TW200944944A - Photocurable film-forming composition and method of forming a photocurable film - Google Patents

Photocurable film-forming composition and method of forming a photocurable film Download PDF

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TW200944944A
TW200944944A TW098105474A TW98105474A TW200944944A TW 200944944 A TW200944944 A TW 200944944A TW 098105474 A TW098105474 A TW 098105474A TW 98105474 A TW98105474 A TW 98105474A TW 200944944 A TW200944944 A TW 200944944A
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film
compound
forming
group
forming composition
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TW098105474A
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Chinese (zh)
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TWI457711B (en
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Satoshi Takei
Yusuke Horiguchi
Tomoya Ohashi
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Nissan Chemical Ind Ltd
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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
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
    • H01L21/02118—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer carbon based polymeric organic or inorganic material, e.g. polyimides, poly cyclobutene or PVC
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • 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
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • 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
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • 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
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/094—Multilayer resist systems, e.g. planarising layers
    • 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
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
    • H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
    • H01L21/02282—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process liquid deposition, e.g. spin-coating, sol-gel techniques, spray coating
    • 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
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02296—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer
    • H01L21/02318—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment
    • H01L21/02345—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment treatment by exposure to radiation, e.g. visible light
    • H01L21/02348—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment treatment by exposure to radiation, e.g. visible light treatment by exposure to UV light

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  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical & Material Sciences (AREA)
  • Structural Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Architecture (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Materials For Photolithography (AREA)
  • Paints Or Removers (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Epoxy Resins (AREA)

Abstract

Disclosed is a film-forming composition for forming by photo-irradiation a level film which is used in the process of leveling an uneven surface. A film-forming composition for forming by photo-irradiation a level film which is used in the process of leveling an uneven surface, the composition containing photo-polymerizable material and a photo-polymerization initiator. Said photo-polymerizable material is a compound which has at least one reactive group which can undergo cationic polymerization and said photo-polymerization initiator is a photo-cationic-polymerization initiator. Alternatively said photo-polymerizable material is a compound which has at least one reactive group which can undergo radical polymerization, and said photo-polymerization initiator is a photo-radical-polymerization initiator.

Description

200944944 六、發明說明： 【發明所屬之技術領域】 本發明係有關利用光照射形成使具有凹凸的面平坦化 之步驟中所使用的平坦化膜用之膜形成組成物。又，係有 關使用該膜形成組成物的膜形成方法。 【先前技術】 〇 先前製造半導體裝置係藉由使用光致抗蝕劑之微影蝕 刻進行微細加工。前述微細加工爲，於矽晶圓等半導體基 板上形成光致抗蝕劑薄膜後，其上方介由描繪半導體裝置 之圖型的圖罩照射紫外線等活性光線，顯像後以所得光致 抗蝕劑圖型爲保護膜對基板進行蝕刻處理，而於基板表面 形成對應前述圖型的微細凹凸之加工法。 製造半導體、發光二極管、固體攝影元件、液晶顯示 器等電子零件時，係於基體上的永久膜上形成平坦化膜， ❿ 再利用該平坦化膜加工其上方重疊層的基體。 例如，爲了解決半導體裝置之圖型規格微細化時明確 的配線遲延問題，檢討使用銅作爲配線材料，同時檢討於 半導體基板上形成配線的方法用之雙波紋步驟。該雙波紋 步驟中係對形成通路孔，具有大長寬比之基板形成防反射 膜。因此相對於該步驟所使用的防反射膜要求可無間隙塡 充孔的塡埋特性，及可於基板表面上形成平坦膜的平坦化 特性。曾提案形成該類膜之方法（參考專利文獻丨、專利 文獻2、專利文獻3 )。 -5- 200944944 基體上係使用無機氧化膜、無機氮化膜、無機氧化氮 化膜等永久膜，其次係於此等永久膜上以形成配線等層之 步驟進行光致抗蝕劑被覆及曝光及顯像的步驟，因此該永 久膜表面具有凹凸時，需平坦化以防光致抗触劑反射。 又，固體攝影元件及液晶顯示器係於彩色瀘光片上形 成微透鏡時備有使彩色瀘光片平坦化之步驟，再於該平坦 化膜上形成微透鏡。 專利文獻1 :國際公開第2006/1 1 5044號報告 © 專利文獻2 :國際公開第2007/066597號報告 專利文獻3:特開平1—117032號公報 【發明內容】 發明所欲解決的課題 本發明係提供利用光照射形成使凹凸面平坦化之步驟 中所使用的平坦化膜用之膜形成組成物。又係提供該膜之 形成方法。 © 解決課題的方法 _ 本發明之第1觀點爲一種膜形成組成物，其爲利用光 ， 照射形成使凹凸面平坦化之步驟中所使用的平坦化膜用之 膜形成組成物中，含有光聚合性物質及光聚合引發劑。 第2觀點爲如第1觀點之膜形成組成物，其中前述光聚 合性物質爲具有至少一個可陽離子聚合之反應性基的光聚 合性化合物，前述光聚合引發劑爲光陽離子聚合引發劑。 -6- 200944944 第3觀點爲如第1觀點之膜形成組成物，其中前述光聚 合性物質爲具有至少一個可自由基聚合之反應性基的光聚 合性化合物’前述光聚合引發劑爲光自由基聚合引發劑。 第4觀點爲如第2觀點或第3觀點之膜形成組成物，其 中前述光聚合性化合物爲糖化合物。 第5觀點爲如第4觀點之膜形成組成物，其中前述糖化 合物爲式（1 ): [化1] (R1-(T)「〇-(CH2)n^—G1~(-(CH2)n-〇-(T)L—R2 ) 式（1) 、 /m ' I p —m (式中， G1爲糖骨架， T爲2價之連結基， R1爲乙烯基或縮水甘油基， R2爲氫原子或羥基， η及L各自獨立爲0或1之整數， ' Ρ爲糖具有之羥基總數的整數’及 m爲1‘mS (p—m)之整數）所表示之化合物。 第6觀點爲如第4觀點或第5觀點之膜形成組成物’其 中前述糖化合物爲單糖類或雙糖類化合物。 第7觀點爲如前述第2觀點之膜形成組成物’其中前述 光聚合性化合物爲脂環式環氧化合物’或脂環式氧雜環丁 烷化合物。 200944944 第8觀點爲如第7觀點之膜形成組成物，其中前述脂環 式環氧化合物爲環環氧化物衍生物。 第9觀點爲如第8觀點之膜形成組成物，其中前述脂環 式環氧化合物爲式（2)或式（3): [化2][Technical Field] The present invention relates to a film forming composition for a flattening film used in a step of flattening a surface having irregularities by light irradiation. Further, it relates to a film forming method using the film forming composition. [Prior Art] 先前 Previously fabricated semiconductor devices were microfabricated by lithography using photoresist. The microfabrication is such that after a photoresist film is formed on a semiconductor substrate such as a germanium wafer, an active light such as ultraviolet rays is irradiated on the upper surface of the pattern of the semiconductor device, and the resulting photoresist is developed. The pattern of the agent is a processing method in which the protective film is etched on the substrate, and a fine unevenness corresponding to the above-described pattern is formed on the surface of the substrate. When manufacturing an electronic component such as a semiconductor, a light-emitting diode, a solid-state imaging device, or a liquid crystal display, a planarizing film is formed on a permanent film on a substrate, and the substrate of the upper overlapping layer is processed by the planarizing film. For example, in order to solve the problem of wiring delay which is clear when the pattern specifications of the semiconductor device are made fine, a double-ripple step for using a method of forming wiring on a semiconductor substrate is reviewed while using copper as a wiring material. In the double corrugation step, the via holes are formed, and the substrate having a large aspect ratio forms an antireflection film. Therefore, the antireflection film used in this step requires the burying property of the gap-free boring hole and the flattening property of forming a flat film on the surface of the substrate. A method of forming such a film has been proposed (refer to Patent Document 专利, Patent Document 2, Patent Document 3). -5- 200944944 A permanent film such as an inorganic oxide film, an inorganic nitride film, or an inorganic oxynitride film is used for the substrate, and the photoresist is coated and exposed by a step of forming a wiring or the like on the permanent film. And the step of developing, so when the surface of the permanent film has irregularities, it needs to be flattened to prevent photo-anti-contact agent reflection. Further, in the solid-state imaging device and the liquid crystal display, when the microlens is formed on the color filter, a step of flattening the color filter is provided, and a microlens is formed on the planarization film. Patent Document 1: International Publication No. 2006/1 1 5044 Report © Patent Document 2: International Publication No. 2007/066597 (Patent Document 3) Japanese Laid-Open Patent Publication No. Hei No. Hei No. Hei. A film forming composition for forming a flattening film used in the step of flattening the uneven surface by light irradiation is provided. Further, a method of forming the film is provided. © Method for solving the problem The first aspect of the present invention is a film-forming composition which is a film-forming composition for forming a flattening film used for the step of flattening the uneven surface by light, and contains light. A polymerizable substance and a photopolymerization initiator. The second aspect is the film-forming composition according to the first aspect, wherein the photopolymerizable substance is a photopolymerizable compound having at least one cationically polymerizable reactive group, and the photopolymerization initiator is a photocationic polymerization initiator. The film formation composition of the first aspect, wherein the photopolymerizable substance is a photopolymerizable compound having at least one radically polymerizable reactive group, and the photopolymerization initiator is optically free. Base polymerization initiator. The fourth aspect is the film-forming composition according to the second aspect or the third aspect, wherein the photopolymerizable compound is a saccharide compound. The fifth aspect is the film forming composition according to the fourth aspect, wherein the sugar compound is of the formula (1): [Chemical Formula 1] (R1-(T)"〇-(CH2)n^-G1~(-(CH2) N-〇-(T)L—R2 ) Formula (1), /m ' I p —m (wherein G1 is a sugar skeleton, T is a divalent linking group, R1 is a vinyl group or a glycidyl group, R2 In the case of a hydrogen atom or a hydroxyl group, η and L are each independently an integer of 0 or 1, and 'Ρ is an integer of the total number of hydroxyl groups of the sugar' and m is an integer represented by an integer of 1'mS (p-m). The film formation composition of the fourth aspect or the fifth aspect, wherein the sugar compound is a monosaccharide or a disaccharide compound. The seventh aspect is the film formation composition of the second aspect, wherein the photopolymerizable compound is An alicyclic epoxy compound or an alicyclic oxetane compound. The present invention is a film-forming composition according to the seventh aspect, wherein the alicyclic epoxy compound is a cyclic epoxide derivative. The viewpoint is the film forming composition of the eighth aspect, wherein the alicyclic epoxy compound is the formula (2) or the formula (3):

(式中， G2爲伸烷基、羰基氧基、雜環基或芳香環基，或此等組合 形成的1價至5價之連結基， G3爲院基、院基羯基、雜環基或芳香環基，或此等組合形 成的有機基， η及m各自獨立爲1至5之整數）所表示的化合物。 第1 〇觀點爲如第1觀點至第9觀點中任何一項之膜形成 組成物，其爲形成製造半導體、發光二極管、固體攝影元 件，或液晶顯示器用之平坦化膜用。 第11觀點爲一種平坦化膜形成方法，其爲包含，將第 1觀點至第1 〇觀點中任何一項之膜形成組成物塗佈於基體 上形成塗佈膜的步驟，及利用光照射前述塗佈膜而硬化之 -8 - 200944944 步驟。 第12觀點爲一種平坦化膜形成方法，其爲包含，於基 體上形成永久膜之步驟，及將第1觀點至第1 0觀點中任何 一項之膜形成組成物塗佈於永久膜上形成塗佈膜的步驟， 及利用光照射前述塗佈膜而硬化之步驟。 第1 3觀點爲如第1 1或1 2觀點之平坦化膜形成方法，其 中前述光照射係以波長150至700 nm之光線進行。 © 第14觀點爲一種電子零件之製造方法，其爲包含，將 第1觀點至第10觀點中任何一項之膜形成組成物塗佈於基 體上形成塗佈膜的步驟，及利用光照射前述塗佈膜而硬化 之步驟。 第15觀點爲一種電子零件之製造方法，其爲包含，於 基體上形成永久膜之步驟’及將第1觀點至第10觀點中任 何一項之膜形成組成物塗佈於永久膜上形成塗佈膜的步驟 ，及利用光照射前述塗佈膜而硬化之步騾。 ® 第16觀點爲如第11觀點或第12觀點之電子零件的製造 方法，其中前述光照射係以波長150至700 nm之光線進行 〇 第17觀點爲如第1 1觀點至第13觀點中任何—項之電子 零件的製造方法’其中前述電子零件爲半導體、發光二極 管、固體攝影元件，或液晶顯示器。 發明的效果 本發明係提供利用光照射形成使具有凹凸的面平坦化 -9- 200944944 之步驟中所使用的平坦化膜用之膜形成組成物。本發明爲 了製造電子零件係使用旋塗法等塗佈法將本發明之膜形成 組成物塗佈於基體上，形成塗佈膜後利用光照射使膜硬化 。光照射之前或後可附加以低溫加熱之步驟。 本發明之膜形成組成物因含有光聚合性物質及光聚合 引發劑及溶劑，故塗佈時可浸透於凹凸面上形成平坦面， 於蒸發溶劑後利用光硬化形成平坦面。 又，本發明之膜形成組成物於塗佈後蒸發溶劑後仍保 @ 有流動性，因此所使用之光聚合性物質較佳爲常溫常壓下 之液狀物質。該類液狀物質於蒸發溶劑後仍保持液體狀態 ，因此可浸透於凹凸面上，使凹凸面平坦化，其後利用光 硬化可形成平坦面。 本發明之膜形成組成物例如作爲半導體裝置製造之光 阻底層膜用時，可得能塡充形成於半導體基板上之孔而無 間隙的底層膜。 又，本發明之膜形成組成物作爲底層膜形成組成物用 © 時，旣使不進行高溫加熱，也可利用光照射形成底層膜。 因此可防止因低分子量成份揮發或昇華而污染周邊裝置。 又，不需高溫加熱下，既使底層膜組成物使用低分子量成 份也無昇華等虞慮，可使用於低分子量成份較多之底層膜 組成物。因此使用黏度較低之底層膜形成組成物可形成底 層膜。可形成具有優良孔塡充性及半導體基板平坦化性之 底層膜。 -10- 200944944 實施發明的最佳形態 本發明之膜形成組成物爲利用光照射形成使具有凹凸 的面平坦化之步驟中所使用的平坦化膜用之組成物中，含 有光聚合性物質及光聚合引發劑。 又，本發明之膜形成組成物爲含有光聚合性物質、光 聚合引發劑及溶劑。又，本發明之膜形成組物可任意含有 表面活性劑及增感劑等之其他成份。 〇 由膜形成組成物去除溶劑而殘存之成份率爲固體成份 ，其可使用之量如使固體成份濃度爲0.5至50質量％或3至 40質量％，或10至3 0質量％之量。 固體成份中之光聚合性物質含量可爲50至99質量％， 或50至97質量％、60至95質量％、70至95質量％。 前述光聚合性物質爲，至少具有一個可陽離子聚合之 反應性基的光聚合性化合物，或具有至少一個可自由基聚 合之反應性基的光聚合性化合物。 ❹ 所使用之光聚合性物質爲至少具有一個可陽離子聚合 之反應性基的光聚合性化合物時，所使用之陽離子聚合引 發劑可爲光陽離子聚合引發劑。 又’所使用之光聚合性物質爲至少具有一個可自由基 聚合之反應性基的光聚合性化合物時，所使用之自由基聚 合引發劑可爲光自由基引發劑。 前述光聚合物質爲糖類時，可使用具有可陽離子聚合 之反應性基的糖’或具有可自由基聚合之反應性基的糖。 本發明之膜形成組成物中的光聚合性物質爲，分子內 -11 - 200944944 具有1個以上藉由光聚合引發劑之作用而聚合的光聚合性 部位之光聚合性化合物。爲了得到對有機溶劑等具有較低 溶解性的硬化膜，以使用具有2個以上光聚合性部位，例 如具有2個至6個，或具有2個至4個之化合物爲佳。 例如光聚合性部位爲自由基聚合性部位之乙烯製不飽 和鍵。又如，光聚合性部位爲陽離子聚合性部位之環氧環 '(wherein G2 is an alkylene group, a carbonyloxy group, a heterocyclic group or an aromatic ring group, or a monovalent to pentavalent linking group formed by such a combination, and G3 is a hospital group, a fluorenyl group, a heterocyclic group Or an aromatic ring group, or an organic group formed by such a combination, η and m are each independently an integer represented by 1 to 5). The film forming composition according to any one of the first aspect to the ninth aspect, which is for forming a semiconductor, a light emitting diode, a solid-state imaging element, or a planarizing film for a liquid crystal display. The eleventh aspect is a method for forming a planarizing film, comprising the steps of: applying a film forming composition according to any one of the first aspect to the first aspect to a substrate to form a coating film, and irradiating the light with the light Coating film and hardening -8 - 200944944 steps. The twelfth aspect is a method for forming a planarizing film, comprising the steps of forming a permanent film on a substrate, and applying the film forming composition of any one of the first aspect to the first aspect to a permanent film. The step of coating the film and the step of hardening by irradiating the coating film with light. The first aspect is the method for forming a planarizing film according to the 1st or 1st aspect, wherein the light irradiation is performed by light having a wavelength of 150 to 700 nm. The fourteenth aspect is a method for producing an electronic component, comprising the steps of: applying a film forming composition according to any one of the first aspect to the tenth aspect to a substrate to form a coating film, and irradiating the light with the light The step of coating the film to harden. The fifteenth aspect is a method for producing an electronic component, comprising the steps of: forming a permanent film on a substrate; and coating the film-forming composition of any one of the first to tenth aspects onto a permanent film to form a coating. The step of coating the film and the step of hardening by irradiating the coating film with light. The method of manufacturing an electronic component according to the eleventh aspect or the twelfth aspect, wherein the light irradiation is performed by light having a wavelength of 150 to 700 nm, and the 17th viewpoint is any one of the first to the thirteenth viewpoints. A method of manufacturing an electronic component, wherein the electronic component is a semiconductor, a light emitting diode, a solid-state imaging element, or a liquid crystal display. Advantageous Effects of Invention The present invention provides a film forming composition for forming a flattening film used in the step of flattening a surface having irregularities by light irradiation -9-200944944. In the production of an electronic component, the film-forming composition of the present invention is applied onto a substrate by a coating method such as a spin coating method to form a coating film, and the film is cured by light irradiation. The step of heating at a low temperature may be added before or after the light irradiation. Since the film-forming composition of the present invention contains a photopolymerizable substance, a photopolymerization initiator, and a solvent, it can be impregnated on the uneven surface to form a flat surface during coating, and can be formed into a flat surface by photocuring after evaporating the solvent. Further, since the film-forming composition of the present invention retains fluidity after evaporating the solvent after coating, the photopolymerizable material to be used is preferably a liquid material at normal temperature and normal pressure. Since such a liquid substance remains in a liquid state after evaporating the solvent, it can penetrate the uneven surface and flatten the uneven surface, and then form a flat surface by photohardening. When the film-forming composition of the present invention is used as a photoresist base film for a semiconductor device, for example, an underlayer film capable of filling a hole formed in a semiconductor substrate without a gap can be obtained. Further, when the film-forming composition of the present invention is used as the underlayer film-forming composition, the underlayer film can be formed by light irradiation without heating at a high temperature. Therefore, it is possible to prevent contamination of peripheral devices due to volatilization or sublimation of low molecular weight components. Further, even if it is not required to be heated under high temperature, even if the underlying film composition is used in a low molecular weight component or sublimation, it can be used for a low-molecular-weight composition of an underlying film composition. Therefore, the underlayer film can be formed by forming the composition using the underlying film having a lower viscosity. An underlayer film having excellent hole chargeability and planarization of a semiconductor substrate can be formed. -10-200944944 BEST MODE FOR CARRYING OUT THE INVENTION The film-forming composition of the present invention contains a photopolymerizable substance and a composition for forming a flattening film used for the step of flattening a surface having irregularities by light irradiation. Photopolymerization initiator. Further, the film-forming composition of the present invention contains a photopolymerizable substance, a photopolymerization initiator, and a solvent. Further, the film-forming composition of the present invention may optionally contain other components such as a surfactant and a sensitizer.成份 The component ratio of the solvent-removing composition to remove the solvent is a solid component, and it can be used in an amount such that the solid component concentration is from 0.5 to 50% by mass or from 3 to 40% by mass, or from 10 to 30% by mass. The photopolymerizable substance content in the solid component may be 50 to 99% by mass, or 50 to 97% by mass, 60 to 95% by mass, and 70 to 95% by mass. The photopolymerizable material is a photopolymerizable compound having at least one cationically polymerizable reactive group or a photopolymerizable compound having at least one radically polymerizable reactive group. When the photopolymerizable substance to be used is a photopolymerizable compound having at least one cationically polymerizable reactive group, the cationic polymerization initiator used may be a photocationic polymerization initiator. Further, when the photopolymerizable substance to be used is a photopolymerizable compound having at least one radically polymerizable reactive group, the radical polymerization initiator to be used may be a photoradical initiator. When the photopolymerizable substance is a saccharide, a sugar having a cationically reactive reactive group or a sugar having a radically polymerizable reactive group can be used. The photopolymerizable substance in the film-forming composition of the present invention is a photopolymerizable compound having one or more photopolymerizable sites polymerized by the action of a photopolymerization initiator in the molecule -11 - 200944944. In order to obtain a cured film having low solubility to an organic solvent or the like, it is preferred to use a compound having two or more photopolymerizable sites, for example, two to six or two to four. For example, the photopolymerizable moiety is an ethylene-unsaturated bond of a radical polymerizable site. In another example, the photopolymerizable moiety is an epoxy ring of a cationically polymerizable moiety.

