TW201135362A - Resin compositions for light imprint, pattern forming method, and etching mask - Google Patents
Resin compositions for light imprint, pattern forming method, and etching mask Download PDFInfo
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- TW201135362A TW201135362A TW099139512A TW99139512A TW201135362A TW 201135362 A TW201135362 A TW 201135362A TW 099139512 A TW099139512 A TW 099139512A TW 99139512 A TW99139512 A TW 99139512A TW 201135362 A TW201135362 A TW 201135362A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F16/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F16/12—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
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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
- G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
- G03F1/60—Substrates
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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
- G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
- G03F1/68—Preparation processes not covered by groups G03F1/20 - G03F1/50
- G03F1/80—Etching
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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
- G03F7/0002—Lithographic processes using patterning methods other than those involving the exposure to radiation, e.g. by stamping
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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
- G03F7/16—Coating processes; Apparatus therefor
- G03F7/161—Coating processes; Apparatus therefor using a previously coated surface, e.g. by stamping or by transfer lamination
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
- B29C59/02—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing
- B29C2059/027—Grinding; Polishing
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Abstract
Description
201135362 六、發明說明: 【發明所屬之技術領域】 本發明係有關一種其硬化物之耐蝕刻性及耐熱性優異 的光壓印用樹脂組成物,使用該光壓印用樹脂組成物之圖 型之形成方法及蝕刻光罩。 【先前技術】 在半導體基板或金屬基板上形成微細圖型的方法,以 往係將感光性樹脂塗佈於基板上,透過光罩藉由曝光形成 圖型之後,使用光微影技術透過光罩蝕刻該感光性樹脂。 然而,光微影技術卻有製程複雜,以及曝光裝置等非 常昂貴的高成本問題。此外,當基板存在變形或微小突起 狀物時,因爲焦點深度的問題,解析度無法提高,所以很 可能產生圖型形成精度上的問題。 因此揭示壓印法作爲藉由接觸製程,以低成本形成微 細圖型的方法(例如參考專利文獻1 )。壓印法是一種將 具有期望圖型的模具壓在基板上所塗佈的樹脂材料上,而 在基材上的樹脂上形成期望圖型的技術。壓印法已知有使 用熱塑性樹脂藉由熱形成圖型的熱壓印法,及使用光硬化 性樹脂藉由光照射形成圖型的光壓印法。尤其是光壓印法 可以在低溫、低壓下形成圖型,故不需要加熱、冷卻的程 序’由於對高產量的期待,因此近年來已成爲受到注目的 技術(參考非專利文獻1、非專利文獻2 )。光壓印所使用 的光硬化性樹脂已知有使用丙烯酸系單體之東洋合成公司 -5- 201135362 製造的ΡΑΚ-01 (非專利文獻3 )。 此外,在基板上加工微細圖型的方法列舉有乾式蝕刻 法’使用光壓印法加工基板時,爲了能用來作爲蝕刻時的 抗蝕光罩,光硬化性樹脂的耐蝕刻性是必要的。專利文獻 2已揭示藉由配合具有環結構之丙烯酸單體來提高耐蝕刻 性的實例9 〔先前技術文獻〕 〔專利文獻〕 〔專利文獻1〕美國專利公報第5,7 7 2,9 0 5號 〔專利文獻2〕特開2007-84625號公報 〔專利文獻3〕特開2007-72374號公報 〔非專利文獻〕 〔非專利文獻 1〕T. Bailey, B. J. Chooi, M. Colburn, M. Meissi,S. Shaya, J. G. Ekerdt, S. V. Screenivasan, C. G. Willson: J. Vac. Sci. Technol., B 1 8 (2000) p. 3 5 72 〔非專利文獻 2〕A. Kumar,G. M. Whitesides: Appl. Phys. Lett, 63 ( 1 993 ) p. 2002 〔非專利文獻3〕東洋合成公司之PAK-01型錄 【發明內容】 然而,以使用丙烯酸系單體的組成物作爲光壓印用樹 脂,被指出有皮膚刺激性強、硬化時的體積收縮大,而且 因爲吸水率高,所以不容易形成精密圖型等許多問題點。 另外,在藉由乾式蝕刻法的基板加工方面,由丙烯酸系單 -6- 201135362 體之硬化物所得到的蝕刻光罩,對於進行難加工材料的加 工或高縱橫比加工而言,其耐蝕刻性是不足的。 此外,雖然專利文獻3已揭示以具有光硬化功能之含 高分子矽化合物的樹脂組成物作爲耐蝕刻性優異的室溫光 壓印用樹脂組成物,但是在樹脂本身具有矽結構的情況下 ’蝕刻後可能會產生含有無機成分的硬質殘渣,恐怕會引 起基板的破損。因此,樹脂結構物係以有機物所構成者爲 較佳。 有鑑於上述實際情況,本發明之目的係提供一種可適 用於光壓印,且作爲用於高精度加工基板之蝕刻光罩之硬 化物耐蝕刻性及耐熱性優異的光壓印用樹脂組成物,及使 用該光壓印用樹脂組成物之圖型之形成方法。 本案發明人爲了達成上述目的銳意探討的結果,發現 使用含有以具有交聯結構之環狀烴結構的特定2種以上乙 烯基醚化合物作爲硬化性單體的光壓印用樹脂組成物所得 到的硬化物,其耐蝕刻性及耐熱性優異,適合作爲高精度 加工基板的蝕刻光罩。 本發明爲基於上述硏究結果且具有下列要點者。 1 . 一種光壓印用樹脂組成物,其特徵係含有硬化性 單體(A)及光聚合引發劑(B),前述硬化性單體(A) 含有下述式(1)所示之脂環族乙烯基醚化合物及式(2) 所示之脂環族乙烯基醚化合物,且式(1)及式(2)所示 之化合物的重量比(式(1)所示之化合物的重量)/(式 (2)所示之化合物的重量)爲20/80〜95/5。 201135362 [化1】 式⑴[Technical Field] The present invention relates to a resin composition for photoimprint which is excellent in etching resistance and heat resistance of a cured product, and a pattern of the resin composition for photoimprinting is used. The forming method and the etching mask. [Prior Art] A method of forming a fine pattern on a semiconductor substrate or a metal substrate. Conventionally, a photosensitive resin is applied onto a substrate, and a pattern is formed by exposure through a mask, and then etched through a mask using photolithography. This photosensitive resin. However, photolithography has complicated processes and high cost and high cost problems such as exposure devices. Further, when the substrate has deformation or minute projections, the resolution cannot be improved because of the problem of the depth of focus, so that the problem of pattern formation accuracy is likely to occur. Therefore, the imprint method is disclosed as a method of forming a fine pattern at a low cost by a contact process (for example, refer to Patent Document 1). Imprinting is a technique in which a mold having a desired pattern is pressed against a resin material coated on a substrate to form a desired pattern on the resin on the substrate. The embossing method is known as a hot embossing method in which a thermoplastic resin is used to form a pattern by heat, and a photo embossing method in which a pattern is formed by light irradiation using a photocurable resin. In particular, photoimprinting can form patterns at low temperatures and low pressures, so there is no need for heating and cooling procedures. 'Because of the high yield, it has become a technology that has attracted attention in recent years (refer to Non-Patent Document 1 and Non-patent). Literature 2).光-01 (Non-Patent Document 3) manufactured by Toyo Seiki Co., Ltd. -5-201135362, which uses an acrylic monomer, is known as a photocurable resin. In addition, a method of processing a fine pattern on a substrate is a dry etching method. When a substrate is processed by photoimprinting, etching resistance of a photocurable resin is necessary in order to be used as a resist mask during etching. . Patent Document 2 discloses an example 9 in which etching resistance is improved by blending an acrylic monomer having a ring structure [Prior Art Document] [Patent Document] [Patent Document 1] U.S. Patent Publication No. 5,7 7 2,9 0 5 [Patent Document 2] JP-A-2007-84625 (Patent Document 3) JP-A-2007-72374 (Non-Patent Document) [Non-Patent Document 1] T. Bailey, BJ Chooi, M. Colburn, M. Meissi , S. Shaya, JG Ekerdt, SV Screenivasan, CG Willson: J. Vac. Sci. Technol., B 1 8 (2000) p. 3 5 72 [Non-Patent Document 2] A. Kumar, GM Whitesides: Appl. Phys Lett, 63 (1 993) p. 2002 [Non-Patent Document 3] PAK-01 Catalogue of Toyo Seisakusho Co., Ltd. [Summary of the Invention] However, it is pointed out that a composition using an acrylic monomer is used as a resin for photoimprinting. It has strong skin irritation and large volume shrinkage at the time of hardening, and because of the high water absorption rate, it is not easy to form many problems such as a precise pattern. In addition, in the processing of the substrate by the dry etching method, the etching mask obtained from the cured product of the acrylic single--6-201135362 body is resistant to etching for processing of difficult-to-machine materials or high aspect ratio processing. Sex is not enough. Further, in Patent Document 3, a resin composition containing a polymer ruthenium compound having a photocuring function is disclosed as a resin composition for room temperature photoimprinting which is excellent in etching resistance, but in the case where the resin itself has a ruthenium structure' After the etching, a hard residue containing an inorganic component may be generated, which may cause damage to the substrate. Therefore, the resin structure is preferably composed of an organic material. In view of the above-described circumstances, it is an object of the present invention to provide a resin composition for photoimprint which is suitable for photoimprinting and which is excellent in etching resistance and heat resistance of a cured film of an etching mask for high-precision processing of a substrate. And a method of forming a pattern of the resin composition for photoimprinting. In order to achieve the above object, the inventors of the present invention have found that a resin composition for photoimprint containing a specific two or more kinds of vinyl ether compounds having a cyclic hydrocarbon structure having a crosslinked structure as a curable monomer is used. The cured product is excellent in etching resistance and heat resistance, and is suitable as an etching mask for processing a substrate with high precision. The present invention is based on the above findings and has the following points. A resin composition for photoimprinting comprising a curable monomer (A) and a photopolymerization initiator (B), wherein the curable monomer (A) contains a fat represented by the following formula (1) The weight ratio of the cyclic vinyl ether compound and the alicyclic vinyl ether compound represented by the formula (2), and the compound represented by the formula (1) and the formula (2) (the weight of the compound represented by the formula (1) / (the weight of the compound represented by the formula (2)) is 20/80 to 95/5. 201135362 [Chemical 1] Formula (1)
{式中,X 表示氫原子、-OH、-ch2-oh、-o-ch = ch2 或-CH2-0-CH = CH2。A1〜A4分別獨立表示氫原子、甲基、 乙基、苯基、-OH、-ch2-oh、-o-ch = ch2 或-ch2-o-ch = ch2。但 X及 ai 〜A4至少 1 個爲-0-ch = ch2或-ch2-o-CH = CH2。m、η、〇表示 0 或 1}。 【化2】In the formula, X represents a hydrogen atom, -OH, -ch2-oh, -o-ch = ch2 or -CH2-0-CH = CH2. A1 to A4 each independently represent a hydrogen atom, a methyl group, an ethyl group, a phenyl group, -OH, -ch2-oh, -o-ch = ch2 or -ch2-o-ch = ch2. However, at least one of X and ai ~ A4 is -0-ch = ch2 or -ch2-o-CH = CH2. m, η, 〇 means 0 or 1}. [Chemical 2]
