TW201219408A - Composition for forming alumina film and method for forming alumina film - Google Patents

Composition for forming alumina film and method for forming alumina film Download PDF

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TW201219408A
TW201219408A TW100138102A TW100138102A TW201219408A TW 201219408 A TW201219408 A TW 201219408A TW 100138102 A TW100138102 A TW 100138102A TW 100138102 A TW100138102 A TW 100138102A TW 201219408 A TW201219408 A TW 201219408A
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forming
oxide film
aluminum oxide
aluminum
compound
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TW100138102A
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Kang-Go Chung
Tatsuya Sakai
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Jsr Corp
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    • H—ELECTRICITY
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    • 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
    • H01L21/02172—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 the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides
    • H01L21/02175—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 the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides characterised by the metal
    • H01L21/02178—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 the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides characterised by the metal the material containing aluminium, e.g. Al2O3
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    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
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    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/06—Aluminium compounds
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    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
    • C23C18/1208—Oxides, e.g. ceramics
    • C23C18/1216—Metal oxides
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    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/125—Process of deposition of the inorganic material
    • C23C18/1279—Process of deposition of the inorganic material performed under reactive atmosphere, e.g. oxidising or reducing atmospheres
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/14—Decomposition by irradiation, e.g. photolysis, particle radiation or by mixed irradiation sources
    • C23C18/143—Radiation by light, e.g. photolysis or pyrolysis
    • H—ELECTRICITY
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    • 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
    • H01L21/02337—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 a gas or vapour
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
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    • 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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Abstract

Provided are: a composition for forming an alumina film, which enables sufficient oxidation of aluminum even in cases where the film is thick; and a method for forming an alumina film, which uses the composition. The composition for forming an alumina film contains an aluminum compound that has a monovalent organic group having 1-12 carbon atoms and an organic solvent. The method for forming an alumina film comprises: a step wherein a composition for forming an alumina film, said composition containing an aluminum compound that has a monovalent organic group having 1-12 carbon atoms and an organic solvent, is applied over a base so that a coating film is formed thereon; and a step wherein the coating film is heated and/or irradiated with light in the presence of an oxidizing gas.

Description

201219408 六、發明說明： 【發明所屬之技術領域】 本發明係關於氧化鋁膜形成用組成物及氧化鋁膜形成 方法。 【先前技術】 DRAM (動態存取記憶體）爲代表的半導體裝置中， 氧化鋁因其高絕緣性與緻密性多被用作爲保護膜或絕緣膜 。氧化鋁的形成方法目前廣用濺鍍法（以氧化鋁爲標靶的 RF磁控濺鏟法、或以鋁爲標靶、與氧氣體共存之反應性濺 鍍法）、化學蒸鍍法（以氯化鋁乃至有機鋁化合物與水爲 原料氣體的手法）。 然而，此等使用濺鍍法或化學蒸鏟法的氧化鋁薄膜形 成方法有需要真空腔室或高壓電流裝置等高價裝置且高成 本、及難以適用大口徑基體的問題。進一步，對於近來半 導體裝置之微細化，在狹溝渠基體上進行氧化鋁成膜時， 產生膜中產生缺陷或階梯覆蓋性降低等問題。 另一方面，在專利文獻1，作爲形成氧化鋁膜之方法 記載使用胺化合物與氫化鋁化合物之錯合物。 〔先前技術文獻〕 〔專利文獻〕 [專利文獻1]特開2007-2S 782 1號公報 【發明內容】 -5- 201219408 〔發明所欲解決課題〕 然而’在專利文獻1所記載的方法，膜厚小之場合（ 例如膜厚爲150nm左右的場合）並無問題，但膜厚大的場 合（例如膜厚爲20 Onm以上之場合），鋁的氧化無法充分 進行至膜之內部，有膜全體以目的的氧化鋁構成困難的問 題。 本發明係有鑑於上述情況而成者，其目的在於提供即 使在膜厚厚之場合，可充分進行鋁之氧化的氧化鋁膜形成 方法。 〔解決課題之手段〕 爲了達成上述目的，本發明者們進行努力硏究，發現 藉由使用含特定鋁化合物之氧化鋁膜形成用組成物，可達 成前述目的，完成本發明。 亦即，本發明提供以下[1]〜[8]。 [1] 含有具有碳數1〜12之1價有機基的鋁化合物及有機 溶劑的氧化鋁膜形成用組成物。 [2] 前述鋁化合物爲由下述式（i_i)所表示的化合物 、下述式（1-2)所表不的化合物、下述式（]-3)所表示 的化合物、含下述式（1-4)所表示的構造單元之化合物 、及含有下述式（1-5)所表示的構造單元之化合物所選 出之至少一種的前述[1]記載之氧化鋁膜形成用組成物。 A1ZlmRl3-mLn (1 — 1) (上述式（1-1)中，Z1爲氫原子或鹵素原子，R1各自獨 -6- 201219408 立爲碳數1〜12之1價有機基，L爲配位基，m爲0〜2之整數 ，11爲0〜2之整數）。 【化1】[Technical Field] The present invention relates to a composition for forming an aluminum oxide film and a method for forming an aluminum oxide film. [Prior Art] In a semiconductor device represented by a DRAM (Dynamic Access Memory), alumina is used as a protective film or an insulating film because of its high insulating property and compactness. Alumina formation methods are currently widely used by sputtering (RF magnetron sputtering method with alumina as the target, or reactive sputtering with aluminum as a target and coexistence with oxygen gas), and chemical vapor deposition ( A method of using aluminum chloride or even an organoaluminum compound and water as a raw material gas). However, such an alumina film forming method using a sputtering method or a chemical shovel method has a problem of requiring a high-priced device such as a vacuum chamber or a high-voltage current device, high cost, and difficulty in application of a large-diameter substrate. Further, in the case of recent miniaturization of semiconductor devices, when aluminum oxide is formed on a narrow trench substrate, problems such as defects in the film and a decrease in step coverage are caused. On the other hand, Patent Document 1 describes a method of forming an aluminum oxide film using a complex of an amine compound and an aluminum hydride compound. [PRIOR ART DOCUMENT] [Patent Document 1] JP-A-2007-2S 782 1 SUMMARY OF THE INVENTION - 5 - 201219408 [Problems to be Solved by the Invention] However, the method described in Patent Document 1 is a film. When the thickness is small (for example, when the film thickness is about 150 nm), there is no problem. However, when the film thickness is large (for example, when the film thickness is 20 nm or more), the oxidation of aluminum cannot be sufficiently performed inside the film. The purpose of the alumina constitutes a difficult problem. The present invention has been made in view of the above circumstances, and an object thereof is to provide a method for forming an aluminum oxide film which can sufficiently perform oxidation of aluminum even when the film thickness is thick. [Means for Solving the Problem] In order to achieve the above object, the present inventors have made an effort to achieve the above object by using a composition for forming an aluminum oxide film containing a specific aluminum compound. That is, the present invention provides the following [1] to [8]. [1] A composition for forming an aluminum oxide film containing an aluminum compound having a monovalent organic group having 1 to 12 carbon atoms and an organic solvent. [2] The aluminum compound is a compound represented by the following formula (i-i), a compound represented by the following formula (1-2), a compound represented by the following formula (]-3), and the following formula; (1-4) A composition for forming an aluminum oxide film according to the above [1], which is a compound of the structural unit and a compound containing a structural unit represented by the following formula (1-5). A1ZlmRl3-mLn (1 - 1) (In the above formula (1-1), Z1 is a hydrogen atom or a halogen atom, and R1 is independently a -6-201219408, and is a monovalent organic group having a carbon number of 1 to 12, and L is a coordination group. Base, m is an integer from 0 to 2, and 11 is an integer from 0 to 2.) 【化1】

