Semiconductor photoresist composition and method for forming pattern using the same

Abstract

A semiconductor photoresist composition and a method of forming a pattern using the same are provided. The semiconductor photoresist composition comprises an organic metal compound containing Sn, a carboxylic acid compound substituted by an oxygen-containing heterocyclic ring and a solvent.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority to and the benefit of Korean Patent Application No. 10-2024-0034113, filed on March 11, 2024, in the Korean Intellectual Property Office, the entire contents of which are incorporated herein by reference. Technical Field

[0003] One or more embodiments of the present disclosure relate to a semiconductor photoresist composition and a method of forming a pattern using the semiconductor photoresist composition. Background Art

[0004] Extreme ultraviolet (EUV) lithography has been recognized (and is gaining attention) as a key (indispensable) technology for the production of next-generation advanced semiconductor devices. EUV lithography is a patterning technology that uses EUV radiation with a wavelength of 13.5 nanometers as an exposure light source. EUV lithography enables the formation of extremely fine patterns (e.g., less than or equal to 20 nanometers) during the exposure process in semiconductor device manufacturing.

[0005] EUV lithography is enabled by the development of compatible photoresists that can be performed at spatial resolutions of 16 nm or less (i.e., compatible photoresists capable of facilitating spatial resolutions of 16 nm or less). Currently, efforts are underway to meet the inadequate specifications of comparable chemically amplified (CA) photoresists for next-generation devices, such as resolution, photospeed, and feature roughness (also known as line edge roughness, or LER).

[0006] The inherent image blurring caused by acid-catalyzed reactions in these polymer types or classes of photoresists limits the resolution of small feature sizes, a situation that has long existed in electron beam (e-beam) lithography. CA photoresists are designed for high sensitivity, but because their typical elemental composition reduces the photoresist's light absorption at a wavelength of 13.5 nm, thereby reducing its sensitivity, CA photoresists may face more difficulties in EUV exposure.

[0007] Furthermore, CA photoresists may encounter difficulties at small feature sizes due to roughness issues, and experiments have shown that line edge roughness (LER) of CA photoresists increases because the photospeed is partially reduced due to the nature of the acid-catalyzed process. Therefore, due to these defects and problems of CA photoresists, the semiconductor industry needs or requires a new type of high-performance photoresist.

[0008] To overcome the aforementioned shortcomings of CA organic photosensitive compositions, inorganic photosensitive compositions have been studied. Inorganic photosensitive compositions are primarily used for negative tone patterning and are resistant to removal by developing compositions due to chemical modification via a non-chemical amplification mechanism. Inorganic compositions contain inorganic elements with higher EUV absorptivity than hydrocarbon groups, ensuring sensitivity through a non-chemical amplification mechanism. Furthermore, they are less sensitive to stochastic effects, making them suitable for achieving low line-edge roughness and a reduced number of defects.

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

[0010] These materials are effective for large-pitch patterning of bilayer configurations at extreme ultraviolet (DUV), X-ray, and electron beam sources. Recently, when using cationic hafnium metal oxide sulfate (HfSO x ) materials together with a peroxide complexing agent achieved impressive performance when imaged at 15nm half-pitch (HP) by projection EUV exposure. This system exhibits the highest performance of non-CA photoresists and has practical photospeeds approaching the requirements of EUV photoresists. However, hafnium metal oxide sulfate materials with peroxide complexing agents have some practical disadvantages. First, these materials are coated in a corrosive sulfuric acid / hydrogen peroxide mixture and have insufficient shelf life stability. Second, structural changes that result in performance improvements as a composite mixture are not easy. Third, development should be carried out in a very concentrated 25 wt% tetramethylammonium hydroxide (TMAH) solution and / or the like.

[0011] Recently, active research has been conducted to address these issues, as it has been recognized that tin-containing molecules have excellent or appropriate absorption of extreme ultraviolet light (i.e., tin-containing molecules exhibit superior absorption characteristics for extreme ultraviolet light). In the case of organotin polymers therein, alkyl ligands dissociate through light absorption or generated secondary electrons, thereby crosslinking with adjacent chains through oxygen bonds, thereby achieving negative-tone patterning that cannot be removed by organic developers. Such organotin polymers exhibit greatly improved sensitivity while maintaining resolution and line edge roughness, but for commercial availability, patterning characteristics need to be further improved (i.e., their patterning properties may need to be further improved to achieve commercial viability). Summary of the Invention

[0012] One or more embodiments of the present disclosure are directed to a semiconductor photoresist composition having excellent or appropriate sensitivity and line edge roughness (LER) characteristics and improved sensitivity.

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

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

[0015] In one or more embodiments, a composition for a semiconductor photoresist may include an organic metal compound containing tin (Sn), a carboxylic acid compound substituted with an oxygen-containing heterocycle, and / or a solvent.

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

[0017] According to one or more embodiments of the present disclosure, the semiconductor photoresist composition of the present disclosure can achieve excellent or appropriate sensitivity and excellent or appropriate LER characteristics. Specifically, the semiconductor photoresist can be prepared using a relatively low-corrosive and economical process without requiring negative tone patterning and size limitations, thereby improving commercial availability. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] Figures 1A to 1E is a cross-sectional view for illustrating a method of forming a pattern using a semiconductor photoresist composition according to one or more embodiments of the present disclosure.

[0019] Description of Reference Numerals

[0020] 100:Semiconductor substrate / substrate

[0021] 102:Film

[0022] 104: resist bottom layer

[0023] 106: Photoresist layer

[0024] 106a: Unexposed area

[0025] 106b: Exposed area

[0026] 108: Photoresist pattern

[0027] 110: Patterned mask

[0028] 112: organic layer pattern

[0029] 114: Thin film pattern DETAILED DESCRIPTION

[0030] The present disclosure can be modified in various alternative forms, and therefore specific embodiments will be illustrated in the drawings and described in more detail. However, it should be understood that there is no intention to limit the present disclosure to the particular forms disclosed, but rather to cover all modifications, equivalents, and alternatives that fall within the spirit and scope of the present disclosure.

[0031] Hereinafter, with reference to the accompanying drawings, embodiments will be described in more detail. In the following description of the disclosure, well-known appropriate functions or structures will not be described in order to clarify the disclosure.

