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 may include an organometallic compound; a polymer additive including a structural unit represented by Chemical Formula 1; and a solvent.

Description

[0001] Cross-reference of related applications

[0002] This application claims priority and benefit to Korean Patent Application No. 10-2024-0060065, filed on May 7, 2024, with the Korean Intellectual Property Office, the entire disclosure of which is incorporated herein by reference. Technical Field

[0003] One or more embodiments of this disclosure relate to semiconductor photoresist compositions and methods of forming or providing patterns using said semiconductor photoresist compositions. 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, fine patterns (e.g., less than or equal to 20 nanometers) can be formed in the exposure process during the manufacturing of semiconductor devices (e.g., semiconductor chips).

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

[0006] In electron beam lithography, inherent image blurring due to acid-catalyzed reactions in the photoresist of a particular polymer type or variety has consistently limited the resolution of small feature sizes. Chemically amplified (CA) photoresists have been designed for high sensitivity. However, their elemental composition reduces light absorption at a wavelength of 13.5 nm, potentially decreasing their sensitivity, and CA photoresists may encounter further difficulties under EUV exposure.

[0007] Chemically amplified (CA) photoresists may encounter difficulties at small feature sizes due to roughness issues, and experiments have shown that the line edge roughness (LER) of CA photoresists can increase with decreasing photosensitivity, partly due to the nature of the acid-catalyzed process. Because of these defects and problems with CA photoresists, the semiconductor industry needs or demands a new type of high-performance photoresist.

[0008] To overcome the drawbacks of the above-mentioned chemically amplified (CA) organic photosensitive compositions, inorganic photosensitive compositions have been investigated. The inorganic photosensitive compositions are mainly or mostly used for negative patterning due to the ability to resist removal of the developer composition by chemical modification through a non-chemically amplified mechanism. The inorganic compositions include inorganic elements having higher EUV absorbance than hydrocarbons, thus, it can ensure the sensitivity through a non-chemically amplified mechanism, and can be less sensitive to random effects, thus, can have low line edge roughness and a relatively small number of defects.

[0009] Tungsten-based peroxy polyacids mixed with tungsten, niobium, titanium and / or tantalum have been reported as inorganic photoresists for patterning as radiation-sensitive materials.

[0010] These materials are effective for double layer configuration of large pitch patterning in far ultraviolet (deep ultraviolet), X-ray, and electron beam sources. Improved performance is obtained when using cationic hafnium metal oxide sulfate (HfSOx) materials with peroxy complexing agents for 15 nanometer half-pitch (HP) imaging by projection EUV exposure. The system exhibits high performance of non-chemically amplified (CA) photoresists and has a practical photosensitive speed close to the requirements of EUV photoresists. However, hafnium metal oxide sulfate materials containing peroxy complexing agents have some practical drawbacks. First, these materials are coated in a corrosive sulfuric acid / hydrogen peroxide mixture and have insufficient shelf stability. Second, material structure variation as a composite mixture to improve performance is challenging. Third, development should be performed in a high concentration of 25 wt% tetramethylammonium hydroxide (TMAH) solution and / or the like.

[0011] To address these issues, research has focused on developing molecules containing tin (Sn) that have excellent or appropriate extreme ultraviolet absorption. For organic tin polymers in tin-containing molecules, alkyl ligands are dissociated by photoabsorption or generated secondary electrons. The dissociated alkyl ligands are then crosslinked with adjacent chains through oxygen bonds, thereby achieving negative patterning that cannot be removed by organic developers. Although this organic tin polymer exhibits improved sensitivity and maintains the required resolution and line edge roughness, for commercial usability, patterning characteristics can need further improvement. SUMMARY

[0012] One or more aspects of embodiments of the present disclosure relate to a semiconductor photoresist composition having excellent or appropriate sensitivity and resolution characteristics, improved or enhanced solubility in a developer, and / or improved or enhanced moisture resistance stability.

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

[0014] Other aspects of embodiments will be apparent from the following description and, in part, will be learned from practice of the presented embodiments of the disclosure.

[0015] The semiconductor photoresist composition according to one or more embodiments can include an organic metal compound, a polymer additive including a structural unit represented by Chemical Formula 1, and a solvent.

[0016] The method of forming or providing a pattern according to one or more embodiments can include forming or providing an etching target layer on a substrate, coating a semiconductor photoresist composition on the etching target layer to form or provide a photoresist film, patterning the photoresist film to form or provide a photoresist pattern, and etching the etching target layer using the photoresist pattern as an etching mask.

[0017] The pattern formed or provided using the semiconductor photoresist composition according to one or more embodiments can have excellent or appropriate sensitivity and resolution, and can have improved or enhanced moisture stability. BRIEF DESCRIPTION OF DRAWINGS

[0018] The above and other aspects and features of certain embodiments of the present disclosure will become more apparent from the following description taken in conjunction with the accompanying drawings, in which:

[0019] Figures 1A-1E Each is a cross-sectional view illustrating a method of forming or providing a pattern using a semiconductor photoresist composition according to one or more embodiments.

[0020] EXPLANATION OF REFERENCE NUMERALS

[0021] 100: substrate

[0022] 102: thin film

[0023] 104: resist underlayer

[0024] 106: photoresist film

[0025] 106a: unexposed region

[0026] 106b: exposed region

[0027] 108: photoresist pattern

[0028] 110: patterning mask

[0029] 112: organic film pattern

[0030] 114: thin film pattern DETAILED DESCRIPTION

[0031] One or more embodiments of the present disclosure are described in greater detail below, with reference to the accompanying drawings. In the following description of the present disclosure, functions or constructions that a person of ordinary skill in the art can generally understand can not be described in detail.

[0032] To clearly illustrate the embodiments of the present disclosure, certain descriptions and relationships can be omitted, and throughout the present disclosure, substantially the same or similar configurations or arrangement elements can be indicated with the same reference numerals. Also, since the size and thickness of each configuration or arrangement shown in the drawings can be arbitrarily shown for better understanding and convenience of description, the embodiments of the present disclosure are not necessarily limited thereto.

[0033] In the drawings, the thickness of layers, films, panels, regions, and / or the like can be exaggerated for clarity. In the drawings, the thickness of some layers or regions and / or the like can be exaggerated for clarity. It will be understood that if (for example, when) a layer, film, region, or substrate is referred to as being "on" another layer, film, region, or substrate, it can be directly on the other layer, film, region, or substrate, or intervening layers, films, regions, or substrates can also be present. If (for example, when) a layer, film, region, or substrate is referred to as being "directly on" another layer, film, region, or substrate, there can be no intervening layers, films, regions, or substrates present.

[0034] 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. Further, the use of "may" when describing embodiments of the present disclosure refers to "one or more embodiments of the present disclosure."

[0035] In the context of the present disclosure, the term "use" can be considered synonymous with the term "utilize," unless otherwise defined.