(上述式（1-2)中，R2各自獨立，爲氫原子、鹵素原子 或碳數1〜12之1價有機基，R3各自獨立，爲碳數1〜12之1 價有機基）。 【化2】 (1-3) R4 Z2 R4 (上述式（I-3)中，R4各自獨立爲碳數1〜12之1價有機 基，Ζ2爲氫原子或鹵素原子）。 【化3】 严5 R6 R6 c I I , (1-4) R5 K R5 (上述式（1-4)中，R5及R6各自獨立，爲碳數1〜12之1 201219408 價有機基）。 【化4】 R7 —^-Al-〇-jf— (1-5) (上述式（1-5)中，R7各自獨立，爲碳數1〜12之1價有 機基）。 [3] 前述氧化鋁膜形成用組成物含有鈦化合物的前述 [1]或[2]記載之氧化鋁膜形成用組成物。 [4] 以含下述（a)及（b)之步驟爲特徵的氧化鋁膜形 成方法。 (a) 在基體上塗佈含有具有碳數1〜12之1價有機基 的鋁化合物及有機溶劑的氧化鋁膜形成用組成物，形成塗 膜之步驟 (b) 在氧化性氣體存在下、對前述塗膜進行選自加 熱及光照射之至少一種處理，形成氧化鋁膜之步驟 [5] 前述鋁化合物爲下述式（1-1)所表示的化合物的 前述[4]記載之氧化鋁膜形成方法。 A 1 Z1mR13_mLn (1-1) (上述式（1-1)中，Z1爲氫原子或鹵素原子，R1各自獨 立爲碳數1〜12之1價有機基，L爲配位基，m爲0〜2之整數 ，11爲0〜2之整數）。 [6] 前述步驟（b)中氣體中氧化性氣體之濃度爲1〜 -8 - 201219408 100莫耳％的前述[4]或[5]記載之氧化鋁膜形成方法。 [7] 前述氧化性氣體爲水蒸氣、氧或臭氧的前述[4]〜 [6]中任一項記載之氧化鋁膜形成方法。 [8] 以使在前述步驟（b)的前述氧化鋁膜具有200nm 以上之膜厚的方式在前述步驟（a)塗佈氧化鋁膜形成用 組成物的前述[4]〜[7]中任一項記載之氧化鋁膜形成方法 〔發明效果〕 根據本發明之氧化鋁膜形成方法，即使在膜厚厚之場 合’可形成至膜內部爲止充分氧化的氧化鋁膜。 又’本發明的氧化鋁膜形成方法因由塗佈等之簡便步 驟所構成，可容易實施。 又’本發明的氧化鋁膜形成方法亦可易於適用大的基 體’又，可達成成本低廉化。 進一步，藉由利用液體原料之浸透力，亦可期待在狹 溝渠基體上有良好成膜。 〔實施發明之最佳形態〕 本發明的氧化鋁膜形成用組成物爲含有具有碳數1〜 12之1價有機基的鋁化合物及有機溶劑。 具有碳數1〜12之1價有機基的鋁化合物，可舉例如具 有一個鋁原子的單核化合物、具有二個以上鋁原子的複核 化合物等。 -9 - 201219408 具有碳數1〜12之I價有機基的鋁化合物，^ 述式（1-1)所表示的化合物、下述式（1_2)戶 PJ物、下述式（1-3)所表示的化合物、含下述 所表示的構造單元的化合物、及含有下述式（ 示的構造單元之化合物，尤以下述式序 合物爲佳。 A1 Z1mRS_mLn (i-i) (上述式（1-1)中，Ζι爲氫原子或鹵素原子， ϋ爲碳數1〜12之1價有機基，l爲配位基，m爲0 ’ η爲0〜2之整數）。 ϊ舉例如下 ΐ表示的化 式（1-4 ) 1-5 )所表 :表示的化 R1各自獨 〜2之整數 【化5】(In the above formula (1-2), R2 is independently a hydrogen atom, a halogen atom or a monovalent organic group having 1 to 12 carbon atoms, and R3 is independently a monovalent organic group having 1 to 12 carbon atoms). (1-3) R4 Z2 R4 (In the above formula (I-3), R4 is each independently a monovalent organic group having 1 to 12 carbon atoms, and ruthenium 2 is a hydrogen atom or a halogen atom). [Chemical 3] Strict 5 R6 R6 c I I , (1-4) R5 K R5 (In the above formula (1-4), R5 and R6 are each independently, and are a carbon number of 1 to 12, and a 201219408 organic group). R7 —^-Al-〇-jf—(1-5) (In the above formula (1-5), R7 is independently and is a monovalent organic group having a carbon number of 1 to 12). [3] The composition for forming an aluminum oxide film according to the above [1] or [2], wherein the composition for forming an aluminum oxide film contains a titanium compound. [4] A method for forming an aluminum oxide film characterized by the steps (a) and (b) below. (a) a step of forming a coating film by coating an aluminum oxide film-forming composition containing an aluminum compound having a monovalent organic group having 1 to 12 carbon atoms and an organic solvent on a substrate, in the presence of an oxidizing gas, The coating film is subjected to at least one treatment selected from the group consisting of heating and light irradiation to form an aluminum oxide film. [5] The aluminum compound is an aluminum oxide according to the above [4], which is a compound represented by the following formula (1-1). Membrane forming method. A 1 Z1mR13_mLn (1-1) (In the above formula (1-1), Z1 is a hydrogen atom or a halogen atom, and R1 is independently a monovalent organic group having a carbon number of 1 to 12, L is a ligand, and m is 0. An integer of ~2, 11 is an integer from 0 to 2). [6] The method for forming an aluminum oxide film according to the above [4] or [5], wherein the concentration of the oxidizing gas in the gas in the step (b) is 1 to -8 - 201219408 100 mol%. [7] The method for forming an aluminum oxide film according to any one of the above [4] to [6], wherein the oxidizing gas is water vapor, oxygen or ozone. [8] In the above [4] to [7] in which the aluminum oxide film-forming composition is coated in the step (a), the aluminum oxide film of the above step (b) has a film thickness of 200 nm or more. A method for forming an aluminum oxide film according to the present invention. According to the method for forming an aluminum oxide film of the present invention, even when the film thickness is thick, an aluminum oxide film which is sufficiently oxidized to the inside of the film can be formed. Further, the method for forming an aluminum oxide film of the present invention can be easily carried out by a simple step of coating or the like. Further, the method for forming an aluminum oxide film of the present invention can be easily applied to a large substrate, and the cost can be reduced. Further, by utilizing the penetration force of the liquid raw material, it is also expected to have a good film formation on the narrow trench substrate. [Best Mode for Carrying Out the Invention] The composition for forming an aluminum oxide film of the present invention is an aluminum compound containing an organic group having a monovalent number of carbon atoms of 1 to 12 and an organic solvent. The aluminum compound having a monovalent organic group having 1 to 12 carbon atoms may, for example, be a mononuclear compound having one aluminum atom, a compound having two or more aluminum atoms, or the like. -9 - 201219408 An aluminum compound having an I-valent organic group having 1 to 12 carbon atoms, a compound represented by the formula (1-1), a PJ compound of the following formula (1_2), and the following formula (1-3) The compound to be represented, the compound containing the structural unit represented below, and the compound containing the structural unit represented by the following formula are preferably the following formula: A1 Z1mRS_mLn (ii) (The above formula (1- 1), Ζι is a hydrogen atom or a halogen atom, ϋ is a monovalent organic group having a carbon number of 1 to 12, and l is a ligand, and m is 0' η is an integer of 0 to 2). Formula (1-4) 1-5) Table: The integers represented by R1 are each unique to 2 [5]

(上述式（I-2)中，R2各自獨立，爲氫原子、 或碳數1〜12之1價有機基，R3各自獨立，爲碳婁 價有機基）。 鹵素原子 1〜1 2之1(In the above formula (I-2), R2 is independently a hydrogen atom or a monovalent organic group having 1 to 12 carbon atoms, and R3 is independently a carbon valent organic group). Halogen atom 1~1 2 of 1

【化6】 R\ /Z\ /R4，丨、，丨c R4 、Z2 V (1-3) (上述式（1-3)中’ R4各自獨立爲碳數1〜12 基，Z2爲氫原子或鹵素原子）。 1價有機 -10- 201219408 【化7】 R6 R6 5 I I c (1-4) R5—AL ,AI—R5[Chemical 6] R\ /Z\ /R4,丨,,丨c R4 , Z2 V (1-3) (In the above formula (1-3), 'R4 is independently a carbon number of 1 to 12, and Z2 is hydrogen. Atom or halogen atom). 1 price organic -10- 201219408 【化7】 R6 R6 5 I I c (1-4) R5—AL , AI—R5

R5 R6 V (上述式（1-4)中’ R5及R6各自獨立，爲碳數i〜12之1 價有機基）。 【化8】 R7 十A卜〇十 (1-5) (上述式（1-5)中，R7各自獨立，爲碳數i〜12之1價有 機基）。 前述鹵素原子，可舉例如氟原子、氯原子、溴原子、 碘原子等。 前述碳數1〜1 2之1價有機基，可舉例如碳數1〜1 2之1 價烴基、碳數1〜1 2之1價鹵化烴基、含氧原子的碳數1〜 1 2之1價烴基、以及含氧原子的碳數1〜1 2之1價鹵化烴基 等。 碳數1〜1 2之1價烴基，可舉例如碳數1〜1 2之直鏈或 分支鏈的烴基、碳數3〜12之脂環式烴基及碳數6〜12之芳 香族烴基等= 碳數1〜12之直鏈或分支鏈的烴基以碳數1〜8的直鍵 -11 - 201219408 或分支鏈的烴基爲佳、碳數1〜5的直鏈或分支鏈的烴基更 佳。 直鏈或分支鏈的烴基的較佳具體例，可舉例如甲基、 乙基、η-丙基、異丙基、η-丁基、sec-丁基、tert-丁基、 η-戊基、η-己基及η-庚基等。 碳數3〜12之脂環式烴基以碳數3〜8的脂環式烴基爲 佳、碳數3或4的脂環式烴基更佳。 碳數3〜1 2之脂環式烴基的較佳具體例，可舉例如環 丙基、環丁基、環戊基及環己基等之環烷基；環丁烯基、 環戊烯基及環己烯基等之環烯基。該脂環式烴基之鍵結部 位可爲脂環上任一的碳原子。 碳數6〜12之芳香族烴基，可舉例如苯基、聯苯基及 萘基等。該芳香族烴基之鍵結部位可爲芳香族環上任一的 碳原子。 碳數1〜1 2之1價鹵化烴基，可舉例如上述碳數1〜1 2 之烴基的氫原子之至少一個被鹵素原子取代的基。鹵素原 子，可舉例如氟原子、氯原子、溴原子、碘原子，但以氟 原子、氯原子爲佳。 含氧原子的碳數1〜12之1價烴基，可舉例如具有醚鍵 結、羰基及酯基的碳數1〜1 2之烴基等。 具有醚鍵結之碳數1〜12之烴基’可舉例如碳數1〜12 之烷氧基、碳數2〜12之烯氧基、碳數2〜12之炔氧基、碳 數6〜12之芳氧基及碳數1〜12之烷氧基烷基等。具體上可 舉例如甲氧基、乙氧基、丙氧基、異丙氧基、丁氧基、苯 -12- 201219408 氧基、丙烯氧基、環己氧基及甲氧基甲基等。 又，具有羰基的碳數1〜12之烴基，可舉例如碳數2〜 12之醯基等。具體上可舉例如乙醯基、丙醯基、異丙醯基 及苯甲醯基等。 具有酯基的碳數1〜12之烴基，可舉例如碳數2〜12之 醯氧基等。具體上可舉例如乙醯氧基、丙醯氧基、異丙醯 氧基及苯甲醯氧基等。 含氧原子的碳數1〜12之1價鹵化烴基，可舉例如上述 含氧原子的碳數1〜12之1價烴基的氫原子之至少一個被鹵 素原子取代的基。鹵素原子，可舉例如氟原子、氯原子、 溴原子、碘原子，但以氟原子、氯原子爲佳。 L所表示的配位基，可舉例如胺化合物、卩比陡化合物 、氮雜環化合物、醯胺化合物、腈化合物、膦化合物、硫 化物化合物、醇化合物、醚化合物、酯化合物、磺化合物 等。 式（1 -1 )所表示的鋁化合物之具體例，可舉例如三 甲基鋁、三乙基鋁、三-η-丙基鋁、三環丙基鋁、三-η_τ 基鋁、三異丁基鋁、三-t-丁基鋁、三-2-甲基丁基鋁、三_ η -己基銘、二環己基鋁、三（2 -乙基己基）鋁、三辛基銘 、三（十二基）鋁、三苯基鋁、三苄基鋁、二甲基苯基鋁 、二乙基苯基鋁、二異丁基苯基鋁、甲基二苯基鋁、乙基 二苯基鋁、異丁基二苯基鋁、三甲氧基鋁、三乙氧基鋁、 三η-两氧基鋁、三異丙氧基鋁、三心丁氧基鋁、三sec-丁 氧基鋁、三tert-丁氧基鋁、二乙基鋁氫化物、二異丁基鋁 -13- 201219408 氫化物、二苯基鋁氫化物、二甲基甲基丙烯鋁、二甲基（ 苯基乙炔基）鋁、二苯基（苯基乙炔基）鋁、二甲基胺· 二甲基鋁氫化物、二乙基胺•二乙基鋁氫化物、二甲基胺 •二乙基鋁氫化物、二乙基胺•二甲基鋁氫化物、二苯基 胺•二甲基鋁氫化物、二苯基胺•二乙基鋁氫化物、二乙 基鋁氟化物、二異丁基鋁氟化物、二苯基鋁氟化物、二甲 基鋁氟化物、二乙基胺•二乙基鋁氟化物、二甲基胺•二 乙基鋁氟化物、二乙基胺•二甲基鋁氟化物、二苯基胺· 二甲基鋁氟化物、二苯基胺•二乙基鋁氟化物、二乙基鋁 氯化物、二異丁基鋁氯化物、二苯基鋁氯化物、二甲基鋁 氯化物、二乙基胺•二乙基鋁氯化物、二甲基胺·二乙基 鋁氯化物、二乙基胺•二甲基鋁氯化物、二苯基胺•二甲 基鋁氯化物、二苯基胺·二乙基鋁氯化物等。 又，式（1 -2 )所表示的鋁化合物之具體例，可舉例 如 Al2(p-CH3)2(CH3)4、Al2b-C2H5)2(C2H5)4、 Al2(p-C3H7)2(C3H7)4、Al2(p-C4H9)2(C4H9)4、 Al2(p-OCH3)2(CH3)4、Al2(p-OC2H5)2(C2H5)4、 Al2(p-OC3H7)2(C3H7)4、Al2(p-OC4H9)2(C4H9)4、 Al2(p-OCH3)2(OCH3)4、Al2(p-OC2H5)2(OC2H5)4、 Al2(e-OC3H7)2(OC3H7)4、Al2(p-OC4H9)2(OC4H9)4等。 