TW202041513A - Semiconductor photoresist composition and method of forming patterns using the composition - Google Patents

Semiconductor photoresist composition and method of forming patterns using the composition Download PDF

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TW202041513A
TW202041513A TW109114182A TW109114182A TW202041513A TW 202041513 A TW202041513 A TW 202041513A TW 109114182 A TW109114182 A TW 109114182A TW 109114182 A TW109114182 A TW 109114182A TW 202041513 A TW202041513 A TW 202041513A
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金宰賢
文京守
蔡承龍
南宮爛
韓承
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南韓商三星Ｓｄｉ股份有限公司
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0042—Photosensitive materials with inorganic or organometallic light-sensitive compounds not otherwise provided for, e.g. inorganic resists
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • G03F7/2002—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image
    • G03F7/2004—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image characterised by the use of a particular light source, e.g. fluorescent lamps or deep UV light
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • G03F7/2002—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image
    • G03F7/2012—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image using liquid photohardening compositions, e.g. for the production of reliefs such as flexographic plates or stamps
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
    • H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
    • H01L21/0273—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers characterised by the treatment of photoresist layers
    • H01L21/0274—Photolithographic processes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
    • H01L21/033—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising inorganic layers
    • H01L21/0334—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising inorganic layers characterised by their size, orientation, disposition, behaviour, shape, in horizontal or vertical plane
    • H01L21/0337—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising inorganic layers characterised by their size, orientation, disposition, behaviour, shape, in horizontal or vertical plane characterised by the process involved to create the mask, e.g. lift-off masks, sidewalls, or to modify the mask, e.g. pre-treatment, post-treatment
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/3105—After-treatment
    • H01L21/311—Etching the insulating layers by chemical or physical means

Abstract

Disclosed are a semiconductor photoresist composition including an organometal compound represented by Chemical Formula 1, an organometal compound represented by Chemical Formula 2, and a solvent, and a method of forming patterns using the same.

Description

半導體光阻組成物及使用組成物形成圖案的方法Semiconductor photoresist composition and method of using composition to form pattern

本發明有關一種半導體光阻組成物以及一種使用所述組成物形成圖案的方法。 [相關申請的交叉參考]The present invention relates to a semiconductor photoresist composition and a method of using the composition to form a pattern. [Cross reference to related applications]

本申請案主張2019年4月30日在韓國智慧財產權局提出申請的韓國專利申請第10-2019-0050856號及2019年12月4日在韓國智慧財產權局提出申請的韓國專利申請第10-2019-0160169號的優先權及權益，所述專利申請案的全部內容併入本文供參考。This application claims that the Korean Patent Application No. 10-2019-0050856 filed at the Korean Intellectual Property Office on April 30, 2019 and the Korean Patent Application No. 10-2019 filed at the Korean Intellectual Property Office on December 4, 2019 The priority and rights of No.-0160169, the entire content of the patent application is incorporated herein for reference.

極紫外光（extreme ultraviolet，EUV）微影作為製造下一代半導體裝置的一項關鍵技術受到關注。EUV微影是使用波長為約13.5 nm的EUV射線作為曝光光源的圖案形成技術。根據EUV微影，眾所周知，可在半導體裝置的製造期間的曝光製程中形成非常精細的圖案（例如，小於或等於約20 nm）。Extreme ultraviolet (EUV) lithography has attracted attention as a key technology for manufacturing next-generation semiconductor devices. EUV lithography is a patterning technology that uses EUV rays with a wavelength of about 13.5 nm as an exposure light source. According to EUV lithography, it is well known that very fine patterns (for example, less than or equal to about 20 nm) can be formed in the exposure process during the manufacture of semiconductor devices.

極紫外光（EUV）微影通過開發相容的光阻來實現，所述光阻可以小於或等於約16 nm的空間解析度來執行。目前，正在努力滿足用於下一代裝置的傳統化學放大（chemically amplified，CA）光阻的不足規格，例如解析度、感光速度及特徵粗糙度（或稱為線邊緣粗糙度（line edge roughness，LER））。Extreme ultraviolet (EUV) lithography is achieved through the development of compatible photoresist, which can be performed with a spatial resolution of less than or equal to about 16 nm. At present, efforts are being made to meet the insufficient specifications of traditional chemically amplified (CA) photoresists used in next-generation devices, such as resolution, sensitivity speed, and characteristic roughness (or line edge roughness (LER) )).

由於這些聚合物型光阻中的酸催化反應而導致的固有圖像模糊會限制小特徵尺寸的解析度，這在電子束（e-beam）微影中早已眾所周知。化學放大（CA）光阻被設計用於高靈敏度，但由於其典型的元素構成會降低光阻在約13.5 nm波長下的光吸收率且因此降低其靈敏度，因此化學放大（CA）光阻在EUV曝光下可能部分地具有更多的困難。The inherent image blur due to the acid-catalyzed reaction in these polymer photoresists will limit the resolution of small feature sizes, which has long been known in electron beam (e-beam) lithography. Chemically amplified (CA) photoresist is designed for high sensitivity, but because its typical element composition will reduce the light absorption of the photoresist at a wavelength of about 13.5 nm and therefore reduce its sensitivity, chemically amplified (CA) photoresist EUV exposure may partly have more difficulties.

此外，由於粗糙度問題，CA光阻在小特徵尺寸上可能有困難，且實驗證明CA光阻的線邊緣粗糙度（LER）增加，因為感光速度部分地由於酸催化劑製程的本質而降低。因此，由於CA光阻的這些缺陷及問題，在半導體工業中需要新穎高性能光阻。In addition, due to roughness issues, CA photoresists may have difficulties in small feature sizes, and experiments have shown that the line edge roughness (LER) of CA photoresists is increased because the photosensitive speed is partially reduced due to the nature of the acid catalyst process. Therefore, due to these deficiencies and problems of CA photoresist, novel high-performance photoresists are required in the semiconductor industry.

已報導基於與鎢、鈮、鈦及/或鉭混合的鎢的過氧多元酸的無機光阻作為用於圖案化的輻射敏感材料（US5061599，H.岡本、T.岩崎、K.莫奇、H.梅崎、T.工藤（H. Okamoto, T. Iwayanagi, K. Mochiji, H. Umezaki, T. Kudo），應用物理學快報（Applied Physics Letters），49(5)，298-300，1986）。Inorganic photoresists based on peroxypolyacids of tungsten mixed with tungsten, niobium, titanium and/or tantalum have been reported as radiation sensitive materials for patterning (US5061599, H. Okamoto, T. Iwasaki, K. Mochi, H. Umezaki, T. Kudo (H. Okamoto, T. Iwayanagi, K. Mochiji, H. Umezaki, T. Kudo), Applied Physics Letters, 49(5), 298-300, 1986) .

這些材料有效地用遠紫外線（ultraviolet，UV）（深UV）、X射線及電子束源對雙層配置的大節距進行圖案化。最近，當陽離子鉿金屬氧化物硫酸鹽（HfSOx）材料與過氧絡合劑一起用於通過投影EUV曝光對15 nm半節距（half-pitch，HP）成像時，獲得了令人印象深刻的性能（US2011-0045406；J. K.斯托爾斯、A.特萊基、M.科奇斯、B.L.克拉克、D.A.凱茲勒、A.葛籣維爾、C.N.安德森、P.P.納勞（J. K. Stowers, A. Telecky, M. Kocsis, B. L. Clark, D. A. Keszler, A. Grenville, C. N. Anderson, P. P. Naulleau），國際光學工程學會會議錄（Proc. SPIE），7969，796915，2011）。此系統表現出非CA光阻的最高性能，且具有接近EUV光阻要求的可實行感光速度。然而，具有過氧絡合劑的鉿金屬氧化物硫酸鹽材料具有一些實際缺點。首先，這些材料是以腐蝕性硫酸/過氧化氫的混合物來塗布，且保質期穩定性不足。第二，作為一種複合混合物，為改善性能而改變其結構是不容易的。第三，顯影應在約25重量%的極高濃度的四甲基氫氧化銨（tetramethylammonium hydroxide，TMAH）溶液等中進行。These materials effectively use extreme ultraviolet (ultraviolet, UV) (deep UV), X-ray and electron beam sources to pattern large pitches in double-layer configurations. Recently, when the cationic hafnium metal oxide sulfate (HfSOx) material is used with a peroxygen complexing agent to image 15 nm half-pitch (HP) by projection EUV exposure, impressive performance has been obtained (US2011-0045406; JK Stowers, A. Telecky, M. Cochs, BL Clark, DA Kezler, A. Gardwell, CN Anderson, PP Narau (JK Stowers, A. Telecky) , M. Kocsis, BL Clark, DA Keszler, A. Grenville, CN Anderson, PP Naulleau), Proc. SPIE, 7969, 796915, 2011). This system exhibits the highest performance of non-CA photoresist and has a practicable photosensitive speed close to the requirements of EUV photoresist. However, hafnium metal oxide sulfate materials with peroxygen complexing agents have some practical disadvantages. First, these materials are coated with a corrosive sulfuric acid/hydrogen peroxide mixture, and the shelf life stability is insufficient. Second, as a composite mixture, it is not easy to change its structure to improve performance. Third, development should be performed in a very high concentration of tetramethylammonium hydroxide (TMAH) solution of about 25% by weight.

為克服化學放大（CA）感光性組成物的上述缺點，已研究了無機感光性組成物。所述無機感光性組成物主要用於負型圖案化，所述負型圖案化由於通過非化學放大機制進行的化學改性而具有抵抗被顯影劑組成物移除的抵抗力。無機組成物包含EUV吸收率高於烴的無機元素，且因此可通過非化學放大機制確保靈敏度，此外，對隨機效應不太敏感，因此已知具有低的線邊緣粗糙度及少量缺陷。In order to overcome the above shortcomings of chemically amplified (CA) photosensitive compositions, inorganic photosensitive compositions have been studied. The inorganic photosensitive composition is mainly used for negative patterning, and the negative patterning has resistance to being removed by the developer composition due to chemical modification by a non-chemical amplification mechanism. The inorganic composition contains inorganic elements with EUV absorption higher than hydrocarbons, and therefore can ensure sensitivity through a non-chemical amplification mechanism, and is less sensitive to random effects, so it is known to have low line edge roughness and few defects.

近年來，已進行了積極的研究，因為已知含有錫的分子具有優異的極紫外光線吸收。關於其中的有機錫聚合物，烷基配體通過光吸收或由此產生的二次電子離解，且通過氧代鍵與相鄰鏈交聯，從而能夠實現有機顯影溶液可能無法移除的負型圖案化。這種有機錫聚合物表現出極大改善的靈敏度，並保持解析度及線邊緣粗糙度，但為了商業可用性，需要額外改善圖案化特性。In recent years, active research has been conducted because it is known that molecules containing tin have excellent absorption of extreme ultraviolet light. Regarding the organotin polymer, the alkyl ligand is dissociated by light absorption or secondary electrons generated therefrom, and is cross-linked with adjacent chains through oxo bonds, thereby achieving a negative type that may not be removed by the organic developing solution. Patterned. This organotin polymer exhibits greatly improved sensitivity and maintains resolution and line edge roughness, but for commercial availability, additional improvements in patterning characteristics are required.

一實施例提供一種具有改善的耐蝕刻性、靈敏度、解析度及圖案形成能力的半導體光阻組成物。An embodiment provides a semiconductor photoresist composition with improved etching resistance, sensitivity, resolution, and patterning ability.

另一個實施例提供一種使用半導體光阻組成物形成圖案的方法。Another embodiment provides a method of forming a pattern using a semiconductor photoresist composition.

根據實施例的半導體光阻組成物包含由化學式1表示的有機金屬化合物、由化學式2表示的有機金屬化合物及溶劑。 [化學式1]

Figure 02_image009
在化學式1中， R是經取代或未經取代的C1到C20烷基、經取代或未經取代的C3到C20環烷基、包含至少一個雙鍵或三鍵的經取代或未經取代的C2到C20脂族不飽和有機基、經取代或未經取代的C6到C30芳基、環氧乙烷基、環氧丙烷基或其組合， X、Y及Z獨立地為-OR1 或-OC(=O)R2 ， R1 是經取代或未經取代的C1到C20烷基、經取代或未經取代的C3到C20環烷基、經取代或未經取代的C2到C20烯基、經取代或未經取代的C2到C20炔基、經取代或未經取代的C6到C30芳基或其組合，且 R2 是氫、經取代或未經取代的C1到C20烷基、經取代或未經取代的C3到C20環烷基、經取代或未經取代的C2到C20烯基、經取代或未經取代的C2到C20炔基、經取代或未經取代的C6到C30芳基或其組合。 [化學式2]
Figure 02_image011
在化學式2中， X'為-OR3 或-OC(=O)R4 ， R3 是經取代或未經取代的C1到C20烷基、經取代或未經取代的C3到C20環烷基、經取代或未經取代的C2到C20烯基、經取代或未經取代的C2到C20炔基、經取代或未經取代的C6到C30芳基或其組合，且 R4 是氫、經取代或未經取代的C1到C20烷基、經取代或未經取代的C3到C20環烷基、經取代或未經取代的C2到C20烯基、經取代或未經取代的C2到C20炔基、經取代或未經取代的C6到C30芳基或其組合。The semiconductor photoresist composition according to the embodiment includes the organometallic compound represented by Chemical Formula 1, the organometallic compound represented by Chemical Formula 2, and a solvent. [Chemical formula 1]
Figure 02_image009
In Chemical Formula 1, R is substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted containing at least one double bond or triple bond C2 to C20 aliphatic unsaturated organic group, substituted or unsubstituted C6 to C30 aryl group, ethylene oxide group, propylene oxide group or a combination thereof, X, Y and Z are independently -OR 1 or- OC(=O)R 2 , R 1 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 , Substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl or a combination thereof, and R 2 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基 or a combination thereof. [Chemical formula 2]
Figure 02_image011
In Chemical Formula 2, X'is -OR 3 or -OC(=O)R 4 , and R 3 is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group , 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 R 4 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 alkyne Group, substituted or unsubstituted C6 to C30 aryl group, or a combination thereof.