或氧雜環丁烷等環狀醚構造等。所使用之光聚合性化合物 較佳爲，室溫（20°C左右）下爲液體之化合物。光聚合性 Q 化合物之分子量較佳爲100以上。分子量如，100至2000， 或150至1500，或150至1000，或150至800。此等分子量可 由，藉由GPC分析以聚苯乙烯換算而得之分子量求取。 GPC之測定條件如，GPC裝置（商品名HLC _ 8220GPC、東 索股份公司製）、GPC柱（商品名ShodexKF803L、KF802 、KF801、昭和電工製）、柱溫度爲40°C、溶離液（溶出 溶劑）爲四氫呋喃、流量（流速）爲l.Oml/min，及標準試 料爲聚苯乙烯（昭和電工股份公司製）。 〇 光聚合性物質可爲糖化合物。例如可使用前述式（1 )所表示之糖化合物。前述式（1)中，G1爲糖骨架，T爲 2價連結基，R1爲乙烯基或縮水甘油基，R2爲氫原子或羥 基。η及L各自獨立爲〇或1之整數，p爲該糖具有之羥基總 數的整數。m爲滿足ISmS (p— m)之整數。 例如葡萄糖、果糖、半乳糖之羥基總數爲5個，因此 P = 5 ’海藻糖、蔗糖、乳糖、麥芽糖、纖維二糖之羥基總 數爲8個，因此p = 8。 -12- 200944944 該R1或TR1爲與糖之羥基反應的光聚合性基，存在於 糖之羥基以1個以上之比率與光聚合性化合物反應時，可 得具有光聚合性基之糖化合物。糖化合物較佳爲液體，羥 基數較少時易液狀化，因此又以糖全體之羥基的80%以上 ，較佳爲糖全體之羥基總數被光聚合性基取代的化合物爲 佳。 式（1)中τ爲羰基，碳原子數1至6之伸烷基、氧基伸 〇 烷基、伸苯基等。此等糖化合物可使用市售品，也可由下 述合成方法而得。 製造具有乙烯基之糖時，例如將糖及含有乙烯基之化 合物溶解於溶劑後，可於存在過氧化苯醯、二-t-丁基氫過 氧化物、t-丁基氫過氧化物、枯烯基過氧化物、枯烯氫過 氧化物、二異丙基苯氫過氧化物、t_ 丁基過氧化苯甲酸酯 、月桂基過氧化物、乙醯過氧化物、t-丁基過氧化-2-乙基 己酸酯等過氧化物、α，α:’-偶氮雙異丁腈、偶氮雙二甲基 ® 戊腈、偶氮雙環己烷腈等偶氮化合物等之自由基聚合引發 劑下’以反應溫度80至95 °C利用溶液聚合法進行。製造時 較佳之有機溶劑爲，能溶解糖及含有乙烯基之化合物，且 對乙烯基爲不活性之物，例如乙酸甲酯、乙酸乙酯、乙酸 丙酯、乙酸丁酯、乙酸異丁酯、乙酸戊酯、3_甲氧基丁基 乙酸酯、乙酸苄酯、乙酸環己酯、丙酸甲酯、丙酸乙酯、 丙酸丁酯、己二酸二辛酯 '草酸乙酯、酒石酸二丁酯、檸 檬酸三丁酯、癸二酸酯、酞酸酯、乙二醇一乙酸酯、乙酸 溶纖劑、乙酸卡必醇等酯系溶劑、丙酮、甲基乙基酮、2- -13- 200944944 庚酮、2-己酮、甲基異丁基酮、異佛爾酮、環己酮等酮系 溶劑’此等可單獨或2種以上適當選用。含有乙烯基之化 合物如，乙烯基羧酸、乙烯基羧酸丁醇酯、乙烯基羧酸乙 二醇酯、乙烯基羧酸二乙二醇酯、乙烯基羧酸四乙二醇酯 等。 製造具有縮水甘油基之糖時，分子內所具有的化合物 取代法如可爲脫水縮合，即，使糖化合物與環氧鹵丙烷反 應而得。該反應所使用的環氧鹵丙烷如，環氧氯丙烷、環 d 氧溴丙烷'環氧碘丙烷等，但以工業上易取得且價廉之環 氧氯丙烷爲佳。該反應可依先前已知的由環氧鹵丙烷及羥 基而得聚縮水甘油醚之方法進行。 例如將氫氧化鈉、氫氧化鉀等鹼金屬氫氧化物之固體 加入化合物及過量之環氧氯丙烷的混合物中，或加入的同 時以20至120 °C之溫度反應。會依導入之化合物的反應性 的強度而異，但反應時間較佳爲30分鐘以上，更佳爲30至 3〇〇分鐘。爲了促進反應可使用觸媒。此時所使用之鹼金 © 屬氫氧化物可爲水溶液，其方法可爲，連續添加該鹼金屬 氫氧化物，同時於反應系內減壓下，或常壓下連續餾出水 及環氧氯丙烷再分液，去除水分後連續將環氧氯丙烷送返 反應系內。含有縮水甘油基之化合物如，縮水甘油基辛基 醚、縮水甘油基環己基醚、縮水甘油基己酸酯、縮水甘油 基壬基醚等。 所使用的糖化合物較佳如單糖類、雙糖類。單糖類如 ，5員環、6員環之糖類。5員環之糖類如果糖衍生物，6員 -14- 200944944 環之糖類如葡萄糖衍生物、半乳糖衍生物。 雙糖類如，蔗糖衍生物、乳糖衍生物、麥芽糖衍生物 、纖維二糖衍生物。 此等糖類如下述例示。 [化3] ❿Or a cyclic ether structure such as oxetane or the like. The photopolymerizable compound to be used is preferably a compound which is liquid at room temperature (about 20 ° C). The photopolymerizable Q compound preferably has a molecular weight of 100 or more. The molecular weight is, for example, 100 to 2,000, or 150 to 1,500, or 150 to 1,000, or 150 to 800. These molecular weights can be determined by GPC analysis of the molecular weight obtained in terms of polystyrene. GPC measurement conditions are as follows: GPC apparatus (trade name: HLC _ 8220GPC, manufactured by Tosoh Corporation), GPC column (trade name: Shodex KF803L, KF802, KF801, manufactured by Showa Denko), column temperature of 40 ° C, and eluent (dissolved solvent) It is tetrahydrofuran, the flow rate (flow rate) is 1.0 ml/min, and the standard sample is polystyrene (manufactured by Showa Denko Co., Ltd.). 〇 The photopolymerizable substance may be a sugar compound. For example, a sugar compound represented by the above formula (1) can be used. In the above formula (1), G1 is a sugar skeleton, T is a divalent linking group, R1 is a vinyl group or a glycidyl group, and R2 is a hydrogen atom or a hydroxyl group. η and L are each independently an integer of 〇 or 1, and p is an integer of the total number of hydroxyl groups of the sugar. m is an integer satisfying ISmS (p-m). For example, the total number of hydroxyl groups of glucose, fructose, and galactose is five, so the total number of hydroxyl groups of P = 5 'trehalose, sucrose, lactose, maltose, and cellobiose is eight, so p = 8. -12-200944944 The R1 or TR1 is a photopolymerizable group which reacts with a hydroxyl group of a sugar, and when a hydroxyl group of a sugar is reacted with a photopolymerizable compound at a ratio of one or more, a photopolymerizable group-containing sugar compound can be obtained. The sugar compound is preferably a liquid, and is easily liquidified when the number of hydroxyl groups is small. Therefore, it is preferably a compound having 80% or more of the hydroxyl groups of the entire sugar, and preferably a compound having a total hydroxyl group of the sugar substituted by a photopolymerizable group. In the formula (1), τ is a carbonyl group, an alkyl group having 1 to 6 carbon atoms, an alkyl group having an alkyl group, a phenyl group, and the like. These sugar compounds can be used commercially or by the following synthesis methods. When a vinyl sugar is produced, for example, after the sugar and the vinyl group-containing compound are dissolved in a solvent, benzoquinone peroxide, di-t-butyl hydroperoxide, t-butyl hydroperoxide, or the like may be present. Cycloalkenyl peroxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, t-butyl peroxybenzoate, lauryl peroxide, acetam peroxide, t-butyl Peroxide such as peroxy-2-ethylhexanoate, azo compound such as α,α: '-azobisisobutyronitrile, azobisdimethyl valeronitrile or azobiscyclohexanecarbonitrile The radical polymerization initiator is carried out by a solution polymerization method at a reaction temperature of 80 to 95 °C. Preferred organic solvents for production are those which are capable of dissolving sugars and compounds containing vinyl groups and which are inactive to vinyl groups, such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate, isobutyl acetate, Amyl acetate, 3-methoxybutyl acetate, benzyl acetate, cyclohexyl acetate, methyl propionate, ethyl propionate, butyl propionate, dioctyl adipate, ethyl oxalate, Dibutyl tartrate, tributyl citrate, sebacate, phthalate, ethylene glycol monoacetate, cellosolve acetate, carbitol acetate ester solvent, acetone, methyl ethyl ketone, 2--13-200944944 A ketone-based solvent such as heptanone, 2-hexanone, methyl isobutyl ketone, isophorone or cyclohexanone can be used singly or in combination of two or more kinds. The vinyl group-containing compound is, for example, a vinyl carboxylic acid, a vinyl carboxylic acid butanol ester, a vinyl carboxylic acid ethylene glycol ester, a vinyl carboxylic acid diethylene glycol ester, a vinyl carboxylic acid tetraethylene glycol ester or the like. When a glycidyl group-containing sugar is produced, the compound substitution method in the molecule can be obtained by dehydration condensation, that is, by reacting a sugar compound with an epihalohydrin. The epihalohydrin used in the reaction is, for example, epichlorohydrin, cyclodoxypropanepropane, iodopropylidene or the like, but it is preferably an industrially available and inexpensive oxychloropropane. This reaction can be carried out by a previously known method of obtaining a polyglycidyl ether from an epihalohydrin and a hydroxyl group. For example, a solid of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide may be added to a mixture of the compound and an excess of epichlorohydrin, or may be added at a temperature of from 20 to 120 °C. The reaction may vary depending on the strength of the reactivity of the introduced compound, but the reaction time is preferably 30 minutes or longer, more preferably 30 to 3 minutes. A catalyst can be used to promote the reaction. The alkali metal hydroxide used in this case may be an aqueous solution by continuously adding the alkali metal hydroxide while continuously distilling off water and epoxy chlorine under reduced pressure or under normal pressure in the reaction system. The propane is re-distributed to remove the water and the epichlorohydrin is continuously returned to the reaction system. A glycidyl group-containing compound such as glycidyl octyl ether, glycidyl cyclohexyl ether, glycidyl hexanoate, glycidyl decyl ether or the like. The sugar compound to be used is preferably a monosaccharide or a disaccharide. Monosaccharides such as 5-membered rings and 6-membered rings of sugar. 5-member ring sugars, if sugar derivatives, 6 members -14- 200944944 Ring sugars such as glucose derivatives, galactose derivatives. Disaccharides such as sucrose derivatives, lactose derivatives, maltose derivatives, cellobiose derivatives. These sugars are exemplified below. [化3] ❿

OH OHOH OH

oocch=ch2 ch2〇〇cch=ch2Oocch=ch2 ch2〇〇cch=ch2

oocch=ch2 (1 一 1 ) ch2oocch=ch2 oocch=ch2Oocch=ch2 (1 - 1 ) ch2oocch=ch2 oocch=ch2

och3 (1-2) oocch=ch2 CH2〇〇CCH=CH2 ch2〇〇cch=ch2Och3 (1-2) oocch=ch2 CH2〇〇CCH=CH2 ch2〇〇cch=ch2

oocch=ch2 oocch=ch2 OOCCH=CH^ 0〇cch=ch2 oocch=ch2 (1-3) -15- 200944944 [化4] CH2OOCCH=CH2Oocch=ch2 oocch=ch2 OOCCH=CH^ 0〇cch=ch2 oocch=ch2 (1-3) -15- 200944944 [Chemical 4] CH2OOCCH=CH2