式⑵ {式中,P、Q分別獨立表示氫原子或-(CH2)a-ORI5 ( R15表示乙烯基或氫原子,a分別表示0或1。)。但P和Q至 少一個爲-((^^-(^^(尺^爲乙烯基。)表示氫原子 、甲基或乙基}。 2. 上述1所記載之光壓印用樹脂組成物,其含有49〜 99重量%的硬化性單體(Α),相對於100重i份的該硬化 性單體(A ),含有0.01〜30重量份的光聚合引發劑(B ) 〇 3. 上述1或2所記載之光壓印用樹脂組成物,其中硬 化性單體(A)所含有之式(1)及式(2)所示之脂環族 -8- 201135362 乙烯基醚化合物的合計量爲8 0重量%以上。 4. 上述1至3中任一項所記載之光壓印用樹脂組成物 ,其相對於100重量份的硬化性單體(Α),進一步含有 0.1〜100重量份的黏度調節劑(C)。 5. 上述4所記載之光壓印用樹脂組成物,其中黏度調 節劑(C )爲1種以上之分子量(Mw ) 1,000以上的高分子 量聚合物》 6. 上述1至5中任一項所記載之光壓印用樹脂組成物 ,其中紫外線照射後之硬化物的玻璃轉移溫度(在氮氣流 中,利用示差掃描量熱法)爲80°C以上。 7- 一種光壓印用樹脂薄膜,其爲上述1至6中任一項 所記載之光壓印用樹脂組成物所得到之膜厚爲1 〇 nm〜40 μ m的硬化物。 8. 一種圖型之形成方法,其包含將上述1至6中任一 項所記載之光壓印用樹脂組成物塗佈於基材上之形成塗膜 的步驟、使具有期望圖型之模具的圖型面與前述樹脂組成 物的塗膜表面接觸,加壓使樹脂組成物塡充在圖型內的步 驟、透過光照射使該塡充樹脂組成物硬化的步驟,以及使 硬化樹脂從模具剝離的步驟》 9. 上述8所記載之圖型之形成方法,進一步包含以硬 化樹脂作爲光罩來蝕刻前述基材的步驟。 10. —種微構造,其係由使具有期望圖型之模具的圖 型形狀與上述1至6中任一項所記載之光壓印用樹脂組成物 的樹脂表面接觸,加壓使樹脂組成物塡充在圖型內,透過 -9- 201135362 光照射該塡充樹脂組成物使樹脂組成物硬化後,使 脂表面從模具剝離而得。 11.—種蝕刻光罩,其係由上述1至6中任一項 之光壓印用樹脂組成物的硬化物所構成。 使用本發明之光壓印用樹脂組成物所得到的硬 其耐蝕刻性及耐熱性優異,適合作爲高精度加工基 刻光罩。 【實施方式】 本發明之光壓印用樹脂組成物含有上述式(1 之脂環族乙烯基醚化合物及上述式(2)所示之脂 烯基醚化合物作爲硬化性單體(A )。 上述式(1)所示之乙烯基醚化合物的式(1) 較佳爲氫原子、-OH、-CH2-OH、-〇-CH = CH2 或-CH = CH2,再者,A1〜A4較佳爲氫原子、甲基、乙 基、-OH、-CH2-OH、-0-CH = CH2 或-CH2-0-CH = CH η、〇較佳爲0或1。 式(1 )所示之乙烯基醚化合物的較佳實例列 下化合物。 硬化樹 所記載 化物, 板的蝕 )所示 環族乙 中,X C Η 2 * 0 -基、苯 2 ' m ' 舉有以 -10- 201135362 【化3】In the formula (2), P and Q each independently represent a hydrogen atom or -(CH2)a-ORI5 (wherein R15 represents a vinyl group or a hydrogen atom, and a represents 0 or 1 respectively). However, at least one of P and Q is -((^^-(^^(feet^ is vinyl)) represents a hydrogen atom, a methyl group or an ethyl group.) 2. The resin composition for photoimprint described in the above 1, It contains 49 to 99% by weight of a curable monomer (Α), and contains 0.01 to 30 parts by weight of the photopolymerization initiator (B) with respect to 100 parts by weight of the curable monomer (A). The resin composition for photoimprint according to 1 or 2, wherein the total of the alicyclic-8-201135362 vinyl ether compound represented by the formula (1) and the formula (2) contained in the curable monomer (A) The amount of the resin composition for photoimprint according to any one of the above 1 to 3, further comprising 0.1 to 100 by weight based on 100 parts by weight of the curable monomer (Α). 5. The viscosity-adjusting agent (C). The resin composition for photoimprint according to the above 4, wherein the viscosity modifier (C) is one or more kinds of high molecular weight polymers having a molecular weight (Mw) of 1,000 or more. The resin composition for photoimprint according to any one of the above 1 to 5, wherein the glass transition temperature of the cured product after ultraviolet irradiation (utilization in a nitrogen stream) The film thickness of the resin composition for photoimprint according to any one of the above 1 to 6 is 1 〇. A cured product of nm to 40 μm. 8. A method of forming a pattern comprising coating a resin composition for photoimprint according to any one of the above 1 to 6 on a substrate to form a coating film. a step of bringing the pattern surface of the mold having the desired pattern into contact with the surface of the coating film of the resin composition, pressurizing the resin composition to fill the pattern, and hardening the filling resin composition by light irradiation. The step of forming the cured resin from the mold. The method for forming the pattern described in the above 8, further comprising the step of etching the substrate with a cured resin as a mask. 10. A microstructure By bringing the pattern shape of the mold having the desired pattern into contact with the resin surface of the resin composition for photoimprint described in any one of the above 1 to 6, and pressurizing the resin composition to fill the pattern, Irradiating the enamel resin composition through -9-201135362 light After the resin composition is cured, the surface of the grease is peeled off from the mold. 11. An etching mask comprising the cured product of the resin composition for photoimprint according to any one of the above 1 to 6. The resin composition for photoimprinting of the present invention is excellent in etch resistance and heat resistance, and is suitable as a high-precision processing reticle. [Embodiment] The resin composition for photoimprint of the present invention contains the above formula. (1) an alicyclic vinyl ether compound and an aliphatic alkenyl ether compound represented by the above formula (2) as a curable monomer (A). Formula (1) of the vinyl ether compound represented by the above formula (1) Preferably, it is a hydrogen atom, -OH, -CH2-OH, -〇-CH=CH2 or -CH=CH2, and further, A1 to A4 are preferably a hydrogen atom, a methyl group, an ethyl group, -OH, -CH2- OH, -0-CH = CH2 or -CH2-0-CH = CH η, 〇 is preferably 0 or 1. Preferred examples of the vinyl ether compound represented by the formula (1) are listed below. In the case of the hardened tree, the etch of the plate is shown in the ring group B, X C Η 2 * 0 - group, benzene 2 ' m ' is given by -10- 201135362 [Chemical 3]
-11 - 201135362 【化4l-11 - 201135362
产。Production.
OHOH
OHOH
HOHO
HOHO
上述化合物尤其是以下式所示之化合物爲更佳。 【化5】The above compound is particularly preferably a compound represented by the following formula. 【化5】
-12- 201135362 【化6】-12- 201135362 【化6】
尤其是以下式所示之化合物爲特佳。 【化7】In particular, the compounds represented by the following formulas are particularly preferred. 【化7】
也可使用2種以上之上述化合物作爲上述式(1 )之乙 烯基醚化合物。 另一方面,上述式(2)所示之乙烯基醚化合物的式 (2 )中,P 較佳爲氫原子、-OH、-CH2-OH、-0-CH = CH2 或- ch2-o-ch = ch2,Q較佳爲氫原子、-OH、-ch2-oh、- -13- 201135362 o-ch = ch2^-ch2-o-ch = ch2 >再者,z較佳爲氫原子、甲 基或乙基。 式(2 )所示之乙烯基醚化合物的較佳實例列舉有以 下化合物。 【化8】Two or more of the above compounds may also be used as the vinyl ether compound of the above formula (1). On the other hand, in the formula (2) of the vinyl ether compound represented by the above formula (2), P is preferably a hydrogen atom, -OH, -CH2-OH, -0-CH = CH2 or -ch2-o-. Ch = ch2, Q is preferably a hydrogen atom, -OH, -ch2-oh, -13-201135362 o-ch = ch2^-ch2-o-ch = ch2 > further, z is preferably a hydrogen atom, Methyl or ethyl. Preferred examples of the vinyl ether compound represented by the formula (2) are as follows. 【化8】
-14- 201135362 尤其是以下式所示之化合物爲更佳。 【化9】-14- 201135362 Especially the compounds shown by the following formula are more preferred. 【化9】
也可使用2種以上之上述化合物作爲此式(2 乙烯基醚化合物。 在本發明中,式(1)所示之乙烯基醚化合半 )所示之乙烯基醚化合物的重量比((式(1) 合物的重量)/(式(2)所示之化合物的重量) 〜95/5,較佳爲20/80〜9 0/10。在式(1)所示之 化合物含量少的情況下,樹脂的成膜性不佳,塗 上時’樹脂容易皺縮,塗佈性不佳。另一方面, 的情況下’光硬化物的玻璃轉移溫度、耐乾式蝕 低,所以不佳。 再者,本發明所使用之前述硬化性單體(A 有的前述式(1)及式(2)所示之乙烯基醚化合 量,較佳爲8 0重量%以上,更佳爲90重量%以上 化性單體(A )中所含有的前述式(1 )及式(2 乙烯基醚化合物以外的硬化性單體雖然可列舉各 ,但可含有例如丁二醇二乙烯基醚、辛二醇二乙 乙二醇二乙烯基醚、二乙二醇二乙烯基醚、三乙 烯基醚等’以賦予柔軟性,可含有例如環己烷二 烯基醚、氫化雙酚A二乙烯基醚、三羥甲基丙烷 )所示之 3與式(2 所示之化 )爲 20/80 乙烯基醚 佈在基板 在含量多 刻性會變 )中所含 物的合計 。前述硬 )所示之 種化合物 烯基醚、 二醇二乙 甲醇二乙 三乙烯基 -15- 201135362 醚等,以提高交聯密度進而增加表面硬度。其調配量可在 不損及硬化樹脂之耐蝕刻性、耐熱性、基板附著性的範圍 內適當地使用。 此外,本發明之光壓印用樹脂組成物中,前述硬化性 單體(A)的含量,除了視需要而含有的溶劑外,較佳爲 49〜99重量%,更佳爲60〜95重量%,再更佳爲70〜95重 量%。 本發明之光壓印用樹脂組成物中所使用的光聚合引發 劑(B ),雖然以光自由基聚合引發劑或光陽離子聚合引 發劑爲較佳,但是並無限制,因此兩者均可使用。尤其是 以光陽離子聚合引發劑爲較佳,可使用已知者,例如鎮鹽 、毓鹽、鳞鹽等,作爲光陽離子聚合引發劑。 光陽離子聚合引發劑列舉例如二(烷基苯基)碘鑰六 氟磷酸鹽、二苯基碘鑰六氟磷酸鹽、二苯基碘鑰六氟銻酸 鹽、二(十二烷基苯基)碘鑰四(五氟苯基)硼酸鹽、二 〔4-(二苯基鏑基)苯基〕硫醚二六氟磷酸鹽、二〔4-( 二苯基鏑基)苯基〕硫醚二六氟銻酸鹽、二〔4-(二苯基 鏑基)苯基〕硫醚二四氟硼酸鹽、二〔4-(二苯基鏑基) 苯基〕硫醚四(五氟苯基)硼酸鹽、二苯基-4-(苯基硫) 苯基鏑六氟磷酸鹽、二苯基-4-(苯基硫)苯基锍六氟銻酸 鹽、二苯基-4-(苯基硫)苯基鏑四氟硼酸鹽、二苯基-4-(苯基硫)苯基鏑四(五氟苯基)硼酸鹽、三苯基锍六氟 磷酸鹽、三苯基毓六氟銻酸鹽、三苯基鏑四氟硼酸鹽、三 苯基鏑四(五氟苯基)硼酸鹽、二〔4-(二(4-(2-羥基 -16- 〔4- 201135362 乙氧基))苯基锍基)苯基〕硫醚二六氟磷酸鹽、二 (二(4- ( 2-羥基乙氧基))苯基锍基)苯基〕硫醚 氟銻酸鹽、二〔4-(二(4-(2 -羥基乙氧基))苯基 )苯基〕硫醚二四氟硼酸鹽、二〔4-(二(4-(2 -羥 氧基))苯基鏑基)苯基〕硫醚四(五氟苯基)硼酸 。尤其是以二(烷基苯基)碘鑰六氟磷酸鹽或二苯基 六氟磷酸鹽爲較佳。 上述光聚合引發劑可單獨使用或結合2種以上一 用。此外’若考慮在組成物中的分散性,則上述光聚 發劑也可含有溶劑。 本發明之光壓印用樹脂組成物中,相對於1 〇〇重 的硬化性單體(A ),光聚合引發劑(B )的含量較 0.01〜30重量份’更佳爲〇.1〜15重量份,特佳爲0.5 重量份。此外’爲提高該等光聚合引發劑的效率以促 聚合反應’該等光聚合引發劑也可含有已知的增感劑 素。尤其是增感劑對於提高陽離子聚合引發劑的效率 效的。 增感劑列舉例如蒽、噻噸酮、二苯基酮噻噸酮、 嗪類(phenothiazene )、茈等。此外,增感色素例示 代吡喃鑰鹽系色素、部花青素系色素、喹啉系色素、 烯基喹啉系色素、香豆素酮系色素、噻噸系色素、咕 色素、氧雜菁系色素、菁系色素、若丹明系色素、吡 鹽系色素等。尤其是蒽系增感劑與陽離子聚合引發劑 使用時’會大大提高感度。二丁氧基蒽、二丙氧基蒽 —* «—1_. ——/\ 鏡基 基乙 鹽等 碘鑰 起使 合引 量份 佳爲 〜10 進光 、色 是有 吩噻 有硫 苯乙 噸系 喃鑰 -倂 (川 -17- 201135362 崎化成公司製造的UVS-1331、UVS-1221)等可有效地作 爲蒽的化合物。 本發明之光壓印用樹脂組成物較佳爲含有黏度調節劑 (C)。黏度調節劑(C)係用來調節由該組成物形成薄膜 時組成物的黏度,及調整組成物的塗佈性和所得到之薄膜 的厚度。可使用已知的熱塑性樹脂、熱固性樹脂或液態樹 脂的高分子量聚合物來作爲黏度調節劑(C)。尤其是以 含有1種以上之分子量(Mw) 1,〇〇〇〜1,〇〇〇,〇〇〇的高分子 量聚合物爲較佳,也可視情形結合數種一起使用。 前述黏度調節劑(C )係以與光聚合引發劑(B )互溶 性佳的含芳環樹脂或含有環結構之樹脂爲更佳,列舉有乙 烯/甲基苯基降冰片烯共聚物(例如特開2005-239975中所 記載者)、乙烯/降冰片烯/甲基苯基降冰片烯共聚物(例 如特開2005-239975中所記載者)、聚苯乙烯、三環癸烷 乙烯基醚聚合物(例如特開2005-113049中所記載者)、 甲基苯基降冰片烷乙烯基醚聚合物、乙烯/降冰片烯類共 聚物(例如Ticona公司製造的Topas、三井化學公司製造 的Apel)、環烯烴類開環聚合物的加氫物(例如日本瑞翁 (Zeon )公司製造的ZEONEX · ZEONOR )、含有極性基 之環烯烴類開環聚合物的加氫物(例如JSR公司製造的 ARTON)等。 另外,可使用含有羥基的樹脂,或者也可適當地使用 該羥基受保護的樹脂來作爲用以提高基板附著性的黏度調 節劑(C )。列舉例如聚羥基苯乙烯、苯乙烯/羥基苯乙烯 -18- 201135362 共聚物、苯乙烯/羥基苯乙烯共聚物的縮醛保護聚合物、 羥基苯乙烯/三環癸烷乙烯基醚共聚物、羥基苯乙烯/三環 癸烷乙烯基醚共聚物的縮醛保護物、羥基苯乙烯/乙基乙 烯基醚的嵌段共聚物、無規共聚物等。 雖然可適當地使用上述黏度調節劑(C ),但特別是 以乙烯/甲基苯基降冰片烯共聚物、甲基苯基降冰片烷乙 烯基醚聚合物、聚羥基苯乙烯、或苯乙烯/羥基苯乙烯共 聚物及其縮醛保護物爲較佳。 該等黏度調節劑(C)可單獨使用,也可結合2種以上 —起使用。樹脂組成物中,相對於1 〇〇重量份的上述硬化 性單體(A),黏度調節劑(C)的含量較佳爲〇.1〜1〇〇重 量份,更佳爲0.5〜50重量份,特佳爲0.5〜10重量份。黏 度調節劑(C )中也可使用含有羥基的樹脂,但是得在不 影響硬化單體之聚合的情況下使樹脂組成物硬化。 可適當地使用旋轉塗佈法、溶液澆鑄法(溶液流延法 )、浸漬法、滴入法等已知方法來作爲使用本發明之光壓 印用樹脂組成物的薄膜形成方法。由本發明之光壓印用樹 脂組成物所構成之光壓印用樹脂薄膜的厚度,可使用藉由 黏度調節劑(C )調節黏度或藉由溶劑稀釋等方式來任意 地調節樹脂組成物的黏度。可發揮適用於光壓印之成膜性 、面內均勻性的硬化前膜厚,較佳爲10 nm〜40 μιη,更佳 爲 30nm 〜ΙΟμπι。 可任意使用至少其表面爲矽、鋁、銅、藍寶石、Si02 (氧化矽)、SiC (碳化矽)、GaN (氮化鎵)、inGaN ( -19- 201135362 氮化銦鎵)、GaAs (砷化鎵)、AlGaAs (砷化鋁鎵)、 AlGaP (磷化鋁鎵)、ITO (氧化銦錫)、玻璃、樹脂薄膜 等來作爲形成薄膜時塗佈樹脂組成物的支撐基材。 形成可光壓印之樹脂薄膜時,係以薄膜中殘留揮發性 成分少者爲較佳。殘留揮發性成分大量存在時,光壓印時 樹脂薄膜上會出現發泡現象等,而使得圖型的轉印精度降 低。 如上所述,由本發明之光壓印用樹脂組成物形成樹脂 薄膜時,以使用溶劑爲較佳。溶劑可任意使用,只要是能 溶解該組成物者即可,以使用有機溶劑爲較佳。舉例而言 ,酮系溶劑列舉有環己酮、環戊酮、甲基乙基酮、甲基異 丁基酮等,酯系溶劑列舉有乙二醇一甲基醚乙酸酯、二乙 二醇一甲基醚一乙酸酯、二乙二醇一乙基醚一乙酸酯、三 乙二醇一乙基醚一乙酸酯、二乙二醇一丁基醚一乙酸酯、 丙二醇一甲基醚乙酸酯、丁二醇一甲基醚乙酸酯、聚乙二 醇一甲基醚乙酸酯等,芳族烴系溶劑列舉有甲苯、二甲苯 、均三甲苯、氯苯、乙苯、二乙苯等《尤其是以二甲苯' 環己酮或聚乙二醇一甲基醚乙酸酯爲較佳。 該等溶劑可單獨使用,但也可結合2種以上的溶劑一 起使用。在樹脂組成物中添加溶劑的情況下,適當加溫進 行溶解以溶解樹脂也沒有關係。可依照形成的薄膜厚度任 意地調配溶劑。 藉由旋轉塗佈法製膜時,由於高速旋轉的氣流可提高 溶劑的蒸發速度,在旋轉塗佈過程中使溶劑揮發,得到可 -20- 201135362 適用於光壓印之殘留揮發性成分少的樹脂薄膜。爲了確保 旋塗膜的面內均勻性,旋轉塗佈所使用之溶劑的沸點較佳 爲70 °C〜25 0 °C,可適當地使用沸點低於所使用之硬化性 單體(A )的沸點的溶劑。此外,爲了更減少薄膜中的殘 留揮發性成分’旋轉塗佈後,也可利用熱板、熱風乾燥機 、真空乾燥機等進行加熱乾燥,得到光壓印用樹脂薄膜。 再者’此情況下的加熱乾燥溫度,係以低於所使用之硬化 性單體(A)的沸點的溫度爲較佳。另一方面,由於使用 溶液澆鑄法(溶液流延法)、浸漬法、滴入法等,在塗佈 時不易使溶劑揮發,因此使用溶劑時,塗佈後的風乾燥或 加熱乾燥程序是必要的。作爲可減少薄膜中殘留揮發性成 分的膜厚,係以所形成之薄膜的膜厚在硬化前爲40 μπι以 下者爲更佳。 在本發明中,由光壓印用樹脂組成物形成薄膜時,也 可以配合平坦劑。可使用已知物來作爲平坦劑,但以矽酮 系化合物、氟系化合物、丙烯酸系化合物、丙烯酸/矽酮 系化合物爲較佳。矽酮系化合物列舉例如楠本化成公司製 造的 DISPARLON 1761、DISPARLON 1711EF,氟系化合 物列舉例如大日本油墨化學公司製造的MEGAFACE F-470 、F-470,丙烯酸系化合物列舉例如DISPARLON LF-1980 、LF- 1 9 82,丙烯酸/矽酮系化合物列舉例如DISPARLON UVX-270、UVX-27 1 等。 平坦劑的添加量係於不損及耐蝕刻性及基板附著性的 範圍內進行選擇加以使用。 -21 - 201135362 再者,必要時,也可以在本發明之光壓印用樹脂組成 物中調入消泡劑、抗氧化劑、耐熱穏定劑、耐候穩定劑、 光穩定劑等。此外,也可以調入雙酚A、氫化雙酚A、1-金 剛烷醇、2·金剛烷醇、三環癸醇、杯芳烴等具有羥基之化 合物作爲用以提高對基板之附著性的附著性賦予劑。其調 配量可在不損及樹脂組成物之耐熱性、耐蝕刻性等功能的 範圍內適當地使用已知化合物。 雖然在光壓印時也可以直接使用該樹脂組成物,但是 從提高轉印精度的觀點來看,爲了除去由於異物而產生的 顆粒狀物,係以使用已知方法進行過濾爲較佳。也可根據 所使用之樹脂組成物的種類來變更適當的過濾材質。此外 ,也可適當地使用沒有電荷捕捉能力的過濾器。過濾器孔 徑係以0.45 μηι以下爲特佳。 本發明之光壓印用樹脂組成物係藉由紫外線等的照射 使其硬化,其照射條件可依照樹脂組成物的種類和組成比 例、膜厚等而做適當的變更。照射的紫外線波長可依照光 聚合引發劑及增感劑的種類等而適當地選擇使用具有高感 度的照射源。紫外線照射光源可列舉例如高壓水銀燈、超 高壓水銀燈、氙氣燈、金屬鹵素燈、LED燈、陽光、碳弧 等。除了紫外線之外,還可以使用例如可見光、紅外線、 X射線、α射線、β射線、γ射線、電子射線等作爲活化能射 線。 再者,必要時,也可在光壓印時紫外線等活化能射線 照射過程中,或是照射脫模後加熱樹脂。可藉由加熱減少 -22- 201135362 硬化樹脂中的未反應物、提高樹脂的硬化性或是與支撐基 材的附著性。加熱通常以30〜8(TC爲較佳,而且以低於硬 化後樹脂的玻璃轉移溫度爲較佳。此外,進一步照射紫外 線以提高樹脂硬化率的後UV硬化也可適用於照射紫外線 脫模後的硬化膜。 由本發明之光壓印用樹脂組成物所得到之紫外線照射 後的硬化物具有筒玻璃轉移溫度。再者,使用硬化物作爲 基板加工的蝕刻光罩時,由於乾式蝕刻等條件的加工表面 溫度較高,因此蝕刻光罩係以高玻璃轉移溫度的材料爲較 佳。由本發明之光壓印用樹脂組成物所構成之硬化物的玻 璃轉移溫度(在氮氣流下,利用示差掃描量熱計測定法) 較佳爲80°C以上,更佳爲100°C以上,再更佳爲120。(:以上 〇 本發明之光壓印用樹脂組成物可使用已知的光壓印法 ’在基材上形成微構造。所得到之微構造可在基材微加工 時用來作爲蝕刻光罩。 在光壓印法方面,本發明之圖型之形成方法較佳爲包 含以下步驟者。 (1 )將本發明之光壓印用樹脂組成物塗佈於基材上 之形成塗膜的步驟, (2) 使具有期望圖型之模具的圖型面與所形成的塗 膜表面接觸,加壓使樹脂組成物塡充在圖型內的步驟, (3) 透過光照射使塡充在圖型內的樹脂組成物硬化 的步驟, -23- 201135362 (4 )使硬化之樹脂組成物的硬化物從模具表面剝離 的步驟,以及進一步包含 (5 )以所形成之微構造作爲光罩來蝕刻前述基材的 步驟 可以從各種上市的產品中,選定適當的裝置來作爲進 行光壓印用之裝置。爲了實現圖型轉印精度優異且生產性 獲得改善的製程,係以模製壓力小、模製時間短的壓印條 件爲較佳。此外,在大氣中使模具與樹脂表面接觸時,由 於圖型尺寸、形狀或樹脂黏度的因素,會產生氣泡混入的 圖型缺陷。另外,大氣中的水分或氧所導致的光聚合阻礙 也會造成樹脂的硬化不足。因此,必要時也可以適用對裝 置系統內部進行減壓處理,在減壓下使模具與樹脂表面接 觸,加壓使其光硬化之減壓下的光壓印法》此外,也可以 用惰性氣體、乾燥空氣或是不會阻礙樹脂硬化的其他氣體 置換裝置系統內部來進行光壓印。 本發明之蝕刻光罩爲使用上述光壓印用樹脂組成物, 藉由光壓印法在基材上形成預定圖案之微構造,可蝕刻附 有此蝕刻光罩之基材而在基材本體上形成預定的圖案。爲 了能快速地經由蝕刻對基材形成圖型,較佳爲在蝕刻光罩 上所形成之圖型上的樹脂殘膜(殘留在圖型凹部底面的樹 脂)是薄的。 可適用物理蝕刻或化學蝕刻等乾式蝕刻、濕式蝕刻等 一般的技術來進行蝕刻。例如也可使用反應性離子蝕刻》 此外,蝕刻後殘留樹脂的殘膜只要藉由能溶解該樹脂的溶 -24- 201135362 劑或是灰化等處理來除去即可。 使用本發明之光壓印用樹脂組成物之光壓印製品的用 途’列舉有L E D、有機E L、太陽能板等環境調和型領域、 光波導路、導光板、繞射光柵等光學裝置類、以生物晶片 爲代表的生物元件領域、微流路、微反應器等流體元件、 資料儲存用媒體、線路基板的用途。 〔實施例〕 經由以下實施例說明本發明,但不應解讀爲本發明限 定於該等實施例。 A :樹脂組成物的調製方法 <實施例1〜2 1、比較例1〜4〉 如表1所示,使用硬化性單體(A )、光聚合引發劑( B )、黏度調節劑(C )、附著性賦予劑(D )、增感劑( E)、平坦劑(F)及溶劑(G)來調製實施例1〜21、比較 例1〜4的光壓印用樹脂組成物。 另外,在表1中,光聚合引發‘劑(B )、黏度調節劑( C )、附著性賦予劑(D )、增感劑(E )、平坦劑(F ) 及溶劑(G )的値爲相對於1 00重量份之硬化性單體的含量 (重量份)。 在已遮斷波長500nm以下紫外線之螢光燈下的黃光室 內,按以下步驟進行各組成物的調製。 1 .在預定容器內稱量硬化性單體(A )、黏度調節劑 -25- 201135362 (c )、附著性賦予劑(D )、增感劑(E ),進行攪拌混 合。 2·將光聚合引發劑(B)、平坦劑(ρ)投入上述1的 容器中’使用ThinkyMixer(THINKY公司)進行混合、脫 泡。 3 ·使用溶劑(G )調和’按預定比例稱量溶劑(G )與 上述2所得到的樹脂組成物,進行攪拌溶解。 4·用0.45 μηι的尼龍製過濾器(住友3M公司製造的 Li fe AS SURE )進行過濾’調製光壓印用樹脂組成物。 以下表示表1中所記載之各成分。 •硬化性單體(A ):如表2中所記載。 •光聚合引發劑(B) B-1:二(烷基苯基)碘鑰六氟磷酸鹽之5 0重量%碳酸 丙烯酯溶液(和光純藥工業公司製造的WPI-1 13 ) •黏度調節劑(C ) 黏度調節劑(C)所使用之樹脂C-1的重量平均分子量 (Mw )係藉由凝膠滲透層析法(GPC ),使用Waters公司 製造的GPC裝置,在管柱:Shodex公司製造的K-805L/K-806L、管柱溫度:40 °C 、溶劑:氯仿、通液量: 0.8mL/min的條件下測定。黏度調節劑(C)所使用之樹脂 C-2、C-3、C-4的重量平均分子量(Mw)係使用東曹公司 製造的GPC裝置,在管柱:東曹公司製造的TSK G2000Hx2 支 /TSK G3000H/TSK G4000H、管柱溫度:4 0°C、溶齊U : T H F、通液量:1 . 0 m L / m i η的條件下測定。 -26- 201135362 C-1:乙烯/5-甲基-5·苯基雙環[2,2,1]庚-2-嫌共聚物 (Mw: 50,000,特開2005 -23 997 5記載之乙烯/甲基苯基降 冰片烯共聚物) C-2:三環癸烷乙烯基醚聚合物(Mw: 18,000’特開 2 00 5-113 049記載之三環癸烷乙烯基醚聚合物) C-3:聚羥基苯乙烯(九善石油化學公司製造的 MARUKA LYNCUR M S-2,Mw4,000 〜6,0〇〇) C-4:苯乙烯/羥基苯乙烯共聚物之經由三環癸烷乙烯 基醚保護的羥基縮醛保護物(Mw: 8,5〇〇) •附著性賦予劑(D ) D-l : 1-金剛院基乙嫌基酸 D-2 :氫化雙酚A •增感劑(E ) E-l:9,10-二丙氧基蒽(川崎化成公司製造的UVS- 1221) •平坦劑(F ) F-1 :矽酮系平坦劑(楠本化成公司製造的 DISP ARLON 1761) •溶劑(G ) G-1 :二甲苯 G-2 :環己酮 <比較例5、比較例7 > 使用丙烯酸系光硬化樹脂PAK-01 (東洋合成公司製造 -27- 201135362 )的相似物作爲比較例5、7。 <比較例6、比較例8 > 使用環氧系光硬化樹脂SU-8_3010(日本化藥公司製 造)作爲比較例6、8。 B :樹脂薄膜的製作 用以下的旋轉塗佈法塗佈實施例1〜16、實施例18〜 2 1、比較例1〜8的樹脂組成物。 基板係使用在濕度25%以下的乾燥庫中保存24小時以 上的2吋Si晶圓(E&M公司製造,面方位1. 0. 0) 、2吋藍 寶石基板(京瓷(Kyocera)公司製造,面方位0· 0. 0. 1 )。 使用旋轉塗佈器(EHC公司製造的SC-308H)將光壓 印用樹脂組成物塗佈於基板上,製作光壓印用樹脂薄膜。 比較例6、8的樹脂薄膜係依照樹脂溶液說明書,在旋轉塗 佈後,爲了使溶劑揮發,於熱板上進行95 °C x2min的預烘 〇 實施例1 7的樹脂組成物係利用以下的棒塗佈法製膜。 基板係使用在濕度25%以下的乾燥庫中保存24小時以 上的4吋Si晶圓(E&M公司製造,面方位1.0.0)。 將光壓印用樹脂組成物滴在Si基板上,用塗佈器進行 塗佈。 -28- 201135362 C:樹脂薄膜的硬化方法 以上述方式製作的樹脂薄膜中,實施例1〜2 1、比較 例1〜4、6、8在空氣中乾燥,比較例5、7在氮氣氛中進行 UV照射。實施例1〜4、1 7、比較例1、比較例5〜8使用高 壓水銀燈(表1中記載爲Hg )作爲UV光源,實施例5〜1 6 、18〜21'比較例2〜4使用波長365nm的LED燈(HOYA公 司製造的EXECURE-H-1VC )作爲UV光源,以照度 50mW/cm2及表1所示的UV照射量進行硬化。 比較例6、8的樹脂硬化膜係依照樹脂說明書,在UV 照射後,爲了促使樹脂硬化,於UV硬化後,用熱風乾燥 機(在氮氣流下)進行9 5 °C X 2 m i η的後烘。 此外,在實施例10的黏度調節劑(C )中,使用C-4 : 苯乙烯/羥基苯乙烯共聚物之經由三環癸烷乙烯基醚保護 的縮醛保護物,在40 °C的熱板上,隔著脫模劑處理過的透 明薄膜進行UV照射使其硬化。 D =樹脂薄膜的評估 對由光壓印用樹脂組成物所製作的樹脂薄膜,進行塗 佈性、膜厚、基板附著性、硬化膜之玻璃轉移溫度的測定 。此外,對於在Si基板上所形成的硬化膜,根據Si蝕刻條 件,由蝕刻率來評估S i蝕刻選擇比。對於在藍寶石(以下 稱爲S ap )基板上所形成的硬化膜,根據S ap蝕刻條件,由 蝕刻率來評估S ap蝕刻選擇比。其結果示於表1。 -29- 201135362 蝕刻率 (塗佈性) 觀察硬化性組成物在利用旋轉塗佈或棒塗佈器塗佈於 Si或Sap基板上之後的表面狀態,觀察是否形成均勻的塗 膜,根據下述基準進行評估。 〇:得到均句的塗膜。 X:觀察到塗膜有不均勻、皺縮的情形。 塗佈性爲X的樣品不進行以下評估。 (膜厚) 對於塗佈性評估爲〇的樣品,在UV硬化後,測定硬 化膜的膜厚。實施例1〜16、18〜21、比較例1、5〜8之硬 化膜的膜厚係利用反射膜厚計(大塚電子公司製造的FE-3 000 )測定。K施例17之硬化膜的膜厚係利用高頻式膜厚 計(Kett科學硏究所製造的雙重式膜厚計LZ-3 00 )測定。 (基板附著性) 對於塗佈性評估爲〇的樣品,利用舊JI S K5 40 0的1 mm 棋盤格試驗,藉由纖維素膠帶剝離法,在100格當中,評 估殘留在基板上的格數。 例如在100格當中殘留50格時,爲50/1 00。 (玻璃轉移溫度:Tg) 對於在實施例1、3、5、6、16〜20、比較例1、5之Si -30- 201135362 基板上所形成之980nm以上的硬化膜,使用示差掃描熱分 析儀(精工電子工業公司製造的EXSTAR6000、DSC6200 ),由升溫時的吸熱峰得到玻璃轉移溫度。 由於示差掃描熱分析儀無法檢出比較例6之si基板上 交聯硬化膜的吸熱峰,因此藉由使用附有應力應變測定功 能之熱機械分析儀(精工電子工業公司製造的 EXSTAR6000、TMA/SS6000 ),以固定荷重將石英探針前 端壓在硬化膜上,升溫使樹脂軟化,讓石英探針前端嵌入 的動作得到玻璃轉移溫度。 (Si蝕刻選擇比) 對於在實施例1、3、5〜9、1 1〜1 4、2 0、比較例1、5 、6之Si基板上所形成的硬化膜,利用以下方法進行評估 〇 以聚醯亞胺膠帶遮蔽所製作之樹脂硬化膜表面的一部 分,製成樣品。接著,使用乾式蝕刻機,在使用氟系氣體 的一般S i蝕刻條件下蝕刻處理本樣品。撕下遮蔽膠帶,藉 由測定處理面與非處理面的高低差來測定蝕刻率。進一步 在相同條件下進行蝕刻,由S i基板的蝕刻率來評估s i蝕刻 選擇比=Si的蝕刻率/樹脂的蝕刻率。 (Sap蝕刻選擇比) 對於在實施例2、4、比較例7、8之S ap基板上所形成 的硬化膜,利用以下方法進行評估。 -31 - 201135362 以遮蔽構件遮蔽所製作之樹脂硬化膜表面的一部分, 製成樣品。接著,使用乾式蝕刻機,在使用C12系氣體的 S ap蝕刻條件下蝕刻處理本樣品。剝下遮蔽構件,藉由測 定處理面與非處理面的高低差來測定蝕刻率。進一步在相 同條件下進行蝕刻,由S ap基板的蝕刻率來評估S ap蝕刻選 擇比=S ap的蝕刻率/樹脂的蝕刻率。 201135362 ΐ 【1術】 wn i m 〇 ο 卜 1 30. 0 1 88.5 ο t-re ◦ C3 CO L/3 eJ o OO CQ s •_a s t— (/) 眯 m 担 is s 鲣 it m 〇 S CM 100/100 1 實施例14| | 72. 0 | d> οό 9 α> 86.2 Ο s 9 e>J c»i 〇 1 657. 0 1 ca CiJ o LT3 〇 岩 I loo/ioo I σ> iB cn i 闺 躺 1 18. 0 I ο ο %£> ΟΟ ο ο Ο Cvj o c*i 〇 1 850· 0 I s s C— 〇 1Λ 1 loo/ioo I LA CO 實施例12| ! 80. 0 1 ο CM CO ΟΟ e ο e C^0 e-ϊ o o (β c— 2 一 o Lf» 〇 尝 1 loo/ioo | C·- 二 實施例11 ! 70. 0 | 1 30.0 1 88.5 ο ιτΐ o o μ k/» esa | 378. 0 1 S o iA LO 〇 C*3 I loo/ioo | ! 1.87 實施例10 [ 70.0 ] 1 30. 〇Π 87.7 ο ΙΛ o u? s 〇 Irt tJ〇 〇 s LO | loo/ioo | 實施例9 | 70. 0 1 1 30.0 1 88.9 Ο LT» ο LA LA o | 376. 0 | s 1-3 9 lo 〇 t*« I loo/ioo | 1-1¾ OO 00 揭 Q 〇 1*- 1 30.0 1 Ο LO o Ξ LA e | 212.0 | s «-J s 卜 bO 〇 芑 | loo/ioo | 1.83 卜 握 佩 〇 C> t— ο Η 90.9 Ο LT9 o un C>0 | 369. 0 | s s 卜 bO 〇 CO «〇 [95/100 1 丨 1.84 VO 闺 Κ Ο ο ο ύ 92.2 Ο LO o bO o s o |Λ 〇 i 1078 I ! 70/100 1 U*d LA XT) m m in Γ 80^1 1 20. 0 1 91.3 Ο LT3 o c〇a LA Q s s r·— «Λ 〇 | 1089 | [32/100 1 1.67 闺 佩 1 90. 0 1 ο ο 86.2 1_10JJ e css 〇 C*3 Q | looo | & ra c/5 〇 | 1052 | | loo/ioo | 1 0.35 1 實施例3 1 90. 0 1 丨—10.0—1 81.4 9 LT> ΙΟ ec Cl 老 | looo | bO 〇 1 '118 1 | 30/100 1 t/3 S CS 闺 1K 1 90. 0 1 ο ο 90.7 ο LA 〇 css o «) c»i 〇 bo as I looo | A (0 «✓5 〇 | iioo | 100/100 1 0.37 1 闺 K ο ο ο CO Ο LA 〇 CO I looo | 〇 | 1057 1 | 60/100 I 1.58 τ CM < Jc i V0 i S5g |S s舶 gt-fi- 二 esi ώ CO 了 o ess Λ 1 1 ta. z es« 0 m lirwT 卿 腾 cT B 盔 I基板種類 ! 1塗佈性 1 nS it ffi m 撕 w fc a 經 m Si蝕刻選擇比 Sap蝕刻選擇比 1 硬化性單體 1光聚合引發劑1 黏度調節劑 附著性賦予劑 |增感劑 | |平坦劑 | 溶劑 -33- 201135362 【T丨3«】 比較例8 o o a fO O-J 1樹脂薄膜的fffe結果 〇 S 〇〇 100/100 CO o 比較例7 Μ) tZ3 o o 〇. to (/*3 〇 ο s 0/100 <0.21 比較例6 ω o o ς〇 〇 ο 芑 0/100 S O 丨比較例5 I e o fcO 〇 ο 〇〇 σ> 0/100 r— s c> 比較例4 〇 CD Ln 〇〇 e**3 esi cr> ο u1» Ο LO Ο I 253. 0 I s o ΙΛ A (9 to X 比較例3 I loo.o | Cvj esj Ο LA Ο ΙΛ ο 1 253. 0 1 s s Γ- S C/3 X 丨比較例2丨 〇 〇 ο s (Λ 窆 Ο LA ο un Lrt esi i 441.0 s s P"· CO X 丨比較例1J I ιοο.οΙ Ο U9 cr> Ο e-i ο CO o s o o 〇 ΙΛ S 2/100 eo esi 丨實施例21| ο s o s CM 〇> ο Ln ο LT3 o | 253.0 ] s s 卜 cx (Q VO Ο CO 1 100/100 I實施例20丨 ο s o CVJ C0 σ» ο Ln ο ΙΛ 二 o s s t- t/3 〇 〇〇 c*·» 11/100 CO C*9 s 丨實施例19 ο ο o s C-J c-4 σ> Ο bT9 ο LA o s s Γ— 〇 10/100 ΙΛ CN} 實施例18 e s ο s σ» CD ui <=> U9 Q s s e— •J; 〇 ITS 100/100 5 丨實施例17| ο ο ο g σι QO 〇〇 CD iA ο ο ro UT9 o ec B3 a o 1/3 〇 39000 2/100 t— 丨實施例16| 〇 〇 ο s CM OS) σ> 〇 ΙΛ ο ΙΛ o | 108. 5 I a Uj o Γ— 〇 t— 88/100 «SJ 1^9 <c CM Jc T LT5 to i匡 •fvllIP Λ C«J Λ CJ5 了 ο A Cn> 丄 z I z uv光源觀 CN 1 _ % 盔 基板觀 塗佈性 (nra) 基板附著性 b 鐘 i s 經 银 Si蝕刻選擇比 m 糊 塚 00 硬化性單體 艇§ 嘛fl· 光聚合引發劑 黏度調節劑 附著性賦予劑 1增感劑 1 平坦劑 溶劑 -34- 201135362 【表3】 表2 硬化性單體(A」 簡稱 彳h合物名稱 A-1 TCDVE =援癸烷乙烯基醚 A-2 MPNBVE s-田基-5-苯基雙環[2,2,11庚-2-乙烯基醚 A-3 1-AdVE 1-余剛烷基乙烯基醚 A-4 2-AdVE 2·金剛院基乙儲基酸 A-5 TDO-DVE 二擐癸烷二乙烯基醚 A-6 BDDVE 丁二醇二乙烯基醚 根據表1所示的結果’由本發明之光壓印用樹脂組成 物所得到的硬化物’其評估項目之玻璃轉移溫度、S丨蝕刻 選擇比或Sap蝕刻選擇比的數値高’顯示其耐熱性、耐蝕 刻性優異。 另一方面,如表1所示’硬化性單體爲只含有式(1) 或式(2)之化合物的其中一種而不含另一種的組成物( 比較例1、3 ),及式(1 )或式(2 )之化合物的比例在本 發明以外的組成物(比較例2 ' 4),其塗佈性不佳,無法 在基板上良好地形成薄膜,或是所得到之硬化膜的玻璃轉 移溫度低。此外,使用現有組成物的比較例5〜8,其玻璃 轉移溫度低或是Si蝕刻選擇比及Sap蝕刻選擇比低。 E :微構造的製作 以下’微構造的製作例係示於實施例22〜27。 使用氟系脫模劑處理過的石英模、透明樹脂模,藉由 -35- 201135362 UV壓印製作基板上的微構造。 <實施例22 > :使用石英模的微構造製作 使用實施例4所記載的光壓印用樹脂組成物,按以下 方法,在Si基板上形成微構造。 (1 )將實施例4所記載的光壓印用樹脂組成物旋轉塗 佈在2吋Si基板上,得到膜厚1 052nm的樹脂薄膜。 (2)將表面上形成寬度10 μπι、深度350 nm之孔圖型 的10mm角石英模,以0.2MPa的壓力壓在樹脂薄膜表面上 ’維持10秒鐘,使樹脂塡充在圖型內。 (3 )用波長3 65nm的LED燈,以照射量lOOOmJ/cm2的 紫外線進行照射,使樹脂硬化。 (4)解除壓力後,由樹脂表面脫模,在Si基板上得 到微構造》 <實施例23 > :使用石英模的微構造製作 使用實施例5所記載的光壓印用樹脂組成物,按以下 方法,在Si基板上形成微構造。 (1 )將實施例5所記載的光壓印用樹脂組成物旋轉塗 佈在2吋Si基板上,得到膜厚1 08 9nm的樹脂薄膜。 (2 )將表面上形成寬度10 μιη、深度3 5 0nm之孔圖型 的10mm角石英模,以0.2MPa的壓力壓在樹脂薄膜表面上 ’維持1 0秒鐘,使樹脂塡充在圖型內。 (3 )用波長3 65 nm的LED燈,以照射量7 5 0mJ/cm2的 -36- 201135362 紫外線進行照射,使樹脂硬化。 (4)解除壓力後,由樹脂表面脫模,在Si基板上形 成微構造。 <實施例24 > :使用透明樹脂模的微構造製作 使用實施例8所記載的光壓印用樹脂組成物,按以下 方法,在Sap基板上形成微構造》 (1 )將實施例8所記載的光壓印用樹脂組成物旋轉塗 佈在2吋Sap基板上,得到膜厚3 3 0nm的樹脂薄膜。 (2) 將旋轉塗佈過的基板置入可減壓處理的系統內 ,進行減壓處理到10, OOOPa,在減壓下,將表面上形成直 徑23 7nm、高度188nm之柱圖型的直徑2吋透明樹脂模,以 IMP a的壓力壓在樹脂薄膜表面上,維持丨〇秒鐘,使樹脂塡 充在圖型內。 , (3) 用波長365nm的LED燈,以照射量i〇〇〇mJ/cm2的 紫外線進行照射,使樹脂硬化。 (4 )使減壓的系統內部回到常壓,解除壓力後,由 樹脂表面脫模,在Sap基板上形成微構造。 <實施例2 5〉:使用透明樹脂模的微構造製作 使用實施例9所記載的光壓印用樹脂組成物,按以下 方法,在Si基板上形成微構造。 (1 )將實施例9的光壓印用樹脂組成物旋轉塗佈在2 吋Si基板上,得到膜厚171 nm的樹脂薄膜。 -37- 201135362 (2 )將表面上形成直徑23 7nm、高度188nm之柱圖型 的直徑2吋透明樹脂模,以IMPa的壓力壓在樹脂薄膜表面 上,維持10秒鐘,使樹脂塡充在圖型內。 (3 )用波長365nm的LED燈,以照射量750mJ/cm2的 紫外線進行照射,使樹脂硬化。 (4)解除壓力後,由樹脂表面脫模,在Si基板上形 成微構造。 <實施例26 > :使用透明樹脂模的微構造製作 使用實施例1 〇所記載的光壓印用樹脂組成物,按以下 方法,在Si基板上形成微構造。 (1 )將實施例1 〇的光壓印用樹脂組成物旋轉塗佈在2 吋Si基板上,得到膜厚173 nm的樹脂薄膜》 (2)將旋轉塗佈過的基板放置在40°C的熱板上,將 表面上形成直徑237nm、高度188nm之柱圖型的直徑2吋透 明樹脂模,以IMPa的壓力壓在樹脂薄膜表面上,維持10秒 鐘,使樹脂塡充在圖型內。 (3 )用波長3 65nm的LED燈,使照度在20mW/cm2, 維持38秒鐘,以照射量760mJ/秒m2的紫外線進行照射,使 樹脂硬化。 (4)解除壓力後,由樹脂表面脫模,在Si基板上形 成微構造。 <實施例2 7 > :使用透明樹脂模的微構造製作 -38- 201135362 使用實施例1 1所記載的光壓印用樹脂組成物,按以下 方法,在Si基板上形成微構造。 (1 )將實施例1 1的光壓印用樹脂組成物旋轉塗佈在2 吋Si基板上,得到膜厚173nm的樹脂薄膜。 (2)將表面上形成直徑237nm、高度188nm之柱圖型 的直徑2吋透明樹脂模,以IMPa的壓力壓在樹脂薄膜表面 上,維持10秒鐘,使樹脂塡充在圖型內。 (3 )用波長3 65nm的LED燈’使照度在20mW/cm2, 維持38秒鐘,以照射量760mJ/cm2的紫外線進行照射,使 樹脂硬化。 (4)解除壓力後’由樹脂表面脫模,在Si基板上形 成微構造。 F :微構造之轉印性評估 對於實施例22〜27所得到之基板上的微構造進行評估 ,利用U V壓印能精密轉印模具圖型者評估爲〇’不能精 密轉印模具圖型者評估爲X,其結果記載於表3。 【表4】 表 3_____ UV壓印實例 光壓印用樹脂組成物 圖型轉印性評估 實施例22 實施例4的樹脂組成物 〇 實施例23 實施例5的樹脂組成物 〇 實施例24 實施例啲樹脂組成物 〇 實施例25 實施例9的樹脂組成物 〇 實施例26 實施例10的樹脂組成物 〇 實施例27 實施例1啲樹脂組成物 〇 -39- 201135362 實施例22所得到之微構造表面的雷射顯微鏡照片係示 於圖1。 微構造之柱圖型爲寬度10 μηι、高度355 nm。 使用反射膜厚計測定圖型凹部膜厚的結果,測量到殘 膜20nm (殘留在圖型凹部底面的樹脂厚度)。 實施例25所得到之微構造剖面、表面的SEM照片係示 於圖2、3。 微構造之孔圖型爲直徑240nm、深度184nm、殘膜9nm (殘留在圖型凹部底面的樹脂厚度)。 實施例27所得到之微構造剖面的SEM照片係示於圖4 〇 微構造之孔圖型爲直徑240nm、深度184nm、殘膜 2 5 nm (殘留在圖型凹部底面的樹脂厚度)。 以上結果係根據本發明之圖型之形成方法,由石英模 和相同形狀的微構造而得。此外,可藉由配合圖型尺寸, 調整初期的塗佈膜厚來控制微構造的殘膜(殘留在圖型凹 部底面的樹脂厚度)。 G :基板加工評估 〈實施例2 8 > 以實施例2 5所得到的微構造作爲蝕刻光罩,乾式蝕刻 加工Si基板。使用乾式蝕刻機,在使用氟系氣體的一般Si 蝕刻條件下蝕刻處理附有蝕刻光罩之基板。 -40- 201135362 所得到之Si基板加工品剖面的SEM照片係示於圖5。 經由前述蝕刻製程,在Si表面上形成直徑243nm、深 度1 77nm的微細圖型。 〈實施例2 9 > 以實施例2 7所得到的微構造作爲蝕刻光罩,乾式蝕刻 加工Si基板。使用乾式蝕刻機,在使用氟系氣體的一般Si 蝕刻條件下蝕刻處理附有蝕刻光罩之基板。 所得到之Si基板加工品剖面的SEM照片係示於圖6。 經由前述蝕刻製程,在Si表面上形成直徑243 nm、深 度175nm的微細圖型❶ 實施例28及實施例29的結果顯示本發明之微構造的耐 蝕刻性優異,用來作爲蝕刻光罩可以高精度地加工基板。 如以上說明,本發明可提供一種耐蝕刻性、耐熱性優 異的光壓印用樹脂組成物及其圖型之形成方法,以及使用 該樹脂組成物之蝕刻光罩。 〔產業上利用性〕 本發明之光壓印用樹脂組成物可用來製造在半導體基 板或金屬基板上形成微細圖型用的蝕刻光罩。 【圖式簡單說明】 圖1爲表示本發明實施例22所得到之微構造表面的雷 射顯微鏡照片。 -41 - 201135362 圖2爲表示本發明實施例25所得到之微構造剖面的 SEM照片。 圖3爲表示本發明實施例25所得到之微構造表面的 SEM照片。 圖4爲表示本發明實施例27所得到之微構造剖面的 SEM照片。 圖5爲表示本發明實施例28所得到之Si基板加工品剖 面的SEM照片。 圖6爲表示本發明實施例29所得到之Si基板加工品剖 面的SEM照片。 -42 -Two or more of the above compounds may also be used as the weight ratio of the vinyl ether compound represented by the formula (2 vinyl ether compound. In the present invention, the vinyl ether compound half represented by the formula (1)) (1) The weight of the compound) / (weight of the compound represented by the formula (2)) ~ 95/5, preferably 20/80 to 9 0/10. The content of the compound represented by the formula (1) is small. In this case, the film forming property of the resin is not good, and when the coating is applied, the resin is easily shrunk and the coating property is not good. On the other hand, the glass transition temperature and the dry etching resistance of the photocured material are low, so that it is not good. Further, the amount of the vinyl ether compound represented by the above formula (1) and formula (2) used in the present invention is preferably 80% by weight or more, and more preferably 90%. The curable monomer other than the above formula (1) and formula (2) contained in the above-mentioned compound (1) and the above-mentioned vinyl ether compound may be, for example, butanediol divinyl ether. Octylene glycol diethylene glycol divinyl ether, diethylene glycol divinyl ether, trivinyl ether, etc. to impart softness, may contain For example, cyclohexanedienyl ether, hydrogenated bisphenol A divinyl ether, trimethylolpropane) 3 and formula (2) are 20/80 vinyl ether cloth in the substrate. The total content of the material contained in the above-mentioned hard), the compound alkenyl ether shown in the above hard), diol diethylethanol, diethylenetrivinyl-15-201135362 ether, etc., to increase the crosslinking density and increase the surface hardness. . The blending amount can be suitably used within a range that does not impair the etching resistance, heat resistance, and substrate adhesion of the cured resin. Further, in the resin composition for photoimprint of the present invention, the content of the curable monomer (A) is preferably 49 to 99% by weight, more preferably 60 to 95%, in addition to the solvent contained as necessary. %, more preferably 70 to 95% by weight. The photopolymerization initiator (B) used in the resin composition for photoimprint of the present invention is preferably a photoradical polymerization initiator or a photocationic polymerization initiator, but is not limited, and thus both may be used. use. In particular, a photocationic polymerization initiator is preferred, and a known one such as a salt of a salt, a phosphonium salt or a scale salt can be used as a photocationic polymerization initiator. The photocationic polymerization initiator is exemplified by, for example, bis(alkylphenyl)iodonium hexafluorophosphate, diphenyliodide hexafluorophosphate, diphenyliodide hexafluoroantimonate, di(dodecylphenyl). Iodine tetrakis(pentafluorophenyl)borate, bis[4-(diphenylindenyl)phenyl]thioether dihexafluorophosphate, bis[4-(diphenylfluorenyl)phenyl]sulfide Ether dihexafluoroantimonate, bis[4-(diphenylfluorenyl)phenyl] sulfide ditetrafluoroborate, bis[4-(diphenylfluorenyl)phenyl] sulfide tetrakis(pentafluoro) Phenyl)borate, diphenyl-4-(phenylthio)phenylphosphonium hexafluorophosphate, diphenyl-4-(phenylthio)phenylphosphonium hexafluoroantimonate, diphenyl-4 -(phenylthio)phenylhydrazine tetrafluoroborate, diphenyl-4-(phenylthio)phenylphosphonium tetrakis(pentafluorophenyl)borate, triphenylsulfonium hexafluorophosphate, triphenyl Hexafluoroantimonate, triphenylsulfonium tetrafluoroborate, triphenylsulfonium tetrakis(pentafluorophenyl)borate, bis[4-(2-(2-hydroxy-16-[4-201135362] Ethoxy))phenylphenyl)phenyl]thioether dihexafluorophosphate, di(di(4-(2-hydroxyethoxy)) Phenylfluorenyl)phenyl]thioether fluorodecanoate, bis[4-(bis(4-(2-hydroxyethoxy))phenyl)phenyl]thioether ditetrafluoroborate, bis[4 -(bis(4-(2-hydroxy)oxyphenyl)phenyl]thioether tetrakis(pentafluorophenyl)boronic acid. In particular, di(alkylphenyl)iodonium hexafluorophosphate or diphenylhexafluorophosphate is preferred. These photopolymerization initiators may be used alone or in combination of two or more. Further, the above photopolymerizer may contain a solvent in consideration of dispersibility in the composition. In the resin composition for photoimprint of the present invention, the content of the photopolymerization initiator (B) is more preferably 0.01 to 30 parts by weight with respect to 1 part by weight of the curable monomer (A). 15 parts by weight, particularly preferably 0.5 parts by weight. Further, in order to increase the efficiency of the photopolymerization initiators to promote polymerization, the photopolymerization initiators may also contain known sensitizing agents. In particular, the sensitizer is effective for increasing the cationic polymerization initiator. The sensitizers are exemplified by hydrazine, thioxanthone, diphenylketone thioxanthone, phenothiazene, anthraquinone and the like. Further, the sensitizing dye is exemplified by a pyranyl salt-based dye, a merocyanine-based dye, a quinoline-based dye, an alkenylquinoline-based dye, a coumarin-based dye, a thioxanthene dye, an anthraquinone dye, or an oxalate. A cyanine dye, a cyanine dye, a rhodamine dye, a pyridinium dye, or the like. In particular, when the lanthanide sensitizer and the cationic polymerization initiator are used, the sensitivity is greatly improved. Dibutoxy oxime, dipropoxy fluorene-* «—1_. ——/\ iodine base and other iodine key to make the combined amount is preferably ~10 light, color is phenothiazine thiobenzene It is effective as a compound of ruthenium, such as ketone-type 倂-倂 (UVS-1331, UVS-1221 manufactured by Kawasaki Kasei Co., Ltd.). The resin composition for photoimprint of the present invention preferably contains a viscosity adjusting agent (C). The viscosity modifier (C) is used to adjust the viscosity of the composition when the film is formed from the composition, and to adjust the coatability of the composition and the thickness of the obtained film. As the viscosity modifier (C), a known thermoplastic resin, a thermosetting resin or a high molecular weight polymer of a liquid resin can be used. In particular, a high molecular weight polymer containing one or more kinds of molecular weights (Mw) 1, 〇〇〇 〜 1, 〇〇〇, 〇〇〇 is preferable, and may be used in combination with several kinds as appropriate. The viscosity adjusting agent (C) is preferably an aromatic ring-containing resin or a ring-containing resin which is excellent in compatibility with the photopolymerization initiator (B), and examples thereof include an ethylene/methylphenyl norbornene copolymer (for example). JP-A-2005-239975), ethylene/norbornene/methylphenyl norbornene copolymer (for example, as described in JP-A-2005-239975), polystyrene, tricyclodecane vinyl ether A polymer (for example, those described in JP-A-2005-113049), a methylphenylnorbornane vinyl ether polymer, and an ethylene/norbornene copolymer (for example, Topas manufactured by Ticona Co., Ltd., Apel manufactured by Mitsui Chemicals, Inc.) a hydrogenated product of a cyclic olefin ring-opening polymer (for example, ZEONEX · ZEONOR manufactured by Zeon Corporation, Japan), and a hydrogenated product of a cyclic olefin ring-opening polymer containing a polar group (for example, manufactured by JSR Corporation) ARTON) and so on. Further, a hydroxyl group-containing resin may be used, or the hydroxyl group-protected resin may be suitably used as the viscosity adjuster (C) for improving the adhesion of the substrate. For example, polyhydroxystyrene, styrene/hydroxystyrene-18-201135362 copolymer, acetal protective polymer of styrene/hydroxystyrene copolymer, hydroxystyrene/tricyclodecane vinyl ether copolymer, hydroxyl group An acetal protective material of a styrene/tricyclodecane vinyl ether copolymer, a block copolymer of a hydroxystyrene/ethyl vinyl ether, a random copolymer, and the like. Although the above viscosity adjusting agent (C) can be suitably used, it is especially an ethylene/methylphenyl norbornene copolymer, a methylphenylnorbornane vinyl ether polymer, polyhydroxystyrene, or styrene. The /hydroxystyrene copolymer and its acetal protector are preferred. These viscosity modifiers (C) may be used singly or in combination of two or more. In the resin composition, the content of the viscosity modifier (C) is preferably 0.1 to 1 part by weight, more preferably 0.5 to 50 parts by weight per 1 part by weight of the above curable monomer (A). It is particularly preferably 0.5 to 10 parts by weight. A resin containing