Semiconductor photoresist composition and method of forming pattern using the same

Abstract

A semiconductor photoresist composition and a method of forming or providing a pattern using the same are disclosed. The semiconductor photoresist composition may include an organometallic compound represented by Chemical Formula 1, and a solvent.

Description

[0001] Cross-reference of related applications

[0002] This application claims priority and benefit to Korean Patent Application No. 10-2024-0156547, filed on November 6, 2024, with the Korean Intellectual Property Office, the entire disclosure of which is incorporated herein by reference. Technical Field

[0003] One or more embodiments of this disclosure relate to a semiconductor photoresist composition and a method of forming or providing patterns using the semiconductor photoresist composition. Background Technology

[0004] Extreme ultraviolet (EUV) lithography has attracted attention as a key technology for manufacturing next-generation semiconductor devices. EUV lithography is a patterning technique that uses EUV rays with a wavelength of 13.5 nm as the exposure source. According to EUV lithography, extremely fine patterns (e.g., less than or equal to 20 nm) can be formed or provided in the exposure process during the manufacturing of semiconductor devices.

[0005] Extreme ultraviolet (EUV) lithography is achieved through the development of compatible photoresists, which can be performed at a spatial resolution of less than or equal to 16 nm. Efforts are underway to overcome the limitations or inapplicability of chemically amplified (CA) photoresists typically available for next-generation devices, such as resolution, photospeed, and feature roughness (or line edge roughness, or LER).

[0006] The inherent image blurring caused by acid-catalyzed reactions in the aforementioned polymer types or varieties of photoresists limits the resolution of small feature sizes, a problem that has long existed in electron beam lithography. Chemically amplified (CA) photoresists are designed to achieve high sensitivity, but their elemental composition reduces absorbance at 13.5 nm wavelength, thus decreasing sensitivity, which may present additional challenges when performing EUV exposures with CA photoresists.

[0007] Furthermore, due to roughness issues, CA photoresists may face difficulties with small feature sizes, and experiments have shown that the line edge roughness (LER) of CA photoresists increases because the photosensitivity is reduced in part due to the nature of the acid catalyst process. Therefore, due to these defects and problems of CA photoresists, a novel high-performance photoresist is needed or desired in the semiconductor industry.

[0008] To overcome the drawbacks of chemically amplified (CA) organic photosensitive compositions, an inorganic photosensitive composition has been developed. This inorganic photosensitive composition is primarily or dominantly used for negative tone patterning, which resists removal by the developer composition due to chemical modification achieved through a non-chemical amplification mechanism. The inorganic composition contains inorganic elements with higher EUV absorbance than hydrocarbons, thus ensuring sensitivity through a non-chemical amplification mechanism. Furthermore, it is less sensitive to stochastic effects and therefore may exhibit low line edge roughness and fewer defects.

[0009] Inorganic photoresists based on tungsten peroxypolyacids mixed with tungsten, niobium, titanium, and / or tantalum are radiation-sensitive materials used for patterning. These materials are as effective or suitable as far-ultraviolet (deep UV), X-ray, and electron beam sources for patterning large-pitch configurations or arrangements of two layers.

[0010] Utilizing cationic hafnium metal oxide sulfate (HfSO) x Hafnium oxide sulfate materials with peroxide complexing agents exhibit the highest performance among non-CA photoresists for imaging 15 nm half-pitch (HP) via projection EUV exposure, and possess practical sensing speeds approaching those required for EUV photoresists. However, hafnium metal oxide sulfate materials with peroxide complexing agents have several practical drawbacks. First, these materials are coated in the form of a corrosive sulfuric acid / hydrogen peroxide mixture, resulting in insufficient or unsuitable shelf-life stability. Second, modifying the material structure to improve or enhance the performance of the composite mixture is challenging. Third, development must be carried out in an extremely high concentration of tetramethylammonium hydroxide (TMAH) solution, such as 25% by weight.

[0011] Molecules containing tin (Sn) exhibit excellent or suitable absorption of extreme ultraviolet (EUV) radiation. In organotin polymers, alkyl ligands are dissociated through light absorption and / or the resulting secondary electrons, and crosslinked with adjacent chains via oxo bonds, thus enabling negative patterning that is not removed by organic developers. These organotin polymers show greatly or significantly improved or enhanced sensitivity while maintaining resolution and line edge roughness; however, further improvements or enhancements to the patterning properties are necessary for commercial availability. Summary of the Invention

[0012] One or more aspects of the embodiments of this disclosure relate to a semiconductor photoresist composition capable of implementing photoresist patterns with excellent or suitable sensitivity and LER characteristics and suppressing bridging defects (or reducing the degree or incidence of bridging defects).

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

[0014] Additional aspects of the embodiments will be set forth in part in the following description, and will become apparent in part from reading the description, or may be learned by practicing the embodiments presented in this disclosure.

[0015] A semiconductor photoresist composition according to one or more embodiments comprises an organometallic compound represented by chemical formula 1, and a solvent.

[0016] Chemical Formula 1

[0017]

[0018] In chemical formula 1,

[0019] R 1 Selected from substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C2 to C30 heteroalkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C30 heterocycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C2 to C30 heteroaryl, substituted or unsubstituted C7 to C30 aralkyl, substituted or unsubstituted C4 to C30 heteroaryl, and substituted or unsubstituted C1 to C30 alkyl carbonyl.

[0020] X, Y, and Z are each independently selected from substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C2 to C30 heteroalkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C30 heterocycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C2 to C30 heteroaryl, substituted or unsubstituted C7 to C30 aralkyl, substituted or unsubstituted C4 to C30 heteroaryl, substituted or unsubstituted C1 to C30 alkylcarbonyl, -OL a -R a -SL b -R band -O(CO)-L c -R c ,

[0021] At least one of X, Y, and Z is -OL a -R a -SL b -R b , or -O(CO)-L c -R c ,

[0022] L a L b and L c Each is independently a single bond (e.g., a single covalent bond) or a substituted or unsubstituted C1 to C10 alkylene group.

[0023] R a R b and R c Each independently is -C(R) 2 )=C(R 3 (R) 4 ) or -C≡C(R 5 ),

[0024] R 2 It is hydrogen, a substituted or unsubstituted C1 to C20 alkyl, a substituted or unsubstituted C3 to C20 cycloalkyl, a substituted or unsubstituted C2 to C20 alkenyl, a substituted or unsubstituted C2 to C20 alkynyl, or a substituted or unsubstituted C6 to C30 aryl.