R可為經取代或未經取代的C1到C8烷基、經取代或未經取代的C3到C8環烷基、包含至少一個雙鍵或三鍵的經取代或未經取代的C2到C8脂族不飽和有機基、經取代或未經取代的C6到C20芳基、環氧乙烷基、環氧丙烷基或其組合，且 R1 及R3 可獨立地為經取代或未經取代的C1到C8烷基、經取代或未經取代的C3到C8環烷基、經取代或未經取代的C2到C8烯基、經取代或未經取代的C2到C8炔基、經取代或未經取代的C6到C20芳基或其組合，且 R2 及R4 可獨立地為氫、經取代或未經取代的C1到C8烷基、經取代或未經取代的C3到C8環烷基、經取代或未經取代的C2到C8烯基、經取代或未經取代的C2到C8炔基、經取代或未經取代的C6到C20芳基或其組合。R can be substituted or unsubstituted C1 to C8 alkyl, substituted or unsubstituted C3 to C8 cycloalkyl, substituted or unsubstituted C2 to C8 lipid containing at least one double bond or triple bond Group unsaturated organic group, substituted or unsubstituted C6 to C20 aryl group, ethylene oxide group, propylene oxide group or a combination thereof, and R 1 and R 3 may be independently 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 A substituted C6 to C20 aryl group or a combination thereof, and R 2 and R 4 may independently be hydrogen, a substituted or unsubstituted C1 to C8 alkyl group, a substituted or unsubstituted C3 to C8 cycloalkyl group , 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.

R可為甲基、乙基、丙基、丁基、異丙基、叔丁基、2,2-二甲基丙基、環丙基、環丁基、環戊基、環己基、乙烯基、丙烯基、丁烯基、乙炔基、丙炔基、丁炔基、苯基、甲苯基、二甲苯基、苄基、環氧乙烷基、環氧丙烷基或其組合， R1 及R3 可獨立地是甲基、乙基、丙基、丁基、異丙基、叔丁基、2,2-二甲基丙基、環丙基、環丁基、環戊基、環己基、乙烯基、丙烯基、丁烯基、乙炔基、丙炔基、丁炔基、苯基、甲苯基、二甲苯基、苄基或其組合，且 R2 及R4 可獨立地是氫、甲基、乙基、丙基、丁基、異丙基、叔丁基、2,2-二甲基丙基、環丙基、環丁基、環戊基、環己基、乙烯基、丙烯基、丁烯基、乙炔基、丙炔基、丁炔基、苯基、甲苯基、二甲苯基、苄基或其組合。R 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, ethylene oxide, propylene oxide or combinations thereof, R 1 and R 3 can be independently methyl, ethyl, propyl, butyl, isopropyl, tert-butyl, 2,2-dimethylpropyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, Ethyl, propenyl, butenyl, ethynyl, propynyl, butynyl, phenyl, tolyl, xylyl, benzyl or a combination thereof, and R 2 and R 4 may independently be hydrogen, methyl Base, ethyl, propyl, butyl, isopropyl, tert-butyl, 2,2-dimethylpropyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, vinyl, propenyl, Butenyl, ethynyl, propynyl, butynyl, phenyl, tolyl, xylyl, benzyl, or combinations thereof.

所述由化學式1表示的化合物可為由化學式3表示的化合物、由化學式4表示的化合物、由化學式5表示的化合物、由化學式6表示的化合物或其組合。 [化學式3]

Figure 02_image013
[化學式4]
Figure 02_image015
[化學式5]
Figure 02_image017
[化學式6]
Figure 02_image019
在化學式3到化學式6中， R與化學式1中所定義的相同， Ra 、Rb 、Rc 、Ri 、Rk 及Rl 獨立地與化學式1中對R1 的定義相同，且 Rd 、Re 、Rf 、Rg 、Rh 及Rj 獨立地與化學式1中對R2 的定義相同。The compound represented by Chemical Formula 1 may be a compound represented by Chemical Formula 3, a compound represented by Chemical Formula 4, a compound represented by Chemical Formula 5, a compound represented by Chemical Formula 6, or a combination thereof. [Chemical formula 3]
Figure 02_image013
[Chemical formula 4]
Figure 02_image015
[Chemical formula 5]
Figure 02_image017
[Chemical formula 6]
Figure 02_image019
In Chemical Formula 3 to Chemical Formula 6, R is the same as defined in Chemical Formula 1, R a , R b , R c , R i , R k and R l are independently the same as the definition of R 1 in Chemical Formula 1, and R d, R e, R f, R g, R h and R j are independently the same as in chemical formula 1 in the definition of R 2.

半導體光阻組成物可包含重量比為約20:1到約1:1的所述由化學式1表示的有機金屬化合物及所述由化學式2表示的有機金屬化合物。The semiconductor photoresist composition may include the organometallic compound represented by Chemical Formula 1 and the organometallic compound represented by Chemical Formula 2 in a weight ratio of about 20:1 to about 1:1.

以100重量%的所述半導體光阻組成物計，所述半導體光阻組成物可包含約0.01重量%到約30重量%的所述由化學式1表示的有機金屬化合物及約0.01重量%到約15重量%的所述由化學式2表示的有機金屬化合物。Based on 100% by weight of the semiconductor photoresist composition, the semiconductor photoresist composition may include about 0.01% to about 30% by weight of the organometallic compound represented by Chemical Formula 1 and about 0.01% to about 15% by weight of the organometallic compound represented by Chemical Formula 2.

半導體光阻組成物還可包含表面活性劑、交聯劑、流平劑或其組合的添加劑。The semiconductor photoresist composition may also include additives such as surfactants, crosslinking agents, leveling agents, or combinations thereof.

根據另一實施例的形成圖案的方法包括：在基板上形成蝕刻目標層，在蝕刻目標層上塗布半導體光阻組成物以形成光阻層，對光阻層進行圖案化以形成光阻圖案，以及使用光阻圖案作為蝕刻罩幕來蝕刻所述蝕刻目標層。A method for forming a pattern according to another embodiment includes: forming an etching target layer on a substrate, coating a semiconductor photoresist composition on the etching target layer to form a photoresist layer, and patterning the photoresist layer to form a photoresist pattern, And using the photoresist pattern as an etching mask to etch the etching target layer.

所述光阻圖案可使用波長為約5 nm到約150 nm的光來形成。The photoresist pattern may be formed using light having a wavelength of about 5 nm to about 150 nm.

形成圖案的方法還可包括設置形成在所述基板與所述光阻層之間的抗蝕劑底層。The method of forming a pattern may further include providing a resist underlayer formed between the substrate and the photoresist layer.

光阻圖案可具有約5 nm到約100 nm的寬度。The photoresist pattern may have a width of about 5 nm to about 100 nm.

根據實施例的半導體光阻組成物具有相對改善的耐蝕刻性、靈敏度、解析度及圖案形成能力，因此可提供具有改善的靈敏度及高縱橫比而沒有圖案塌陷的光阻圖案。The semiconductor photoresist composition according to the embodiment has relatively improved etching resistance, sensitivity, resolution, and patterning ability, and therefore can provide a photoresist pattern with improved sensitivity and high aspect ratio without pattern collapse.

在下文中，將參考所附圖式詳細闡述本發明的示例性實施例。然而，在本發明的說明中，為闡明本發明的要點，將省略對已知功能或元件的說明。Hereinafter, exemplary embodiments of the present invention will be explained in detail with reference to the accompanying drawings. However, in the description of the present invention, in order to clarify the gist of the present invention, the description of known functions or elements will be omitted.

為清楚地闡述本發明，省略與說明不相關的部分，且在本說明書全文中，相同的圖式標號指代相同或相似的元件。此外，由於可選地表示圖中所示的每個元件的大小及厚度以便於闡述，因此本發明不限於圖示。In order to clearly illustrate the present invention, parts that are not related to the description are omitted, and throughout this specification, the same drawing symbols refer to the same or similar elements. In addition, since the size and thickness of each element shown in the figure are optionally indicated for ease of explanation, the present invention is not limited to the illustration.

在圖式中，為清楚起見，誇大層、膜、面板、區等的厚度。在圖式中，為清楚起見，誇大層或區的一部分的厚度等。將理解，當稱一元件（例如層、膜、區、或基板）位於另一元件“上（on）”時，所述元件可直接位於所述另一元件上，或者也可存在中間元件。In the drawings, the thickness of layers, films, panels, regions, etc., are exaggerated for clarity. In the drawings, the thickness of a part of a layer or region is exaggerated for clarity. It will be understood that when an element (such as a layer, film, region, or substrate) is referred to as being “on” another element, the element can be directly on the other element, or intervening elements may also be present.

在本發明中，“經取代的”是指氫原子被以下置換：氘、鹵素、羥基、氰基、硝基、-NRR'（其中，R及R'獨立地是氫、經取代或未經取代的C1到C30飽和或不飽和脂族烴基、經取代或未經取代的C3到C30飽和或不飽和脂環族烴基或者經取代或未經取代的C6到C30芳族烴基）、-SiRR'R''（其中，R、R'及R''獨立地是氫、經取代或未經取代的C1到C30飽和或不飽和脂族烴基、經取代或未經取代的C3到C30飽和或不飽和脂環族烴基或者經取代或未經取代的C6到C30芳族烴基）、C1到C30烷基、C1到C10鹵代烷基、C1到C10烷基矽烷基、C3到C30環烷基、C6到C30芳基、C1到C20烷氧基或其組合。“未經取代的”是指氫原子未被另一個取代基及剩餘的氫原子置換。In the present invention, "substituted" means that a hydrogen atom is replaced by deuterium, halogen, hydroxyl, cyano, nitro, -NRR' (wherein, R and R'are independently hydrogen, substituted or unsubstituted Substituted C1 to C30 saturated or unsaturated aliphatic hydrocarbon group, substituted or unsubstituted C3 to C30 saturated or unsaturated alicyclic hydrocarbon group or substituted or unsubstituted C6 to C30 aromatic hydrocarbon group), -SiRR' R" (wherein, R, R'and R" are independently hydrogen, substituted or unsubstituted C1 to C30 saturated or unsaturated aliphatic hydrocarbon groups, substituted or unsubstituted C3 to C30 saturated or unsubstituted Saturated alicyclic hydrocarbon group or substituted or unsubstituted C6 to C30 aromatic hydrocarbon group), C1 to C30 alkyl, C1 to C10 haloalkyl, C1 to C10 alkylsilyl, C3 to C30 cycloalkyl, C6 to C30 aryl, C1 to C20 alkoxy, or a combination thereof. "Unsubstituted" means that the hydrogen atom is not replaced by another substituent and the remaining hydrogen atoms.

如本文所用，當沒有另外提供定義時，“雜”是指包括選自N、O及S的1到3個雜原子。烷基可為沒有任何雙鍵或三鍵的“飽和烷基”。As used herein, when no other definition is provided, "hetero" refers to including 1 to 3 heteroatoms selected from N, O, and S. The alkyl group may be a "saturated alkyl group" without any double or triple bonds.

烷基可為C1到C8烷基。例如，烷基可為C1到C7烷基、C1到C6烷基、C1到C5烷基或C1到C4烷基。例如，C1到C4烷基可為甲基、乙基、丙基、異丙基、正丁基、異丁基、仲丁基、叔丁基或2,2-二甲基丙基。The alkyl group can 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, a C1 to C5 alkyl group, or a C1 to C4 alkyl group. For example, the C1 to C4 alkyl group may be methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, or 2,2-dimethylpropyl.

如本文所用，當沒有另外提供定義時，“環烷基”是指單價環狀脂族烴基。As used herein, when no definition is provided otherwise, "cycloalkyl" refers to a monovalent cyclic aliphatic hydrocarbon group.