又，式（1 -3 )所表示的鋁化合物之具體例，可舉例 如 Α12(μ-Η)2((：Η3)4、Α12(μ-Η)2((：2Η5)4、Α12(μ-Η)2((：3Η7)4 、Α12(μ-Η)2((：4Η9)4、Al2b-F)2(CH3)4、A12 ( μ - F) 2 (C 2 Η 5) 4 、A12(p-F)2(C3H7)4、A12(p-F)2(C4H9)4、Al2(p-C1)2(CH3)4 -14- 201219408 、Α12(μ-(：1)2((：2Η5)4、Al2h-C1)2(C3H7)4、 \ A12(p-C1)2(C4H9)4 等。 又’具有式（1-4)所表示的構造單元的鋁化合物之 具體例，可舉例如 Α13(μ-〇(：Η3)3((：Η3)6、 Α13(μ-0(：2Η5)3((：2Η5)6、Α13(μ-0(：3Η7)3((：3Η7)6、 Al3(p-OC4H9)3(C4H9)6、A13(p-OCH3)3(〇CH3)6、 Al3(p-OC2H5)3(〇C2H5)6、Al3(p-OC3H7)3(〇C3H7)6、 Al3(p-OC4H9)3(〇C4H9)6 等。 又’具有式（1-5)所表示的構造單元的鋁化合物之 具體例’可舉例如三甲基環三鋁氧烷、三乙基環三鋁氧烷 、三丙基環三鋁氧烷、三丁基環三鋁氧烷、甲基鋁氧烷、 乙基鋁氧烷、丙基鋁氧烷、丁基鋁氧烷等。 又’因應必要，可進而添加具有碳數1〜12之1價有機 基的鋁化合物以外的鋁化合物。添加之鋁化合物雖未特別 限制’具體上可舉例如氫鋁與胺化合物之錯合物等。 本發明的氧化鋁膜形成用組成物所含有的有機溶劑雖 未特別限制，可使用例如烴溶劑、醚溶劑、其他極性溶劑 等。 上述烴溶劑，可舉例如η-戊烷、環戊烷、η-己烷、環 己烷、η-庚烷、環庚烷、η-辛烷、環辛烷、癸烷、環癸烷 、二環戊二烯的氫化物、苯、甲苯、二甲苯、tert-丁基苯 、均四甲苯、茚、四氫萘、十氫萘、海鮫油等。 上述醚溶劑，可舉例如二乙基醚、二丙基醚、二丁基 醚、乙二醇二甲基醚、乙二醇二乙基醚、乙二醇甲基乙基 -15- 201219408 醚、二乙二醇二甲基醚 '二乙二醇二乙基醚、二乙二醇甲 基乙基醚、四氫呋喃、四氫吡喃、雙（2 -甲氧基乙基）醚 、P-二噁烷、苯甲醚、2 -甲基苯甲醚、3 -甲基苯甲醚、4-甲基苯甲醚、酚妥拉明、2-甲基酚妥拉明、3-甲基酚妥拉 明、4 -甲基酚妥拉明、藜蘆醚、2 -乙氧基苯甲醚、1,4 -二 甲氧基苯等。 上述極性溶劑’可舉例如二氯甲烷、氯仿等。 上述有機溶劑可單獨或2種以上混合使用。 此等中’由溶解性、及形成溶液安定性之觀點來看， 以使用烴溶劑或烴溶劑與醚溶劑之混合溶劑爲佳。此時， 作爲烴溶劑’以使用例如η-戊烷、環戊烷、η-己烷、環己 院、η -庚院、環庚院' η -辛院、苯、甲苯、二甲苯、或 tert-丁基苯爲佳，醚溶劑方面，以使用例如二乙基醚、二 丙基醚、二丁基醚、乙二醇二乙基醚、乙二醇甲基乙基醚 、四氫呋喃、四氫吡喃、苯甲醚、2 -甲基苯甲醚、3 -甲基 苯甲醚、4-甲基苯甲醚、酚妥拉明、藜蘆醚' 2-乙氧基苯 甲醚、I，4-二甲氧基苯爲佳。 本發明的氧化鋁膜形成用組成物含有鋁化合物及有機 溶劑作爲必須成分，此外因應需要，亦可含鈦化合物。 上述鈦化合物，可舉例如下述式（2 )所表示的化合 物、下述式（3)所表示的化合物、下述式（4)所表示的 化合物、下述式（5)所表示的化合物、及下述式（6)所 表示的化合物。 T i (OR14) 4 - . . (2) -16- 201219408 (上述式（2)中，R14爲碳數1〜10之院基、苯基、鹵化 烷基或鹵化苯基）。 T i (OR15) XZ4_X . . · (3) (上述式（3 )中，R15與上述式（2 )的R14相同，Z爲下 述式（7)所表示的基，R9及Rie可相同或相異’爲碳數1 〜10之烷基、苯基、烷氧基、鹵化烷基、或鹵化苯基，X 爲0〜3之整數）。 【化9】R5 R6 V (in the above formula (1-4), R5 and R6 are each independently a monovalent organic group having a carbon number of i to 12). [Chemical 8] R7 Ten A 〇 〇 ( (1-5) (In the above formula (1-5), R7 is independent of each other, and has a base of a carbon number i to 12). The halogen atom may, for example, be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. The monovalent organic group having 1 to 12 carbon atoms may, for example, be a monovalent hydrocarbon group having 1 to 12 carbon atoms, a monovalent halogenated hydrocarbon group having 1 to 12 carbon atoms, or a carbon number of 1 to 12 containing an oxygen atom. A monovalent hydrocarbon group and a monovalent halogenated hydrocarbon group having 1 to 12 carbon atoms and containing an oxygen atom. Examples of the monovalent hydrocarbon group having 1 to 12 carbon atoms include a linear or branched hydrocarbon group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 12 carbon atoms, and an aromatic hydrocarbon group having 6 to 12 carbon atoms. = a linear or branched hydrocarbon group having a carbon number of 1 to 12 is preferably a linear bond of from 1 to 8 carbon atoms, a hydrocarbon group having a branched chain, and a linear or branched hydrocarbon group having a carbon number of from 1 to 5. . Preferred examples of the linear or branched hydrocarbon group include, for example, methyl, ethyl, η-propyl, isopropyl, η-butyl, sec-butyl, tert-butyl, η-pentyl. , η-hexyl and η-heptyl, and the like. The alicyclic hydrocarbon group having 3 to 12 carbon atoms is more preferably an alicyclic hydrocarbon group having 3 to 8 carbon atoms and an alicyclic hydrocarbon group having 3 or 4 carbon atoms. Preferable examples of the alicyclic hydrocarbon group having 3 to 12 carbon atoms include a cycloalkyl group such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group and a cyclohexyl group; a cyclobutenyl group; a cyclopentenyl group; A cycloalkenyl group such as cyclohexenyl. The bonding moiety of the alicyclic hydrocarbon group may be any carbon atom on the alicyclic ring. Examples of the aromatic hydrocarbon group having 6 to 12 carbon atoms include a phenyl group, a biphenyl group, and a naphthyl group. The bonding site of the aromatic hydrocarbon group may be any carbon atom on the aromatic ring. The monovalent halogenated hydrocarbon group having 1 to 12 carbon atoms may, for example, be a group in which at least one of the hydrogen atoms of the hydrocarbon group having 1 to 12 carbon atoms is substituted with a halogen atom. The halogen atom may, for example, be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, but a fluorine atom or a chlorine atom is preferred. The monovalent hydrocarbon group having 1 to 12 carbon atoms of the oxygen atom may, for example, be a hydrocarbon group having 1 to 12 carbon atoms having an ether bond, a carbonyl group or an ester group. The hydrocarbon group having an ether bond of 1 to 12 carbon atoms may, for example, be an alkoxy group having 1 to 12 carbon atoms, an alkenyloxy group having 2 to 12 carbon atoms, an alkoxy group having 2 to 12 carbon atoms, or a carbon number of 6 to 12 An aryloxy group of 12 and an alkoxyalkyl group having 1 to 12 carbon atoms. Specifically, for example, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a benzene-12-201219408 oxy group, a propyleneoxy group, a cyclohexyloxy group, a methoxymethyl group and the like can be given. Further, the hydrocarbon group having a carbon number of 1 to 12 having a carbonyl group may, for example, be a fluorenyl group having 2 to 12 carbon atoms. Specific examples thereof include an ethyl group, a propyl group, an isopropyl group, and a benzamidine group. The hydrocarbon group having 1 to 12 carbon atoms having an ester group may, for example, be a decyloxy group having 2 to 12 carbon atoms. Specific examples thereof include an ethenyloxy group, a propenyloxy group, an isopropoxycarbonyl group, and a benzamidineoxy group. The monovalent halogenated hydrocarbon group having 1 to 12 carbon atoms of the oxygen atom is, for example, a group in which at least one of the hydrogen atoms of the monovalent hydrocarbon group having 1 to 12 carbon atoms of the oxygen atom is substituted with a halogen atom. The halogen atom may, for example, be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, but a fluorine atom or a chlorine atom is preferred. Examples of the ligand represented by L include an amine compound, a ruthenium compound, a nitrogen heterocyclic compound, a guanamine compound, a nitrile compound, a phosphine compound, a sulfide compound, an alcohol compound, an ether compound, an ester compound, a sulfonic compound, and the like. . Specific examples of the aluminum compound represented by the formula (1-1) include, for example, trimethyl aluminum, triethyl aluminum, tri-η-propyl aluminum, tricyclopropyl aluminum, tri-η_τ based aluminum, and triiso Butyl aluminum, tri-t-butyl aluminum, tri-2-methylbutyl aluminum, tri-n-hexylamine, dicyclohexyl aluminum, tris(2-ethylhexyl)aluminum, trioctylamine, three (ten Di-based) aluminum, triphenyl aluminum, tribenzyl aluminum, dimethylphenyl aluminum, diethyl phenyl aluminum, diisobutyl phenyl aluminum, methyl diphenyl aluminum, ethyl diphenyl aluminum , isobutyldiphenylaluminum, trimethoxyaluminum, triethoxyaluminum, tris-n-oxyaluminum, triisopropoxyaluminum, tri-n-butoxyaluminum, tris-butoxyaluminum, Triter-butoxyaluminum, diethylaluminum hydride, diisobutylaluminum-13- 201219408 hydride, diphenylaluminum hydride, dimethyl methacrylate, dimethyl (phenylethynyl) Aluminum, diphenyl(phenylethynyl)aluminum, dimethylamine·dimethylaluminum hydride, diethylamine•diethylaluminum hydride, dimethylamine•diethylaluminum hydride, Diethylamine•dimethylaluminum hydride, diphenylamine•dimethyl Aluminum hydride, diphenylamine•diethylaluminum hydride, diethylaluminum fluoride, diisobutylaluminum fluoride, diphenylaluminum fluoride, dimethylaluminum fluoride,diethylamine Diethylaluminum fluoride, dimethylamine•diethylaluminum fluoride, diethylamine•dimethylaluminum fluoride, diphenylamine·dimethylaluminum fluoride, diphenylamine•diethyl Aluminium fluoride, diethyl aluminum chloride, diisobutyl aluminum chloride, diphenyl aluminum chloride, dimethyl aluminum chloride, diethylamine, diethyl aluminum chloride, dimethylamine • diethylaluminum chloride, diethylamine•dimethylaluminum