Semiconductor photoresist composition and method of forming pattern using the same

Abstract

Disclosed are a semiconductor photoresist composition and a method of forming or providing a pattern using the same, the semiconductor photoresist composition including an organometallic compound, a pyrrole-based compound including pyrrole, a pyrrole derivative, or a combination thereof, and a solvent.

Description

[0001] Cross-reference of related applications

[0002] This application claims priority and benefit to Korean Patent Application No. 10-2024-0160355, filed on November 12, 2024, with the Korean Intellectual Property Office, the entire contents of which are incorporated herein by reference. Technical Field

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

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

[0005] Extreme ultraviolet (EUV) lithography is achieved by developing compatible photoresists that can be applied at a spatial resolution of 16 nanometers or less. Efforts have been made to address the inadequacies or unsuitability of chemically amplified (CA) photoresists for next-generation devices, such as insufficient resolution, photosensitivity, and feature roughness (also known as line-edge roughness or LER).

[0006] The inherent image blurring caused by acid-catalyzed reactions in polymeric or similar photoresists limits resolution at small feature sizes, a long-standing experience in electron beam lithography. Chemically amplified (CA) photoresists are designed for high sensitivity, but their elemental composition reduces light absorption at a wavelength of 13.5 nm, thus decreasing their sensitivity. Therefore, CA photoresists may present additional challenges under EUV exposure.

[0007] Furthermore, CA photoresists may face difficulties with small feature sizes due to roughness issues, and the line edge roughness (LER) of CA photoresists has been experimentally shown to increase because the photosensitivity is reduced in part due to the nature of the acid catalyst process. Therefore, due to these defects and problems with CA photoresists, the semiconductor industry needs or expects a new type of high-performance photoresist.

[0008] To overcome the drawbacks of chemically amplified (CA) organic photosensitive compositions, inorganic photosensitive compositions have been investigated. Inorganic photosensitive compositions are primarily or dominantly used for negative tone patterning through chemical modification via non-chemical amplification mechanisms, thereby achieving resistance to developer composition removal. Inorganic compositions contain inorganic elements with higher EUV absorbance than hydrocarbons, thus ensuring sensitivity through non-chemical amplification mechanisms. Furthermore, they are less sensitive to stochastic effects, resulting in lower line edge roughness and fewer defects.

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

[0010] These materials are effective or suitable for large-pitch patterning of dual-layer configurations in terms of far-ultraviolet (deep UV) light, X-rays, and electron beam sources. Impressive performance was achieved for 15 nm half-pitch (HP) imaging using cationic hafnium oxide sulfate (HfSOx) materials with peroxide complexing agents via projection EUV exposure. This system exhibits top performance among non-CA photoresists and has practical photosensitivity close to that required for EUV photoresists. However, hafnium oxide sulfate materials with peroxide complexing agents have some practical drawbacks. First, these materials are coated in a mixture of corrosive sulfuric acid / hydrogen peroxide and have insufficient or unsuitable shelf-life stability. Structural changes to improve the performance of the composite mixture are not readily available. Third, development must be carried out in a very high concentration of 25 wt% tetramethylammonium hydroxide (TMAH) solution and / or similar solutions.

[0011] Molecules including tin (Sn) possess excellent or suitable extreme ultraviolet absorption. For organotin polymers, alkyl ligands achieve negative tone patterning that cannot be removed by organic developers through light absorption and / or the resulting secondary electron dissociation, and crosslinking with adjacent chains via oxo bonds. While such organotin polymers exhibit significantly or substantially improved sensitivity while maintaining resolution and line edge roughness, the patterning properties should be further improved or enhanced for commercial availability. Summary of the Invention

[0012] Some exemplary embodiments of this disclosure provide semiconductor photoresist compositions that exhibit excellent resolution characteristics and pattern adhesion by reducing the influence of variables during patterning, thereby improving critical dimension (CD) stability.

[0013] Some exemplary embodiments provide methods for forming or providing patterns using semiconductor photoresist compositions.

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

[0015] Semiconductor photoresist compositions according to some exemplary embodiments include organometallic compounds; pyrrole compounds including pyrrole, pyrrole derivatives, or combinations thereof; and solvents.

[0016] Patterns formed using semiconductor photoresist compositions according to some exemplary embodiments can achieve excellent resolution by improving CD stability. Attached Figure Description

[0017] 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.

[0018] Figures 1A-1E This is a cross-sectional view illustrating a method for forming patterns using a semiconductor photoresist composition according to some exemplary embodiments.

[0019] Explanation of icon numbers

[0020] 100: Substrate;

[0021] 102: Film;

[0022] 104: Resist underlayer;

[0023] 106: Photoresist film;

[0024] 106a: Unexposed area;

[0025] 106b: Exposure area;

[0026] 108: Photoresist pattern;

[0027] 110: Patterned mask;

[0028] 112: Organic film pattern;

[0029] 114: Thin film pattern. Detailed Implementation

[0030] The subject matter of this disclosure will be described more fully below with reference to the accompanying drawings, which illustrate embodiments of the disclosure. As those skilled in the art will recognize, the described embodiments can be modified in one or more suitable ways without departing from the spirit or scope of this disclosure. The drawings and descriptions are to be regarded as illustrative in nature and not restrictive. The same reference numerals always refer to the same elements, and their repeated description may not be provided in the specification.