OHOH

(1-4) oocch=ch2 OC3H6OOCCH=CH2 oocch=ch2(1-4) oocch=ch2 OC3H6OOCCH=CH2 oocch=ch2

〇(ch2ch2 ;ch=ch2 CH2〇(CH2CH20〉2〇CCH=CH2〇(ch2ch2 ;ch=ch2 CH2〇(CH2CH20>2〇CCH=CH2

och3 (1-5) o(ch2ch2o)2occh=ch2 0(CH2CH20)2OCCH=CH2 9H20(CH2CH20)4OCCH=CH21 -os 0(CH2CH20 ;ch=ch2Och3 (1-5) o(ch2ch2o)2occh=ch2 0(CH2CH20)2OCCH=CH2 9H20(CH2CH20)4OCCH=CH21 -os 0(CH2CH20 ;ch=ch2

och3 (1-6) o(ch2ch2o)4occh=ch2 o(ch2ch2o)4occh=ch2 [化5]Och3 (1-6) o(ch2ch2o)4occh=ch2 o(ch2ch2o)4occh=ch2 [化5]

-16- 200944944 [化6] ch2o (1-10)-16- 200944944 [Chemical 6] ch2o (1-10)

OH ❹ ,^νΖΑ oc3h6o ο ch2o(ch2ch2o)2OH ❹ , ^νΖΑ oc3h6o ο ch2o(ch2ch2o)2

(1-11) ▲ o(ch2ch2o)2 0(CH2CH20)2Ny^y CH2〇(CH2CH20)4^ 乂 0(CH2CH20)>O^^ OCH3 (1-12) o(ch2ch2o>4, 0(CH2CH2O)4Ny^y 前述光聚合性化合物可爲脂環式環氧化合物 的脂環式環氧化合物可爲環環氧化物衍生物。 環環氧化物衍生物可具有前述式（2 )之構造 前述式（2)中，G2爲伸烷基、羰基氧基、 芳香環基，或此等組合形成的1價至5價連結基。 、烷基羰基、雜環基或芳香環基，或此等組合形 基。 烷基如碳原子數1至6之下述基。例如甲基、 丙基、i-丙基、環丙基、η-丁基、i-丁基、s-丁基 、環丁基、1-甲基-環丙基、2-甲基-環丙基' n-甲基-η-丁基、2-甲基-η-丁基、3-甲基-η-丁基、 基-η·丙基、1，2 - _甲基-η -丙基、2,2 - __甲基-η -丙 。所使用 〇 雜環基或 G 3爲院基 成的有機 乙基、η-、t-丁基 戊基、1-1,1-二甲 基、1-乙 -17- 200944944 9甲基-瓌丁基、3_ 基-Π-丙基、環戊基、1-甲基-環丁基、2-中楚 甲基-環丙基、 卜甲基戊基 甲基-環丁基、1，2-二甲基-環丙基、2,3〃 1-乙基-環丙基、2-乙基-環丙基、η-己基 .η-戊基、丨，1- 、2-甲基-η-戊基、3-甲基-η-戊基、4-甲基 甲基-η-丁基、1,2-二甲基-η-丁基、1，3_ 二 ，一田基-η-」 、3,3_—中密 甲基-η-丙基 —„ 乙基_ 、1，2,2-三甲基-η-丙基、1-乙基-1-甲基 2-甲基·η-丙基、環己基、1-甲基-環戊基 β «摄丁基、 、3-甲基-環戊基、1-乙基-環丁基、2-乙基-吻 甲基-瓌丁基、 二甲基-環 2-η-两基- 2,2-二甲基-η-丁基、2,3-二甲基-η-丁基 基、1-乙基-η-丁基、2-乙基-η-丁基、I，1’2 甲基-η-丁基 _η_丙基、 _甲基-環戊基 -乙(1-11) ▲ o(ch2ch2o)2 0(CH2CH20)2Ny^y CH2〇(CH2CH20)4^ 乂0(CH2CH20)>O^^ OCH3 (1-12) o(ch2ch2o>4, 0(CH2CH2O 4Ny^y The epoxidized epoxy compound in which the photopolymerizable compound may be an alicyclic epoxy compound may be a cyclic epoxide derivative. The cyclic epoxide derivative may have the above formula (2). In (2), G2 is an alkylene group, a carbonyloxy group, an aromatic ring group, or a monovalent to pentavalent linking group formed by such a combination, an alkylcarbonyl group, a heterocyclic group or an aromatic ring group, or a combination thereof The alkyl group is, for example, a group having 1 to 6 carbon atoms, such as methyl, propyl, i-propyl, cyclopropyl, η-butyl, i-butyl, s-butyl, cyclobutyl. , 1-methyl-cyclopropyl, 2-methyl-cyclopropyl ' n-methyl-η-butyl, 2-methyl-η-butyl, 3-methyl-η-butyl, -η·propyl, 1,2-methyl-η-propyl, 2,2-methyl-η-propyl. The heterocyclic group or G 3 used is an organic ethyl group. Η-, t-butylpentyl, 1-1,1-dimethyl, 1-ethyl-17- 200944944 9-methyl-p-butyl, 3-phenyl-hydrazine-propyl, cyclopentyl, 1-methyl Base-cyclobutyl, 2- Neutral-methyl-cyclopropyl, propylmethylpentylmethyl-cyclobutyl, 1,2-dimethyl-cyclopropyl, 2,3 〃 1-ethyl-cyclopropyl, 2-ethyl-cyclo Propyl, η-hexyl.η-pentyl, indole, 1-, 2-methyl-η-pentyl, 3-methyl-η-pentyl, 4-methylmethyl-η-butyl, 1 ,2-dimethyl-η-butyl, 1,3_di,mono-yl-η-", 3,3_-middle methyl-η-propyl-„ethyl_, 1,2,2- Trimethyl-η-propyl, 1-ethyl-1-methyl 2-methyl·η-propyl, cyclohexyl, 1-methyl-cyclopentyl β « butyl, 3-methyl -cyclopentyl, 1-ethyl-cyclobutyl, 2-ethyl-lens-methyl-p-butyl, dimethyl-cyclo 2-η-diyl- 2,2-dimethyl-η-butyl Base, 2,3-dimethyl-η-butyl, 1-ethyl-η-butyl, 2-ethyl-η-butyl, I,1'2 methyl-η-butyl_η _propyl, _methyl-cyclopentyl-B

基-環丁基、1，2-二甲基-環丁基、1，3_ 2,2-二甲基-環丁基、2,3-二甲基-環丁基、2’4_ 丁基、3，3-二甲基-環丁基、1-η-丙基·瓌丙基、 環丙基、Ι-i-丙基-環丙基、2-i-丙基-瓌丙基 甲基-環丙基、 、2-乙基 1,2,2 甲 基-環丙基、1，2,3-三甲基-環丙基、2,2,3_ 1-乙基-2-甲基-環丙基、2-乙基-1-甲基-環两基 甲基-環丙基及2-乙基-3-甲基-環丙基等。 甘 & m宜、伸乙基 之物，例如伸甲基-cyclobutyl, 1,2-dimethyl-cyclobutyl, 1,3_2,2-dimethyl-cyclobutyl, 2,3-dimethyl-cyclobutyl, 2'4-butyl , 3,3-Dimethyl-cyclobutyl, 1-η-propyl·decylpropyl, cyclopropyl, Ι-i-propyl-cyclopropyl, 2-i-propyl-hydrazinyl -cyclopropyl, 2-ethyl 1,2,2 methyl-cyclopropyl, 1,2,3-trimethyl-cyclopropyl, 2,2,3-1-ethyl-2-yl Base-cyclopropyl, 2-ethyl-1-methyl-cyclodidomethyl-cyclopropyl, 2-ethyl-3-methyl-cyclopropyl and the like.甘和amp; m should be, stretch ethyl, such as methyl

伸烷基爲由上述烷基衍生 、伸丙基等有機基。 烷基羰基如碳原子數2至7之下述基。例如甲基鑛基、 乙基羰基' η-丙基羰基、i-丙基羰基、環丙基羰基、n_ 丁 基羰基、i-丁基羰基、s-丁基羰基、t-丁基羰基、環丁基羰 基、1-甲基-環丙基羰基、2-甲基-環丙基羰基、n-戊基羰 基、1-甲基-η-丁基羰基、2-甲基-η-丁基羰基、3-甲基-η- -18- 200944944 丁基羰基、1，1-二甲基-η-丙基羰基、1,2-二甲基- η-丙基羰 基、2,2-二甲基·η-丙基羰基、1-乙基-η-丙基羰基、環戊基 羰基、1-甲基-環丁基羰基、2-甲基-環丁基羰基、3-甲基-環丁基羰基、1,2-二甲基-環丙基羰基、2,3-二甲基-環丙基 羰基、1-乙基-環丙基羰基、2-乙基-環丙基羰基、η-己基 鑛基、1-甲基-n -戊基鑛基、2 -甲基-η -戊基鑛基、3 -甲基_ η-戊基羰基、4·甲基-η-戊基羰基、1，1-二甲基-η-丁基羰基 Ο 、1，2-二甲基-η-丁基羰基、1,3-二甲基-η-丁基羰基、2,2-二甲基-η-丁基羰基、2,3-二甲基-η-丁基羰基、3,3-二甲 基-η-丁基羰基、1-乙基-η-丁基羰基、2-乙基-η-丁基羰基 、1，1，2-三甲基-η-丙基羰基、1,2,2-三甲基-η-丙基羰基、 1-乙基-1-甲基丙基撰基、1-乙基-2-甲基- η-丙基羯基、 環己基羰基、1-甲基-環戊基羰基、2-甲基-環戊基羰基、 3-甲基-環戊基羰基、1-乙基-環丁基羰基、2-乙基-環丁基 羰基、3-乙基-環丁基羰基、1,2-二甲基-環丁基羰基、1,3-φ 二甲基-環丁基羰基、2,2-二甲基-環丁基羰基、2,3-二甲 基-環丁基羰基、2,4-二甲基·環丁基羰基、3,3-二甲基-環 丁基羰基、1-η-丙基-環丙基羰基、2-η •丙基-環丙基羰基 、Ι-i-丙基-環丙基羰基、2-卜丙基-環丙基羰基、1，2,2-三 甲基-環丙基羰基、1，2,3-三甲基-環丙基羰基、2,2,3-三甲 基-環丙基羰基、1-乙基-2-甲基-環丙基羰基、2-乙基-卜甲 基-環丙基羰基、2-乙基-2-甲基-環丙基羰基及2-乙基-3-甲 基-環丙基羰基等。 所使用之雜環基可爲環氧環基或三嗪環基。所使用之 -19- 200944944 芳香環基可爲苯環基、萘環基、蒽環基等。n&m各自獨立 爲1至5之整數。 脂環式環氧化合物之具體例如下所述。 [化7] ΟThe alkylene group is an organic group derived from the above alkyl group and a propyl group. The alkylcarbonyl group is, for example, the following group having 2 to 7 carbon atoms. For example, methyl ortho, ethylcarbonyl ' η-propylcarbonyl, i-propylcarbonyl, cyclopropylcarbonyl, n-butylcarbonyl, i-butylcarbonyl, s-butylcarbonyl, t-butylcarbonyl, Cyclobutylcarbonyl, 1-methyl-cyclopropylcarbonyl, 2-methyl-cyclopropylcarbonyl, n-pentylcarbonyl, 1-methyl-η-butylcarbonyl, 2-methyl-η-butyl Carbonyl, 3-methyl-η- -18- 200944944 butylcarbonyl, 1,1-dimethyl-η-propylcarbonyl, 1,2-dimethyl-η-propylcarbonyl, 2,2- Dimethyl η-propylcarbonyl, 1-ethyl-η-propylcarbonyl, cyclopentylcarbonyl, 1-methyl-cyclobutylcarbonyl, 2-methyl-cyclobutylcarbonyl, 3-methyl -cyclobutylcarbonyl, 1,2-dimethyl-cyclopropylcarbonyl, 2,3-dimethyl-cyclopropylcarbonyl, 1-ethyl-cyclopropylcarbonyl, 2-ethyl-cyclopropyl Carbonyl, η-hexyl ore, 1-methyl-n-pentyl ore, 2-methyl-η-pentyl ore, 3-methyl-η-pentylcarbonyl, 4·methyl-η- Pentylcarbonyl, 1,1-dimethyl-η-butylcarbonylhydrazine, 1,2-dimethyl-η-butylcarbonyl, 1,3-dimethyl-η-butylcarbonyl, 2,2 - dimethyl-η-butylcarbonyl, 2,3-dimethyl-η-butylcarbonyl, 3,3- Methyl-η-butylcarbonyl, 1-ethyl-η-butylcarbonyl, 2-ethyl-η-butylcarbonyl, 1,1,2-trimethyl-η-propylcarbonyl, 1,2 ,2-trimethyl-η-propylcarbonyl, 1-ethyl-1-methylpropyl, 1-ethyl-2-methyl-η-propylindenyl, cyclohexylcarbonyl, 1- Methyl-cyclopentylcarbonyl, 2-methyl-cyclopentylcarbonyl, 3-methyl-cyclopentylcarbonyl, 1-ethyl-cyclobutylcarbonyl, 2-ethyl-cyclobutylcarbonyl, 3- Ethyl-cyclobutylcarbonyl, 1,2-dimethyl-cyclobutylcarbonyl, 1,3-φ dimethyl-cyclobutylcarbonyl, 2,2-dimethyl-cyclobutylcarbonyl, 2, 3-dimethyl-cyclobutylcarbonyl, 2,4-dimethylcyclobutylcarbonyl, 3,3-dimethyl-cyclobutylcarbonyl, 1-η-propyl-cyclopropylcarbonyl, 2 -η • propyl-cyclopropylcarbonyl, Ι-i-propyl-cyclopropylcarbonyl, 2-propyl-cyclopropylcarbonyl, 1,2,2-trimethyl-cyclopropylcarbonyl, 1,2 ,3-trimethyl-cyclopropylcarbonyl, 2,2,3-trimethyl-cyclopropylcarbonyl, 1-ethyl-2-methyl-cyclopropylcarbonyl, 2-ethyl-methyl-ring Propylcarbonyl, 2-ethyl-2-methyl-cyclopropylcarbonyl, 2-ethyl-3-methyl-cyclopropylcarbonyl, and the like. The heterocyclic group used may be an epoxy ring group or a triazine ring group. The -19-200944944 aromatic ring group used may be a benzene ring group, a naphthalene ring group, an anthracene ring group or the like. n&m are each independently an integer from 1 to 5. Specific examples of the alicyclic epoxy compound are as follows. [化7] Ο

