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 a first organic metal compound represented by (R1) a-M < 1 >-X < 1b >, a second organic metal compound represented by (R2) c-M < 2 >-X < 2d >, and a solvent.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This disclosure claims priority to and the benefit of Korean Patent Application No. 10-2024-0022094, filed on February 15, 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 attracted widespread attention as a fundamental technology for manufacturing next-generation semiconductor devices. In other words, EUV lithography has garnered significant attention as a key technology for the production of next-generation semiconductor devices. EUV lithography is a patterning technology that uses EUV radiation with a wavelength of 13.5 nanometers as an exposure light source. Using EUV lithography, extremely fine patterns (e.g., less than or equal to 20 nanometers) can be formed during the exposure process during the manufacturing of semiconductor devices (e.g., semiconductor chips).

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

[0006] Intrinsic image blurring caused by acid-catalyzed reactions in these polymer-based resists limits resolution of small features, a long-standing problem in electron beam (e-beam) lithography. Chemically amplified (CA) resists, designed for high sensitivity, may have reduced sensitivity due to their typical elemental composition, which reduces the resist's absorption of light at 13.5 nm. Furthermore, CA resists may encounter additional difficulties with EUV exposure.

[0007] Furthermore, CA photoresists may encounter difficulties at small feature sizes due to roughness issues, and the line edge roughness (LER) of CA photoresists may increase in experiments because the photospeed may be partially reduced due to the nature of the acid catalysis 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 shortcomings of chemically amplified (CA) organic photosensitive compositions, inorganic photosensitive compositions have been studied. These compositions are primarily or predominantly 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 hydrocarbons, ensuring sensitivity through a non-chemical amplification mechanism. They are also less susceptible to stochastic effects, resulting in lower line-edge roughness and fewer 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 with extreme ultraviolet (deep ultraviolet), X-ray, and electron beam sources. x ) materials together with a peroxide complexing agent obtained improved performance when imaged at 15 nm half-pitch (HP) by projection EUV exposure. The system exhibits high performance of non-CA photoresists and has practical photosensitivity close to 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 mixture of corrosive sulfuric acid / hydrogen peroxide and have insufficient shelf life stability. Second, changes in the material structure as a composite mixture to improve performance are challenging. Third, development should be carried out in a very concentrated 25 wt% tetramethylammonium hydroxide (TMAH) solution and / or the like.

[0011] To address these issues, research has focused on developing tin-containing molecules with excellent or moderate extreme ultraviolet (EUV) absorption. In the case of organotin polymers, the alkyl ligands in these tin-containing molecules dissociate through light absorption or the generation of secondary electrons. The dissociated alkyl ligands then crosslink with adjacent chains via oxygen bonds, enabling negative-tone patterning that cannot be removed by organic developers. While such organotin polymers exhibit greatly improved sensitivity while maintaining resolution and line-edge roughness, further improvement in patterning properties is required for commercial viability. Summary of the Invention

[0012] One or more aspects of the embodiments of the present disclosure relate to semiconductor photoresist compositions having excellent or appropriate coating properties and line edge roughness (LER).

[0013] One or more aspects of the embodiments of the present disclosure relate to a method of 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] According to one or more embodiments of the present disclosure, a semiconductor photoresist composition includes a first organometallic compound represented by Chemical Formula 1, a second organometallic compound represented by Chemical Formula 2, and a solvent.

[0016] Chemical formula 1

[0017] (R 1 ) a -M 1 -X 1 b

[0018] Chemical formula 2

[0019] (R 2 ) c -M 2 -X 2 d

[0020] In Chemical Formula 1 and Chemical Formula 2,

[0021] M 1 and M 2 can each independently be tin (Sn) or tellurium (Te),

[0022] R 1 It may be a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, or -L a -OR a (where L a is a single bond or a substituted or unsubstituted C1 to C20 alkylene group, and R a is a substituted or unsubstituted C1 to C20 alkyl group),

[0023] R 2 may be a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 heterocycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C2 to C30 heteroaryl group,

[0024] X 1 and X 2 can be independently selected from alkoxy or aryloxy (-OR b , where Rb 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, a substituted or unsubstituted C7 to C30 aralkyl group, or a combination thereof (e.g., any suitable combination), a carboxyl group (-O(CO)R c , where R c It may 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, a substituted or unsubstituted C7 to C30 aralkyl group, or a combination thereof (e.g., any suitable combination), an alkylamide group, or a dialkylamide group (—NR d R e , where R d and R e each independently represents 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, a substituted or unsubstituted C7 to C30 aralkyl group, or a combination thereof (e.g., any suitable combination), an amido group (-NR f (COR g ), where R f and R g 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, a substituted or unsubstituted C7 to C30 aralkyl group, or a combination thereof (e.g., any suitable combination), an amidinato group (-NR h C(NR i )R j , where R h 、R i and R jThe 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, a substituted or unsubstituted C7 to C30 aralkyl group, or a combination thereof (e.g., any suitable combination), an alkylthio group, or an arylthio group (-SR k , where R k 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, a substituted or unsubstituted C7 to C30 aralkyl group, or any suitable combination thereof, and a thiocarboxyl group (-S(CO)R l , where R l It can be 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, substituted or unsubstituted C7 to C30 aralkyl, or (for example, any suitable) combination thereof,

[0025] a, b, c and d can each independently be an integer from 1 to 5,

[0026] a+b is an integer of 4 or 6, and

[0027] c+d is an integer of 4 or 6.

[0028] According to one or more embodiments, a method of forming a pattern includes forming an etching target layer (e.g., 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.

[0029] The semiconductor photoresist composition according to one or more embodiments may provide a photoresist pattern having excellent or appropriate coating properties and line edge roughness. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] The above and other aspects, features and advantages of certain embodiments of the present disclosure will become more apparent from the following description taken in conjunction with the accompanying drawings, in which:

[0031] Figure 1A-1Eis 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.