[0031] For clarity of this disclosure, certain descriptions and relationships may be omitted, and throughout the disclosure, identical or similar configurations or arrangements of elements may be designated by the same reference numerals. Furthermore, because the dimensions and thicknesses of each configuration shown in the figures may be arbitrarily depicted for better understanding and ease of illustration, embodiments of this disclosure are not necessarily limited thereto.

[0032] In the accompanying drawings, the thickness of layers, films, panels, regions, and / or the like may be exaggerated for clarity. The thickness of a portion of a layer or region and / or the like may be exaggerated for ease of illustration. It should be understood that if (e.g., when) an element such as a layer, film, region, or substrate is referred to as being "on" another element, it may be directly on that other element, or there may be intermediate elements between them. Conversely, if (e.g., when) an element is referred to as being "directly on" another element, there are no intermediate elements between them.

[0033] When describing embodiments of this disclosure, the word "may" means "one or more embodiments of this disclosure".

[0034] In the context of this application and unless otherwise defined, the terms "use", "currently being used" and "being used" may be considered synonymous with the terms "adopted", "currently being adopted" and "being adopted", respectively.

[0035] As used herein, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise. Singular expressions include plural expressions unless the context clearly indicates otherwise.

[0036] As used herein, the terms "and / or" or "or" include any and all combinations of one or more of the listed items.

[0037] Throughout this disclosure, expressions such as "at least one," "one of," and "selected from" modify the entire list of elements and not individual elements of the list when they precede it (e.g., when). 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," and / or similar expressions indicate only a, only b, only c, simultaneously (e.g., simultaneously) a and b, simultaneously (e.g., simultaneously) a and c, simultaneously (e.g., simultaneously) b and c, indicating all of a, b, and c, or variations thereof.

[0038] As used herein, "combinations thereof" may refer to mixtures, stacks, complexes, copolymers, alloys, blends, reaction products and / or similar substances of the components.

[0039] In this disclosure, the terms "comprise(s) / comprising," "include(s) / including," or "have / has / having" are understood to specify the presence of the stated features, integers, steps, operations, elements, and / or components, but do not exclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and / or groups thereof. Furthermore, the terms "comprise(s) / comprising," "include(s) / including," "have / has / having," or 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 without or substantially without the presence of other features, integers, steps, operations, elements, components, and / or groups thereof.

[0040] As used herein, the terms "substantially," "about," or similar terms are used as approximate terms rather than terms of degree and are intended to describe inherent deviations in measured or calculated values ​​that would be recognized by a person skilled in the art. "About," as used herein, includes the stated value and refers to an acceptable deviation of the particular value as determined by a person skilled in the art, taking into account the measurement in question and errors associated with the measurement of the particular quantity (e.g., limitations of the measurement system). For example, "about" may refer to 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 (e.g., when) the terms "about," "approximately," or "substantially" are not expressly recited in a given element (e.g., a claim element), the scope of such elements is intended to include minor variations or variations understood by 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 a person skilled in the art, and elements (e.g., the claimed element) should be interpreted accordingly to cover such equivalents.

[0041] 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 (and including) the described minimum value of 1.0 and the described maximum value of 10.0, such as having a minimum value equal to or greater than 1.0 and a maximum value equal to or less than 10.0, like, 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 modify the disclosure (including the claims) to expressly describe any subranges falling within the scope expressly described herein.

[0042] As used herein, "substituted" refers to a hydrogen atom replaced by deuterium, halogen, hydroxyl, carboxyl, thiol, cyano, nitro, -NRR' (where R and R' are each independently hydrogen, substituted or unsubstituted C1 to C30 saturated or unsaturated aliphatic hydrocarbon groups, substituted or unsubstituted C3 to C30 saturated or unsaturated alicyclic hydrocarbon groups, or substituted or unsubstituted C6 to C30 aromatic hydrocarbon groups), -SiRR'R" (where R, R', and R" are each independently hydrogen, substituted or unsubstituted C1 to C30 saturated or unsaturated aliphatic hydrocarbon groups, etc. The substituents are C3 to C30 saturated or unsaturated alicyclic hydrocarbon groups (or 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 thioether groups, or combinations thereof. "Unsubstituted" means that the hydrogen atom is not replaced by another substituent and the hydrogen atom is retained.

[0043] As used herein, unless otherwise defined, "alkyl" refers to a straight-chain or branched aliphatic hydrocarbon group. An alkyl group can 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).

[0044] The alkyl group can be a substituted or unsubstituted C1 to C8 alkyl group. For example, the alkyl group can be a substituted or unsubstituted C1 to C7 alkyl group, a substituted or unsubstituted C1 to C6 alkyl group, or a substituted or unsubstituted C1 to C5 alkyl group. For example, a substituted or unsubstituted C1 to C5 alkyl group can be methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, or 2,2-dimethylpropyl.

[0045] As used herein, unless otherwise defined, "cycloalkyl" refers to a monovalent cyclic aliphatic saturated hydrocarbon group.

