Semiconductor photoresist composition and method of forming pattern using the same

Abstract

The invention provides a semiconductor photoresist composition and a method for forming a pattern by using the semiconductor photoresist composition. The semiconductor photoresist composition comprises an organic metal compound and a carboxylic acid compound represented by a chemical formula 1, and a solvent. Chemical formula 1

Description

[0001] Patent application related documents

[0002] This application claims priority and benefit to Korean Patent Application No. 10-2024-0153667, filed on November 1, 2024, with the Korean Intellectual Property Office, the entire contents of which are incorporated herein by reference. Technical Field

[0003] One or more embodiments of this disclosure relate to semiconductor photoresist compositions and methods of patterning using the same. Background Technology

[0004] Extreme ultraviolet (EUV) lithography has become an important technology for manufacturing next-generation semiconductor devices, such as advanced semiconductor chips (e.g., next-generation semiconductor chips). EUV lithography uses EUV radiation with a wavelength of 13.5 nanometers as an exposure source, enabling the formation of extremely fine patterns, such as patterns with a critical size of 20 nanometers or smaller.

[0005] Achieving high-resolution patterning using EUV lithography requires the development of compatible photoresists capable of resolutions below 16 nanometers. However, chemically amplified (CA) photoresists currently face limitations in resolution, photosensitivity, and line edge roughness (LER), which hinder their performance in advanced lithography processes.

[0006] In CA photoresists, acid-catalyzed reactions can lead to image blurring, particularly at small feature sizes; this limitation has also been observed in electron beam lithography. Although CA photoresists are designed for high sensitivity, their typical elemental composition results in low absorbance at 13.5 nm, thus reducing sensitivity under EUV exposure.

[0007] Furthermore, CA photoresists typically exhibit an increasing LER (Low Resistivity) as photosensitivity decreases, partly due to the stochastic nature of acid diffusion and reactions. These limitations create a need or expectation for novel, high-performance photoresist materials suitable for EUV lithography.

[0008] In response, research has shifted to inorganic photoresist compositions, primarily for negative-tone patterning. These compositions undergo chemical modification through non-chemical amplification mechanisms, providing resistance to developer solutions. Inorganic photoresists typically contain elements with higher EUV absorption than hydrocarbons, offering improved sensitivity, reduced stochastic effects, and lower LER.

[0009] Inorganic photoresists based on tungsten peroxopolyacids, which may be mixed with elements such as niobium, titanium, and / or tantalum, have been explored as radiation-sensitive materials for patterning.

[0010] These materials have demonstrated effectiveness in patterning large-pitch features using bilayer configurations and various radiation sources, including deep UV, X-rays, and electron beams. For example, cationic metal oxide hafnium sulfate (HfSOx) materials, when combined with peroxide miscible agents, have been able to image 15 nm half-pitch features via EUV projection exposure. While this system offers high performance and acceptable photosensitivity, it suffers from practical drawbacks: (i) the coating process involves a corrosive sulfuric acid / hydrogen peroxide mixture, resulting in poor shelf-life stability; (ii) structural modification for performance enhancement is difficult; and (iii) development requires a high concentration of tetramethylammonium hydroxide (TMAH) solution (e.g., 25 wt%).

[0011] To address these issues and challenges, recent efforts have focused on tin-containing molecules with strong EUV absorption. Among these molecules, organotin polymers have shown promise. During EUV exposure, alkyl ligands dissociate and form oxygen bonds with adjacent chains, enabling negative-tone patterning resistant to organic developers. Although these organotin polymers exhibit improved sensitivity, resolution, and LER, further enhancements are needed or desired to meet commercial performance requirements. Summary of the Invention

[0012] One or more aspects of the embodiments of this disclosure are directed to semiconductor photoresist compositions that improve CD (critical dimension) stability by reducing the influence of variables during patterning and thus exhibiting excellent or suitable resolution characteristics and pattern adhesion.

[0013] One or more aspects of the embodiments of this disclosure are related to a method of forming patterns using semiconductor photoresist compositions.

[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 practicing the embodiments presented in this disclosure.

[0015] According to one or more embodiments of this disclosure, the semiconductor photoresist composition comprises an organometallic compound, a carboxylic acid compound represented by Formula 1, and a solvent:

[0016] [Chemical Formula 1]

[0017]

[0018] In chemical formula 1, L can be a single bond, a substituted or unsubstituted C1 to C10 alkylene group, a substituted or unsubstituted C2 to C10 alkenyl group, or a substituted or unsubstituted C2 to C10 alkyne group, and Z 1 To Z 3 Each of these groups can be independently hydrogen, hydroxyl, halogen, cyano, cyano-containing, ammonium, amide, nitro, carboxyl, ester, sulfone, sulfonate, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, or combinations thereof, provided that they are selected from L and Z. 1 To Z 3 At least one of them includes (for example, nitro).

[0019] According to one or more embodiments of the present disclosure, a method of forming a pattern includes forming an etch target layer on a substrate, coating a semiconductor photoresist composition on the etch target layer to form a photoresist film, patterning the photoresist film to form a photoresist pattern, and using the photoresist pattern as an etch mask to etch the etch target layer.

[0020] Patterns formed using semiconductor photoresist compositions according to one or more embodiments can achieve excellent or suitable resolution by improving CD stability. For example, the customized chemical structure of the composition, particularly containing nitro-functionalized carboxylic acid compounds and organometallic components, helps reduce variability during the patterning process, thereby enhancing the uniformity and fidelity of the resulting features. This contributes to more consistent pattern transfer and better process control. Attached Figure Description

[0021] The accompanying drawings are included to provide a further understanding of the present disclosure and are incorporated in and constitute a part of this disclosure. The drawings illustrate embodiments of the present disclosure and, together with the description, serve to explain the principles of the present disclosure. The above and other aspects, features, and advantages of certain embodiments of the present disclosure will become more apparent from the following description in conjunction with the accompanying drawings, wherein:

[0022] Figures 1A to 1E This is a cross-sectional view illustrating a method of forming a pattern using a semiconductor photoresist composition according to one or more embodiments of the present disclosure.