[0025] R 3 and R 4 Each is independently hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C6 to C30 aryl, -L 1 -C=C(R 6 (R) 7 ), or -L 2 -C≡C(R 8 ),

[0026] Selected from R 3 and R 4 At least one of them is a substituted or unsubstituted C1 to C20 alkyl, a substituted or unsubstituted C3 to C20 cycloalkyl, a substituted or unsubstituted C6 to C30 aryl, or -L 1 -C=C(R 6 (R) 7 ), or -L 2 -C≡C(R 8 ),

[0027] R 5 It is a substituted or unsubstituted C1 to C20 alkyl, a substituted or unsubstituted C3 to C20 cycloalkyl, a substituted or unsubstituted C6 to C30 aryl, or -L 1 -C=C(R 6 (R) 7 ), or -L 2 -C≡C(R 8 ),

[0028] L 1 and L 2 It is a substituted or unsubstituted C1 to C10 alkylene group, and

[0029] R 6 To R 8 Each is independently hydrogen, a substituted or unsubstituted C1 to C20 alkyl, a substituted or unsubstituted C3 to C20 cycloalkyl, a substituted or unsubstituted C2 to C20 alkenyl, a substituted or unsubstituted C2 to C20 alkynyl, or a substituted or unsubstituted C6 to C30 aryl.

[0030] A method of forming or providing a pattern according to one or more embodiments includes: forming or providing an etch target layer on a substrate; coating the etch target layer with a semiconductor photoresist composition as described in one or more embodiments to form or provide a photoresist film; exposing and developing the photoresist film to form or provide a photoresist film on which a photoresist pattern is formed or provided (e.g., exposing and developing the photoresist film to form a photoresist pattern on the photoresist film); and using the photoresist pattern as an etch mask to etch the etch target layer.

[0031] The semiconductor photoresist composition according to one or more embodiments can provide a photoresist pattern with improved or enhanced sensitivity and LER characteristics, as well as suppressed bridging defects (or reduced bridging defect degree or bridging defect incidence). Attached Figure Description

[0032] The above and other aspects and features of certain embodiments of this disclosure will become more apparent from the following description taken in conjunction with the accompanying drawings.

[0033] Figures 1A to 1E This 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.

[0034] Explanation of icon numbers

[0035] 100: Substrate

[0036] 102: Film

[0037] 104: Resist underlayer

[0038] 106: Photoresist film

[0039] 106a: Non-exposure area

[0040] 106b: Exposure Zone

[0041] 108: Photoresist pattern

[0042] 110: Mask

[0043] 112: Organic membrane pattern

[0044] 114: Thin Film Pattern Detailed Implementation

[0045] The subject matter of this disclosure will be more fully explained below with reference to the accompanying drawings, which illustrate embodiments of the present disclosure. As will be appreciated by those skilled in the art, the illustrated embodiments may be modified in one or more suitable ways without departing from the spirit or scope of this disclosure. The drawings and descriptions are intended to be illustrative rather than restrictive. Throughout the document, the same reference numerals denote the same elements, and repeated descriptions of the same elements may not be provided in the specification.

[0046] For clarity of illustration, no descriptions or relationships are provided, and throughout this disclosure, substantially identical or similar configurations or arrangements of elements may be designated using the same reference numerals. Furthermore, since the dimensions and thicknesses of each configuration or arrangement illustrated in the figures may be arbitrarily shown for better understanding and ease of explanation, embodiments of this disclosure are not necessarily limited thereto.

[0047] In the accompanying drawings, for clarity, the thickness of each layer, film, panel, area, etc., may be exaggerated. In the accompanying drawings, for ease of explanation, the thickness of a portion of each layer, area, etc., may be exaggerated.

[0048] It will be understood that if an element (e.g., a layer, film, region, or substrate) is said to be "on" another element (e.g., when an element (e.g., a layer, film, region, or substrate) is said to be "on" another element), then the element may be directly on the other element, or there may be an intermediate element between them. In contrast, if an element is said to be "directly on" another element (e.g., when an element is said to be "directly on" another element), then there is no intermediate element between them.

[0049] When describing embodiments of this disclosure (e.g., when describing embodiments of this disclosure), the word "may" refers to "one or more embodiments of this disclosure".

[0050] In the context of this application and unless otherwise defined, the terms “use / using” and “used” may be considered synonymous with the terms “utilize / utilizing” and “utilized”, respectively.

[0051] Unless the context clearly indicates otherwise, the singular forms “a / an” and “the” as used herein are intended to include the plural forms as well. Unless the context clearly indicates otherwise, singular expressions include plural expressions.

[0052] The terms “and / or” or “or” as used herein include any and all combinations of one or more of the associated listed items.

[0053] Throughout this disclosure, expressions such as "at least one of...", "one of...", and "selected from" indicate, if placed before a list element (when placed before a list element), that modify the entire list, not individual elements of the list. For example, "at least one of a, b, or c", "selected from at least one of a, b, and c", "selected from at least one of a to c", indicate only a, only b, only c, both a and b (e.g., simultaneously), both a and c (e.g., simultaneously), both b and c (e.g., simultaneously), all of a, b, and c, or variations thereof.

[0054] As used herein, “combinations thereof” may refer to mixtures, stacks, complexes, copolymers, alloys, blends, reaction products and / or similar substances of the components.

[0055] In this disclosure, it will be understood that the terms “comprise(s) / comprising,” “include(s) / including,” or “have / has / having” specify the presence of the stated 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. Furthermore, the terms “comprise,” “include,” “have,” or similar terms, including or supporting the terms “composed of,” and “substantially composed of,” indicate the presence of the stated features, integers, steps, operations, elements, and / or components, while other features, integers, steps, operations, elements, components, and / or groups thereof are absent or substantially absent.

[0056] The terms “substantially,” “about,” or similar terms used herein are used as approximations rather than as terms of degree, and are intended to take into account the inherent biases of measured or calculated values ​​that would be recognized by a person skilled in the art. As used herein, “about” includes the stated value and refers to a specific value within an acceptable range of deviation determined by a person skilled in the art, considering the measurement in question and errors associated with the measurement of the particular quantity (e.g., 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. Furthermore, it should be understood that even when the terms “about,” “about,” or “substantially” are not explicitly stated in a given element (e.g., a claim element), the scope of such elements is intended to include non-substantialgesic variations or variations within the understanding of a person skilled in the art. For example, the numerical values ​​and ranges provided herein are intended to include tolerances and measurement uncertainties that would be recognized by one of ordinary skill in the art, and the elements (e.g., claim elements) should be interpreted accordingly to encompass such equivalents.

[0057] Any numerical range described herein is intended to include all subranges of the same numerical precision falling within the described range. For example, the range “1.0 to 10.0” is intended to include all subranges between the described minimum value 1.0 and the described maximum value 10.0 (and inclusive of both), such as having a minimum value equal to or greater than 1.0 and a maximum value equal to or less than 10.0, for example, 2.4 to 7.6. Any maximum numerical limit described herein is intended to include all lower numerical limits falling within it, and any minimum numerical limit described in this disclosure is intended to include all higher numerical limits falling within it. Therefore, the applicant reserves the right to amend this disclosure (including the claims) to expressly describe any subranges falling within the range expressly described herein.