[0046] The cycloalkyl group can be a substituted or unsubstituted C3 to C8 cycloalkyl group, such as a substituted or unsubstituted C3 to C7 cycloalkyl group, or a substituted or unsubstituted C3 to C6 cycloalkyl group. For example, the cycloalkyl group can be cyclopropyl, cyclobutyl, cyclopentyl, or cyclohexyl, but is not limited thereto.

[0047] As used herein, "aryl" refers to a cyclic substituent in which all atoms have p orbitals and these p orbitals are conjugated, and may include monocyclic or polycyclic functional groups (e.g., rings sharing adjacent carbon atom pairs).

[0048] As used herein, "heteroaryl" can refer to an aryl group comprising 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 (e.g., when) a heteroaryl group comprises two or more rings, the two or more rings may be fused together. If (e.g., when) a heteroaryl group is a fused ring, each ring may comprise one to three heteroatoms.

[0049] As used herein, unless otherwise defined, "alkenyl" refers to an aliphatic unsaturated alkenyl group that includes at least one double bond (e.g., a carbon-carbon double bond) as a straight-chain or branched aliphatic hydrocarbon group.

[0050] As used herein, unless otherwise defined, "alkynyl" refers to an aliphatic unsaturated alkynyl group that includes at least one triple bond (e.g., a carbon-carbon triple bond) as a straight-chain or branched aliphatic hydrocarbon group.

[0051] The following describes a semiconductor photoresist composition according to some exemplary embodiments.

[0052] Semiconductor photoresist compositions according to some exemplary embodiments include: an organometallic compound; a pyrrole compound including pyrrole, pyrrole derivatives, or combinations thereof; and a solvent.

[0053] A method for forming or providing a pattern using a semiconductor photoresist composition comprising an organometallic compound includes coating the photoresist composition onto an etch target layer such that the organometallic compound and / or its cluster molecules in the 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.

[0054] In the embodiments, the patterning of metal oxides is affected by various variables, such as temperature, solvent, concentration, catalyst, atmosphere, and / or the like, and, for example, the smaller the pattern size, the greater the impact. Because patterns formed by photoresist compositions comprising organometallic compounds have very small dimensions in the range of a few nanometers to tens of nanometers, metal oxide patterning may be more susceptible to process conditions than other photoresists.

[0055] The concentration of nitrogen oxides (NOx) in the atmosphere affects patterning performed using photoresist compositions comprising organometallic compounds. NOx is a highly reactive substance present in the atmosphere and can react with atmospheric moisture, sunlight, and / or the like to cause phenomena such as smog and / or the like. If, for example, the NOx concentration exceeds a set or predetermined level, there is a problem where the pattern width and / or the like, as inspected after development, differs from the target value.

[0056] In the embodiments, pyrrole has an aromatic ring including nitrogen atoms, and because it is rich in electrons within the ring, it can be readily oxidized and readily react with electrophilic agents. Therefore, in the embodiments of this disclosure, a photoresist composition has been developed that can suppress or reduce the amplification of free radical reactions by introducing pyrrole compounds and allowing organometallic compounds to bind with the pyrrole compounds rather than with nitrogen oxides in the air during the patterning process, and can also suppress or reduce the propagation of free radicals generated by the reaction between the organometallic compounds and nitrogen oxides, thereby suppressing or reducing the phenomenon of pattern width deformation caused by changes in the concentration of nitrogen oxides in the air.

[0057] Pyrrole compounds can be represented by chemical formula 1:

[0058] Chemical Formula 1

[0059]

[0060] In chemical formula 1, L 1 To L 5 Each of these groups is independently a single bond (e.g., a single covalent bond), a carbonyl group, a substituted or unsubstituted C1 to C10 alkylene group, a substituted or unsubstituted C2 to C10 alkenyl group, a substituted or unsubstituted C3 to C10 cycloalkylene group, a substituted or unsubstituted C6 to C20 aryl group, or a combination thereof, and, for example, L 1 To L 5 Each is independently a single bond (e.g., a single covalent bond), a carbonyl group, a substituted or unsubstituted C1 to C10 alkylene group or a combination thereof.

[0061] In chemical formula 1, R 1 To R 5 Each group is independently hydrogen, deuterium, hydroxyl, halogen, cyano, amino, amino, aldehyde, acetyl, carboxyl, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C2 to C10 alkenyl, substituted or unsubstituted C2 to C10 alkynyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C6 to C20 aryl, or combinations thereof. For example, R 1 To R 5 Each group is independently hydrogen, hydroxyl, halogen, cyano, amino, amino, aldehyde, acetyl, carboxyl, substituted or unsubstituted C1 to C5 alkyl, substituted or unsubstituted C2 to C5 alkenyl, substituted or unsubstituted C2 to C5 ynyl, or a combination thereof. For example, R 1 To R 5Each of the following is independently hydrogen, hydroxyl, halogen, cyano, amino, amino, aldehyde, acetyl, carboxyl, substituted or unsubstituted C1 to C5 alkyl groups or combinations thereof.

[0062] Pyrrole compounds refer to compounds including pyrrole, oligopyrrole, pyrrole derivatives, and combinations thereof, for example, at least one selected from Group 1:

[0063] Group 1

[0064] .