[0032] 100:Semiconductor substrate / substrate

[0033] 102:Film

[0034] 104: resist bottom layer

[0035] 106: Photoresist layer

[0036] 106a: Unexposed area

[0037] 106b: Exposed area

[0038] 108: Photoresist pattern

[0039] 110: Patterned mask

[0040] 112: organic layer pattern

[0041] 114: Thin film pattern DETAILED DESCRIPTION

[0042] 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.

[0043] Hereinafter, exemplary embodiments of the present disclosure will be described in more detail with reference to the accompanying drawings. In the following description of the present disclosure, established functions or structures will not be described in order to simplify the present disclosure.

[0044] 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 shown for better understanding and ease of description, the present disclosure is not necessarily limited thereto.

[0045] In the accompanying drawings, the thickness of layers, films, panels, regions, and / or the like may be exaggerated for clarity. In the accompanying drawings, the thickness of portions of layers or regions and / or the like may be 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 may be directly on the other element, or there may be intervening elements therebetween. Conversely, when an element is referred to as being "directly on" another element, there are no intervening elements therebetween.

[0046] As used herein, "substituted" refers to the replacement of hydrogen with deuterium, halogen, hydroxyl, carboxyl, thiol, cyano, nitro, -NRR' (wherein R and R' are each independently hydrogen, substituted or unsubstituted C1 to C30 saturated or unsaturated aliphatic hydrocarbon groups, substituted or unsubstituted C3 to C30 saturated or unsaturated alicyclic hydrocarbon groups, or substituted or unsubstituted C6 to C30 aromatic hydrocarbon groups), -SiRR'R" (wherein R, R' and R" are each independently hydrogen, The term "unsubstituted" refers to a C1 to C30 saturated or unsaturated aliphatic hydrocarbon group, a substituted or unsubstituted C3 to C30 saturated or unsaturated alicyclic hydrocarbon group, or a substituted or unsubstituted C6 to C30 aromatic hydrocarbon group), 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" means that a hydrogen is not replaced by another substituent and the hydrogen remains.

[0047] As used herein, if (for example, when) no further definition is provided, the term "alkyl" refers 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.

[0048] The alkyl group may be a C1 to C10 alkyl group. For example, the alkyl group may be a C1 to C8 alkyl group, 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.

[0049] As used herein, if (eg, when) no definition is otherwise provided, the term "cycloalkyl" refers to a monovalent cyclic aliphatic hydrocarbon group.

[0050] The cycloalkyl group may be a C3 to C10 cycloalkyl group, for example, a C3 to C8 cycloalkyl group, a C3 to C7 cycloalkyl group, or a C3 to C6 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.

[0051] As used herein, the term "aryl" refers to a cyclic substituent in which all atoms have p orbitals and these p orbitals are conjugated, and may include monocyclic or fused-ring polycyclic functional groups (ie, rings that share adjacent pairs of carbon atoms).

[0052] As used herein, unless otherwise defined, the term "alkenyl" refers to an aliphatically unsaturated alkenyl group that is a straight or branched aliphatic hydrocarbon group containing at least one carbon-carbon double bond.

[0053] As used herein, unless otherwise defined, the term "alkynyl" refers to an aliphatic unsaturated alkynyl group that is a straight or branched aliphatic hydrocarbon group containing at least one carbon-carbon triple bond.

[0054] In the chemical formulae described herein, t-Bu refers to tert-butyl.

[0055] Hereinafter, a semiconductor photoresist composition according to one or more embodiments will be described in more detail.

[0056] A semiconductor photoresist composition according to one or more embodiments includes a first organometallic compound represented by Chemical Formula 1, a second organometallic compound represented by Chemical Formula 2, and a solvent.

[0057] Chemical formula 1

[0058] (R 1 ) a -M 1 -X 1 b

[0059] Chemical formula 2

[0060] (R 2 ) c -M 2 -X 2 d

[0061] In Chemical Formula 1 and Chemical Formula 2,

[0062] M 1 and M 2 can be Sn or Te,

[0063] R 1 It may be a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, or -L a -OR a (where L a is a single bond or a substituted or unsubstituted C1 to C20 alkylene group, and R a is a substituted or unsubstituted C1 to C20 alkyl group),

[0064] R 2 may be a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 heterocycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C2 to C30 heteroaryl group,

[0065] X 1 and X 2 can be independently selected from alkoxy or aryloxy (-OR b , where R bIt 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, a substituted or unsubstituted C7 to C30 aralkyl group, or a combination thereof (e.g., any suitable combination), a carboxyl group (-O(CO)R c , where R c It may 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, a substituted or unsubstituted C7 to C30 aralkyl group, or a combination thereof (e.g., any suitable combination), an alkylamide group, or a dialkylamide group (—NR d R e , where R d and R e each independently hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C7 to C30 aralkyl group, or a combination thereof (e.g., any suitable combination), an amide group (-NR f (COR g ), where R f and R g 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, a substituted or unsubstituted C7 to C30 aralkyl group, or a combination thereof (e.g., any suitable combination), an amidino group (-NR h C(NR i )R j , where R h 、R i and R j 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, a substituted or unsubstituted C7 to C30 aralkyl group, or a combination thereof (e.g., any suitable combination), an alkylthio group, or an arylthio group (-SR k , where R kIt 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, a substituted or unsubstituted C7 to C30 aralkyl group, or a combination thereof (e.g., any suitable combination), and a thiocarboxyl group (-S(CO)R l , R l It can be 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, substituted or unsubstituted C7 to C30 aralkyl, or (for example, any suitable) combination thereof,

[0066] a, b, c and d can each independently be an integer from 1 to 5,

[0067] a+b is an integer of 4 or 6, and

[0068] c+d is an integer of 4 or 6.

[0069] In the present disclosure, two types (kinds) of organometallic compounds, namely, a first organometallic compound with high EUV absorptivity and a second organometallic compound, are mixed to ensure stability to moisture and heat without additional organic additives, and to reduce crystallinity by introducing one or more appropriate ligands, thereby achieving excellent or appropriate coating performance and LER.