[0058] As used in this article, "substituted" refers to hydrogen atoms replaced by: deuterium, halogen, hydroxyl, carboxyl, thiol, cyano, nitro, -NRR' (where 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'' (where R, R', and R'' are each independently hydrogen, a substituted or unsubstituted C1 to C30 saturated or unsaturated alicyclic hydrocarbon group, or an substituted or unsubstituted aromatic hydrocarbon group), and -SiRR'R'' (where R, R', and R'' are each independently hydrogen, a substituted or unsubstituted C1 to C30 saturated or unsaturated alicyclic hydrocarbon group). The following groups are included: alkyl groups (C3 to C30 saturated or unsaturated alicyclic hydrocarbon groups, substituted or unsubstituted C6 to C30 aromatic hydrocarbon groups), substituted or unsubstituted C1 to C30 alkyl groups, substituted or unsubstituted C1 to C10 haloalkyl groups, substituted or unsubstituted C1 to C10 alkylsilyl groups, substituted or unsubstituted C3 to C30 cycloalkyl groups, substituted or unsubstituted C6 to C30 aryl groups, substituted or unsubstituted C1 to C20 alkoxy groups, substituted or unsubstituted C1 to C20 sulfide groups, or combinations thereof. "Unsubstituted" means that the hydrogen atom is not replaced by another substituent and the remaining hydrogen atom.

[0059] Unless otherwise defined (e.g., when no definition is provided), “alkyl” as used herein refers to a straight-chain or branched aliphatic hydrocarbon group. An alkyl group may be a “saturated alkyl” that does not have any double bonds (e.g., carbon-carbon double bonds) or triple bonds (e.g., carbon-carbon triple bonds).

[0060] The alkyl group can be C1 to C8 alkyl. For example, the alkyl group can be C1 to C7 alkyl, C1 to C6 alkyl, or C1 to C5 alkyl. For example, C1 to C5 alkyl can be methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, or 2,2-dimethylpropyl.

[0061] Unless otherwise defined (e.g., when no other definition is provided), “cycloalkyl” as used herein refers to a monovalent cyclic aliphatic hydrocarbon group.

[0062] The cycloalkyl group can be C3 to C8 cycloalkyl, such as C3 to C7 cycloalkyl, C3 to C6 cycloalkyl, C3 to C5 cycloalkyl, or C3 to C4 cycloalkyl. The cycloalkyl group can be cyclopropyl, cyclobutyl, cyclopentyl, or cyclohexyl, but the embodiments disclosed herein are not limited thereto.

[0063] In this specification, "aliphatic unsaturated organic group" refers to a hydrocarbon group in which the bonds between carbon atoms in the molecule are double bonds (e.g., carbon-carbon double bonds), triple bonds (e.g., carbon-carbon triple bonds), or combinations thereof.

[0064] Aliphatic unsaturated organic groups can be C2 to C8 aliphatic unsaturated organic groups. For example, aliphatic unsaturated organic groups can be C2 to C7, C2 to C6, C2 to C5, or C2 to C4 aliphatic unsaturated organic groups. For example, C2 to C4 aliphatic unsaturated organic groups can be vinyl, ethynyl, allyl, 1-propenyl, 1-methyl-1-propenyl, 2-propenyl, 2-methyl-2-propenyl, 1-propynyl, 1-methyl-1-propynyl, 2-propynyl, 2-methyl-2-propynyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-butynyl, 2-butynyl, or 3-butynyl.

[0065] As used herein, “aryl” refers to a substituent in which all atoms in a cyclic substituent have p orbitals and these p orbitals are conjugated, and may include monocyclic or polycyclic (e.g., rings sharing adjacent carbon atom pairs) functional groups.

[0066] As used herein, "heteroaryl" can 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 are directly linked by σ bonds, or if the heteroaryl group comprises two or more rings (e.g., when the heteroaryl group comprises two or more rings), the two or more rings may be fused. If the heteroaryl group is a fused ring (e.g., when the heteroaryl group is a fused ring), each ring may comprise one to three heteroatoms.

[0067] Unless otherwise defined, “alkenyl” as used herein refers to an aliphatic unsaturated alkenyl group comprising at least one double bond (e.g., a carbon-carbon double bond), as a straight-chain or branched aliphatic hydrocarbon group.

[0068] Unless otherwise defined, “alkynyl” as used herein refers to an aliphatic unsaturated alkynyl group comprising at least one triple bond (e.g., a carbon-carbon triple bond), as a straight-chain or branched aliphatic hydrocarbon group.

[0069] In the following text, a semiconductor photoresist composition according to one or more embodiments is described in more detail.

[0070] The semiconductor photoresist composition according to one or more embodiments may comprise an organometallic compound represented by chemical formula 1, and a solvent.

[0071] Chemical Formula 1

[0072]

[0073] In chemical formula 1,

[0074] R 1The substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C2 to C30 heteroalkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C30 heterocycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C2 to C30 heteroaryl, substituted or unsubstituted C7 to C30 aralkyl, substituted or unsubstituted C4 to C30 heteroaryl, and substituted or unsubstituted C1 to C30 alkyl carbonyl.

[0075] X, Y, and Z can each be independently selected from substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C2 to C30 heteroalkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C30 heterocycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C2 to C30 heteroaryl, substituted or unsubstituted C7 to C30 aralkyl, substituted or unsubstituted C4 to C30 heteroaryl, substituted or unsubstituted C1 to C30 alkylcarbonyl, -OL a -R a -SL b -R b and -O(CO)-L c -R c ,

[0076] At least one of X, Y, and Z can be -OL a -R a -SL b -R b , or -O(CO)-L c -R c ,

[0077] L a L b and L c They can each be independently a single bond (e.g., a single covalent bond) or a substituted or unsubstituted C1 to C10 alkylene group.

[0078] R a R b and R c Each can be independently -C(R) 2 )=C(R 3 (R) 4 ) or -C≡C(R 5 ),

[0079] R2 It can 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, or substituted or unsubstituted C6 to C30 aryl.

[0080] R 3 and R 4 Each can be independently hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C6 to C30 aryl, -L 1 -C=C(R 6 (R) 7 ), or -L 2 -C≡C(R 8 ),

[0081] Selected from R 3 and R 4 At least one of them may be a substituted or unsubstituted C1 to C20 alkyl, a substituted or unsubstituted C3 to C20 cycloalkyl, a substituted or unsubstituted C6 to C30 aryl, or -L 1 -C=C(R 6 (R) 7 ), or -L 2 -C≡C(R 8 ),

[0082] R 5 It can be a substituted or unsubstituted C1 to C20 alkyl, a substituted or unsubstituted C3 to C20 cycloalkyl, a substituted or unsubstituted C6 to C30 aryl, or -L 1 -C=C(R 6 (R) 7 ), or -L 2 -C≡C(R 8 ),

[0083] L 1 and L 2 It can be a substituted or unsubstituted C1 to C10 alkylene group, and

[0084] R 6 To R 8 Each of them can 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, or substituted or unsubstituted C6 to C30 aryl.