光聚合引發劑 本發明之膜形成組成物的光聚合引發劑可爲，具有利 用光照射引發前述光聚合性物質聚合之作用的化合物，並 -20- 200944944 無特別限定。可使用利用光照射發生酸（布朗氏台德酸或 路易斯酸）、鹼、自由基或陽離子之化合物。 例如可利用光照射發生活性自由基而使前述光聚合性 化合物產生自由基聚合之化合物，即光自由基聚合引發劑 ，及可利用光照射發生質子酸及碳陽離子等陽離子種而使 前述光聚合性化合物與具有光聚合性基之高分子化合物產 生陽離子聚合的化合物，即光陽離子聚合引發劑等。 ❿ 光照射例如可使用波長150 nm至700 nm，或193 nm至 700 nm，或300 nm至600 nm之光線進行。因此所使用的光 聚合引發劑較佳爲，可利用曝光量1至2000 mJ/cm2，或10 至1500 mJ/cm2，或50至1000 mJ/cm2發生活性自由基之光 自由基聚合引發劑，或可發生陽離子種之光陽離子聚合引 發劑。 光自由基聚合引發劑如，咪唑化合物、二偶氮化合物 、雙咪唑化合物、N-芳基甘胺酸化合物、有機疊氮化合物 Ο 、二茂鈦化合物、鋁酸鹽化合物、有機過氧化物、N-烷氧 基吡啶鎗鹽化合物、及噻噸酮化合物等。疊氮化合物如， P-疊氮苯甲醛、P-疊氮乙醯苯、P-疊氮苯甲酸、P-疊氮亞 苄基乙醯苯、4,4’-二疊氮查耳酮、4,4’-二疊氮二苯基硫化 物、及2,6 -雙（4，-疊氮亞苄基）-4 -甲基環己酮等。二偶氮 化合物如，1-二偶氮-2,5-二乙氧基-4-p_甲苯基锍基苯硼氟 化物、1-二偶氮-4-Ν,Ν-二甲基胺基苯氯化物，及1-二偶 氮-4-Ν，Ν-二乙基胺基苯硼氟化物等。雙咪唑化合物如， 2,2，-雙（〇-氯苯基）-4,5,4，，5，-四（3,4,5-三甲氧基苯基） -21 - 200944944 1，2’-雙咪唑，及2,2’-雙（〇-氯苯基）4,5,4’，5’-四苯基-1,2’·雙咪唑等。二茂鈦化合物如，二環戊二烯基-鈦-二氯 化物、二環戊二烯基-鈦-雙苯酯、二環戊二烯基-鈦-雙（ 2.3.4.5.6- 五氟苯基）、二環戊二烯基-鈦-雙（2,3,5,6-四 氟苯基）、二環戊二烯基-鈦-雙（2,4,6-三氟苯基）、二 環戊二烯基-鈦·雙（2,6-二氟苯酯）、二環戊二烯基-鈦-雙 (2,4 -二氟苯酯）、雙（甲基環戊二烯基）-鈦-雙（ 2.3.4.5.6- 五氟苯基）、雙（甲基環戊二烯基）-鈦-雙（ ❿ 2.3.5.6- 四氟苯基）、雙（甲基環戊二烯基）-鈦·雙（2,6-二氟苯酯），及二環戊二烯基-鈦-雙（2,6-二氟-3- ( 1H-吡咯-1-基）-苯酯）等。 光自由基聚合引發劑又如，1,3-二（tert-丁基二氧基 羰基）二苯甲酮、3,3’，4,4’-四〇61^-丁基二氧基羰基）二 苯甲酮、3 -苯基-5-異噁唑酮、2 -锍基苯并咪唑、2,2 -二甲 氧基-1，2·二苯基乙烷-1-酮、1-羥基-環己基-苯基-酮，及 2 -苄基-2-二甲基胺基-1-( 4 -嗎啉基苯基）· 丁酮等。 〇 光陽離子聚合引發劑如，磺酸酯、磺醯亞胺化合物、 二磺醯重氮甲烷化合物、二烷基-4-羥基锍鹽、芳基磺酸-P-硝基苄基酯、矽烷醇-鋁錯合物，（7? 6-苯）5-環戊 二烯基）鐵（II)等。 磺醯亞胺化合物如，N-(三氟甲烷磺醯氧基）琥珀醯 亞胺、N-(九氟-正丁烷磺醯氧基）琥珀醯亞胺、N-(莰 磺醯氧基）琥珀醯亞胺及N-(三氟甲烷磺醯氧基）萘醯亞 胺等。 -22- 200944944 二磺醯重氮甲烷化合物如，雙（三氟甲基磺醯）重氮 甲烷、雙（環己基磺醯）重氮甲烷、雙（苯基磺醯）重氮 甲烷、雙（P-甲苯磺醯）重氮甲烷、雙（2,4-二甲基苯磺 醯）重氮甲烷，及甲基磺醯-P-甲苯磺醯重氮甲烷等。 光陽離子聚合引發劑又如，2-甲基-1-(4-甲基噻吩基 )-2-嗎啉基丙烷-1-酮。 又，芳香族碘鎗鹽化合物、芳香族銃鹽化合物、芳香 〇 族重氮鑰鹽化合物、芳香族鳞鹽化合物、三嗪化合物及鐵 芳烴錯合物化合物等可作爲光自由基聚合引發劑、光陽離 子聚合引發劑用。 芳香族碘鎗鹽化合物如，二苯基碘鍮六氟磷酸鹽、二 苯基碘鎗三氟甲烷磺酸鹽、二苯基碘鑰九氟·正丁烷磺酸 鹽、二苯基碘鎗全氟-正辛烷磺酸鹽、二苯基碘鍚莰磺酸 鹽、雙（4-tert-丁基苯基）碘鎗莰磺酸鹽及雙（4-tert-丁 基苯基）碘鍚三氟甲烷磺酸鹽等。 〇 芳香族锍鹽化合物如，三苯基锍六氟銻酸鹽、三苯基 锍九氟正丁烷磺酸鹽、三苯基锍莰磺酸鹽及三苯基毓三氟 甲烷磺酸鹽等。 本發明之膜形成組成物的光聚合引發劑可單獨使用一 種，或二種以上組合使用。 本發明之膜形成組成物中光聚合性物質及光聚合引發 劑的含量，相對於光聚合性物質100質量份之光聚合引發 劑例如爲1至20質量份，或3至10質量份。光聚合引發劑量 少於此時，將無法充分進行聚合反應，而形成膜之硬度及 -23- 200944944 耐摩耗性不足之物。光聚合引發劑量多於此時，僅膜表面 附近會硬化，而難完全硬化至膜內部。 本發明之膜形成組成物中，所使用的光聚合性物質爲 具有乙烯性不飽和鍵作爲自由基聚合性部位用之化合物時 ，所使用的光聚合引發劑較佳爲光自由基聚合引發劑。所 使用的光聚合性物質爲具有乙烯醚構造、環氧環或氧雜環 丁烷環作爲陽離子聚合性部位用之化合物時，所使用的光 聚合引發劑較佳爲光陽離子聚合引發劑。 本發明之膜形成組成物中除了上述光聚合性物質及光 聚合引發劑外，必要時可添加表面活性劑、增感劑、胺化 合物、聚合物化合物、防氧化劑、熱聚合禁止劑、表面改 質劑及脫泡劑等。 添加表面活性劑可抑制針孔或擴張等發生，又可提升 底層膜形成組成物之塗佈性。表面活性劑如，聚環氧乙院 月桂醚、聚環氧乙烷硬脂醯醚及聚環氧乙烷油醚等聚環氧 乙烷烷基醚化合物、聚環氧乙烷辛基苯酚醚及聚環氧乙院 壬基苯酚醚等聚環氧乙烷烷基烯丙醚化合物、聚環氧乙院 •聚環氧丙烷嵌段共聚物化合物、山梨糖醇酐一月桂酸醋 、山梨糖醇酐一棕櫚酸酯、山梨糖醇酐一硬脂酸醋、山梨 糖醇酐三油酸酯及山梨糖醇酐三硬脂酸酯等山梨糖醇酐脂 肪酸酯化合物、聚環氧乙烷山梨糖醇酐一月桂酸醋、聚環 氧乙院山梨糖醇酐一棕櫚酸醋、聚環氧乙院山梨糖醇肝— 硬脂酸酯及聚環氧乙院山梨糖醇酐三硬脂酸醋等聚環氧= 烷山梨糖醇酐脂肪酸酯化合物。又如，商品名耶佛；^ -24- 200944944 EF301、EF303、EF352 (特肯姆（股）製）、商品名美凱 番F171、F173、R-08、R-30(大日本油墨（股）製）、佛 洛拉FC-43 0、FC431 (住友3M (股）製）商品名阿撒西 AG710、撒佛隆 S-382、SC101、SC102、SCI 03 ' SCI 04、 SC105、SC106(旭硝子（股）製）等氟系表面活性劑， 及有機矽氧烷聚合物KP341 (信越化學工業（股）製）等 。使用表面活性劑時，其添加量相對於光聚合性物質100 0 質量份例如爲0.1至5質量份，或0.5至2質量份。 爲了增加前述光聚合引發劑對光之敏感度可使用增感 劑。增感劑如，2,6-二乙基-1,3,5,7,8-五甲基伸甲基吡咯-BF2錯合物及1,3,5,7,8-五甲基伸甲基吡咯-BF2錯合物等伸 甲基吡咯錯合物化合物、曙紅、乙基曙紅、赤蘚紅鈉鹽、 熒光素及玫瑰紅等咕噸系色素、1-(1-甲基萘[1,2-d]噻唑-2(lH)-亞基-4·(2,3,6,7)四氫-lH,5H-苯并[ij]喹嗪-9-基）-3-丁烯-2-酮、1-(3-甲基苯并噻唑-2 (3H)-亞基-4-〇 (P-二甲基胺基苯基）-3-丁烯-2-酮等酮噻唑啉化合物、 2-(p-二甲基胺基苯乙烯基）-萘[1,2-d]噻唑、2-[4-(p-二 甲基胺基苯基）-1,3-丁二烯基]-萘[l，2-d]噻唑等苯乙烯基 或苯基丁二烯基雜環化合物等。又如，2,4-二苯基-6- ( p-二甲基胺基苯乙烯基）-1,3,5 -三嗪、2,4 -二苯基-6-( [2,3,6,7]四氫-1H,5H-萘并[ij]喹嗪-9-基）-1-乙烯-2-基）-1,3,5-***酮菲-([2,3,6,7]四氫-111，511-萘并[丨』]喹嗪-9-基 )-1-乙烯-2-基）酮及2,5-雙（p-二甲基胺基亞肉桂基）環 戊酮、5,10,15，20四苯基卟啉等。使用增感劑時，其添加 -25- 200944944 量相對於光聚合性物質100重量份例如爲0.1至20質量份。 爲了防止前述光聚合引發劑因氧阻礙而降低敏感度可 使用胺化合物。所使用的胺化合物可爲脂肪族胺化合物及 芳香族胺化合物等各種胺化合物。使用胺化合物時，其添 加量相對於光聚合性物質100質量份例如可爲0.1至10質量 份。Photopolymerization Initiator The photopolymerization initiator of the film-forming composition of the present invention may be a compound having an action of initiating polymerization of the photopolymerizable substance by light irradiation, and is not particularly limited. A compound which generates an acid (Brown's Teddy acid or Lewis acid), a base, a radical or a cation by light irradiation can be used. For example, a photoradical polymerization initiator which is a compound which radically polymerizes the photopolymerizable compound by light irradiation, and a photopolymerizable initiator such as a proton acid or a carbocation can be generated by light irradiation to cause photopolymerization. The compound which is cationically polymerized with the polymer compound having a photopolymerizable group, that is, a photocationic polymerization initiator or the like. Xenon illumination can be performed, for example, using light from 150 nm to 700 nm, or from 193 nm to 700 nm, or from 300 nm to 600 nm. Therefore, the photopolymerization initiator to be used is preferably a photoradical polymerization initiator which generates an active radical by using an exposure amount of 1 to 2000 mJ/cm 2 , or 10 to 1500 mJ/cm 2 , or 50 to 1000 mJ/cm 2 . Alternatively, a photocationic polymerization initiator of a cationic species may occur. a photoradical polymerization initiator such as an imidazole compound, a diazo compound, a diimidazole compound, an N-arylglycine compound, an organic azide compound 二, a titanocene compound, an aluminate compound, an organic peroxide, An N-alkoxypyridine gun salt compound, a thioxanthone compound, and the like. Azide compounds such as P-azidobenzaldehyde, P-azidobenzene, P-azidobenzoic acid, P-azidobenzylidene benzene, 4,4'-diazide chalcone, 4,4'-diazide diphenyl sulfide, and 2,6-bis(4,-azidobenzylidene)-4-methylcyclohexanone. Diazo compounds such as 1-diazo-2,5-diethoxy-4-p-tolylnonylbenzene boron fluoride, 1-diazo-4-indole, anthracene-dimethylamine Alkyl benzene chloride, and 1-diazo-4-indene, fluorene-diethylaminophenyl boron fluoride, and the like. Biimidazole compounds such as, 2,2,-bis(〇-chlorophenyl)-4,5,4,5,-tetrakis(3,4,5-trimethoxyphenyl)-21-200944944 1,2 '-Diimidazole, and 2,2'-bis(indolyl-phenylphenyl) 4,5,4',5'-tetraphenyl-1,2'-bisimidazole. Titanocene compounds such as dicyclopentadienyl-titanium-dichloride, dicyclopentadienyl-titanium-diphenyl ester, dicyclopentadienyl-titanium-bis ( 2.3.4.5.6- Fluorophenyl), dicyclopentadienyl-titanium-bis(2,3,5,6-tetrafluorophenyl), dicyclopentadienyl-titanium-bis(2,4,6-trifluorobenzene , dicyclopentadienyl-titanium bis(2,6-difluorophenyl), dicyclopentadienyl-titanium-bis(2,4-difluorophenyl), bis(methyl ring) Pentadienyl)-titanium-bis( 2.3.4.5.6-pentafluorophenyl), bis(methylcyclopentadienyl)-titanium-bis( ❿ 2.3.5.6-tetrafluorophenyl), bis ( Methylcyclopentadienyl)-titanium bis(2,6-difluorophenyl), and dicyclopentadienyl-titanium-bis(2,6-difluoro-3-(1H-pyrrole-1) -yl)-phenyl ester) and the like. The photoradical polymerization initiator is, for example, 1,3-bis(tert-butyldioxycarbonyl)benzophenone, 3,3',4,4'-tetradecene 61^-butyldioxycarbonyl ) benzophenone, 3-phenyl-5-isoxazolone, 2-mercaptobenzimidazole, 2,2-dimethoxy-1,2·diphenylethane-1-one, 1 - hydroxy-cyclohexyl-phenyl-ketone, and 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)butanone and the like. A photo-cationic polymerization initiator such as a sulfonate, a sulfonimide compound, a disulfonyldiazomethane compound, a dialkyl-4-hydroxyindole salt, an arylsulfonic acid-P-nitrobenzyl ester, a decane Alcohol-aluminum complex, (7? 6-benzene) 5-cyclopentadienyl) iron (II) and the like. Sulfonimide compounds such as N-(trifluoromethanesulfonyloxy) succinimide, N-(nonafluoro-n-butanesulfonyloxy) succinimide, N-(sulfonyloxy) Amber imine and N-(trifluoromethanesulfonyloxy)naphthyl imine. -22- 200944944 Disulfonium diazomethane compounds such as bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane, double ( P-toluenesulfonate) Diazomethane, bis(2,4-dimethylphenylsulfonate)diazomethane, and methylsulfonium-P-toluenesulfonium diazomethane. The photocationic polymerization initiator is, for example, 2-methyl-1-(4-methylthienyl)-2-morpholinylpropan-1-one. Further, an aromatic iodine salt compound, an aromatic sulfonium salt compound, an aromatic steroidal heavy nitrogen salt compound, an aromatic scale salt compound, a triazine compound, and an iron aromatic hydrocarbon compound can be used as a photoradical polymerization initiator. Used as a photocationic polymerization initiator. Aromatic iodine salt compounds such as diphenyliodonium hexafluorophosphate, diphenyl iodine trifluoromethanesulfonate, diphenyl iodine hexafluoro-n-butane sulfonate, diphenyl iodine gun Perfluoro-n-octane sulfonate, diphenyliodonium sulfonate, bis(4-tert-butylphenyl) iodonium sulfonate and bis(4-tert-butylphenyl) iodine钖Trifluoromethanesulfonate and the like. 〇Aromatic sulfonium salt compounds such as triphenylsulfonium hexafluoroantimonate, triphenylsulfonium nonafluorobutane sulfonate, triphenylsulfonium sulfonate and triphenylsulfonium trifluoromethanesulfonate Wait. The photopolymerization initiator of the film-forming composition of the present invention may be used alone or in combination of two or more. The content of the photopolymerizable material and the photopolymerization initiator in the film-forming composition of the present invention is, for example, 1 to 20 parts by mass, or 3 to 10 parts by mass, per 100 parts by mass of the photopolymerizable substance. When the amount of the photopolymerization initiator is less than this, the polymerization reaction may not be sufficiently performed to form a film having a hardness and a wear resistance of -23-200944944. The photopolymerization initiating dose is more than this, and only the vicinity of the film surface hardens, and it is difficult to completely harden to the inside of the film. In the film-forming composition of the present invention, when the photopolymerizable substance is a compound having an ethylenically unsaturated bond as a radical polymerizable site, the photopolymerization initiator to be used is preferably a photoradical polymerization initiator. . When the photopolymerizable material to be used is a compound having a vinyl ether structure, an epoxy ring or an oxetane ring as a cationically polymerizable site, the photopolymerization initiator to be used is preferably a photocationic polymerization initiator. In addition to the photopolymerizable substance and the photopolymerization initiator, the film-forming composition of the present invention may contain a surfactant, a sensitizer, an amine compound, a polymer compound, an antioxidant, a thermal polymerization inhibitor, and a surface modification, if necessary. Reagents and defoamers. The addition of a surfactant suppresses the occurrence of pinholes or expansion, and enhances the coatability of the underlying film forming composition. Surfactants such as polyepoxyethylene alkyl ether compounds such as polyepoxyether lauryl ether, polyethylene oxide stearyl ether and polyethylene oxide oleyl ether, polyethylene oxide octylphenol ether And polyethylene oxide alkyl allyl ether compound such as polyepoxyphenol decyl phenol ether, polyepoxyethylene polyoxypropylene block copolymer compound, sorbitan lauric acid vinegar, sorbose Sorbitol fatty acid ester compound such as alcoholic acid monopalmitate, sorbitan monostearate, sorbitan trioleate and sorbitan tristearate, polyethylene oxide Sorbitol lauric acid lauric acid, polyepoxyethylene sorbitan-palmitic acid vinegar, polyepoxylyl sorbitol liver-stearate and polyepoxyethylene sorbitan tristearyl Polyepoxy acid such as vinegar = sorbitan fatty acid ester compound. Another example is the product name Yefo; ^ -24- 200944944 EF301, EF303, EF352 (Tekken (stock) system), the trade name of the United States Kaifan F171, F173, R-08, R-30 (Daily ink (shares) )), Flora FC-43 0, FC431 (Sumitomo 3M (share) system) trade name Asahi AG710, Safron S-382, SC101, SC102, SCI 03 'SCI 04, SC105, SC106 (Asahi Glass) (Fluor), etc., a fluorine-based surfactant, and an organic siloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.). When the surfactant is used, the amount thereof is, for example, 0.1 to 5 parts by mass, or 0.5 to 2 parts by mass, per 100 parts by mass of the photopolymerizable substance. A sensitizer can be used in order to increase the sensitivity of the aforementioned photopolymerization initiator to light. Sensitizers such as 2,6-diethyl-1,3,5,7,8-pentamethyl-methylpyrrole-BF2 complex and 1,3,5,7,8-pentamethyl Methylpyrrole-BF2 complexes such as methylpyrrole complex compounds, eosin, ethyl ruthenium, erythrosine red sodium salt, fluorescein and rose red, etc. xanthene pigment, 1-(1-methyl Naphthalene [1,2-d]thiazole-2(lH)-subunit-4·(2,3,6,7)tetrahydro-lH,5H-benzo[ij]quinolizin-9-yl)-3 -buten-2-one, 1-(3-methylbenzothiazole-2(3H)-ylidene-4-indole (P-dimethylaminophenyl)-3-buten-2-one Isoketone thiazoline compound, 2-(p-dimethylaminostyryl)-naphthalene [1,2-d]thiazole, 2-[4-(p-dimethylaminophenyl)-1, a styryl or phenylbutadienyl heterocyclic compound such as 3-butadienyl]-naphthalene [l,2-d]thiazole, etc. Another example is 2,4-diphenyl-6-(p-di Methylaminostyryl)-1,3,5-triazine, 2,4-diphenyl-6-([2,3,6,7]tetrahydro-1H,5H-naphtho[j] Quinazine-9-yl)-1-ethen-2-yl)-1,3,5-triazolone phenanthrene-([2,3,6,7]tetrahydro-111,511-naphtho[丨" Quinazine-9-yl)-1-vinyl-2-yl)one and 2,5-bis(p-dimethylamino cinnamyl)cyclopentanone, 5,10,15,20 tetraphenyl Porphyrin . When the sensitizer is used, the amount of -25 to 200944944 is, for example, 0.1 to 20 parts by mass based on 100 parts by weight of the photopolymerizable substance. In order to prevent the aforementioned photopolymerization initiator from being lowered in sensitivity due to oxygen inhibition, an amine compound can be used. The amine compound to be used may be various amine compounds such as an aliphatic amine compound and an aromatic amine compound. When the amine compound is used, the amount thereof may be, for example, 0.1 to 10 parts by mass based on 100 parts by mass of the photopolymerizable substance.