[0032] In order to clearly illustrate the present disclosure, unnecessary descriptions and relationships are omitted, and the same or similar configuration elements are designated by the same reference numerals throughout the disclosure. In addition, since the size and thickness of each configuration shown in the drawings are arbitrarily shown for better understanding and ease of description, the disclosure is not necessarily limited thereto.

[0033] In the accompanying drawings, the thickness of layers, films, panels, regions, and / or the like is exaggerated for clarity. In the accompanying drawings, the thickness of portions of layers or regions and / or the like is exaggerated for clarity. It should be understood that if (for example, when) an element such as a layer, film, region, or substrate is referred to as being "on" another element, it can be directly on the other element or there can be intervening elements. Conversely, when an element is referred to as being "directly on" another element, there are no intervening elements.

[0034] As used herein, "substituted" may refer to hydrogen atoms being replaced by deuterium, halogen, hydroxyl, carboxyl, thiol, cyano, nitro, -NRR' (wherein R and R' are each independently hydrogen, a substituted or unsubstituted C1 to C30 saturated or unsaturated aliphatic hydrocarbon group, a substituted or unsubstituted C3 to C30 saturated or unsaturated alicyclic hydrocarbon group, and / or a substituted or unsubstituted C6 to C30 aromatic hydrocarbon group), -SiRR'R" (wherein R, R' and R" are each independently hydrogen, The term "substituted" may be substituted with a substituted or unsubstituted C1 to C30 saturated or unsaturated aliphatic hydrocarbon group, a substituted or unsubstituted C3 to C30 saturated or unsaturated alicyclic hydrocarbon group, and / 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 thioether group, and / or (for example, any suitable) combination thereof. "Unsubstituted" may mean that a hydrogen atom is not replaced by another substituent and the hydrogen atom remains.

[0035] As used herein, if (e.g., when) no definition is otherwise provided, "alkyl" may refer to a linear or branched aliphatic hydrocarbon group. The alkyl group may be a "saturated alkyl group" that does not contain any double or triple bonds.

[0036] In one or more embodiments, the alkyl group may be a C1 to C8 alkyl group. For example, the alkyl group may 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 may be a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, or a 2,2-dimethylpropyl group.

[0037] As used herein, if (eg, when) no definition is otherwise provided, "cycloalkyl" may refer to a monovalent cyclic aliphatic hydrocarbon group.

[0038] In one or more embodiments, the cycloalkyl group may be a C3 to C8 cycloalkyl group, for example, a C3 to C7 cycloalkyl group, a C3 to C6 cycloalkyl group, a C3 to C5 cycloalkyl group, and / or a C3 to C4 cycloalkyl group. For example, the cycloalkyl group may be a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, or a cyclohexyl group, but the present disclosure is not limited thereto.

[0039] As used herein, "aliphatic unsaturated organic group" may refer to a hydrocarbon group containing double bonds, triple bonds, and / or (eg, any suitable) combinations thereof between carbon atoms in the molecule.

[0040] In one or more embodiments, the aliphatic unsaturated organic group can be a C2 to C8 aliphatic unsaturated organic group. For example, the aliphatic unsaturated organic group can be a C2 to C7 aliphatic unsaturated organic group, a C2 to C6 aliphatic unsaturated organic group, a C2 to C5 aliphatic unsaturated organic group and / or a C2 to C4 aliphatic unsaturated organic group. For example, the C2 to C4 aliphatic unsaturated organic group can be vinyl, ethynyl, allyl, 1-propenyl, 1-methyl-1-propenyl, 2-propenyl, 2-methyl-2-propenyl, 1-propynyl, 1-methyl-1-propynyl, 2-propynyl, 2-methyl-2-propynyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-butynyl, 2-butynyl and / or 3-butynyl.

[0041] As used herein, "aryl" may refer to a substituent wherein all atoms in the cyclic substituent have p orbitals, which may be conjugated, and may include monocyclic or fused-ring polycyclic functionalities (eg, rings that share adjacent pairs of carbon atoms).

[0042] As used herein, "heteroaryl" may refer to an aryl group comprising at least one heteroatom selected from nitrogen (N), oxygen (O), sulfur (S), phosphorus (P), and / or silicon (Si). Two or more heteroaryl groups may be directly linked by a sigma bond, or if (e.g., when) the heteroaryl group comprises two or more rings, the two or more rings may be fused. In one or more embodiments, if (e.g., when) the heteroaryl group is a fused ring, each ring may comprise one to three heteroatoms.

[0043] As utilized herein, unless otherwise defined, "alkenyl" may refer to an aliphatically unsaturated alkenyl group that is a linear and / or branched aliphatic hydrocarbon group containing at least one double bond.

[0044] As utilized herein, unless otherwise defined, "alkynyl" may refer to an aliphatically unsaturated alkynyl group that is a linear and / or branched aliphatic hydrocarbon group containing at least one triple bond.

[0045] Semiconductor photoresist compositions according to one or more embodiments are described below.

[0046] In one or more embodiments, the semiconductor photoresist composition may include a Sn-containing organometallic compound, a carboxylic acid compound substituted with an oxygen (O)-containing heterocycle, and a solvent.

[0047] In one or more embodiments, a semiconductor photoresist composition may include a carboxylic acid compound substituted with an oxygen-containing heterocycle, thereby improving sensitivity and line-edge roughness and achieving excellent or moderate resolution. Specifically, in one or more embodiments, the semiconductor photoresist composition includes a tin-containing organometallic compound and an oxygen-containing heterocycle carboxylic acid compound, which together enhance sensitivity and line-edge roughness while achieving excellent resolution.

[0048] The carboxylic acid compound substituted with an oxygen-containing heterocycle may be represented by Chemical Formula 1.

[0049] [Chemical Formula 1]

[0050]

[0051] In Chemical Formula 1,

[0052] A1 may be an oxygen-containing heterocycle,

[0053] L 1 It may be a single bond, a substituted or unsubstituted C1 to C10 alkylene group, a substituted or unsubstituted C2 to C10 alkenylene group, a substituted or unsubstituted C2 to C10 alkynylene group, and / or a substituted or unsubstituted C6 to C20 arylene group.

[0054] The oxygen-containing heterocycle can be substituted or unsubstituted furan, substituted or unsubstituted tetrahydrofuran, substituted or unsubstituted pyran, substituted or unsubstituted dihydropyran, substituted or unsubstituted maleic anhydride, substituted or unsubstituted succinic anhydride, substituted or unsubstituted butyrolactone, and / or (e.g., any appropriate) combinations thereof.