[0085] The organometallic compounds disclosed herein may further improve or enhance sensitivity and LER properties by enabling cross-linking between ligands and facilitating the formation of metal clusters due to the presence of unsaturated bonds in the hydrolyzable functional groups.

[0086] For example, since unsaturated bonds are located inside the hydrolyzable ligand rather than at its end, reactivity may be reduced or decreased, thereby suppressing or reducing the incidence of bridging defects after pattern formation.

[0087] In one or more embodiments, the hydrolyzable ligand may include a triple bond (e.g., a carbon-carbon triple bond).

[0088] For example, R a R b and R c It can be -C≡C(R) 5 ).

[0089] If the hydrolyzable ligand includes a triple bond (e.g., a carbon-carbon triple bond) (e.g., when the hydrolyzable ligand includes a triple bond (e.g., a carbon-carbon triple bond)), the sensitivity can be further improved or enhanced.

[0090] In one or more embodiments, X, Y, and Z can each be independently -OL. a -R a -SL b -R b , or -O(CO)-L c -R c .

[0091] In one or more embodiments, X, Y, and Z may be the same as each other.

[0092] For example, R 1 It can be selected from substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C2 to C20 heteroalkyl, substituted or unsubstituted C3 to C12 cycloalkyl, substituted or unsubstituted C2 to C20 heterocycloalkyl, substituted or unsubstituted C2 to C10 alkenyl, substituted or unsubstituted C2 to C10 alkynyl, substituted or unsubstituted C6 to C20 aryl, substituted or unsubstituted C2 to C20 heteroaryl, substituted or unsubstituted C7 to C20 aralkyl, substituted or unsubstituted C4 to C20 heteroaryl, and substituted or unsubstituted C1 to C20 alkyl carbonyl.

[0093] For example, R 1It 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-pentyl, substituted or unsubstituted 1-methylpropyl, substituted or unsubstituted 1,1-dimethylpropyl, 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 propynyl, substituted or unsubstituted butynyl, substituted or unsubstituted phenyl, substituted or unsubstituted tolyl, substituted or unsubstituted xylylyl, or substituted or unsubstituted benzyl.

[0094] For example, R 2 It can 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, or substituted or unsubstituted C6 to C20 aryl.

[0095] R 3 and R 4 Each can be independently hydrogen, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C3 to C10 cycloalkyl, substituted or unsubstituted C6 to C20 aryl, -L 1 -C=C(R 6 (R) 7 ), or -L 2 -C≡C(R 8 ),

[0096] Selected from R 3 and R 4 At least one of them may be a substituted or unsubstituted C1 to C10 alkyl, a substituted or unsubstituted C3 to C10 cycloalkyl, a substituted or unsubstituted C6 to C20 aryl, or -L 1 -C=C(R 6 (R) 7 ), or -L 2 -C≡C(R 8 ),

[0097] R 5 It can be a substituted or unsubstituted C1 to C10 alkyl, a substituted or unsubstituted C3 to C10 cycloalkyl, a substituted or unsubstituted C6 to C20 aryl, or -L 1 -C=C(R6 (R) 7 ), or -L 2 -C≡C(R 8 ),

[0098] L 1 and L 2 It can be a substituted or unsubstituted C1 to C6 alkylene group.

[0099] R 6 To R 8 Each of them can 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, or substituted or unsubstituted C6 to C20 aryl.

[0100] In one or more embodiments, the organometallic compound represented by Formula 1 may be selected from the compounds listed in Group 1.

[0101] Group 1

[0102]

[0103]

[0104]

[0105]

[0106]

[0107] Organometallic compounds represented by chemical formula 1 can strongly absorb extreme ultraviolet light at 13.5 nm, and therefore have excellent or suitable sensitivity to high-energy light.

[0108] In the semiconductor photoresist composition according to one or more embodiments, the amount of the organometallic compound represented by Formula 1, based on 100% by weight of the semiconductor photoresist composition, can be from about 0.5% by weight to about 30% by weight, for example, from about 1% by weight to about 30% by weight, for example, from about 1% by weight to about 25% by weight, for example, from about 1% by weight to about 20% by weight, for example, from about 1% by weight to about 15% by weight, for example, from about 1% by weight to about 10% by weight, for example, from about 1% by weight to about 5% by weight, but the embodiments of this disclosure are not limited thereto. If the content (e.g., amount) of the organometallic compound is within the aforementioned range (e.g., when the content (e.g., amount) of the organometallic compound is within the aforementioned range), the storage stability and etch resistance of the semiconductor photoresist composition can be improved or enhanced, and the resolution characteristics can be improved or enhanced.

[0109] Semiconductor photoresist compositions according to one or more embodiments may have excellent or suitable sensitivity and patterning properties by comprising organometallic compounds as described in one or more embodiments.

[0110] 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 similar compounds), an alcohol (e.g., 4-methyl-2-pentanol, 4-methyl-2-propanol, 1-butanol, methanol, isopropanol, 1-propanol and / or similar alcohols), an ether (e.g., anisole, tetrahydrofuran and / or similar ethers), an ester (e.g., n-butyl acetate, propylene glycol monomethyl ether acetate, ethyl acetate, ethyl lactate and / or similar esters), a ketone (e.g., methyl ethyl ketone, 2-heptanone and / or similar ketones), or a mixture of said solvents, but the embodiments of this disclosure are not limited thereto.

[0111] In addition to the organometallic compounds and solvents described in one or more embodiments, the semiconductor photoresist compositions according to one or more embodiments may further comprise a resin.

[0112] The resin may be a phenolic resin comprising at least one of the aromatic fractions listed in Group 2.

[0113] Group 2

[0114]

[0115] The resin may have a weight-average molecular weight (Mw) in the range of about 500 g / mol to about 20,000 g / mol.

[0116] The amount of resin may range from about 0.1% to about 50% by weight, based on the total amount of the semiconductor photoresist composition (e.g., based on 100% by weight of the semiconductor photoresist composition).

[0117] If the resin is within the aforementioned content (e.g., amount) range (e.g., when the resin is within the aforementioned content (e.g., amount) range), the semiconductor photoresist composition may have excellent or suitable etch resistance and heat resistance.

[0118] In one or more embodiments, the semiconductor photoresist composition may be composed of organometallic compounds, solvents, and resins as described in one or more embodiments. However, the semiconductor photoresist composition according to one or more embodiments may also include additives as needed or desired. Examples of additives may be surfactants, crosslinking agents, leveling agents, organic acids, quenchers, or combinations thereof.

[0119] The surfactant may include, for example, alkylbenzene sulfonates, alkylpyridinium salts, polyethylene glycol, quaternary ammonium salts, or combinations thereof, but the embodiments disclosed herein are not limited thereto.