使用聚合物化合物可調節由本發明之膜形成組成物形 成的膜之折射率、衰減係數及吸光性能等。例如使用具有 Q 苯環之聚合物化合物時，可提高對ArF準分子雷射（波長 193 nm)之膜的吸光性能。又，例如使用具有萘環或蒽環 之聚合物化合物時，可提高對KrF準分子雷射（波長248 nm )之膜的吸收性能。 聚合物化合物之種類並無特別限制，可使用重量平均 分子量爲1000至1000000之各種化合物。例如具有苯環、The refractive index, attenuation coefficient, light absorption property and the like of the film formed from the film-forming composition of the present invention can be adjusted by using a polymer compound. For example, when a polymer compound having a Q benzene ring is used, the light absorbing property of a film of an ArF excimer laser (wavelength 193 nm) can be improved. Further, for example, when a polymer compound having a naphthalene ring or an anthracene ring is used, the absorption property to a KrF excimer laser (wavelength: 248 nm) film can be improved. The kind of the polymer compound is not particularly limited, and various compounds having a weight average molecular weight of 1,000 to 1,000,000 can be used. For example, having a benzene ring,

萘環或蒽環之丙烯酸酯聚合物、甲基丙烯酸酯聚合物、酚 醛清漆聚合物、苯乙烯聚合物、聚醯胺、聚醯胺酸、聚酯 Q 及聚醯亞胺等。 又’將本發明之膜形成組成物使用於製造半導體裝置 之微影蝕刻步驟中’光致抗蝕劑底層之防反射膜時，也可 使用吸光性能優良之聚合物化合物。使用該類聚合物化合 物’可提高由本發明之膜形成組成物形成的膜作爲防反射 膜用之性能。 使用聚合物化合物時，其添加量相對於光聚合性物質 1〇〇質量份例如可爲0.1至50質量份。 -26- 200944944 本發明之膜形成組成物較佳爲使用，前述光聚合性化 合物等之各成份（以下稱爲「固體成份」）溶於溶劑之溶 液狀態。所使用的溶劑可爲，能溶解固體成份形成均勻溶 液之物。例如，乙二醇一甲基醚、乙二醇一乙基醚、甲基 溶纖劑乙酸酯、乙基溶纖劑乙酸酯、二乙二醇一甲基醚、 二乙二醇一乙基醚、丙二醇、丙二醇一甲基醚、丙二醇一 甲基醚乙酸酯、丙二醇丙基醚乙酸酯、甲苯、二甲苯、甲 ❹ 基乙基酮、環戊酮、環己酮、2-羥基丙酸乙酯、2-羥基-2-甲基丙酸乙酯、乙氧基乙酸乙酯、羥基乙酸乙酯、2-羥基-3-甲基丁酸甲酯、3-甲氧基丙酸甲酯、3-甲氧基丙酸乙酯 、3-乙氧基丙酸乙酯、3-乙氧基丙酸甲酯、丙酮酸甲酯、 丙酮酸乙酯、乙酸乙酯、乙酸丁酯、乳酸乙酯、乳酸丁酯 、N-二甲基甲醯胺、N-二甲基乙醯胺、二甲基亞碾及N-甲 基吡咯烷酮等。此等溶劑可單獨或二種以上組合使用。所 使用之溶劑較佳爲，沸點爲80至250 °C，或100至200 °C， β 或120至180°C之溶劑。溶劑沸點較低時，塗佈膜形成組成 物中會蒸發大量溶劑而提高黏度，而造成塗佈性降低。溶 . 劑沸點較高時，塗佈膜形成組成物後需時間乾燥。溶劑之 使用量爲，可使膜形成組成物之固體成份濃度例如爲0.5 至50質量％，或3至40質量％，或10至30質量％之量。 下面將說明光阻底層膜使用本發明之膜形成組成物的 方法。例如，使用旋塗機、棒塗機等之適當塗佈方法將本 發明之膜形成組成物塗佈於製造半導體裝置用的半導體基 板（例如矽/二氧化矽被覆基板、矽晶圓、矽氮化物基板 -27- 200944944 、玻璃基板、ITO基板、聚醯亞胺基板及低電容率材料（ low-k材料）被覆基板等）上形成塗佈膜。又將光照射於 塗佈膜之前，必要時可進行乾燥步驟。使用含有溶劑之膜 形成組成物時，較佳爲進行乾燥步驟。 乾燥步驟可爲，以高溫加熱之方法並無特別限制。但 以高溫（例如1 50 °c，或以上之溫度）加熱時，推斷會使 塗佈膜所含的固體成份昇華等而污染裝置。因此乾燥步驟 可如，於熱板上以50至lOOt將基板加熱〇.1至1〇分鐘。又 ❹ 如’以室溫（20°C )風乾。 其次對塗佈膜進行光照射。光照射可爲，使前述光聚 合引發劑起作用而聚合光聚合性物質之方法，並無特別限 制使用。光照射例如可使用波長150 nm至700 nm，或193 至700 nm，或300至600 nm之光線進行。光照射例如可使 用超高壓水銀燈、閃光UV燈、高壓水銀燈、低壓水銀燈 、DEEP-UV (深紫外）燈、氙短弧燈短弧金屬鹵素燈、 YAG雷射激發用燈、氙氣閃光燈等進行。例如，使用超高 © 壓水銀燈時可以含有，以紫外域289 nm、297 nm、303 nm 、313 nm(j線）、334 nm、365 nm(i線），及可視光域 405 nm ( h線）、436 nm ( g線）、546 nm、579 nm波長爲 峰的亮線光譜之波長150 nm至700 nm的全波長進行照射。 利用光照射藉由塗佈膜中之光聚合引發劑發生陽離子 種或活性自由基，再藉由此等使塗佈膜中之光聚合性化合 物產生聚合反應。該聚合反應之結果可形成膜。所形成的 膜可爲，例如於其上層塗佈光致抗蝕劑時，對塗佈之光致 -28- 200944944 抗蝕劑用組成物所使用的溶劑，例如乙二醇一甲基醚、乙 基溶纖劑乙酸酯、二乙二醇一乙基醚、丙二醇、丙二醇一 甲基醚、丙二醇一甲基醚乙酸酯、丙二醇丙基醚乙酸酯、 甲苯、甲基乙基酮、環己醇、2-羥基丙酸乙酯、2-羥基-2-甲基丙酸乙酯、乙氧基乙酸乙酯、丙酮酸甲酯、乳酸乙酯 及乳酸丁酯等的溶解性較低之物。因此由本發明之膜形成 組成物形成的膜不會混入光致抗蝕劑。 ❹ 本發明之膜形成組成物適用於如圖1所示般，具有孔 深（b ) /直徑（e )所示長寬比爲1以上，例如1至1 〇，或2 至5之孔的半導體基板。又本發明之膜形成組成物可作爲 塡充用，形成使該類孔無間隙之膜。又，具有疏密的長寬 比1以上之孔的半導體基板（具有孔密部分及孔疏部分之 基板）適用本發明之膜形成組成物。本發明之膜形成組成 物可作爲，使存在該類疏密孔的基板表面形成平坦膜用。 又，本發明之膜形成組成物可使用於具有長寬比小於 G 1之孔的半導體基板，或具有段差之半導體基板。 基體表面上由本發明之膜形成組成物形成的膜之膜厚 例如可爲20至2000 nm，或30至1000 nm，或50至800 nm。 由本發明之膜形成組成物形成的膜上方可形成光致抗 蝕劑。如此可於半導體基板上形成底層膜及光致抗鈾劑之 層合構造。形成光致抗蝕劑可使用已知之方法，即將光致 抗蝕劑用組成物溶液塗佈於底層膜上再加熱。形成於本發 明之膜上方的光致抗蝕劑並無特別限制，可使用汎用之負 型光致抗蝕劑、正型光致抗蝕劑中任何1種。例如由酚醛 -29- 200944944 清漆樹脂及1，2-萘醌二疊氮磺酸酯形成之正型光致抗蝕劑 ，由具有藉由酸而分解可提升鹼溶解速度之基的黏合劑及 光酸發生劑形成之化學加強型光致抗蝕劑，由藉由酸而分 解可提升光致抗蝕劑之鹼溶解速度的低分子化合物及鹼可 溶性黏合劑及光酸發生劑形成之化學加強型光致抗蝕劑， 由具有藉由酸而分解可提升鹼溶解速度之基的黏合劑及藉 由酸而分解可提升光致抗蝕劑之鹼溶解速度的低分子化合 物及光酸發生劑形成的化學加強型光致抗蝕劑等，例如聲 ^ 寶公司製商品名APEX-E、住友化學工業（股）製商品名 PAR710、信越化學工業（股）製商品名SEP R4 30等。 其次通過一定圖罩進行曝光。曝光時可使用KrF準分 子雷射（波長248 nm ) 、ArF準分子雷射（波長193 nm ) 及F2準分子雷射（波長157 nm)等。曝光後必要時可進行 曝光後加（post exposure bake )。曝光後加熱可由加熱溫 度70 °C至150 °C，加熱時間0.3至10分鐘中適當選擇。 接著使用顯像液進行顯像。例如使用正型光致抗蝕劑 © 時，此時可去除曝光部分之光致抗蝕劑，形成光致抗蝕劑 之圖型。 顯像液如’氫氧化鉀、氫氧化鈉等鹼金屬氫氧化物之 水溶液、氫氧化四甲基銨 '氫氧化四乙基銨、膽鹼等氫氧 化四級銨之水溶液、乙醇胺、丙基胺、伸乙基二胺等胺水 溶液等之鹼性水溶液。另外此等顯像液可添加表面活性劑 等。顯像條件可由溫度5至50°C、時間0.1至5分鐘中適當 選擇。 -30- 200944944 其後以由此形成之光致抗蝕劑圖型爲保護膜，進行底 層膜去除及半導體基板加工。去除底層膜時可使用四氟甲 烷（CF4)、全氟環丁烷（C4F8 )、全氟丙烷（c3f8 )、 三氟甲烷、一氧化碳、氬、氧、氮、六氟化硫、二氟甲烷 、三氟化氮及三氟化氯等氣體進行乾蝕刻。去除底層膜可 於半導體基板上形成由底層膜及光致抗蝕劑形成之圖型。 又，將本發明之膜形成組成物使用於形成底層膜用時 Φ ，可於該底層膜上方形成光致抗鈾劑之前形成防反射膜層 。該防反射膜並無特別限制，可使用既存之防反射膜。例 如使用先前微影蝕刻步驟所慣用之防反射膜形成用組成物 ，利用慣用方法，例如旋塗機、棒塗機塗佈於底層膜上， 再焙燒而形成防反射膜。防反射膜組成物如，主成份爲吸 光性化合物、樹脂及溶劑之物，主成份爲具有藉由化學鍵 連結之吸光性基的樹脂、交聯劑及溶劑之物、主成份爲吸 光性化合物、交聯劑及溶劑之物、主成份爲具有吸光性之 Φ 高分子交聯劑及溶劑之物等。此等防反射膜組成物必要時 可含有酸成份、酸發生劑成份、液流調整劑等。所使用之 吸光性化合物可爲，對設置於防反射膜上之光致抗蝕劑中 感光成份的感光特性波長領域中之光具有高吸收能之物， 例如二苯甲酮化合物、苯并***化合物、偶氮化合物、萘 化合物、蒽化合物、蒽醌化合物、三嗪化合物等。樹脂如 ，聚酯、聚醯亞胺、聚苯乙烯、酚醛清漆樹脂、聚縮醛樹 脂、丙烯酸樹脂等。具有藉由化學鍵連結之吸光性基的樹 脂如，具有蒽環、萘環、苯環、喹啉環、喹喔啉環、噻唑 -31 - 200944944 環之吸光性芳香環構造的樹脂。 由本發明之膜形成組成物形成的底層膜又爲，相對於 微影蝕刻步驟所使用之光的波長’對該光具有吸收性。此 時具有，作爲具有防止由基板反射光之效果的層，即防反 射膜用之機能。另外本發明之膜可作爲防止基板與光致抗 蝕劑之相互作用的層、防止光致抗蝕劑用材料或光致抗蝕 劑曝光時所生成的物質對半導體基板產生不良影響之層、 加熱焙燒時防止半導體基板所生成的物質擴散至上層光致 抗蝕劑之層用等。 下面將以實施例更具體說明本發明，但本發明非限定 於此。 【實施方式】 實施例1An acrylate polymer of a naphthalene ring or an anthracene ring, a methacrylate polymer, a novolac polymer, a styrene polymer, a polyamine, a poly-proline, a polyester Q, and a polyimine. Further, when the film-forming composition of the present invention is used for producing an antireflection film of a photoresist underlayer in a photolithography etching step of a semiconductor device, a polymer compound excellent in light absorption performance can also be used. The use of such a polymer compound' improves the performance of the film formed of the film-forming composition of the present invention as an antireflection film. When the polymer compound is used, the amount thereof may be, for example, 0.1 to 50 parts by mass based on 1 part by mass of the photopolymerizable substance. -26-200944944 The film-forming composition of the present invention is preferably used, and each component (hereinafter referred to as "solid component") of the photopolymerizable compound is dissolved in a solvent solution. The solvent to be used may be one which dissolves a solid component to form a homogeneous solution. For example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol one Ethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, toluene, xylene, methyl ketone ethyl ketone, cyclopentanone, cyclohexanone, 2 -ethyl hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methoxy Methyl propionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, acetic acid Butyl ester, ethyl lactate, butyl lactate, N-dimethylformamide, N-dimethylacetamide, dimethyl submilling and N-methylpyrrolidone. These solvents may be used alone or in combination of two or more. The solvent to be used is preferably a solvent having a boiling point of 80 to 250 ° C, or 100 to 200 ° C, β or 120 to 180 ° C. When the boiling point of the solvent is low, a large amount of solvent is evaporated in the coating film-forming composition to increase the viscosity, resulting in a decrease in coatability. When the boiling point of the solvent is high, it takes time to dry after the coating film forms a composition. The solvent is used in an amount such that the solid content of the film-forming composition is, for example, 0.5 to 50% by mass, or 3 to 40% by mass, or 10 to 30% by mass. Next, a method of forming a composition using the film of the present invention of the photoresist underlayer film will be explained. For example, the film-forming composition of the present invention is applied to a semiconductor substrate for manufacturing a semiconductor device using a suitable coating method such as a spin coater or a bar coater (for example, a tantalum/cerium oxide-coated substrate, a tantalum wafer, or a niobium nitrogen). A coating film is formed on the substrate -27-200944944, the glass substrate, the ITO substrate, the polyimide substrate, and the low-permittivity material (low-k material-coated substrate). Further, before the light is applied to the coating film, a drying step may be carried out if necessary. When a composition is formed using a film containing a solvent, it is preferred to carry out a drying step. The drying step may be such that the method of heating at a high temperature is not particularly limited. However, when it is heated at a high temperature (e.g., a temperature of 1 50 ° C or more), it is estimated that the solid content contained in the coating film is sublimated or the like to contaminate the apparatus. Therefore, the drying step may be, for example, heating the substrate at 50 to 100 t on a hot plate for 1 to 1 minute. Also, for example, 'dry at room temperature (20 ° C). Next, the coated film was irradiated with light. The light irradiation may be a method in which the photopolymerization initiator acts to polymerize the photopolymerizable substance, and is not particularly limited. Light irradiation can be performed, for example, using light having a wavelength of 150 nm to 700 nm, or 193 to 700 nm, or 300 to 600 nm. The light irradiation can be performed, for example, by using an ultrahigh pressure mercury lamp, a flash UV lamp, a high pressure mercury lamp, a low pressure mercury lamp, a DEEP-UV (deep ultraviolet) lamp, a short arc arc metal halide lamp, a YAG laser excitation lamp, a xenon flash lamp, or the like. For example, when using an ultra-high pressure mercury lamp, it can be contained in the ultraviolet range 289 nm, 297 nm, 303 nm, 313 nm (j line), 334 nm, 365 nm (i line), and visible light field 405 nm (h line) ), the 436 nm (g line), 546 nm, and 579 nm wavelengths of the bright line spectrum of the peak wavelength of 150 nm to 700 nm are irradiated. The photopolymerization agent or the living radical is generated by the photopolymerization initiator in the coating film by light irradiation, and the photopolymerizable compound in the coating film is thereby subjected to a polymerization reaction. As a result of the polymerization, a film can be formed. The film to be formed may be, for example, a solvent used for the composition of the coated photo-catalyst -28-200944944, such as ethylene glycol monomethyl ether, when the photoresist is applied to the upper layer thereof. Ethyl cellosolve acetate, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, toluene, methyl ethyl ketone , cyclohexanol, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, methyl pyruvate, ethyl lactate and butyl lactate Low things. Therefore, the film formed of the film-forming composition of the present invention does not mix into the photoresist.膜 The film-forming composition of the present invention is suitably used as shown in FIG. 1 and has an aspect ratio of pore depth (b) / diameter (e) of 1 or more, for example, 1 to 1 Å, or 2 to 5 pores. Semiconductor substrate. Further, the film-forming composition of the present invention can be used as a film for forming a film which does not have such a gap. Further, a semiconductor substrate (a substrate having a hole-tight portion and a hole-diffusing portion) having a dense hole having an aspect ratio of 1 or more is suitable for the film-forming composition of the present invention. The film-forming composition of the present invention can be used for forming a flat film on the surface of a substrate in which such a pore-like pore exists. Further, the film-forming composition of the present invention can be used for a semiconductor substrate having a hole having an aspect ratio smaller than G 1 or a semiconductor substrate having a step. The film thickness of the film formed of the film-forming composition of the present invention on the surface of the substrate may be, for example, 20 to 2000 nm, or 30 to 1000 nm, or 50 to 800 nm. A photoresist can be formed over the film formed from the film-forming composition of the present invention. Thus, a laminated structure of the underlayer film and the photo-induced uranium agent can be formed on the semiconductor substrate. To form a photoresist, a known method is employed in which a photoresist composition solution is applied onto an underlying film and heated. The photoresist formed on the film of the present invention is not particularly limited, and any of a general-purpose negative photoresist and a positive photoresist can be used. For example, a positive photoresist formed of phenol -29-200944944 varnish resin and 1,2-naphthoquinonediazide sulfonate, which is composed of a binder having a base which can be decomposed by an acid to increase the alkali dissolution rate and A chemically amplified photoresist formed by a photoacid generator, which is chemically strengthened by decomposition of a low molecular compound and an alkali soluble binder and a photoacid generator which can be decomposed by an acid to increase the alkali dissolution rate of the photoresist. Type photoresist, a low molecular compound and a photoacid generator which have a base which can be decomposed by an acid to increase the alkali dissolution rate, and which are decomposed by an acid to increase the alkali dissolution rate of the photoresist. The chemically amplified photoresist to be formed, for example, is commercially available under the trade name APEX-E, manufactured by Sumitomo Chemical Co., Ltd., and sold under the trade name PAR710 by Sumitomo Chemical Industries Co., Ltd., and under the trade name SEP R4 30 manufactured by Shin-Etsu Chemical Co., Ltd. Secondly, exposure is performed through a certain mask. KrF quasi-molecular laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm) and F2 excimer laser (wavelength 157 nm) can be used for exposure. Post exposure bake can be performed if necessary after exposure. The post-exposure heating can be suitably selected from a heating temperature of 70 ° C to 150 ° C and a heating time of 0.3 to 10 minutes. The development is then carried out using a developing solution. For example, when a positive photoresist 106 is used, the exposed portion of the photoresist can be removed at this time to form a pattern of the photoresist. The developing solution is an aqueous solution of an alkali metal hydroxide such as potassium hydroxide or sodium hydroxide, an aqueous solution of tetramethylammonium hydroxide, tetraethylammonium hydroxide, quaternary ammonium hydroxide such as choline, ethanolamine or propyl group. An alkaline aqueous solution such as an amine or an aqueous amine solution such as ethyldiamine. Further, a surfactant or the like may be added to these developing solutions. The development conditions can be appropriately selected from a temperature of 5 to 50 ° C and a time of 0.1 to 5 minutes. -30- 200944944 Thereafter, the thus formed photoresist pattern is used as a protective film to perform underlayer film removal and semiconductor substrate processing. When removing the underlayer film, tetrafluoromethane (CF4), perfluorocyclobutane (C4F8), perfluoropropane (c3f8), trifluoromethane, carbon monoxide, argon, oxygen, nitrogen, sulfur hexafluoride, difluoromethane, Gases such as nitrogen trifluoride and chlorine trifluoride are dry etched. The removal of the underlying film forms a pattern formed by the underlying film and the photoresist on the semiconductor substrate. Further, when the film-forming composition of the present invention is used for forming the underlayer film Φ, an anti-reflection film layer can be formed before the photo-induced uranium-repellent agent is formed over the underlayer film. The antireflection film is not particularly limited, and an existing antireflection film can be used. For example, a composition for forming an antireflection film which is conventionally used in the previous photolithography etching step is applied onto an underlayer film by a conventional method such as a spin coater or a bar coater, and then fired to form an antireflection film. The antireflection film composition is, for example, a main component is a light absorbing compound, a resin, and a solvent, and the main component is a resin having a light absorbing group linked by a chemical bond, a crosslinking agent, and a solvent, and the main component is a light absorbing compound. The main component of the crosslinking agent and the solvent is a Φ polymer cross-linking agent having a light absorbing property and a solvent. These antireflection film compositions may contain an acid component, an acid generator component, a liquid flow regulator, etc., if necessary. The light absorbing compound to be used may be a substance having high absorption energy for light in the wavelength range of the photosensitive characteristic of the photosensitive component in the photoresist provided on the antireflection film, such as a benzophenone compound or a benzotriene. An azole compound, an azo compound, a naphthalene compound, an anthraquinone compound, an anthraquinone compound, a triazine compound, or the like. Resins such as polyester, polyimine, polystyrene, novolac resin, polyacetal resin, acrylic resin, and the like. A resin having a light-absorbing group bonded by a chemical bond, for example, a resin having an anthracene ring, a naphthalene ring, a benzene ring, a quinoline ring, a quinoxaline ring, or a thiazole-31 - 200944944 ring light-absorbing aromatic ring structure. The underlayer film formed of the film-forming composition of the present invention is further absorbing the light with respect to the wavelength ' of light used in the lithography etching step. At this time, it functions as a layer having an effect of preventing light from being reflected by the substrate, that is, an antireflection film. Further, the film of the present invention can be used as a layer for preventing interaction between the substrate and the photoresist, and a layer for preventing the photoresist material from being exposed to the semiconductor substrate by the material formed by exposure of the photoresist or the photoresist. When heating and baking, the substance generated by the semiconductor substrate is prevented from diffusing to the layer of the upper layer photoresist or the like. The invention will now be more specifically illustrated by the examples, but the invention is not limited thereto. Embodiments Embodiment 1