[0055] As an example, the carboxylic acid compound substituted with an oxygen-containing heterocycle may be represented by any one of (eg, selected from) Chemical Formula 1-1 to Chemical Formula 1-7.

[0056] [Chemical Formula 1-1] [Chemical Formula 1-2] [Chemical Formula 1-3] [Chemical Formula 1-4]

[0057]

[0058] [Chemical Formula 1-5] [Chemical Formula 1-6] [Chemical Formula 1-7]

[0059]

[0060] In Chemical Formulas 1-1 to 1-7,

[0061] R 1 to R 6 Each may independently be hydrogen, halogen, hydroxyl, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C6 to C30 aryl, and / or (for example, any appropriate) combination thereof.

[0062] L 1It may be a single bond, a substituted or unsubstituted C1 to C10 alkylene group, a substituted or unsubstituted C2 to C10 alkenylene group, a substituted or unsubstituted C2 to C10 alkynylene group, and / or a substituted or unsubstituted C6 to C20 arylene group.

[0063] m1 and m3 may each independently be one of integers from 1 to 7, m2 may be one of integers from 1 to 5, m4 and m5 may each independently be one of integers from 1 to 3, and m6 is 1.

[0064] When m1 is 2 or greater, each R 1 Can be the same or different.

[0065] When m2 is 2 or greater, each R 2 Can be the same or different.

[0066] When m3 is 2 or greater, each R 3 Can be the same or different.

[0067] When m4 is 2 or greater, each R 4 Can be the same or different.

[0068] When m5 is 2 or greater, each R 5 Can be the same or different.

[0069] When m6 is 2 or greater, each R 6 Can be the same or different.

[0070] In some embodiments, the carboxylic acid compound substituted with an oxygen-containing heterocycle can be any one selected from the compounds listed in Group 1.

[0071] [Group 1]

[0072]

[0073] The carboxylic acid compound substituted with an oxygen-containing heterocycle may be included in an amount of about 0.001 to about 10 wt %, based on 100 wt % of the total weight of the semiconductor photoresist composition.

[0074] For example, the carboxylic acid compound substituted with an oxygen-containing heterocycle may be included in an amount of about 0.01 to about 10 wt %, about 0.01 to about 5 wt %, about 0.05 to about 5 wt %, or about 0.1 to about 5 wt %, based on 100 wt % of the total weight of the semiconductor photoresist composition.

[0075] The Sn-containing organometallic compound may be included in an amount of about 0.5 wt % to about 30 wt % based on 100 wt % of the total weight of the semiconductor photoresist composition.

[0076] In one or more embodiments, the semiconductor photoresist composition can improve the sensitivity of the photoresist by including the Sn-containing organometallic compound and the carboxylic acid compound substituted with an oxygen-containing heterocycle within the above content (eg, amount) range.

[0077] In one or more embodiments, the semiconductor photoresist composition may include a Sn-containing organometallic compound and a carboxylic acid compound substituted by an oxygen-containing heterocycle in a weight ratio of about 99:1 to about 60:40. For example, the semiconductor photoresist composition may include a Sn-containing organometallic compound and a carboxylic acid compound substituted by an oxygen-containing heterocycle in a weight ratio of about 90:10 to about 60:40.

[0078] If (for example, when) the weight ratio of the Sn-containing organometallic compound to the carboxylic acid compound satisfies the above range, a semiconductor photoresist composition having excellent or appropriate sensitivity can be provided.

[0079] In one or more embodiments, the Sn-containing organometallic compound may include at least one organic oxy group and / or organic carbonyloxy group.

[0080] The Sn-containing organometallic compound may be represented by Chemical Formula 2.

[0081] [Chemical Formula 2]

[0082]

[0083] In Chemical Formula 2,

[0084] R 9 The group 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 / or a substituted or unsubstituted C6 to C30 aralkyl group.

[0085] R 10 to R 12 Each of the alkyl groups may be independently 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 (e.g., -OR a , where R aThe alkyl group 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, and / or (for example, any appropriate) combination thereof), a carboxyl group (for example, -O(CO)R b , where R b 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, and / or (e.g., any appropriate) combination thereof), an alkylamido group, or a dialkylamido group (e.g., -NR c R d , where R c and R d may each independently be hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, and / or (for example, any appropriate) combination thereof), an amido group (for example, -NR e (COR f ), where R e and R f may each independently be hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, and / or (for example, any appropriate) combination thereof), an amidinato group (for example, -NR g C(NR h )R i , where R g 、R h and R i The alkyl groups may each independently be hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, and / or (e.g., any appropriate) combination thereof), an alkylthio group, or an arylthio group (e.g., -SR j , where R jThe alkyl group 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, and / or (for example, any appropriate) combination thereof) or a thiocarboxyl group (for example, -S(CO)R k , where R k It may be hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, and / or (e.g., any appropriate) combination thereof).

[0086] R 10 to R 12 At least one of them can be selected from alkoxy or aryloxy (e.g., -OR a , where R a The alkyl group 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, and / or (for example, any appropriate) combination thereof), a carboxyl group (for example, -O(CO)R b , where R b 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, and / or (e.g., any appropriate) combination thereof), an alkylamide group, or a dialkylamide group (e.g., -NR c R d , where R c and R d The alkyl radicals may each independently be hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, and / or (for example, any appropriate) combination thereof), an amide group (for example, -NR e (COR f ), where R e and R fmay each independently be hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, and / or (e.g., any appropriate) combination thereof), an amidino group (e.g., -NR g C(NR h )R i , where R g 、R h and R i The alkyl groups may each independently be hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, and / or (e.g., any appropriate) combination thereof), an alkylthio group, or an arylthio group (e.g., -SR j , where R j 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, and / or (e.g., any appropriate) combination thereof) and a thiocarboxy group (e.g., -S(CO)R k , where R k is selected from hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, and / or (e.g., any appropriate combination thereof).

[0087] R 10 to R 12 At least one of them can be selected from alkoxy or aryloxy (e.g., -OR a , where R a 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, and / or (e.g., any appropriate) combination thereof) and a carboxyl group (e.g., —O(CO)R b , where R bis selected from hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, and / or (e.g., any appropriate combination thereof).