chloride, diphenylamine•dimethylaluminum chloride, diphenylamine·diethylaluminum chloride, and the like. Further, specific examples of the aluminum compound represented by the formula (1-2) include, for example, Al2(p-CH3)2(CH3)4, Al2b-C2H5)2(C2H5)4, and Al2(p-C3H7)2 ( C3H7)4, Al2(p-C4H9)2(C4H9)4, Al2(p-OCH3)2(CH3)4, Al2(p-OC2H5)2(C2H5)4, Al2(p-OC3H7)2(C3H7) 4. Al2(p-OC4H9)2(C4H9)4, Al2(p-OCH3)2(OCH3)4, Al2(p-OC2H5)2(OC2H5)4, Al2(e-OC3H7)2(OC3H7)4, Al2(p-OC4H9)2(OC4H9)4 and the like. Further, specific examples of the aluminum compound represented by the formula (1-3) include, for example, Α12(μ-Η)2((:Η3)4, Α12(μ-Η)2((:2Η5)4, Α12( Η-Η)2((:3Η7)4, Α12(μ-Η)2((:4Η9)4, Al2b-F)2(CH3)4, A12(μ-F) 2 (C 2 Η 5) 4 , A12(pF)2(C3H7)4, A12(pF)2(C4H9)4, Al2(p-C1)2(CH3)4 -14- 201219408, Α12(μ-(:1)2((:2Η5 4, Al2h-C1)2(C3H7)4, \A12(p-C1)2(C4H9)4, etc. Further, a specific example of the aluminum compound having a structural unit represented by the formula (1-4) can be exemplified Such as Α13 (μ-〇(:Η3)3((:Η3)6, Α13(μ-0(:2Η5)3((:2Η5)6, Α13(μ-0(:3Η7)3((:3Η7) 6. Al3(p-OC4H9)3(C4H9)6, A13(p-OCH3)3(〇CH3)6, Al3(p-OC2H5)3(〇C2H5)6, Al3(p-OC3H7)3(〇C3H7 6. Al3(p-OC4H9)3(〇C4H9)6, etc. Further, a specific example of the aluminum compound having a structural unit represented by the formula (1-5) may, for example, be trimethylcyclotrialuminoxane. Triethylcyclotrialuminoxane, tripropylcyclotrialuminoxane, tributylcyclotrialuminoxane, methylaluminoxane, ethylaluminoxane, propylaluminoxane, butylaluminoxane Etc. And 'in response to the need, can enter An aluminum compound other than the aluminum compound having a monovalent organic group having 1 to 12 carbon atoms is added. The aluminum compound to be added is not particularly limited, and specific examples thereof include a complex of aluminum aluminum and an amine compound, and the like. The organic solvent contained in the film-forming composition is not particularly limited, and for example, a hydrocarbon solvent, an ether solvent, or another polar solvent can be used. Examples of the hydrocarbon solvent include η-pentane, cyclopentane, and η-hexane. Cyclohexane, η-heptane, cycloheptane, η-octane, cyclooctane, decane, cyclodecane, hydride of dicyclopentadiene, benzene, toluene, xylene, tert-butylbenzene And tetramethylbenzene, anthracene, tetrahydronaphthalene, decahydronaphthalene, sea bream oil, etc. The ether solvent may, for example, be diethyl ether, dipropyl ether, dibutyl ether or ethylene glycol dimethyl ether. Ethylene glycol diethyl ether, ethylene glycol methyl ethyl-15- 201219408 ether, diethylene glycol dimethyl ether 'diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, tetrahydrofuran , tetrahydropyran, bis(2-methoxyethyl)ether, P-dioxane, anisole, 2-methylanisole, 3-methylbyl Ether, 4-methylanisole, phentolamine, 2-methyl phentolamine, 3-methyl phentolamine, 4-methyl phentolamine, veratrol, 2-ethoxy Alkylaniline, 1,4-dimethoxybenzene, and the like. The above polar solvent 'is, for example, dichloromethane or chloroform. These organic solvents may be used singly or in combination of two or more kinds. Among these, it is preferred to use a hydrocarbon solvent or a mixed solvent of a hydrocarbon solvent and an ether solvent from the viewpoint of solubility and stability of solution formation. In this case, as a hydrocarbon solvent, for example, η-pentane, cyclopentane, η-hexane, cyclohexan, η-Gengyuan, Gengyuan' η-Xinyuan, benzene, toluene, xylene, or Tert-butylbenzene is preferred, and ether solvent is used, for example, diethyl ether, dipropyl ether, dibutyl ether, ethylene glycol diethyl ether, ethylene glycol methyl ethyl ether, tetrahydrofuran, four Hydropyran, anisole, 2-methylanisole, 3-methylanisole, 4-methylanisole, phentolamine, cucurbitin' 2-ethoxyanisole, I,4-dimethoxybenzene is preferred. The composition for forming an aluminum oxide film of the present invention contains an aluminum compound and an organic solvent as essential components, and may contain a titanium compound if necessary. The titanium compound, for example, a compound represented by the following formula (2), a compound represented by the following formula (3), a compound represented by the following formula (4), or a compound represented by the following formula (5), And a compound represented by the following formula (6). T i (OR14) 4 - . . (2) -16- 201219408 (In the above formula (2), R14 is a group having a carbon number of 1 to 10, a phenyl group, a halogenated alkyl group or a halogenated phenyl group). T i (OR15) XZ4_X . . . (3) (In the above formula (3), R15 is the same as R14 of the above formula (2), Z is a group represented by the following formula (7), and R9 and Rie may be the same or The difference 'is an alkyl group having a carbon number of 1 to 10, a phenyl group, an alkoxy group, a halogenated alkyl group, or a halogenated phenyl group, and X is an integer of 0 to 3). 【化9】

T i (OR16) y (X) 4” . · ·⑷ (上述式（4)中，R16爲烷基或苯基’ X爲鹵素原子，y爲 0〜3之整數）。 T i (NR17) 4 · · · (5) (上述式（5)中，R17爲院基或苯基）。 T i (〇 ρ) η (γ) 4_n . . . (6) (上述式（6)中’ CP爲環戊二烯基，Y爲鹵素原子或烷基 ，η爲1〜4的整數）。 上述式（2 ) 、η-丙基、i-丙基 丙氧基、i-丙氧基 (3)中，R14及R15較佳爲甲基、乙基 n'丁基、t-丁基、甲氧基、乙氧基、n- n-丁氧基、t-丁氧基、己基、環己基 -17- 201219408 、苯氧基、甲基苯氧基、三氟甲基，更佳爲甲基、乙基、 η-丙基、i-丙基、η-丁基、t-丁基、己基、環己基、苯基》 又，上述式（7)中，R9乃至R1Q較佳爲甲基、乙基、η-丙 基、i-丙基、η-丁基、t-丁基、甲氧基、乙氧基、η-丙氧基 、i-丙氧基、η-丁氧基、t-丁氧基、苯氧基、甲基苯氧基 、三氟甲基。尤佳爲甲基、乙基、i-丙基、t-丁基、甲氧 基、乙氧基、i-丙氧基、t-丁氧基、三氟甲基。 上述式（2 )所表示的鈦化合物之具體例，可舉例如 鈦甲氧化物、鈦乙氧化物、鈦-η-丙氧化物、鈦-η-壬氧化 物、鈦硬脂醯氧化物、鈦異丙氧化物、鈦-η-丁氧化物、鈦 異丁氧化物、鈦-t- 丁氧化物、鈦三甲基矽氧化物（ Siloxide )、鈦-2-乙基六氧化物、鈦甲氧基丙氧化物、鈦 苯氧化物、鈦甲基苯氧化物、鈦氟甲氧化物及鈦氯苯氧化 物等。 上述式（3 )所表示的鈦化合物之具體例，可舉例如 肆（戊-2，4-二酮）鈦、肆（2，2,6，6-四甲基庚-3,5-二酮） 鈦、肆（1-乙氧基丁 -1,3-二酮）鈦、肆（1，1，1，5,5,5-六氟 戊-2,4-二酮）鈦、（2,2-二甲基己-3,5-二酮）鈦 '雙（ 戊-2,4-二酮）鈦二甲氧化物、雙（2,2,6,6-四甲基庚_3,5_ 二酮）鈦二甲氧化物、雙（1-乙氧基丁 -1,3-二酮）欽二甲 氧化物、雙（1，1，1，5,5,5-六氟戊-2,4-二酮）鈦二甲氧化物 、（2,2-二甲基己-3,5-二酮）鈦二甲氧化物、雙（戊_2,4_ 二酮）鈦二i-丙氧化物、雙（2,2,6,6-四甲基庚-3,5_二酮） 鈦二i-丙氧化物、雙（丨-乙氧基丁-丨，3_二酮）鈦二丙氧 -18- 201219408 化物、雙（1，1，1，5,5,5-六氟戊-2,4-二酮）鈦二丨-丙氧化物 、（2,2-二甲基己- 3,5-二酮）鈦二i-丙氧化物等。 上述式（4 )所表示的鈦化合物之具體例，可舉例如 三甲氧基鈦氯化物、三乙氧基鈦氯化物、三-η-丙氧基鈦氯 化物、三-i-丙氧基鈦氯化物、三-η-丁氧基鈦氯化物、三_ t-丁氧基鈦氯化物、三異硬脂醯基鈦氯化物、二甲氧基鈦 二氯化物、二乙氧基鈦二氯化物、二- η-丙氧基鈦二氯化物 、二-i -丙氧基鈦二氯化物、二-η -丁氧基駄二氯化物、二-t-丁氧基鈦二氯化物、二異硬脂醯基鈦二氯化物、甲氧基 鈦三氯化物、乙氧基鈦三氯化物、η-丙氧基鈦三氯化物、 i -丙氧基鈦三氯化物、η- 丁氧基鈦三氯化物、t- 丁氧基鈦 三氯化物、異硬脂醯基鈦三氯化物、鈦四氯化物等。 上述式（5 )所表示的鈦化合物之具體例，可舉例如 肆（二甲基胺基）鈦、肆（二乙基胺基）鈦、肆（二-t-丁 氧基胺基）鈦、肆（二-i-丙氧基胺基）鈦、肆（二苯基胺 基）鈦。 上述式（6 )所表示的鈦化合物之具體例，可舉例如 二環戊二烯基鈦二氯化物、二環戊二烯基鈦二溴化物、環 戊二烯基鈦三氯化物、環戊二烯基鈦三溴化物、二環戊二 烯基二甲基鈦、二環戊二烯基二乙基鈦、二環戊二烯基 二-t-丁基鈦、二環戊二烯基苯基鈦氯化物、二環戊二烯基 甲基鈦氯化物等。 本發明的氧化鋁膜形成用組成物中的鋁化合物之質量 比例可因應欲成膜之氧化鋁的膜厚而適宜設定，而以5〜 -19- 201219408 90質量％爲佳、10〜85質量％更佳、20〜80質量％又更佳、 30〜70質量％特別佳。 本發明的氧化鋁膜形成用組成物含有鈦化合物之場合 ，鈦化合物之濃度相對鋁化合物及鈦化合物之合計，較佳 爲1莫耳％以下，更較佳爲0.00001〜1莫耳％、又更佳爲 0.00005〜0.01莫耳％。藉由鈦化合物在此範圍之含量，可 兼具良好埋入性與組成物之安定性。 本發明的氧化鋁膜形成用組成物中的鋁化合物含有具 有碳數1〜12之1價有機基的鋁化合物以外的鋁化合物之場 合，其濃度相對組成物之全體而言，較佳爲40質量％以下 ，更佳爲20質量％以下。 本發明的氧化鋁膜形成用組成物，其製造方法未特別 限定。例如使上述鋁化合物在溶劑存在下合成後，可將使 副產物等之不溶物以過濾器等除去的溶液直接用作爲氧化 鋁膜形成用組成物。或，亦可在該溶液加入所期望之溶劑 後，藉由將反應所使用的溶劑、例如二乙基醚在減壓下除 去，做成氧化鋁膜形成用組成物。 本發明的氧化鋁膜形成用組成物爲含有鈦化合物者之 場合，在其製造上，例如可於含上述般製造的鋁化合物之 溶液，邊攪拌邊添加特定量的含鈦化合物之溶液以進行調 製。添加時的溫度較佳爲0〜150°C、更佳爲5〜100°C。攪 拌時間，較佳爲0.1〜120分、更較佳爲0.2〜60分。藉由在 如此條件下混合，可得到安定的氧化鋁膜形成組成物。 接著，說明關於本發明的氧化鋁膜形成方法。本發明 -20- 201219408 的氧化鋁膜形成方法之特徵係含有下述（a)及（b)之步 驟。 (a)在基體上塗佈含有具有碳數ι〜12之1價有機基 的鋁化合物及有機溶劑的氧化鋁膜形成用組成物，形成塗 膜之步驟 (b )氧化性氣體的存在下、對塗膜進行選自加熱及 光照射之至少一種處理，形成氧化鋁膜之步驟 以下、說明各步驟。 <步驟（a ) > 本發明中，構成基體本體的材質雖無特別限制，但以 可耐受次步驟的熱處理者爲佳。又，基體本體的形狀並無 特別制限，可爲例如上面爲平面或有段差的非平面。 基體本體的材質之具體例，可舉例如玻璃、金屬、塑 膠、陶瓷等。玻璃，可舉例如石英玻璃、硼矽酸玻璃、鈉 鈣玻璃、鉛玻璃等。金屬，可舉例如金、銀、銅、鎳、矽 、鋁、鐵、不鏽鋼等。塑膠，可舉例如聚醯亞胺、聚醚颯 等。 基體本體的形狀之具體例，可舉例如塊狀形狀、板狀 、薄膜形狀等。 本發明使用的基體，例如爲在基體本體的表面形成底 層膜而成者。如此的基體，例如在基體本體具有含有由鋁 、鈦、銅、鈷、釕、鉬、鎢、鋁、鎳、鈀、及金選出之至 少一種金屬原子的底層膜於表面而成。因該底層膜，氧化 -21 - 201219408 鋁膜的成膜性變佳。 作爲在基體本體形成底層膜的方法雖未特別限制，例 如可使用旋轉塗佈法、輥塗佈法、淋幕塗佈法、浸漬塗佈 法、噴霧塗佈法、液滴吐出法等之塗佈法、CVD法、PVD 法、濺鍍法等之各種成膜方法。 又，基體本體的材質之具體例，可舉例如玻璃、塑膠 、陶瓷、矽基板等。玻璃，可使用石英玻璃、硼矽酸玻璃 、鈉鈣玻璃、鉛玻璃。塑膠，可舉例如聚醯亞胺、聚醚楓 等。進而此等之材質形狀爲塊狀形狀、板狀、薄膜形狀等 而無特別限制者。 以塗佈法形成底層膜之場合，例如可將含有含由鋁、 鈦、銅、銘、钌、鉬、鎢、銘、鎳、銷、及金所選出之至 少一種金屬原子的有機金屬化合物之溶液（本說明書中， 亦稱「底層膜形成用組成物」）。作爲底層膜形成用材料 進行塗佈，接著經熱處理而得。 上述含鈦原子之有機金屬化合物，可舉例如鈦烷氧化 物、具胺基之鈦化合物、與β-二酮之鈦化合物、具環戊二 烯基之鈦化合物、具鹵素基之鈦化合物等。 上述含鈀原子之有機金屬化合物，可舉例如具鹵素原 子之鈀錯合物、鈀之乙酸酯化合物、鈀之β-二酮錯合物、 鈀與具共軛羰基之化合物的錯合物、膦系鈀錯合物等。 該有機金屬化合物之具體例’含鈦原子之有機金屬化 合物可舉例如與前述氧化鋁膜形成用組成物可含有之鈦化 合物中例示者相同的鈦化合物。 -22- 201219408 含鈀 物可舉例 (苯甲腈 鈀之 鈀之 二酮鈀等 鈀與 基丙酮） 膦系 鈀、雙（ 、二乙酸 乙烷]鈀、 三苯基膦 三苯基膦 此等 酮）鈦二 二酮鈀、 此等 化合物之 物之任意 '烴類、 上述 、乙二醇 醚等； 原子之有機金屬化合物中，具鹵素原子之 如烯丙基鈀氯化物、二氯雙（乙腈）鈀、 )鈀等； 乙酸酯化合物，例如鈀乙酸酯等； β -二酮錯合物，例如戊烷-2,4 -二酮鈀、六 具共軛羰基之化合物之錯合物，例如雙（ 鈀等； 鈀錯合物，例如雙[1，2 -雙（二苯基膦基： 三苯基膦）鈀氯化物、雙（三苯基膦）鈀 酯雙（三苯基鱗）鈀、二氯[1，2-雙（二苯 反式-二氯雙（三環己基膦）鈀、反式-二 )鈀、反式-二氯雙（三-〇-甲苯基膦）鈀 )鈀等。 中，以使用鈦異丙氧化物、雙（乙氧基丁 異丙氧化物、四（戊烷-2,4-二酮）鈦、戊 六氟戊烷-2,4-二酮鈀爲佳。 含有鈦及鈀選出之至少一種金屬原子的有 溶液所使用溶劑，可使用能溶解該有機金 溶劑。此等溶劑，可舉例如醚類、具醚基 醇類、非質子性極性溶劑等及此等之混合: 醚類，例如四氫呋喃、二噁烷、乙二醇二 二乙基醚、二乙二醇二甲基醚、二乙二醇 鈀錯合 二氯雙 氟戊烷 二亞苄 >乙烷] 乙酸酯 基膦） 氯雙（ 、肆（ -1，3-二 烷-2,4- 機金屬 屬化合 的酯類 溶劑。 甲基醚 二乙基 -23- 201219408 上述具醚基的酯類’例如乙二醇單甲基醚乙酸酯、乙 二醇單乙基醚乙酸酯、丙二醇單甲基醚乙酸酯、丙二醇單 乙基醚乙酸酯、2-乙醯氧基-1-甲氧基丙烷等； 上述烴類’例如甲苯、二甲苯、己烷、環己烷、辛烷 、萘烷、四氫化萘、均四甲苯等； 上述醇類，例如甲醇、乙醇、丙醇等； 上述非質子性極性溶劑，各自可舉例如N -甲基吡咯烷 酮、N，N-二甲基甲醯胺、N，N-二甲基乙醯胺、六甲基磷醯 胺、γ-丁內酯等。 有機金屬化合物之溶液中的有機金屬化合物之含量， 較佳爲0 · 1〜1 0質量％、更較佳爲0.1〜5質量％。 底層膜形成用組成物對基體本體之塗佈可以例如旋轉 塗佈法、輥塗佈法、淋幕塗佈法、浸漬塗佈法、噴霧塗佈 法、液滴吐出法等之適宜方法進行。又，基體具有溝渠構 造之場合，其開口寬爲300nm以下，且溝渠之長寬比在5以 上之場合，使底層膜形成用組成物塗佈於基體本體後，藉 由使基體暫時在減壓下放置，可使有機金屬化合物更均一 塗佈於溝渠內部。 如此形成的底層膜進而被加熱。加熱溫度較佳爲30〜 3 5 0°C、更佳爲40〜300°C。加熱時間較佳爲5〜90分鐘、更 較佳爲10〜60分鐘。 底層膜的塗佈至加熱爲止的環境以氮、氨、氬等惰性 氣體所構成之環境爲佳。進而因應必要以混入氫等還原性 氣體的環境爲佳。又，溶劑或添加物以使用除去水或氧者 -24- 201219408 爲宜。 本發明中，底層膜的厚度，溶劑除去後膜厚以0.001 〜5μιη爲佳、0.005〜0·5μιη更佳。 在本發明，在基體上將上述氧化鋁膜形成用組成物使 用例如旋轉塗佈法、輥塗佈法、淋幕塗佈法、浸漬塗佈法 、噴霧塗佈法、液滴吐出法等之適宜方法進行塗佈。 在此等之塗佈步驟，因基體的形狀、大小等，採用氧 化鋁形成用組成物可分佈到基體的各角落爲止的塗佈條件 。例如塗佈法採用旋轉塗佈法之場合中，旋轉體的旋轉數 可爲 300 〜2,500rpm、較佳爲 500 〜2,000rpm。 塗膜的厚度，乾燥狀態（次步驟使有機溶劑除去後之 狀態）的厚度，通常爲1 nm以上。又，該厚度考量即使氧 化鋁膜的膜厚大、可使膜全體以目的氧化鋁形成的本發明 效果，較佳爲l〇〇nm以上、更佳爲200nm以上、尤佳爲 250nm以上。該厚度上限値通常爲400nm。 此氧化鋁膜形成組成物之塗佈時的環境以氮、氨、氬 等惰性氣體在99.9莫耳％以上、較佳爲99.95莫耳％以上。 進而亦可因應必要在混入氫等還原性氣體或氧等氧化性氣 體的環境下實施。 <步驟（b ) > 接著、藉由在氧化性氣體的存在下，於步驟（a)所 得的塗膜進行加熱及光照射選出之至少一者而於基體上形 成氧化鋁膜。 -25- 201219408 加熱的場合，以使基體的溫度在6〇°C以上爲佳、〜 6 0 0 °C更佳、1 〇 〇〜4 0 0。(：特別佳。加熱時間較佳爲3 〇秒〜 120分鐘、更較佳爲1〜90分鐘、又更佳爲10〜60分鐘。 又，光照射使用的光源，可舉例如水銀燈、重氫燈' 稀有氣體的放電光、YAG雷射、氬雷射、碳酸氣體雷射、 稀有氣體鹵素準分子雷射等。上述水銀燈，可舉例如低壓 水銀燈或高壓水銀燈。上述稀有氣體的放電光使用的稀有 氣體，可舉例如氬、氪、氙等。上述稀有氣體鹵素準分子 雷射使用的稀有氣體鹵素，可舉例如又6?、又6(：1、乂681·、 KrF 、 KrCl 、 ArF 、 ArCl等。 此等之光源的輸出方面，較佳爲10〜5,00 0W、更較佳 爲100〜1，000W。此等之光源的波長雖未特別限制，較佳 爲170nm〜600nm。又，由形成的氧化鋁膜的膜質之觀點 來看，以使用雷射光特別佳。 又，以形成更良好氧化鋁膜爲目的亦可在氧化性氣體 環境下使電漿氧化。此時電漿氧化之氧化條件方面，例如 RF電力爲20〜100W、導入氣體之氧氣體爲90〜100%、其 餘爲氬氣體、導入氣體的導入壓爲0.05kPa〜0.2MPa、電 獎氧化時間爲1 0秒〜2 4 0秒。 步驟（b )中氧化性氣體的濃度較佳爲1〜1 〇〇莫耳％、 更佳爲3〜99莫耳％、尤佳爲30〜95莫耳％。 氧化性氣體，可舉例如水蒸氣、氧、臭氧、一氧化碳 、碳數1〜3的過氧化物、醇、醛等，其中以水蒸氣、氧、 臭氧爲佳。將氧化性氣體與惰性氣體混合由氧化條件之控 -26- 201219408 制觀點來看爲佳。惰性氣體，可舉例如氮、氦、氬等。 本步驟中’上述加熱及光照射可僅進行其中一者，或 m行1力卩熱ί &光照射之兩者。進行加熱及光照射之兩者之場 合’不問其前後順序，亦可同時進行加熱及光照射。此等 中’以僅進行加熱、或進行加熱及光照射之兩者爲佳。 以本發明的方法可形成的氧化鋁膜的厚度通常爲lnm 〜1 μηι。 以本發明的方法形成的氧化鋁膜的厚度通常爲lnm以 上°又’該厚度考量即使氧化鋁膜的膜厚大、可使膜全體 以目的氧化鋁形成的本發明效果，較佳爲100nm以上、更 佳爲200nm以上、尤佳爲250nm以上。該厚度的上限値雖 未特別限制’通常爲5 0 0 n m。 又’上述步驟（a)與步驟（b)間，可加入使步驟（ a )所得的塗膜中所含有的有機溶劑等之低沸點成分除去 之步驟。 此步驟中爲了除去有機溶劑等，亦可進行加熱處理。 加熱之溫度及時間因使用溶劑種類、沸點（蒸氣壓）而異 ’例如可在100〜3 50°C中，5〜90分鐘。此時，藉由使系 統全體減壓，使溶劑除去亦可在更低溫進行》較佳爲100 〜250 °C中，10〜60分鐘。 此步驟’在氧化性氣體、例如水蒸氣、氧、臭氧、一 氧化碳、碳數爲1〜3的過氧化物、醇、醛等（較佳爲水蒸 氣、氧、臭氧）之濃度爲〇.〇5〜5莫耳％、較佳爲0.1〜1莫 耳％之環境下進行。 -27- 201219408 通常、環境中的氧化性氣體以外的氣體爲氮、氮、氬 等惰性氣體。 【實施方式】 〔實施例〕 以下、將本發明以實施例更具體說明。又，以下操作 除特別記載場合，皆在乾燥氮環境下實施。又，使用溶劑 皆事前以分子篩4A (優你歐昭和（股）製）脫水，且藉由使 氮氣體通氣而脫氣。 (合成例1-1 )含鈦化合物溶液之調製 將環戊二烯基鈦三氯化物O.llg置入30mL玻璃容器， 此中加入4-甲基苯甲醚使全量爲25.00g»充分攪拌後，在 室溫、4小時靜置，接著將此使用聚四氯乙烯製的孔徑 〇·1μιη之膜過濾器（Whatman Inc.製）進行過濾，得到含 環戊二烯基鈦三氯化物20pmol/g之溶液。 (合成例1-2)三乙基胺與氫化鋁之錯合物之調製 在加入磁氣攪拌子的200mL三口燒瓶中加入氫化鋰鋁 3.8 0g。在三口燒瓶之3個接續口各自連接100m L的粉體添 加用漏斗、接續氮氣流的吸引栓三向活栓及玻璃栓。使三 乙基胺的氯化氫酸鹽17.80g加入粉體添加用漏斗後，使三 口燒瓶以透過吸引栓三向活栓使其處於氮密封下。 於上述三口燒瓶使用玻璃製注射器加入己烷1 OOmL。 -28- 201219408 藉由磁攪拌器以旋轉數l,000rpm邊攪拌、邊使三乙基胺的 氯化氫酸鹽花費10分鐘緩緩落下至三口燒瓶中後，再繼續 進行2小時攪拌。 之後、使用聚四氯乙烯製的管前端塞有脫脂綿（曰本 藥局方脫脂綿）者，使反應混合物以壓送取出至別容器， 接著以聚四氯乙烯製的孔徑0.1 μιη之膜過濾器（Whatman Inc.製）進行過濾。濾液以30 0mL茄型燒瓶承受，過濾完 畢後加入磁氣攪拌子，裝設吸引栓三向活栓。 使此吸引栓三向活栓透過阱與真空泵接續，藉由磁攪 拌器以旋轉數3 00rpm邊攪拌減壓邊將溶劑除去。溶劑除去 後使殘存物以聚四氯乙烯製的孔徑〇·1μιη之膜過濾器（ Whatman Inc.製）進行過濾，得到三乙基胺與氫化鋁之錯 合物1 0 · 2 5 g之無色透明液體（收率5 5 % )。 (合成例1 -3 )氧化鋁膜形成用組成物之調製 於此三乙基胺與氫化鋁之錯合物2.00g中加入二異丁 基鋁氫化物2.00g後，添加4-甲基苯甲醚使全量成爲10. 〇〇g ，調製含三乙基胺與氫化鋁之錯合物與二異丁基鋁氫化物 之混合物40質量％之溶液。進而於上述溶液0.5 OmL，將（ 合成例1-1)中調製的含環戊二烯基鈦三氯化物20 μιηοΐ/g 之溶液16μί在室溫、攪拌下加入，接著藉由繼續1分鐘攪 拌，調製氧化鋁膜形成用組成物。 (合成例2 )氧化鋁膜形成用組成物之調製 -29 - 201219408 於（合成例1-2)中合成的三乙基胺與氫化鋁之錯合 物l.OOg中加入三（十二基）鋁（（C12H25)3A1) l.OOg後， 藉由添加4-甲基苯甲醚使全量成爲10.00g，調製含三乙基 胺與氫化鋁之錯合物與三（十二基）鋁的混合物20質量％ 之溶液。進而於上述溶液〇.50mL，將（合成例1-1)中調 製的含環戊二烯基鈦三氯化物20pmol/g之溶液16μί在室溫 、攪拌下加入，接著藉由繼續1分鐘攪拌而調製氧化鋁膜 形成用組成物。 (合成例3 )氧化鋁膜形成用組成物之調製 加入二異丁基鋁氫化物4.00g後，藉由加入4-甲基苯甲 醚使全量成爲10. 〇〇g，而調製含二異丁基鋁氫化物40質量 %之溶液。進而於上述溶液〇.5〇mL，將（合成例1-1)中調 製的含環戊二烯基鈦三氯化物20μιη〇1/β之溶液16pL在室溫 、攪拌下加入，接著藉由繼續1分鐘攪拌而調製氧化鋁膜 形成用組成物。 (合成例4 )氧化鋁膜形成用組成物之調製 加入三辛基錫（（C8Hi7)3A1) 3.00g後藉由加入tert -丁 基苯使全量成爲10.〇〇g，而調製含三辛基鋁30質量％之溶 液。進而於上述溶液〇. 5 〇mL，將（合成例1 -1 )中調製的 含環戊二烯基鈦三氯化物20pmol/g之溶液16μί在室溫、攪 拌下加入，接著藉由繼續1分鐘攪拌而調製氧化鋁膜形成 用組成物。 -30- 201219408 (合成例5 )氧化鋁膜形成用組成物之調製 加入三（十二基）銘（（C12H25)3A1) 2.50g後，藉由 添加丙二醇單甲基醚乙酸酯使全量成爲lO.OOg，而調製含 三（十二基）鋁25質量％之溶液。進而於上述溶液〇.50niL ，將（合成例I-1)中調製的含環戊二烯基鈦三氯化物 20pmol/g之溶液16μί、及二甲基聚砂氧院-聚氧基伸烷基 共聚物（Dow corning Toray製）16PL在室溫、攪拌下加 入，接著藉由繼續1分鐘攪拌而調製氧化鋁膜形成用組成 物。 (合成例6 )氧化鋁膜形成用組成物之調製 加入三sec-丁氧基鋁5.00g後，藉由添加丙二醇單甲基 醚乙酸酯使全量成爲10.〇〇g，而調製含三sec-丁氧基鋁50 質量％之氧化鋁膜形成用組成物。 (合成例7 )氧化鋁膜形成用組成物之調製 藉由於三乙基胺與氫化鋁之錯合物6.00g中加入4-甲基 苯甲醚使全量成爲10. 〇〇g，而調製含三乙基胺與氫化鋁之 錯合物60質量％之溶液。進而於上述溶液0.50mL，將（合 成例1-1 )中調製的含環戊二烯基鈦三氯化物20Hmol/g之 溶液1 6μί在室溫、攪拌下加入，接著藉由繼續1分鐘攪拌 而調製氧化鋁膜形成用組成物。 -31 - 201219408 (合成例B-l )底層膜形成用組成物之調製 將雙（戊-2,4-二酮）鈦（IV)二異丙氧化物〇.3〇g及 肆（二甲基胺基）鈦64μι裝入20mL玻璃容器，於此中加 入丙二醇單甲基醚乙酸酯使全量成爲18.00g。使混合物充 分攪拌後，在室溫靜置2小時。接著將此使用聚四氯乙烯 製的孔徑Ο.ίμιη之膜過濾器（Whatman Inc.製）進行過濾 ，得到底層膜形成用組成物。 (合成例B -2 )底層膜形成用組成物之調製 於聚二丁基鈦酸酯0.5 〇g中加入丙二醇單甲基醚使全 量成爲100.00g。使混合物充分攪拌後，在室溫靜置2小時 。接著將此使用聚四氯乙烯製的孔徑〇·1 μπι之膜過濾器（ Whatman Inc.製）進行過濾，得到底層膜形成用組成物。 (實施例1 ) 使矽基板裝設在旋轉塗佈機，在氮氣體環境下，滴下 (合成例B- 1 )所調製的底層膜形成用組成物1 mL，以旋轉 數3,000rpm進行10秒鐘旋轉。使此基板置於設定在150°C的 加熱板，進行25分鐘加熱。底層膜的厚度爲5 nm。 (a)接著使此基板在氮環境下再度裝設於旋轉塗佈 機，滴下（合成例1-3)中調製的氧化鋁形成用組成物之 全量，以旋轉數800rpm進行1 0秒鐘旋轉。 使此基板在調整氧氣體/氮氣體分壓比=1/99的大氣壓 氣體環境下、在150 °C之加熱板進行10分鐘加熱。 -32- 201219408 (b)之後使基板移送至調整氧氣體/氮氣體分壓比 = 90/10的大氣壓氣體環境下，再以250°C進行30分鐘加熱， 基板表面被淡黃色透明膜被覆。得到的膜經ESCA分析， 可知此膜爲膜厚35 Onm之氧化鋁膜。 (實施例2 ) 作爲氧化鋁膜形成用組成物除使用（合成例2 )中調 製的氧化鋁膜形成用組成物以外，以與實施例1同樣地進 行，基板表面被淡黃色透明膜被覆。得到的膜經ESC A分 析，可知此膜爲膜厚290ητη之氧化鋁膜。 (實施例3 ) 作爲氧化鋁膜形成用組成物除使用（合成例3 )中調 製的氧化鋁膜形成用組成物以外，以與實施例1同樣地進 行，基板表面被淡黃色透明膜被覆。得到的膜經ESCΑ分 析，可知此膜爲膜厚260nm之氧化鋁膜。 (實施例4 ) 於矽基板以濺鍍法使金屬銅成膜。厚度爲5 nm。 (a) 接著使此基板在氮環境下再度裝設於旋轉塗佈 機，將（合成例4 )所調製的氧化鋁膜形成用組成物之全 量滴下，以旋轉數600rpm進行10秒鐘旋轉。使此基板在 1 5 0°C之加熱板進行5分鐘加熱。 (b) 之後、使基板移送至調整氧氣體/氮氣體分壓比 -33- 201219408 = 90/10的大氣壓氣體環境下，再於250°C進行30分鐘加熱’ 基板表面被淡黃色透明膜被覆。得到的膜經ESCA分析’ 可知此膜爲膜厚340 nm之氧化鋁膜。 (實施例5 ) 使矽基板裝設在旋轉塗佈機’在氮氣體環境下’滴下 (合成例B-2 )所調製的底層膜形成用組成物lmL ’以旋轉 數3,000rpm進行10秒鐘旋轉。使此基板放置於設定在200°C 的加熱板，進行10分鐘加熱。底層膜的厚度爲5 nm。 (a) 接著使此基板在氮環境下再度裝設於旋轉塗佈 機，滴下（合成例5)所調製的氧化鋁膜形成用組成物之 全量，以旋轉數600rpm進行10秒鐘旋轉。使此基板在 1 5 0°C之加熱板進行5分鐘加熱。 (b) 之後、使基板移送至調整氧氣體/氮氣體分壓比 = 90/10的大氣壓氣體環境下，再於250°C進行30分鐘加熱， 基板表面被淡黃色透明膜被覆。得到的膜經ESCA分析， 可知此膜爲膜厚320nm之氧化鋁膜。 (實施例6 ) 作爲氧化鋁膜形成用組成物除使用（合成例6 )所調 製的氧化鋁形成用組成物以外以與實施例5同樣地進行， 基板表面被淡黃色透明膜被覆。得到的膜經ESCA分析， 可知此膜爲膜厚310nm之氧化鋁膜。 -34- 201219408 (比較例1 ) 使矽基板裝設在旋轉塗佈機，在氮氣體環境下，滴下 (合成例B-1)所調製的底層膜形成用組成物lmL，以旋轉 數3,000rpm進行10秒鐘旋轉。使此基板置於設定在150°C的 加熱板，進行25分鐘加熱。底層膜的厚度爲5nm。 (a) 接著使此基板在氮環境下再度裝設於旋轉塗佈 機，滴下（合成例7 )所調製的氧化鋁形成用組成物之全 量，以旋轉數600rpm進行10秒鐘旋轉。使此基板在150°C 之加熱板進行5分鐘加熱。 (b) 之後、使基板移送至調整氧氣體/氮氣體分壓比 = 90/10的大氣壓氣體環境下，再於250°C進行30分鐘加熱， 基板表面被淡黃色透明膜被覆。得到的膜經ESCA分析， 可知此膜爲膜厚290nm且上層部170nm爲氧化鋁膜者，但 下層部120nm成爲混合金屬鋁與氧化鋁之膜。 -35-T ( ( ( ( ( ( ( ( ( ( ( 4 · · · (5) (In the above formula (5), R17 is a hospital base or a phenyl group.) T i (〇ρ) η (γ) 4_n . . . (6) (CP in the above formula (6) Is a cyclopentadienyl group, Y is a halogen atom or an alkyl group, and η is an integer of 1 to 4.) The above formula (2), η-propyl group, i-propylpropoxy group, i-propoxy group (3) Wherein R14 and R15 are preferably methyl, ethyl n'butyl, t-butyl, methoxy, ethoxy, n-n-butoxy, t-butoxy, hexyl, cyclohexyl -17- 201219408, phenoxy, methylphenoxy, trifluoromethyl, more preferably methyl, ethyl, η-propyl, i-propyl, η-butyl, t-butyl, hexyl Further, in the above formula (7), R9 or R1Q is preferably a methyl group, an ethyl group, an η-propyl group, an i-propyl group, an η-butyl group, a t-butyl group or a methoxy group. Base, ethoxy, η-propoxy, i-propoxy, η-butoxy, t-butoxy, phenoxy, methylphenoxy, trifluoromethyl. More preferably methyl , ethyl, i-propyl, t-butyl, methoxy And a specific example of the titanium compound represented by the above formula (2), for example, titanium methoxide, titanium ethoxide, Titanium-η-propoxide, titanium-η-壬 oxide, titanium stearin oxide, titanium isopropoxide, titanium-η-butoxide, titanium isobutoxide, titanium-t-butoxide , titanium trimethyl sulfonium oxide ( Siloxide ), titanium-2-ethyl hexaoxide, titanium methoxy propylene oxide, titanium phenoxide, titanium methyl phenoxide, titanium fluoromethoxide and titanium chloride Specific examples of the titanium compound represented by the above formula (3) include yttrium (penta-2,4-dione) titanium and ruthenium (2,2,6,6-tetramethylheptane). 