photoresist pattern 108.

[0131] Hereinafter, 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. However, one or more embodiments of the present disclosure are not technically limited by the following examples.

[0132] Synthesis of the first organometallic compound

[0133] Synthesis Example 1

[0134] In a 250 ml two-necked round-bottom flask, 20 g (51.9 mmol) of triphenyltin chloride (Ph3SnCl) was dissolved in 70 ml of tetrahydrofuran (THF) and then cooled to 0°C in an ice bath. Subsequently, a 1 M (mol / L) solution of tert-butylmagnesium chloride (t-BuMgCl) in THF (62.3 mmol) was slowly added dropwise. After the addition was complete, the resulting mixture was stirred at room temperature (25 ± 3°C) for 12 hours to obtain a t-BuSnPh3 compound.

[0135] Then, t-BuSnPh3 (10 g, 24.6 mmol) was dissolved in 50 ml of dichloromethane (CH2Cl2), and 3 equivalents (73.7 mmol) of a 2 mol / L hydrogen chloride (HCl) diethyl ether solution was slowly added dropwise at -78°C for 30 minutes. After the obtained mixture was stirred at room temperature for 12 hours, the solvent was concentrated and vacuum distilled to obtain a t-BuSnCl3 compound.

[0136] Then, 32 ml of propionic acid was slowly added dropwise to 10 g (25.6 mmol) of t-BuSnCl3 at room temperature, followed by heating under reflux for 12 hours. After the temperature was raised to room temperature, propionic acid was vacuum distilled to obtain a compound represented by Chemical Formula 1a.

[0137] Chemical formula 1a

[0138]

[0139] Synthesis Example 2

[0140] A compound represented by Chemical Formula 1b was obtained in substantially the same manner as in Synthesis Example 1, except that neopentylmagnesium chloride (neopentylMgCl) was used instead of tert-butylmagnesium chloride (t-BuMgCl).

[0141] Chemical formula 1b

[0142]

[0143] Synthesis Example 3

[0144] A compound represented by Chemical Formula 1c was obtained in substantially the same manner as in Synthesis Example 1, except that isobutylmagnesium chloride (i-BuMgCl) was used instead of tert-butylmagnesium chloride (t-BuMgCl).

[0145] Chemical formula 1c

[0146]

[0147] Synthesis Example 4

[0148] A compound represented by Chemical Formula 1d was obtained in substantially the same manner as in Synthesis Example 1, except that n-butylmagnesium chloride (n-BuMgCl) was used instead of tert-butylmagnesium chloride (t-BuMgCl).

[0149] Chemical formula 1d

[0150]

[0151] Synthesis Example 5

[0152] In a 250 ml two-necked round-bottom flask, 20 g (51.9 mmol) of Ph SnCl was dissolved in 70 ml of THF and then cooled to 0°C in an ice bath. Subsequently, a 1 mol / L THF solution of tert-butyl magnesium chloride (t-BuMgCl) (62.3 mmol) was slowly added dropwise. After the addition was complete, the resulting mixture was stirred at room temperature for 12 hours to obtain a t-BuSnPh compound in an 89% yield.

[0153] Subsequently, t-BuSnPh3 (10 g, 24.6 mmol) was dissolved in 50 ml of CH2Cl2, and 3 equivalents (73.7 mmol) of 2 mol / L HCl in ether were slowly added dropwise at -78°C for 30 minutes. After the mixture was stirred at room temperature for 12 hours, the solvent was concentrated and vacuum distilled to obtain t-BuSnCl3 compound.

[0154] Subsequently, 30 ml of anhydrous pentane was added to 10 g (35.4 mmol) of t-BuSnCl3, and then cooled to 0°C. Then, 7.8 g (106.3 mmol) of diethylamine was slowly added dropwise, and 10.9 g (106.3 mmol) of methyl isobutyl carbinol was added, followed by stirring at room temperature for 1 hour. When the reaction was complete, the resulting product was filtered, concentrated, and vacuum-dried to obtain the compound represented by Chemical Formula 1e in a 60% yield.

[0155] Chemical formula 1e

[0156]

[0157] Synthesis Example 6

[0158] Referring to the synthesis method described in Publication No. KR10-2020-0126884, the compound represented by Chemical Formula 1f was obtained with a yield of 60%.

[0159] Chemical formula 1f

[0160]

[0161] Synthesis of the second organometallic compound

[0162] Synthesis Example 7

[0163] The compound represented by Chemical Formula 2a was obtained in substantially the same manner as in Synthesis Example 5, except that neopentylmagnesium chloride (neopentylMgCl) was used instead of t-butylmagnesium chloride (t-BuMgCl), and N-methylpropionamide was used instead of methyl isobutylcarbinol.

[0164] Chemical formula 2a

[0165]

[0166] Synthesis Example 8

[0167] The compound represented by Chemical Formula 2b was obtained in substantially the same manner as in Synthesis Example 5, except that isobutylmagnesium chloride (i-BuMgCl) was used instead of tert-butylmagnesium chloride (t-BuMgCl), and methylphosphonicacid was used instead of methyl isobutylcarbinol.