[0088] In one or more embodiments, the compound represented by Chemical Formula 2 may include -OR a and / or -OC(=O)R b As a ligand, in order to utilize the compound represented by Chemical Formula 2 (which includes -OR a and / or -OC(=O)R b The pattern formed by the semiconductor photoresist composition containing a photosensitive adhesive as a ligand can exhibit excellent or appropriate limiting resolution.

[0089] In addition, -OR a and / or -OC(=O)R b The ligand may determine the solubility of the compound represented by Chemical Formula 2 in a solvent.

[0090] R 9 may be a substituted or unsubstituted C1 to C8 alkyl group, a substituted or unsubstituted C3 to C8 cycloalkyl group, a substituted or unsubstituted C2 to C8 aliphatic unsaturated organic group including one or more double bonds and / or triple bonds, a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C4 to C20 heteroaryl group, a carbonyl group, an ethoxy group, a propoxy group, and / or (for example, any appropriate) combinations thereof,

[0091] R a It may be a substituted or unsubstituted C1 to C8 alkyl group, a substituted or unsubstituted C3 to C8 cycloalkyl group, a substituted or unsubstituted C2 to C8 alkenyl group, a substituted or unsubstituted C2 to C8 alkynyl group, a substituted or unsubstituted C6 to C20 aryl group, and / or (e.g., any appropriate) combination thereof.

[0092] R b 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, and / or (e.g., any appropriate) combination thereof.

[0093] R 9It 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, formyl, acetyl, propionyl, butyryl, valeryl, ethoxy, propoxy, and / or its (e.g., any suitable) combination.

[0094] R a It 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, and / or its (e.g., any suitable) combination.

[0095] R b 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, and / or its (e.g., any suitable) combination.

[0096] In addition, the Sn-containing organometallic compound can be represented by Chemical Formula 3 or Chemical Formula 4.

[0097] [Chemical Formula 3]

[0098] R 12 z SnO (2-(z / 2)-(x / 2)) (OH) x

[0099] In Chemical Formula 3,

[0100] R 12 can be a C1 to C31 hydrocarbon group, 0 < z ≤ 2, and 0 < (z + x) ≤ 4;

[0101] [Chemical Formula 4]

[0102] R 13 a1 Sn b1 X c1 Y d1

[0103] In Chemical Formula 4,

[0104] R 13The group 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 aliphatic unsaturated organic group containing one or more double bonds or triple bonds, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C4 to C30 heteroaryl group, a carbonyl group, an ethylene oxide group, a propylene oxide group, and / or (for example, any suitable) combination thereof.

[0105] X may be sulfur (S), selenium (Se) and / or tellurium (Te).

[0106] Y can be -OR l and / or -OC(=O)R m , where R l It 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, and / or (e.g., any suitable) combination thereof.

[0107] R m It may be hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, and / or (e.g., any suitable) combination thereof.

[0108] a1, b1, c1, and d1 may each independently be an integer of 1 to 20.

[0109] In one or more embodiments, the solvent of the semiconductor photoresist composition may be an organic solvent, 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 and / or 1-propanol), an ether (e.g., anisole, tetrahydrofuran), an ester (e.g., n-butyrate, propylene glycol monomethyl ether acetate, ethyl acetate and / or ethyl lactate), a ketone (e.g., methyl ethyl ketone and / or 2-heptanone) and / or a mixture thereof (e.g., any suitable mixture), but the present disclosure is not limited thereto.

[0110] In one or more embodiments, the semiconductor photoresist composition may further include a resin in addition to the aforementioned Sn-containing organometallic compound, carboxylic acid compound and / or solvent.

[0111] The resin may be a phenolic resin comprising at least one (eg, any) aromatic moiety (eg, selected from moieties of Group 2).

[0112] [Group 2]

[0113]

[0114] In one or more embodiments, the resin may have a weight average molecular weight of about 500 to about 20,000.

[0115] In one or more embodiments, the resin may be included in an amount of about 0.1 wt % to about 50 wt % based on 100 wt % of the total amount of the semiconductor photoresist composition.

[0116] If (eg, when) the resin is included in the above content (eg, amount) range, the semiconductor photoresist composition may have excellent or appropriate etching resistance and heat resistance.

[0117] In contrast, in one or more embodiments, the semiconductor photoresist composition may include (eg, be composed of) the aforementioned Sn-containing organometallic compound, carboxylic acid compound, solvent, and / or resin.

[0118] In some embodiments, the semiconductor photoresist composition may further include additives as needed. Examples of the additives may include surfactants, crosslinking agents, leveling agents, organic acids, quenchers, and / or any suitable combination thereof.

[0119] The surfactant may include, for example, alkylbenzene sulfonate, alkylpyridinium salt, polyethylene glycol, quaternary ammonium salt, and / or (eg, any suitable) combination thereof, but the present disclosure is not limited thereto.

[0120] The crosslinking agent may be, for example, a melamine-based crosslinking agent, a substituted urea-based crosslinking agent, an acrylic-based crosslinking agent, an epoxy-based crosslinking agent, and / or a polymer-based crosslinking agent, but the present disclosure is not limited thereto. It may be a cross-linking agent having at least two cross-linking-forming substituents, for example, a compound such as methoxymethylated glycoluril, butoxymethylated biuret, methoxymethylated melamine, butoxymethylated melamine, methoxymethylated benzoguanamine, butoxymethylated benzoguanamine, 4-hydroxybutyl acrylate, acrylic acid, urethane acrylate, methyl acrylate, 1,4-butanediol diglycidyl ether, glycidol, diglycidyl 1,2-cyclohexane dicarboxylate, trimethylpropane triglycidyl ether, 1,3-bis(glycidyloxypropyl)tetramethyldisiloxane, methoxymethylated urea, butoxymethylated urea, methoxymethylated thiourea, and / or the like.

[0121] The leveling agent may be used to improve the flatness of the coating during the printing process, and may be a suitable leveling agent available on the market.

[0122] The organic acid may include p-toluenesulfonic acid, benzenesulfonic acid, p-dodecylbenzenesulfonic acid, 1,4-naphthalene disulfonic acid, methanesulfonic acid, sulfonium fluoride, malonic acid, citric acid, propionic acid, methacrylic acid, oxalic acid, lactic acid, glycolic acid, succinic acid and / or a combination thereof (e.g., any suitable combination), but the present disclosure is not limited thereto.