a hydroxyl group can also be used in the viscosity modifier (C), but the resin composition can be cured without affecting the polymerization of the hardening monomer. A known method such as a spin coating method, a solution casting method (solution casting method), a dipping method, or a dropping method can be suitably used as the film forming method using the resin composition for photoimprint of the present invention. The thickness of the resin film for photoimprint formed by the resin composition for photoimprint of the present invention can be arbitrarily adjusted to adjust the viscosity of the resin composition by adjusting the viscosity by the viscosity adjusting agent (C) or by dilution with a solvent. . The film thickness before hardening suitable for film formation and in-plane uniformity of photoimprinting is preferably 10 nm to 40 μm, more preferably 30 nm to ΙΟμπι. It can be used at least on the surface of yttrium, aluminum, copper, sapphire, SiO 2 (yttria), SiC (yttrium carbide), GaN (gallium nitride), inGaN (-19-201135362 indium gallium nitride), GaAs (arsenic) Gallium), AlGaAs (aluminum gallium arsenide), AlGaP (aluminum phosphide), ITO (indium tin oxide), glass, a resin film, or the like is used as a support substrate to which a resin composition is applied when a film is formed. When a photo-imprintable resin film is formed, it is preferred that the film has a small amount of residual volatile components. When a large amount of residual volatile components are present, a foaming phenomenon or the like occurs on the resin film during photoimprinting, and the transfer precision of the pattern is lowered. As described above, when a resin film is formed from the resin composition for photoimprint of the present invention, a solvent is preferably used. The solvent can be used arbitrarily as long as it can dissolve the composition, and it is preferred to use an organic solvent. For example, the ketone solvent is exemplified by cyclohexanone, cyclopentanone, methyl ethyl ketone, methyl isobutyl ketone, etc., and the ester solvent is exemplified by ethylene glycol monomethyl ether acetate and diethylene glycol. Alcohol monomethyl ether monoacetate, diethylene glycol monoethyl ether monoacetate, triethylene glycol monoethyl ether monoacetate, diethylene glycol monobutyl ether monoacetate, propylene glycol Monomethyl ether acetate, butanediol monomethyl ether acetate, polyethylene glycol monomethyl ether acetate, etc., aromatic hydrocarbon solvents are listed as toluene, xylene, mesitylene, chlorobenzene Ethylbenzene, diethylbenzene, etc., especially xylene 'cyclohexanone or polyethylene glycol monomethyl ether acetate is preferred. These solvents may be used singly or in combination of two or more solvents. When a solvent is added to the resin composition, it is also possible to dissolve by appropriately heating to dissolve the resin. The solvent can be optionally formulated in accordance with the thickness of the formed film. When the film is formed by the spin coating method, the evaporation rate of the solvent can be increased by the high-speed rotation of the gas stream, and the solvent is volatilized during the spin coating process to obtain a resin which can be used for photoimprinting with a small amount of residual volatile components in the -20-201135362 film. In order to ensure the in-plane uniformity of the spin coating film, the boiling point of the solvent used for spin coating is preferably from 70 ° C to 25 ° C, and a boiling point lower than that of the curable monomer (A ) used may be suitably used. The solvent of the boiling point. In addition, in order to further reduce the residual volatile component in the film, after spin coating, it may be heated and dried by a hot plate, a hot air dryer, a vacuum dryer or the like to obtain a resin film for photoimprint. Further, the heating and drying temperature in this case is preferably a temperature lower than the boiling point of the curable monomer (A) to be used. On the other hand, since the solvent casting method (solution casting method), the dipping method, the dropping method, and the like are used, it is difficult to volatilize the solvent during coating. Therefore, when a solvent is used, it is necessary to apply a wind drying or a heating drying process after coating. of. The film thickness which can reduce the residual volatile component in the film is preferably such that the film thickness of the formed film is 40 μm or less before curing. In the present invention, when a film is formed from a resin composition for photoimprint, a flat agent may be blended. A known material can be used as the flattening agent, but an anthrone compound, a fluorine compound, an acrylic compound, or an acrylic acid/anthrone compound is preferable. Examples of the fluorenone-based compound include DISPARLON 1761 and DISPARLON 1711EF manufactured by Nanben Chemical Co., Ltd., and fluorine-based compounds include, for example, MEGAFACE F-470 and F-470 manufactured by Dainippon Ink Chemical Co., Ltd., and acrylic compounds such as DISPARLON LF-1980, LF-. 1 9 82, an acrylic acid/fluorenone compound is exemplified by, for example, DISPARLON UVX-270, UVX-27 1 and the like. The amount of the flat agent to be added is selected and used within a range that does not impair the etching resistance and the substrate adhesion. Further, if necessary, an antifoaming agent, an antioxidant, a heat-resistant stabilizer, a weathering stabilizer, a light stabilizer or the like may be added to the resin composition for photoimprint of the present invention. Further, a compound having a hydroxyl group such as bisphenol A, hydrogenated bisphenol A, 1-adamantanol, 2·adamantanol, tricyclodecanol or calixarene may be added as an adhesion for improving adhesion to a substrate. Sexual imparting agent. The amount of the compound can be appropriately used within a range that does not impair the functions such as heat resistance and etching resistance of the resin composition. Although the resin composition can be used as it is in the case of photoimprinting, it is preferred to remove the particulate matter due to foreign matter from the viewpoint of improving the transfer precision by filtration using a known method. It is also possible to change an appropriate filter material depending on the type of the resin composition to be used. Further, a filter having no charge trapping ability can also be suitably used. The filter hole diameter is preferably 0.45 μηι or less. The resin composition for photoimprint of the present invention is cured by irradiation with ultraviolet rays or the like, and the irradiation conditions can be appropriately changed depending on the type and composition ratio of the resin composition, the film thickness, and the like. The ultraviolet ray wavelength to be irradiated can be appropriately selected and used as an irradiation source having high sensitivity in accordance with the type of the photopolymerization initiator and the sensitizer. Examples of the ultraviolet irradiation light source include a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, a metal halide lamp, an LED lamp, sunlight, a carbon arc, and the like. In addition to ultraviolet rays, for example, visible light, infrared rays, X rays, alpha rays, ? rays, gamma rays, electron rays, or the like can be used as the activation energy ray. Further, if necessary, the resin may be heated during irradiation of an active energy ray such as ultraviolet rays during photoimprinting or after irradiation. The unreacted material in the hardened resin can be reduced by heating, and the hardenability of the resin or the adhesion to the supporting substrate can be improved by heating. The heating is usually 30 to 8 (TC is preferable, and the glass transition temperature of the resin is preferably lower than that of the resin after curing. Further, the post-UV curing by further irradiating ultraviolet rays to increase the curing rate of the resin can also be applied to the ultraviolet demolition after irradiation. The cured product obtained by the ultraviolet ray irradiation of the resin composition for photoimprint of the present invention has a cylindrical glass transition temperature. Further, when a cured product is used as an etching mask for substrate processing, conditions such as dry etching are used. The processing surface temperature is high, and therefore the etching mask is preferably a material having a high glass transition temperature. The glass transition temperature of the cured product composed of the resin composition for photoimprint of the present invention (under a nitrogen stream, using a differential scanning amount) The calorimetry method is preferably 80 ° C or more, more preferably 100 ° C or more, and still more preferably 120. (: The above photo-embossing resin composition of the present invention can be used by known photoimprint method. 