[0023] Explanation of icon numbers

[0024] 100:Substrate;

[0025] 102: Film;

[0026] 104: Resist underlayer;

[0027] 106: Photoresist film;

[0028] 106a: Unexposed area;

[0029] 106b: Exposure area;

[0030] 108: Photoresist pattern;

[0031] 110: Patterned dome;

[0032] 112: Organic film pattern;

[0033] 114: Thin film pattern. Detailed Implementation

[0034] This disclosure can be modified in many alternative forms, and therefore specific embodiments will be illustrated and described in more detail in the accompanying drawings. However, it should be understood that this disclosure is not intended to be limited to the specific forms disclosed, but rather to cover all modifications, equivalents, and alternatives that fall within the spirit and scope of this disclosure.

[0035] Hereinafter, with reference to the accompanying drawings, one or more embodiments of the present disclosure will be described in more detail. In the following description of the present disclosure, well-known functions or structures will not be described in order to keep the disclosure brief.

[0036] For clarity of illustration, certain necessary descriptions and relationships have been omitted, and throughout the disclosure, identical or similar configuration components are indicated by the same reference numerals. Furthermore, since the size and thickness of each configuration shown in the accompanying drawings are illustrated for better understanding and ease of explanation, this disclosure is not necessarily limited thereto.

[0037] In the accompanying drawings, the thickness of layers, films, panels, regions, etc., may be enlarged for clarity. In the accompanying drawings, the thickness of a portion of a layer or region may be enlarged for ease of illustration. It will be understood that when a component (e.g., when) is referred to as being "on" another component, it may be directly on the other component, or one or more intervening components may also be present therein. Conversely, when a component is referred to as being "directly on" another component, no intervening components are present therein.

[0038] As used herein, “substituted” means that hydrogen is replaced by deuterium, halogen, hydroxyl, carboxyl, thiol, cyano, nitro, -NRR' (where R and R' can each be independently hydrogen, substituted or unsubstituted C1 to C30 saturated or unsaturated aliphatic hydrocarbon group, substituted or unsubstituted C3 to C30 saturated or unsaturated alicyclic hydrocarbon group, or substituted or unsubstituted C6 to C30 aromatic hydrocarbon group), -SiRR'R'' (where R, R', and R'' can each be independently hydrogen, substituted or unsubstituted C1 to C30 saturated or unsaturated alicyclic hydrocarbon group, substituted or unsubstituted C6 to C30 aromatic hydrocarbon group), or -SiRR'R'' (where R, R', and R'' can each be independently hydrogen, substituted or unsubstituted C1 to C30 saturated or unsaturated alicyclic hydrocarbon group, substituted or unsubstituted C3 to C30 aromatic hydrocarbon group). The substitution is independent of 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), C1 to C30 alkyl, C1 to C10 haloalkyl, C1 to C10 alkylsilyl, C3 to C30 cycloalkyl, C6 to C30 aryl, C1 to C20 alkoxy, C1 to C20 thioether, or a combination thereof. "Unsubstituted" means that hydrogen has not been replaced by another substituent and hydrogen is retained.

[0039] As used herein, unless otherwise defined, the term "alkyl" refers to a straight-chain or branched aliphatic hydrocarbon group. An alkyl group may be a "saturated alkyl" that does not have any double or triple bonds.

[0040] 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, dibutyl, tributyl, or 2,2-dimethylpropyl.

[0041] As used herein, unless otherwise defined, the term "cycloalkyl" refers to a monovalent cyclic aliphatic saturated hydrocarbon group.

[0042] The cycloalkyl group can be a C3 to C8 cycloalkyl group, for example, a C3 to C7 cycloalkyl group or a C3 to C6 cycloalkyl group. For example, the cycloalkyl group can be cyclopropyl, cyclobutyl, cyclopentyl, or cyclohexyl, but the embodiments disclosed herein are not limited thereto.

[0043] As used herein, the term "aryl" refers to a cyclic substituent in which all atoms have p orbitals and these p orbitals are conjugated, and may include monocyclic or fused-ring polycyclic functional groups (i.e., rings that share adjacent carbon atom pairs).

[0044] As used herein, the term "heteroaryl" can refer to an aryl group comprising at least one heteroatom selected from N, O, S, P, and Si. Two or more heteroaryl groups may be directly linked by σ bonds, or if (for example, when) a heteroaryl group comprises two or more rings, the two or more rings may be fused. When a heteroaryl group is a fused ring, one or more of its rings may comprise one to three heteroatoms.

[0045] As used herein, unless otherwise defined, the term "alkenyl" refers to a straight-chain or branched aliphatic hydrocarbon group comprising at least one double bond as an aliphatic unsaturated alkenyl group.

[0046] As used herein, unless otherwise defined, the term "alkynyl" refers to a straight-chain or branched aliphatic hydrocarbon group that includes at least one parameter as an aliphatic unsaturated alkynyl group.

[0047] The following describes a semiconductor photoresist composition according to one or more embodiments.

[0048] The semiconductor photoresist composition according to one or more embodiments may include an organometallic compound; a carboxylic acid compound represented by Formula 1; and a solvent:

[0049] Chemical Formula 1

[0050] .

[0051] In chemical formula 1, L can be a single bond, a substituted or unsubstituted C1 to C10 alkylene group, a substituted or unsubstituted C2 to C10 alkenyl group, or a substituted or unsubstituted C2 to C10 alkyne group, and Z 1 To Z 3 Each of these groups can be independently hydrogen, hydroxyl, halogen, cyano, cyano-containing, ammonium, amide, nitro, carboxyl, ester, sulfone, sulfonate, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, or combinations thereof, wherein the group selected is L and Z. 1 To Z 3 At least one of them includes (for example, nitro).

[0052] A method for forming a pattern using a semiconductor photoresist composition including an organometallic compound includes coating the semiconductor photoresist composition onto an etch target layer such that the organometallic compound or its cluster molecules in the semiconductor photoresist composition can be coated onto the etch target layer, and then performing a first baking process, an exposure process, a second baking process, and a development process to remove the organic material in the photoresist composition, thereby patterning the metal oxide (i.e., the etch target layer).

[0053] Here, the patterning of metal oxides is affected by various variables, such as temperature, solvent, concentration, catalyst, atmosphere, and / or the like, and in particular, the smaller the pattern size, the greater the influence. For example, because patterns formed from photoresist compositions including organometallic compounds have very small sizes ranging from several nanometers (nm) to tens of nanometers, metal oxide patterning may be more affected by process conditions than photoresist.

[0054] For example, nitrogen oxides (NOx) in the atmosphere x The concentration of (NO) may affect patterning performed by photoresist compositions including organometallic compounds. x It is a highly reactive substance present in the atmosphere and can react with atmospheric moisture, sunlight, and / or similar substances to cause phenomena such as smog and / or similar phenomena. If (e.g., when) NO x If the concentration exceeds the set or predetermined level, there may be a problem where the pattern width and / or similar values ​​checked after development differ from the target value.