[0123] The quencher can be diphenyl(p-tolyl)amine, methyldiphenylamine, triphenylamine, phenylenediamine, naphthylamine, diaminonaphthalene, and / or (eg, any suitable) combinations thereof.

[0124] The amount of additives used can be controlled or selected according to desired or suitable properties.

[0125] In addition, the semiconductor photoresist composition may further include a silane coupling agent as an adhesion enhancer to improve the close contact force with the substrate (for example, to improve 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; or 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, p-phenylyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, trimethoxy[3-(phenylamino)propyl]silane; and / or the like, but the present disclosure is not limited thereto.

[0126] The semiconductor photoresist composition can form a pattern with a high aspect ratio without collapse. In one or more embodiments, in order to form a fine pattern having a width (e.g., line width) of, for example, about 5 nanometers to about 100 nanometers, such as about 5 nanometers to about 80 nanometers, such as about 5 nanometers to about 70 nanometers, such as about 5 nanometers to about 50 nanometers, such as about 5 nanometers to about 40 nanometers, such as about 5 nanometers to about 30 nanometers, or such as about 5 nanometers to about 20 nanometers, the semiconductor photoresist composition can be used for a photolithography process utilizing light having a wavelength in the range of about 5 nanometers to about 150 nanometers, such as about 5 nanometers to about 100 nanometers, about 5 nanometers to about 80 nanometers, about 5 nanometers to about 50 nanometers, about 5 nanometers to about 30 nanometers, or about 5 nanometers to about 20 nanometers. Therefore, in one or more embodiments, the semiconductor photoresist composition can be used for realizing extreme ultraviolet lithography utilizing an EUV light source having a wavelength of about 13.5 nanometers.

[0127] In one or more embodiments, a method for forming a pattern using the semiconductor photoresist composition may be provided. For example, the pattern may be a photoresist pattern.

[0128] In one or more embodiments, the method of forming a pattern may include forming an etching target layer on a substrate, coating a semiconductor photoresist composition on the etching target layer to form a photoresist layer, patterning the photoresist layer to form a photoresist pattern, and etching the etching target layer using the photoresist pattern as an etching mask.

[0129] The following reference Figures 1A to 1E Methods for forming patterns using semiconductor photoresist compositions are described. Figures 1A to 1E is a cross-sectional view illustrating a method for forming a pattern using a semiconductor photoresist composition according to one or more embodiments.

[0130] Reference Figure 1AAn object for etching (e.g., an etching target layer or etching target layer) may be prepared. The object for etching may be a thin film 102 formed on a semiconductor substrate 100. Hereinafter, the object for etching may be defined as the thin film 102. The surface of the thin film 102 is cleaned to remove impurities and / or the like remaining thereon. The thin film 102 may be, for example, a silicon nitride layer, a polysilicon layer, and / or a silicon oxide layer.

[0131] Subsequently, a resist base layer composition for forming the resist base layer 104 is spin-coated on the surface of the cleaned thin film 102. However, one or more embodiments are not limited thereto, and one or more suitable coating methods, such as spray coating, dip coating, doctor blade coating, printing methods such as inkjet printing and screen printing, and / or the like, may be used.

[0132] The process of coating the resist primer layer may not be provided, and the process including coating the resist primer layer will be described below.

[0133] Then, the applied composition is dried and baked to form a resist bottom layer 104 on the thin film 102. The baking may be performed at a temperature of about 100°C to about 500°C, for example, about 100°C to about 300°C.

[0134] The resist bottom layer 104 is formed between the substrate 100 and the photoresist layer 106, thereby preventing or reducing the non-uniformity of the photoresist line width and pattern formation when light reflected from the interface between the substrate 100 and the photoresist layer 106 or the interlayer hard mask is scattered to an unintended photoresist area.

[0135] Reference Figure 1B The photoresist layer 106 is formed by coating a semiconductor photoresist composition on the resist bottom layer 104. The photoresist layer 106 is obtained by coating the semiconductor photoresist composition on the thin film 102 formed on the substrate 100 and then curing the semiconductor photoresist composition by heat treatment.

[0136] More specifically, forming a pattern using a semiconductor photoresist composition may include coating the semiconductor resist composition on the substrate 100 having the thin film 102 by spin coating, slit coating, inkjet printing and / or the like, and then drying the semiconductor photoresist composition to form a photoresist layer 106 .

[0137] The composition of semiconductor photoresist has been described in detail and will not be repeated here.

[0138] Subsequently, the substrate 100 having the photoresist layer 106 is subjected to a first baking process (eg, heat treatment). The first baking process may be performed at a temperature of about 80°C to about 120°C.

[0139] Reference Figure 1C, the photoresist layer 106 may be selectively exposed using a patterned mask 110 .

[0140] For example, exposure can utilize activation radiation of light having a high energy wavelength, such as EUV (e.g., extreme ultraviolet with a wavelength of approximately 13.5 nanometers), E-Beam (e.g., electron beam), and / or similar light sources, as well as light having a wavelength such as i-line (e.g., a wavelength of approximately 365 nanometers), KrF excimer laser (e.g., a wavelength of approximately 248 nanometers), ArF excimer laser (a wavelength of approximately 193 nanometers), and / or the like.

[0141] More specifically, in one or more embodiments, the light or exposure beam used for exposure can have a wavelength in the range of about 5 nanometers to about 150 nanometers, and / or a high-energy wavelength, for example, can be EUV (for example, extreme ultraviolet light with a wavelength of 13.5 nanometers), and / or can be an electron beam (E-Beam), and / or a similar light source.

[0142] The exposed region 106 b of the photoresist layer 106 has a different solubility from the unexposed region 106 a of the photoresist layer 106 by a cross-linking reaction to form a polymer, such as condensation between organic metal compounds.

[0143] Subsequently, the substrate 100 is subjected to a second baking process (eg, heat treatment). The second baking process may be performed at a temperature of about 90° C. to about 200° C. Due to the second baking process, the exposed region 106 b of the photoresist layer 106 becomes easily insoluble to a developer.

[0144] exist Figure 1D In the process, the unexposed regions 106a of the photoresist layer are dissolved and removed using a developer to form a photoresist pattern 108. For example, the unexposed regions 106a of the photoresist layer are dissolved and removed using an organic solvent such as 2-heptanone and / or the like to complete the photoresist pattern 108 corresponding to a negative tone image.