3,5-dione) Titanium, bismuth (1-ethoxybutane-1,3-dione) titanium, bismuth (1,1,1,5,5,5-hexafluoropentene-2,4-di Ketone) titanium, (2,2-dimethylhex-3,5-dione) titanium 'bis(penta-2,4-dione) titanium dimethoxide, bis(2,2,6,6- Tetramethylheptyl-3,5-dione) titanium dimethoxide, bis(1-ethoxybutane-1,3-dione) dimethyl dimethoxide, bis(1,1,1,5,5, 5-hexafluoropenta-2,4-dione) Titanium dimethoxide, (2,2-dimethylhex-3,5-dione) titanium dimethoxide, bis(penta-2,4-dione) titanium di-propoxide, double (2 , 2,6,6-tetramethylhept-3,5-dione) Titanium di-propoxide, bis(indenyl-ethoxybutane-indole, 3-dione) titanium dipropoxy-18- 201219408 Compound, bis(1,1,1,5,5,5-hexafluoropenta-2,4-dione) titanium dioxime-propoxide, (2,2-dimethylhexyl-3,5- Diketone) Titanium di-propoxide and the like. Specific examples of the titanium compound represented by the above formula (4) include, for example, trimethoxytitanium chloride, triethoxytitanium chloride, tris-n-propoxytitanium chloride, and tri-i-propoxy group. Titanium chloride, tri-n-butoxytitanium chloride, tri-t-butoxytitanium chloride, triisostearate titanium chloride, dimethoxy titanium dichloride, diethoxy titanium Dichloride, di-n-propoxy titanium dichloride, di-i-propoxy titanium dichloride, di-n-butoxy ruthenium dichloride, di-t-butoxy titanium dichloride , diisostearyl fluorenyl titanium dichloride, methoxy titanium trichloride, ethoxy titanium trichloride, η-propoxy titanium trichloride, i-propoxy titanium trichloride, η - butoxytitanium trichloride, t-butoxytitanium trichloride, isostearyl decyl titanium trichloride, titanium tetrachloride, and the like. Specific examples of the titanium compound represented by the above formula (5) include yttrium (dimethylamino) titanium, ruthenium (diethylamino) titanium, and ruthenium (di-t-butoxyamino) titanium. , bis(i-i-propoxyamino) titanium, bismuth (diphenylamino) titanium. Specific examples of the titanium compound represented by the above formula (6) include dicyclopentadienyl titanium dichloride, dicyclopentadienyl titanium dibromide, cyclopentadienyl titanium trichloride, and a ring. Pentadienyl titanium tribromide, dicyclopentadienyl dimethyl titanium, dicyclopentadienyl diethyl titanium, dicyclopentadienyl di-t-butyl titanium, dicyclopentadiene Phenylphenyltitanium chloride, dicyclopentadienylmethyltitanium chloride, and the like. The mass ratio of the aluminum compound in the composition for forming an aluminum oxide film of the present invention can be appropriately set in accordance with the film thickness of the alumina to be film-formed, and is preferably 5 to 190 to 199 to 198 More preferably, 20 to 80% by mass and more preferably 30 to 70% by mass. When the composition for forming an aluminum oxide film of the present invention contains a titanium compound, the concentration of the titanium compound is preferably 1 mol% or less, more preferably 0.00001 to 1 mol%, based on the total of the aluminum compound and the titanium compound. More preferably 0.00005 to 0.01 mol%. By the content of the titanium compound in this range, both good embedding property and stability of the composition can be achieved. When the aluminum compound in the composition for forming an aluminum oxide film of the present invention contains an aluminum compound other than the aluminum compound having a monovalent organic group having 1 to 12 carbon atoms, the concentration is preferably 40 as a whole of the composition. The mass% or less is more preferably 20% by mass or less. The method for producing an aluminum oxide film of the present invention is not particularly limited. For example, after the above-mentioned aluminum compound is synthesized in the presence of a solvent, a solution obtained by removing a by-product or the like into a filter or the like can be used as a composition for forming an aluminum oxide film. Alternatively, after adding a desired solvent to the solution, the solvent used in the reaction, for example, diethyl ether, may be removed under reduced pressure to prepare a composition for forming an aluminum oxide film. When the composition for forming an aluminum oxide film of the present invention is a compound containing a titanium compound, for example, a solution containing a specific amount of a titanium-containing compound may be added to a solution containing the aluminum compound produced as described above while stirring. modulation. The temperature at the time of addition is preferably from 0 to 150 ° C, more preferably from 5 to 100 ° C. The stirring time is preferably from 0.1 to 120 minutes, more preferably from 0.2 to 60 minutes. By mixing under such conditions, a stable alumina film forming composition can be obtained. Next, a method of forming an aluminum oxide film according to the present invention will be described. The method for forming an aluminum oxide film of the present invention -20-201219408 is characterized by the following steps (a) and (b). (a) applying a composition for forming an aluminum oxide film containing an aluminum compound having a monovalent organic group having a carbon number of 1-4 to an organic solvent and an organic solvent to the substrate, and forming a coating film (b) in the presence of an oxidizing gas, The coating film is subjected to at least one treatment selected from the group consisting of heating and light irradiation to form an aluminum oxide film, and each step will be described below. <Step (a) > In the present invention, the material constituting the base body is not particularly limited, but a heat treatment which can withstand the secondary step is preferred. Further, the shape of the base body is not particularly limited, and may be, for example, a flat surface having a flat surface or a non-planar surface having a step. Specific examples of the material of the base body include glass, metal, plastic, ceramics, and the like. Examples of the glass include quartz glass, borosilicate glass, soda lime glass, lead glass, and the like. The metal may, for example, be gold, silver, copper, nickel, ruthenium, aluminum, iron, stainless steel or the like. The plastic may, for example, be a polyimine or a polyether oxime. Specific examples of the shape of the base body include a block shape, a plate shape, and a film shape. The substrate used in the present invention is, for example, a film formed on the surface of the substrate body. Such a substrate is formed, for example, on the surface of a substrate having an underlayer film containing at least one metal atom selected from aluminum, titanium, copper, cobalt, rhenium, molybdenum, tungsten, aluminum, nickel, palladium, and gold. Due to the underlying film, the film formation property of the oxidized -21 - 201219408 aluminum film is improved. The method of forming the underlayer film on the substrate body is not particularly limited, and for example, a spin coating method, a roll coating method, a curtain coating method, a dip coating method, a spray coating method, a droplet discharge method, or the like can be used. Various film forming methods such as a cloth method, a CVD method, a PVD method, and a sputtering method. Further, specific examples of the material of the base body include glass, plastic, ceramic, tantalum substrate and the like. Glass, quartz glass, borosilicate glass, soda lime glass, lead glass can be used. Plastics include, for example, polyimine and polyether maple. Further, the material shape of these is a block shape, a plate shape, a film shape, or the like, and is