[0120] The crosslinking agent may be, for example, a melamine-based crosslinking agent, a substituted urea-based crosslinking agent, an acrylic-based crosslinking agent, an epoxy-based crosslinking agent, or a polymer-based crosslinking agent, but the embodiments disclosed herein 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 glycourea, butoxymethylated glycourea, methoxymethylated melamine, butoxymethylated melamine, methoxymethylated benzoguanamine, butoxymethylated benzoguanamine, 4-hydroxybutyl acrylate, acrylic acid, urethane acrylate, propylene methacrylate, 1,4-butanediol diglycidyl ether, glycidyl, 1,2-cyclohexanedicarboxylic acid diglycidyl ether, trimethylpropane triglycidyl ether, 1,3-bis(glycidoxypropyl)tetramethyldisiloxane, methoxymethylated urea, butoxymethylated urea, methoxymethylated thiourea, and / or similar materials.

[0121] Leveling agents can be used to improve or enhance the smoothness of coatings during printing, and can be commonly available or commonly used leveling agents.

[0122] Organic acids may include p-toluenesulfonic acid, benzenesulfonic acid, p-dodecylbenzenesulfonic acid, 1,4-naphthalenedisulfonic acid, methanesulfonic acid, fluorinated sulfonate, malonic acid, citric acid, propionic acid, methacrylic acid, oxalic acid, lactic acid, glycolic acid, succinic acid, or combinations thereof, but the embodiments disclosed herein are not limited thereto.

[0123] The quenching agent may be diphenyl(p-tolyl)amine, methyldiphenylamine, triphenylamine, phenylenediamine, naphthylamine, diaminonaphthalene, or a combination thereof.

[0124] The amount of each additive can be controlled or selected according to the desired properties.

[0125] In one or more embodiments, the semiconductor photoresist composition may further comprise a silane coupling agent as an adhesion enhancer to improve or enhance the tightness of contact with the substrate (e.g., 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 comprising carbon-carbon unsaturated bonds, such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltri(β-methoxyethoxy)silane, 3-methacryloyloxypropyltrimethoxysilane, 3-acryloyloxypropyltrimethoxysilane, p-styryltrimethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropylmethyldiethoxysilane, trimethoxy[3-(phenylamino)propyl]silane, and / or similar silane compounds, but the embodiments of this disclosure are not limited thereto.

[0126] Semiconductor photoresist compositions can be formed into patterns with a high aspect ratio without collapse. Therefore, in order to form or provide fine patterns with widths ranging from, for example, about 5 nm to about 100 nm, for example, about 5 nm to about 80 nm, for example, about 5 nm to about 70 nm, for example, about 5 nm to about 50 nm, for example, about 5 nm to about 40 nm, for example, about 5 nm to about 30 nm, for example, about 5 nm to about 20 nm, or for example, about 5 nm to about 10 nm, the semiconductor photoresist composition can be used in photoresist processes using light with wavelengths ranging from about 5 nm to about 150 nm, for example, about 5 nm to about 100 nm, about 5 nm to about 80 nm, about 5 nm to about 50 nm, about 5 nm to about 30 nm, or about 5 nm to about 20 nm. Therefore, the semiconductor photoresist composition according to one or more embodiments can be used to implement or provide extreme ultraviolet lithography using an EUV light source with a wavelength of about 13.5 nm.

[0127] According to one or more embodiments, a method is provided for forming or providing a pattern using the semiconductor photoresist composition described in one or more embodiments. For example, the pattern produced may be a photoresist pattern.

[0128] A method of forming or providing a pattern according to one or more embodiments may include: forming or providing an etch target layer on a substrate; coating the etch target layer with a semiconductor photoresist composition as described in one or more embodiments to form or provide a photoresist film; exposing and developing the photoresist film to form or provide a photoresist film on which a photoresist pattern is formed or provided (e.g., exposing and developing the photoresist film to form or provide a photoresist pattern on the photoresist film); and using the photoresist pattern as an etch mask to etch the etch target layer.

[0129] In the following text, refer to Figures 1A to 1E The method of forming or providing patterns using semiconductor photoresist compositions is described in more detail. Figures 1A to 1E This 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.

[0130] Reference Figure 1A An object to be etched can be prepared. The object to be etched can be a thin film 102 formed or provided on a semiconductor substrate 100. Hereinafter, the object to be etched may be limited to the thin film 102. The surface of the thin film 102 can be cleaned to remove impurities and / or similar substances remaining thereon. The thin film 102 can be, for example, a silicon nitride layer, a polycrystalline silicon layer, or a silicon oxide layer.

[0131] Subsequently, the resist underlayer composition used to form or provide the resist underlayer 104 can be spin-coated onto the surface of the cleaned film 102. However, the embodiments of this disclosure are not limited thereto, and one or more generally available suitable coating methods can be used, such as spraying, dip coating, blade coating, printing methods (e.g., inkjet printing and screen printing) and / or similar coating methods.

[0132] The coating process for the resist underlayer may not be provided, and the coating process including the resist underlayer is described in more detail below.

[0133] The coated composition can then be dried and baked to form or provide a resist underlayer 104 on the film 102. Baking can be performed at about 100°C to about 500°C, for example, about 100°C to about 300°C.

[0134] A resist underlayer 104 may be formed or provided between the substrate 100 and the photoresist film 106, and thus prevents (or reduces) the degree or occurrence of photoresist linewidth inhomogeneity and pattern formability (e.g., when rays reflected from the interface between the substrate 100 and the photoresist film 106 or the interlayer hard mask are scattered into unintended photoresist areas).

[0135] Reference Figure 1B A photoresist film 106 can be formed or provided by coating a semiconductor photoresist composition as described in one or more embodiments onto a resist underlayer 104. The photoresist film 106 can be obtained by coating a semiconductor photoresist composition as described in one or more embodiments onto a thin film 102 formed or provided on a substrate 100, and then curing the semiconductor photoresist composition by heat treatment.

[0136] For example, patterning using a semiconductor photoresist composition may include coating a semiconductor photoresist composition on a substrate 100 having a thin film 102 by spin coating, slot coating, inkjet printing and / or similar methods, and then drying the semiconductor photoresist composition to form or provide a photoresist film 106.

[0137] The semiconductor photoresist composition has been illustrated in more detail and will not be illustrated again.

[0138] Subsequently, a first baking process can be performed on the substrate 100 having the photoresist film 106. The first baking process can be performed at a temperature of about 80°C to about 120°C.

[0139] Reference Figure 1C The photoresist film 106 can be selectively exposed using a patterned mask 110.

[0140] For example, exposure can be achieved using activation radiation with the following light sources: light with high energy wavelengths, such as extreme ultraviolet (EUV; wavelength approximately 13.5 nm); and other sources, such as electron beams (e-beam); and light with low energy wavelengths, such as i-lines (wavelength approximately 365 nm), KrF excited molecular lasers (wavelength approximately 248 nm), ArF excited molecular lasers (wavelength approximately 193 nm).

[0141] For example, the light used for exposure according to one or more embodiments may be light with a short wavelength and high energy wavelength in the range of about 5 nm to about 150 nm, such as extreme ultraviolet (EUV; wavelength of 13.5 nm); and other sources, such as electron beams (e-beams).