[0036] As used herein, the term "about" or similar terms are used as approximating language and not degree language, and are intended to consider the inherent errors in measuring or calculating values that would be recognized by those of ordinary skill in the art. "About" or "approximately" as used herein also includes the stated value and means within an acceptable range of deviation from the particular value, taking into account the error in measurement and measurement related to the measurement of a particular quantity (e.g., limitations of the measurement system), as determined by those of ordinary skill in the art. For example, "about" can refer within one or more standard deviations, or within ±30%, 20%, 10%, or 5% of the stated value.

[0037] Any numerical range recited herein is intended to include all sub-ranges of substantially identical numbers within the recited range. For example, a range of "1.0 to 10.0" is intended to include all sub-ranges, half -ranges, whole number ranges, and decimal ranges, within the prescribed range, e.g., 2.4 to 7.6, 5.5 to 6.9, 3.14 to 4.44, 0.1 to 0.8, 0.1 to 0.277, etc. Any maximum numerical limitation recited herein is intended to include all lower numerical limitations subsumed therein and any minimum numerical limitation recited herein is intended to include all higher numerical limitations subsumed therein. Accordingly, Applicant reserves the right to amend the specification, including the claims, to expressly recite any sub-range subsumed within the ranges expressly recited in the specification.

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

[0039] As used herein, if (e.g., when) not otherwise provided, "alkyl" means a straight chain or branched chain aliphatic hydrocarbon group. The alkyl group can be a "saturated alkyl" that does not contain any double or triple bonds.

[0040] The alkyl group can be a C1 to C8 alkyl group. For example, the alkyl group can be a C1 to C7 alkyl group, a C1 to C6 alkyl group, or a C1 to C5 alkyl group. For example, the C1 to C5 alkyl group can be a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a sec-butyl group, a t-butyl group, or a 2,2-dimethylpropyl group.

[0041] As used herein, if (e.g., when) not otherwise provided, "cycloalkyl" means a monovalent cyclic aliphatic hydrocarbon group.

[0042] Cycloalkyl groups can be C3to C8cycloalkyl groups, for example, C3to C7cycloalkyl groups, C3to C6cycloalkyl groups, C3to C5cycloalkyl groups, or C3to C4cycloalkyl groups. For example, cycloalkyl groups can be cyclopropyl, cyclobutyl, cyclopentyl, or cyclohexyl, although embodiments of the present disclosure are not limited thereto.

[0043] As used herein, "aliphatic unsaturated organic group" refers to a hydrocarbon group that includes a bond between carbon atoms in the molecule that is a double bond, a triple bond, or a combination thereof.

[0044] Aliphatic unsaturated organic groups can be C2to C8aliphatic unsaturated organic groups. For example, aliphatic unsaturated organic groups can be C2to C7aliphatic unsaturated organic groups, C2to C6aliphatic unsaturated organic groups, C2to C5aliphatic unsaturated organic groups, or C2to C4aliphatic unsaturated organic groups. For example, C2to C4aliphatic unsaturated organic groups can be ethenyl, ethynyl, allyl, 1-propenyl, 1-methyl-1-propenyl, 2-propenyl, 2-methyl-2-propenyl, 1-propynyl, 1-methyl-1-propynyl, 2-propynyl, 2-methyl-2-propynyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-butynyl, 2-butynyl, or 3-butynyl.

[0045] As used herein, "aryl" refers to a cyclic substituent in which all atoms have p-orbitals, and these p-orbitals are conjugated, and can include monocyclic or fused polycyclic functional groups (e.g., rings that share pairs of adjacent carbon atoms).

[0046] As used herein, "heteroaryl" can refer to an aryl group that includes at least one heteroatom selected from nitrogen (N), oxygen (O), sulfur (S), phosphorus (P), and silicon (Si). Two or more heteroaryl groups can be directly connected by a sigma bond (e.g., a single covalent bond), or, if (e.g., when) the heteroaryl groups include two or more rings, the two or more rings can be fused. If (e.g., when) the heteroaryl group is a fused ring, each ring can include one to three heteroatoms.

[0047] As used herein, unless otherwise defined, "alkenyl" refers to an aliphatic unsaturated alkenyl group that includes at least one double bond.

[0048] As used herein, unless otherwise defined, "alkynyl" refers to an aliphatic unsaturated alkynyl group that includes at least one triple bond.

[0049] A semiconductor photoresist composition according to one or more embodiments is described below.

[0050] A semiconductor photoresist composition according to one or more embodiments can include an organometallic compound, a polymer additive including a structural unit represented by Chemical Formula 1, and / or a solvent.

[0051] Chemical Formula 1

[0052]

[0053] In Chemical Formula 1,

[0054] R 1 may be hydrogen or a substituted or unsubstituted C1 to C10 alkyl group,

[0055] R 2 may be a substituted or unsubstituted C1 to C20 alkyl group including a trifluoromethyl group and / or a hydroxyl group,

[0056] R 3 to R 6 may each independently be hydrogen, fluorine, a hydroxyl group, a substituted or unsubstituted C1 to C20 alkyl group, or a combination thereof,

[0057] n1 and n2 may each independently be an integer of 0 to 10,

[0058] n1 + n2 may be 1 or more than 1,

[0059] X 1 may be a single bond (e.g., a single covalent bond), -O-, -S-, -S(O)-, -S(O)2-, -C(O)-, -(CO)O-, -O(CO)-, -O(CO)O-, -NR a -(wherein, R a may be hydrogen, deuterium, or a substituted or unsubstituted C1 to C10 alkyl group) or a combination thereof, and

[0060] *may be a connection point.

[0061] The polymer additive included in the semiconductor photoresist composition can improve or enhance sensitivity and / or LER by including fluorine (e.g., one or more fluorine atoms). For example, due to the hydrophobicity of the fluorine (e.g., one or more fluorine atoms) of the polymer additive, the defect improvement or enhancement effect can be excellent or appropriate, and moisture stability can be improved or enhanced.

[0062] In one or more embodiments, by including an alkylene chain in the structural unit, the solubility of the polymer additive and / or the semiconductor photoresist composition in a developer can be improved or enhanced.

[0063] As an example, R 2 may be a C1 to C20 alkyl group substituted with at least one trifluoromethyl group and / or at least one hydroxyl group.

[0064] For example, R 2 may be a C1 to C20 alkyl group substituted with at least two trifluoromethyl groups and / or at least one hydroxyl group.

[0065] For example, R 2 may be C1 to C20 alkyl substituted with two trifluoromethyl groups and / or one hydroxyl group.

[0066] In one or more embodiments, R 2 may be C1 to C10 alkyl substituted with two trifluoromethyl groups and / or one hydroxyl group.

[0067] In one or more embodiments, R 2 may be C1 to C5 alkyl substituted with two trifluoromethyl groups and / or one hydroxyl group.

[0068] In one or more embodiments, R 2 may be C1 to C3 alkyl substituted with two trifluoromethyl groups and / or one hydroxyl group.

[0069] In one or more embodiments, R 2 may be methyl substituted with two trifluoromethyl groups and / or one hydroxyl group.

[0070] For example, Chemical Formula 1 can be represented by Chemical Formula 1-1.