[0070] For example, in embodiments of chain-type or species organometallic compounds having substantially uniform structures, they may not be uniformly coated due to high crystallinity during coating. However, if (e.g., when) cyclic organometallic compounds are mixed as described in the present disclosure, crystals are less likely to form during coating, which may improve coating performance. That is, using only chain-like organometallic compounds makes it difficult to achieve uniform coating due to their tendency to crystallize, while adding cyclic organometallic compounds may (e.g., should) prevent crystal formation and improve coating uniformity.

[0071] For example, in one or more embodiments, the first organometallic compound and the second organometallic compound may be included in a weight ratio of about 90:10 to about 40:60.

[0072] In one or more embodiments, the first organometallic compound and the second organometallic compound may be included in a weight ratio of about 80:20 to about 40:60, for example, about 70:30 to about 40:60.

[0073] In one or more embodiments, R 1 It may be a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C2 to C10 alkenyl group, a substituted or unsubstituted C2 to C10 alkynyl group, or -L a -OR a (where L a is a single bond or a substituted or unsubstituted C1 to C20 alkylene group, and R a is a substituted or unsubstituted C1 to C20 alkyl group),

[0074] R 2 may be a substituted or unsubstituted C3 to C10 cycloalkyl group, a substituted or unsubstituted C2 to C10 heterocycloalkyl group, a substituted or unsubstituted C6 to C20 aryl group, or a substituted or unsubstituted C2 to C20 heteroaryl group, and

[0075] X 1 and X 2 can be independently selected from alkoxy or aryloxy (-OR b , where R b It may be a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C3 to C10 cycloalkyl group, a substituted or unsubstituted C2 to C10 alkenyl group, a substituted or unsubstituted C2 to C10 alkynyl group, a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C7 to C20 aralkyl group, or a combination thereof (e.g., any suitable combination), a carboxyl group (—O(CO)R c , where R c It may be hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C3 to C10 cycloalkyl group, a substituted or unsubstituted C2 to C10 alkenyl group, a substituted or unsubstituted C2 to C10 alkynyl group, a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C7 to C20 aralkyl group, or a combination thereof (e.g., any suitable combination), an alkylamide group, or a dialkylamide group (-NR d R e , where R d and R e and (-NR ) may each independently be hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C3 to C10 cycloalkyl group, a substituted or unsubstituted C2 to C10 alkenyl group, a substituted or unsubstituted C2 to C10 alkynyl group, a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C7 to C20 aralkyl group, or a combination thereof (e.g., any suitable combination), an amide group (-NR f (COR g ), where R f and Rg may each independently be hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C3 to C10 cycloalkyl group, a substituted or unsubstituted C2 to C10 alkenyl group, a substituted or unsubstituted C2 to C10 alkynyl group, a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C7 to C20 aralkyl group, or a combination thereof (e.g., any suitable combination), an amidino group (-NR h C(NR i )R j , where R h 、R i , and R j The alkyl groups may each independently be hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C3 to C10 cycloalkyl group, a substituted or unsubstituted C2 to C10 alkenyl group, a substituted or unsubstituted C2 to C10 alkynyl group, a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C7 to C20 aralkyl group, or a combination thereof (e.g., any suitable combination), an alkylthio group, or an arylthio group (-SR k , where R k It may be a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C3 to C10 cycloalkyl group, a substituted or unsubstituted C2 to C10 alkenyl group, a substituted or unsubstituted C2 to C10 alkynyl group, a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C7 to C20 aralkyl group, or a combination thereof (e.g., any suitable combination), and a thiocarboxyl group (-S(CO)R l , where R l The radical may be selected from hydrogen, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C3 to C10 cycloalkyl, substituted or unsubstituted C2 to C10 alkenyl, substituted or unsubstituted C2 to C10 alkynyl, substituted or unsubstituted C6 to C20 aryl, substituted or unsubstituted C7 to C20 aralkyl, or any suitable combination thereof.

[0076] In one or more embodiments, R 1may be a substituted or unsubstituted methyl group, a substituted or unsubstituted ethyl group, a substituted or unsubstituted propyl group, a substituted or unsubstituted butyl group, a substituted or unsubstituted isopropyl group, a substituted or unsubstituted tert-butyl group, a substituted or unsubstituted 2,2-dimethylpropyl group, a substituted or unsubstituted tert-amyl group, a substituted or unsubstituted vinyl group, a substituted or unsubstituted propenyl group, a substituted or unsubstituted butenyl group, a substituted or unsubstituted ethynyl group, a substituted or unsubstituted propynyl group, a substituted or unsubstituted butynyl group, a substituted or unsubstituted benzyl group, a substituted or unsubstituted methoxy group, a substituted or unsubstituted ethoxy group, a substituted or unsubstituted propoxy group, or any suitable combination thereof,

[0077] R 2 may be a substituted or unsubstituted cyclopropyl group, a substituted or unsubstituted cyclobutyl group, a substituted or unsubstituted cyclopentyl group, a substituted or unsubstituted cyclohexyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthracenyl group, a substituted or unsubstituted tolyl group, a substituted or unsubstituted xylyl group, a substituted or unsubstituted pyridyl group, a substituted or unsubstituted pyrrolidinyl group, a substituted or unsubstituted piperidinyl group, a substituted or unsubstituted pyrrolyl group, a substituted or unsubstituted furanyl group (furanyl group or furyl group), a substituted or unsubstituted tetrahydrofuranyl group, a substituted or unsubstituted pyranyl group, a substituted or unsubstituted tetrahydropyranyl group, a substituted or unsubstituted dioxanyl group, a substituted or unsubstituted morpholinyl group, or any suitable combination thereof,

[0078] R b may be substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted propyl, substituted or unsubstituted butyl, substituted or unsubstituted isopropyl, substituted or unsubstituted tert-butyl, substituted or unsubstituted tert-amyl, substituted or unsubstituted 2,2-dimethylpropyl, substituted or unsubstituted cyclopropyl, substituted or unsubstituted cyclobutyl, substituted or unsubstituted cyclopentyl, substituted or unsubstituted cyclohexyl, substituted or unsubstituted vinyl, substituted or unsubstituted propenyl, substituted or unsubstituted butenyl, substituted or unsubstituted ethynyl, substituted or unsubstituted propynyl, substituted or unsubstituted butynyl, substituted or unsubstituted phenyl, substituted or unsubstituted tolyl, substituted or unsubstituted xylyl, substituted or unsubstituted benzyl, or any suitable combination thereof, and