[0142] By utilizing cross-linking reactions (e.g., condensation between organometallic compounds) to form or provide polymers, the exposed region 106b of the photoresist film 106 may have a different solubility than the non-exposed region 106a of the photoresist film 106.

[0143] Subsequently, a second baking process can be performed on the substrate 100. The second baking process can be carried out at a temperature of about 90°C to about 200°C. Due to the second baking process, the exposure area 106b of the photoresist film 106 can become more insoluble in the developer.

[0144] exist Figure 1D In this process, a developer can be used to dissolve and remove the non-exposed areas 106a of the photoresist film to form or provide a photoresist pattern 108. For example, an organic solvent such as 2-heptanone and / or similar solvents can be used to dissolve and remove the non-exposed areas 106a of the photoresist film to complete the photoresist pattern 108 corresponding to the negative image.

[0145] As described in one or more embodiments, the developer used in the method of forming or providing a pattern according to one or more embodiments may be an organic solvent. The organic solvent used in the method of 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 similar ketones; alcohols, such as 4-methyl-2-propanol, 1-butanol, isopropanol, 1-propanol, methanol and / or similar alcohols; esters, such as propylene glycol monomethyl ether acetate, ethyl acetate, ethyl lactate, n-butyl acetate, butyrolactone and / or similar esters; aromatic compounds, such as benzene, xylene, toluene and / or similar aromatic compounds or combinations thereof.

[0146] However, the photoresist pattern according to one or more embodiments is not necessarily limited to negative images, but can also be formed or provided as having a positive image. Here, the developer used to form or provide the positive image can be a quaternary ammonium hydroxide composition, such as tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, or a combination thereof.

[0147] As described in one or more embodiments, exposure to light can provide a photoresist pattern 108 having a thickness in the range of about 5 nm to about 100 nm: light with high-energy wavelengths, such as extreme ultraviolet (EUV; wavelength of 13.5 nm); and other sources, such as electron beams (e-beams); and light with low-energy wavelengths, such as i-lines (wavelength of about 365 nm), KrF excited molecular lasers (wavelength of about 248 nm), ArF excited molecular lasers (wavelength of about 193 nm), etc. For example, the photoresist pattern 108 may have a thickness in the range of about 5 nm to about 90 nm, about 5 nm to about 80 nm, about 5 nm to about 70 nm, about 5 nm to about 60 nm, about 5 nm to about 50 nm, about 5 nm to about 40 nm, about 5 nm to about 30 nm, about 5 nm to about 20 nm, or about 5 nm to about 10 nm.

[0148] In one or more embodiments, the photoresist pattern 108 may have a pitch of less than or equal to about 50 nm, for example less than or equal to about 40 nm, for example less than or equal to about 30 nm, for example less than or equal to about 20 nm, or for example less than or equal to about 10 nm, and the photoresist pattern 108 may have a linewidth roughness of less than or equal to about 5 nm, less than or equal to about 3 nm, less than or equal to about 2 nm, or less than or equal to about 1 nm.

[0149] According to one or more embodiments, a photoresist film can be provided that is manufactured by a method of forming or providing a pattern as described in one or more embodiments.

[0150] Subsequently, the photoresist pattern 108 formed or provided on the photoresist film can be used as an etching mask to etch the resist underlayer 104. Through this etching process, an organic film pattern 112 can be formed or provided. The organic film pattern 112 may also have a width corresponding to the width of the photoresist pattern 108.

[0151] Reference Figure 1E The exposed thin film 102 can be etched by applying a photoresist pattern 108 as an etching mask. Therefore, the thin film can be formed or provided as a thin film pattern 114.

[0152] The etching of the thin film 102 can be, for example, dry etching using an etching gas, and the etching gas can be, for example, CHF3, CF4, Cl2, BCl3 and mixtures thereof.

[0153] In the exposure process, the thin film pattern 114 formed or provided using the photoresist pattern 108 (the photoresist pattern 108 is formed or provided by an exposure process performed using an EUV light source) may have a width corresponding to the width of the photoresist pattern 108. For example, the thin film pattern 114 may have a width in the range of about 5 nm to about 100 nm, said width being equal to the width of the photoresist pattern 108. For example, like the width of the photoresist pattern 108, the thin film pattern 114 formed or provided using the photoresist pattern 108 (the photoresist pattern 108 is formed or provided by an exposure process performed using an EUV light source) may have a width in the range of about 5 nm to about 90 nm, about 5 nm to about 80 nm, about 5 nm to about 70 nm, about 5 nm to about 60 nm, about 5 nm to about 50 nm, about 5 nm to about 40 nm, about 5 nm to about 30 nm, or about 5 nm to about 20 nm, and for example, has a width less than or equal to about 20 nm.

[0154] In the following, one or more embodiments of the present disclosure will be described in more detail by way of examples of the preparation of semiconductor photoresist compositions as described in one or more embodiments. However, the embodiments of the present disclosure are not limited to the following examples.

[0155] Example

[0156] Synthesis of organometallic compounds

[0157] Synthesis example 1

[0158] 40.7 g of tert-butyltriphenyltin (t-ButylSnPh3) and 300 g of 2-butyn-1-ol were added to a 100 mL round-bottom flask and heated under reflux for 24 hours. Unreacted material was removed under reduced pressure to obtain the compound represented by chemical formula 2.

[0159] Chemical formula 2

[0160]

[0161] Synthesis example 2

[0162] Except that 3-pentyn-1-ol (300 g) was used instead of 2-butyn-1-ol, the compound represented by chemical formula 3 was obtained by performing essentially the same procedure as in Synthesis Example 1.

[0163] Chemical formula 3

[0164]

[0165] Synthesis example 3

[0166] Except that 3,6-dimethyl-2,5-heptadien-1-ol (300 g) was used instead of 2-butyn-1-ol, the compound represented by chemical formula 4 was obtained by performing essentially the same procedure as in Synthesis Example 1.

[0167] Chemical Formula 4

[0168]

[0169] Synthesis example 4

[0170] Except that 1-propen-1-thiol (300 g) was used instead of 2-butyn-1-ol, the compound represented by chemical formula 5 was obtained by performing essentially the same procedure as in Synthesis Example 1.

[0171] Chemical formula 5

[0172]

[0173] Synthesis example 5

[0174] Except that crotonic acid (300 g) was used instead of 2-butyn-1-ol, the compound represented by chemical formula 6 was obtained by performing essentially the same procedure as in Synthesis Example 1.

[0175] Chemical Formula 6

[0176]

[0177] Comparative Synthesis Example 1

[0178] In a 250 mL double-necked round-bottom flask, 20 g of Ph3SnCl (51.9 mmol) was dissolved in 70 mL of THF, and then cooled to 0 °C in an ice bath. Subsequently, a 1 M solution of butyl magnesium chloride (BuMgCl) in THF (62.3 mmol) was slowly added dropwise. When the addition was complete, the mixture was stirred at room temperature for 12 hours to obtain the compound represented by chemical formula A-1.