[0071] Chemical Formula 1-1

[0072]

[0073] In Chemical Formula 1-1,

[0074] R 1 may be hydrogen or substituted or unsubstituted C1 to C10 alkyl,

[0075] R 3 to R 6 may each independently be hydrogen, fluorine, hydroxyl, substituted or unsubstituted C1 to C20 alkyl, or a combination thereof,

[0076] n1 and n2 may each independently be an integer of 0 to 10,

[0077] n1 + n2 may be 1 or more than 1,

[0078] X 1 may be a single bond (e.g., a single covalent bond), -O-, -S-, -S(O)-, -S(O)2-, -C(O)-, -(CO)O-, -O(CO)-, -O(CO)O-, -NR a -(wherein, R a may be hydrogen, deuterium, or substituted or unsubstituted C1 to C10 alkyl) or a combination thereof, and

[0079] *may be a connection point.

[0080] If (for example, when) n1 is 2 or more, each R 3 may be the same or different from each other.

[0081] If (for example, when) n1 is 2 or more, each R 4 may be the same or different from each other.

[0082] If (for example, when) n2 is 2 or more, each R 5 may be the same or different from each other.

[0083] If (for example, when) n2 is 2 or more, each R 6 may be the same or different from each other.

[0084] For example, the structural unit represented by Chemical Formula 1 can be one selected from among the structural units listed below.

[0085] Group 1

[0086]

[0087] In Group 1,

[0088] R 1 may be hydrogen or methyl, and

[0089] *may be a connection point.

[0090] The polymer additive including the structural unit represented by Chemical Formula 1 can be included in an amount of about 0.001 wt% to about 10 wt% based on 100 wt% of the semiconductor photoresist composition.

[0091] For example, the polymer additive including the structural unit represented by Chemical Formula 1 can be included in an amount of about 0.01 wt% to about 10 wt%, about 0.01 wt% to about 5 wt%, about 0.05 wt% to about 5 wt%, or about 0.1 wt% to about 5 wt% based on 100 wt% of the semiconductor photoresist composition.

[0092] The organometallic compound can be included in an amount of about 0.5 wt% to about 30 wt% based on 100 wt% of the semiconductor photoresist composition.

[0093] The semiconductor photoresist composition according to one or more embodiments can improve or enhance the sensitivity of the photoresist by including the organometallic compound and / or the polymer additive including the structural unit represented by Chemical Formula 1 in the above content (for example, amount) range.

[0094] The semiconductor photoresist composition according to one or more embodiments can include the organometallic compound and the polymer additive including the structural unit represented by Chemical Formula 1 in a weight ratio of about 99:1 to about 60:40. For example, the semiconductor photoresist composition can include the organometallic compound and the polymer additive including the structural unit represented by Chemical Formula 1 in a weight ratio of about 90:10 to about 60:40.

[0095] If (for example, when) the weight ratio of the organometallic compound and the polymer additive according to one or more embodiments satisfies the above range, a semiconductor photoresist composition having excellent or appropriate sensitivity can be provided.

[0096] The organometallic compound can be an organotin (Sn) compound including an organoxy group and / or an organocarbonyloxy group.

[0097] The organometallic compound can be represented by Chemical Formula 2.

[0098] Chemical Formula 2

[0099]

[0100] In Chemical Formula 2,

[0101] R 9 may be selected from a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, and a substituted or unsubstituted C6 to C30 aralkyl group,

[0102] R 10 to R 12 may each independently be a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C6 to C30 aralkyl group, an alkoxy group, or an aryloxy group (-OR b wherein R b may be a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof), a carboxyl group (-O(CO)R c wherein R cmay be hydrogen, substituted or unsubstituted C1to C20alkyl, substituted or unsubstituted C3to C20cycloalkyl, substituted or unsubstituted C2to C20alkenyl, substituted or unsubstituted C2to C20alkynyl, substituted or unsubstituted C6to C30aryl, or a combination thereof), alkylamino or dialkylamino (-NR d R e may each independently be hydrogen, substituted or unsubstituted C1to C20alkyl, substituted or unsubstituted C3to C20cycloalkyl, substituted or unsubstituted C2to C20alkenyl, substituted or unsubstituted C2to C20alkynyl, substituted or unsubstituted C6to C30aryl, or a combination thereof), amido (-NR d and R e may each independently be hydrogen, substituted or unsubstituted C1to C20alkyl, substituted or unsubstituted C3to C20cycloalkyl, substituted or unsubstituted C2to C20alkenyl, substituted or unsubstituted C2to C20alkynyl, substituted or unsubstituted C6to C30aryl, or a combination thereof), amido (-NR f (COR g ), where R f and R g may each independently be hydrogen, substituted or unsubstituted C1to C20alkyl, substituted or unsubstituted C3to C20cycloalkyl, substituted or unsubstituted C2to C20alkenyl, substituted or unsubstituted C2to C20alkynyl, substituted or unsubstituted C6to C30aryl, or a combination thereof), amidine (-NR h C(NR i )R j , where R h , R i , and R j may each independently be hydrogen, substituted or unsubstituted C1to C20alkyl, substituted or unsubstituted C3to C20cycloalkyl, substituted or unsubstituted C2to C20alkenyl, substituted or unsubstituted C2to C20alkynyl, substituted or unsubstituted C6to C30aryl, or a combination thereof), alkylthio or arylthio (-SR k , where R k may be substituted or unsubstituted C1to C20alkyl, substituted or unsubstituted C3to C20cycloalkyl, substituted or unsubstituted C2to C20alkenyl, substituted or unsubstituted C2to C20alkynyl, substituted or unsubstituted C6to C30aryl, or a combination thereof), or thio carboxyl (-S(CO)R l , where R l may be hydrogen, substituted or unsubstituted C1to C20alkyl, substituted or unsubstituted C3to C20cycloalkyl, substituted or unsubstituted C2to C20alkenyl, substituted or unsubstituted C2to C20alkynyl, substituted or unsubstituted C6to C30aryl, or a combination thereof), and

[0103] R 10 to R 12at least one selected from the group consisting of alkoxy or aryloxy (-OR b wherein R b may be substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, or a combination thereof, carboxyl (-O(CO)R c wherein R c may be hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, or a combination thereof, alkylamino or dialkylamino (-NR d R e wherein R d and R e may each independently be hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, or a combination thereof, amido (-NR f (COR g ), wherein R f and R g may each independently be hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, or a combination thereof, guanidino (-NR h C(NR i )R j wherein R h , R i and R j may each independently be hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, or a combination thereof, alkylthio or arylthio (-SR k wherein R k may be substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, or a combination thereof, and thio carboxyl (-S(CO)Rl wherein R l may be hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, or a combination thereof.

[0104] R 10 to R 12 at least one of which can be selected from alkoxy or aryloxy (-OR b wherein R b may be substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, or a combination thereof) and carboxyl (-O(CO)R c wherein R c 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.

[0105] In one or more embodiments, the compound represented by Chemical Formula 2 can include -OR b or -OC(=O)R c as a ligand, so that a pattern formed or provided using a semiconductor photoresist composition including the compound can exhibit excellent or appropriate ultimate resolution.