[0079] R c 、R d 、Re 、R f 、R g 、R h 、R i 、R j 、R k and R l and substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted propyl, substituted or unsubstituted butyl, substituted or unsubstituted isopropyl, substituted or unsubstituted tert-butyl, substituted or unsubstituted tert-amyl, substituted or unsubstituted 2,2-dimethylpropyl, substituted or unsubstituted cyclopropyl, substituted or unsubstituted cyclobutyl, substituted or unsubstituted cyclopentyl, substituted or unsubstituted cyclohexyl, substituted or unsubstituted vinyl, substituted or unsubstituted propenyl, substituted or unsubstituted butenyl, substituted or unsubstituted ethynyl, substituted or unsubstituted propynyl, substituted or unsubstituted butynyl, substituted or unsubstituted phenyl, substituted or unsubstituted tolyl, substituted or unsubstituted xylyl, substituted or unsubstituted benzyl, or any suitable combination thereof.

[0080] In one or more embodiments, the second organometallic compound may be any one selected from the compounds listed in Group 2.

[0081] Group 2

[0082]

[0083]

[0084] The first organometallic compound may be any one selected from the compounds listed in Group 1.

[0085] Group 1

[0086]

[0087]

[0088] The organometallic compound strongly absorbs extreme ultraviolet light at 13.5 nanometers and may have excellent or moderate sensitivity to high-energy light.

[0089] In the semiconductor photoresist composition according to one or more embodiments, the first and second organometallic compounds may each be added in an amount of about 1 wt % to about 30 wt %, for example, about 1 wt % to about 25 wt %, for example, about 1 wt % to about 20 wt %, for example, about 1 wt % to about 15 wt %, for example, about 1 wt % to about 10 wt %, or for example, about 1 wt % to about 5 wt %, based on 100 wt % of the total weight of the semiconductor photoresist composition. If the organometallic compounds are each included in an amount within the above range, the storage stability and etching resistance of the semiconductor photoresist composition are improved, and the resolution characteristics are improved.

[0090] The semiconductor photoresist composition according to one or more embodiments includes the first and second organometallic compounds described above, thereby providing a semiconductor photoresist composition having excellent or appropriate sensitivity and pattern forming performance.

[0091] The solvent of the semiconductor photoresist composition according to one or more embodiments may be an organic solvent, and may be selected, for example, from aromatic compounds (e.g., xylene, toluene and / or the like), alcohols (e.g., 4-methyl-2-pentanol, 4-methyl-2-propanol, 1-butanol, methanol, isopropanol, 1-propanol), ethers (e.g., anisole, tetrahydrofuran), esters (n-butyrate, propylene glycol monomethyl ether acetate, ethyl acetate, ethyl lactate), ketones (e.g., methyl ethyl ketone, 2-heptanone) and / or (e.g., any suitable) mixtures thereof, but the present disclosure is not limited thereto.

[0092] In one or more embodiments, the semiconductor photoresist composition may further include a resin in addition to the first organometallic compound, the second organometallic compound, and the solvent.

[0093] The resin may be a phenolic resin comprising at least one aromatic moiety selected from Group 3.

[0094] Group 3

[0095]

[0096] The resin may have a weight average molecular weight of about 500 to about 20,000.

[0097] 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.

[0098] When the resin is included in the above content (eg, amount) range, it may have excellent or appropriate etching resistance and heat resistance.

[0099] In addition, the semiconductor photoresist composition according to one or more embodiments may include (for example, be composed of) the above-mentioned first organometallic compound, the second organometallic compound, a solvent and a resin. In the present disclosure, the semiconductor photoresist composition according to one or more embodiments may further include one or more additives as needed. The non-limiting examples of additives may be surfactants, cross-linking agents, leveling agents, organic acids, quenchers and / or their (for example, any appropriate) combination.

[0100] The surfactant may include, for example, alkylbenzene sulfonate, alkylpyridinium salt, polyethylene glycol, quaternary ammonium salt, and / or (eg, any suitable) combination thereof, but embodiments of the present disclosure are not limited thereto.

[0101] The cross-linking agent may be, for example, a melamine-based cross-linking agent, a substituted urea-based cross-linking agent, an acrylic-based cross-linking agent, an epoxy-based cross-linking agent, or a polymer-based cross-linking agent, but the embodiments of the present disclosure are 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.

[0102] 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.

[0103] 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 embodiments of the present disclosure are not limited thereto.

[0104] The quencher can be diphenyl(p-tolyl)amine, methyldiphenylamine, triphenylamine, phenylenediamine, naphthylamine, diaminonaphthalene, or (eg, any suitable) combination thereof.

[0105] The amount of additives included in the semiconductor photoresist composition can be controlled or selected according to desired or suitable properties.

[0106] In one or more embodiments, 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-phenylenyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane; trimethoxy[3-(phenylamino)propyl]silane; and / or the like, but the embodiments of the present disclosure are not limited thereto.

[0107] The semiconductor photoresist composition can form a pattern with a high aspect ratio (aspect ratio) without collapse. Therefore, in order to form a fine pattern with 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, such as about 5 nanometers to about 20 nanometers, or such as about 5 nanometers to about 10 nanometers, the semiconductor photoresist composition can be used for a photolithography process using a wavelength 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, the semiconductor photoresist composition according to one or more embodiments can be used to realize extreme ultraviolet lithography using an EUV light source with a wavelength of about 13.5 nanometers.

[0108] According to one or more embodiments, a method for forming a pattern using the semiconductor photoresist composition is provided. For example, the pattern formed can be a photoresist pattern.

[0109] The method of forming a pattern according to one or more embodiments includes forming an etching target layer (e.g., 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.

[0110] Below, we will refer to Figures 1A to 1E A method of forming a pattern using a semiconductor photoresist composition is described in more detail. 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.