將前述式（1-3)所表示之光聚合性海藻糖化合物衍 生物3.47g (群榮化學工業（股）製商品名GS-TG001 ) 、 Q 光聚合引發劑：1-羥基-環己基-苯基-酮（吉巴斯（股）製 商品名IRGACURE1 84 ) 0.3 5g，及雙（2,4,6-三甲基苯醯基 )-苯基鱗氧化物（吉巴斯（股）製商品名IRGACURE819 )〇.17g加入環己酮13.57g、丙二醇一甲基醚乙酸酯9.05g 中’形成15質量％溶液。使用孔徑〇.2"m之聚乙烯製微濾 器過濾’調製底層膜形成組成物之溶液。 實施例2 -32- 200944944 將則述式（1-4)所表示之光聚合性丁基葡糖苷化合 物衍生物3.53g(群榮化學工業（股）製商品*GS_BG〇〇1 )、光聚合引發劑：1-羥基·環己基_苯基_酮（吉巴斯（股 )製商品名IRGACURE184) 〇.35g，及雙（2,4,6_三甲基苯 醯基）-苯基膦氧化物（吉巴斯（股）製商品名 IRGACURE8 1 9 ) 0.1 8g加入環己酮丨3 8丨g、丙二醇甲基醚 乙酸醋9.21g中，形成15質量％溶液。使用孔徑〇.2#m之聚 〇 乙烯製微濾器過濾’調製底層膜形成組成物之溶液。 實施例3 將前述式（1-5)所表示之光聚合性甲基葡萄糖環氧 乙烷化合物衍生物3.23g (群榮化學工業（股）製商品名 GS-E〇G001)、光聚合引發劑：卜羥基·環己基_苯基_醒（ 吉巴斯（股）製商品名IRGACURE184) 〇.32g，及雙（ 2，4,6·三甲基苯醯基）-苯基膦氧化物（吉巴斯（股）製商 粵 品名IRGACURE819) 〇.16g加入環己酮i2.63g、丙二醇一 甲基酸乙酸酯8.42g中，形成15質量％溶液。使用孔徑〇.2 之聚乙烯製微濾器過濾，調製底層膜形成組成物之溶 液。 實施例4 將前述式（1-6)所表示之光聚合性甲基葡萄糖環氧 乙烷化合物衍生物3 · 2 1 g (群榮化學工業（股）製商品名 GS-E〇G002 )、光聚合引發劑：1·羥基-環己基-苯基-酮（ -33- 200944944 吉巴斯（股）製商品名IRGACURE184 ) 0_32g，及雙（ 2,4,6-三甲基苯醯基）-苯基鱗氧化物（吉巴斯（股）製商 品名IRGACURE819) 0.16g加入環己酮12.54g、丙二醇-甲 基醚乙酸酯8.36g中，形成15質量％溶液。使用孔徑0.2 /z m 之聚乙烯製微濾器過濾，調製底層膜形成組成物之溶液。 實施例5 將前述式（1-6)所表示之光聚合性甲基葡萄糖環氧 乙烷化合物衍生物3.21g(群榮化學工業（股）製商品名 GS-EOG002 )、前述式（1-2)所表示之光聚合性甲基葡萄 糖化合物衍生物3.21g (群榮化學工業（股）製商品名GS-MG002 )、光聚合引發劑：1-羥基-環己基-苯基-酮（吉巴 斯（股）製商品名IRGACURE 1 84 ) 0.64g，及雙（2,4,6-三 甲基苯醯基）-苯基膦氧化物（吉巴斯（股）製商品名 IRGACURE819 ) 〇.32g，及表面活性劑（大曰本油墨化學 工業（股）製商品名美凱番R30) O.Olg加入環己酮25.09g 、丙二醇一甲基醚乙酸酯16.72g中，形成15質量％溶液。 使用孔徑〇.2/zm之聚乙烯製微濾器過濾，調製底層膜形成 組成物之溶液。 實施例6 將光聚合化合物：2,2-雙（羥基甲基）-1-丁醇之1,2-環氧-4- ( 2 -環氧乙烷基）環己烷加成物及3,4 -環氧環己烯 基甲基-3’，4’-環氧環己烯羧酸酯之混合物（泰歇爾化學工 -34- 200944944 業（股）製商品名液狀型EHPEL3150CE，前述式（2-9) 所表示之化合物及前述式（2-1)所表示之化合物的混合 物，前述式（2-9)所表示之化合物爲分子量2234) 1〇.〇〇g ’及光聚合引發劑：三苯基毓三氟甲烷磺酸鹽（綠化學（ 股）製商品名TPS105) l.〇〇g加入環己酮39.10g、丙二醇 一甲基醚乙酸酯26.07g中，形成15質量％溶液。使用孔徑 0.2 〇 #«!之聚乙烯製微濾器過濾，調製底層膜形成組成物之溶 液。 實施例7 將前述式（2-1 )所表示之光聚合性3,4-環氧環己基甲 基-3，4-環氧環己烷羧酸酯（泰歇爾化學工業（股）製商品 名歇洛吉202 1 P ) 10. 〇〇g，及光聚合引發劑：三苯基鏑三 氟甲烷磺酸鹽（綠化學（股）製商品名TPS105) 0.25g加 © 入環己酮39」0g中’形成15質量％溶液。使用孔徑0.2vm 之聚乙烯製微濾器過濾，調製底層膜形成組成物之溶液。 實施例8 將具有前述式（2-4)所表示之光聚合性環己烯氧化 物骨架的脂環式環氧樹脂化合物（泰歇爾化學工業（股） 製商品名歇洛吉2081，η爲1) 10.00g，及光聚合引發劑： 三苯基毓三氟甲烷磺酸鹽（綠化學（股）製商品名TPS105 )〇.25g加入環己酮39.10g中，形成15質量％溶液。使用孔 -35- 200944944 徑0.2# m之聚乙烯製微濾器過濾，調製底層膜形成組成物 之溶液。 比較合成例1 將縮水甘油基甲基丙烯酸酯30.〇g (東京化成工業股 份公司）、甲基甲基丙烯酸酯24.1 g溶解於乙酸乙酯21 6g 中，使溶液中氮流動30分鐘後，升溫至70 °C。將反應溶液 保存於70°C下加入偶氮雙丁腈1.62g及卜十二烷硫醇1.62g Q 。氮氣，7〇t下攪拌8小時後，加入4 -甲氧基苯酚〇.lg’得 縮水甘油基甲基丙烯酸酯及甲基甲基丙烯酸酯之共聚物的 溶液。對所得共聚物進行GPC分析，結果數平均分子量Μη 爲6000，重量平均分子量（標準聚苯乙烯換算）Mw爲 12000 ° 比較例1 將含有比較合成例1所得的縮水甘油基甲基丙烯酸酯 〇 及甲基甲基丙烯酸酯之共聚物的溶液（固體成份濃度 20.0%) 50g，光聚合引發劑：三苯基鏡三氟甲烷磺酸鹽（ 綠化學（股）製商品名TPS105) 〇.5g，及表面活性劑（大 日本油墨化學工業（股）製商品名美凱番R3〇) 〇.〇5g加入 乙酸乙酯30g中，形成15質量％溶液。使用孔徑之聚 乙烯製微濾器過濾，調製底層膜形成組成物之溶液。 對光致抗蝕劑溶劑之溶出試驗 -36- 200944944 使用旋塗機將實施例1至8 ’及比較例1所得的膜形成 組成物之溶液各自塗佈於半導體基板（矽晶圓）上形成塗 佈膜。其次使用超高壓水銀燈（烏西歐電氣（股）製，型 式UIS-5011MIKY，輸出功力5 00W)，以燈全波長5.5 mW 之照射條件照射塗佈膜2分鐘（曝光量660 mJ/cm2 )。爲 了去除溶劑進行乾燥，將其置於熱板上以1 〇〇 °C加熱1分鐘 ，形成犧牲膜（膜厚450-500 nm )。將此等犧牲膜浸漬於 φ 光致抗蝕劑用溶劑之丙二醇一甲基醚中，結果不溶於該溶 劑，確認藉由光反應可形成光硬化膜。 平坦化率及塡充性之試驗 使用旋塗機將實施例1至8所得的膜形成組成物之溶液 各自塗佈於具有孔（直徑0.30/zm，深度1.0/zrn，即長寬 比3.3)，及孔（直徑1.0//m，深度1.0/zm，即長寬比1.0 )之二氧化矽（Si 02晶圓）基板上形成塗佈膜。所使用的 〇 基板爲，如圖1所示具有孔之Iso (粗）及Dense (密）圖 型的基板。Iso圖型爲，孔中心至接鄰之孔中心的間隔爲 該孔之直徑的5倍之圖型。又，Dense圖型爲，孔中心至接 鄰之孔中心的間隔爲該孔之直徑的1倍之圖型。孔深度爲 1.0// m，孔直徑爲 〇.30或 1.0" m。 使用超高壓水銀燈（烏西歐電氣（股）製，型式UIS-5011MIKY，輸出功力5 00W)，以燈全波長5.5 mW之照射 條件照射塗佈膜2分鐘（曝光量660 mJ/cm2 )。爲了去除 溶劑進行乾燥’將其置於熱板上以1 30。(：加熱2分鐘後，形 -37- 200944944 成犧牲膜。膜厚爲，附近無孔的圖型之開放領域的膜厚爲 460-4 8 0 nm。使用掃描型電子顯微鏡（SEM )觀察基板剖 面形狀，由犧牲膜評估平坦化率。平坦化率可由下式求取 。基板上孔完全平坦化時之平坦化率爲1 〇〇%。結果如表1 所示。 平坦化率={1-(孔中心部之底層膜凹陷深度a)/(孔深度3.47 g of the photopolymerizable trehalose compound derivative represented by the above formula (1-3) (trade name: GS-TG001, manufactured by Kyoei Chemical Industry Co., Ltd.), Q photopolymerization initiator: 1-hydroxy-cyclohexyl group Phenyl-ketone (trade name: IRGACURE1 84 manufactured by Gibbs) 0.3 5g, and bis(2,4,6-trimethylphenylhydrazino)-phenyl squamous oxide (made by Gibbs Co., Ltd.) Trade name: IRGACURE 819 ) 〇. 17 g of cyclohexanone 13.57 g, propylene glycol monomethyl ether acetate 9.05 g of 'formed 15% by mass solution. A solution of the underlying film forming composition was prepared by filtering using a polyethylene microfilter having a pore size of 22 " m. Example 2 -32-200944944 The photopolymerizable butyl glucoside derivative derivative represented by the formula (1-4) is 3.53 g (product of GS Chemical Co., Ltd. *GS_BG〇〇1), photopolymerization Initiator: 1-hydroxycyclohexyl-phenyl-ketone (trade name: IRGACURE 184, manufactured by Gibbs) 〇.35g, and bis(2,4,6-trimethylphenylhydrazyl)-phenylphosphine Oxide (trade name: IMGACURE 8 1 9 manufactured by Gibbs Co., Ltd.) 0.1 8 g of cyclohexanone oxime 38 g and propylene glycol methyl ether acetate vinegar 9.21 g were added to form a 15% by mass solution. A solution of the composition of the underlayer film was prepared by using a polyelectrolytic filter of a pore size of 2.2#m. Example 3 3.23 g of a photopolymerizable methyl glucose oxirane compound derivative represented by the above formula (1-5) (trade name: GS-E〇G001, manufactured by Qunrong Chemical Industry Co., Ltd.), photopolymerization initiation Agent: hydroxy-cyclohexyl phenyl group _ awake (product name IRGACURE 184 manufactured by Gibbs) 〇.32g, and bis(2,4,6-trimethylphenyl fluorenyl)-phenylphosphine oxide (Gibbas (trade) manufacturer's product name IRGACURE 819) 16.16g was added to cyclohexanone i2.63g, propylene glycol monomethyl acetate acetate 8.42g to form a 15% by mass solution. The mixture was filtered using a polyethylene microfilter having a pore size of 22 to prepare a solution of the underlying film to form a composition. Example 4 The photopolymerizable methyl glucose oxirane compound derivative represented by the above formula (1-6) is 3 · 2 1 g (trade name: GS-E〇G002, manufactured by Gunei Chemical Industry Co., Ltd.), Photopolymerization initiator: 1·hydroxy-cyclohexyl-phenyl-ketone (-33- 200944944 by Gimbas Co., Ltd. under the trade name IRGACURE 184) 0_32g, and bis(2,4,6-trimethylphenylhydrazino) -Phenyl squamous oxide (trade name: IRGACURE 819, manufactured by Gibbs) 0.16 g of cyclohexanone 12.54 g and propylene glycol-methyl ether acetate 8.36 g were added to form a 15 mass% solution. The solution of the underlayer film forming composition was prepared by filtering using a polyethylene microfilter having a pore size of 0.2 /z m. Example 5 3.21 g of a photopolymerizable methyl glucose oxirane compound derivative represented by the above formula (1-6) (trade name: GS-EOG002, manufactured by Qunrong Chemical Industry Co., Ltd.), and the above formula (1) 2) The photopolymerizable methyl glucose compound derivative represented by 3.21 g (trade name: GS-MG002, manufactured by Gunei Chemical Industry Co., Ltd.), photopolymerization initiator: 1-hydroxy-cyclohexyl-phenyl-ketone (吉Basil (trade name) manufactured by IRGACURE 1 84 ) 0.64g, and bis(2,4,6-trimethylphenylhydrazino)-phenylphosphine oxide (trade name IRGACURE819, manufactured by Gibbs) 〇 .32g, and a surfactant (trade name of the company), O.Olg, added cyclohexanone 25.09g, propylene glycol monomethyl ether acetate 16.72g, forming 15 mass % solution. The mixture was filtered through a polyethylene microfilter having a pore size of 22/zm to prepare a solution of the underlayer film to form a composition. Example 6 Photopolymerizable compound: 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol and 3 , a mixture of 4-epoxycyclohexenylmethyl-3',4'-epoxycyclohexenecarboxylate (Taylor Chem.-34-200944944, trade name, liquid type EHPEL3150CE, a mixture of the compound represented by the above formula (2-9) and the compound represented by the above formula (2-1), wherein the compound represented by the above formula (2-9) has a molecular weight of 2234) 1〇.〇〇g 'and light Polymerization initiator: triphenylsulfonium trifluoromethanesulfonate (trade name TPS105, manufactured by Green Chemical Co., Ltd.) l. 〇〇g was added to cyclohexanone 39.10 g and propylene glycol monomethyl ether acetate 26.07 g to form 15% by mass solution. The mixture was filtered using a polyethylene microfilter having a pore size of 0.2 〇 #«! to prepare a solution of the underlying film to form a composition. Example 7 Photopolymerizable 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate represented by the above formula (2-1) (Tacher Chemical Industry Co., Ltd.) Product name: shanggeji 202 1 P ) 10. 〇〇g, and photopolymerization initiator: triphenyl sulfonium trifluoromethane sulfonate (trade name TPS105, manufactured by Green Chemical Co., Ltd.) 0.25g plus © cyclohexanone 39"0g" formed a 15% by mass solution. The solution of the underlayer film forming composition was prepared by filtration using a polyethylene microfilter having a pore size of 0.2 vm. Example 8 An alicyclic epoxy resin compound having a photopolymerizable cyclohexene oxide skeleton represented by the above formula (2-4) (trade name of Michelle Chemical Industry Co., Ltd.) 1) 10.00 g, and photopolymerization initiator: Triphenylsulfonium trifluoromethanesulfonate (trade name TPS105, manufactured by Green Chemical Co., Ltd.) 25. 25 g was added to 39.10 g of cyclohexanone to form a 15% by mass solution. A solution of the composition of the underlayer film was prepared by filtering a hole-35-200944944 polyethylene microfilter having a diameter of 0.2# m. Comparative Synthesis Example 1 Glycidyl methacrylate 30. 〇g (Tokyo Chemical Industry Co., Ltd.) and methyl methacrylate 24.1 g were dissolved in 21 6 g of ethyl acetate, and nitrogen was allowed to flow in the solution for 30 minutes. Warm up to 70 °C. The reaction solution was stored at 70 ° C to add 1.62 g of azobisbutyronitrile and 1.62 g of dodecanethiol. After stirring under nitrogen for 7 hours at 7 Torr, a solution of a copolymer of glycidyl methacrylate and methyl methacrylate was obtained by adding 4-methoxyphenol 〇.lg'. GPC analysis of the obtained copolymer showed that the number average molecular weight Μη was 6000, and the weight average molecular weight (standard polystyrene conversion) Mw was 12,000 °. Comparative Example 1 The glycidyl methacrylate obtained by Comparative Synthesis Example 1 was contained. a solution of a copolymer of methyl methacrylate (solid content: 20.0%) 50 g, photopolymerization initiator: triphenyl mirror trifluoromethanesulfonate (trade name TPS105, manufactured by Green Chemical Co., Ltd.) 〇.5g, And a surfactant (manufactured by Dainippon Ink Chemicals Co., Ltd. under the trade name Meikefan R3). 5 g of ethyl acetate was added to 30 g of ethyl acetate to form a 15% by mass solution. The solution of the underlayer film forming composition was prepared by filtration using a polyethylene microfilter of a pore size. Dissolution test for photoresist solvent-36-200944944 The solutions of the film-forming compositions obtained in Examples 1 to 8' and Comparative Example 1 were each applied onto a semiconductor substrate (矽 wafer) using a spin coater. Coating film. Next, an ultrahigh pressure mercury lamp (Ussio Electric Co., Ltd., type UIS-5011MIKY, output power of 500 W) was used, and the coating film was irradiated for 2 minutes (exposure amount 660 mJ/cm2) under the irradiation condition of a lamp full wavelength of 5.5 mW. To remove the solvent for drying, it was placed on a hot plate and heated at 1 ° C for 1 minute to form a sacrificial film (film thickness 450-500 nm). These sacrificial films were immersed in propylene glycol monomethyl ether of a solvent for φ photoresist, and as a result, they were insoluble in the solvent, and it was confirmed that a photocured film was formed by photoreaction. Test for flattening rate and tackiness The solutions of the film-forming compositions obtained in Examples 1 to 8 were each coated with a hole (diameter: 0.30/zm, depth: 1.0/zrn, ie, aspect ratio 3.3) using a spin coater. And a coating film was formed on the ceria (Si 02 wafer) substrate of the hole (1.0/m in diameter, 1.0/zm in depth, ie, aspect ratio 1.0). The ruthenium substrate used is a substrate having an Iso (coarse) and Dense (dense) pattern as shown in Fig. 1. The Iso pattern is such that the distance from the center of the hole to the center of the adjacent hole is 5 times the diameter of the hole. Further, the Dense pattern is such that the interval from the center of the hole to the center of the adjacent hole is one-fold the diameter of the hole. The hole depth is 1.0//m and the hole diameter is 〇.30 or 1.0" m. The coating film was irradiated for 2 minutes (exposure amount 660 mJ/cm2) using an ultrahigh pressure mercury lamp (Ussian Electric Co., Ltd., type UIS-5011MIKY, output power of 500 W) at a full wavelength of 5.5 mW. Drying was carried out in order to remove the solvent, and it was placed on a hot plate at 1 30. (: After heating for 2 minutes, the shape -37-200944944 is a sacrificial film. The film thickness is 460-4 80 nm in the open field of the non-porous pattern nearby. The substrate is observed using a scanning electron microscope (SEM). The shape of the cross section was evaluated by the sacrificial film. The flattening rate was obtained by the following equation: The flattening ratio of the hole on the substrate was completely flattened by 1%. The results are shown in Table 1. Flattening rate = {1 - (the depth of the underlying film depression in the center of the hole a) / (hole depth)