環烷基可為C3到C8環烷基，例如C3到C7環烷基、C3到C6環烷基、C3到C5環烷基或C3到C4環烷基。例如，環烷基可為環丙基、環丁基、環戊基或環己基，但不限於此。The cycloalkyl group may be a C3 to C8 cycloalkyl group, such as a C3 to C7 cycloalkyl group, a C3 to C6 cycloalkyl group, a C3 to C5 cycloalkyl group, or a C3 to C4 cycloalkyl group. For example, the cycloalkyl group may be cyclopropyl, cyclobutyl, cyclopentyl, or cyclohexyl, but is not limited thereto.

如本文所用，“脂族不飽和有機基”是指分子中碳原子與碳原子之間的鍵是雙鍵、三鍵或其組合的包括所述鍵的烴基。As used herein, "aliphatic unsaturated organic group" refers to a hydrocarbon group including the bond in which the bond between carbon atoms in the molecule is a double bond, a triple bond, or a combination thereof.

脂族不飽和有機基可為C2到C8脂族不飽和有機基。例如，脂族不飽和有機基可為C2到C7脂族不飽和有機基、C2到C6脂族不飽和有機基、C2到C5脂族不飽和有機基或C2到C4脂族不飽和有機基。例如，C2到C4脂族不飽和有機基可為乙烯基、乙炔基、烯丙基、1-丙烯基、1-甲基-1-丙烯基、2-丙烯基、2-甲基-2-丙烯基、1-丙炔基、1-甲基-1-丙炔基、2-丙炔基、2-甲基-2-丙炔基、1-丁烯基、2-丁烯基、3-丁烯基、1-丁炔基、2-丁炔基或3-丁炔基。The aliphatic unsaturated organic group may be a C2 to C8 aliphatic unsaturated organic group. For example, the aliphatic unsaturated organic group may 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, or a C2 to C4 aliphatic unsaturated organic group. For example, C2 to C4 aliphatic unsaturated organic groups can be vinyl, ethynyl, allyl, 1-propenyl, 1-methyl-1-propenyl, 2-propenyl, 2-methyl-2- Propanyl, 1-propynyl, 1-methyl-1-propynyl, 2-propynyl, 2-methyl-2-propynyl, 1-butenyl, 2-butenyl, 3 -Butenyl, 1-butynyl, 2-butynyl or 3-butynyl.

如本文所用，“芳基”是指其中環狀取代基中的所有原子都具有p軌道，且這些p軌道是共軛的取代基，並且可包括單環或稠環多環（即，共用相鄰碳原子對的環）官能基。As used herein, "aryl" refers to wherein all atoms in the cyclic substituent have p orbitals, and these p orbitals are conjugated substituents, and may include monocyclic or fused-ring polycyclic (ie, share phase The ring of adjacent carbon atom pairs) functional group.

如本文所用，除非另有定義，否則“烯基”是指包括至少一個雙鍵的脂族不飽和烯基，作為直鏈或支鏈脂族烴基。As used herein, unless defined otherwise, "alkenyl" refers to an aliphatic unsaturated alkenyl group that includes at least one double bond, as a linear or branched aliphatic hydrocarbon group.

如本文所用，除非另有定義，否則“炔基”是指包括至少一個三鍵的脂族不飽和炔基，作為直鏈或支鏈脂族烴基。As used herein, unless defined otherwise, "alkynyl" refers to an aliphatic unsaturated alkynyl group including at least one triple bond, as a straight or branched chain aliphatic hydrocarbon group.

下文中，闡述根據實施例的半導體光阻組成物。Hereinafter, the semiconductor photoresist composition according to the embodiment is explained.

根據本發明實施例的半導體光阻組成物包含有機金屬化合物及溶劑，且有機金屬化合物由化學式1及化學式2表示的化合物組成。 [化學式1]

Figure 02_image021
在化學式1中， R是經取代或未經取代的C1到C20烷基、經取代或未經取代的C3到C20環烷基、包含至少一個雙鍵或三鍵的經取代或未經取代的C2到C20脂族不飽和有機基、經取代或未經取代的C6到C30芳基、環氧乙烷基、環氧丙烷基或其組合， X、Y及Z獨立地為-OR1 或-OC(=O)R2 ， R1 是經取代或未經取代的C1到C20烷基、經取代或未經取代的C3到C20環烷基、經取代或未經取代的C2到C20烯基、經取代或未經取代的C2到C20炔基、經取代或未經取代的C6到C30芳基或其組合，且 R2 是氫、經取代或未經取代的C1到C20烷基、經取代或未經取代的C3到C20環烷基、經取代或未經取代的C2到C20烯基、經取代或未經取代的C2到C20炔基、經取代或未經取代的C6到C30芳基或其組合。 [化學式2]
Figure 02_image022
在化學式2中， X'為-OR3 或-OC(=O)R4 ， R3 是經取代或未經取代的C1到C20烷基、經取代或未經取代的C3到C20環烷基、經取代或未經取代的C2到C20烯基、經取代或未經取代的C2到C20炔基、經取代或未經取代的C6到C30芳基或其組合，且 R4 是氫、經取代或未經取代的C1到C20烷基、經取代或未經取代的C3到C20環烷基、經取代或未經取代的C2到C20烯基、經取代或未經取代的C2到C20炔基、經取代或未經取代的C6到C30芳基或其組合。The semiconductor photoresist composition according to the embodiment of the present invention includes an organometallic compound and a solvent, and the organometallic compound is composed of compounds represented by Chemical Formula 1 and Chemical Formula 2. [Chemical formula 1]
Figure 02_image021
In Chemical Formula 1, R is substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted containing at least one double bond or triple bond C2 to C20 aliphatic unsaturated organic group, substituted or unsubstituted C6 to C30 aryl group, ethylene oxide group, propylene oxide group or a combination thereof, X, Y and Z are independently -OR 1 or- OC(=O)R 2 , R 1 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 , Substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl or a combination thereof, and R 2 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基 or a combination thereof. [Chemical formula 2]
Figure 02_image022
In Chemical Formula 2, X'is -OR 3 or -OC(=O)R 4 , and R 3 is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group , 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 R 4 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 alkyne Group, substituted or unsubstituted C6 to C30 aryl group, or a combination thereof.

包括由化學式1及化學式2表示的有機金屬化合物的有機錫共聚物可通過將以下共聚來製備：由化學式1表示的有機金屬化合物，具有被一個R基及三個-OR1 或-OC(=O)R2 取代的錫原子；及由化學式2表示的有機金屬化合物，具有被四個-OR1 或-OC(=O)R2 取代的錫原子。The organotin copolymer including the organometallic compound represented by Chemical Formula 1 and Chemical Formula 2 can be prepared by copolymerizing the following: The organometallic compound represented by Chemical Formula 1 has an R group and three -OR 1 or -OC (= O) R 2 substituted tin atoms; and the organometallic compound represented by Chemical Formula 2 having four tin atoms substituted by -OR 1 or -OC(=O)R 2 .

由化學式1及化學式2表示的化合物是有機錫化合物，其中錫可強烈吸收13.5 nm的極紫外光（UV）光，因此對於具有高能量的光具有優異的靈敏度，且化學式1的R可對由化學式1表示的化合物賦予感光性，且此外，可結合到錫並形成Sn-R鍵，從而對有機錫化合物賦予有機溶劑的溶解度。此外，化學式1的X、Y及Z、-OR3 或-OC(=O)R4 及化學式2的X'可確定這兩種化合物對溶劑的溶解度。The compounds represented by Chemical Formula 1 and Chemical Formula 2 are organotin compounds, in which tin can strongly absorb extreme ultraviolet (UV) light of 13.5 nm, and therefore has excellent sensitivity to light with high energy, and R of Chemical Formula 1 can be The compound represented by Chemical Formula 1 imparts photosensitivity, and in addition, can bind to tin and form a Sn-R bond, thereby imparting solubility of an organic solvent to the organic tin compound. In addition, X, Y, and Z of Chemical Formula 1, -OR 3 or -OC(=0)R 4, and X'of Chemical Formula 2 can determine the solubility of these two compounds to solvents.

關於化學式1的R，當具有由化學式1及化學式2表示的結構單元並通過化合物的共聚形成的有機錫共聚物暴露於極紫外光線（UV）時，R官能基從Sn-R鍵離解並形成自由基，且此自由基形成額外的-Sn-O-Sn-鍵並引發有機錫共聚物之間的縮聚反應，從而有助於由根據實施例的所述組成物形成半導體光阻。Regarding R of Chemical Formula 1, when an organotin copolymer having structural units represented by Chemical Formula 1 and Chemical Formula 2 and formed by copolymerization of compounds is exposed to extreme ultraviolet light (UV), the R functional group is dissociated from the Sn-R bond and formed A radical, and this radical forms an additional -Sn-O-Sn- bond and initiates a polycondensation reaction between the organotin copolymer, thereby helping to form a semiconductor photoresist from the composition according to the embodiment.

在由化學式1表示的有機金屬化合物中，由R表示的取代基可為經取代或未經取代的C1到C20烷基、經取代或未經取代的C3到C20環烷基、包含至少一個雙鍵或三鍵的經取代或未經取代的C2到C20脂族不飽和有機基、經取代或未經取代的C6到C30芳基、環氧乙烷基、環氧丙烷基或其組合。In the organometallic compound represented by Chemical Formula 1, the substituent represented by R may be a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, including at least one double A substituted or unsubstituted C2 to C20 aliphatic unsaturated organic group of a bond or a triple bond, a substituted or unsubstituted C6 to C30 aryl group, an ethylene oxide group, a propylene oxide group, or a combination thereof.

除了取代基R之外，由化學式1表示的化合物還可包括三個有機配體X、Y及Z，其各自被水解形成Sn-O鍵。此外，由化學式2表示的化合物被水解，因此包括與錫元素形成Sn-O鍵的四個X'取代基。X、Y、Z及X'可獨立地為-OR1 或-OC(=O)R2 ，其有機配體可在酸性或鹼性催化劑下通過熱處理或非熱處理水解，從而在有機錫化合物之間形成Sn-O-Sn鍵，且因此，由化學式1及化學式2表示的有機金屬化合物可形成有機錫共聚物。In addition to the substituent R, the compound represented by Chemical Formula 1 may also include three organic ligands X, Y, and Z, each of which is hydrolyzed to form a Sn-O bond. In addition, the compound represented by Chemical Formula 2 is hydrolyzed, and thus includes four X'substituents forming Sn-O bonds with tin elements. X, Y, Z, and X'can independently be -OR 1 or -OC(=O)R 2 , and the organic ligands can be hydrolyzed by heat treatment or non-heat treatment under acidic or basic catalysts, so as Sn-O-Sn bonds are formed therebetween, and therefore, the organometallic compounds represented by Chemical Formula 1 and Chemical Formula 2 may form an organotin copolymer.

根據本發明實施例的半導體光阻組成物同時包含由化學式1表示的有機金屬化合物及由化學式2表示的有機金屬化合物，因此與僅包含由化學式1或化學式2表示的有機金屬化合物的半導體光阻組成物相比，可表現出改善的靈敏度。The semiconductor photoresist composition according to the embodiment of the present invention contains both the organometallic compound represented by Chemical Formula 1 and the organometallic compound represented by Chemical Formula 2, and is therefore different from a semiconductor photoresist containing only the organometallic compound represented by Chemical Formula 1 or 2 Compared with the composition, the sensitivity can be improved.

共聚物中由化學式1表示的有機金屬化合物及化學式2表示的有機金屬化合物的比率可適當控制，以調整由R表示的配體與共聚物的離解度（dissociation degree），且因此調整通過配體與相鄰鏈離解產生的自由基的氧代鍵（oxo bond）的交聯度，因而提供具有優異靈敏度、小的線邊緣粗糙度及優異解析度的半導體光阻。換句話說，通過包含由化學式1表示的有機金屬化合物及化學式2表示的有機金屬化合物兩者，可提供具有改善的靈敏度、線邊緣粗糙度及解析度的半導體光阻。The ratio of the organometallic compound represented by Chemical Formula 1 and the organometallic compound represented by Chemical Formula 2 in the copolymer can be appropriately controlled to adjust the dissociation degree of the ligand represented by R and the copolymer, and thus the adjustment through the ligand The degree of cross-linking of oxo bonds of radicals generated by dissociation from adjacent chains provides a semiconductor photoresist with excellent sensitivity, small line edge roughness, and excellent resolution. In other words, by including both the organometallic compound represented by Chemical Formula 1 and the organometallic compound represented by Chemical Formula 2, a semiconductor photoresist with improved sensitivity, line edge roughness, and resolution can be provided.