[0106] In one or more embodiments, -OR b or -OC(=O)R c as a ligand can appropriately adjust or determine the solubility of the compound represented by Chemical Formula 2 in a solvent.

[0107] R 9 may be substituted or unsubstituted C1 to C8 alkyl, substituted or unsubstituted C3 to C8 cycloalkyl, substituted or unsubstituted C2 to C8 aliphatically unsaturated organic group including one or more double or triple bonds, substituted or unsubstituted C6 to C20 aryl, substituted or unsubstituted C4 to C20 heteroaryl, carbonyl, ethoxy, propoxy, or a combination thereof,

[0108] R bmay be substituted or unsubstituted C1to C8alkyl, substituted or unsubstituted C3to C8cycloalkyl, substituted or unsubstituted C2to C8alkenyl, substituted or unsubstituted C2to C8alkynyl, substituted or unsubstituted C6to C20aryl, or combinations thereof, and

[0109] R c may be hydrogen, substituted or unsubstituted C1to C8alkyl, substituted or unsubstituted C3to C8cycloalkyl, substituted or unsubstituted C2to C8alkenyl, substituted or unsubstituted C2to C8alkynyl, substituted or unsubstituted C6to C20aryl, or combinations thereof.

[0110] R 9 may be methyl, ethyl, propyl, butyl, isopropyl, t-butyl, 2,2-dimethylpropyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, ethenyl, propenyl, butenyl, ethynyl, propynyl, butynyl, phenyl, tolyl, xylyl, benzyl, formyl, acetyl, propionyl, butyryl, valeryl, ethoxy, propoxy, or combinations thereof,

[0111] R b may be ethyl, propyl, butyl, isopropyl, t-butyl, 2,2-dimethylpropyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, ethenyl, propenyl, butenyl, ethynyl, propynyl, butynyl, phenyl, tolyl, xylyl, benzyl, or combinations thereof, and

[0112] R c may be hydrogen, ethyl, propyl, butyl, isopropyl, t-butyl, 2,2-dimethylpropyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, ethenyl, propenyl, butenyl, ethynyl, propynyl, butynyl, phenyl, tolyl, xylyl, benzyl, or combinations thereof.

[0113] In one or more embodiments, the tin (Sn) containing organometallic compound can be represented by Chemical Formula 3 or Chemical Formula 4.

[0114] Chemical Formula 3

[0115] R 13 z SnO (2-(z / 2)-(x / 2)) (OH) x

[0116] In Chemical Formula 3,

[0117] R 13 may be C1to C31hydrocarbyl, 0<z≤2, and 0<(z+x)≤4;

[0118] Chemical Formula 4

[0119] R 14a Sn b X c Y d

[0120] wherein, in Chemical Formula 4,

[0121] R 14 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 aliphatic unsaturated organic group including one or more double bonds or triple bonds, a substituted or unsubstituted C6 to C30 aryl, a substituted or unsubstituted C4 to C30 heteroaryl, a carbonyl, an oxiranyl, an oxetanyl, or a combination thereof,

[0122] X can be sulfur (S), selenium (Se), or tellurium (Te),

[0123] Y can be -OR m or -OC(=O)R n ,

[0124] wherein R m 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,

[0125] R n may be 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

[0126] a, b, c, and d can each independently be an integer of 1 to 20.

[0127] According to one or more embodiments, the solvent included in the semiconductor photoresist composition can be an organic solvent, and can 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, isopropyl alcohol, 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 (PGMEA), 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 embodiments of the present disclosure are not limited thereto.

[0128] The semiconductor photoresist composition according to one or more embodiments can further include a resin in addition to the organometallic compound, the polymer additive, and the solvent described in one or more embodiments.

[0129] The resin can be a phenolic resin including at least one aromatic moiety selected from the moieties listed in Group 2.

[0130] Group 2

[0131]

[0132] The resin can have a weight average molecular weight (Mw) of about 500 g / mol to about 20,000 g / mol. w

[0133] The resin can be included in an amount of about 0.1 wt% to about 50 wt% based on the total amount of the semiconductor photoresist composition.

[0134] If (for example, when) the resin is included in the above content (for example, amount) range, a pattern formed or provided using the semiconductor photoresist composition according to one or more embodiments can have excellent or appropriate etching resistance and / or heat resistance.

[0135] In one or more embodiments, the semiconductor photoresist composition according to one or more embodiments can consist of or can include the organometallic compound, the polymer additive, the solvent, and / or the resin described in one or more embodiments.

[0136] In one or more embodiments, the semiconductor photoresist composition according to one or more embodiments can further include an additive as needed or desired. Examples of the additive can be a surfactant, a crosslinking agent, a leveling agent, an organic acid, a quencher, or a combination thereof, but embodiments of the present disclosure are not limited thereto.

[0137] The surfactant can include, for example, an alkyl benzene sulfonate, an alkyl pyridine salt, a polyethylene glycol, a quaternary ammonium salt, or a combination thereof, but embodiments of the present disclosure are not limited thereto.

[0138] ​The crosslinking agent can be, for example, a melamine-based crosslinking agent, a substituted urea-based crosslinking agent, an acrylic-based crosslinking agent, an epoxy-based crosslinking agent, and / or a polymer-based crosslinking agent, although embodiments of the present disclosure are not limited thereto. The crosslinking agent can be a crosslinking agent having at least two crosslink-forming substituents, such as, for example, methoxymethylated biuret, butoxymethylated biuret, methoxymethylated melamine, butoxymethylated melamine, methoxymethylated benzoguanamine, butoxymethylated benzoguanamine, 4-hydroxybutyl acrylate, acrylic acid, urethane acrylate, methacrylate acrylate, 1,4-butanediol diglycidyl ether, glycidol, 1,2-cyclohexanedicarboxylic acid diglycidyl ester, trimethylolpropane triglycidyl ether, 1,3-bis(glycidylpropyl)tetramethyldisiloxane, methoxymethylated urea, butoxymethylated urea, methoxymethylated thiourea, and / or the like.

[0139] The leveling agent can be used to improve or enhance coating levelness during printing, and can be a commercially available or generally available leveling agent.

[0140] The organic acid can include p-toluenesulfonic acid, benzene sulfonic acid, p-dodecylbenzenesulfonic acid, 1,4-naphthalenedisulfonic acid, methanesulfonic acid, fluorinated sulfonium salt, malonic acid, citric acid, propionic acid, methacrylic acid, oxalic acid, lactic acid, glycolic acid, succinic acid, or combinations thereof, although embodiments of the present disclosure are not limited thereto.

[0141] The quenching agent can be diphenyl(p-tolyl)amine, methyldiphenylamine, triphenylamine, phenylenediamine, naphthylamine, diaminonaphthalene, or combinations thereof.

[0142] The amount of the additive used can be appropriately controlled or adjusted according to appropriate or desired properties.