[0065] The content of pyrrole compounds, based on 100% by weight of the semiconductor photoresist composition, may be from about 0.01% by weight to about 5% by weight, from about 0.02% by weight to about 5% by weight, from about 0.03% by weight to about 5% by weight, or from about 0.05% by weight to about 5% by weight. If (for example, when) the pyrrole compounds are within the above-mentioned content range, it is possible to maintain the pattern formation while suppressing or reducing the influence of NOx.

[0066] The content of the organometallic compound, based on 100% by weight of the semiconductor photoresist composition, may be from about 0.5% by weight to about 30% by weight. In the semiconductor photoresist composition according to some exemplary embodiments, the content of the organometallic compound, based on 100% by weight of the semiconductor photoresist composition, may 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, or for example, from about 1% by weight to about 5% by weight.

[0067] Semiconductor photoresist compositions according to some exemplary embodiments can improve photoresist sensitivity by including organometallic compounds in the above-described content range.

[0068] Organometallic compounds can be organotin compounds that include at least one selected from organooxy groups and organocarbonyloxy groups.

[0069] Organometallic compounds can be represented by chemical formula 2:

[0070] Chemical formula 2

[0071]

[0072] In chemical formula 2,

[0073] R 6Selected 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.

[0074] R 7 To R 9 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, an alkoxy, or an aryloxy (-OR) group. 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), a carboxyl or acyloxy group (-O(CO)R c , where R c The group 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 combinations thereof, alkylamide and dialkylamide (-NR). d R e , where R d and R e Each of the following is independently hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof), or an amide group (-NR). f (COR g ), 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), and an amidine (-NR) group. h C(NR i )Rj , 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), alkylthio and / or arylthio (-SR). k , where R k The 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 combinations thereof, and thiocarbonyl (-S(CO)R) l , where R l (which 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 selected from R 7 To R 9 At least one of them is an alkoxy and / 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), a carboxyl or acyloxy group (-O(CO)R c , where R c The group 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 combinations thereof, alkylamide and / or dialkylamide (-NR) d R e , where R d and R e Each of the following is independently hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof), or an amide group (-NR).f (COR g ), 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), and an amidine (-NR) group. h C(NR i )R j , 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), alkylthio and / or arylthio (-SR). k , where R k The 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 combinations thereof, and / or thiocarbonyl (-S(CO)R) l , 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.

[0075] Selected from R 7 To R 9 At least one of them may be selected from alkoxy and aryloxy (-OR) b , where R b The 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 combinations thereof, and carboxyl or acyloxy (-O(CO)R) c , where R cIt 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.

[0076] In the embodiments, because the compound represented by chemical formula 2 includes -OR b or -O(CO)R c As ligands, patterns formed or provided using semiconductor photoresist compositions containing compounds according to embodiments of the present disclosure can exhibit excellent limiting resolution.

[0077] In the embodiment, -OR b or -O(CO)R c The ligands can determine the solubility of the compound represented by chemical formula 2 in the solvent.

[0078] R 6 It may 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 ynyl, substituted or unsubstituted C6 to C20 aryl, and substituted or unsubstituted C7 to C20 aralkyl.

[0079] R b It can 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

[0080] R c It can 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.

[0081] R 6 It can be methyl, ethyl, propyl, butyl, isopropyl, tert-butyl, 2,2-dimethylpropyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, vinyl, propenyl, butenyl, ethynyl, propynyl, butynyl, phenyl, tolyl, xylyl, benzyl, or combinations thereof.

[0082] R bIt can be ethyl, propyl, butyl, isopropyl, tert-butyl, 2,2-dimethylpropyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, vinyl, propenyl, butenyl, ethynyl, propynyl, butynyl, phenyl, tolyl, xylyl, benzyl, or combinations thereof, and R c It can be hydrogen, ethyl, propyl, butyl, isopropyl, tert-butyl, 2,2-dimethylpropyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, vinyl, propenyl, butenyl, ethynyl, propynyl, butynyl, phenyl, tolyl, xylyl, benzyl, or a combination thereof.

[0083] In the embodiments, the organometallic compound may be represented by chemical formula 3 or chemical formula 4.

[0084] Chemical formula 3

[0085] R 10 z SnO (2-(z / 2)-(x / 2)) (OH) x

[0086] In chemical formula 3,

[0087] R 10 For C1 to C31 hydrocarbon groups, 0 < z ≤ 2, and 0 < (z+x) ≤ 4;

[0088] Chemical Formula 4

[0089] R 11 a Sn b X c Y d

[0090] In chemical formula 4,

[0091] R 11 The following are substituted or unsubstituted C1 to C20 alkyl groups, substituted or unsubstituted C3 to C20 cycloalkyl groups, substituted or unsubstituted C2 to C20 aliphatic unsaturated organic groups including one or more double bonds (e.g., carbon-carbon double bonds) or triple bonds (e.g., carbon-carbon triple bonds), substituted or unsubstituted C6 to C30 aryl groups, substituted or unsubstituted C4 to C30 heteroaryl groups, carbonyl groups, ethylene oxide groups, propylene oxide groups, or combinations thereof.

[0092] X is sulfur (S), selenium (Se), or tellurium (Te).

[0093] Y is –OR m or -OC(=O)R n ,

[0094] Where R mIt 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, 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 each of a, b, c and d is an integer from 1 to 20 independently.