R可為例如經取代或未經取代的C1到C8烷基、經取代或未經取代的C3到C8環烷基、包括至少一個雙鍵或三鍵的經取代或未經取代的C2到C8脂族不飽和有機基、經取代或未經取代的C6到C20芳基、環氧乙烷基、環氧丙烷基或其組合，例如甲基、乙基、丙基、丁基、異丙基，叔丁基、2,2-二甲基丙基、環丙基、環丁基、環戊基、環己基、乙烯基、丙烯基、丁烯基、乙炔基、丙炔基、丁炔基、苯基、甲苯基、二甲苯基、苄基、環氧乙烷基、環氧丙烷基或其組合。R can be, for example, substituted or unsubstituted C1 to C8 alkyl, substituted or unsubstituted C3 to C8 cycloalkyl, substituted or unsubstituted C2 to C8 including at least one double bond or triple bond Aliphatic unsaturated organic groups, substituted or unsubstituted C6 to C20 aryl groups, ethylene oxide groups, propylene oxide groups or combinations thereof, such as methyl, ethyl, propyl, butyl, isopropyl , Tert-butyl, 2,2-dimethylpropyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, vinyl, propenyl, butenyl, ethynyl, propynyl, butynyl , Phenyl, tolyl, xylyl, benzyl, ethylene oxide, propylene oxide or a combination thereof.

R1 及R3 可獨立地為例如經取代或未經取代的C1到C8烷基、經取代或未經取代的C3到C8環烷基、經取代或未經取代的C2到C8烯基、經取代或未經取代的C2到C8炔基、經取代或未經取代的C6到C20芳基或其組合，例如甲基、乙基、丙基、丁基、異丙基、叔丁基、2,2-二甲基丙基、環丙基、環丁基、環戊基、環己基、乙烯基、丙烯基、丁烯基、乙炔基、丙炔基、丁炔基、苯基、甲苯基、二甲苯基、苄基或其組合。R 1 and R 3 may independently be, for example, 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, such as methyl, ethyl, propyl, butyl, isopropyl, tert-butyl, 2,2-Dimethylpropyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, vinyl, propenyl, butenyl, ethynyl, propynyl, butynyl, phenyl, toluene Benzyl, xylyl, benzyl, or combinations thereof.

R2 及R4 可獨立地為例如氫、經取代或未經取代的C1到C8烷基、經取代或未經取代的C3到C8環烷基、經取代或未經取代的C2到C8烯基、經取代或未經取代的C2到C8炔基、經取代或未經取代的C6到C20芳基或其組合，例如氫、甲基、乙基、丙基、丁基、異丙基、叔丁基、2,2-二甲基丙基、環丙基、環丁基、環戊基、環己基、乙烯基、丙烯基、丁烯基、乙炔基、丙炔基、丁炔基、苯基、甲苯基、二甲苯基、苄基或其組合。R 2 and R 4 may independently be, for example, hydrogen, substituted or unsubstituted C1 to C8 alkyl, substituted or unsubstituted C3 to C8 cycloalkyl, substituted or unsubstituted C2 to C8 alkene Group, substituted or unsubstituted C2 to C8 alkynyl, substituted or unsubstituted C6 to C20 aryl or a combination thereof, such as hydrogen, methyl, ethyl, propyl, butyl, isopropyl, Tert-butyl, 2,2-dimethylpropyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, vinyl, propenyl, butenyl, ethynyl, propynyl, butynyl, Phenyl, tolyl, xylyl, benzyl or combinations thereof.

所述由化學式1表示的化合物可包括由化學式3表示的化合物、由化學式4表示的化合物、由化學式5表示的化合物、由化學式6表示的化合物或其組合。 [化學式3]

Figure 02_image023
[化學式4]
Figure 02_image025
[化學式5]
Figure 02_image027
[化學式6]
Figure 02_image029
在化學式3到化學式6中， R與化學式1中所定義的相同， Ra 、Rb 、Rc 、Ri 、Rk 及Rl 獨立地與化學式1中對R1 的定義相同，且 Rd 、Re 、Rf 、Rg 、Rh 及Rj 獨立地與化學式1中對R2 的定義相同。The compound represented by Chemical Formula 1 may include a compound represented by Chemical Formula 3, a compound represented by Chemical Formula 4, a compound represented by Chemical Formula 5, a compound represented by Chemical Formula 6, or a combination thereof. [Chemical formula 3]
Figure 02_image023
[Chemical formula 4]
Figure 02_image025
[Chemical formula 5]
Figure 02_image027
[Chemical formula 6]
Figure 02_image029
In Chemical Formula 3 to Chemical Formula 6, R is the same as defined in Chemical Formula 1, R a , R b , R c , R i , R k and R l are independently the same as the definition of R 1 in Chemical Formula 1, and R d, R e, R f, R g, R h and R j are independently the same as in chemical formula 1 in the definition of R 2.

根據本發明實施例的半導體光阻組成物同時包含具有分別與結合到錫原子的三個氧原子連接的取代基且如化學式1或化學式3到化學式6所示的化合物以及如化學式2所示具有與結合到錫原子的氧原子連接的四個取代基的化合物，且因此提供包括通過化合物共聚獲得的有機金屬共聚物的光阻圖案，並且此光阻具有相對改善的耐蝕刻性、靈敏度及解析度以及優異的圖案形成能力，因此，儘管具有高縱橫比，其圖案仍不會被破壞。The semiconductor photoresist composition according to the embodiment of the present invention simultaneously includes a compound having a substituent group respectively connected to three oxygen atoms bonded to a tin atom and is shown in Chemical Formula 1 or Chemical Formula 3 to Chemical Formula 6 and has a compound shown in Chemical Formula 2 A compound of four substituents connected to an oxygen atom bonded to a tin atom, and thus a photoresist pattern including an organometallic copolymer obtained by copolymerization of the compound is provided, and this photoresist has relatively improved etching resistance, sensitivity, and resolution It has excellent pattern forming ability, so the pattern will not be destroyed despite the high aspect ratio.

由化學式1表示的有機金屬化合物及由化學式2表示的有機金屬化合物可以約20:1到約1:1、例如約18:1到約1:1、約15:1到約1:1、約12:1到約1:1、約10:1到約1:1、約8:1到約1:1、約5:1到約1:1、約3:1到約1:1或約2:1到約2:1的重量比包含在半導體光阻組成物中，但不限於此。當由化學式1表示的有機金屬化合物及由化學式2表示的有機金屬化合物的重量比滿足所述範圍時，可提供具有改善的靈敏度的半導體光阻組成物。The organometallic compound represented by Chemical Formula 1 and the organometallic compound represented by Chemical Formula 2 may be about 20:1 to about 1:1, for example, about 18:1 to about 1:1, about 15:1 to about 1:1, about 12:1 to about 1:1, about 10:1 to about 1:1, about 8:1 to about 1:1, about 5:1 to about 1:1, about 3:1 to about 1:1 or about The weight ratio of 2:1 to about 2:1 is included in the semiconductor photoresist composition, but is not limited thereto. When the weight ratio of the organometallic compound represented by Chemical Formula 1 and the organometallic compound represented by Chemical Formula 2 satisfies the range, a semiconductor photoresist composition with improved sensitivity can be provided.

以100重量%的所述半導體光阻組成物計，所述半導體光阻組成物可包含約0.01重量%到約30重量%的所述由化學式1表示的有機金屬化合物及約0.01重量%到約15重量%的所述由化學式2表示的有機金屬化合物。例如，其可包含約0.1重量%到約20重量%的由化學式1表示的有機金屬化合物及約0.1重量%到約10重量%的由化學式2表示的有機金屬化合物，例如，約0.1重量%到約10重量%的由化學式1表示的有機金屬化合物及約0.1重量%到約5重量%的由化學式2表示的有機金屬化合物，但不限於此。Based on 100% by weight of the semiconductor photoresist composition, the semiconductor photoresist composition may include about 0.01% to about 30% by weight of the organometallic compound represented by Chemical Formula 1 and about 0.01% to about 15% by weight of the organometallic compound represented by Chemical Formula 2. For example, it may include about 0.1% to about 20% by weight of the organometallic compound represented by Chemical Formula 1 and about 0.1% to about 10% by weight of the organometallic compound represented by Chemical Formula 2, for example, about 0.1% to About 10% by weight of the organometallic compound represented by Chemical Formula 1 and about 0.1% to about 5% by weight of the organometallic compound represented by Chemical Formula 2, but not limited thereto.

根據實施例的半導體光阻組成物包含在所述範圍內的由化學式1表示的有機金屬化合物及由化學式2表示的有機金屬化合物，當由所述組成物形成光阻時，可有利於塗布製程，且可改善光阻的靈敏度。The semiconductor photoresist composition according to the embodiment includes the organometallic compound represented by Chemical Formula 1 and the organometallic compound represented by Chemical Formula 2 within the range, and when the photoresist is formed from the composition, it may be advantageous for the coating process , And can improve the sensitivity of the photoresist.

根據實施例的半導體光阻組成物中包含的溶劑可為有機溶劑。所述溶劑可為例如芳族化合物（例如二甲苯、甲苯等）、醇（例如，4-甲基-2-戊烯醇、4-甲基-2-丙醇、1-丁醇、甲醇、異丙醇、1-丙醇等）、醚（例如苯甲醚、四氫呋喃等）、酯（乙酸正丁酯、丙二醇單甲醚乙酸酯、乙酸乙酯、乳酸乙酯）、酮（例如甲乙酮、2-庚酮）或其混合物，但不限於此。The solvent included in the semiconductor photoresist composition according to the embodiment may be an organic solvent. The solvent may be, for example, aromatic compounds (such as xylene, toluene, etc.), alcohols (such as 4-methyl-2-pentenol, 4-methyl-2-propanol, 1-butanol, methanol, Isopropanol, 1-propanol, etc.), ethers (such as anisole, tetrahydrofuran, etc.), esters (n-butyl acetate, propylene glycol monomethyl ether acetate, ethyl acetate, ethyl lactate), ketones (such as methyl ethyl ketone) , 2-heptanone) or a mixture thereof, but not limited thereto.

在實施例中，除前述有機金屬化合物及溶劑之外，半導體光阻組成物可更包含樹脂。In an embodiment, in addition to the aforementioned organometallic compound and solvent, the semiconductor photoresist composition may further include a resin.

所述樹脂可為包括群組1的至少一個或多個芳族部分的苯酚系樹脂。 [群組1]

Figure 02_image031
The resin may be a phenol-based resin including at least one or more aromatic moieties of group 1. [Group 1]
Figure 02_image031

所述樹脂的重量平均分子量可為約500到約20,000。The weight average molecular weight of the resin may be about 500 to about 20,000.

以所述半導體抗蝕劑組成物的總量計，可以約0.1重量%到約50重量%的量包含所述樹脂。The resin may be included in an amount of about 0.1% by weight to about 50% by weight based on the total amount of the semiconductor resist composition.

當樹脂包含在所述量範圍內時，其可具有優異的耐蝕刻性及耐熱性。When the resin is included in the amount range, it can have excellent etching resistance and heat resistance.

另一方面，根據實施例的半導體抗蝕劑組成物理想地由有機金屬化合物、溶劑及樹脂構成。然而，根據上述實施例的半導體抗蝕劑組成物還可根據需要包含添加劑。所述添加劑的實例可包括表面活性劑、交聯劑、流平劑或其組合。On the other hand, the semiconductor resist composition according to the embodiment is desirably composed of an organometallic compound, a solvent, and a resin. However, the semiconductor resist composition according to the above-described embodiments may further include additives as necessary. Examples of the additives may include surfactants, crosslinking agents, leveling agents, or combinations thereof.

表面活性劑可包括例如烷基苯磺酸鹽、烷基吡啶鹽、聚乙二醇、季銨鹽或其組合，但不限於此。The surfactant may include, for example, alkyl benzene sulfonate, alkyl pyridine salt, polyethylene glycol, quaternary ammonium salt, or a combination thereof, but is not limited thereto.

交聯劑可為例如三聚氰胺系交聯劑、取代的脲系交聯劑或聚合物系交聯劑，但不限於此。例如，其可為具有至少兩個交聯形成取代基的交聯劑，例如甲氧基甲基化甘脲、丁氧基甲基化甘脲、甲氧基甲基化三聚氰胺、丁氧基甲基化三聚氰胺、甲氧基甲基化苯並胍胺、丁氧基甲基化苯並胍胺、甲氧基甲基化脲、丁氧基甲基化脲、甲氧基甲基化硫脲等化合物。The crosslinking agent may be, for example, a melamine-based crosslinking agent, a substituted urea-based crosslinking agent, or a polymer-based crosslinking agent, but is not limited thereto. For example, it may be a crosslinking agent having at least two crosslinking forming substituents, such as methoxymethylated glycoluril, butoxymethylated glycoluril, methoxymethylated melamine, butoxymethyl Alkylated melamine, methoxymethylated benzoguanamine, butoxymethylated benzoguanamine, methoxymethylated urea, butoxymethylated urea, methoxymethylated thiourea And other compounds.

流平劑可用於改善印刷期間的塗層平坦度，且可為市售的已知流平劑。The leveling agent can be used to improve the flatness of the coating during printing, and may be a commercially known leveling agent.

可依據所需特性來控制添加劑的使用量。The amount of additives used can be controlled according to the required characteristics.