[0111] Reference Figure 1A , an object for etching (e.g., an etching target layer or etching target layer) is prepared. The object for etching may be a thin film 102 formed on a semiconductor substrate 100. Hereinafter, the object for etching is 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, or a silicon oxide layer.

[0112] 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, the embodiments of the present disclosure 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 / or screen printing), and / or the like, may be used.

[0113] In one or more embodiments, a resist base coating process may not be provided. The following describes a process including resist base coating.

[0114] Then, the applied resist base layer composition is dried and baked to form a resist base 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.

[0115] The resist bottom layer 104 is formed between the substrate 100 and the photoresist layer 106, thereby preventing or reducing the non-uniformity and pattern formation of the photoresist line width when, for example, radiation reflected from the interface between the substrate 100 and the photoresist layer 106 or the interlayer hard mask is scattered into unintended photoresist areas (for example, when this occurs).

[0116] 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 it through heat treatment.

[0117] In one or more embodiments, forming a pattern using the 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 to form the photoresist layer 106 .

[0118] The composition of semiconductor photoresist has been described in detail and will not be repeated here.

[0119] Subsequently, the substrate 100 having the photoresist layer 106 is subjected to a first baking (heat treatment) process. The first baking process may be performed at a temperature of about 80°C to about 120°C.

[0120] Reference Figure 1C , the photoresist layer 106 may be selectively exposed using a patterned mask 110 .

[0121] For example, exposure can use activation radiation of light having a high-energy wavelength, such as EUV (extreme ultraviolet; wavelength of about 13.5 nanometers), electron beam (E-Beam) and / or similar light sources, as well as short-wavelength light sources 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 similar light sources.

[0122] For example, the light or exposure beam used for exposure according to one or more embodiments may have a short wavelength in the range of about 5 nanometers to about 150 nanometers, and / or a high energy wavelength, for example, may be EUV (extreme ultraviolet; wavelength 13.5 nanometers), and / or may be an electron beam (E-Beam), and / or a similar light source.

[0123] 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 forming a polymer (eg, through a cross-linking reaction such as condensation between organic metal compounds).

[0124] Subsequently, a second baking (heat treatment) process may be performed on the substrate 100. 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 may become insoluble to a developer.

[0125] exist Figure 1D In the process, the unexposed region 106a of the photoresist layer is dissolved and removed using a developer to form a photoresist pattern 108. For example, the unexposed region 106a of the photoresist layer is 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.

[0126] As described above, the developer used in the method for forming a pattern according to one or more embodiments may be an organic solvent. The organic solvent used in the method for forming a pattern according to one or more embodiments may be, for example, ketones such as methyl ethyl ketone, acetone, cyclohexanone, 2-heptanone, and / or the like, alcohols such as 4-methyl-2-propanol, 1-butanol, isopropanol, 1-propanol, methanol, and / or the like, esters such as propylene glycol monomethyl ether acetate, ethyl acetate, ethyl lactate, n-butyl acetate, butyrolactone, and / or the like, aromatic compounds such as benzene, xylene, toluene, and / or the like, or (for example, any suitable) combination thereof.

[0127] However, the photoresist pattern according to one or more embodiments is not necessarily limited to a negative tone image, but can be formed to have a positive tone image. Here, the developer used to form the positive tone image can be a quaternary ammonium hydroxide composition, such as tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, or (e.g., any suitable) combination thereof.

[0128] As described above, exposure to light having high energy, such as EUV (extreme ultraviolet; wavelength 13.5 nm), electron beam (E-Beam), and / or similar light sources, and / or light having a short wavelength, such as i-line (wavelength of approximately 365 nm), KrF excimer laser (wavelength of approximately 248 nm), ArF excimer laser (wavelength of approximately 193 nm), and / or similar light sources, can provide a photoresist pattern 108 having a thickness or width of approximately 5 nm to approximately 100 nm. For example, in one or more embodiments, the photoresist pattern 108 can have a thickness or width of approximately 5 nm to approximately 90 nm, approximately 5 nm to approximately 80 nm, approximately 5 nm to approximately 70 nm, approximately 5 nm to approximately 60 nm, approximately 5 nm to approximately 50 nm, approximately 5 nm to approximately 40 nm, approximately 5 nm to approximately 30 nm, or approximately 5 nm to approximately 20 nm, or approximately 5 nm to approximately 10 nm.

[0129] In one or more embodiments, the photoresist pattern 108 may have a pitch (center-to-center distance of adjacent features in the pattern) having a half pitch 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 10 nanometers, and a line width roughness less than or equal to about 5 nanometers, less than or equal to about 3 nanometers, less than or equal to about 2 nanometers, or less than or equal to about 1 nanometer.

[0130] 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.

[0131] 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.

[0132] 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 a mixed gas thereof.

[0133] In the exposure process, the thin film pattern 114 formed using the photoresist pattern 108 formed by the exposure process performed using the EUV light source may have a width corresponding to the photoresist pattern 108. For example, in one or more embodiments, the thin film pattern 114 may have a width (e.g., line width) of about 5 nanometers to about 100 nanometers, which is equal to the width of the photoresist pattern 108. For example, in one or more embodiments, the thin film pattern 114 formed using the photoresist pattern 108 formed by the exposure process performed 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, for example, a width (e.g., line width) less than or equal to about 20 nanometers, which is similar to the width of the photoresist pattern 108.

[0134] Hereinafter, the present disclosure will be described in more detail by taking the preparation examples of the semiconductor photoresist composition as an example. However, the present disclosure is not technically limited by the following examples.

[0135] Synthesis of the first organometallic compound

[0136] Synthesis Example 1

[0137] In a 250 ml 2-neck round-bottom flask, Ph3SnCl (20 g, 51.9 mmol) was dissolved in 100 ml of anhydrous tetrahydrofuran (THF) and the temperature was lowered to 0°C in an ice bath. Then, tert-butylmagnesium bromide 1M THF solution (62.3 mmol) was slowly added dropwise. After the addition was complete, the mixture was stirred at 25°C for 12 hours. After vacuum distillation, 50 ml of isobutyric acid was slowly added dropwise at 25°C and heated under reflux for 12 hours. After the temperature was lowered to 25°C, isobutyric acid was vacuum distilled to obtain the compound represented by Chemical Formula 1a.