[0055] Therefore, in this disclosure, a method has been developed that can inhibit or reduce the reactivity of the central metal to free radicals by introducing a compound represented by Formula 1 and allowing the compound to coordinate with the central metal of the organometallic compound, thereby reducing the reactivity of the central metal and stabilizing the generated free radicals to reduce reactivity. x The photoresist composition that causes pattern width distortion.

[0056] In one or more embodiments, L of Formula 1 may be, for example, a single bond, a substituted or unsubstituted C1 to C5 alkylene group, a substituted or unsubstituted C2 to C5 alkenyl group, or a substituted or unsubstituted C2 to C5 alkyne group. In one or more embodiments, L of Formula 1 may be, for example, a single bond or a substituted or unsubstituted C1 to C10 alkylene group, or may be, for example, a substituted or unsubstituted C1 to C10 alkylene group, such as an unsubstituted C1 to C5 alkylene group, or a nitro-substituted C1 to C10 alkylene group.

[0057] Z of chemical formula 1 1 To Z 3 Each of these groups can independently be hydrogen, hydroxyl, halogen, cyano, cyano-containing, ammonium, amide, nitro, carboxyl, ester, sulfone, sulfonate, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C2 to C10 alkenyl, substituted or unsubstituted C2 to C10 alkynyl, or a combination thereof. In one or more embodiments, Z of Formula 1... 1 To Z 3 It can be, for example, hydrogen, cyano, cyano-containing, ammonium, amide, nitro, carboxyl, ester, sulfone, sulfonate, or a combination thereof. In one or more embodiments, Z of Formula 1 1 To Z 3 It can be, for example, hydrogen, cyano, ammonium, amide, nitro, carboxyl, ester or a combination thereof, or, for example, hydrogen or nitro.

[0058] In chemical formula 1, from L and Z 1 To Z 3At least one of the selected components includes a nitro group. For example, in one or more embodiments, L may be a nitro-substituted alkylene group, a nitro-substituted alkenyl group, or a nitro-substituted ynylene group, and / or, for example, from Z. 1 To Z 3 At least one of the selected groups may be a nitro group, a nitro-substituted alkyl group, a nitro-substituted alkenyl group, or a nitro-substituted alkynyl group.

[0059] In one or more embodiments, the carboxylic acid compound represented by Formula 1 may be one of the compounds selected from those listed in Group 1:

[0060] Group 1

[0061] .

[0062] The carboxylic acid compound represented by Formula 1 may be included in an amount from about 0.01 wt% to about 5 wt% based on 100 wt% of the total weight of the semiconductor photoresist composition. In one or more embodiments, the carboxylic acid compound represented by Formula 1 may be included in an amount from about 0.01 wt% to about 5 wt%, about 0.02 wt% to about 5 wt%, about 0.03 wt% to about 5 wt%, or about 0.05 wt% to about 5 wt% based on 100 wt% of the total weight of the semiconductor photoresist composition. When the carboxylic acid compound represented by Formula 1 is included in the above-mentioned amount range, it is possible to achieve the inhibition or reduction of NO. x While influencing the pattern formation, it maintains the overall effect.

[0063] The organometallic compound may be included in an amount from about 0.5% to about 30% by weight, based on 100% of the total weight of the semiconductor photoresist composition. In the semiconductor photoresist composition according to one or more embodiments, the organometallic compound may be included in an amount from about 0.5% to about 30% by weight, for example, from about 1% to about 30% by weight, for example, from about 1% to about 25% by weight, for example, from about 1% to about 20% by weight, for example, from about 1% to about 15% by weight, for example, from about 1% to about 10% by weight, or for example, from about 1% to about 5% by weight, based on 100% of the total weight of the semiconductor photoresist composition.

[0064] Semiconductor photoresist compositions according to one or more embodiments can improve photoresist sensitivity by including organometallic compounds within the above-described amount range.

[0065] Organometallic compounds may be organotin compounds that include at least one of an organooxy group or an organocarbonyl group.

[0066] In one or more embodiments, the organometallic compound may be represented by chemical formula 2:

[0067] Chemical formula 2

[0068]

[0069] In chemical formula 2,

[0070] R 1 It can be selected from substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, and substituted or unsubstituted C7 to C30 arylalkyl.

[0071] R 2 To R 4 Each of these can be independently 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, a substituted or unsubstituted C6 to C30 aryl, a substituted or unsubstituted C7 to C30 arylalkyl, an alkoxy, or an aryloxy (-OR) b , where R b It can be 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, a substituted or unsubstituted C6 to C30 aryl, or a combination thereof), or a carboxyl group (-O(CO)R). c , where R c It may be hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, or a combination thereof, alkylamide or dialkylamide (-NR) d R e , where R d and R e Each of these can be independently hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, or a combination thereof), or an amide group (-NR). f (COR g ), where R f and R gEach of these can be 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, a substituted or unsubstituted C6 to C30 aryl, or a combination thereof), or an amidine (-NR) group. h C(NR i )R j , where R h R i and R j Each of these can be 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, a substituted or unsubstituted C6 to C30 aryl, or a combination thereof, alkylthio or arylthio (-SR). k , where R k It can be 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, a substituted or unsubstituted C6 to C30 aryl, or a combination thereof) or a thiocarboxyl (-S(CO)R) l , where R l 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, substituted or unsubstituted C6 to C30 aryl, or a combination thereof), and

[0072] R 2 To R 4 At least one of them is selected as alkoxy or aryloxy (-OR) b , where R b It can be 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, a substituted or unsubstituted C6 to C30 aryl, or a combination thereof), or a carboxyl group (-O(CO)R). c , where R c It may be hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, or a combination thereof, alkylamide or dialkylamide (-NR) d R e , where R d and Re Each of these can be independently hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, or a combination thereof), or an amide group (-NR). f (COR) g ), where R f and R g Each of these can be 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, a substituted or unsubstituted C6 to C30 aryl, or a combination thereof), or an amidine (-NR) group. h C(NR i )R j , where R h R i and R j Each of these can be 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, a substituted or unsubstituted C6 to C30 aryl, or a combination thereof, alkylthio or arylthio (-SR). k , where R k It can be 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, a substituted or unsubstituted C6 to C30 aryl, or a combination thereof) or a thiocarboxyl (-S(CO)R) l , where R l It may be hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, or a combination thereof.