'Forming a microstructure on the substrate. The resulting microstructure can be used as an etch mask when the substrate is micromachined. In terms of photoimprint, the pattern of the invention is preferably formed. The following steps are included: (1) a step of forming a coating film by applying the resin composition for photoimprint of the present invention to a substrate, and (2) forming a pattern surface of the mold having a desired pattern and formed The step of contacting the surface of the coating film, pressurizing the resin composition to fill the pattern, and (3) the step of hardening the resin composition filled in the pattern by irradiation of light, -23-201135362 (4) hardening The step of peeling off the cured product of the resin composition from the surface of the mold, and further comprising (5) etching the aforementioned substrate with the formed microstructure as a mask can select an appropriate device from among various products listed In order to realize a process excellent in pattern transfer precision and improved in productivity, it is preferable to use an imprinting condition with a small molding pressure and a short molding time. Further, the mold is made in the atmosphere. When it comes into contact with the surface of the resin, due to the size, shape or resin viscosity of the pattern, pattern defects of air bubbles may be generated. In addition, photopolymerization hindered by moisture or oxygen in the atmosphere may also cause hardening of the resin. Therefore, if necessary, it is also possible to apply a photo-imprint method in which the inside of the apparatus system is subjected to a reduced pressure treatment, the mold is brought into contact with the surface of the resin under reduced pressure, and the light is hardened under pressure to reduce the light. The embossing reticle of the present invention is used for photoimprinting by using an inert gas, dry air, or other gas displacement device system that does not hinder the hardening of the resin. The etch mask of the present invention is formed by photoimprinting using a resin composition for photoimprinting. Forming a microstructure of a predetermined pattern on the material, and etching the substrate with the etch mask to form a predetermined pattern on the substrate body. In order to quickly form a pattern on the substrate via etching, it is preferred to etch light The resin residual film (resin remaining on the bottom surface of the pattern concave portion) formed on the cover is thin. The etching can be performed by a general technique such as dry etching or wet etching such as physical etching or chemical etching. For example, reactive ion etching may be used. Further, the residual film of the residual resin after etching may be removed by treatment such as dissolving the resin in the solution - 24, 2011, 35362 or ashing. The use of the photoimprint product using the resin composition for photoimprint of the present invention is exemplified by an environmentally-friendly type such as an LED, an organic EL or a solar panel, an optical device such as an optical waveguide, a light guide plate, or a diffraction grating. The use of biological devices such as bio-components, fluid elements such as microfluidics and microreactors, data storage media, and circuit boards. [Examples] The present invention is illustrated by the following examples, but should not be construed as being limited to the examples. A: Modulation method of resin composition <Examples 1 to 2 1. Comparative Examples 1 to 4> As shown in Table 1, a curable monomer (A), a photopolymerization initiator (B), a viscosity modifier (C), and an adhesion imparting agent were used ( D), a sensitizer (E), a flat agent (F), and a solvent (G) were used to prepare the resin compositions for photoimprint of Examples 1 to 21 and Comparative Examples 1 to 4. Further, in Table 1, the photopolymerization initiator 'B (B), the viscosity modifier (C), the adhesion imparting agent (D), the sensitizer (E), the flat agent (F), and the solvent (G) It is the content (parts by weight) relative to 100 parts by weight of the curable monomer. The composition of each composition was prepared in the yellow light chamber under a fluorescent lamp having a wavelength of 500 nm or less. 1. The curable monomer (A), the viscosity modifier -25-201135362 (c), the adhesion imparting agent (D), and the sensitizer (E) are weighed in a predetermined container, and stirred and mixed. 2. The photopolymerization initiator (B) and the flattening agent (ρ) were placed in the container of the above 1 and mixed and defoamed using ThinkyMixer (THINKY Co., Ltd.). 3. Reconciliation using a solvent (G) The solvent (G) and the resin composition obtained in the above 2 were weighed in a predetermined ratio, and stirred and dissolved. 4. A filter made of a 0.45 μηι nylon filter (Li fe AS SURE manufactured by Sumitomo 3M Co., Ltd.) was used to prepare a resin composition for photoimprint. The components described in Table 1 are shown below. • Hardenable monomer (A): as described in Table 2. • Photopolymerization initiator (B) B-1: 50% by weight of propylene carbonate solution of di(alkylphenyl) iodine hexafluorophosphate (WPI-1 13 manufactured by Wako Pure Chemical Industries, Ltd.) • Viscosity adjustment Agent (C) The weight average molecular weight (Mw) of the resin C-1 used in the viscosity modifier (C) is by gel permeation chromatography (GPC) using a GPC apparatus manufactured by Waters, in the column: Shodex The company's K-805L/K-806L, column temperature: 40 °C, solvent: chloroform, liquid volume: 0.8mL / min. The weight average molecular weight (Mw) of the resins C-2, C-3, and C-4 used in the viscosity modifier (C) is a GPC apparatus manufactured by Tosoh Corporation, and is used in the column: TSK G2000Hx2 manufactured by Tosoh Corporation. /TSK G3000H/TSK G4000H, column temperature: 40 ° C, dissolved U: THF, liquid volume: 1.0 m L / mi η. -26- 201135362 C-1: Ethylene/5-methyl-5-phenylbicyclo[2,2,1]hept-2-copolymer (Mw: 50,000, JP-A-2005-23997 5) Methylphenyl norbornene copolymer) C-2: tricyclodecane vinyl ether polymer (Mw: tributyl decane vinyl ether polymer described in 18,000 Å 2 00 5-113 049) C- 3: Polyhydroxystyrene (MARUKA LYNCUR M S-2 manufactured by Jiushan Petrochemical Co., Ltd., Mw4,000~6,0〇〇) C-4: Styrene/hydroxystyrene copolymer via tricyclodecane ethylene Hydroxy acetal protection protected by ether (Mw: 8,5〇〇) • Adhesion imparting agent (D) Dl : 1-Golden base basal acid D-2 : hydrogenated bisphenol A • sensitizer ( E) El: 9,10-dipropoxy fluorene (UVS-1221 manufactured by Kawasaki Kasei Co., Ltd.) • Flat agent (F) F-1: anthrone-based flat agent (DISP ARLON 1761 manufactured by Nanben Chemical Co., Ltd.) • Solvent (G) G-1 : xylene G-2 : cyclohexanone <Comparative Example 5, Comparative Example 7 > Comparative Examples 5 and 7 were used as the similar products of the acrylic photocurable resin PAK-01 (manufactured by Toyo Seisakusho Co., Ltd., -27 to 201135362). <Comparative Example 6 and Comparative Example 8> Epoxy photocurable resin SU-8_3010 (manufactured by Nippon Kayaku Co., Ltd.) was used as Comparative Examples 6 and 8. B: Preparation of Resin Film The resin compositions of Examples 1 to 16 and Examples 18 to 21 and Comparative Examples 1 to 8 were applied by the following spin coating method. The substrate was stored in a dry library having a humidity of 25% or less for 24 hours or more (manufactured by E&M Co., Ltd., surface orientation 1.0.0), and 2 sapphire substrate (Kyocera). Face orientation 0· 0. 0. 1 ). The resin composition for photoimprinting was applied onto a substrate by a spin coater (SC-308H manufactured by EHC Co., Ltd.) to prepare a resin film for photoimprint. The resin films of Comparative Examples 6 and 8 were pre-baked at 95 ° C for 2 min on a hot plate after spin coating in order to volatilize the solvent according to the resin solution specification. The resin composition of Example 17 was used as follows. Film formation by bar coating. The substrate was stored in a dry library having a humidity of 25% or less for 4 hours or more (manufactured by E&M Co., Ltd., surface orientation 1.0.0). The resin composition for photoimprint was dropped on a Si substrate and coated with an applicator. -28- 201135362 C: Hardening method of resin film In the resin film produced as described above, Examples 1 to 2, Comparative Examples 1 to 4, 6, and 8 were dried in the air, and Comparative Examples 5 and 7 were placed in a nitrogen atmosphere. UV irradiation was performed. In Examples 1 to 4 and 17, and Comparative Example 1 and Comparative Examples 5 to 8, high-pressure mercury lamps (described as Hg in Table 1) were used as UV light sources, and Examples 5 to 16 and 18 to 21' Comparative Examples 2 to 4 were used. An LED lamp (EXECURE-H-1VC manufactured by HOYA Co., Ltd.) having a wavelength of 365 nm was used as a UV light source and hardened by an irradiation dose of 50 mW/cm 2 and a UV irradiation amount shown in Table 1. The resin cured films of Comparative Examples 6 and 8 were post-baked at 95 ° C X 2 m i η in a hot air dryer (under a nitrogen stream) after UV curing in order to promote curing of the resin after UV irradiation according to the resin specification. Further, in the viscosity modifier (C) of Example 10, a C-4: styrene/hydroxystyrene copolymer acetal protection protected by tricyclodecane vinyl ether, heat at 40 ° C was used. The transparent film treated with the release agent on the plate was subjected to UV irradiation to be hardened. D = Evaluation of the resin film The resin film produced from the resin composition for photoimprint was measured for coating property, film thickness, substrate adhesion, and glass transition temperature of the cured film. Further, for the cured film formed on the Si substrate, the S i etching selection ratio was evaluated from the etching rate in accordance with the Si etching condition. For the cured film formed on the sapphire (hereinafter referred to as S ap ) substrate, the S ap etching selection ratio was evaluated from the etching rate in accordance with the S ap etching conditions. The results are shown in Table 1. -29- 201135362 Etching rate (coating property) Observe the surface state of the hardenable composition after it is applied onto a Si or Sap substrate by spin coating or a bar coater, and observe whether or not a uniform coating film is formed, according to the following. Benchmarks are evaluated. 