[0095] In addition to the organometallic compounds, pyrrole compounds, and solvents described above, the semiconductor photoresist composition according to exemplary embodiments may also include a resin.

[0096] The resin may be a phenolic resin comprising at least one aromatic moiety listed in Group 2.

[0097] Group 2

[0098]

[0099] The weight-average molecular weight of the resin can be from about 500 g / mol to about 20,000 g / mol.

[0100] In the embodiments, it is suitable or desirable for the semiconductor photoresist composition to consist of the above-mentioned organometallic compound, pyrrole compounds including pyrrole, pyrrole derivatives or combinations thereof, solvent and resin.

[0101] The solvent included in the semiconductor photoresist composition according to an exemplary embodiment may be an organic solvent, and may be, for example, an aromatic compound (e.g., xylene, toluene and / or the like), an alcohol (e.g., 4-methyl-2-pentanol, 4-methyl-2-propanol, 1-butanol, methanol, isopropanol, 1-propanol and / or the like), an ether (e.g., anisole, tetrahydrofuran and / or the like), an ester (n-butyl acetate, propylene glycol monomethyl ether acetate, ethyl acetate, ethyl lactate and / or the like), a ketone (e.g., methyl ethyl ketone, 2-heptanone and / or the like), or a mixture thereof, but is not limited thereto.

[0102] However, the semiconductor photoresist composition according to the above embodiments may further include additives as needed or desired. 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 are not limited thereto.

[0104] The crosslinking agent can be, for example, a melamine crosslinking agent, a substituted urea crosslinking agent, an acrylic crosslinking agent, an epoxy crosslinking agent, a polymer crosslinking agent, or a combination thereof, but is not limited thereto. It can be a crosslinking agent having at least two crosslinking-forming substituents, such as compounds of methoxymethylated oxaluron, butoxymethylated oxaluron, methoxymethylated melamine, butoxymethylated melamine, methoxymethylated benzoguanamine, butoxymethylated benzoguanamine, 4-hydroxybutyl acrylate, acrylic acid, urethane acrylate, methacrylate, 1,4-butanediol diglycidyl ether, glycidyl, 1,2-cyclohexanedicarboxylic acid diglycidyl ether, trimethylpropane triglycidyl ether, 1,3-bis(glycidyloxypropyl)tetramethyldisiloxane, methoxymethylated urea, butoxymethylated urea, methoxymethylated thiourea, and / or similar compounds.

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

[0106] Organic acids may include, but are not limited to, 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.

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

[0108] The amount of each additive used can be controlled according to the appropriate or desired properties.

[0109] In 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; and / or 3-methacryloyloxypropyltrimethoxysilane, 3-acryloyloxypropyltrimethoxysilane, p-styryltrimethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropylmethyldiethoxysilane; trimethoxy[3-(phenylamino)propyl]silane and / or similar compounds, but is not limited thereto.

[0110] Semiconductor photoresist compositions can be formed into patterns with a high aspect ratio and no (or substantially no) collapse. Therefore, in order to form fine patterns with widths of, for example, about 5 nanometers to about 100 nanometers (e.g., 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 (e.g., 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 some exemplary embodiments can be used to implement extreme ultraviolet lithography using EUV light sources with wavelengths of about 13.5 nanometers.

[0111] According to some exemplary embodiments, a method for forming a pattern using the above-described semiconductor photoresist composition is provided. For example, the pattern produced may be a photoresist pattern.

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

[0113] The following is for reference. Figures 1A to 1E Describes a method for forming patterns using a semiconductor photoresist composition. Figures 1A to 1E A cross-sectional view illustrating a method for forming a pattern using a semiconductor photoresist composition according to some exemplary embodiments.

[0114] refer to Figure 1A Prepare the object to be etched. The object to be etched can be a thin film 102 formed on the semiconductor substrate 100. Hereinafter, the object to be etched is defined as the thin film 102. Clean the surface of the thin film 102 to remove impurities and / or similar substances remaining thereon. The thin film 102 can be, for example, a silicon nitride layer, a polysilicon layer, and / or a silicon oxide layer.

[0115] Subsequently, the resist underlay composition used to form or provide the resist underlay 104 is spin-coated onto the surface of the cleaned film 102. However, the embodiments are not limited thereto, and various suitable coating methods can be used, such as spraying, dip coating, blade coating, printing methods such as inkjet printing and / or screen printing and / or similar methods.

[0116] The coating process for the resist underlayer can be omitted; the following description includes the coating process for the resist underlayer.

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

[0118] The resist underlayer 104 is formed between the substrate 100 and the photoresist film 106, so that if (for example, when) light reflected from the interface between the substrate 100 and the photoresist film 106 or from the hard mask between layers is scattered into the unintended photoresist area, non-uniformity can be prevented or reduced and the patterning capability of the photoresist linewidth can be improved.

[0119] refer to Figure 1B A photoresist film 106 is formed by coating a semiconductor photoresist composition onto a resist underlayer 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 an embodiment, forming a pattern using a semiconductor photoresist composition may include coating the semiconductor photoresist composition onto a substrate 100 having a thin film 102 by spin coating, slot coating, inkjet printing and / or similar methods, and then drying it to form a photoresist film 106.

[0121] The semiconductor photoresist composition has been described in detail, and its repetitive description need not be repeated here.