[0138] Chemical formula 1a

[0139]

[0140] Synthesis Example 2

[0141] In a 250 ml 2-neck round-bottom flask, Ph SnCl (20 g, 51.9 mmol) was dissolved in 100 ml of anhydrous tetrahydrofuran (THF), and the temperature was lowered to 0 ° C in an ice bath. Then, isopropylmagnesium bromide 1M THF solution (62.3 mmol) was slowly added dropwise. After the addition was completed, it was stirred at 25 ° C for 12 hours. After reduced pressure distillation, the resulting product was dissolved in 50 ml of CH Cl and 3 equivalents (155.7 mmol) of 2M HCl ether solution were slowly added dropwise at -78 ° C for 30 minutes. After stirring at 25 ° C for 12 hours, the solvent was concentrated, vacuum distilled, and then dissolved in 50 ml of CH Cl , 3 equivalents of tert-butyl silver oxide (silver tert-butoxide) (51.9 mmol) were added dropwise at 0 ° C, and the resulting solid was filtered. After filtration, the filtrate was distilled to obtain the compound represented by Chemical Formula 2a.

[0142] Chemical formula 2a

[0143]

[0144] Synthesis Example 3

[0145] A compound represented by Chemical Formula 3a was obtained in substantially the same manner as in Synthesis Example 1, except that a 1 M THF solution (62.3 mmol) of 1-propylene-2-magnesium bromide was used instead of tert-butylmagnesium bromide.

[0146] Chemical formula 3a

[0147]

[0148] Synthesis of the second organometallic compound

[0149] Synthesis Example 4

[0150] A compound represented by Chemical Formula 1b was obtained in substantially the same manner as in Synthesis Example 1, except that a 1 M THF solution (62.3 mmol) of cyclopentylmagnesium bromide was used instead of tert-butylmagnesium bromide.

[0151] Chemical formula 1b

[0152]

[0153] Synthesis Example 5

[0154] In a 250 ml 2-neck round-bottom flask, Ph SnCl (20 g, 51.9 mmol) was dissolved in 100 ml of anhydrous tetrahydrofuran (THF), and the temperature was lowered to 0 ° C in an ice bath. Then, a 1M THF solution (62.3 mmol) of cyclohexylmagnesium bromide was slowly added dropwise. After the addition was completed, it was stirred at 25 ° C for 12 hours. After reduced pressure distillation, the resulting product was dissolved in 50 ml of CH Cl and 3 equivalents (155.7 mmol) of 2M HCl ether solution were slowly added dropwise at -78 ° C for 30 minutes. After stirring at 25 ° C for 12 hours, the solvent was concentrated, vacuum distilled, and then dissolved in 50 ml of CH Cl , 3 equivalents of tert-butyl silver oxide (51.9 mmol) were added dropwise at 0 ° C, and the resulting solid was filtered. After filtration, the filtrate was distilled to obtain a compound represented by Chemical Formula 2b.

[0155] Chemical formula 2b

[0156]

[0157] Synthesis Example 6

[0158] In a 250 ml 2-neck round-bottom flask, Sn (NEt2) 4 (20 g, 49.1 mmol) was dissolved in 100 ml of anhydrous tetrahydrofuran (THF), and the temperature was reduced to -50 ° C in an ice bath. Then, a 1M THF solution (10.0 mmol) of phenyl lithium was slowly added dropwise. After the addition was complete, it was stirred at 25 ° C for 12 hours. Excessive isopropyl alcohol (100 mmol) was added at -50 ° C, and the temperature was gradually raised to room temperature. The solvent was removed by distillation under reduced pressure, and the remaining material was separated and purified under reduced pressure to obtain phenyl triisopropoxide (phenyltin triisopropoxide, PhSn (OiPr) 3). 50 ml of anhydrous toluene was added thereto, and isobutyric acid was slowly added dropwise at -20 ° C, heated to reflux for 2 hours, and then vacuum distilled to obtain the compound represented by chemical formula 3b.

[0159] Chemical formula 3b

[0160]

[0161] Synthesis Example 7

[0162] In a 250 ml 2-neck round-bottom flask, Sn (NEt2) 4 (20 g, 49.1 mmol) was dissolved in 100 ml of anhydrous tetrahydrofuran (THF), and the temperature was lowered to -50 ° C in an ice bath. Then, a 1M THF solution (10.0 mmol) of pyridine magnesium bromide was slowly added dropwise. After the addition was completed, it was stirred at 25 ° C for 12 hours. Excess isopropanol (100 mmol) was added at -50 ° C, and the temperature was gradually raised to room temperature. The solvent was removed by distillation under reduced pressure, and the remaining material was separated and purified under reduced pressure to obtain pyridine triisopropoxy tin (PySn (OiPr) 3). 50 ml of anhydrous toluene was added thereto, and isobutyric acid was slowly added dropwise at -20 ° C, heated to reflux for 2 hours, and then vacuum distilled to obtain the compound represented by Chemical Formula 4b.

[0163] Chemical formula 4b

[0164]

[0165] Preparation of semiconductor photoresist compositions

[0166] Examples 1 to 12 and Comparative Examples 1 to 7

[0167] According to Table 1, a pair of corresponding compounds were selected from the compounds represented by Chemical Formula 1a, Chemical Formula 2a, Chemical Formula 3a, Chemical Formula 1b, Chemical Formula 2b, Chemical Formula 3b, and Chemical Formula 4b obtained in Synthesis Examples 1 to 7, dissolved in propylene glycol monomethyl ether acetate (PGMEA) at a concentration of 3 wt %, and filtered through a 0.1 μm PTFE syringe filter to prepare a corresponding photoresist composition.