此外，半導體抗蝕劑組成物還可包含矽烷偶合劑作為黏附增強劑，以便提高與基板的緊密接觸力（例如，以便提高半導體抗蝕劑組成物對基板的黏附）。矽烷偶合劑可為例如包括碳-碳不飽和鍵的矽烷化合物，例如乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、乙烯基三氯矽烷、乙烯基三(β-甲氧基乙氧基)矽烷；或3-甲基丙烯氧基丙基三甲氧基矽烷、3-丙烯氧基丙基三甲氧基矽烷、對苯乙烯基三甲氧基矽烷、3-甲基丙烯氧基丙基甲基二甲氧基矽烷、3-甲基丙烯氧基丙基甲基二乙氧基矽烷；三甲氧基[3-(苯基氨基)丙基]矽烷等，但不限於此。In addition, the semiconductor resist composition may also 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 resist composition to the substrate). The silane coupling agent may be, for example, a silane compound including a carbon-carbon unsaturated bond, such as vinyl trimethoxy silane, vinyl triethoxy silane, vinyl trichlorosilane, vinyl tris (β-methoxyethoxy Group) Silane; or 3-methacryloxypropyltrimethoxysilane, 3-propenoxypropyltrimethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyl Dimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane; trimethoxy[3-(phenylamino)propyl]silane, etc., but not limited thereto.

半導體光阻組成物可形成為具有高縱橫比而沒有塌陷的圖案。因此，為了形成具有例如約5 nm到約100 nm、約5 nm到約80 nm、約5 nm到約70 nm、約5 nm到約50 nm、約5 nm到約40 nm、約5 nm到約30 nm或約5 nm到約20 nm的寬度的精細圖案，半導體抗蝕劑組成物可用於使用波長介於約5 nm到約150 nm、例如約5 nm到約100 nm、約5 nm到約80 nm、約5 nm到約50 nm、約5 nm到約30 nm或約5 nm到約20 nm範圍內的光的光阻製程。因此，根據實施例的半導體光阻組成物可用於使用波長為約13.5 nm的EUV光源實現極紫外光（UV）微影。The semiconductor photoresist composition can be formed into a pattern with a high aspect ratio without collapse. Therefore, in order to form, for example, about 5 nm to about 100 nm, about 5 nm to about 80 nm, about 5 nm to about 70 nm, about 5 nm to about 50 nm, about 5 nm to about 40 nm, about 5 nm to For fine patterns with a width of about 30 nm or about 5 nm to about 20 nm, the semiconductor resist composition can be used for wavelengths ranging from about 5 nm to about 150 nm, for example, about 5 nm to about 100 nm, and about 5 nm to about 5 nm. Photoresist process for light in the range of about 80 nm, about 5 nm to about 50 nm, about 5 nm to about 30 nm, or about 5 nm to about 20 nm. Therefore, the semiconductor photoresist composition according to the embodiment can be used to realize extreme ultraviolet (UV) lithography using an EUV light source with a wavelength of about 13.5 nm.

根據另一實施例，提供一種使用半導體光阻組成物形成圖案的方法。例如，所製造的圖案可為光阻圖案。According to another embodiment, a method of forming a pattern using a semiconductor photoresist composition is provided. For example, the manufactured pattern may be a photoresist pattern.

根據實施例的形成圖案的方法包括：在基板上形成蝕刻目標層，在蝕刻目標層上塗布半導體光阻組成物以形成光阻層，對光阻層進行圖案化以形成光阻圖案，以及使用光阻圖案作為蝕刻罩幕來蝕刻所述蝕刻目標層。A method for forming a pattern according to an embodiment includes: 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 using The photoresist pattern serves as an etching mask to etch the etching target layer.

以下，參考圖1到圖5闡述使用半導體光阻組成物形成圖案的方法。圖1到圖5是解釋根據實施例的使用半導體抗蝕劑組成物形成圖案的方法的剖視圖。Hereinafter, a method of forming a pattern using a semiconductor photoresist composition will be explained with reference to FIGS. 1 to 5. 1 to 5 are cross-sectional views explaining a method of forming a pattern using a semiconductor resist composition according to an embodiment.

參考圖1，製備用於蝕刻的物體。用於蝕刻的物體可為形成在半導體基板100上的薄層102。在下文中，用於蝕刻的物體被限制於薄層102。洗滌薄層102的整個表面以移除殘留在其上的雜質等。薄層102可為例如氮化矽層、多晶矽層或氧化矽層。Referring to Fig. 1, an object for etching is prepared. The object used for etching may be a thin layer 102 formed on the semiconductor substrate 100. In the following, the object for etching is limited to the thin layer 102. The entire surface of the thin layer 102 is washed to remove impurities and the like remaining thereon. The thin layer 102 can be, for example, a silicon nitride layer, a polysilicon layer, or a silicon oxide layer.

隨後，將用於形成抗蝕劑底層104的抗蝕劑底層組成物旋塗在經洗滌的薄層102的表面上。然而，實施例不限於此，且可使用已知的各種塗布方法，例如噴塗、浸塗、刀口塗布、印刷方法（例如噴墨印刷及網版印刷）等。Subsequently, the resist underlayer composition for forming the resist underlayer 104 is spin-coated on the surface of the washed thin layer 102. However, the embodiment is not limited thereto, and various known coating methods such as spray coating, dip coating, knife edge coating, printing methods (such as inkjet printing and screen printing), etc. may be used.

可省略抗蝕劑底層的塗布製程，且在下文中，闡述包括抗蝕劑底層的塗布的製程。The coating process of the resist bottom layer may be omitted, and the process including the coating of the resist bottom layer will be described below.

然後，乾燥並烘烤塗布的組成物，以在薄層102上形成抗蝕劑底層104。烘烤可在約100℃到約500℃、例如約100℃到約300℃下進行。Then, the coated composition is dried and baked to form a resist underlayer 104 on the thin layer 102. Baking can be performed at about 100°C to about 500°C, for example, about 100°C to about 300°C.

抗蝕劑底層104形成在基板100與光阻層106之間，因此當從基板100與光阻層106之間的介面或各層之間的硬罩幕上反射的射線被散射到非預期的光阻區中時，可防止光阻線寬的不均勻性及圖案形成能力。The resist bottom layer 104 is formed between the substrate 100 and the photoresist layer 106, so when the rays reflected from the interface between the substrate 100 and the photoresist layer 106 or the hard mask between the layers are scattered to unexpected light When in the resist zone, it can prevent the unevenness of the photoresist line width and the pattern forming ability.

參考圖2，通過在抗蝕劑底層104上塗布半導體抗蝕劑組成物來形成光阻層106。光阻層106是通過將上述半導體抗蝕劑組成物塗布在形成於基板100上的薄層102上，然後通過熱處理將其固化而獲得的。Referring to FIG. 2, a photoresist layer 106 is formed by coating a semiconductor resist composition on a resist underlayer 104. The photoresist layer 106 is obtained by coating the above-mentioned semiconductor resist composition on the thin layer 102 formed on the substrate 100 and then curing it by heat treatment.

更具體來說，通過使用半導體抗蝕劑組成物形成圖案可包括通過旋塗、狹縫塗布、噴墨印刷等將半導體抗蝕劑組成物塗布在具有薄層102的基板100上，然後將其乾燥以形成光阻層106。More specifically, forming a pattern by using the semiconductor resist composition may include coating the semiconductor resist composition on the substrate 100 having the thin layer 102 by spin coating, slit coating, inkjet printing, etc., and then applying it. Dry to form the photoresist layer 106.

半導體抗蝕劑組成物已詳細說明，且將不再說明。The semiconductor resist composition has been described in detail and will not be described again.

隨後，使具有光阻層106的基板100經受第一烘烤製程。第一烘烤製程可在約80℃到約120℃下進行。Subsequently, the substrate 100 with the photoresist layer 106 is subjected to a first baking process. The first baking process can be performed at about 80°C to about 120°C.

參考圖3，可將光阻層106選擇性地曝光。Referring to FIG. 3, the photoresist layer 106 may be selectively exposed.

例如，曝光可使用具有以下光的啟動輻射：具有高能量波長的光，例如極紫外光線（EUV；約13.5 nm的波長）、電子束（E-Beam）等；以及具有短波長的光，例如i線（約365 nm的波長）、KrF准分子鐳射（約248 nm的波長）、ArF准分子鐳射（約193 nm的波長）等。For example, the exposure may use starting radiation with the following light: light with high energy wavelength, such as extreme ultraviolet light (EUV; wavelength of about 13.5 nm), electron beam (E-Beam), etc.; and light with short wavelength, such as i-line (about 365 nm wavelength), KrF excimer laser (about 248 nm wavelength), ArF excimer laser (about 193 nm wavelength), etc.

更具體來說，根據實施例，用於曝光的光可具有介於約5 nm到約150 nm的短波長及高能量波長，例如極紫外光線（EUV；約13.5 nm的波長）、電子束（E-Beam）等。More specifically, according to embodiments, the light used for exposure may have short wavelengths and high energy wavelengths ranging from about 5 nm to about 150 nm, such as extreme ultraviolet light (EUV; wavelength of about 13.5 nm), electron beam ( E-Beam) and so on.

通過交聯反應（例如有機金屬化合物之間的縮合）形成聚合物，光阻層106的被暴露區106a（即未被圖案化硬罩幕110覆蓋的區域）具有與光阻層106的未暴露區106b不同的溶解度。The polymer is formed by a cross-linking reaction (for example, condensation between organometallic compounds), and the exposed area 106a of the photoresist layer 106 (that is, the area not covered by the patterned hard mask 110) has an unexposed area with the photoresist layer 106. Zone 106b has different solubility.

隨後，使基板100經受第二烘烤製程。第二烘烤製程可在約90℃到約200℃的溫度下進行。由於第二烘烤製程，光阻層106的被暴露區106a變得容易不溶於顯影溶液。Subsequently, the substrate 100 is subjected to a second baking process. The second baking process can be performed at a temperature of about 90°C to about 200°C. Due to the second baking process, the exposed area 106a of the photoresist layer 106 becomes easily insoluble in the developing solution.

在圖4中，使用顯影溶液來溶解並移除光阻層的未曝露區106b，以形成光阻圖案108。具體來說，通過使用例如2-庚酮等有機溶劑來溶解及移除光阻層的未曝露區106b，以完成對應於負型圖像的光阻圖案108。In FIG. 4, a developing solution is used to dissolve and remove the unexposed regions 106b of the photoresist layer to form the photoresist pattern 108. Specifically, an organic solvent such as 2-heptanone is used to dissolve and remove the unexposed region 106b of the photoresist layer to complete the photoresist pattern 108 corresponding to the negative image.

如上所述，根據實施例的形成圖案的方法中使用的顯影溶液可為有機溶劑。在根據實施例的形成圖案的方法中使用的有機溶劑可為例如酮，例如甲乙酮、丙酮、環己酮、2-庚酮等；醇，例如4-甲基-2-丙醇、1-丁醇、異丙醇、1-丙醇、甲醇等；酯，例如丙二醇單甲醚乙酸酯、乙酸乙酯、乳酸乙酯、乙酸正丁酯、丁內酯等；芳族化合物，例如苯、二甲苯、甲苯等；或其組合。As described above, the developing solution used in the method of forming a pattern according to the embodiment may be an organic solvent. The organic solvent used in the method of forming a pattern according to the embodiment may be, for example, a ketone, such as methyl ethyl ketone, acetone, cyclohexanone, 2-heptanone, etc.; an alcohol, such as 4-methyl-2-propanol, 1-butanone, etc. Alcohol, isopropanol, 1-propanol, methanol, etc.; esters, such as propylene glycol monomethyl ether acetate, ethyl acetate, ethyl lactate, n-butyl acetate, butyrolactone, etc.; aromatic compounds, such as benzene, Xylene, toluene, etc.; or a combination thereof.

然而，根據實施例的光阻圖案不必限於負型圖像，而是可被形成為具有正型圖像。本文中，用於形成正型圖像的顯影劑可為季銨氫氧化物組成物，例如四乙基氫氧化銨、四丙基氫氧化銨、四丁基氫氧化銨或其組合。However, the photoresist pattern according to the embodiment is not necessarily limited to a negative type image, but may be formed to have a positive type image. Herein, the developer used to form the positive image may be a quaternary ammonium hydroxide composition, such as tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, or a combination thereof.

如上所述，暴露於例如極紫外光線（EUV；約13.5 nm的波長）、電子束（E-Beam）等具有高能量的光以及具有例如i線（約365 nm的波長）、KrF准分子鐳射（約248 nm的波長）、ArF准分子鐳射（約193 nm的波長）等波長的光可提供具有約5 nm到約100 nm的寬度的光阻圖案108。例如，光阻圖案108可具有約5 nm到約90 nm、約5 nm到約80 nm、約5 nm到約70 nm、約5 nm到約60 nm、約10 nm到約50 nm、約10 nm到約40 nm、約10 nm到約30 nm或約10 nm到約20 nm的寬度。As mentioned above, exposure to high-energy light such as extreme ultraviolet light (EUV; wavelength of about 13.5 nm), electron beam (E-Beam), etc., as well as lasers with i-line (wavelength of about 365 nm), KrF excimer Light of a wavelength (wavelength of about 248 nm), ArF excimer laser (wavelength of about 193 nm), etc. can provide a photoresist pattern 108 having a width of about 5 nm to about 100 nm. For example, the photoresist pattern 108 may have 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 10 nm to about 50 nm, about 10 nm. nm to about 40 nm, about 10 nm to about 30 nm, or about 10 nm to about 20 nm in width.