[0073] In one or more embodiments, R 2 To R 4 At least one of the selected components may be chosen from alkoxy and aryloxy (-OR) b , where R bIt can be 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, a substituted or unsubstituted C6 to C30 aryl, or a combination thereof) and a carboxyl group (-O(CO)R). c , where R c It may be hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, or a combination thereof.

[0074] In one or more embodiments, because the organometallic compound represented by chemical formula 2 includes -OR b or -O(CO)R c As ligands, patterns formed using semiconductor photoresist compositions including organometallic compounds can exhibit excellent or suitable limiting resolution.

[0075] In addition, -OR b or -O(CO)R c The ligands can determine the solubility of organometallic compounds represented by chemical formula 2 in solvents.

[0076] In one or more embodiments, R 1 It can be selected from substituted or unsubstituted C1 to C8 alkyl, substituted or unsubstituted C3 to C8 cycloalkyl, substituted or unsubstituted C2 to C8 alkenyl, substituted or unsubstituted C2 to C8 alkynyl, substituted or unsubstituted C6 to C20 aryl and substituted or unsubstituted C7 to C20 arylalkyl.

[0077] R b It may be a substituted or unsubstituted C1 to C8 alkyl, a substituted or unsubstituted C3 to C8 cycloalkyl, a substituted or unsubstituted C2 to C8 alkenyl, a substituted or unsubstituted C2 to C8 alkynyl, a substituted or unsubstituted C6 to C20 aryl, or a combination thereof, and

[0078] R c It may be hydrogen, substituted or unsubstituted C1 to C8 alkyl, substituted or unsubstituted C3 to C8 cycloalkyl, substituted or unsubstituted C2 to C8 alkenyl, substituted or unsubstituted C2 to C8 alkynyl, substituted or unsubstituted C6 to C20 aryl, or a combination thereof.

[0079] In one or more embodiments, R 1It may be methyl, ethyl, propyl, butyl, isopropyl, tributyl, 2,2-dimethylpropyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, vinyl, propenyl, butenyl, ethynyl, propynyl, butynyl, phenyl, tolyl, xylylyl, benzyl, or a combination thereof.

[0080] R b It may be ethyl, propyl, butyl, isopropyl, tributyl, 2,2-dimethylpropyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, vinyl, propenyl, butenyl, ethynyl, propynyl, butynyl, phenyl, tolyl, xylylyl, benzyl, or a combination thereof, and

[0081] R c It may be hydrogen, ethyl, propyl, butyl, isopropyl, tributyl, 2,2-dimethylpropyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, vinyl, propenyl, butenyl, ethynyl, propynyl, butynyl, phenyl, tolyl, xylylyl, benzyl, or a combination thereof.

[0082] In one or more embodiments, the organometallic compound may be a Sn-containing organometallic compound represented by chemical formula 3 or chemical formula 4.

[0083] Chemical formula 3

[0084] R 5 z SnO (2-(z / 2)-(x / 2)) (OH) x

[0085] In chemical formula 3,

[0086] R 5 It can be a C1 to C31 hydrocarbon group, 0 < z ≤ 2, and 0 < (z+x) ≤ 4.

[0087] Chemical Formula 4

[0088] R 6 a Sn b X c Y d

[0089] In chemical formula 4, R 6 It can 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 aliphatic unsaturated organogroup including one or more double bonds or triple bonds, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C4 to C30 heteroaryl group, a carbonyl group, an ethylene oxide group, an propylene oxide group, or a combination thereof.

[0090] X can be sulfur (S), selenium (Se), or tellurium (Te).

[0091] Y can be -OR m or -OC(=O)R n ,

[0092] Where R m It may be 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, a substituted or unsubstituted C6 to C30 aryl, or a combination thereof, and

[0093] R n It may be hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, or a combination thereof, and

[0094] a, b, c, and d can each be an integer from 1 to 20 independently.

[0095] In addition to the aforementioned organometallic compounds, carboxylic acid compounds represented by Formula 1, and solvents, the semiconductor photoresist composition according to one or more embodiments may further include resins.

[0096] The resin may be a phenolic resin comprising at least one aromatic portion selected from the portions listed in Group 2.

[0097] Group 2

[0098]

[0099] The resin may have a weight average molecular weight of about 500 g / mol to about 20,000 g / mol.

[0100] In one or more embodiments, the semiconductor photoresist composition is ideally composed of the aforementioned organometallic compound, the carboxylic acid compound represented by Formula 1, a solvent, and a resin.

[0101] The solvent contained in the semiconductor photoresist composition according to one or more embodiments may be an organic solvent, and may be selected from, for example, aromatic compounds (e.g., xylene, toluene, etc.), alcohols (e.g., 4-methyl-2-pentanol, 4-methyl-2-propanol, 1-butanol, methanol, isopropanol, 1-propanol), ethers (e.g., anisole, tetrahydrofuran), esters (n-butyl acetate, propylene glycol monomethyl ether acetate, ethyl acetate, ethyl lactate), ketones (e.g., methyl ethyl ketone, 2-heptanone), or mixtures thereof, but the embodiments of this disclosure are not limited thereto.

[0102] According to one or more embodiments of this disclosure, the semiconductor photoresist composition may further include one or more additives as needed. Non-limiting examples of additives may be surfactants, crosslinking agents, leveling agents, organic acids, quenchers, or combinations thereof.

[0103] Surfactants 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.

[0104] The crosslinking agent may be, for example, a melamine-based crosslinking agent, a substituted urea-based crosslinking agent, an acrylic crosslinking agent, an epoxy resin-based crosslinking agent, or a polymer crosslinking agent, but the embodiments of this disclosure are not limited thereto. In one or more embodiments, it may be a crosslinking agent having at least two crosslinking-forming substituents, 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 other compounds.

[0105] Leveling agents can be used to improve the flatness of the coating during printing, and suitable leveling agents are available commercially.

[0106] 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.

[0107] The quencher may be diphenyl(p-tolyl)amine, methyldiphenylamine, triphenylamine, phenylenediamine, naphthylamine, diaminonaphthalene, or a combination thereof.

[0108] The amounts of each additive included in the semiconductor photoresist composition can be controlled or selected depending on the desired or suitable properties.