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

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

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

[0125] For example, according to some exemplary embodiments, the light used for exposure can be light with a wavelength of about 5 nanometers to about 150 nanometers and a high energy wavelength, such as extreme ultraviolet (EUV; wavelength 13.5 nanometers), electron beam (E-Beam), and / or similar light.

[0126] The exposed region 106b of the photoresist film 106 forms a polymer by utilizing a cross-linking reaction (e.g., condensation between organometallic compounds, such as a condensation reaction)), thereby having a different solubility than the unexposed region 106a of the photoresist film 106.

[0127] Subsequently, a second baking process is performed on the substrate 100. The second baking process can be performed at a temperature of about 90°C to about 200°C. Due to the second baking process, the exposed areas 106b of the photoresist film 106 become less soluble relative to the developer.

[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 organic solvents such as 2-heptanone and / or similar solvents to complete the photoresist pattern 108 corresponding to a negative image.

[0129] As described above, the developer used in the patterning method according to some exemplary embodiments can be an organic solvent. The organic solvent used in the patterning method according to some exemplary embodiments can 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 some exemplary embodiments is not necessarily limited to negative images, but can be formed to have positive images. In embodiments, the developer used to form or provide a positive image can be a quaternary ammonium hydroxide composition, such as tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, or a combination thereof.

[0131] As described above, exposure to light such as extreme ultraviolet (EUV; wavelength 13.5 nm), electron beam (E-Beam) and / or similar light, and light such as i-line (wavelength about 365 nm), KrF excimer laser (wavelength about 248 nm), ArF excimer laser (wavelength about 193 nm) and / or similar light, can provide a photoresist pattern 108 with a width of about 5 nm to about 100 nm. For example, the photoresist pattern 108 can 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 an embodiment, the photoresist pattern 108 may have a pitch of less than or equal to about 50 nanometers (e.g., less than or equal to about 40 nanometers, for example, less than or equal to about 30 nanometers, for example, less than or equal to about 20 nanometers, or for example, less than or equal to about 15 nanometers) and a linewidth roughness of 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. An organic film pattern 112 is formed through the etching process. The organic film pattern 112 may also have a width corresponding to the photoresist pattern 108.

[0134] refer to Figure 1E The exposed thin film 102 is etched by applying a photoresist pattern 108 as an etching mask. As a result, the thin film is formed into 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 and / or a mixture thereof.

[0136] In the exposure process, the width of the thin film pattern 114 formed using the photoresist pattern 108 can correspond to the width of the photoresist pattern 108, which is formed by an exposure process using an EUV light source. For example, the thin film pattern 114 can have a width of about 5 nanometers to about 100 nanometers, which is equal to that of the photoresist pattern 108. For example, the thin film pattern 114 formed by the photoresist pattern 108 formed by an exposure process using an EUV light source can have a width of about 5 nanometers to about 90 nanometers, about 5 nanometers to about 80 nanometers, about 5 nanometers to about 70 nanometers, about 5 nanometers to about 60 nanometers, about 5 nanometers to about 50 nanometers, about 5 nanometers to about 40 nanometers, about 5 nanometers to about 30 nanometers, or about 5 nanometers to about 20 nanometers, and more specifically, a width of less than or equal to about 20 nanometers, like the photoresist pattern 108.

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

[0138] Synthesis of organometallic compounds

[0139] Synthesis example 1

[0140] 40.7 g of tert-butyltriphenyltin (t-butylSnPh3) and 300 g of propionic acid were added to a 250 mL double-necked round-bottom flask, and the mixture was heated under reflux for 24 hours. Unreacted propionic acid was removed 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 tert-amyltin trichloride (t-AmylSnCl3), and while maintaining the temperature at 0°C, 7.4 g of diethylamine and 6.1 g of ethanol were added, followed by stirring at room temperature for 1 hour. When the reaction was complete, the result 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 compositions

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

[0149] The organometallic compounds represented by chemical formulas 5 and 6 obtained in Synthetic Examples 1 and 2 were each dissolved at a concentration of 3% by weight in propylene glycol monomethyl ether acetate (PGMEA), and pyrrole compounds C1 to C3 and comparative example compound C4 or C5 were each added and dissolved at the concentrations listed in Table 1. The mixtures were then filtered through a 0.1-micron polytetrafluoroethylene (PTFE) syringe filter to prepare the respective semiconductor photoresist compositions according to the Examples and Comparative Examples. These compositions were coated onto silicon wafers to a thickness of 240 angstroms, and then patterned films were fabricated using post-apply bake (PAB), exposure, post-exposure bake (PEB), and development processes.

[0150] Table 1

[0151]

[0152] C1: Pyrrole-2-carboxaldehyde

[0153] C2: Pyrrole-2-carbonitrile

[0154] C3: 2-(Trifluoroacetyl)pyrrole

[0155] C4: Benzoic acid

[0156] C5: 4-Methylbenzoic acid

[0157] Evaluation 1: Evaluation of sensitivity and LER characteristics

[0158] Each photoresist composition according to the examples and comparative examples was spin-coated at 1500 rpm for 30 seconds onto a 200 mm circular silicon wafer on which hexamethyldisilazane (HMDS) was deposited, baked at 110°C for 60 seconds (post-apply bake, PAB) and then left at room temperature (23±2°C) for 30 seconds.