另一方面，光阻圖案108可具有小於或等於約50 nm、例如小於或等於約40 nm、小於或等於約30 nm或者小於或等於約25 nm的半節距的節距以及小於或等於約10 nm或者小於或等於約5 nm的線寬粗糙度。On the other hand, the photoresist pattern 108 may have a half pitch of less than or equal to about 50 nm, for example, less than or equal to about 40 nm, less than or equal to about 30 nm, or less than or equal to about 25 nm, and a pitch less than or equal to about 25 nm. Line width roughness of 10 nm or less than or equal to about 5 nm.

隨後，使用光阻圖案108作為蝕刻罩幕來蝕刻抗蝕劑底層104。通過此蝕刻製程，形成有機層圖案112。有機層圖案112也可具有與光阻圖案108的寬度對應的寬度。Subsequently, the photoresist pattern 108 is used as an etching mask to etch the resist bottom layer 104. Through this etching process, an organic layer pattern 112 is formed. The organic layer pattern 112 may also have a width corresponding to the width of the photoresist pattern 108.

參考圖5，應用光阻圖案108作為蝕刻罩幕來蝕刻被暴露的薄層102。結果，薄層形成有薄層圖案114。Referring to FIG. 5, the photoresist pattern 108 is used as an etching mask to etch the exposed thin layer 102. As a result, the thin layer is formed with a thin layer pattern 114.

薄層102的蝕刻可為例如使用蝕刻氣體的乾蝕刻，且蝕刻氣體可為例如CHF3 、CF4 、Cl2 、BCl3 及其混合氣體。The etching of the thin layer 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 and mixed gases thereof.

在曝光製程中，通過使用光阻圖案108形成的薄層圖案114可具有與光阻圖案108的寬度對應的寬度，光阻圖案108是通過使用EUV光源執行的曝光製程形成的。例如，薄層圖案114可具有約5 nm到約100 nm的寬度，所述寬度等於光阻圖案108的寬度。例如，像光阻圖案108的寬度一樣，通過使用光阻圖案108形成的薄層圖案114可具有約5 nm到約90 nm、約5 nm到約80 nm、約5 nm到約70 nm、約5 nm到約60 nm、約10 nm到約50 nm、約10 nm到約40 nm、約10 nm到約30 nm及約10 nm到約20 nm或者具體來說小於或等於約20 nm的寬度，光阻圖案108是通過使用EUV光源執行的曝光製程形成的。In the exposure process, the thin layer pattern 114 formed by using the photoresist pattern 108 may have a width corresponding to the width of the photoresist pattern 108, and the photoresist pattern 108 is formed by an exposure process performed using an EUV light source. For example, the thin layer pattern 114 may have a width of about 5 nm to about 100 nm, which is equal to the width of the photoresist pattern 108. For example, like the width of the photoresist pattern 108, the thin layer pattern 114 formed by using the photoresist pattern 108 may have 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 10 nm to about 50 nm, about 10 nm to about 40 nm, about 10 nm to about 30 nm, and about 10 nm to about 20 nm, or specifically less than or equal to about 20 nm in width The photoresist pattern 108 is formed by an exposure process performed using EUV light sources.

下文中，通過關於上述半導體光阻組成物的製備的實例更詳細地闡述本發明。然而，本發明在技術上不受以下實例的限制。Hereinafter, the present invention will be explained in more detail through an example regarding the preparation of the above-mentioned semiconductor photoresist composition. However, the present invention is not technically limited by the following examples.

實例Instance

合成例Synthesis example 11

將20 g（51.9 mmol）Ph3 SnCl溶解在250 mL的2頸圓底燒瓶中的70 ml四氫呋喃（tetrahydrofuran，THF）中，然後在冰浴中冷卻到0℃。隨後，向其中緩慢滴加了1 M丁基氯化鎂（BuMgCl）THF溶液（62.3 mmol）。當滴加完成時，將所得混合物在室溫下攪拌了12小時，從而以85%的產率獲得由化學式7表示的化合物。 [化學式7]

Figure 02_image033
Dissolve 20 g (51.9 mmol) of Ph 3 SnCl in 70 ml of tetrahydrofuran (THF) in a 250 mL 2-neck round bottom flask, and then cool to 0°C in an ice bath. Subsequently, 1 M butyl magnesium chloride (BuMgCl) THF solution (62.3 mmol) was slowly added dropwise thereto. When the dropwise addition was completed, the resulting mixture was stirred at room temperature for 12 hours, thereby obtaining the compound represented by Chemical Formula 7 with a yield of 85%. [Chemical formula 7]
Figure 02_image033

合成例Synthesis example 22

除了在合成例1中使用2 M異丙基氯化鎂（iPrMgCl）THF溶液（62.3 mmol）代替1 M丁基氯化鎂（BuMgCl）THF溶液之外，根據與合成例1相同的方法以88%的產率獲得了由化學式8表示的化合物。 [化學式8]

Figure 02_image035
Except for using 2 M isopropyl magnesium chloride (iPrMgCl) THF solution (62.3 mmol) instead of 1 M butyl magnesium chloride (BuMgCl) THF solution in Synthesis Example 1, the yield was 88% according to the same method as Synthesis Example 1. The compound represented by Chemical Formula 8 was obtained. [Chemical formula 8]
Figure 02_image035

合成例Synthesis example 33

除了在合成例1中使用1 M新戊基氯化鎂THF溶液（62.3 mmol）代替1 M丁基氯化鎂（BuMgCl）THF溶液之外，根據與合成例1相同的方法以76%的產率獲得了由化學式9表示的化合物。 [化學式9]

Figure 02_image037
Except that 1 M neopentylmagnesium chloride THF solution (62.3 mmol) was used instead of 1 M butylmagnesium chloride (BuMgCl) THF solution in Synthesis Example 1, according to the same method as Synthesis Example 1, it was obtained with a yield of 76%. The compound represented by Chemical Formula 9. [Chemical formula 9]
Figure 02_image037

合成例Synthesis example 44

將根據合成實例1的由化學式7表示的化合物（10 g，24.6 mmol）溶解在50 mL的CH2 Cl2 中，且在-78℃下歷時30分鐘向其中緩慢滴加了3當量（73.7 mmol）的2 M HCl二乙醚溶液。隨後，將所得混合物在室溫下攪拌了12小時，然後，通過濃縮溶劑並進行真空蒸餾，以80%的產率獲得了由化學式10表示的化合物。 [化學式10]

Figure 02_image039
The compound represented by Chemical Formula 7 (10 g, 24.6 mmol) according to Synthesis Example 1 was dissolved in 50 mL of CH 2 Cl 2 , and 3 equivalents (73.7 mmol) were slowly added dropwise thereto at -78° C. over 30 minutes ) 2 M HCl diethyl ether solution. Subsequently, the resulting mixture was stirred at room temperature for 12 hours, and then, by concentrating the solvent and performing vacuum distillation, the compound represented by Chemical Formula 10 was obtained with a yield of 80%. [Chemical formula 10]
Figure 02_image039

合成例Synthesis example 55

除了使用根據合成例2的由化學式8表示的化合物代替根據合成例1的由化學式7表示的化合物以外，根據與合成例4相同的方法以75%的產率獲得了由化學式11表示的化合物。 [化學式11]

Figure 02_image041
Except for using the compound represented by Chemical Formula 8 according to Synthesis Example 2 instead of the compound represented by Chemical Formula 7 according to Synthesis Example 1, the compound represented by Chemical Formula 11 was obtained according to the same method as Synthesis Example 4 with a yield of 75%. [Chemical formula 11]
Figure 02_image041

合成例Synthesis example 66

除了使用根據合成例3的由化學式9表示的化合物代替根據合成例1的由化學式7表示的化合物以外，根據與合成例4相同的方法以70%的產率獲得了由化學式12表示的化合物。 [化學式12]

Figure 02_image043
Except for using the compound represented by Chemical Formula 9 according to Synthesis Example 3 instead of the compound represented by Chemical Formula 7 according to Synthesis Example 1, the compound represented by Chemical Formula 12 was obtained according to the same method as Synthesis Example 4 with a yield of 70%. [Chemical formula 12]
Figure 02_image043

合成例Synthesis example 77

在室溫下，將25 mL乙酸緩慢滴加到10 g（25.6 mmol）根據合成例4的由化學式10表示的化合物中，然後加熱並回流了12小時。將溫度降到室溫，然後將乙酸真空蒸餾，從而以90%的產率獲得由化學式13表示的化合物。 [化學式13]

Figure 02_image045
At room temperature, 25 mL of acetic acid was slowly added dropwise to 10 g (25.6 mmol) of the compound represented by Chemical Formula 10 according to Synthesis Example 4, and then heated and refluxed for 12 hours. The temperature was lowered to room temperature, and then acetic acid was vacuum distilled, thereby obtaining the compound represented by Chemical Formula 13 in a yield of 90%. [Chemical formula 13]
Figure 02_image045

合成例Synthesis example 88

在室溫下，將25 mL丙烯酸緩慢滴加到10 g（25.4 mmol）根據合成例5的由化學式11表示的化合物中，然後在80℃下加熱並回流了6小時。將溫度降到室溫，然後將丙烯酸真空蒸餾，從而以50%的產率獲得由化學式14表示的化合物。 [化學式14]

Figure 02_image047
At room temperature, 25 mL of acrylic acid was slowly added dropwise to 10 g (25.4 mmol) of the compound represented by Chemical Formula 11 according to Synthesis Example 5, and then heated and refluxed at 80° C. for 6 hours. The temperature was lowered to room temperature, and then acrylic acid was vacuum distilled, thereby obtaining the compound represented by Chemical Formula 14 in a yield of 50%. [Chemical formula 14]
Figure 02_image047

合成例Synthesis example 99

在室溫下，將25 mL丙酸緩慢滴加到10 g（23.7 mmol）根據合成例6的由化學式12表示的化合物中，然後在110℃下加熱並回流了12小時。將溫度降到室溫，然後將丙酸真空蒸餾，從而以40%的產率獲得由化學式15表示的化合物。 [化學式15]

Figure 02_image049
At room temperature, 25 mL of propionic acid was slowly added dropwise to 10 g (23.7 mmol) of the compound represented by Chemical Formula 12 according to Synthesis Example 6, and then heated and refluxed at 110° C. for 12 hours. The temperature was lowered to room temperature, and then propionic acid was vacuum distilled, thereby obtaining the compound represented by Chemical Formula 15 in a yield of 40%. [Chemical formula 15]
Figure 02_image049

合成例Synthesis example 1010

將30 mL無水戊烷添加到10 g（35.4 mmol）根據合成例4的由化學式10表示的化合物中，然後冷卻到0℃。向其中緩慢滴加了7.8 g（106.3 mmol）二乙胺，隨後向其中添加了7.9 g（106.3 mmol）叔丁醇，然後在室溫下攪拌了1小時。當反應完成時，將所得物過濾、濃縮並真空乾燥，從而以60%的產率獲得由化學式16表示的化合物。 [化學式16]

Figure 02_image051
30 mL of anhydrous pentane was added to 10 g (35.4 mmol) of the compound represented by Chemical Formula 10 according to Synthesis Example 4, and then cooled to 0°C. 7.8 g (106.3 mmol) of diethylamine was slowly added dropwise thereto, and then 7.9 g (106.3 mmol) of tert-butanol was added thereto, followed by stirring at room temperature for 1 hour. When the reaction is completed, the resultant is filtered, concentrated, and vacuum dried, thereby obtaining the compound represented by Chemical Formula 16 in a yield of 60%. [Chemical formula 16]
Figure 02_image051

合成例Synthesis example 1111

將30 mL無水戊烷添加到10 g（37.3 mmol）根據合成例5的由化學式11表示的化合物中，然後冷卻到0℃。向其中緩慢滴加了8.2 g（111.9 mmol）二乙胺，隨後向其中添加了6.7 g（111.9 mmol）異丙醇，然後在室溫下攪拌了1小時。當反應完成時，將所得物過濾、濃縮並真空乾燥，從而以60%的產率獲得由化學式17表示的化合物。 [化學式17]

Figure 02_image053
30 mL of anhydrous pentane was added to 10 g (37.3 mmol) of the compound represented by Chemical Formula 11 according to Synthesis Example 5, and then cooled to 0°C. 8.2 g (111.9 mmol) of diethylamine was slowly added dropwise thereto, and then 6.7 g (111.9 mmol) of isopropanol was added thereto, followed by stirring at room temperature for 1 hour. When the reaction is complete, the resultant is filtered, concentrated, and vacuum dried, thereby obtaining the compound represented by Chemical Formula 17 in a yield of 60%. [Chemical formula 17]
Figure 02_image053

合成例Synthesis example 1212

將30 mL無水戊烷添加到10 g（18.7 mmol）根據合成例6的由化學式12表示的化合物中，然後冷卻到0℃。向其中緩慢滴加了7.4 g（101.3 mmol）二乙胺，隨後向其中添加了6.1 g（101.3 mmol）乙醇，然後在室溫下攪拌了1小時。當反應完成時，將所得物過濾、濃縮並真空乾燥，從而以60%的產率獲得由化學式18表示的化合物。 [化學式18]

Figure 02_image055
30 mL of anhydrous pentane was added to 10 g (18.7 mmol) of the compound represented by Chemical Formula 12 according to Synthesis Example 6, and then cooled to 0°C. 7.4 g (101.3 mmol) of diethylamine was slowly added dropwise thereto, and then 6.1 g (101.3 mmol) of ethanol was added thereto, followed by stirring at room temperature for 1 hour. When the reaction is complete, the resultant is filtered, concentrated, and vacuum dried, thereby obtaining the compound represented by Chemical Formula 18 in a yield of 60%. [Chemical formula 18]
Figure 02_image055

合成例Synthesis example 1313

將10 g（25.4 mmol）由化學式8表示的化合物放入100 mL圓底燒瓶中，且在室溫下向其中緩慢滴加了25 mL甲酸，然後在100℃下加熱並回流了24小時。10 g (25.4 mmol) of the compound represented by Chemical Formula 8 was put into a 100 mL round bottom flask, and 25 mL of formic acid was slowly added dropwise thereto at room temperature, and then heated and refluxed at 100° C. for 24 hours.