not particularly limited. In the case where the underlayer film is formed by a coating method, for example, an organometallic compound containing at least one metal atom selected from aluminum, titanium, copper, indium, lanthanum, molybdenum, tungsten, indium, nickel, pin, and gold may be used. The solution (also referred to as "the composition for forming an underlayer film" in this specification). Coating is carried out as a material for forming an underlayer film, followed by heat treatment. The organometallic compound containing a titanium atom may, for example, be a titanium alkoxide, a titanium compound having an amine group, a titanium compound with a β-diketone, a titanium compound having a cyclopentadienyl group, a titanium compound having a halogen group, or the like. . The organometallic compound containing a palladium atom may, for example, be a palladium complex having a halogen atom, an acetate compound of palladium, a β-diketone complex of palladium, or a complex of a compound of palladium and a conjugated carbonyl group. , a phosphine palladium complex, and the like. Specific examples of the organometallic compound The titanium compound-containing organometallic compound is, for example, the same as the titanium compound exemplified as the titanium compound which can be contained in the composition for forming an aluminum oxide film. -22- 201219408 Palladium-containing materials can be exemplified by palladium and acetonide such as p-phenylene palladium palladium diketone palladium, phosphine palladium, bis(diacetate) palladium, triphenylphosphine triphenylphosphine, etc. a ketone) titanium diedone palladium, any 'hydrocarbons of the compounds, the above, a glycol ether, etc.; an organometallic compound of an atom having a halogen atom such as allyl palladium chloride or dichlorobis ( Acetonitrile) palladium, palladium, etc.; acetate compound, such as palladium acetate, etc.; β-diketone complex, such as pentane-2,4-dione palladium, a compound of six conjugated carbonyl groups For example, bis (palladium, etc.; palladium complex, such as bis[1,2-bis(diphenylphosphino:triphenylphosphine)palladium chloride, bis(triphenylphosphine)palladium bis(triphenyl) Palladium, dichloro [1,2-bis(diphenyltrans-dichlorobis(tricyclohexylphosphine)palladium, trans-di)palladium, trans-dichlorobis(tri-indolyl-tolyl) Phosphine) palladium) palladium and the like. In order to use titanium isopropoxide, bis(ethoxybutoxyisopropoxide, tetrakis(pentane-2,4-dione)titanium, pentafluoropentane-2,4-dione palladium is preferred The solvent used for the solution containing at least one metal atom selected from titanium and palladium may be used to dissolve the organic gold solvent. Examples of such solvents include ethers, ether alcohols, aprotic polar solvents, and the like. Mixing of these: ethers such as tetrahydrofuran, dioxane, ethylene glycol diethylene ether, diethylene glycol dimethyl ether, diethylene glycol palladium, dichlorodifluoropentane dibenzyl bromide &gt ; ethane] acetate phosphine) chlorobis(, hydrazine-(1,3-1,3-dioxane-2,4-metalloid) ester solvent. methyl ether diethyl-23- 201219408 Base esters such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 2-ethyl hydrazine Oxy-1-methoxypropane or the like; the above hydrocarbons such as toluene, xylene, hexane, cyclohexane, octane, decalin, tetralin, tetramethylbenzene, etc.; the above alcohols, For example, methanol, ethanol, propanol, etc.; each of the above aprotic polar solvents may, for example, be N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, hexa The content of the organometallic compound in the solution of the organometallic compound is preferably from 0.1 to 10% by mass, more preferably from 0.1 to 5% by mass. The application of the composition to the substrate body can be carried out, for example, by a spin coating method, a roll coating method, a curtain coating method, a dip coating method, a spray coating method, a droplet discharge method, or the like. In the case of having a trench structure, when the opening width is 300 nm or less and the aspect ratio of the trench is 5 or more, the underlayer film forming composition is applied to the substrate body, and the substrate is temporarily placed under reduced pressure. The organometallic compound can be more uniformly applied to the inside of the trench. The underlayer film thus formed is further heated. The heating temperature is preferably 30 to 350 ° C, more preferably 40 to 300 ° C. The heating time is preferably 5 ~90 minutes, more preferably 10~60 minutes. Coating of the underlying film The environment to be heated is preferably an environment composed of an inert gas such as nitrogen, ammonia or argon. Further, it is preferable to mix an environment in which a reducing gas such as hydrogen is mixed. Further, a solvent or an additive is used to remove water or oxygen - In the present invention, the thickness of the underlayer film and the film thickness after the solvent removal are preferably 0.001 to 5 μm, more preferably 0.005 to 0.5 μm. In the present invention, the composition for forming the above aluminum oxide film is formed on the substrate. The coating is applied by a suitable method such as a spin coating method, a roll coating method, a curtain coating method, a dip coating method, a spray coating method, or a droplet discharge method. The shape, size, and the like of the substrate are coating conditions in which the composition for forming an alumina can be distributed to each corner of the substrate. For example, in the case where the coating method is a spin coating method, the number of revolutions of the rotating body may be 300 to 2,500 rpm, preferably 500 to 2,000 rpm. The thickness of the coating film and the thickness of the dried state (the state in which the organic solvent is removed in the secondary step) are usually 1 nm or more. Further, in consideration of the thickness, the effect of the present invention in which the film thickness of the aluminum oxide film is large and the entire film can be formed of the target alumina is preferably 10 nm or more, more preferably 200 nm or more, and still more preferably 250 nm or more. The upper limit of the thickness 値 is usually 400 nm. The atmosphere at the time of coating the composition of the aluminum oxide film is 99.9 mol% or more, preferably 99.95 mol% or more, of an inert gas such as nitrogen, ammonia or argon. Further, it may be carried out in an environment where a reducing gas such as hydrogen or an oxidizing gas such as oxygen is mixed. <Step (b) > Next, an aluminum oxide film is formed on the substrate by at least one of heating and light irradiation selection of the coating film obtained in the step (a) in the presence of an oxidizing gas. -25- 201219408 In the case of heating, the temperature of the substrate is preferably 6 〇 ° C or higher, more preferably 1600 ° C, and 1 〇 〇 ~ 4 0 0. (It is particularly preferable. The heating time is preferably from 3 sec to 120 minutes, more preferably from 1 to 90 minutes, still more preferably from 10 to 60 minutes. Further, the light source used for light irradiation may, for example, be a mercury lamp or a heavy hydrogen. Lamp 'discharge light of rare gas, YAG laser, argon laser, carbon dioxide gas laser, rare gas halogen excimer laser, etc. The above mercury lamp may, for example, be a low pressure mercury lamp or a high pressure mercury lamp. The discharge light of the above rare gas is used. Examples of the rare gas include argon, helium, neon, etc. The rare gas halogen used in the rare gas halogen excimer laser may be, for example, 6 or 6 (: 1, 乂681·, KrF, KrCl, ArF, ArCl, etc. The output of the light source is preferably 10 to 5,00 0 W, more preferably 100 to 1,000 W. The wavelength of the light source is not particularly limited, but is preferably 170 nm to 600 nm. From the viewpoint of the film quality of the formed aluminum oxide film, it is particularly preferable to use laser light. Further, in order to form a more excellent aluminum oxide film, plasma can be oxidized in an oxidizing gas atmosphere. In terms of oxidation conditions, such as RF The force