[0145] As described above, in one or more embodiments, the developer used in the method for forming the pattern can be an organic solvent. In one or more embodiments, the organic solvent used in the method for forming the pattern 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, and / or (e.g., any suitable) combination thereof.

[0146] However, in one or more embodiments, the photoresist pattern is not necessarily limited to a negative tone image, but may be formed to have a positive tone image. Here, the developer used to form the positive tone image may be a quaternary ammonium hydroxide composition, such as tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and / or (e.g., any suitable) combination thereof.

[0147] As described above, exposure to light having high energy, such as EUV (e.g., extreme ultraviolet with a wavelength of 13.5 nanometers), E-Beam (e.g., electron beam), and / or similar light sources and having wavelengths, such as i-line (wavelength of approximately 365 nanometers), KrF excimer laser (wavelength of approximately 248 nanometers), ArF excimer laser (wavelength of approximately 193 nanometers), and / or similar light sources, can provide a photoresist pattern 108 having a thickness (e.g., thickness / width) of about 5 nanometers to about 100 nanometers. In other words, the application of high energy light / beam sources, such as EUV (e.g., extreme ultraviolet with a wavelength of 13.5 nanometers) and / or E-Beam (electron beam), and / or other light sources, such as i-line (365 nanometers), KrF excimer laser (248 nanometers), and / or ArF excimer laser (193 nanometers), can result in the formation of a photoresist pattern 108. The pattern can exhibit a range of thicknesses, typically from about 5 nanometers to about 100 nanometers. For example, the photoresist pattern 108 can have a thickness (e.g., a width of thickness) 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.

[0148] In addition, the photoresist pattern 108 can have a pitch with a half pitch (width) less than or equal to about 50 nanometers, for example, less than or equal to about 40 nanometers, for example, less than or equal to about 30 nanometers, for example, less than or equal to about 20 nanometers, or for example, less than or equal to about 15 nanometers, and a line width roughness less than or equal to about 10 nanometers, or less than or equal to about 5 nanometers, less than or equal to about 3 nanometers, or less than or equal to about 2 nanometers.

[0149] Subsequently, the resist bottom layer 104 is etched using the photoresist pattern 108 as an etching mask. Through this etching process, an organic layer pattern 112 is formed. The organic layer pattern 112 may also have a width corresponding to that of the photoresist pattern 108.

[0150] Reference Figure 1E The exposed thin film 102 is etched by using the photoresist pattern 108 as an etching mask. As a result, the thin film is formed into a thin film pattern 114.

[0151] The etching of the thin film 102 may be, for example, dry etching using an etching gas, and the etching gas may be, for example, CHF 3 , CF 4 , Cl 2 , BCl 3 , or (for example, any suitable) mixed gas thereof.

[0152] In the exposure process, the thin film pattern 114 formed using the photoresist pattern 108 formed by the exposure process using the EUV light source may have a width (e.g., line width) corresponding to the photoresist pattern 108. For example, the thin film pattern 114 may have a width (e.g., line width) of about 5 nanometers to about 100 nanometers, which may be equal to the width of the photoresist pattern 108. For example, the thin film pattern 114 formed using the photoresist pattern 108 formed by the exposure process using the EUV light source may have a width (e.g., line width) of about 5 nanometers to about 90 nanometers, about 5 nanometers to about 80 nanometers, about 5 nanometers to about 70 nanometers, about 5 nanometers to about 60 nanometers, about 5 nanometers to about 50 nanometers, about 5 nanometers to about 40 nanometers, about 5 nanometers to about 30 nanometers, or about 5 nanometers to about 20 nanometers, and more specifically, like the width of the photoresist pattern 108, has a width less than or equal to about 20 nanometers.

[0153] Hereinafter, the present disclosure will be described in more detail by way of an example of preparing the semiconductor photoresist composition. However, the present disclosure is not technically limited to the following example.

[0154] Synthesis of organometallic compounds

[0155] Synthesis Example 1

[0156] 40.7 g of t-butyltriphenyltin (t-butylSnPh3) and 300 g of propionic acid were added to a 250 ml two-necked round-bottom flask and heated under reflux for 24 hours.

[0157] By removing unreacted propionic acid under reduced pressure, the compound represented by Chemical Formula 5 was obtained.

[0158] [Chemical Formula 5]

[0159]

[0160] Synthesis Example 2

[0161] 30 ml of anhydrous pentane was added to 10 g of t-amyltin trichloride (t-AmylSnCl3), and the temperature was maintained at 0°C. 7.4 g of diethylamine and 6.1 g of ethanol were then added, and the mixture was stirred at room temperature for 1 hour. After the reaction was complete, the mixture was filtered, concentrated, and vacuum-dried to obtain the compound represented by Chemical Formula 6.

[0162] [Chemical Formula 6]

[0163]

[0164] Synthesis Example 3

[0165] 10 g of dibutyltin dichloride was dissolved in 30 ml of diethyl ether, and 70 ml of a 1 M (mol per liter) sodium hydroxide (NaOH) aqueous solution was added, followed by stirring for 1 hour. After stirring, the resulting solid was filtered, washed three times with 25 ml of deionized water, and dried under reduced pressure at 100°C to obtain an organometallic compound represented by Chemical Formula 7 having a weight average molecular weight of 1,500.

[0166] [Chemical Formula 7]

[0167]

[0168] (Preparation of Semiconductor Photoresist Composition)

[0169] Examples 1 to 18 and Comparative Examples 1 to 3

[0170] The Sn-containing organometallic compounds represented by Chemical Formulas 5 to 7 obtained in Synthesis Examples 1 to 3 and the carboxylic acid compounds represented by A1 to A5 were mixed with propylene glycol methylether acetate (PGMEA) in the weight ratio shown in Table 1 and dissolved at a concentration of 3 wt %, and then filtered through a 0.1 μm polytetrafluoroethylene (PTFE) syringe filter to prepare semiconductor photoresist compositions according to Examples 1 to 18 and Comparative Examples 1 to 3.

[0171]

[0172] (Table 1)

[0173]

[0174] Evaluation 1: Evaluation of sensitivity and line edge roughness (LER)

[0175] Each photoresist composition according to Examples 1 to 18 and Comparative Examples 1 to 3 was spin coated on a 200 mm circular silicon wafer with HMDS deposited on the surface at a speed of 1500 revolutions per minute (rpm) for 30 seconds, baked at 110°C for 60 seconds (e.g., post-apply baked (PAB)), and then allowed to stand at room temperature (23±2°C) for 30 seconds.