〇: Get a uniform film. X: A case where the coating film was uneven and shrunk was observed. The sample having a coatability of X was not evaluated as follows. (Thickness) For the sample evaluated as the coating property, the film thickness of the hardened film was measured after UV curing. The film thicknesses of the hardened films of Examples 1 to 16, 18 to 21 and Comparative Examples 1 and 5 to 8 were measured by a reflection film thickness meter (FE-3 000 manufactured by Otsuka Electronics Co., Ltd.). The film thickness of the cured film of Example 17 was measured by a high-frequency film thickness meter (double film thickness meter LZ-3 00 manufactured by Kett Scientific Research Institute). (Substrate adhesion) For the sample whose evaluation property was evaluated as 〇, the number of cells remaining on the substrate was evaluated in 100 cells by the 1 mm checkerboard test of the old JI S K5 40 0 by the cell tape peeling method. . For example, when there are 50 cells remaining in 100 cells, it is 50/1 00. (glass transition temperature: Tg) For the cured film of 980 nm or more formed on the substrates of Si -30-201135362 of Examples 1, 3, 5, 6, 16 to 20, and Comparative Examples 1, 5, differential scanning calorimetry was used. The instrument (EXSTAR6000, DSC6200 manufactured by Seiko Instruments Inc.) obtained the glass transition temperature from the endothermic peak at the time of temperature rise. Since the differential scanning calorimeter could not detect the endothermic peak of the crosslinked cured film on the si substrate of Comparative Example 6, a thermomechanical analyzer with a stress-strain measurement function (EXSTAR 6000, TMA/ manufactured by Seiko Instruments Inc.) was used. SS6000), the quartz probe tip is pressed against the cured film with a fixed load, and the temperature is increased to soften the resin, and the action of embedding the front end of the quartz probe to obtain the glass transition temperature. (Si etching selection ratio) The cured films formed on the Si substrates of Examples 1, 3, 5 to 9, 1 1 to 14 and 20, and Comparative Examples 1, 5, and 6 were evaluated by the following methods. A part of the surface of the cured resin film produced was masked with a polyimide tape to prepare a sample. Next, the sample was etched under a general S i etching condition using a fluorine-based gas using a dry etching machine. The masking tape was peeled off, and the etching rate was measured by measuring the difference in height between the treated surface and the non-treated surface. Further, etching was performed under the same conditions, and the etching rate of the Si substrate was evaluated by the etching rate of the Si substrate. The etching ratio of the etching ratio of Si = the etching rate of the resin. (Sap etching selection ratio) The cured films formed on the S ap substrates of Examples 2 and 4 and Comparative Examples 7 and 8 were evaluated by the following methods. -31 - 201135362 A part of the surface of the resin cured film produced by the shielding member is shielded to form a sample. Next, the sample was etched under a S ap etching condition using a C12-based gas using a dry etching machine. The shielding member was peeled off, and the etching rate was measured by measuring the difference in height between the treated surface and the non-treated surface. Further, etching was performed under the same conditions, and the etching rate of the S ap etching selection ratio = S ap / the etching rate of the resin was evaluated from the etching rate of the S ap substrate. 201135362 ΐ [1] wn im 〇ο 卜1 30. 0 1 88.5 ο t-re ◦ C3 CO L/3 eJ o OO CQ s •_a st— (/) 眯m 担is s 鲣it m 〇S CM 100/100 1 Example 14| | 72. 0 | d> οό 9 α> 86.2 Ο s 9 e>J c»i 〇1 657. 0 1 ca CiJ o LT3 〇岩 I loo/ioo I σ> iB cn i 闺 lie 1 18. 0 I ο ο %£> ΟΟ ο ο Ο Cvj oc*i 〇1 850· 0 I ss C— 〇1Λ 1 loo/ioo I LA CO Example 12| ! 80. 0 1 ο CM CO ΟΟ e ο e C^0 e-ϊ oo (β c— 2 a o Lf» 〇 1 loo/ioo | C·- II Example 11 ! 70. 0 | 1 30.0 1 88.5 ο ιτΐ oo μ k /» esa | 378. 0 1 S o iA LO 〇C*3 I loo/ioo | ! 1.87 Example 10 [ 70.0 ] 1 30. 〇Π 87.7 ο ΙΛ ou? s 〇Irt tJ〇〇s LO | loo/ Ioo | Example 9 | 70. 0 1 1 30.0 1 88.9 Ο LT» ο LA LA o | 376. 0 | s 1-3 9 lo 〇t*« I loo/ioo | 1-13⁄4 OO 00 Rev Q 〇1 *- 1 30.0 1 Ο LO o Ξ LA e | 212.0 | s «-J s 卜bO 〇芑| loo/ioo | 83 卜握佩〇C> t— ο Η 90.9 Ο LT9 o un C>0 | 369. 0 | ss 卜bO 〇CO «〇[95/100 1 丨1.84 VO 闺Κ Ο ο ο ύ 92.2 Ο LO o bO Oso |Λ 〇i 1078 I ! 70/100 1 U*d LA XT) mm in Γ 80^1 1 20. 0 1 91.3 Ο LT3 oc〇a LA Q ssr·— «Λ 〇| 1089 | [32/100 1 1.67 闺佩1 90. 0 1 ο ο 86.2 1_10JJ e css 〇C*3 Q | looo | & ra c/5 〇| 1052 | | loo/ioo | 1 0.35 1 Example 3 1 90. 0 1 丨—10.0—1 81.4 9 LT> ΙΟ ec Cl old | looo | bO 〇1 '118 1 | 30/100 1 t/3 S CS 闺1K 1 90. 0 1 ο ο 90.7 ο LA 〇css o «) c» i 〇bo as I looo | A (0 «✓5 〇| iioo | 100/100 1 0.37 1 闺K ο ο ο CO Ο LA 〇CO I looo | 〇| 1057 1 | 60/100 I 1.58 τ CM < Jc i V0 i S5g |S s gt-fi- two esi ώ CO oo ess Λ 1 1 ta. z es« 0 m lirwT Qing Teng cT B Helmet I substrate type! 1Coatability 1 nS it ffi m tear w fc a m Si etching selection ratio Sap etching selection ratio 1 hardening monomer 1 photopolymerization initiator 1 viscosity adjuster adhesion imparting agent|sensitizer| | flattening agent|solvent-33- 201135362 [T丨3«] Comparative Example 8 fffe results of ooa fO OJ 1 resin film 〇S 〇〇100/100 CO o Comparative Example 7 Μ) tZ3 oo 〇. to (/*3 〇ο s 0/100 <0.21 Comparative Example 6 ω oo ς〇〇ο 芑0/100 SO 丨Comparative Example 5 I eo fcO 〇ο 〇〇σ> 0/100 r- s c> Comparative Example 4 〇CD Ln 〇〇e**3 Esi cr> ο u1» Ο LO Ο I 253. 0 I so ΙΛ A (9 to X Comparative Example 3 I loo.o | Cvj esj Ο LA Ο ΙΛ ο 1 253. 0 1 ss Γ- SC/3 X 丨Compare Example 2丨〇〇ο s (Λ 窆Ο LA ο un Lrt esi i 441.0 ss P"· CO X 丨 Comparative Example 1J I ιοο.οΙ Ο U9 cr> Ο ei ο CO osoo 〇ΙΛ S 2/100 eo esi 丨Example 21| ο sos CM 〇> ο Ln ο LT3 o | 253.0 ] ss 卜 cx (Q VO Ο CO 1 100/100 I embodiment 20 丨ο so CVJ C0 σ» ο Ln ο ΙΛ two oss t-t /3 〇〇〇c*·» 11/100 CO C*9 s 丨Example 19 ο ο os CJ c-4 σ> Ο bT9 ο LA oss Γ—〇10/100 ΙΛ CN} Example 18 es ο s σ» CD ui <=> U9 Q sse— •J; 〇ITS 100/100 5 丨Example 17| ο ο ο g σι QO 〇〇CD iA ο ο ro UT9 o ec B3 ao 1/3 〇39000 2/100 t —丨Example 16| 〇〇ο s CM OS) σ> 〇ΙΛ ο ΙΛ o | 108. 5 I a Uj o Γ — 〇t— 88/100 «SJ 1^9 <c CM Jc T LT5 to i匡•fvllIP Λ C«J Λ CJ5 ο A Cn> 丄z I z uv light source CN 1 _ % Helmet substrate coating (nra) substrate adhesion b Silver Si etching selection ratio m paste 00 hardening single boat § Fl fl · photopolymerization initiator viscosity modifier adhesion imparting agent 1 sensitizer 1 flat agent solvent -34- 201135362 [Table 3] Table 2 Sturdy single (A) abbreviated as 彳h compound name A-1 TCDVE = ketone vinyl ether A-2 MPNBVE s-Tianji-5-phenyl bicyclo [2,2,11hept-2-vinyl ether A- 3 1-AdVE 1-Resinyl vinyl ether A-4 2-AdVE 2·金刚院基乙储酸 A-5 TDO-DVE Dioxane Divinyl Ether A-6 BDDVE Butanediol II According to the results shown in Table 1, the cured product obtained from the resin composition for photoimprint of the present invention has a glass transition temperature, an S? etching selectivity ratio or a Sap etching selection ratio of the evaluation item. It is excellent in heat resistance and etching resistance. On the other hand, as shown in Table 1, the hardening monomer is one of the compounds containing only the formula (1) or the formula (2) and does not contain the other. The composition (Comparative Examples 1 and 3), and the composition of the formula (1) or the formula (2) in the composition other than the present invention (Comparative Example 2' 4) had poor coatability and could not be on the substrate. The film was formed well, or the glass transition temperature of the obtained cured film was low. Further, in Comparative Examples 5 to 8 using the conventional composition, the glass transition temperature was low or the Si etching selectivity ratio and the Sap etching selection ratio were low. : Production of Microstructures The following examples of the fabrication of the microstructures are shown in Examples 22 to 27. The quartz mold and the transparent resin mold treated with the fluorine-based release agent were fabricated by UV-embossing on -35-201135362. Microstructure. <Example 22>: Microstructure preparation using a quartz mold Using the resin composition for photoimprint described in Example 4, a microstructure was formed on a Si substrate by the following method. (1) The resin composition for photoimprint described in Example 4 was spin-coated on a 2-inch Si substrate to obtain a resin film having a film thickness of 1,052 nm. (2) A 10 mm-angle quartz mold having a hole pattern of a width of 10 μm and a depth of 350 nm was formed on the surface, and pressed against the surface of the resin film by a pressure of 0.2 MPa for 10 seconds to fill the resin in the pattern. (3) The resin is cured by irradiation with an ultraviolet light having an irradiation amount of 100 μm/cm 2 using an LED lamp having a wavelength of 3 65 nm. (4) After the pressure is released, the surface of the resin is released from the mold, and the microstructure is obtained on the Si substrate. <Example 23>: Microstructure preparation using a quartz mold Using the resin composition for photoimprint described in Example 5, a microstructure was formed on a Si substrate by the following method. (1) The resin composition for photoimprint described in Example 5 was spin-coated on a 2 Å Si substrate to obtain a resin film having a film thickness of 809 nm. (2) A 10 mm angle quartz mold having a hole pattern of a width of 10 μm and a depth of 305 nm was formed on the surface, and pressed against the surface of the resin film by a pressure of 0.2 MPa for 10 seconds to fill the resin in the pattern. . (3) The LED is irradiated with an ultraviolet light having a wavelength of 3 to 65 nm and irradiated with -36 to 201135362 of an irradiation amount of 750 mJ/cm2 to harden the resin. (4) After the pressure is released, the surface of the resin is released from the mold, and a microstructure is formed on the Si substrate. <Example 24>: Using the microstructure of the transparent resin mold, the resin composition for photoimprint described in Example 8 was used, and a microstructure was formed on the Sap substrate by the following method. (1) Example 8 The resin composition for photoimprint described above was spin-coated on a 2-inch Sap substrate to obtain a resin film having a film thickness of 340 nm. (2) The spin-coated substrate is placed in a system capable of decompression treatment, and subjected to a reduced pressure treatment to 10, OOOPa, and a diameter of a column pattern of 23 7 nm in diameter and 188 nm in height is formed on the surface under reduced pressure. 