[0168] Evaluation 1: Evaluation of coating surface roughness

[0169] Each of the photoresist compositions of Examples 1 to 14 and Comparative Examples 1 to 7 was coated on a wafer, exposed on a hot plate at 100° C. for 60 seconds, and the surface roughness (Rq) was measured using an atomic force microscope (AFM). The results were evaluated according to the following criteria and are shown in Table 1.

[0170] Surface roughness (Rq value)

[0171] ○: less than or equal to 0.4

[0172] △: greater than 0.4 and less than or equal to 0.7

[0173] X: greater than 0.7

[0174] Evaluation 2: Evaluation of Line Edge Roughness (LER)

[0175] Using EUV light (Lawrence Berkeley National Laboratory Micro Exposure Tool (MET)), a linear array of 50 circular pads with a diameter of 500 μm was projected onto a wafer coated with one of the photoresist compositions of Examples 1 to 14 and Comparative Examples 1 to 7. The exposure time of the pads was adjusted to apply an increasing EUV dose to each pad.

[0176] Subsequently, the resist and substrate were exposed on a 160°C hot plate for 120 seconds and then baked. The baked film was immersed in a developer (2-heptanone) for 30 seconds each, then washed with the same developer for another 10 seconds to form a negative tone image, i.e., to remove the unexposed portions of the coating. Finally, the process was completed by baking on a 150°C hot plate for 2 minutes.

[0177] The line edge roughness (LER) of the line and space patterns was measured using an electron microscope. These results were evaluated according to the following criteria and are shown in Table 1.

[0178] Line Edge Roughness (LER)

[0179] ○: less than or equal to 4 nanometers

[0180] △: greater than 4 nanometers and less than or equal to 7 nanometers

[0181] X: greater than 7 nanometers

[0182] Table 1

[0183]

[0184] As can be seen from the results of Table 1, each semiconductor photoresist composition according to the example shows a reduced surface roughness compared with the comparative examples, demonstrating excellent or suitable coating properties and excellent or suitable line edge roughness. In other words, each semiconductor photoresist composition in the provided example shows a reduction in surface roughness compared with the comparative examples. This shows that these compositions have superior or suitable coating quality and show excellent or suitable line edge roughness.

[0185] 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.

[0186] 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.

[0187] 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."

[0188] 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.

[0189] 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.

[0190] 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.

[0191] 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.

[0192] The pattern forming device, semiconductor forming device and / or any other related device or component according to the embodiments described in the present disclosure 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 similar devices. 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.

[0193] While specific embodiments of the present disclosure have been described and illustrated, it will be apparent to those skilled in the art that the present disclosure is not limited to the 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 ideas and aspects of the present disclosure, and such modified embodiments are within the scope of the claims of the present disclosure and their equivalents.

Claims

1. A semiconductor photoresist composition comprising: a first organometallic compound represented by Chemical Formula 1; a second organometallic compound represented by Chemical Formula 2; and Solvent: Chemical formula 1 (R 1 ) a -M 1 -X 1 b Chemical formula 2 (R 2 ) c -M 2 -X 2 d Wherein, in Chemical Formula 1 and Chemical Formula 2, M 1 and M 2 are each independently Sn or Te, R 1 is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, or -L a -OR a , where L a is a single bond or a substituted or unsubstituted C1 to C20 alkylene group, and R a is a substituted or unsubstituted C1 to C20 alkyl group, R 2 is a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 heterocycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C2 to C30 heteroaryl group, X 1 and X 2 Each independently selected from -OR b , where 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, a substituted or unsubstituted C7 to C30 aralkyl group, or a combination thereof; -O(CO)R c , where R c 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, substituted or unsubstituted C7 to C30 aralkyl, or a combination thereof; -NR d R e , where R d and R e each independently represents 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, substituted or unsubstituted C7 to C30 aralkyl, or a combination thereof; -NR f (COR g ), where R f and R g each independently represents 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, substituted or unsubstituted C7 to C30 aralkyl, or a combination thereof; -NR h C(NR i )R j , where R h 、R i and R j each independently represents 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, substituted or unsubstituted C7 to C30 aralkyl, or a combination thereof; -SR k , where R k is 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, substituted or unsubstituted C7 to C30 aralkyl, or a combination thereof; and -S(CO)R l , where R l 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, substituted or unsubstituted C7 to C30 aralkyl, or a combination thereof, a, b, c and d are each independently an integer from 1 to 5, a+b is an integer of 4 or 6, and c+d is an integer of 4 or 6.

2. The semiconductor photoresist composition according to claim 1, wherein A weight ratio of the first organometallic compound to the second organometallic compound is 90:10 to 40:

60.

3. The semiconductor photoresist composition according to claim 1, wherein A weight ratio of the first organometallic compound to the second organometallic compound is 80:20 to 40:

60.