[0176] Subsequently, a linear array of 50 circular pads, each 500 micrometers in diameter, was projected onto the wafer coated with each photoresist composition using extreme ultraviolet light (Lawrence Berkeley National Laboratory Micro Exposure Tool (MET)). The pad exposure time was adjusted to ensure an increasing EUV dose was applied to each pad.

[0177] 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 a PGMEA solvent to form a negative tone image. Finally, the obtained film was baked again on a hot plate at 150°C for 2 minutes to complete the process.

[0178] The residual resist thickness of the exposed pads was measured using an ellipsometer. The remaining thickness at each exposure dose was measured and plotted as a function of exposure dose to measure sensitivity, and LER was measured from field emission scanning electron microscope (FE-SEM) images. Sensitivity and line edge roughness were evaluated according to the following criteria, and the results are shown in Tables 2 to 4.

[0179] [Evaluation criteria for sensitivity]

[0180] -A: less than 50 mJ / cm2 (mJ / cm 2 )

[0181] -B: greater than or equal to 50 mJ / cm2

[0182] [LER evaluation criteria]

[0183] -○: less than or equal to 2 nanometers

[0184] -△: greater than 2 nanometers and less than or equal to 5 nanometers

[0185] -X: greater than 5 nanometers

[0186] Evaluation 2: Evaluation of resolution

[0187] After completing the process, a line / space critical dimension (CD) pattern was formed on the patterned wafer, which was then transferred to a CD-SEM measurement device (GC-9380, Hitachi) to measure the CD size of the mask pattern at a half-pitch of 14 nm. The minimum value in the pitch CD (i.e., the distance between lines) is shown in Tables 2 to 4.

[0188] (Table 2)

[0189]

[0190] (Table 3)

[0191]

[0192] (Table 4)

[0193]

[0194] It can be seen from the results in Tables 2 to 4 that the patterns formed using the semiconductor photoresist compositions of Examples 1 to 18 exhibit superior sensitivity, line edge roughness, and resolution characteristics compared to Comparative Examples 1 to 3.

[0195] In this disclosure, the terms "and / or" and "or" may include any and all combinations of one or more of the listed items. An expression such as "at least one of" when preceding a list of elements modifies the entire list of elements and does not modify the individual elements of the list.

[0196] It will be further understood that the terms "comprising", "including" or "having" used in this disclosure specify the presence of the features, integers, steps, operations, elements and / or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components and / or groups thereof. The " / " used hereinafter may be interpreted as "and" or "or" as appropriate.

[0197] In the present disclosure, the singular forms "a," "an," and "the" are intended to include the plural forms unless the context clearly indicates otherwise. In addition, the use of "may" when describing embodiments of the present disclosure refers to "one or more embodiments of the present disclosure."

[0198] In the context of the present disclosure, unless defined otherwise, the terms "use," "using," and "used" may be considered synonymous with the terms "utilize," "utilizing," and "utilized," respectively.

[0199] In this disclosure, the term "about" or similar terms are used as terms of approximation, rather than terms of degree, to account for the inherent variations in measured or calculated values ​​recognized by those of ordinary skill in the art. As used herein, "about" or "approximately" is inclusive of the stated value and means within an acceptable range of deviation for the particular value as determined by one of ordinary skill in the art, taking into account the measurement in question and the errors associated with the measurement of the particular quantity (i.e., the limitations of the measurement system). For example, "about" may mean within one or more standard deviations, or within ±30%, 20%, 10%, or 5% of the stated value.

[0200] Any numerical range described herein is intended to include all subranges of the same numerical precision within the described range. For example, a range of "1.0 to 10.0" is intended to include all subranges between (and including) the described minimum value of 1.0 and the described maximum value of 10.0, i.e., having a minimum value equal to or greater than 1.0 and a maximum value equal to or less than 10.0, such as, for example, 2.4 to 7.6. Any maximum numerical limit described herein is intended to include all lower numerical limits contained therein, and any minimum numerical limit described in this specification is intended to include all higher numerical limits contained therein. Therefore, the applicant reserves the right to amend this specification (including the claims) to explicitly describe any subranges contained within the range explicitly described herein.

[0201] A person of ordinary skill in the art will understand, based on the entire content of this disclosure, that each appropriate feature of the various embodiments of the disclosure may be partially or completely combined with each other or with other features, and may be technically locked and operated with each other in various appropriate manners, and each embodiment may be implemented independently or in conjunction with each other in any appropriate manner, unless otherwise specified or implied.

[0202] The pattern forming device, semiconductor forming device and / or any other related device or component according to the embodiments of the present invention can be implemented using any appropriate hardware, firmware (e.g., application-specific integrated circuit), software, or a combination of software, firmware, and hardware. For example, the various components of the device can be formed on an integrated circuit (IC) chip or on separate IC chips. In addition, the various components of the device can be implemented on a flexible printed circuit film, a tape carrier package (TCP), a printed circuit board (PCB), or formed on a substrate. In addition, the various components of the device can be processes or threads running on one or more processors in one or more computing devices, executing computer program instructions and interacting with other system components to perform the various functions described herein. The computer program instructions are stored in a memory, which can be implemented in a computing device using a standard storage device (e.g., random access memory (RAM)). The computer program instructions can also be stored in other non-transient computer-readable media, such as a CD-ROM, a flash drive, or a similar device. Furthermore, those skilled in the art will recognize that the functionality of various computing devices may be combined or integrated into a single computing device, or that the functionality of a particular computing device may be distributed across one or more other computing devices without departing from the scope of the present disclosure.

[0203] While specific embodiments have been described and illustrated herein, it will be apparent to those skilled in the art that the present disclosure is not limited to the one or more described embodiments and that various modifications and conversions may be made without departing from the spirit and scope of the present disclosure. Therefore, such modified or converted embodiments should not be understood separately from the technical concepts and aspects of the present disclosure, and such modified embodiments are within the scope of the claims of the present disclosure.

Claims

1. A semiconductor photoresist composition comprising: Tin-containing organometallic compounds; Carboxylic acid compounds substituted with oxygen-containing heterocycles; as well as solvent.