[0179] The compound represented by chemical formula A-1 (10 g, 24.6 mmol) was dissolved in 50 mL of CH₂Cl₂, and a 2 M HCl diethyl ether solution (3 equivalents, 73.7 mmol) was slowly added dropwise over 30 minutes at -78 °C. Subsequently, after stirring the mixture at room temperature for 12 hours, the solvent was concentrated and vacuum distilled to obtain the compound represented by chemical formula A-2.

[0180] The compound represented by chemical formula A-2 (5 g, 17.7 mmol) was dissolved in 50 mL of THF and then cooled to 0 °C in an ice bath. Subsequently, a 2 M solution of allyl magnesium chloride (allylMgCl) in THF (58 mmol) was slowly added dropwise. When the addition was complete, the mixture was stirred at room temperature for 12 hours to obtain the compound represented by chemical formula 7.

[0181] Chemical formula A-1

[0182]

[0183] Chemical formula A-2

[0184]

[0185] Chemical Formula 7

[0186]

[0187] Comparative Synthesis Example 2

[0188] Except that 300g of 3-butyn-1-ol was used instead of 2-butyn-1-ol, the compound represented by chemical formula 8 was obtained in substantially the same manner as in Synthesis Example 1.

[0189] Chemical Formula 8

[0190]

[0191] Comparative Synthesis Example 3

[0192] Except that 300g of 3-butyn-1-thiol was used instead of 2-butyn-1-ol, the compound represented by chemical formula 9 was obtained in substantially the same manner as in Synthesis Example 1.

[0193] Chemical formula 9

[0194]

[0195] Comparative Synthesis Example 4

[0196] Except that 300g of 3-butenoic acid was used instead of 2-butyn-1-ol, the compound represented by chemical formula 10 was obtained in substantially the same manner as in Synthesis Example 1.

[0197] Chemical Formula 10

[0198]

[0199] Preparation of semiconductor photoresist compositions

[0200] Examples 1 to 5 and Comparative Examples 1 to 4

[0201] The organometallic compounds obtained in Synthetic Examples 1 to 5 and Comparative Synthetic Examples 1 to 4 were each dissolved in 3% by weight of propylene glycol monomethyl ether acetate (PGMEA) and filtered through a 0.1 μm polytetrafluoroethylene (PTFE) syringe filter to prepare photoresist compositions.

[0202] Evaluation 1: Evaluation of sensitivity and line edge roughness (LER)

[0203] Each of the photoresist compositions according to the examples and comparative examples was spin-coated at 1500 rpm onto a 200 mm circular silicon wafer (the surface of which was deposited with hexamethyldisilazane (HMDS)) for 30 seconds, and then baked at 110°C for 60 seconds. After application, the photoresist composition was baked (post-apply bake (PAB)) and then left at room temperature (23±2°C) for 30 seconds.

[0204] Then, using EUV light (Lawrence Berkeley National Laboratory Micro Exposure Tool (MET)), a linear array of 50 circular pads, each 500 μm in diameter, was projected onto the wafer coated with the photoresist composition. Here, the pad exposure time was adjusted to ensure that an increased dose of EUV light was applied to each pad.

[0205] Then, after exposure, the resist and substrate are baked on a hot plate at 160°C for 120 seconds. The baked film is then developed in PGMEA solvent to form a negative image. Finally, the obtained film is baked again on a hot plate at 150°C for 2 minutes to complete the process.

[0206] The residual resist thickness of the exposed pads was measured using an ellipsometry. The residual thickness was measured for each exposure dose and then plotted as a function of exposure dose to measure sensitivity. The line edge roughness (LER) was measured from field emission scanning electron microscope (FE-SEM) images to evaluate the line edge roughness. The results are then presented in Table 1.

[0207] Assessment 2: Assessment of Defects

[0208] A lower SiON film, a spin-coated carbon film, and an upper SiON film were sequentially formed on a 12-inch silicon substrate. On the upper SiON film, a 1:1 line / spaced photoresist pattern with a spacing of 36 nm was formed using EUV lithography using each of the photoresist compositions according to the examples and comparative examples. The photoresist pattern was transferred to the lower SiON film by dry etching using plasma. Then, all defects, including bridging defects between line patterns, were inspected in a bright field using a defect analysis apparatus employing a deep ultraviolet (DUV) laser. The inspected defects were classified using SEM and then displayed as the number of classified defects per unit area (units / cm²). 2 ).

[0209] In this paper, when the number of SLO (Single Line Open) defects is converted to 100, “○” is given if the number of defects is less than or equal to 80%, and “X” is given if the number of defects is greater than 80%.

[0210] Table 1

[0211]

[0212] According to the results in Table 1, compared with Comparative Examples 1 to 4, the patterns formed using the semiconductor photoresist compositions according to Examples 1 to 5 exhibited superior sensitivity, LER, and resolution characteristics.

[0213] In the foregoing, certain embodiments of this disclosure have been described and illustrated. However, it will be apparent to those skilled in the art that this disclosure is not limited to the described embodiments, but can be appropriately modified and varied without departing from the spirit and scope of this disclosure. Modified or varied embodiments may be understood without separating them from the technical concept and aspects of one or more embodiments of this disclosure, and modified embodiments may fall within the scope of the appended claims and their equivalents.

Claims

1. A semiconductor photoresist composition comprising: Organometallic compounds represented by chemical formula 1; and Solvent: Chemical Formula 1 In chemical formula 1, R 1 Selected from substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C2 to C30 heteroalkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C30 heterocycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C2 to C30 heteroaryl, substituted or unsubstituted C7 to C30 aralkyl, substituted or unsubstituted C4 to C30 heteroaryl, and substituted or unsubstituted C1 to C30 alkyl carbonyl. X, Y, and Z are each independently selected from substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C2 to C30 heteroalkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C30 heterocycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C2 to C30 heteroaryl, substituted or unsubstituted C7 to C30 aralkyl, substituted or unsubstituted C4 to C30 heteroaryl, substituted or unsubstituted C1 to C30 alkylcarbonyl, -OL a -R a -SL b -R b and -O(CO)-L c -R c , At least one of X, Y, and Z is -OL a -R a -SL b -R b , or -O(CO)-L c -R c , L a L b and L c Each is independently a single bond or a substituted or unsubstituted C1 to C10 alkylene group. R a R b and R c Each independently is -C(R) 2 )=C(R 3 (R) 4 ) or -C≡C(R 5 ), R 2 It is hydrogen, a substituted or unsubstituted C1 to C20 alkyl, a substituted or unsubstituted C3 to C20 cycloalkyl, a substituted or unsubstituted C2 to C20 alkenyl, a substituted or unsubstituted C2 to C20 alkynyl, or a substituted or unsubstituted C6 to C30 aryl. R 3 and R 4 Each is independently hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C6 to C30 aryl, -L 1 -C=C(R 6 (R) 7 ), or -L 2 -C≡C(R 8 ), Selected from R 3 and R 4 At least one of them is a substituted or unsubstituted C1 to C20 alkyl, a substituted or unsubstituted C3 to C20 cycloalkyl, a substituted or unsubstituted C6 to C30 aryl, or -L 1 -C=C(R 6 (R) 7 ), or -L 2 -C≡C(R 8 ), R 5 It is a substituted or unsubstituted C1 to C20 alkyl, a substituted or unsubstituted C3 to C20 cycloalkyl, a substituted or unsubstituted C6 to C30 aryl, or -L 1 -C=C(R 6 (R) 7 ), or -L 2 -C≡C(R 8 ), L 1 and L 2 It is a substituted or unsubstituted C1 to C10 alkylene group, and R 6 To R 8 Each is independently hydrogen, a substituted or unsubstituted C1 to C20 alkyl, a substituted or unsubstituted C3 to C20 cycloalkyl, a substituted or unsubstituted C2 to C20 alkenyl, a substituted or unsubstituted C2 to C20 alkynyl, or a substituted or unsubstituted C6 to C30 aryl.