隨後，將溫度降到室溫，然後將甲酸真空蒸餾，從而以90%的產率獲得由化學式19表示的化合物。 [化學式19]

Figure 02_image057
Subsequently, the temperature was lowered to room temperature, and then the formic acid was vacuum distilled, thereby obtaining the compound represented by Chemical Formula 19 in a yield of 90%. [Chemical formula 19]
Figure 02_image057

合成例Synthesis example 1414

將Ph4 Sn（20 g，46.8 mmol）放入100 mL圓底燒瓶中，且向其中緩慢滴加了50 ml丙酸，然後在110℃下加熱並回流了26小時。隨後，將溫度降到室溫，且將丙酸真空蒸餾，從而以95%的產率獲得由化學式20表示的化合物。 [化學式20]

Figure 02_image059
Ph 4 Sn (20 g, 46.8 mmol) was put into a 100 mL round bottom flask, and 50 ml of propionic acid was slowly dropped into it, and then heated and refluxed at 110°C for 26 hours. Subsequently, the temperature was lowered to room temperature, and propionic acid was vacuum distilled, thereby obtaining the compound represented by Chemical Formula 20 in a yield of 95%. [Chemical formula 20]
Figure 02_image059

合成例Synthesis example 1515

將154 mL 1 M乙醇鈉乙醇溶液放入100 mL圓底燒瓶中，且在0℃下向其中緩慢滴加了10 g（38.4 mmol）SnCl4 。將溫度升到室溫，然後將所得混合物攪拌了12小時並真空蒸餾，從而以70%的產率獲得由化學式21表示的化合物。 [化學式21]

Figure 02_image061
Put 154 mL of 1 M sodium ethoxide ethanol solution into a 100 mL round bottom flask, and slowly drop 10 g (38.4 mmol) SnCl 4 into it at 0°C. The temperature was raised to room temperature, and then the resulting mixture was stirred for 12 hours and vacuum distilled, thereby obtaining the compound represented by Chemical Formula 21 in a yield of 70%. [Chemical formula 21]
Figure 02_image061

實例Instance 11 到實例To instance 1414

將根據合成例7到合成例13的化合物13到化合物19分別以2重量%的濃度溶解在二甲苯中，此外，將根據合成例14及合成例15的化合物20及化合物21分別以0.2重量%的濃度溶解在分別溶解有根據合成例7到合成例13的化合物13到化合物19的二甲苯中，然後，用0.1 μm聚四氟乙烯（polytetrafluoroethylene，PTFE）注射過濾器過濾，以製備根據實例1到實例14的半導體光阻組成物。半導體光阻組成物的具體化合物組合示於表1中。Compounds 13 to 19 according to Synthesis Example 7 to Synthesis Example 13 were respectively dissolved in xylene at a concentration of 2% by weight. In addition, Compound 20 and Compound 21 according to Synthesis Example 14 and Synthesis Example 15 were respectively dissolved at 0.2% by weight. The concentration was dissolved in xylene in which compounds 13 to 19 according to Synthesis Example 7 to Synthesis Example 13 were dissolved respectively, and then filtered with a 0.1 μm polytetrafluoroethylene (PTFE) injection filter to prepare according to Example 1. To the semiconductor photoresist composition of Example 14. The specific compound combinations of the semiconductor photoresist composition are shown in Table 1.

將具有天然氧化物表面及4英寸直徑的盤形矽晶圓用作薄膜塗布的基板，並在塗布組成物之前在紫外臭氧清潔系統中處理了10分鐘。在經處理的基板上，分別將根據實例1到實例14的半導體光阻組成物在1500 rpm下旋塗了30秒，然後在100℃下烘烤（施用之後進行烘烤，施用後烘烤（post-apply bake，PAB））了120秒以形成光阻薄膜。A disc-shaped silicon wafer with a natural oxide surface and a diameter of 4 inches was used as a substrate for film coating, and was treated in an ultraviolet ozone cleaning system for 10 minutes before coating the composition. On the treated substrates, the semiconductor photoresist compositions according to Examples 1 to 14 were spin-coated at 1500 rpm for 30 seconds, and then baked at 100°C (baked after application, baked after application ( Post-apply bake (PAB)) took 120 seconds to form a photoresist film.

在塗布及烘烤之後，通過橢偏儀測量了膜的厚度，所述厚度為約25 nm。After coating and baking, the thickness of the film was measured by an ellipsometer, and the thickness was about 25 nm.

比較例Comparative example 11

除了將根據合成例7的由化學式13表示的化合物以2重量%的濃度溶解在二甲苯中以外，根據與實例相同的方法製造了根據比較例1的半導體光阻組成物及包含所述組成物的光阻薄膜。在塗布及烘烤後，膜的厚度為約25 nm。Except that the compound represented by Chemical Formula 13 according to Synthesis Example 7 was dissolved in xylene at a concentration of 2% by weight, a semiconductor photoresist composition according to Comparative Example 1 and including the composition were manufactured according to the same method as the example. Photoresist film. After coating and baking, the thickness of the film is about 25 nm.

比較例Comparative example 22

除了使用nBuSnOOH（銻希愛公司（TCI Inc.））代替由化學式13表示的化合物以外，根據與實例1相同的方法製造了根據比較例2的半導體光阻組成物及包含所述組成物的光阻薄膜。在塗布及烘烤後，膜的厚度為約25 nm。Except for using nBuSnOOH (TCI Inc.) instead of the compound represented by Chemical Formula 13, a semiconductor photoresist composition according to Comparative Example 2 and a light containing the composition were manufactured according to the same method as Example 1. Resistance film. After coating and baking, the thickness of the film is about 25 nm.

（表1）   有機金屬化合物（A） 有機金屬化合物（B） 實例1 化學式13 化學式20 實例2 化學式14 化學式20 實例3 化學式15 化學式20 實例4 化學式16 化學式20 實例5 化學式17 化學式20 實例6 化學式18 化學式20 實例7 化學式19 化學式20 實例8 化學式13 化學式21 實例9 化學式14 化學式21 實例10 化學式15 化學式21 實例11 化學式16 化學式21 實例12 化學式17 化學式21 實例13 化學式18 化學式21 實例14 化學式19 化學式21 比較例1 化學式13 - 比較例2 nBuSnOOH（銻希愛公司） 化學式20 (Table 1) Organometallic compound (A) Organometallic compound (B) Example 1 Chemical formula 13 Chemical formula 20 Example 2 Chemical formula 14 Chemical formula 20 Example 3 Chemical formula 15 Chemical formula 20 Example 4 Chemical formula 16 Chemical formula 20 Example 5 Chemical formula 17 Chemical formula 20 Example 6 Chemical formula 18 Chemical formula 20 Example 7 Chemical formula 19 Chemical formula 20 Example 8 Chemical formula 13 Chemical formula 21 Example 9 Chemical formula 14 Chemical formula 21 Example 10 Chemical formula 15 Chemical formula 21 Example 11 Chemical formula 16 Chemical formula 21 Example 12 Chemical formula 17 Chemical formula 21 Example 13 Chemical formula 18 Chemical formula 21 Example 14 Chemical formula 19 Chemical formula 21 Comparative example 1 Chemical formula 13 - Comparative example 2 nBuSnOOH (Antimony Xi'ai Company) Chemical formula 20

評價Evaluation

通過改變能量及焦點，將在塗布方法中形成在盤形矽晶圓上的根據實例1到實例14及比較例1到比較例2的膜暴露於極紫外光線（UV）以形成12 nm到100 nm的線/空間圖案。曝光後，將膜在180℃下烘烤了120秒，隨後，在含有2-庚酮的培養皿中浸漬了60秒並取出，且用相同的溶劑洗滌了10秒。最後，將膜在150℃下烘烤了5分鐘，然後通過掃描電子顯微鏡（scanning electron microscopy，SEM）獲得了其圖案圖像。通過SEM圖像，最高解析度、最佳能量及線邊緣粗糙度（LER）提供於表2中。By changing the energy and focus, the films according to Examples 1 to 14 and Comparative Examples 1 to 2 formed on the disc-shaped silicon wafer in the coating method were exposed to extreme ultraviolet light (UV) to form 12 nm to 100 nm line/space pattern. After exposure, the film was baked at 180°C for 120 seconds, and then immersed in a petri dish containing 2-heptanone for 60 seconds and taken out, and washed with the same solvent for 10 seconds. Finally, the film was baked at 150°C for 5 minutes, and then the pattern image was obtained by scanning electron microscopy (SEM). Through the SEM image, the highest resolution, best energy and line edge roughness (LER) are provided in Table 2.

（表2） 解析度（nm） 能量（mJ/cm2 ） LER（nm） 實例1 15.0 53 2.5 實例2 16.0 35 2.9 實例3 15.1 48 2.5 實例4 14.5 50 3.0 實例5 15.6 48 3.0 實例6 15.0 42 3.3 實例7 15.6 35 3.0 實例8 15.3 55 2.5 實例9 15.8 35 3.0 實例10 14.8 44 3.2 實例11 15.5 52 2.5 實例12 15.0 44 2.9 實例13 14.3 37 3.6 實例14 15.2 35 3.2 比較例1 18.5 75 4.6 比較例2 19.1 96 4.5 (Table 2) Resolution (nm) Energy (mJ/cm 2 ) LER (nm) Example 1 15.0 53 2.5 Example 2 16.0 35 2.9 Example 3 15.1 48 2.5 Example 4 14.5 50 3.0 Example 5 15.6 48 3.0 Example 6 15.0 42 3.3 Example 7 15.6 35 3.0 Example 8 15.3 55 2.5 Example 9 15.8 35 3.0 Example 10 14.8 44 3.2 Example 11 15.5 52 2.5 Example 12 15.0 44 2.9 Example 13 14.3 37 3.6 Example 14 15.2 35 3.2 Comparative example 1 18.5 75 4.6 Comparative example 2 19.1 96 4.5

參考表2，通過使用根據實例1到實例14的同時包含由化學式13到化學式19表示的化合物中的一者及由化學式20或化學式21表示的化合物的半導體光阻組成物形成的光阻薄膜表現出優異的解析度、靈敏度及線邊緣粗糙度（LER）。With reference to Table 2, performance by using a photoresist film formed according to Example 1 to Example 14 while including one of the compounds represented by Chemical Formula 13 to Chemical Formula 19 and the compound represented by Chemical Formula 20 or 21 Outstanding resolution, sensitivity and line edge roughness (LER).

相反，與實例的解析度、能量及線邊緣粗糙度相比，由僅包含由化學式13表示的化合物的比較例1的半導體光阻組成物以及包含nBuSnOOH（銻希愛公司）及由化學式20表示的化合物的比較例2的半導體光阻組成物形成的光阻薄膜都表現出最高的解析度、最佳能量及優異的線邊緣粗糙度（LER）。On the contrary, compared with the resolution, energy, and line edge roughness of the examples, the semiconductor photoresist composition of Comparative Example 1 containing only the compound represented by Chemical Formula 13 and nBuSnOOH (Antimony Xiai Company) and represented by Chemical Formula 20 The photoresist film formed by the semiconductor photoresist composition of the compound of Comparative Example 2 all showed the highest resolution, the best energy, and excellent line edge roughness (LER).