2. The semiconductor photoresist composition according to claim 1, wherein the carboxylic acid compound substituted with an oxygen-containing heterocycle is represented by Chemical Formula 1: [Chemical Formula 1] In Chemical Formula 1, A1 is an oxygen-containing heterocycle, and L 1 is a single bond, a substituted or unsubstituted C1 to C10 alkylene group, a substituted or unsubstituted C2 to C10 alkenylene group, a substituted or unsubstituted C2 to C10 alkynylene group, or a substituted or unsubstituted C6 to C20 arylene group.

3. The semiconductor photoresist composition according to claim 1, wherein the oxygen-containing heterocycle is substituted or unsubstituted furan, substituted or unsubstituted tetrahydrofuran, substituted or unsubstituted pyran, substituted or unsubstituted dihydropyran, substituted or unsubstituted maleic anhydride, substituted or unsubstituted succinic anhydride, substituted or unsubstituted butyrolactone, or a combination thereof.

4. The semiconductor photoresist composition according to claim 1, wherein the carboxylic acid compound substituted with an oxygen-containing heterocycle is represented by any one of Chemical Formulas 1-1 to 1-7: [Chemical Formula 1-1] [Chemical Formula 1-2] [Chemical Formula 1-3] [Chemical Formula 1-4] [Chemical Formula 1-5] [Chemical Formula 1-6] [Chemical Formula 1-7] In Chemical Formulas 1-1 to 1-7, R 1 to R 6 are each independently hydrogen, halogen, hydroxy, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C6 to C30 aryl, or a combination thereof, L 1 is a single bond, a substituted or unsubstituted C1 to C10 alkylene group, a substituted or unsubstituted C2 to C10 alkenylene group, a substituted or unsubstituted C2 to C10 alkynylene group, or a substituted or unsubstituted C6 to C20 arylene group, m1 and m3 are each independently an integer from 1 to 7, m2 is an integer from 1 to 5, m4 and m5 are each independently an integer from 1 to 3, and m6 is 1.

5. The semiconductor photoresist composition according to claim 1, wherein the carboxylic acid compound substituted with an oxygen-containing heterocycle is any one selected from the compounds listed in Group 1: [Group 1] 6 . The semiconductor photoresist composition according to claim 1 , wherein the amount of the carboxylic acid compound substituted with an oxygen-containing heterocycle is 0.001 to 10 wt % based on 100 wt % of the total weight of the semiconductor photoresist composition. 7 . The semiconductor photoresist composition according to claim 1 , wherein the amount of the carboxylic acid compound substituted with an oxygen-containing heterocycle is 0.1 to 5 wt % based on 100 wt % of the total weight of the semiconductor photoresist composition. 8 . The semiconductor photoresist composition according to claim 1 , wherein an amount of the tin-containing organometallic compound is 0.5 wt % to 30 wt % based on 100 wt % of the total weight of the semiconductor photoresist composition. 9 . The semiconductor photoresist composition according to claim 1 , wherein the semiconductor photoresist composition further comprises an additive of a surfactant, a cross-linking agent, a leveling agent, an organic acid, a quencher, or a combination thereof.

10. The semiconductor photoresist composition according to claim 1, wherein the tin-containing organometallic compound comprises at least one organic oxygen group and an organic carbonyl oxygen group.

11. The semiconductor photoresist composition according to claim 1, wherein the tin-containing organometallic compound is represented by Chemical Formula 2: [Chemical Formula 2] In Chemical Formula 2, R 9 selected from substituted or unsubstituted C1 to C20 alkyl groups, substituted or unsubstituted C3 to C20 cycloalkyl groups, substituted or unsubstituted C2 to C20 alkenyl groups, substituted or unsubstituted C2 to C20 alkynyl groups, substituted or unsubstituted C6 to C30 aryl groups, and substituted or unsubstituted C6 to C30 aralkyl groups, R 10 to R 12 are each independently 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, an alkylamido group or a dialkylamido group, or a thiocarbonyl group, R 10 to R 12 At least one of the groups is an alkoxy or aryloxy group, a carboxyl group, an alkylamide or dialkylamide group, an amide group, an amidine group, an alkylthio or arylthio group, or a thiocarbonyl group.

12. The semiconductor photoresist composition according to claim 11, wherein R 10 to R 12 At least one from -OR a or -O(CO)R b Select from the following: a 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, wherein R b 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.

13. The semiconductor photoresist composition according to claim 12, wherein R 9 is a substituted or unsubstituted C1 to C8 alkyl group, a substituted or unsubstituted C3 to C8 cycloalkyl group, a substituted or unsubstituted C2 to C8 aliphatic unsaturated organic group containing one or more double bonds or triple bonds, a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C4 to C20 heteroaryl group, a carbonyl group, an ethoxy group, a propoxy group, or a combination thereof, R a is a substituted or unsubstituted C1 to C8 alkyl group, a substituted or unsubstituted C3 to C8 cycloalkyl group, a substituted or unsubstituted C2 to C8 alkenyl group, a substituted or unsubstituted C2 to C8 alkynyl group, a substituted or unsubstituted C6 to C20 aryl group, or a combination thereof, and R b 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.

14. The semiconductor photoresist composition according to claim 1, wherein the tin-containing organometallic compound is represented by Chemical Formula 3 or Chemical Formula 4: [Chemical Formula 3] R 12 z SnO (2-(z / 2)-(x / 2)) (OH) x , In Chemical Formula 3, R 12 is a C1 to C31 hydrocarbon group, 0 < z ≤ 2, and 0 < (z + x) ≤ 4; [Chemical Formula 4] R 13 a1 Sn b1 X c1 Y d1 , In Chemical Formula 4, R 13 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 aliphatic unsaturated organic group containing one or more double bonds or triple bonds, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C4 to C30 heteroaryl group, a carbonyl group, an ethylene oxide group, a propylene oxide group, or a combination thereof, X is sulfur, selenium or tellurium, and Y is -OR l or -OC(=O)R m ,and where R l 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, R m 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 a1, b1, c1 and d1 are each independently an integer of 1 to 20.

15. A method comprising: forming an etching target layer on a substrate; coating the semiconductor photoresist composition according to any one of claims 1 to 14 on the etching target layer to form a photoresist layer; patterning the photoresist layer to form a photoresist pattern; and etching the etching target layer using the photoresist pattern as an etching mask, The method described herein is a method for forming a pattern.

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