2 吋 Transparent resin mold, pressed against the surface of the resin film by the pressure of IMP a, maintained for 丨〇 second, so that the resin is filled in the pattern. (3) The resin is cured by irradiation with an ultraviolet light having an irradiation amount of i〇〇〇mJ/cm2 using an LED lamp having a wavelength of 365 nm. (4) The inside of the system under reduced pressure is returned to normal pressure, and after the pressure is released, the surface of the resin is released from the mold to form a microstructure on the Sap substrate. <Example 2 2: Preparation of a microstructure using a transparent resin mold The resin composition for photoimprint described in Example 9 was used to form a microstructure on a Si substrate by the following method. (1) The resin composition for photoimprint of Example 9 was spin-coated on a 2 吋 Si substrate to obtain a resin film having a film thickness of 171 nm. -37- 201135362 (2) A 2-inch transparent resin mold having a column shape of 23 7 nm and a height of 188 nm was formed on the surface, and pressed against the surface of the resin film at a pressure of 10 MPa for 10 seconds to fill the resin. Within the pattern. (3) The resin was cured by irradiation with an ultraviolet light having an irradiation amount of 750 mJ/cm 2 using an LED lamp having a wavelength of 365 nm. (4) After the pressure is released, the surface of the resin is released from the mold, and a microstructure is formed on the Si substrate. <Example 26>: Microstructure preparation using a transparent resin mold The resin composition for photoimprint described in Example 1 was used to form a microstructure on a Si substrate by the following method. (1) The resin composition for photoimprint of Example 1 was spin-coated on a 2 吋Si substrate to obtain a resin film having a film thickness of 173 nm. (2) The spin-coated substrate was placed at 40 ° C. On the hot plate, a 2 inch diameter transparent resin mold having a column shape of 237 nm and a height of 188 nm was formed on the surface, and pressed against the surface of the resin film at a pressure of 10 MPa for 10 seconds to fill the resin in the pattern. . (3) The LED lamp having a wavelength of 3 to 65 nm was used to maintain the illuminance at 20 mW/cm 2 for 38 seconds, and irradiated with ultraviolet rays having an irradiation amount of 760 mJ/s m 2 to cure the resin. (4) After the pressure is released, the surface of the resin is released from the mold, and a microstructure is formed on the Si substrate. <Example 2 7>: Microstructure using a transparent resin mold -38-201135362 Using the resin composition for photoimprint described in Example 1 1, a microstructure was formed on a Si substrate by the following method. (1) The resin composition for photoimprint of Example 1 1 was spin-coated on a 2 吋 Si substrate to obtain a resin film having a film thickness of 173 nm. (2) A 2-inch transparent resin mold having a column shape of 237 nm in diameter and 188 nm in height was formed on the surface, and pressed against the surface of the resin film at a pressure of 1 MPa for 10 seconds to fill the resin in the pattern. (3) The illuminance was maintained at 20 mW/cm 2 for 38 seconds using an LED lamp having a wavelength of 3 65 nm, and irradiated with ultraviolet rays having an irradiation amount of 760 mJ/cm 2 to cure the resin. (4) After the pressure is released, the surface of the resin is released, and a microstructure is formed on the Si substrate. F: Transferability evaluation of microstructures The microstructures on the substrates obtained in Examples 22 to 27 were evaluated, and those who used the UV imprinting precision transfer mold pattern were evaluated as those who could not accurately transfer the mold pattern. The evaluation was X, and the results are shown in Table 3. [Table 4] Table 3_____ UV Imprint Example Resin Composition for Photoimprint Pattern Transfer Evaluation Example 22 Resin Composition of Example 4 Example 23 Resin Composition of Example 5 Example 24 Example啲 resin composition 〇 Example 25 Resin composition of Example 9 〇 Example 26 Resin composition of Example 10 〇 Example 27 Example 1 啲 resin composition 〇-39- 201135362 The microstructure obtained in Example 22 The laser microscope photograph of the surface is shown in Fig. 1. The column pattern of the microstructure is 10 μηι in width and 355 nm in height. As a result of measuring the film thickness of the pattern concave portion by a reflection film thickness meter, the residual film 20 nm (the thickness of the resin remaining on the bottom surface of the pattern concave portion) was measured. The microstructural cross section and the SEM photograph of the surface obtained in Example 25 are shown in Figs. The pore pattern of the microstructure is 240 nm in diameter, 184 nm in depth, and 9 nm in residual film (resin thickness remaining on the bottom surface of the concave portion of the pattern). The SEM photograph of the microstructured cross section obtained in Example 27 is shown in Fig. 4. The pore pattern of the micro structure is 240 nm in diameter, 184 nm in depth, and 25 nm in residual film (resin thickness remaining on the bottom surface of the recess of the pattern). The above results are obtained by a quartz mold and a microstructure of the same shape according to the method of forming the pattern of the present invention. Further, the residual film thickness of the microstructure (the thickness of the resin remaining on the bottom surface of the concave portion of the pattern) can be controlled by adjusting the initial coating film thickness in accordance with the pattern size. G: Evaluation of substrate processing <Example 2 8 > The microstructure obtained in Example 25 was used as an etching mask, and the Si substrate was dry-etched. The substrate to which the etching mask is attached is etched under a general Si etching condition using a fluorine-based gas using a dry etching machine. -40-201135362 The SEM photograph of the cross section of the Si substrate processed product obtained is shown in Fig. 5. A fine pattern having a diameter of 243 nm and a depth of 1 77 nm was formed on the surface of Si via the above etching process. <Example 2 9> The microstructure obtained in Example 27 was used as an etching mask, and the Si substrate was dry-etched. The substrate to which the etching mask is attached is etched under a general Si etching condition using a fluorine-based gas using a dry etching machine. The SEM photograph of the obtained Si substrate processed product cross section is shown in Fig. 6. A fine pattern of 243 nm in diameter and 175 nm in depth was formed on the Si surface by the etching process. The results of Example 28 and Example 29 show that the microstructure of the present invention is excellent in etching resistance and can be used as an etching mask. The substrate is processed with precision. As described above, the present invention can provide a resin composition for photoimprint which is excellent in etching resistance and heat resistance, a method for forming the pattern thereof, and an etching mask using the resin composition. [Industrial Applicability] The resin composition for photoimprint of the present invention can be used for producing an etching mask for forming a fine pattern on a semiconductor substrate or a metal substrate. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a photograph of a laser microscope showing a microstructured surface obtained in Example 22 of the present invention. -41 - 201135362 Fig. 2 is a SEM photograph showing a microstructural section obtained in Example 25 of the present invention. Fig. 3 is a SEM photograph showing the microstructured surface obtained in Example 25 of the present invention. Fig. 4 is a SEM photograph showing a microstructure cross section obtained in Example 27 of the present invention. Fig. 5 is a SEM photograph showing a cross section of a processed article of a Si substrate obtained in Example 28 of the present invention. Fig. 6 is a SEM photograph showing a cross section of a processed article of a Si substrate obtained in Example 29 of the present invention. -42 -
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JP2010020620A JP2011157482A (en) | 2010-02-01 | 2010-02-01 | Photoimprinting resin composition, pattern forming method and etching mask |
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US10048582B2 (en) | 2015-12-16 | 2018-08-14 | Industrial Technology Research Institute | Photo-imprinting resin composition, photo-imprinting resin film and patterning process |
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JP5788759B2 (en) | 2011-10-18 | 2015-10-07 | 富士フイルム株式会社 | Curable composition for imprint and storage method thereof |
JP5541265B2 (en) * | 2011-11-18 | 2014-07-09 | 信越化学工業株式会社 | Etching mask film evaluation method |
JP5541266B2 (en) * | 2011-11-18 | 2014-07-09 | 信越化学工業株式会社 | Method for evaluating etching conditions of pattern forming film |
JP5975814B2 (en) * | 2012-09-14 | 2016-08-23 | 株式会社トクヤマ | Photocurable nanoimprint composition and pattern formation method |
JP6460672B2 (en) * | 2013-09-18 | 2019-01-30 | キヤノン株式会社 | Film manufacturing method, optical component manufacturing method, circuit board manufacturing method, and electronic component manufacturing method |
KR20160111918A (en) | 2014-01-29 | 2016-09-27 | 주식회사 다이셀 | Photocurable composition for nanoimprinting, and method for forming ultrafine pattern using the composition |
JP6733163B2 (en) * | 2015-12-03 | 2020-07-29 | 大日本印刷株式会社 | Imprint mold, manufacturing method thereof, and imprint method |
WO2017150261A1 (en) * | 2016-02-29 | 2017-09-08 | 富士フイルム株式会社 | Method for manufacturing pattern stacked body, method for manufacturing inverted pattern, and pattern stacked body |
US11549020B2 (en) | 2019-09-23 | 2023-01-10 | Canon Kabushiki Kaisha | Curable composition for nano-fabrication |
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2010
- 2010-02-01 JP JP2010020620A patent/JP2011157482A/en not_active Withdrawn
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US10048582B2 (en) | 2015-12-16 | 2018-08-14 | Industrial Technology Research Institute | Photo-imprinting resin composition, photo-imprinting resin film and patterning process |
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