[0143] In one or more embodiments, the semiconductor photoresist composition can further include a silane coupling agent as an adhesion enhancer to improve or enhance the force of intimate contact with the substrate (e.g., to improve or enhance the adhesion of the semiconductor photoresist composition to the substrate). The silane coupling agent can be, for example, a silane compound containing a carbon-carbon unsaturated bond, such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltris(β-methoxyethoxy)silane; and / or 3-methacryloyloxypropyltrimethoxysilane, 3-acryloyloxypropyltrimethoxysilane, p-styryltrimethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropylmethyldiethoxysilane; trimethoxy[3-(phenylamino)propyl]silane, and / or the like, although embodiments of the present disclosure are not limited thereto.

[0144] Semiconductor photoresist compositions can form or provide patterns with high aspect ratios without collapse. In one or more embodiments, to form or provide fine patterns with, for example, a width (e.g., line width) of from about 5 nm to about 100 nm, for example, from about 5 nm to about 80 nm, for example, from about 5 nm to about 70 nm, for example, from about 5 nm to about 50 nm, for example, from about 5 nm to about 40 nm, for example, from about 5 nm to about 30 nm, or for example, from about 5 nm to about 20 nm, semiconductor photoresist compositions can be used in a photoresist process using light having a wavelength ranging from about 5 nm to about 150 nm, for example, from about 5 nm to about 100 nm, from about 5 nm to about 80 nm, from about 5 nm to about 50 nm, from about 5 nm to about 30 nm, or from about 5 nm to about 20 nm. In one or more embodiments, semiconductor photoresist compositions according to one or more embodiments can be used to implement or provide extreme ultraviolet lithography using an EUV light source having a wavelength of about 13.5 nm.

[0145] According to one or more embodiments, methods of forming or providing a pattern using a semiconductor photoresist composition as described in one or more embodiments are provided. For example, the pattern manufactured can be a photoresist pattern.

[0146] Methods of forming or providing a pattern according to one or more embodiments can include 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 etching the etch target layer using the photoresist pattern as an etch mask.

[0147] Reference is made to the following drawings Figures 1A-1E Methods of forming or providing a pattern using a semiconductor photoresist composition are described. Figures 1A-1E Each is a cross-sectional view illustrating a method of forming or providing a pattern using a semiconductor photoresist composition according to one or more embodiments.

[0148] Reference is made to the following drawings Figure 1A An object for etching (e.g., an etch target layer or an etch target material layer) can be prepared. The object for etching can be a thin film 102 that can be formed or provided on a semiconductor substrate 100. Hereinafter, the object for etching can be defined as the thin film 102. A surface of the thin film 102 can be cleaned to remove impurities and / or the like remaining thereon. The thin film 102 can be, for example, a silicon nitride layer, a polysilicon layer, and / or a silicon oxide layer.

[0149] Subsequently, a resist underlayer composition forming or providing a resist underlayer 104 can be spin-coated on the surface of the cleaned thin film 102. However, embodiments of the present disclosure are not limited thereto, and one or more suitable coating methods, for example, spraying, dipping, blade coating, printing methods such as inkjet printing and / or screen printing, and / or the like can be used.

[0150] The coating process of the resist underlayer can not be provided, and the following description includes a process of coating the resist underlayer.

[0151] The coated composition can then be dried and baked to form or provide the resist underlayer 104 on the film 102. The baking (e.g., heat treatment) can be performed at about 100 °C to about 500 °C, such as about 100 °C to about 300 °C.

[0152] The resist underlayer 104 can be formed or provided between the substrate 100 and the photoresist film 106, and thus can prevent or reduce non-uniformity (e.g., substantial non-uniformity) and pattern formation of the photoresist line width if (e.g., when) the rays reflected from the interface or interlayer hard mask between the substrate 100 and the photoresist film 106 are scattered to unintended photoresist areas.

[0153] Referring to Figure 1B The photoresist film 106 can be formed or provided by coating a semiconductor photoresist composition on the resist underlayer 104. The photoresist film 106 can be obtained or provided by coating a semiconductor photoresist composition according to one or more embodiments on the film 102 that can be formed or provided on the substrate 100, and then curing it by heat treatment.

[0154] For example, forming a pattern using the semiconductor photoresist composition can include coating the semiconductor resist composition on the substrate 100 having the film 102 by spin coating, slot coating, inkjet printing, and / or the like, and then drying it to form or provide the photoresist film 106.

[0155] The semiconductor photoresist composition has been described in more detail, and can not be described again.

[0156] Subsequently, the substrate 100 having the photoresist film 106 can be subjected to a first baking process (e.g., heat treatment). The first baking process can be performed at about 80 °C to about 120 °C.

[0157] Referring to Figure 1C The photoresist film 106 can be selectively exposed using a patterning mask 110.

[0158] For example, the exposure can use active radiation including light or beams having a high energy wavelength, such as EUV (Extreme Ultraviolet; wavelength of about 13.5 nanometers), E-Beam (Electron Beam), and / or the like, and light having a short wavelength, such as i-line (wavelength of about 365 nanometers), KrF excimer laser (wavelength of about 248 nanometers), ArF excimer laser (wavelength of about 193 nanometers), and / or the like.

[0159] For example, the light or beam for exposure according to one or more embodiments can have a short wavelength and high energy wavelength in a range of about 5 nanometers to about 150 nanometers, for example, EUV (extreme ultraviolet; wavelength 13.5 nanometers), E-Beam (electron beam), and / or the like.

[0160] By forming or providing a polymer resulting from a cross-linking reaction, for example, condensation between organometallic compounds (for example, condensation reaction between organometallic compounds), the exposed region 106b of the photoresist film 106 can have a different solubility from the unexposed region 106a of the photoresist film 106.

[0161] Subsequently, the substrate 100 can be subjected to a second baking process (for example, heat treatment). 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 region 106b of the photoresist film 106 can become easily insoluble in a developer.

[0162] In Figure 1D , the unexposed region 106a of the photoresist film can be dissolved and removed by using a developer to form or provide a photoresist pattern 108. For example, the unexposed region 106a of the photoresist film can be dissolved and removed by using an organic solvent, such as 2-heptanone and / or the like, to complete the photoresist pattern 108 corresponding to a negative image.

[0163] According to one or more embodiments, the developer used in the method of forming or providing a pattern according to one or more embodiments can be an organic solvent. The organic solvent used in the method of forming or providing a pattern according to one or more 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, isopropyl alcohol, 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 a combination thereof.

[0164] However, the photoresist pattern according to one or more embodiments is not necessarily limited to a negative image, but can form or provide a positive image. Here, the developer for forming or providing a positive image can be a quaternary ammonium hydroxide composition, such as tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, or a combination thereof.

[0165] According to one or more embodiments, exposure to light or a beam having a high energy wavelength, such as EUV (extreme ultraviolet; wavelength 13.5 nanometers), E-Beam (electron beam), and / or the like, and light having a short wavelength, such as i-line (wavelength of about 365 nanometers), KrF excimer laser (wavelength of about 248 nanometers), ArF excimer laser (wavelength of about 193 nanometers), and / or the like, can provide a photoresist pattern 108 having a width of about 5 nanometers to about 100 nanometers. For example, the photoresist pattern 108 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.