[0109] In one or more embodiments, the semiconductor photoresist composition may further include a silane coupling agent as an adhesion enhancer to improve the tightness of contact with the substrate (e.g., to improve 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, etc., but the embodiments of this disclosure are not limited thereto.

[0110] Semiconductor photoresist compositions can be formed into patterns with a high aspect ratio without collapse. Therefore, in order to form fine patterns with widths (e.g., linewidths) of, for example, about 5 nanometers to about 100 nanometers, about 5 nanometers to about 80 nanometers, about 5 nanometers to about 70 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, semiconductor photoresist compositions can be used in photoresist processes using light with wavelengths ranging from about 5 nanometers to about 150 nanometers, for example, about 5 nanometers to about 100 nanometers, about 5 nanometers to about 80 nanometers, about 5 nanometers to about 50 nanometers, about 5 nanometers to about 30 nanometers, or about 5 nanometers to about 20 nanometers. Therefore, semiconductor photoresist compositions according to one or more embodiments can be used to achieve extreme ultraviolet lithography using an EUV light source with a wavelength of about 13.5 nanometers.

[0111] According to one or more embodiments, a method for forming a pattern using the aforementioned semiconductor photoresist composition is provided. For example, the pattern produced may be a photoresist pattern.

[0112] A method for forming a pattern according to one or more embodiments includes forming an etch target layer on a substrate, coating a semiconductor photoresist composition on the etch target layer to form a photoresist film, patterning the photoresist film to form a photoresist pattern, and using the photoresist pattern as an etch mask to etch the etch target layer.

[0113] The following will refer to Figures 1A to 1E Describes a method for forming patterns using semiconductor photoresist compositions. Figures 1A to 1E This is a cross-sectional view illustrating a method of forming a pattern using a semiconductor photoresist composition according to one or more embodiments of the present disclosure.

[0114] Reference Figure 1AThe etching target layer is prepared. The etching target may be a thin film 102 formed on the semiconductor substrate 100. Hereinafter, the etching target is limited to the thin film 102. The surface of the thin film 102 is washed to remove impurities and / or similar substances remaining thereon. The thin film 102 may be, for example, a silicon nitride layer, a polysilicon layer, or a silicon oxide layer.

[0115] Subsequently, the resist underlayer composition for forming the resist underlayer 104 is spin-coated onto the surface of the washed film 102. However, embodiments of the present disclosure are not limited thereto, and various suitable coating methods may be used, such as spraying, dip coating, knife coating, printing methods (e.g., inkjet printing and screen printing) and / or similar methods.

[0116] In one or more embodiments, the coating process for the resist underlayer may not be provided. However, the following describes a process that includes coating the resist underlayer.

[0117] The coated resist underlayer composition is then dried and baked to form a resist underlayer 104 on the film 102. Baking may be performed at about 100°C to about 500°C, for example, about 100°C to about 300°C.

[0118] The resist underlayer 104 is formed between the substrate 100 and the photoresist film 106, and thus prevents or reduces the non-uniformity of the photoresist linewidth patterning capability when rays reflected from the interface or hard mask between the substrate 100 and the photoresist film 106 are scattered into the unintended photoresist area.

[0119] Reference Figure 1B A photoresist film 106 is formed by coating a semiconductor photoresist composition onto a resist substrate 104. The photoresist film 106 is obtained by coating the aforementioned semiconductor photoresist composition onto a thin film 102 formed on a substrate 100 and then curing it by heat treatment.

[0120] In one or more embodiments, patterning using a semiconductor photoresist composition may include applying the semiconductor photoresist composition to a substrate 100 having a thin film 102 by spin coating, slot coating, inkjet printing and / or similar operations, and then drying it to form a photoresist film 106.

[0121] The composition of semiconductor photoresist has been described in detail and will not be described again.

[0122] Subsequently, the substrate 100 having the photoresist film 106 is subjected to a first baking process. The first baking process may be performed at about 80°C to about 120°C.

[0123] Reference Figure 1C The photoresist film 106 can be selectively exposed using a patterned mask 110.

[0124] For example, exposure can use activating radiation with high-energy wavelengths such as EUV (extreme ultraviolet; wavelength of about 13.5 nm), E-Beam (electron beam) and / or similar, as well as light such as i-line (wavelength of about 365 nm), KrF excimer laser (wavelength of about 248 nm), ArF excimer laser (wavelength of about 193 nm) and / or similar.

[0125] In one or more embodiments, the light or exposure beam used for exposure may be light in the range of about 5 nanometers to about 150 nanometers and / or high-energy wavelengths, such as EUV (extreme ultraviolet; wavelength of 13.5 nanometers), and / or may be E-Beam (electron beam) and / or the like.

[0126] The exposed region 106b of the photoresist film 106 has a different solubility than the unexposed region 106a of the photoresist film 106 by forming a polymer through a cross-linking reaction (e.g., condensation between organometallic compounds).

[0127] Subsequently, the substrate 100 is subjected to a second baking process. The second baking process can be performed at a temperature of about 90°C to about 200°C. The exposed area 106b of the photoresist film 106 becomes insoluble in the developer due to the second baking process.

[0128] exist Figure 1D In this process, a developer is used to dissolve and remove the unexposed areas 106a of the photoresist film to form a photoresist pattern 108. For example, the unexposed areas 106a of the photoresist film are dissolved and removed using an organic solvent such as 2-heptanone and / or similar substances to complete the photoresist pattern 108 corresponding to a negative image.

[0129] As described above, the developer used in the pattern forming method according to one or more embodiments may be an organic solvent. The organic solvent used in the pattern forming method 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.

[0130] However, the photoresist pattern according to one or more embodiments is not limited to a negative image, but can be formed to have a positive image. Here, the developer used to form the positive image can be a quaternary ammonium hydroxide composition, such as tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, or combinations thereof.

[0131] As described above, exposure to high-energy light (such as EUV (extreme ultraviolet; wavelength of 13.5 nm), E-Beam (electron beam) and / or the like) and / or exposure to light (such as i-line (wavelength of about 365 nm), KrF excimer laser (wavelength of about 248 nm), ArF excimer laser (wavelength of about 193 nm) and / or the like) can provide a photoresist pattern 108 with a width of about 5 nm to about 100 nm. For example, in one or more embodiments, the photoresist pattern 108 may have a width of about 5 nm to about 90 nm, about 5 nm to about 80 nm, about 5 nm to about 70 nm, about 5 nm to about 60 nm, about 5 nm to about 50 nm, about 5 nm to about 40 nm, about 5 nm to about 30 nm, or about 5 nm to about 20 nm.