2. The semiconductor photoresist composition according to claim 1, wherein: R a R b and R c It is -C≡C(R) 5 ), R 5 It is a substituted or unsubstituted C1 to C20 alkyl, a substituted or unsubstituted C3 to C20 cycloalkyl, a substituted or unsubstituted C6 to C30 aryl, or -L 1 -C=C(R 6 (R) 7 ), or -L 2 -C≡C(R 8 ), L 1 and L 2 It is a substituted or unsubstituted C1 to C10 alkylene group, and R 6 To R 8 Each is independently hydrogen, a substituted or unsubstituted C1 to C20 alkyl, a substituted or unsubstituted C3 to C20 cycloalkyl, a substituted or unsubstituted C2 to C20 alkenyl, a substituted or unsubstituted C2 to C20 alkynyl, or a substituted or unsubstituted C6 to C30 aryl.

3. The semiconductor photoresist composition according to claim 1, wherein: X, Y, and Z are each independently -OL a -R a -SL b -R b , or -O(CO)-L c -R c .

4. The semiconductor photoresist composition according to claim 3, wherein: X, Y, and Z are the same as each other.

5. The semiconductor photoresist composition according to claim 1, wherein: R 1 It is selected from substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C2 to C20 heteroalkyl, substituted or unsubstituted C3 to C12 cycloalkyl, substituted or unsubstituted C2 to C20 heterocycloalkyl, substituted or unsubstituted C2 to C10 alkenyl, substituted or unsubstituted C2 to C10 alkynyl, substituted or unsubstituted C6 to C20 aryl, substituted or unsubstituted C2 to C20 heteroaryl, substituted or unsubstituted C7 to C20 aralkyl, substituted or unsubstituted C4 to C20 heteroaryl, and substituted or unsubstituted C1 to C20 alkylcarbonyl.

6. The semiconductor photoresist composition according to claim 1, wherein: R 1 It 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-pentyl, substituted or unsubstituted 1-methylpropyl, substituted or unsubstituted 1,1-dimethylpropyl, 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 propynyl, substituted or unsubstituted butynyl, substituted or unsubstituted phenyl, substituted or unsubstituted tolyl, substituted or unsubstituted xylylyl, or substituted or unsubstituted benzyl.

7. The semiconductor photoresist composition according to claim 1, wherein: R 2 It 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, or substituted or unsubstituted C6 to C20 aryl. R 3 and R 4 Each is independently hydrogen, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C3 to C10 cycloalkyl, substituted or unsubstituted C6 to C20 aryl, -L 1 -C=C(R 6 (R) 7 ), or -L 2 -C≡C(R 8 ), Selected from R 3 and R 4 At least one of them is a substituted or unsubstituted C1 to C10 alkyl, a substituted or unsubstituted C3 to C10 cycloalkyl, a substituted or unsubstituted C6 to C20 aryl, or -L 1 -C=C(R 6 (R) 7 ), or -L 2 -C≡C(R 8 ), R 5 It is a substituted or unsubstituted C1 to C10 alkyl, a substituted or unsubstituted C3 to C10 cycloalkyl, a substituted or unsubstituted C6 to C20 aryl, or -L 1 -C=C(R 6 (R) 7 ), or -L 2 -C≡C(R 8 ), L 1 and L 2 It is a substituted or unsubstituted C1 to C6 alkylene group, and R 6 To R 8 Each is independently hydrogen, a substituted or unsubstituted C1 to C10 alkyl, a substituted or unsubstituted C3 to C10 cycloalkyl, a substituted or unsubstituted C2 to C10 alkenyl, a substituted or unsubstituted C2 to C10 alkynyl, or a substituted or unsubstituted C6 to C20 aryl.

8. The semiconductor photoresist composition according to claim 1, wherein: R 2 It is hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C2 to C10 alkenyl group, or a substituted or unsubstituted C2 to C10 alkynyl group. R 3 and R 4 Each is independently hydrogen, substituted or unsubstituted C1 to C10 alkyl, -L 1 -C=C(R 6 (R) 7 ), or -L 2 -C≡C(R 8 ), Selected from R 3 and R 4 At least one of them is a substituted or unsubstituted C1 to C10 alkyl group, -L 1 -C=C(R 6 (R) 7 ), or -L 2 -C≡C(R 8 ), R 5 It is a substituted or unsubstituted C1 to C10 alkyl group, -L 1 -C=C(R 6 (R) 7 ), or -L 2 -C≡C(R 8 ), L 1 and L 2 It is a substituted or unsubstituted C1 to C6 alkylene group, and R 6 To R 8 Each is independently hydrogen, a substituted or unsubstituted C1 to C10 alkyl, a substituted or unsubstituted C2 to C10 alkenyl, or a substituted or unsubstituted C2 to C10 alkynyl.

9. The semiconductor photoresist composition according to claim 1, wherein: The organometallic compounds represented by chemical formula 1 are selected from the compounds listed in group 1: Group 1 。 10. The semiconductor photoresist composition according to claim 1, wherein: The amount of the organometallic compound represented by Formula 1 is from 0.5% to 30% by weight, based on 100% by weight of the semiconductor photoresist composition.

11. The semiconductor photoresist composition according to claim 1, further comprising surfactants, crosslinking agents, leveling agents, organic acids, quenchers, or other additives in combination thereof.

12. A method for forming a pattern, comprising: Form the etch target layer on the substrate; A semiconductor photoresist composition as described in any one of claims 1 to 11 is coated onto the etched target layer to form a photoresist film; The photoresist film is exposed and developed to form a photoresist pattern on the photoresist film; as well as The photoresist pattern is used as an etching mask to etch the target layer.

13. The method according to claim 12, wherein: The exposure and development of the photoresist film are performed using light with wavelengths in the range of 5 nm to 150 nm.

14. The method according to claim 12, wherein: The photoresist pattern has a width in the range of 5 nm to 100 nm.

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