[0168] Chemical formula 2b

[0169]

[0170] Synthesis Example 9

[0171] The compound represented by Chemical Formula 2c was obtained in substantially the same manner as in Synthesis Example 5, except that n-butylmagnesium chloride (n-BuMgCl) was used instead of t-butylmagnesium chloride (t-BuMgCl), and triflic acid was used instead of methyl isobutyl carbinol.

[0172] Chemical formula 2c

[0173]

[0174] Preparation of semiconductor photoresist compositions

[0175] Examples 1 to 14 and Comparative Examples 1 to 7

[0176] Each compound represented by Chemical Formulas 1a to 1f and 2a to 2c in Synthesis Examples 1 to 9 was dissolved in propylene glycol monomethyl ether acetate (PGMEA) at 3 wt %, and then filtered using a 0.1 μm polytetrafluoroethylene (PTFE) syringe filter to prepare a photoresist composition.

[0177] Evaluation 1: Evaluation of coating surface roughness

[0178] Each of the photoresist compositions of Examples 1 to 14 and Comparative Examples 1 to 7 was coated on a wafer and exposed on a hot plate at 100° C. for 60 seconds, and the surface roughness (Rq) was measured using an atomic force microscope (AFM). The results were evaluated according to the following criteria and are shown in Table 1.

[0179] Surface roughness (Rq value)

[0180] -○: less than or equal to 0.4

[0181] -△: greater than 0.4 and less than or equal to 0.7

[0182] -X: greater than 0.7

[0183] Evaluation 2: Evaluation of Line Edge Roughness (LER)

[0184] Using EUV light (Lawrence Berkeley National Laboratory Micro Exposure Tool (MET)), a linear array of 50 circular pads with a diameter of 500 μm was projected onto a wafer coated with each of the photoresist compositions of Examples 1 to 14 and Comparative Examples 1 to 7. The exposure time of the pads was adjusted to apply an increasing EUV dose to each pad.

[0185] Subsequently, the resist and substrate were exposed on a 160°C hot plate for 120 seconds and then baked. The baked film was immersed in a developer (2-heptanone) for 30 seconds each, and then washed with the same developer (2-heptanone) for another 10 seconds to form or provide a negative tone image, i.e., to remove the unexposed portions of the coating. Finally, the process was completed by baking on a 150°C hot plate for 2 minutes.

[0186] The line edge roughness (LER) of the line-to-space pattern was measured using an electron microscope. The results were evaluated according to the following criteria and are then shown in Table 1.

[0187] Line Edge Roughness (LER)

[0188] -○: less than or equal to 4 nanometers

[0189] -△: greater than 4 nanometers and less than or equal to 7 nanometers

[0190] -X: larger than 7 nanometers

[0191] Table 1

[0192]

[0193] Referring to the results of Table 1, the semiconductor photoresist composition according to the embodiment exhibits excellent coating performance due to reduced surface roughness and excellent line edge roughness compared to the semiconductor photoresist composition according to the comparative example.

[0194] Hereinafter, specific 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 may be appropriately modified and transformed without departing from the spirit and scope of the present disclosure. Therefore, 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: a first organometallic compound represented by Chemical Formula 1; a second organometallic compound represented by Chemical Formula 2; and Solvent: Chemical formula 1 Chemical formula 2 Wherein, in Chemical Formula 1 and Chemical Formula 2, R 1 and R 2 each independently a substituted or unsubstituted C1 to C20 alkyl, a substituted or unsubstituted C2 to C20 alkenyl, a substituted or unsubstituted C2 to C20 alkynyl, or -L a -OR a , where L a is a single bond or a substituted or unsubstituted C1 to C20 alkylene group, and R a is a substituted or unsubstituted C1 to C20 alkyl group, X 1 To X 3 Each independently selected from -OR b , where R b is 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 C7 to C30 aralkyl, or a combination thereof; and -O(CO)R c , where R c 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, substituted or unsubstituted C7 to C30 aralkyl, or a combination thereof, X 4 To X 6 Each independently selected from -NR d R e , where R d and R e each independently represents 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 C7 to C30 aralkyl, or a combination thereof; -NR f (COR g ), where R f and R g each independently represents 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 C7 to C30 aralkyl, or a combination thereof; -NR h C(NR i )R j , where R h 、R i and R j each independently represents 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 C7 to C30 aralkyl, or a combination thereof; -SR k , where 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, a substituted or unsubstituted C7 to C30 aralkyl group, or a combination thereof; -S(CO)R l , where R l is hydrogen, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C2-C20 alkenyl, substituted or unsubstituted C2-C20 alkynyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C7-C30 aralkyl, or a combination thereof; -OP(O)OR m R n , where R m and R n 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, substituted or unsubstituted C7 to C30 aralkyl, or a combination thereof; and -OS(O)2R o , where R o 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, substituted or unsubstituted C7 to C30 aralkyl, or a combination thereof.