[0166] In one or more embodiments, the photoresist pattern 108 can have a pitch of less than or equal to about 50 nanometers (e.g., less than or equal to about 40 nanometers, e.g., less than or equal to about 30 nanometers, e.g., less than or equal to about 20 nanometers, or e.g., less than or equal to about 15 nanometers) and a line width roughness of less than or equal to about 10 nanometers, 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.

[0167] Subsequently, the photoresist pattern 108 can be used as an etching mask to etch the resist underlayer 104. Through this etching process, an organic film pattern 112 can be formed or provided. The organic film pattern 112 can also have a width (e.g., line width) corresponding to the photoresist pattern 108.

[0168] Referring to Figure 1E By using the photoresist pattern 108 as an etching mask, the exposed thin film 102 can be etched. As a result, the thin film can be formed or provided as a thin film pattern 114.

[0169] The etching of the thin film 102 can be, for example, dry etching using an etching gas, which can be, for example, CHF3, CF4, Cl2, BCl3, and a mixed gas thereof.

[0170] The thin film pattern 114 formed or provided by the photoresist pattern 108 formed or provided by the exposure process, which can be performed by using an EUV light source, can have a width (e.g., line width) corresponding to the photoresist pattern 108. For example, the thin film pattern 114 can have a width (e.g., line width) of about 5 nm to about 100 nm, which can be equal to the width of the photoresist pattern 108. For example, the thin film pattern 114 formed or provided by the photoresist pattern 108 formed or provided by the exposure process, which can be performed by using an EUV light source, can have a width (e.g., line 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, and, for example, a width (e.g., line width) less than or equal to about 20 nm, similar or analogous to the width of the photoresist pattern 108.

[0171] Hereinafter, the subject matter of the present disclosure will be described in more detail through a preparation example of a semiconductor photoresist composition described in one or more embodiments of the present disclosure. However, one or more embodiments of the present disclosure are not technically limited by the following example.

[0172] Synthesis of an organic metal compound

[0173] Synthesis Example 1

[0174] 40.7 g of t-butyl triphenyl tin and 300 g of propionic acid were added to a 250 mL two-necked round bottom flask, and then heated to reflux for 24 hours.

[0175] The resulting compound represented by Chemical Formula 5 was obtained by removing unreacted propionic acid under reduced pressure.

[0176]

[0177] Synthesis Example 2

[0178] 30 mL of anhydrous pentane was added to 10 g of t-amyl tin chloride and maintained at 0°C, 7.4 g of diethylamine and 6.1 g of ethanol were added thereto, and then stirred at room temperature for 1 hour. When the reaction was completed, the resulting product was filtered, concentrated, and vacuum dried to obtain a compound represented by Chemical Formula 6.

[0179] Chemical Formula 6

[0180]

[0181] Synthesis Example 3

[0182] 10 g of dibutyltin dichloride was dissolved in 30 ml of diethyl ether, 70 ml of 1 M aqueous sodium hydroxide (NaOH) solution was added thereto, and then stirred for 1 hour. After stirring, the generated solid was filtered, washed with 25 ml of deionized water three times, and dried at 100°C under reduced pressure to obtain an organometallic compound represented by Chemical Formula 7 having a weight average molecular weight (Mw) of 1,500 g / mol. w

[0183] Chemical Formula 7

[0184]

[0185] Synthesis Example 4: Synthesis of Compound 1a

[0186] 20 g (59.86 mmol) of hexafluoromethyl-2,3-bis(trifluoromethyl)-2,3-butanediol (perfluoropinacol), 7.79 g (59.86 mmol) of 2-(hydroxyethyl)methyl acrylate, and 18.84 g (71.84 mmol) of triphenylphosphine (Ph3P) were mixed in 110 ml of diethyl ether, and then stirred under a nitrogen atmosphere. After stirring for 30 minutes, the resulting mixture was cooled to 0°C, and another mixture composed of 14.52 g (71.84 mmol) of diisopropyl azodicarboxylate (DIAD) and 35 ml of diethyl ether was slowly dropped for 2 hours. Subsequently, the obtained mixture was stirred at room temperature (23°C) for 24 hours, and then concentrated. The concentrated mixture was dissolved in dichloromethane, and then treated by column chromatography using silica gel to separate the synthesized material. The separated material was distilled again under reduced pressure to synthesize 2-[3,3,3-trifluoro-2-hydroxy-1,1,2-tris(trifluoromethyl)propoxy]ethyl 2-methyl-2-propenoate represented by Chemical Formula 1a.

[0187] * 1 H-NMR (acetone-d6): δ 1.90 (3H, t), 4.36 (4H, m), 5.63 (1H, t), 6.09 (1H, t), 8.34 (1H, s)

[0188] * 19 F-NMR (acetone-d6): δ -70.12 (6F, m), -65.38 (6F, m)

[0189] Chemical Formula 1a

[0190]

[0191] Synthesis Example 5: Preparation of Polymer R1

[0192] ​In a 250 mL two-necked round bottom flask, under a nitrogen atmosphere, was placed 16.1 g (36 mmol) of the compound of Formula la and 110 g of diisoamyl ether (DIAE) and heated to an internal temperature of 85°C. When the internal temperature reached 85°C, 14.7 g of a 25 wt% solution of V-601 in DIAE (3.7 g, 16 mmol of V-601) was added slowly and after 6 hours, the resulting reaction solution was cooled to room temperature and concentrated to a 50% solids content (e.g., amount). To the concentrated solution was then added 270 g of heptane and the resulting polymer was filtered. The filtered polymer was completely dissolved in 34 g of DIAE and then precipitated by the addition of 270 g of heptane, repeated twice, and then completely dried to yield the polymer R1 (M w = 5,000 g / mole).

[0193]

[0194] Synthesis Example 6: Preparation of Polymer R2

[0195] Polymer R2 (M w = 5,500) was obtained essentially the same as in Synthesis Example 5 except that 8.83 g of the compound of Formula lb (HALOCARBON, LLC) was used in place of the compound of Formula la.

[0196] Formula lb

[0197]

[0198] Synthesis Example 7: Preparation of Polymer R3

[0199] Polymer R3 (M w = 5,500) was obtained essentially the same as in Synthesis Example 5 except that 20 g of the compound of Formula lc (HALOCARBON, LLC) was used in place of the compound of Formula la.

[0200] Formula lc

[0201]

[0202] Synthesis Example 8: Preparation of Polymer R4

[0203] Polymer R4 (M w = 5,300) was obtained essentially the same as in Synthesis Example 5 except that 20 g of the compound of Formula Id (HALOCARBON, LLC) was used in place of the compound of Formula la.

[0204]

[0205] Synthesis Example 9: Preparation of Polymer R5

[0206] Polymer R5 (M w was substantially the same as that of Synthesis Example 5, except that 20 g of a compound represented by Chemical Formula 1e (HALOCARBON, LLC) was used instead of the compound represented by Chemical Formula 1a.