又，孔內部未觀察到間隙，觀察到底層膜塡充孔內部Moreover, no gap was observed inside the hole, and the inside of the underlying film was observed.

[表1] 表1孔(直徑0.30//m、深度1.0"m、即長寬比3.3)[Table 1] Table 1 hole (diameter 0.30 / / m, depth 1.0 " m, that is, aspect ratio 3.3)

Iso 膜厚(nm) Dense Bias Iso 平坦化率(％) Dense Bias 實例例1 470 380 90 100 100 0 實例例2 480 400 80 100 100 0 實例例3 480 400 80 100 100 0 實例例4 460 390 70 100 100 0 實例例5 470 400 70 100 100 0 實例例6 480 450 30 100 100 0 實例例7 460 450 10 100 100 0 實例例8 460 460 20 100 100 0 -38- 200944944 [表2] 表2孔値徑1 ·0 /m、深度上gjH』歷里Μ:—9_ Iso 膜厚(ΠΠ1) Dense Bias Iso 平坦化率(〇/〇) Dense Bias 實例例1 470 350 120 100 99 1 實例例2 480 370 110 100 100 0 實例例3 480 370 110 100 100 0 實例例4 460 360 100 100 100 0 實例例5 470 470 100 100 100 0 實例例6 480 420 60 100 100 0 實例例7 460 410 50 100 100 0 實例例8 480 430 50 100 100 0 Ο 實施例1至8之犧牲膜的1so(粗）及Dense (密）圖型 上之膜厚差（Bias )較小。實施例1至8之犧牲膜於特別是 膜厚難固定之微細Dense孔圖型上具有優良流動性。既使 孔基板上每單位面積之孔數（孔密度）爲，Dense部大於 Iso部時，其中多數犧牲膜形成組成物之溶液也可平順流 入，而得一定膜厚’因此推斷其爲可縮小1so部及〇611^部 之膜厚差，且增加平坦化率之物。又’實施例1至8之犧牲 膜無關Iso部及Dense部可平坦化。 乾蝕速度之試驗 使用旋塗機各自將實施例1至8所得的膜形成組成物之 溶液塗佈於半導體基板（矽晶圓）上形成犧牲膜。使用超 高壓水銀燈（烏西歐電氣（股）製，型式UIS-501 1MIKY ’輸出功力5 0 0 W )，以燈全波長5.5 mW之照射條件照射 該膜2分鐘（曝光量660 mJ/cm2 )後，爲了去除溶劑進行 -39- 200944944 乾燥，將其置於熱板上以130 °C加熱2分鐘，形成犧牲膜。 膜厚爲460至480 nm。其次使用日本賽恩提製RIE系統 ES401，以CF4爲乾蝕氣體之條件測定此等犧牲膜的乾鈾速 度（每單位時間之膜厚減少量）。結果如表3所示。表中 選擇性係指，以同KrF雷射微影蝕刻用之光致抗蝕劑（信 越化學工業（股）製商品名SEPR43 0 )之條件下的乾鈾刻 速度爲1.00時，相對於光致抗蝕劑之乾蝕刻速度的犧牲膜 之乾蝕刻速度。 [表3] 表3 速度比 實例例1 2.5 實例例2 2.2 實例例3 2.3 實例例4 2.2 實例例5 2.3 實例例6 1.1 實例例7 1.5 實例例8 1.4Iso film thickness (nm) Dense Bias Iso flattening rate (%) Dense Bias Example 1 470 380 90 100 100 0 Example 2 480 400 80 100 100 0 Example 3 480 400 80 100 100 0 Example 4 460 390 70 100 100 0 Example 5 470 400 70 100 100 0 Example 6 480 450 30 100 100 0 Example 7 460 450 10 100 100 0 Example 8 460 460 20 100 100 0 -38- 200944944 [Table 2] Table 2 Holes 11·0 / m, depth gjH 历历Μ:—9_ Iso film thickness (ΠΠ1) Dense Bias Iso flattening rate (〇/〇) Dense Bias Example 1 470 350 120 100 99 1 Example 2 480 370 110 100 100 0 Example 3 480 370 110 100 100 0 Example 4 460 360 100 100 100 0 Example 5 470 470 100 100 100 0 Example 6 480 420 60 100 100 0 Example 7 460 410 50 100 100 0 EXAMPLES Example 8 480 430 50 100 100 0 Ο The film thickness difference (Bias) on the 1so (coarse) and Dense (dense) patterns of the sacrificial films of Examples 1 to 8 was small. The sacrificial films of Examples 1 to 8 have excellent fluidity particularly in the fine Dense hole pattern in which the film thickness is difficult to fix. Even if the number of holes per unit area (hole density) on the hole substrate is larger than the Iso portion, the solution in which the majority of the sacrificial film forming composition can smoothly flow in, and a certain film thickness is obtained, so it is inferred that it can be reduced. The film thickness difference between the 1so portion and the 〇61 portion is increased, and the flattening rate is increased. Further, the sacrificial film-independent Iso portion and the Dense portion of the first to eighth embodiments can be planarized. Test of dry etching rate A solution of the film-forming compositions obtained in Examples 1 to 8 was applied to a semiconductor substrate (矽 wafer) by a spin coater to form a sacrificial film. Using an ultra-high pressure mercury lamp (Ussio Electric Co., Ltd., type UIS-501 1MIKY 'output power 500 W), the film was irradiated for 2 minutes (exposure 660 mJ/cm2) at a full wavelength of 5.5 mW. In order to remove the solvent, it was dried at -39 to 200944944, and it was placed on a hot plate and heated at 130 ° C for 2 minutes to form a sacrificial film. The film thickness is 460 to 480 nm. Next, the RIE system ES401 manufactured by Seonti, Japan, was used to measure the dry uranium speed (reduction in film thickness per unit time) of these sacrificial films under conditions of CF4 as a dry etching gas. The results are shown in Table 3. The selectivity in the table refers to the dry uranium engraving speed of 1.00 when compared with the photoresist for KrF laser lithography (Shin-Etsu Chemical Co., Ltd. under the trade name SEPR43 0), relative to light. The dry etch rate of the sacrificial film that causes the dry etch rate of the resist. [Table 3] Table 3 Speed ratio Example 1 2.5 Example 2 2.2 Example 3 2.3 Example 4 2.2 Example 5 2.3 Example 6 1.1 Example 7 Example 1.5 Example 1.4