[0159] Then, a 50-nanometer-wide linear array is projected onto the wafer coated with a photoresist composition using EUV light (Lawrence Berkeley National Laboratory Micro Exposure Tool, MET). Here, the pad exposure time is adjusted to ensure that EUV light is applied to each pad at an increased dose.

[0160] Then, after exposure, the resist and substrate were baked on a hot plate at 160°C for 120 seconds. The baked film was developed in PGMEA solvent to form a negative image. Finally, the obtained film was baked again on a hot plate at 150°C for 2 minutes to complete the process.

[0161] The response of resist linewidth to changes in exposure dose (energy) was measured using critical dimension-scanning electron microscopy (CD-SEM). Sensitivity to exposure dose was confirmed from different resist linewidth values ​​formed according to various exposure doses, and the sensitivity and LER were evaluated according to the following criteria. The results are shown in Table 2.

[0162] Sensitivity evaluation criteria

[0163] - A: Less than 16 mJ / cm 2

[0164] - B: Greater than or equal to 16 mJ / cm 2 And less than 18 mJ / cm 2

[0165] - C: Greater than or equal to 18 mJ / cm 2

[0166] LER evaluation criteria

[0167] - ○: Less than 2 nanometers

[0168] - △: Greater than or equal to 2 nanometers and less than 5 nanometers

[0169] - X: 5 nanometers or greater

[0170] Table 2

[0171]

[0172] As can be seen from the results in Table 2, the patterns formed using the semiconductor photoresist compositions according to Examples 1 to 9 exhibit superior sensitivity and lower LER compared to Comparative Examples 1 to 3.

[0173] Evaluation 2: CD Uniformity Evaluation

[0174] The semiconductor photoresist compositions according to Examples 1 to 9 and Comparative Examples 1 to 3 were spin-coated on a 200 mm circular silicon wafer at a speed of 1500 rpm for 30 seconds, and then heated at 110°C for 60 seconds.

[0175] Subsequently, a linear array with a linewidth of 180 nanometers was projected onto a wafer coated with a resist composition for photoresist using KrF light. The resist and substrate were then heated on a hot plate at 180°C for 120 seconds. The baked film was developed with propylene glycol monomethyl ether acetate solvent to form a negative image. Finally, it was baked at 200°C for 180 seconds to complete the process.

[0176] When NOx was absent in the atmosphere and when the NOx concentration was 0.015 ppm or higher, the CD value of the resist was measured using a critical dimension-scanning electron microscopy (CD-SEM), and this value was used to calculate the CD change (ΔCD(%)). The results are shown in Table 3. The NOx concentration was measured using a Sky2000-NOx detector (Safegas). The CD change was calculated according to the following equation.

[0177] Equation

[0178] ΔCD% = (CD ≥0.01ppm NOx / CD w / o NOx ) X 100

[0179] Table 3

[0180]

[0181] As can be seen from the results in Table 3, compared with Comparative Examples 1 to 3, the patterns formed using the semiconductor photoresist compositions according to Examples 1 to 9 exhibited smaller CD changes with changes in NOx concentration, such as excellent resistance to NOx effects.

[0182] Some embodiments of this disclosure have been described and illustrated above. However, those skilled in the art should understand that this disclosure is not limited to the described embodiments, and various suitable modifications and variations can be made without departing from the spirit and scope of this disclosure. Therefore, such modified or varied embodiments can be understood without separating them from the technical concept and aspects of this disclosure, and the modified embodiments are within the scope of the claims of this disclosure and their equivalents.

Claims

1. A semiconductor photoresist composition, comprising: Organometallic compounds; Pyrrole compounds, including pyrrole, pyrrole derivatives, or combinations thereof; as well as Solvent.

2. The semiconductor photoresist composition according to claim 1, wherein the pyrrole compound is represented by chemical formula 1: Chemical Formula 1 in, In chemical formula 1, L 1 To L 5 Each of the following is independently a single bond, carbonyl, substituted or unsubstituted C1 to C10 alkylene, substituted or unsubstituted C2 to C10 alkenyl, substituted or unsubstituted C3 to C10 cycloalkylene, substituted or unsubstituted C6 to C20 arylene, or a combination thereof, and R 1 To R 5 Each of the following groups is independently hydrogen, deuterium, hydroxyl, halogen, cyano, amino, amino, aldehyde, acetyl, carboxyl, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C2 to C10 alkenyl, substituted or unsubstituted C2 to C10 alkynyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C6 to C20 aryl, or a combination thereof.

3. The semiconductor photoresist composition according to claim 2, wherein L of chemical formula 1 1 To L 5 Each is independently a single bond, carbonyl, substituted or unsubstituted C1 to C10 alkylene groups or combinations thereof.

4. The semiconductor photoresist composition according to claim 2, wherein R of chemical formula 1 1 To R 5 Each of the following is independently hydrogen, hydroxyl, halogen, cyano, amino, amino, aldehyde, acetyl, carboxyl, substituted or unsubstituted C1 to C5 alkyl groups or combinations thereof.