[0132] In one or more embodiments, the photoresist pattern 108 may have a pitch (center-to-center distance between adjacent features in the pattern) with 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 15 nanometers, and a linewidth roughness less than or equal to about 10 nanometers, or less than or equal to about 5 nanometers, less than or equal to about 3 nanometers, or less than or equal to about 2 nanometers.

[0133] Subsequently, the photoresist pattern 108 is used as an etching mask to etch the resist substrate 104. Through this etching process, an organic film pattern 112 is formed. The organic film pattern 112 may also have a width corresponding to the photoresist pattern 108.

[0134] Reference Figure 1E The exposed thin film 102 is etched by applying a photoresist pattern 108 as an etching mask. Thus, the thin film is formed as a thin film pattern 114.

[0135] 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 or a mixture thereof.

[0136] In the exposure process, the thin film pattern 114 formed using the photoresist pattern 108 may have a width corresponding to the photoresist pattern 108, which is formed using an exposure process performed with an EUV light source. For example, in one or more embodiments, the thin film pattern 114 may have a width (e.g., linewidth) of about 5 nanometers to about 100 nanometers, which is equal to the width of the photoresist pattern 108. For example, in one or more embodiments, the thin film pattern 114 formed using the photoresist pattern 108 may have a width (e.g., linewidth) 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., linewidth) less than or equal to about 20 nanometers, the same as the width of the photoresist pattern 108, which is formed using an exposure process performed with an EUV light source.

[0137] The present disclosure will be described in more detail below through examples of the preparation of the aforementioned semiconductor photoresist compositions. However, the present disclosure is not technically limited to the following examples.

[0138] Synthesis of organometallic compounds

[0139] Synthesis example 1

[0140] In a 250 mL two-necked round-bottom flask, 40.7 g of t-butylSnPh3 and 300 g of propionic acid were added, and the mixture was heated under reflux for 24 hours. Unreacted propionic acid was removed from the flask under reduced pressure to obtain the compound represented by chemical formula 5.

[0141] Chemical formula 5

[0142]

[0143] Synthesis example 2

[0144] 30 mL of anhydrous pentane was added to 10 g of t-pentyl SnCl3, and while maintaining the temperature at 0°C, 7.4 g of diethylamine and 6.1 g of ethanol were added. The mixture was then stirred at room temperature for 1 hour. When the reaction was complete, the product was filtered, concentrated, and dried under vacuum to obtain the compound represented by chemical formula 6.

[0145] Chemical Formula 6

[0146]

[0147] Preparation of semiconductor photoresist composition

[0148] Examples 1 to 9 and Comparative Examples 1 and 2

[0149] According to the table, organometallic compounds selected from those represented by chemical formulas 5 and 6 obtained in Synthesis Example 1 and Synthesis Example 2 were dissolved in propylene glycol methyl ether acetate (PGMEA) at a concentration of 3%, and individual carboxylic acids selected from carboxylic acid compounds C1 to C3 were added and dissolved at the concentrations listed in Table 1. The mixture was then filtered through a 0.1-micron PTFE (polytetrafluoroethylene) syringe filter to prepare individual semiconductor photoresist compositions according to the examples and comparative examples. Each composition was coated onto a silicon wafer to a thickness of 240 angstroms, and then patterned films were fabricated through PAB (post-coating baking), exposure, PEB (post-exposure baking), and development processes.

[0150] Table 1

[0151]

[0152] C1: Nitroacetic acid

[0153] C2: 3-Nitropropionic acid

[0154] C3: Propionic acid

[0155] Assessment 1: Evaluation of Sensitivity and LER Characteristics

[0156] Each photoresist composition according to the examples and comparative examples was spin-coated at 1500 rpm for 30 seconds on a 200 mm circular silicon wafer with hexamethyldisilazane (HMDS) deposited on its surface, baked at 110 degrees Celsius for 60 seconds (post-apply bake, PAB) and then placed at room temperature (23 ± 2 degrees Celsius) for 30 seconds to prepare individual coated wafers.

[0157] Then, using EUV light (Lawrence Berkeley National Laboratory Micro Exposure Tool, MET), a 50-nanometer-wide linear array was projected onto the wafer coated with the photoresist composition. In this paper, the pad exposure time was adjusted to ensure that an increased dose of EUV light was applied to each pad.

[0158] Then, the resist and substrate are baked on a hot plate at 160 degrees Celsius for 120 seconds after exposure. The baked film is developed in PGMEA solvent to form a negative tone image. Finally, the resulting film is baked again on a hot plate at 150 degrees Celsius for 2 minutes to complete the process.

[0159] The change in resist linewidth to exposure dose (energy) was measured using a critical dimension scanning electron microscope (CD-SEM). The sensitivity to exposure dose was confirmed from the resist linewidth values ​​formed for each exposure dose, and the sensitivity and LER were evaluated according to the following criteria. The results are shown in Table 2.

[0160] Sensitivity evaluation criteria

[0161] A: Less than 16 mJ / cm 2

[0162] B: Greater than or equal to 16 mJ / cm 2 And less than 18 mJ / cm 2

[0163] C: Greater than or equal to 18 mJ / cm 2

[0164] LER Evaluation Criteria

[0165] ○: Less than 2 nanometers

[0166] △: Greater than or equal to 2 nanometers and less than 5 nanometers

[0167] X: 5 nanometers or greater

[0168] Table 2

[0169]

[0170] The results in Table 2 show that the patterns formed using the semiconductor photoresist compositions according to Examples 1 to 9 exhibit superior sensitivity and smaller LER compared to Comparative Examples 1 and 2.

[0171] Assessment 2: Coating Properties Assessment

[0172] The semiconductor photoresist composition according to the examples and comparative examples was spin-coated on a chip at 1500 rpm for 60 seconds and baked at 110°C for 60 seconds to form a thin film. Images of the thin film were captured using an atomic force microscope (AFM) and / or similar instruments, and the surface roughness of the thin film was measured using software (e.g., an optical profiler) according to the following reference. The results are shown in Table 3.

[0173] In surface roughness, root mean square roughness (Rmean) is the roughness measured in squares. q) refers to the root mean square (rms) of the vertical values ​​in the root profile within the reference length.