4. The semiconductor photoresist composition according to claim 1, wherein R 1 is a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C2 to C10 alkenyl group, a substituted or unsubstituted C2 to C10 alkynyl group, or -L a -OR a , where L a is a single bond or a substituted or unsubstituted C1 to C20 alkylene group, and R a is a substituted or unsubstituted C1 to C20 alkyl group, R 2 is a substituted or unsubstituted C3 to C10 cycloalkyl group, a substituted or unsubstituted C2 to C10 heterocycloalkyl group, a substituted or unsubstituted C6 to C20 aryl group, or a substituted or unsubstituted C2 to C20 heteroaryl group, and X 1 and X 2 Each independently selected from -OR b , where R b is a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C3 to C10 cycloalkyl group, a substituted or unsubstituted C2 to C10 alkenyl group, a substituted or unsubstituted C2 to C10 alkynyl group, a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C7 to C20 aralkyl group, or a combination thereof; -O(CO)R c , where R c is hydrogen, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C3 to C10 cycloalkyl, substituted or unsubstituted C2 to C10 alkenyl, substituted or unsubstituted C2 to C10 alkynyl, substituted or unsubstituted C6 to C20 aryl, substituted or unsubstituted C7 to C20 aralkyl, or a combination thereof; -NR d R e , where R d and R e each independently represents hydrogen, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C3 to C10 cycloalkyl, substituted or unsubstituted C2 to C10 alkenyl, substituted or unsubstituted C2 to C10 alkynyl, substituted or unsubstituted C6 to C20 aryl, substituted or unsubstituted C7 to C20 aralkyl, or a combination thereof; -NR f (COR g ), where R f and R g each independently represents hydrogen, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C3 to C10 cycloalkyl, substituted or unsubstituted C2 to C10 alkenyl, substituted or unsubstituted C2 to C10 alkynyl, substituted or unsubstituted C6 to C20 aryl, substituted or unsubstituted C7 to C20 aralkyl, or a combination thereof; -NR h C(NR i )R j , where R h 、R i and R j each independently represents hydrogen, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C2-C10 alkenyl, substituted or unsubstituted C2-C10 alkynyl, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C7-C20 aralkyl, or a combination thereof; -SR k , where R k is substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C3 to C10 cycloalkyl, substituted or unsubstituted C2 to C10 alkenyl, substituted or unsubstituted C2 to C10 alkynyl, substituted or unsubstituted C6 to C20 aryl, substituted or unsubstituted C7 to C20 aralkyl, or a combination thereof; and -S(CO)R l , where R l is hydrogen, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C3 to C10 cycloalkyl, substituted or unsubstituted C2 to C10 alkenyl, substituted or unsubstituted C2 to C10 alkynyl, substituted or unsubstituted C6 to C20 aryl, substituted or unsubstituted C7 to C20 aralkyl, or a combination thereof.

5. The semiconductor photoresist composition according to claim 1, wherein R 1 is substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted propyl, substituted or unsubstituted butyl, substituted or unsubstituted isopropyl, substituted or unsubstituted tert-butyl, substituted or unsubstituted 2,2-dimethylpropyl, substituted or unsubstituted tert-amyl, substituted or unsubstituted vinyl, substituted or unsubstituted propenyl, substituted or unsubstituted butenyl, substituted or unsubstituted ethynyl, substituted or unsubstituted propynyl, substituted or unsubstituted butynyl, substituted or unsubstituted benzyl, substituted or unsubstituted methoxy, substituted or unsubstituted ethoxy, substituted or unsubstituted propoxy, or a combination thereof, R 2 is substituted or unsubstituted cyclopropyl, substituted or unsubstituted cyclobutyl, substituted or unsubstituted cyclopentyl, substituted or unsubstituted cyclohexyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted tolyl, substituted or unsubstituted xylyl, substituted or unsubstituted pyridinyl, substituted or unsubstituted pyrrolidinyl, substituted or unsubstituted piperidinyl, substituted or unsubstituted pyrrolyl, substituted or unsubstituted furanyl, substituted or unsubstituted tetrahydrofuranyl, substituted or unsubstituted pyranyl, substituted or unsubstituted tetrahydropyranyl, substituted or unsubstituted dioxanyl, substituted or unsubstituted morpholinyl, or a combination thereof, R b is substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted propyl, substituted or unsubstituted butyl, substituted or unsubstituted isopropyl, substituted or unsubstituted tert-butyl, substituted or unsubstituted tert-amyl, substituted or unsubstituted 2,2-dimethylpropyl, substituted or unsubstituted cyclopropyl, substituted or unsubstituted cyclobutyl, substituted or unsubstituted cyclopentyl, substituted or unsubstituted cyclohexyl, substituted or unsubstituted vinyl, substituted or unsubstituted propenyl, substituted or unsubstituted butenyl, substituted or unsubstituted ethynyl, substituted or unsubstituted propynyl, substituted or unsubstituted butynyl, substituted or unsubstituted phenyl, substituted or unsubstituted tolyl, substituted or unsubstituted xylyl, substituted or unsubstituted benzyl, or a combination thereof, and R c 、R d 、R e 、R f 、R g 、R h 、R i 、R j 、R k and R l each is independently hydrogen, substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted propyl, substituted or unsubstituted butyl, substituted or unsubstituted isopropyl, substituted or unsubstituted tert-butyl, substituted or unsubstituted tert-amyl, substituted or unsubstituted 2,2-dimethylpropyl, substituted or unsubstituted cyclopropyl, substituted or unsubstituted cyclobutyl, substituted or unsubstituted cyclopentyl, substituted or unsubstituted cyclohexyl, substituted or unsubstituted vinyl, substituted or unsubstituted propenyl, substituted or unsubstituted butenyl, substituted or unsubstituted ethynyl, substituted or unsubstituted propynyl, substituted or unsubstituted butynyl, substituted or unsubstituted phenyl, substituted or unsubstituted tolyl, substituted or unsubstituted xylyl, substituted or unsubstituted benzyl, or a combination thereof.

6. The semiconductor photoresist composition according to claim 1, wherein The second organometallic compound is any one selected from the compounds listed in Group 2: Group 2 7. The semiconductor photoresist composition according to claim 1, wherein the first organometallic compound is any one selected from the compounds listed in Group 1:

8. The semiconductor photoresist composition according to claim 1, wherein Based on 100 wt % of the total weight of the semiconductor photoresist composition, the amount of the first organometallic compound is 1 wt % to 30 wt %, and The amount of the second organometallic compound is 1 wt % to 30 wt %.

9. The semiconductor photoresist composition according to claim 1, wherein The semiconductor photoresist composition further includes an additive selected from a surfactant, a cross-linking agent, a leveling agent, an organic acid, a quencher or a combination thereof.

10. A method for forming a pattern, comprising: forming an etching target layer on a substrate; coating the semiconductor photoresist composition according to any one of claims 1 to 9 on the etching target layer to form a photoresist layer; patterning the photoresist layer to form a photoresist pattern; as well as The etch target layer is etched using the photoresist pattern as an etch mask.

11. The method according to claim 10, wherein The photoresist pattern is formed by using light with a wavelength of 5 nanometers to 150 nanometers.

12. The method according to claim 10, wherein The method further includes providing a resist bottom layer between the substrate and the photoresist layer.

13. The method according to claim 10, wherein The photoresist pattern has a width of 5 nanometers to 100 nanometers.

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