5. The semiconductor photoresist composition according to claim 1, wherein the pyrrole compound is at least one selected from group 1: Group 1 。 6. The semiconductor photoresist composition according to claim 1, wherein the content of the pyrrole compound is from 0.01% to 5% by weight based on 100% by weight of the semiconductor photoresist composition.

7. The semiconductor photoresist composition according to claim 1, wherein the semiconductor photoresist composition further comprises additives, the additives comprising surfactants, crosslinking agents, leveling agents, organic acids, quenchers, or combinations thereof.

8. The semiconductor photoresist composition according to claim 1, wherein the organometallic compound comprises an organotin compound, and the organotin compound comprises at least one selected from organooxy and organocarbonyl groups.

9. The semiconductor photoresist composition according to claim 1, wherein the organometallic compound is represented by chemical formula 2: Chemical formula 2 in, In chemical formula 2, R 6 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 7 To R 9 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 derived from -OR b The alkoxy or aryloxy group represents R. b 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; derived from -O(CO)R c The carboxyl or acyl group represents R. c 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; derived from -NR d R e The alkylamide group or dialkylamide group represents R. d and R e 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, a substituted or unsubstituted C6 to C30 aryl, or a combination thereof; and is composed of -NR f (COR g ) represents an amide group, where R f and R g 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, a substituted or unsubstituted C6 to C30 aryl, or a combination thereof; and is composed of -NR h C(NR i )R j The amidine group is represented by R. h R i and R j 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, a substituted or unsubstituted C6 to C30 aryl, or a combination thereof; derived from -SR k The alkylthio group and / or arylthio group are represented, wherein R k 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; or it is composed of -S(CO)R l The thiocarbonyl group represents 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. Selected from R 7 To R 9 At least one of the choices is OR b The alkoxy and aryloxy groups represent R. b 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; derived from -O(CO)R c The carboxyl or acyl group represents R. c 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; derived from -NR d R e The alkylamide group and dialkylamide group are represented, wherein R d and R e 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, a substituted or unsubstituted C6 to C30 aryl, or a combination thereof; and is composed of -NR f (COR g ) represents an amide group, where R f and R g 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, a substituted or unsubstituted C6 to C30 aryl, or a combination thereof; and is composed of -NR h C(NR i )R j The amidine group is represented by R. h R i and R j 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, a substituted or unsubstituted C6 to C30 aryl, or a combination thereof; derived from -SR k The alkylthio group and / or arylthio group are represented, wherein R k 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 derived from -S(CO)R l The thiocarbonyl group represents 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.

10. The semiconductor photoresist composition according to claim 9, wherein the composition is selected from R 7 To R 9 At least one of the choices is OR b The alkoxy and aryloxy groups represent R. b 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 is derived from -O(CO)R c The carboxyl or acyl group represents 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.

11. The semiconductor photoresist composition according to claim 10, wherein R 6 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 The 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 combinations 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.

12. 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 10 z SnO (2-(z / 2)-(x / 2)) (OH) x in, In chemical formula 3, R 10 For C1 to C31 hydrocarbon groups, 0 < z ≤ 2, and 0 < (z+x) ≤ 4; Chemical Formula 4 R 11 a Sn b X c Y d In chemical formula 4, R 11 The group comprises substituted or unsubstituted C1 to C20 alkyl groups, substituted or unsubstituted C3 to C20 cycloalkyl groups, substituted or unsubstituted C2 to C20 aliphatic unsaturated organic groups including one or more double or triple bonds, substituted or unsubstituted C6 to C30 aryl groups, substituted or unsubstituted C4 to C30 heteroaryl groups, carbonyl groups, ethylene oxide groups, propylene oxide groups, or combinations thereof. X is sulfur (S), selenium (Se), or tellurium (Te). Y is –OR m or -OC(=O)R n , Where R m The 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 combinations thereof, and R n 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 combinations thereof, and a, b, c, and d are each independent integers from 1 to 20.

13. A method for forming a pattern, comprising: Provide an etch target layer on the substrate; The 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.

14. The method for forming a pattern according to claim 13, wherein: The semiconductor photoresist composition further comprises at least one selected from surfactants, dispersants, hygroscopic agents, coupling agents, and combinations thereof.

15. The method for forming a pattern according to claim 14, wherein: The surfactant comprises at least one selected from sulfate esters, sulfonates, phosphate esters, soaps, amine salts, quaternary ammonium salts, polyethylene glycol, alkylphenol ethylene oxide adducts, polyols, nitrogen-containing vinyl polymers, and combinations thereof.

16. The method for forming a pattern according to claim 14, wherein: The amount of surfactant is from 0.001% to 3% by weight, based on 100% by weight of the semiconductor photoresist composition.

17. The method for forming a pattern according to claim 14, wherein: The dispersant comprises at least one selected from epoxy resin, polyvinyl alcohol, polyvinyl butyral, polyvinylpyrrolidone, glucose, sodium dodecyl sulfate, sodium citrate, oleic acid, linoleic acid, and combinations thereof.

18. The method of claim 13, wherein the method is performed in an atmosphere containing nitrogen oxides.

19. A photoresist pattern formed by the method of claim 13, wherein the photoresist pattern has a width of 5 nanometers to 100 nanometers.

20. A photoresist pattern formed by the method of claim 13, wherein the photoresist pattern is formed in an atmosphere containing nitrogen oxides.

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