[0174] Evaluation Criteria

[0175] ○:R q Less than or equal to 0.4 nanometers

[0176] X:R q Greater than 0.4 nanometers

[0177] Table 3

[0178]

[0179] The results in Table 3 show that the patterns formed using the semiconductor photoresist compositions according to Examples 1 to 9 exhibit lower surface roughness, i.e., better coating properties, compared to Comparative Example 1.

[0180] Assessment 3: CD Uniformity Assessment

[0181] The semiconductor photoresist compositions of Examples 1 to 9 and Comparative Examples 1 and 2 were spin-coated on a 200 mm circular silicon chip at 1500 rpm for 30 seconds, and then heated at 110°C for 60 seconds to prepare a thin film.

[0182] Subsequently, a linear array with a linewidth of 180 nm is projected onto a chip coated with a photoresist composition using KrF light. The resist and substrate are then heated on a hot plate at 180°C for 120 seconds. The baked film is developed with PGMEA solvent to form a negative image. Finally, it is baked at 200°C for 180 seconds to complete the process.

[0183] When there is no NO in the atmosphere x When and when NO x At concentrations of 0.01 ppm or higher, the CD value of the inhibitor was measured using CD-SEM, and the CD change (ΔCD (%)) was calculated. The results are shown in Table 4. (Using Sky2000-NO...) x Detector (Safe gas) measures NO x Concentration. Calculate the change in CD according to the following procedure.

[0184] equation

[0185] ΔCD(%)={(CD ≥0.01ppm NOx / CD w / o Nox )×100}

[0186] Table 4

[0187]

[0188] From the results in Table 4, compared with Comparative Example 1 and Comparative Example 2, the patterns formed using the semiconductor photoresist compositions according to Examples 1 to 6, according to NO x The concentration change showed a smaller CD change, i.e., a smaller change in NO concentration. x Excellent or suitable resistance to the influence.

[0189] As used herein, the terms “and / or” and “or” can include any and all combinations of one or more of the associated enumerated items. The “ / ” used below may be interpreted as “and” or “or” as appropriate. In this disclosure, expressions such as “at least one of,” “one of,” and “selected from,” when preceding a list of elements, modify the entire list of elements and 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,” etc., can 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 a, b, and c, or variations thereof.

[0190] It will be further understood that when used in this disclosure, 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. Furthermore, the terms "comprise(s) / comprising," "include(s) / including," "have / has / having," or other similar terms include or support the terms "consisting of" and "consisting essentially of," indicating the presence of the stated features, integers, steps, operations, elements, and / or components, with no or substantially no other features, integers, steps, operations, elements, components, and / or groups.

[0191] As used herein, unless the context clearly indicates otherwise, the singular forms “a,” “an,” and “the” are intended to include all forms. Furthermore, when describing embodiments of this disclosure, the word “may” means “one or more embodiments of this disclosure.”

[0192] In the context of this disclosure and unless otherwise defined, the terms “use,” “using,” and “used” may be considered synonymous with the terms “utilize,” “utilizing,” and “utilized,” respectively.

[0193] As used herein, the term “about” or similar terms are used as approximations rather than terms of degree and are intended to indicate that inherent biases in measured or calculated values ​​will be recognized by those skilled in the art. “About” or “approximately” as used herein also includes the stated value and means within the range of acceptable deviations for a particular value as determined by those skilled in the art, taking into account the measurement in question and the errors associated with the measurement of the particular quantity (i.e., measurement system limitations). 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 if the terms “about,” “approximately,” or “substantially” are not explicitly stated in a given element (e.g., a claim element), such element ranges are intended to include variations that are not significant or understood by those skilled in the art. For example, the provision of numerical values ​​and ranges herein is intended to include tolerances and measurement uncertainties that will be recognized by those skilled in the art, and elements (e.g., claim elements) should be interpreted accordingly to cover such equivalents.

[0194] Any numerical range described herein is intended to include all subranges with the same numerical precision contained within the described range. For example, the range "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 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 herein is intended to include all higher numerical limits contained therein. Therefore, the applicant reserves the right to amend this specification (including the claims) to expressly describe any subranges included within the scope expressly described herein.

[0195] Those skilled in the art will understand, in consideration of the whole disclosure, that various suitable features of the various embodiments of the disclosure may be combined with or intercombined with each other, in whole or in part, and may be technically interlocked and operated in various suitable manners, and that, unless otherwise stated or implied, the embodiments may be implemented independently of each other or in any suitable combination with each other.

[0196] According to embodiments of the present invention, the pattern forming apparatus, semiconductor forming apparatus, and / or any other related apparatus or components described herein can be implemented using any suitable hardware, firmware (e.g., application-specific integrated circuits), software, or a combination of software, firmware, and hardware. For example, various components of the apparatus can be formed on a single integrated circuit (IC) chip or on a discrete IC chip. Furthermore, various components of the apparatus can be implemented on flexible printed circuit films, tape carrier packages (TCPs), printed circuit boards (PCBs), or formed on a single substrate. Additionally, various components of the apparatus can be used to run processes or threads on one or more processors in one or more computing devices, execute computer program instructions, and interact with other system components to perform the various functions described herein. The computer program instructions are stored in memory, which can be implemented in the computing device using standard memory devices (e.g., random-access memory (RAM)). The computer program instructions can also be stored in other non-transitory computer-readable media, such as CD-ROMs, flash drives, or the like. Furthermore, those skilled in the art should recognize that the functions of various computing devices can be combined or integrated into a single computing device, or that specific computing device functions can be distributed across one or more other computing devices without departing from the scope of this disclosure.

[0197] 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 embodiments presented as described, and that various modifications and transformations can be made without departing from the spirit and scope of this disclosure. Therefore, modified or transformed embodiments may not be understood solely from the technical concept and aspects of this disclosure, and the modified embodiments are within the scope of the claims of this disclosure. It should be further understood that the scope of this disclosure is defined by the appended claims and their equivalents rather than the detailed description described above, and all modifications and alterations derived from the claims and their equivalents fall within the scope of this disclosure.

Claims

1. A semiconductor photoresist composition, comprising: Organometallic compounds; Carboxylic acid compounds represented by chemical formula 1; as well as Solvent, Chemical Formula 1 In chemical formula 1, L is a single bond, a substituted or unsubstituted C1 to C10 alkylene group, a substituted or unsubstituted C2 to C10 alkenyl group, or a substituted or unsubstituted C2 to C10 ynylene group, and Z 1 To Z 3 Each of the following groups is independently hydrogen, hydroxyl, halogen, cyano, cyano-containing, ammonium, amide, nitro, carboxyl, ester, sulfone, sulfonate, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, or a combination thereof. L and Z 1 To Z 3 At least one of the selected ones contains a nitro group.