[0207] Chemical Formula 1e

[0208]

[0209] Preparation of Semiconductor Photoresist Composition

[0210] Examples 1 to 15 and Comparative Examples 1 to 4

[0211] A semiconductor photoresist composition of Examples 1 to 15 and Comparative Examples 1 to 4 was prepared by dissolving the organometallic compounds represented by Chemical Formulas 5 to 7 of Synthesis Examples 1 to 3 and the polymers R1 to R5 of Synthesis Examples 5 to 9, respectively, in propylene glycol methyl ether acetate (PGMEA) at a concentration of 3 wt%, in a weight ratio shown in Table 1, and then filtering with a 0.1 μm polytetrafluoroethylene (PTFE) syringe filter.

[0212]

[0213] Evaluation 1: Evaluation of Sensitivity and Line Edge Roughness (LER)

[0214] Each of the photoresist compositions of the examples and comparative examples was spin-coated on a 200 mm circular silicon wafer on which hexamethyldisilazane (HMDS) was deposited on the surface at 1500 rpm for 30 seconds and baked at 110°C for 60 seconds. After application, baking (post-application bake, PAB) was performed and then left to stand at room temperature (23±2°C) for 30 seconds.

[0215] After that, a linear array of 50 circular pads with a diameter of 500 micrometers was projected onto the wafer coated with the photoresist composition using an extreme ultraviolet light (Lawrence Berkeley National Laboratory Micro Exposure Tool, MET). Here, the pad exposure time was adjusted to ensure that each pad received an increasing dose of extreme ultraviolet light.

[0216] Then, after exposure, the resist and the substrate were baked on a hot plate at 160°C for 120 seconds. The baked film was developed with PGMEA solvent to form or provide a negative image. Finally, the obtained film was baked again on a hot plate at 150°C for 2 minutes, completing the process.

[0217] The remaining resist thickness of the exposed pads was measured using an ellipsometer. The remaining thickness was measured for each exposure dose, then plotted as a function of exposure dose to measure sensitivity, and LER was measured from field emission scanning electron microscope (FE-SEM) images to evaluate line edge roughness, then sensitivity and line edge roughness were evaluated according to the following criteria, and the results are shown in Table 2.

[0218] Sensitivity evaluation criteria

[0219] -A: less than 50 mJ / cm 2

[0220] -B: greater than or equal to 50 mJ / cm 2

[0221] LER evaluation criteria

[0222] - O: less than or equal to 2 nanometers

[0223] - Δ: greater than 2 nanometers and less than or equal to 5 nanometers

[0224] - X: greater than 5 nanometers

[0225] Evaluation 2: Evaluation of defects

[0226] On a 12-inch silicon substrate, a lower silicon oxynitride (SiON) film / spin-on carbon film / upper SiON film were sequentially formed or provided. On the upper SiON film, a 1:1 line / space photoresist pattern having a 36-nanometer pitch was formed or provided by an EUV lithography method using each of the photoresist compositions according to Examples and Comparative Examples. The photoresist pattern was transferred onto the lower SiON film by dry etching using plasma. Then, all defects, including bridging defects between line patterns, were inspected in a bright field using a defect analysis apparatus having a DUV laser. The defects inspected were classified using a scanning electron microscope (SEM), and then the number of classified defects per unit area (pieces / cm 2 ) was shown.

[0227] Here, when the number of SLO defects without applying each photoresist composition (for example, when each photoresist composition is not applied) is converted to 100, if the number of defects is less than or equal to 80%, "O" is given, and if the number of defects is greater than 80%, "X" is given.

[0228] Table 2

[0229] Sensitivity LER Defect Evaluation Example 1 A ○ ○ Example 2 A ○ ○ Example 3 A ○ ○ Example 4 A ○ ○ Example 5 A ○ ○ Example 6 A ○ ○ Example 7 A ○ ○ Example 8 A ○ ○ Example 9 A ○ ○ Example 10 A ○ ○ Example 11 A ○ ○ Example 12 A ○ ○ Example 13 A ○ ○ Example 14 A ○ ○ Example 15 A ○ ○ Comparative Example 1 B X X Comparative Example 2 B △ X Comparative Example 3 B X X Comparative Example 4 B △ △

[0230] As can be seen from the results of Table 2, the pattern formed or provided using the semiconductor photoresist compositions according to Examples 1 to 15 exhibited excellent sensitivity, LER, and resolution characteristics compared to Comparative Examples 1 to 4.

[0231] Before the present disclosure is described in detail, certain embodiments of the disclosure will be described and illustrated in conjunction with the accompanying drawings. It is understood that the present disclosure is not limited to the embodiments described and illustrated, and that the examples provided are intended to explain the principles of the disclosure and the concepts underlying the disclosure. Therefore, modifications and variations of the described embodiments are possible without departing from the spirit and scope of the present disclosure. Thus, the modified embodiments can not be understood as separate from the technical ideas and aspects of one or more embodiments of the present disclosure, and the modified embodiments can be within the scope of the appended claims of the present disclosure and their equivalents.