由上述確認由實施例1至8之膜形成組成物而得的犧牲 膜之乾鈾刻速度，比光致抗鈾劑乾蝕刻速度更高。半導體 製造步驟中犧牲膜之乾蝕刻速度比光致抗蝕劑之乾蝕刻速 度更高的必要性爲，將形成於犧牲膜上之光致抗蝕劑顯像 時，藉由乾蝕刻以曝出基板底層之步驟中，可因犧牲膜之 乾蝕刻速度比光致抗蝕劑之乾蝕刻速度更高，而於削取光 -40- 200944944 致抗蝕劑之前去除犧牲膜，故可正確將顯像之光致抗蝕劑 圖型複製於基板上。又必需適合發光二極管、固體攝影元 件或顯示器裝置製造過程中，無機氧化膜、無機氮化膜及 無機氧化氮化膜等底層永久膜之乾蝕刻速度。由實施例1 至8之膜形成組成物而得的犧牲膜因具有1.1至2.5倍之廣泛 範圍的乾蝕刻選擇性，故對發光二極管、固體攝影元件或 顯示器裝置製造過程中所使用的各種底層永久膜及乾蝕刻 Q 條件具有優良適合性。 膜收縮性之試驗 使用旋塗機將實施例1至8，及比較例1所得的膜形成 組成物之溶液各自塗佈於半導體基板（矽晶圓）上形成塗 佈膜。使用超高壓水銀燈（烏西歐電氣（股）製’型式 UIS-5011MIKY，輸出功力5 00W)，以燈全波長5.5 mW之 照射條件照射塗佈膜2分鐘（曝光量660 mJ/cm2 )。使用 φ 光干擾膜厚計測定熱焙燒前之膜厚。光照射前之實施例1 至8所得的膜形成組成物之膜厚爲500至5 3 0 nm。其次爲了 去除溶劑進行乾燥，將其置於熱板上以1 30°C加熱2分鐘’ 形成目的之促進光反應及去除溶劑的犧牲膜。 由焙燒前後之膜厚差評估膜收縮率。 膜收縮率（％) = [(熱焙燒前之膜厚-熱焙燒後之膜厚）/熱 焙燒前之膜厚]χίοο -41 - 200944944 結果如表4所示。 [表4] 表4 膜收縮率0/〇 實例例1 1.5 實例例2 1.6 實例例3 1.9 實例例4 2.0 實例例5 1.9 實例例6 3.7 實例例7 2.8 實例例8 3.0 比較例1 5.8From the above, it was confirmed that the dry uranium engraving speed of the sacrificial film obtained by forming the composition of Examples 1 to 8 was higher than that of the photo-induced uranium etchant. The necessity of the dry etching rate of the sacrificial film in the semiconductor manufacturing step is higher than the dry etching speed of the photoresist, when the photoresist formed on the sacrificial film is developed, it is exposed by dry etching. In the step of the bottom layer of the substrate, the dry etching speed of the sacrificial film may be higher than the dry etching speed of the photoresist, and the sacrificial film may be removed before the photoresist is removed by the light--40-200944944, so that it can be correctly displayed A photoresist pattern is reproduced on the substrate. It is also necessary to be suitable for the dry etching rate of the underlying permanent film such as an inorganic oxide film, an inorganic nitride film, and an inorganic oxynitride film in the manufacturing process of a light-emitting diode, a solid-state imaging device, or a display device. The sacrificial film obtained by forming the composition of the films of Examples 1 to 8 has a wide range of dry etching selectivity of 1.1 to 2.5 times, and thus various underlayers used in the manufacturing process of the light emitting diode, the solid state imaging device, or the display device. Permanent film and dry etch Q conditions have excellent suitability. Film shrinkage test Each of the solutions of the film-forming compositions obtained in Examples 1 to 8 and Comparative Example 1 was applied onto a semiconductor substrate (tantalum wafer) by a spin coater to form a coating film. The coating film was irradiated for 2 minutes (exposure amount: 660 mJ/cm2) using an ultrahigh pressure mercury lamp (Ussau Electric Co., Ltd. type UIS-5011MIKY, outputting a power of 500 W) at a full wavelength of 5.5 mW. The film thickness before hot baking was measured using a φ light interference film thickness meter. The film-forming composition obtained in Examples 1 to 8 before the light irradiation had a film thickness of 500 to 530 nm. Next, in order to remove the solvent for drying, it was placed on a hot plate and heated at 1 30 ° C for 2 minutes to form a desired sacrificial film for promoting photoreaction and solvent removal. The film shrinkage rate was evaluated from the difference in film thickness before and after baking. Film shrinkage ratio (%) = [(film thickness before hot baking - film thickness after hot baking) / film thickness before hot baking] χίοο -41 - 200944944 The results are shown in Table 4. [Table 4] Table 4 Membrane shrinkage ratio 0/〇 Example 1 1.5 Example 2 1.6 Example 3 1.9 Example 4 2.0 Example 5 1.9 Example 6 3.7 Example 7 2.8 Example 8 3.0 Comparative Example 1 5.8

由上述確認由實施例1至8之膜形成組成物而得的犧牲 膜之膜收縮率比比較例1更小。半導體、發光二極管、固 體攝影元件或顯示器裝置製造過程中犧牲膜之膜收縮率較 小的必要性爲，塗佈於凹凸狀底層永久膜時，可得優良表 面平滑性、光澤性、防光散射及爲了保護藥液而降低比表 面積之效果。由實施例1至8之膜形成組成物而得的犧牲膜 對半導體、發光二極管、固體攝影元件或顯示器裝置製造 過程中所使用的各種底層永久膜具有優良適合性。 產業上利用可能性 製造半導體、發光二極管、固體攝影元件、液晶顯示 器之電子零件時，於基體上之永久膜上形成平坦化膜時， 其適用於製作此等平坦化膜。 -42- 200944944 【圖式簡單說明】 圖1爲，具有孔之半導體基板上形成底層膜之狀態下 的剖面圖。 【主要元件符號說明】 a :孔中心之底層膜凹部深度。 b :所使用的半導體基板當初之孔深度。 c :底層膜。 d :半導體基板。 e :孔之直徑。 -43-From the above, it was confirmed that the film shrinkage ratio of the sacrificial film obtained by forming the composition of the films of Examples 1 to 8 was smaller than that of Comparative Example 1. The necessity of a small film shrinkage rate of a sacrificial film during the manufacture of a semiconductor, a light-emitting diode, a solid-state imaging device, or a display device is that when applied to a concave-surface underlayer permanent film, excellent surface smoothness, gloss, and light scattering are obtained. And the effect of reducing the specific surface area in order to protect the chemical solution. The sacrificial film obtained by forming the composition of the films of Examples 1 to 8 has excellent suitability for various underlying permanent films used in the manufacture of semiconductors, light-emitting diodes, solid-state imaging elements, or display devices. INDUSTRIAL APPLICABILITY When manufacturing a semiconductor, a light-emitting diode, a solid-state imaging device, or an electronic component of a liquid crystal display, when a planarization film is formed on a permanent film on a substrate, it is suitable for use in the production of such a planarization film. -42- 200944944 BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a cross-sectional view showing a state in which an underlayer film is formed on a semiconductor substrate having a hole. [Explanation of main component symbols] a : Depth of the underlying film recess in the center of the hole. b : the hole depth of the semiconductor substrate used. c: the underlying film. d : semiconductor substrate. e : diameter of the hole. -43-

Claims (1)

200944944 七、申請專利範圍： 1. 一種膜形成組成物，其爲，利用光照射形成使具有 凹凸的面平坦化之步驟中所使用的平坦化膜用之膜形成組 成物中，其特徵係含有光聚合性物質及光聚合引發劑。 2. 如申請專利範圍第1項之膜形成組成物，其中前述 光聚合性物質爲，至少具有1個可陽離子聚合之反應性基 的光聚合性化合物，前述光聚合引發劑爲光陽離子聚合引 發劑。 3·如申請專利範圍第1項之膜形成組成物，其中前述 光聚合性物質爲，至少具有1個可自由基聚合之反應性基 的光聚合性化合物，前述光聚合引發劑爲光自由基聚合引 發劑。 4 ·如申請專利範圍第2或3項之膜形成組成物，其中前 述光聚合性化合物爲糖化合物。 5.如申請專利範圍第4項之膜形成組成物，其中前述 糖化合物爲式（1 ): [化1] (R1-cn「。- (CH2)n 卜 G1*^-(CH2)n-0-(T)L—R2) (式中， G1爲糖骨架， T爲2價連結基， R1爲乙烯基或縮水甘油基， -44- 200944944 R2爲氫原子或羥基， η及L各自獨立爲〇或1之整數， Ρ爲糖所具有之羥基總數的整數，及 m爲符合ISmS (p—m)之整數）所表示的化合物。 6. 如申請專利範圍第4或5項之膜形成組成物，其中前 述糖化合物爲單糖類或雙糖類化合物。 7. 如申請專利範圍第2項之膜形成組成物，其中前述 0 光聚合性化合物爲脂環式環氧化合物，或脂環式氧雜環丁 烷化合物。 8 ·如申請專利範圍第7項之膜形成組成物，其中前述 脂環式環氧化合物爲環環氧化物衍生物。 9.如申請專利範圍第8項之膜形成組成物，其中前述 脂環式環氧化合物爲式（2)或式（3): [化2]200944944 VII. Patent application range: 1. A film-forming composition which is formed into a film for forming a flattening film used in a step of flattening a surface having irregularities by light irradiation, and is characterized in that it contains Photopolymerizable substance and photopolymerization initiator. 2. The film-forming composition according to claim 1, wherein the photopolymerizable substance is a photopolymerizable compound having at least one cationically polymerizable reactive group, and the photopolymerization initiator is photocationic polymerization-initiated Agent. 3. The film-forming composition according to claim 1, wherein the photopolymerizable substance is a photopolymerizable compound having at least one radically polymerizable reactive group, and the photopolymerization initiator is a photoradical. Polymerization initiator. 4. The film-forming composition according to claim 2, wherein the photopolymerizable compound is a sugar compound. 5. The film-forming composition of claim 4, wherein the sugar compound is of the formula (1): [Chem. 1] (R1-cn ".-(CH2)n Bu G1*^-(CH2)n- 0-(T)L—R2) (wherein G1 is a sugar skeleton, T is a divalent linking group, R1 is a vinyl group or a glycidyl group, and -44-200944944 R2 is a hydrogen atom or a hydroxyl group, and η and L are each independently An integer represented by 〇 or 1 , Ρ is an integer of the total number of hydroxyl groups of the sugar, and m is a compound represented by an integer of ISmS (p-m). 6. Film formation as in claim 4 or 5 The composition, wherein the saccharide compound is a monosaccharide or a disaccharide compound. 7. The film-forming composition according to claim 2, wherein the photopolymerizable compound is an alicyclic epoxy compound or an alicyclic oxygen compound. A film-forming composition according to claim 7, wherein the alicyclic epoxy compound is a cyclic epoxide derivative. 9. The film forming composition of claim 8 And the aforementioned alicyclic epoxy compound is of the formula (2) or the formula (3): [Chemical 2] (式中， G2爲伸烷基、羰基氧基、雜環基或芳香環基，或此等組合 形成的1價至5價之連結基， -45 - 200944944 G3爲烷基、烷基羰基、雜環基或芳香環基，或此等組合形 成的有機基， η及m各自獨立爲1至5之整數）所表示的化合物。 1〇·如申請專利範圍第1或9項中任何1項之膜形成組成 物，其爲形成製造半導體、發光二極管、固體攝影元件， 或液晶顯示器用之平坦化膜用。 11. 一種平坦化膜形成方法，其特徵爲包含，將如申 請專利範圍第1至1 〇項中任何1項之膜形成組成物塗佈於基 Q 體上形成塗佈膜的步驟，及利用光照射前述塗佈膜而硬化 之步驟。 12. —種平坦化膜形成方法，其特徵爲包含，於基體 上形成永久膜之步驟，及將如申請專利範圍第1至1 0項中 任何1項之膜形成組成物塗佈於永久膜上形成塗佈膜的步 驟，及利用光照射前述塗佈膜而硬化之步驟。 1 3 ·如申請專利範圍第U或1 2項之平坦化膜形成方法 ’其中前述光照射係以波長150至700 nm之光線進行。 © 14. 一種電子零件之製造方法，其特徵爲包含，將如 申請專利範圍第1至10項中任何1項之膜形成組成物塗佈於 基體上形成塗佈膜的步驟，及利用光照射前述塗佈膜而硬 化之步驟。 15. —種電子零件之製造方法，其特徵爲包含，於基 體上形成永久膜之步驟，及將如申請專利範圍第1至10項 中任何1項之膜形成組成物塗佈於永久膜上形成塗佈膜的 步驟’及利用光照射前述塗佈膜而硬化之步驟。 -46- 200944944 1 6 .如申請專利範圍第1 1或1 2項之 法，其中前述光照射係以波長150至700 1 7 .如申請專利範圍第1 1至1 3項中fi 的製造方法，其中前述電子零件爲半導 固體攝影元件，或液晶顯示器。 電子零件的製造方 nm之光線進行。 E何1項之電子零件 體、發光二極管、(wherein G2 is an alkylene group, a carbonyloxy group, a heterocyclic group or an aromatic ring group, or a monovalent to pentavalent linking group formed by such a combination, -45 - 200944944 G3 is an alkyl group, an alkylcarbonyl group, A heterocyclic group or an aromatic ring group, or an organic group formed by such a combination, wherein η and m are each independently an integer represented by 1 to 5). The film-forming composition according to any one of the items 1 or 9 of the patent application, which is used for forming a flattening film for producing a semiconductor, a light-emitting diode, a solid-state imaging element, or a liquid crystal display. A method for forming a planarizing film, comprising the step of applying a film-forming composition according to any one of items 1 to 1 of the patent application to a base Q to form a coating film, and utilizing The step of hardening the aforementioned coating film to harden. 12. A method of forming a planarizing film, comprising the steps of: forming a permanent film on a substrate, and applying a film-forming composition according to any one of claims 1 to 10 to a permanent film. The step of forming a coating film thereon and the step of curing by irradiating the coating film with light. 1 3 . The method of forming a planarizing film according to the U or the 12th patent application, wherein the light irradiation is performed by light having a wavelength of 150 to 700 nm. A method of producing an electronic component, comprising the steps of: applying a film-forming composition according to any one of claims 1 to 10 to a substrate to form a coating film, and using light irradiation The step of coating the film to harden. A method of producing an electronic component, comprising the steps of: forming a permanent film on a substrate, and applying a film-forming composition according to any one of claims 1 to 10 to a permanent film. The step of forming a coating film and the step of curing by irradiating the coating film with light. -46-200944944 1 6 . The method of claim 1 or claim 2, wherein the light irradiation is performed at a wavelength of 150 to 700 1 7 , as in the patent application range 1 1 to 13 Wherein the aforementioned electronic component is a semi-conductive solid-state imaging element, or a liquid crystal display. The manufacture of electronic parts is carried out by the light of nm. E? 1 electronic parts, LEDs, -47--47-
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