2. The semiconductor photoresist composition according to claim 1, wherein: R 1 and R 2 are each independently a substituted or unsubstituted C1 to C10 alkyl, a substituted or unsubstituted C2 to C10 alkenyl, a substituted or unsubstituted C2 to C10 alkynyl, or -L a -OR a , where L a is a single bond or a substituted or unsubstituted C1 to C20 alkylene group, and R a is a substituted or unsubstituted C1 to C20 alkyl group, X 1 To X 3 Each independently selected from -OR b , where R b is 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, substituted or unsubstituted C7 to C20 aralkyl, or a combination thereof; and -O(CO)R c , where R c 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, substituted or unsubstituted C7 to C20 aralkyl, or a combination thereof; and X 4 To X 6 Each independently is -NR d R e , where R d and R e each independently represents 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, substituted or unsubstituted C7 to C20 aralkyl, or a combination thereof; -NR f (COR g ), where R f and R g each independently represents 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, substituted or unsubstituted C7 to C20 aralkyl, or a combination thereof; or -NR h C(NR i )R j , where R h 、R i and R j each independently represents 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, substituted or unsubstituted C7-C20 aralkyl, or a combination thereof; -SR k , where R k 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, a substituted or unsubstituted C7 to C20 aralkyl group, or a combination thereof; -S(CO)R l , where R l 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, substituted or unsubstituted C7-C20 aralkyl, or a combination thereof; -OP(O)OR m R n , where R m and R n 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, substituted or unsubstituted C7 to C20 aralkyl, or a combination thereof; and -OS(O)2R o , where R o 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, substituted or unsubstituted C7 to C20 aralkyl, or a combination thereof.

3. The semiconductor photoresist composition according to claim 1, wherein: R 1 and R 2 each independently represents a substituted or unsubstituted methyl, a substituted or unsubstituted ethyl, a substituted or unsubstituted propyl, a substituted or unsubstituted butyl, a substituted or unsubstituted isopropyl, a substituted or unsubstituted tert-butyl, a substituted or unsubstituted 2,2-dimethylpropyl, a substituted or unsubstituted tert-amyl, a substituted or unsubstituted vinyl, a substituted or unsubstituted propenyl, a substituted or unsubstituted butenyl, a substituted or unsubstituted ethynyl, a substituted or unsubstituted propynyl, a substituted or unsubstituted butynyl, a substituted or unsubstituted benzyl, a substituted or unsubstituted methoxy, a substituted or unsubstituted ethoxy, a substituted or unsubstituted propoxy, or a combination thereof, R b 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 c 、R d 、R e 、R f 、R g 、R h 、R i 、R j 、R k 、R l 、R m 、R n and R o 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.

4. The semiconductor photoresist composition according to claim 1, wherein: X 4 To X 6 Each independently selected from -NR d R e , where R d and R e each independently represents 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 C7 to C30 aralkyl, or a combination thereof; -NR f (COR g ), where R f and R g 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, substituted or unsubstituted C7 to C30 aralkyl, or a combination thereof; -S(CO)R l , where R l is hydrogen, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C2-C20 alkenyl, substituted or unsubstituted C2-C20 alkynyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C7-C30 aralkyl, or a combination thereof; -OP(O)OR m R n , where R m and R n 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, substituted or unsubstituted C7 to C30 aralkyl, or a combination thereof; and -OS(O)2R o , where R o 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, substituted or unsubstituted C7 to C30 aralkyl, or a combination thereof.

5. The semiconductor photoresist composition according to claim 1, wherein: The first organometallic compound and the second organometallic compound are included in a weight ratio of 90:10 to 40:

60.

6. The semiconductor photoresist composition according to claim 1, wherein: The first organometallic compound and the second organometallic compound are included in a weight ratio of 70:30 to 40:

60.

7. The semiconductor photoresist composition according to claim 1, wherein: The first organometallic compound is one selected from the compounds listed in Group 1: Group 1 8. The semiconductor photoresist composition according to claim 1, wherein: The second organometallic compound is one selected from the compounds listed in Group 2: Group 2 9. The semiconductor photoresist composition according to claim 1, wherein: The first organometallic compound and the second organometallic compound are included in an amount of 1 wt % to 30 wt % based on 100 wt % of the semiconductor photoresist composition.

10. 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 leveling agent, an organic acid, a quencher or a combination thereof.

11. A method for forming a pattern, comprising: providing an etching target layer on a substrate; coating the semiconductor photoresist composition according to claim 1 on the etching target layer to provide a photoresist layer; patterning the photoresist layer to provide a photoresist pattern; as well as The etch target layer is etched using the photoresist pattern as an etch mask.

12. The method according to claim 11, wherein: The photoresist pattern is provided using light having a wavelength of 5 nm to 150 nm.

13. The method according to claim 11, wherein: The method further includes providing a resist bottom layer between the substrate and the photoresist layer.

14. The method according to claim 11, wherein: The photoresist pattern has a width of 5 nanometers to 100 nanometers.

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