Claims

1.A semiconductor photoresist composition, comprising: an organometallic compound; a polymer additive including a structural unit represented by Chemical Formula 1; and a solvent: Chemical Formula 1 wherein, in Chemical Formula 1, R 1 is hydrogen or substituted or unsubstituted C1to C10alkyl, R 2 is a substituted or unsubstituted C1to C20alkyl comprising a trifluoromethyl and a hydroxyl group, R 3 to R 6 each independently hydrogen, fluorine, hydroxyl, substituted or unsubstituted C1to C20alkyl, or a combination thereof, n1 and n2 are each independently an integer of 0 to 10, n1 + n2 is 1 or more than 1, X 1 is a single bond, -O-, -S-, -S(O)-, -S(O)2-, -C(O)-, -(CO)O-, -O(CO)-, -O(CO)O-, -NR a - or combinations thereof, wherein R a is hydrogen, deuterium, or substituted or unsubstituted C1 to C10 alkyl, and * is a connecting point. 2.The semiconductor photoresist composition according to claim 1, wherein: R 2 is a C1to C20alkyl group substituted by at least one trifluoromethyl group and at least one hydroxyl group. 3.The semiconductor photoresist composition according to claim 1, wherein: R 2 is a C1to C10alkyl group substituted by two trifluoromethyl groups and one hydroxyl group. 4.The semiconductor photoresist composition according to claim 1, wherein: Chemical Formula 1 is represented by Chemical Formula 1-1: Chemical Formula 1-1 wherein, in Chemical Formula 1-1, R 1 is hydrogen or substituted or unsubstituted C1to C10alkyl, R 3 to R 6 each independently is hydrogen, fluorine, hydroxyl, substituted or unsubstituted C1to C20alkyl, or a combination thereof, n1 and n2 are each independently an integer of 0 to 10, n1 + n2 is 1 or more than 1, X 1 is a single bond, -O-, -S-, -S(O)-, -S(O)2-, -C(O)-, -(CO)O-, -O(CO)-, -O(CO)O-, -NR a - or a combination thereof, wherein R a is hydrogen, deuterium, or substituted or unsubstituted C1 to C10 alkyl, and * is a connecting point. 5.The semiconductor photoresist composition according to claim 1, wherein: the structural unit represented by Chemical Formula 1 is one selected from the group 1 listed structural units: Group 1 wherein, in Group 1, R 1 is hydrogen or methyl, and * is a connecting point. 6.The semiconductor photoresist composition according to claim 1, wherein: the polymer additive including a structural unit represented by Chemical Formula 1 is included in an amount of 0.001 to 10% by weight based on 100% by weight of the semiconductor photoresist composition. 7.The semiconductor photoresist composition according to claim 1, wherein: the polymer additive including a structural unit represented by Chemical Formula 1 is included in an amount of 0.1 to 5% by weight based on 100% by weight of the semiconductor photoresist composition. 8.The semiconductor photoresist composition according to claim 1, wherein: the organometallic compound is included in an amount of 0.5 to 30% by weight based on 100% by weight of the semiconductor photoresist composition. 9.The semiconductor photoresist composition according to claim 1, wherein: the semiconductor photoresist composition further includes an additive of a surfactant, a crosslinking agent, a leveling agent, an organic acid, a quencher, or a combination thereof. 10.The semiconductor photoresist composition according to claim 1, wherein: the organometallic compound is an organotin compound including at least one selected from an organic oxy group and an organic carbonyloxy group. 11.The semiconductor photoresist composition according to claim 1, wherein: the organometallic compound is represented by Chemical Formula 2: Chemical Formula 2 wherein, in Chemical Formula 2, R 9 substituted or unsubstituted C1to C20alkyl, substituted or unsubstituted C3to C20cycloalkyl, substituted or unsubstituted C2to C20alkenyl, substituted or unsubstituted C2to C20alkynyl, substituted or unsubstituted C6to C30aryl, and substituted or unsubstituted C6to C30aralkyl, R 10 To R 12 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 C6 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 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 alkylamino or dialkylamino 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 alkylthio or arylthio group represented by -S-R, wherein R k is a substituted or unsubstituted C1to C20alkyl, a substituted or unsubstituted C3to C20cycloalkyl, a substituted or unsubstituted C2to C20alkenyl, a substituted or unsubstituted C2to C20alkynyl, a substituted or unsubstituted C6to C30aryl, or a combination thereof; or a thiocarboxyl group represented by -S(CO)R l , wherein R l is hydrogen, a substituted or unsubstituted C1to C20alkyl, a substituted or unsubstituted C3to C20cycloalkyl, a substituted or unsubstituted C2to C20alkenyl, a substituted or unsubstituted C2to C20alkynyl, a substituted or unsubstituted C6to C30aryl, or a combination thereof, and R 10 to R 12 select at least one from the group consisting of an alkoxy or aryloxy represented by -OR b , wherein R b 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; a carboxyl represented by -O(CO)R c , wherein R c 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; an alkylamino or dialkylamino represented by -NR d R e , wherein R d and R e are each 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; an amido represented by -NR f (COR g ), wherein R f and R g are each 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; a guanidino represented by -NR h C(NR i )R j , wherein R h , R i , and R j are each 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; an alkylthio or arylthio represented by -SR k , wherein R k 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.substituted or unsubstituted C1to C20alkyl, substituted or unsubstituted C3to C20cycloalkyl, substituted or unsubstituted C2to C20alkenyl, substituted or unsubstituted C2to C20alkynyl, substituted or unsubstituted C6to C30aryl, or a combination thereof; and thio-carboxyl represented by -S(CO)R l wherein R l is hydrogen, substituted or unsubstituted C1to C20alkyl, substituted or unsubstituted C3to C20cycloalkyl, substituted or unsubstituted C2to C20alkenyl, substituted or unsubstituted C2to C20alkynyl, substituted or unsubstituted C6to C30aryl, or a combination thereof. 12.The semiconductor photoresist composition according to claim 11, wherein: R 10 to R 12 is selected from at least one selected from an alkoxy or aryloxy group represented by -OR b , wherein R b is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof; and a carboxyl group represented by -O(CO)R c , wherein R c is 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. 13.The semiconductor photoresist composition according to claim 12, wherein: R 9 substituted or unsubstituted C1to C8alkyl, substituted or unsubstituted C3to C8cycloalkyl, substituted or unsubstituted C2to C8aliphatic unsaturated organic group comprising one or more double or triple bonds, substituted or unsubstituted C6to C20aryl, substituted or unsubstituted C4to C20heteroaryl, carbonyl, ethoxy, propoxy, or a combination thereof, R b substituted or unsubstituted C1to C8alkyl, substituted or unsubstituted C3to C8cycloalkyl, substituted or unsubstituted C2to C8alkenyl, substituted or unsubstituted C2to C8alkynyl, substituted or unsubstituted C6to C20aryl, or a combination thereof, and R c is hydrogen, substituted or unsubstituted C1to C8alkyl, substituted or unsubstituted C3to C8cycloalkyl, substituted or unsubstituted C2to C8alkenyl, substituted or unsubstituted C2to C8alkynyl, substituted or unsubstituted C6to C20aryl, or a combination thereof. 14.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 13 z SnO (2-(z / 2)-(x / 2)) (OH) x wherein, in Chemical Formula 3, R 13 is a C1to C31hydrocarbyl group, 0 < z < 2, and 0 < (z+x) < 4; Chemical Formula 4 R 14 a Sn b X c Y d wherein, in Chemical Formula 4, R 14 substituted or unsubstituted C1to C20alkyl, substituted or unsubstituted C3to C20cycloalkyl, substituted or unsubstituted C2to C20aliphatic unsaturated organic group comprising one or more double or triple bonds, substituted or unsubstituted C6to C30aryl, substituted or unsubstituted C4to C30heteroaryl, carbonyl, oxiranyl, oxetanyl, or a combination thereof, X is sulfur, selenium, or tellurium, and Y is -OR m or -OC(=O)R n , wherein R m is a substituted or unsubstituted C1to C20alkyl, a substituted or unsubstituted C3to C20cycloalkyl, a substituted or unsubstituted C2to C20alkenyl, a substituted or unsubstituted C2to C20alkynyl, a substituted or unsubstituted C6to C30aryl, or a combination thereof, R n is hydrogen, a substituted or unsubstituted C1to C20alkyl, a substituted or unsubstituted C3to C20cycloalkyl, a substituted or unsubstituted C2to C20alkenyl, a substituted or unsubstituted C2to C20alkynyl, a substituted or unsubstituted C6to C30aryl, or a combination thereof, and a, b, c, and d are each independently an integer of 1 to 20. 15.A method of forming a pattern, comprising: providing an etching target layer on a substrate; applying the semiconductor photoresist composition according to any one of claims 1 to 14 on the etching target layer to provide a photoresist film; patterning the photoresist film to provide a photoresist pattern; and etching the etching target layer using the photoresist pattern as an etching mask.

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