在上文中，已闡述及說明了本發明的某些示例性實施例，然而，對於本領域中的一般技術人員來說顯而易見的是，本發明不限於所闡述的示例性實施例，且可在不背離本發明的精神及範圍的情況下進行各種修改及變換。因此，修改或變換的示例性實施例本身可不與本發明的技術思想及方面分開理解，且修改的示例性實施例處於本發明的申請專利的範圍內。In the foregoing, certain exemplary embodiments of the present invention have been set forth and described. However, it is obvious to those skilled in the art that the present invention is not limited to the illustrated exemplary embodiments, and can be Various modifications and changes can be made without departing from the spirit and scope of the present invention. Therefore, the modified or transformed exemplary embodiment itself may not be understood separately from the technical ideas and aspects of the present invention, and the modified exemplary embodiment is within the scope of the patent application of the present invention.

100:半導體基板 102:薄層 104:抗蝕劑底層 106:光阻層 106a:被暴露區 106b:未暴露區 108:光阻圖案 112:有機層圖案 114:薄層圖案100: Semiconductor substrate 102: thin layer 104: resist bottom layer 106: photoresist layer 106a: exposed area 106b: unexposed area 108: photoresist pattern 112: Organic layer pattern 114: Thin layer pattern

圖1到圖5是解釋根據實施例的使用半導體抗蝕劑組成物形成圖案的方法的剖視圖。1 to 5 are cross-sectional views explaining a method of forming a pattern using a semiconductor resist composition according to an embodiment.

100:半導體基板 100: Semiconductor substrate

102:薄層 102: thin layer

108:光阻圖案 108: photoresist pattern

112:有機層圖案 112: Organic layer pattern

Claims (11)

一種半導體光阻組成物，包含： 由化學式1表示的有機金屬化合物、由化學式2表示的有機金屬化合物及溶劑： [化學式1]
Figure 03_image063
其中，在化學式1中， R是經取代或未經取代的C1到C20烷基、經取代或未經取代的C3到C20環烷基、包含至少一個雙鍵或三鍵的經取代或未經取代的C2到C20脂族不飽和有機基、經取代或未經取代的C6到C30芳基、環氧乙烷基、環氧丙烷基或其組合， X、Y及Z獨立地為-OR1 或-OC(=O)R2 ， R1 是經取代或未經取代的C1到C20烷基、經取代或未經取代的C3到C20環烷基、經取代或未經取代的C2到C20烯基、經取代或未經取代的C2到C20炔基、經取代或未經取代的C6到C30芳基或其組合，且 R2 是氫、經取代或未經取代的C1到C20烷基、經取代或未經取代的C3到C20環烷基、經取代或未經取代的C2到C20烯基、經取代或未經取代的C2到C20炔基、經取代或未經取代的C6到C30芳基或其組合； [化學式2]
Figure 03_image064
其中，在化學式2中， X'為-OR3 或-OC(=O)R4 ， R3 是經取代或未經取代的C1到C20烷基、經取代或未經取代的C3到C20環烷基、經取代或未經取代的C2到C20烯基、經取代或未經取代的C2到C20炔基、經取代或未經取代的C6到C30芳基或其組合，且 R4 是氫、經取代或未經取代的C1到C20烷基、經取代或未經取代的C3到C20環烷基、經取代或未經取代的C2到C20烯基、經取代或未經取代的C2到C20炔基、經取代或未經取代的C6到C30芳基或其組合。A semiconductor photoresist composition comprising: an organometallic compound represented by chemical formula 1, an organometallic compound represented by chemical formula 2, and a solvent: [Chemical formula 1]
Figure 03_image063
Wherein, in chemical formula 1, R is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group containing at least one double bond or triple bond A substituted C2 to C20 aliphatic unsaturated organic group, a substituted or unsubstituted C6 to C30 aryl group, an ethylene oxide group, a propylene oxide group or a combination thereof, X, Y and Z are independently -OR 1 Or -OC(=O)R 2 , R 1 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, or a combination thereof, and R 2 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 group or a combination thereof; [Chemical formula 2]
Figure 03_image064
Wherein, in the chemical formula 2, X'is -OR 3 or -OC(=O)R 4 , and R 3 is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 ring Alkyl, 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 R 4 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. 如申請專利範圍第1項所述的半導體光阻組成物，其中R是經取代或未經取代的C1到C8烷基、經取代或未經取代的C3到C8環烷基、包含至少一個雙鍵或三鍵的經取代或未經取代的C2到C8脂族不飽和有機基、經取代或未經取代的C6到C20芳基、環氧乙烷基、環氧丙烷基或其組合， R1 及R3 獨立地為經取代或未經取代的C1到C8烷基、經取代或未經取代的C3到C8環烷基、經取代或未經取代的C2到C8烯基、經取代或未經取代的C2到C8炔基、經取代或未經取代的C6到C20芳基或其組合，且 R2 及R4 獨立地為氫、經取代或未經取代的C1到C8烷基、經取代或未經取代的C3到C8環烷基、經取代或未經取代的C2到C8烯基、經取代或未經取代的C2到C8炔基、經取代或未經取代的C6到C20芳基或其組合。The semiconductor photoresist composition described in item 1 of the scope of the patent application, wherein R is a substituted or unsubstituted C1 to C8 alkyl group, a substituted or unsubstituted C3 to C8 cycloalkyl group, and contains at least one double A substituted or unsubstituted C2 to C8 aliphatic unsaturated organic group, a substituted or unsubstituted C6 to C20 aryl group, an ethylene oxide group, a propylene oxide group or a combination thereof, R 1 and R 3 are independently 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, and R 2 and R 4 are independently 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. 如申請專利範圍第1項所述的半導體光阻組成物，其中R是甲基、乙基、丙基、丁基、異丙基、叔丁基、2,2-二甲基丙基、環丙基、環丁基、環戊基、環己基、乙烯基、丙烯基、丁烯基、乙炔基、丙炔基、丁炔基、苯基、甲苯基、二甲苯基、苄基、環氧乙烷基、環氧丙烷基或其組合， R1 及R3 獨立地是甲基、乙基、丙基、丁基、異丙基、叔丁基、2,2-二甲基丙基、環丙基、環丁基、環戊基、環己基、乙烯基、丙烯基、丁烯基、乙炔基、丙炔基、丁炔基、苯基、甲苯基、二甲苯基、苄基或其組合，且 R2 及R4 獨立地是氫、甲基、乙基、丙基、丁基、異丙基、叔丁基、2,2-二甲基丙基、環丙基、環丁基、環戊基、環己基、乙烯基、丙烯基、丁烯基、乙炔基、丙炔基、丁炔基、苯基、甲苯基、二甲苯基、苄基或其組合。The semiconductor photoresist composition described in item 1 of the scope of patent application, wherein R is methyl, ethyl, propyl, butyl, isopropyl, tert-butyl, 2,2-dimethylpropyl, cyclic Propyl, cyclobutyl, cyclopentyl, cyclohexyl, vinyl, propenyl, butenyl, ethynyl, propynyl, butynyl, phenyl, tolyl, xylyl, benzyl, epoxy Ethyl, propylene oxide or a combination thereof, R 1 and R 3 are independently methyl, ethyl, propyl, butyl, isopropyl, tert-butyl, 2,2-dimethylpropyl, Cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, vinyl, propenyl, butynyl, ethynyl, propynyl, butynyl, phenyl, tolyl, xylyl, benzyl or its Combinations, and R 2 and R 4 are independently hydrogen, methyl, ethyl, propyl, butyl, isopropyl, tert-butyl, 2,2-dimethylpropyl, cyclopropyl, cyclobutyl , Cyclopentyl, cyclohexyl, vinyl, propenyl, butenyl, ethynyl, propynyl, butynyl, phenyl, tolyl, xylyl, benzyl, or combinations thereof. 如申請專利範圍第1項所述的半導體光阻組成物，其中所述由化學式1表示的化合物包括由化學式3表示的化合物、由化學式4表示的化合物、由化學式5表示的化合物、由化學式6表示的化合物或其組合： [化學式3]
Figure 03_image065
[化學式4]
Figure 03_image067
[化學式5]
Figure 03_image069
[化學式6]
Figure 03_image071
其中，在化學式3、化學式4、化學式5及化學式6中， R是經取代或未經取代的C1到C20烷基、經取代或未經取代的C3到C20環烷基、包含至少一個雙鍵或三鍵的經取代或未經取代的C2到C20脂族不飽和有機基、經取代或未經取代的C6到C30芳基、環氧乙烷基、環氧丙烷基或其組合， Ra 、Rb 、Rc 、Ri 、Rk 及Rl 獨立地為經取代或未經取代的C1到C20烷基、經取代或未經取代的C3到C20環烷基、經取代或未經取代的C2到C20烯基、經取代或未經取代的C2到C20炔基、經取代或未經取代的C6到C30芳基或其組合，且 Rd 、Re 、Rf 、Rg 、Rh 及Rj 獨立地為氫、經取代或未經取代的C1到C20烷基、經取代或未經取代的C3到C20環烷基、經取代或未經取代的C2到C20烯基、經取代或未經取代的C2到C20炔基、經取代或未經取代的C6到C30芳基或其組合。The semiconductor photoresist composition as described in claim 1, wherein the compound represented by Chemical Formula 1 includes a compound represented by Chemical Formula 3, a compound represented by Chemical Formula 4, a compound represented by Chemical Formula 5, and a compound represented by Chemical Formula 6 Represents the compound or its combination: [Chemical formula 3]
Figure 03_image065
[Chemical formula 4]
Figure 03_image067
[Chemical formula 5]
Figure 03_image069
[Chemical formula 6]
Figure 03_image071
Wherein, in Chemical Formula 3, Chemical Formula 4, Chemical Formula 5 and Chemical Formula 6, R is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, containing at least one double bond Or triple bond substituted or unsubstituted C2 to C20 aliphatic unsaturated organic group, substituted or unsubstituted C6 to C30 aryl group, ethylene oxide group, propylene oxide group or a combination thereof, R a , R b , R c , R i , R k and R l are independently substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted 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 combinations thereof, and R d, R e, R f , R g, R h and R j are independently hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, A substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof. 如申請專利範圍第1項所述的半導體光阻組成物，其中所述由化學式1表示的有機金屬化合物及所述由化學式2表示的有機金屬化合物是以20:1到1:1的重量比被包含。The semiconductor photoresist composition as described in claim 1, wherein the organometallic compound represented by Chemical Formula 1 and the organometallic compound represented by Chemical Formula 2 are in a weight ratio of 20:1 to 1:1 Be included. 如申請專利範圍第1項所述的半導體光阻組成物，其中以100重量%的所述半導體光阻組成物計，所述組成物包含0.01重量%到30重量%的所述由化學式1表示的有機金屬化合物及0.01重量%到15重量%的所述由化學式2表示的有機金屬化合物。The semiconductor photoresist composition according to item 1 of the scope of the patent application, wherein, based on 100% by weight of the semiconductor photoresist composition, the composition contains 0.01% to 30% by weight of the chemical formula 1 And 0.01% to 15% by weight of the organic metal compound represented by Chemical Formula 2. 如申請專利範圍第1項所述的半導體光阻組成物，其中所述半導體光阻組成物包含表面活性劑、交聯劑、流平劑或其組合的添加劑。The semiconductor photoresist composition according to item 1 of the scope of the patent application, wherein the semiconductor photoresist composition contains additives of a surfactant, a crosslinking agent, a leveling agent, or a combination thereof. 一種形成圖案的方法，包括： 在基板上形成蝕刻目標層； 在所述蝕刻目標層上塗布如申請專利範圍第1項所述的半導體抗蝕劑組成物以形成光阻層； 對所述光阻層進行圖案化以形成光阻圖案；及 使用所述光阻圖案作為蝕刻罩幕來蝕刻所述蝕刻目標層。A method of forming a pattern includes: Forming an etching target layer on the substrate; Coating the semiconductor resist composition as described in item 1 of the scope of patent application on the etching target layer to form a photoresist layer; Patterning the photoresist layer to form a photoresist pattern; and The photoresist pattern is used as an etching mask to etch the etching target layer. 如申請專利範圍第8項所述的形成圖案的方法，其中所述光阻圖案是使用波長為5 nm到150 nm的光形成的。The method for forming a pattern as described in item 8 of the scope of patent application, wherein the photoresist pattern is formed using light with a wavelength of 5 nm to 150 nm. 如申請專利範圍第8項所述的形成圖案的方法，其更包括設置形成在所述基板與所述光阻層之間的抗蝕劑底層。The method for forming a pattern as described in item 8 of the scope of the patent application further includes providing a resist underlayer formed between the substrate and the photoresist layer. 如申請專利範圍第8項所述的方法，其中所述光阻圖案具有5 nm到100 nm的寬度。The method described in item 8 of the scope of patent application, wherein the photoresist pattern has a width of 5 nm to 100 nm.
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