2. The semiconductor photoresist composition according to claim 1, wherein L is a single bond or a substituted or unsubstituted C1 to C10 alkylene group.

3. The semiconductor photoresist composition according to claim 1, wherein Z 1 To Z 3 Each is independently hydrogen, cyano, ammonium, amide, nitro, carboxyl, ester, or a combination thereof, wherein Z 1 To Z 3 At least one of them must be nitro.

4. The semiconductor photoresist composition according to claim 1, wherein the amount of the carboxylic acid compound represented by chemical formula 1 is from 0.01% to 5% by weight, based on 100% by weight of the semiconductor photoresist composition.

5. The semiconductor photoresist composition according to claim 1, wherein the carboxylic acid compound represented by formula 1 is selected from compounds listed in group 1: Group 1 。 6. The semiconductor photoresist composition according to claim 1, wherein the semiconductor photoresist composition further comprises one or more additives selected from surfactants, crosslinking agents, leveling agents, organic acids, quenchers, and combinations thereof.

7. The semiconductor photoresist composition according to claim 1, wherein the organometallic compound comprises an organotin compound, and the organotin compound comprises at least one of an organooxy group or an organocarbonyl group.

8. The semiconductor photoresist composition according to claim 1, wherein the organometallic compound is represented by chemical formula 2: Chemical formula 2 ,and in, In chemical formula 2, R 1 Selected from substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, and substituted or unsubstituted C7 to C30 aralkyl. R 2 To R 4 Each of the following is independently 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, a substituted or unsubstituted C6 to C30 aryl, a substituted or unsubstituted C7 to C30 aralkyl, or -OR b -O(CO)R c -NR d R e -NR f (COR g -NR h C(NR i )R j -SR k or -S(CO)R l , Where R b It can be 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, a substituted or unsubstituted C6 to C30 aryl, or a combination thereof. Where R c It is hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, or a combination thereof. Where R d and R e Each of the following 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, a substituted or unsubstituted C6 to C30 aryl, or a combination thereof. Where R f and R g Each of the following 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, a substituted or unsubstituted C6 to C30 aryl, or a combination thereof. Where R h R i and R j Each of the following 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, a substituted or unsubstituted C6 to C30 aryl, or a combination thereof. Where R k It can be 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, a substituted or unsubstituted C6 to C30 aryl, or a combination thereof. Where R l 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, a substituted or unsubstituted C6 to C30 aryl, or a combination thereof, and R 2 To R 4 At least one of them is selected from -OR b -O(CO)R c -NR d R e -NR f (COR g ) 、 -NR h C(NR i )R j -SR k and -S(CO)R l , Where R b It can be 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, a substituted or unsubstituted C6 to C30 aryl, or a combination thereof. Where R c It is hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, or a combination thereof. Where R d and R e Each of the following 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, a substituted or unsubstituted C6 to C30 aryl, or a combination thereof. Where R f and R g Each of the following 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, a substituted or unsubstituted C6 to C30 aryl, or a combination thereof. Where R h R i and R j Each of the following 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, a substituted or unsubstituted C6 to C30 aryl, or a combination thereof. Where R k It can be 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, a substituted or unsubstituted C6 to C30 aryl, or a combination thereof. Where R l It is hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, or a combination thereof.

9. The semiconductor photoresist composition according to claim 8, wherein R 2 To R 4 At least one of them is selected from -OR b and -O(CO)R c , Where R b It can be 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, a substituted or unsubstituted C6 to C30 aryl, or a combination thereof. Where R c It is hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, or a combination thereof.

10. The semiconductor photoresist composition according to claim 9, wherein R 1 Selected from substituted or unsubstituted C1 to C8 alkyl, substituted or unsubstituted C3 to C8 cycloalkyl, substituted or unsubstituted C2 to C8 alkenyl, substituted or unsubstituted C2 to C8 ynyl, substituted or unsubstituted C6 to C20 aryl, and substituted or unsubstituted C7 to C20 aralkyl. R b It is a substituted or unsubstituted C1 to C8 alkyl, a substituted or unsubstituted C3 to C8 cycloalkyl, a substituted or unsubstituted C2 to C8 alkenyl, a substituted or unsubstituted C2 to C8 alkynyl, a substituted or unsubstituted C6 to C20 aryl, or a combination thereof, and R c It is hydrogen, substituted or unsubstituted C1 to C8 alkyl, substituted or unsubstituted C3 to C8 cycloalkyl, substituted or unsubstituted C2 to C8 alkenyl, substituted or unsubstituted C2 to C8 alkynyl, substituted or unsubstituted C6 to C20 aryl, or a combination thereof.

11. The semiconductor photoresist composition according to claim 1, wherein the organometallic compound is represented by chemical formula 3 or chemical formula 4: Chemical formula 3 R 5 z SnO (2-(z / 2)-(x / 2)) (OH) x , In chemical formula 3, R 5 For C1 to C31 hydrocarbon groups, 0 < z ≤ 2, and 0 < (z+x) ≤ 4; and Chemical Formula 4 R 6 a Sn b X c Y d , In chemical formula 4, R 6 The substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 aliphatic unsaturated organogroup containing one or more double bonds or triple bonds, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C4 to C30 heteroaryl, carbonyl, ethylene oxide, propylene oxide, or combinations thereof. X represents sulfur, selenium, or tellurium. Y is -OR m or -OC(=O)R n , Where R m It is 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, a substituted or unsubstituted C6 to C30 aryl, or a combination thereof, and R n 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, a substituted or unsubstituted C6 to C30 aryl, or a combination thereof, and a, b, c, and d are each independent integers from 1 to 20.

12. A method for forming a pattern, comprising: Form the etch target layer on the substrate; A semiconductor photoresist composition as described in claim 1 is coated onto the etched target layer to form a photoresist film; The photoresist film is patterned to form a photoresist pattern; as well as The photoresist pattern is used as an etching mask to etch the target layer.

13. A system for forming patterns, comprising: Apparatus for forming an etched target layer on a substrate; Apparatus for coating the semiconductor photoresist composition as described in claim 1 onto the etched target layer to form a photoresist film; Apparatus for patterning the photoresist film to form a photoresist pattern; as well as Apparatus for etching the target layer by using the photoresist pattern as an etching mask.

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