is 20 to 100 W, the oxygen gas of the introduction gas is 90 to 100%, the rest is argon gas, the introduction pressure of the introduction gas is 0.05 kPa to 0.2 MPa, and the electric charge oxidation time is 10 to 2400 seconds. b) The concentration of the oxidizing gas is preferably from 1 to 1% by mole, more preferably from 3 to 99% by mole, even more preferably from 30 to 95% by mole. The oxidizing gas may, for example, be water vapor or oxygen. Ozone, carbon monoxide, peroxides with a carbon number of 1 to 3, alcohols, aldehydes, etc., among which water vapor, oxygen, and ozone are preferred. Mixing an oxidizing gas with an inert gas is controlled by the oxidation conditions -26-201219408 The inert gas may, for example, be nitrogen, helium, argon or the like. In the present step, the above-mentioned heating and light irradiation may be performed by only one of them, or m-line 1 heat and light irradiation. In the case of both heating and light irradiation, heating and light irradiation may be simultaneously performed regardless of the order of the front and back. In this case, it is preferable to perform only heating, heating, and light irradiation. The thickness of the aluminum oxide film which can be formed by the method is usually from 1 nm to 1 μηι. The thickness of the aluminum oxide film formed by the method is usually 1 nm or more. In view of the thickness, even if the film thickness of the aluminum oxide film is large, the effect of the present invention in which the entire film is formed of the target alumina is preferably 100 nm or more. It is 200 nm or more, and more preferably 250 nm or more. The upper limit of the thickness is not particularly limited to '500 nm. Between the above steps (a) and (b), the step (a) can be added. The step of removing the low-boiling point component such as the organic solvent contained in the coating film. In this step, heat treatment may be performed in order to remove the organic solvent, etc. The temperature and time of heating vary depending on the type of solvent and the boiling point (vapor pressure). For example, it can be used in 100~3 50 °C for 5~90 minutes. At this time, by depressurizing the entire system, the solvent can be removed at a lower temperature, preferably at 100 to 250 ° C for 10 to 60 minutes. In this step, the concentration of an oxidizing gas such as water vapor, oxygen, ozone, carbon monoxide, a peroxide having a carbon number of 1 to 3, an alcohol, an aldehyde, etc. (preferably water vapor, oxygen, ozone) is 〇.〇. It is carried out in an environment of 5 to 5 mol%, preferably 0.1 to 1 mol%. -27- 201219408 Normally, the gas other than the oxidizing gas in the environment is an inert gas such as nitrogen, nitrogen or argon. [Embodiment] [Examples] Hereinafter, the present invention will be more specifically described by way of examples. Further, the following operations were carried out in a dry nitrogen atmosphere unless otherwise specified. Further, the solvent was dehydrated by molecular sieve 4A (manufactured by U.S.A.) and degassed by aeration of the nitrogen gas. (Synthesis Example 1-1) Preparation of titanium-containing compound solution The cyclopentadienyl titanium trichloride O.llg was placed in a 30 mL glass vessel, and 4-methylanisole was added thereto to make the total amount 25.00 g»fully stirred. After that, it was allowed to stand at room temperature for 4 hours, and then filtered using a membrane filter (manufactured by Whatman Inc.) having a pore size of 聚·1 μm made of polytetrafluoroethylene to obtain 20 pmol of a cyclopentadienyl titanium trichloride. /g solution. (Synthesis Example 1-2) Preparation of a complex of triethylamine and aluminum hydride A lithium aluminum hydride 3.8 0 g was placed in a 200 mL three-necked flask to which a magnetic stirrer was added. A 100 m L powder addition funnel, a suction plug three-way stopcock and a glass plug connected to a nitrogen flow were connected to each of the three ports of the three-necked flask. After 17.80 g of a triethylamine hydrogen chloride salt was added to the powder addition funnel, the three-necked flask was passed through a suction plug three-way stopcock to be placed under a nitrogen seal. To the above three-necked flask, 10,000 mL of hexane was added using a glass syringe. -28-201219408 After stirring with a magnetic stirrer at a number of revolutions of 10,000 rpm, the triethylamine hydrochloride was slowly dropped into a three-necked flask for 10 minutes, and stirring was continued for 2 hours. Then, the front end of the tube made of polytetrafluoroethylene was filled with a defatted cotton (the sputum smear), and the reaction mixture was pressure-fed and taken out to another container, followed by a film having a pore diameter of 0.1 μm made of polytetrafluoroethylene. A filter (manufactured by Whatman Inc.) was used for filtration. The filtrate was taken up in a 30 mL flask, and after the filtration, a magnetic stirrer was added to install a three-way stopcock. The suction plug three-way stopcock was passed through the trap and connected to the vacuum pump, and the solvent was removed by stirring with a magnetic stirrer at a number of 300 rpm while stirring. After the solvent was removed, the residue was filtered through a membrane filter (manufactured by Whatman Inc.) having a pore size of 聚·1 μm made of polytetrachloroethylene to obtain a colorless mixture of triethylamine and aluminum hydride of 1 0 · 2 5 g. Transparent liquid (yield 5 5 %). (Synthesis Example 1-3) A composition for forming an aluminum oxide film was prepared by adding 2.00 g of diisobutylaluminum hydride to 2.00 g of a complex of triethylamine and aluminum hydride, and then adding 4-methylbenzene. The methyl ether was made into a total amount of 10. 〇〇g, and a solution containing a mixture of a mixture of triethylamine and aluminum hydride and 40% by mass of a mixture of diisobutylaluminum hydride was prepared. Further, 16 μmL of a solution containing cyclopentadienyltitanium trichloride 20 μmηοΐ/g prepared in (Synthesis Example 1-1) was added to the above solution at 0.5 OmL, and the mixture was stirred at room temperature, followed by stirring for 1 minute. A composition for forming an aluminum oxide film is prepared. (Synthesis Example 2) Preparation of a composition for forming an aluminum oxide film -29 - 201219408 Adding three (twelve groups) to a complex of triethylamine and aluminum hydride synthesized in (Synthesis Example 1-2) After aluminum ((C12H25)3A1) l.OOg, the total amount is made into 10.00g by adding 4-methylanisole to prepare a complex containing triethylamine and aluminum hydride and tris(talladium)aluminum A mixture of 20% by mass of the solution. Further, 16 μL of a solution containing cyclopentadienyl titanium trichloride (preparation 1-1) prepared in (Synthesis Example 1-1) 20 μmol/g was added at room temperature with stirring, followed by stirring for 1 minute. Further, a composition for forming an aluminum oxide film is prepared. (Synthesis Example 3) Preparation of a composition for forming an aluminum oxide film After adding 4.00 g of diisobutylaluminum hydride, the total amount was changed to 10. 〇〇g by adding 4-methylanisole, and the preparation was different. A solution of 40% by mass of butyl aluminum hydride. Further, 16 μL of a solution containing cyclopentadienyltitanium trichloride 20 μm〇〇1/β prepared in (Synthesis Example 1-1) was added at room temperature with stirring in the above solution 〇5〇mL, followed by stirring. The composition for forming an aluminum oxide film was prepared by stirring for 1 minute. (Synthesis Example 4) Modification of a composition for forming an aluminum oxide film was carried out by adding trioctyltin ((C8Hi7)3A1) to 3.00 g, and then adding a total amount of 10.〇〇g by adding tert-butylbenzene to prepare a trioctane. A solution of 30% by mass of base aluminum. Further, 16 μί of a solution containing cyclopentadienyl titanium trichloride prepared in (Synthesis Example 1-1), 20 pmol/g, was added at room temperature with stirring, and then continued by 1 in the above solution. The composition for forming an aluminum oxide film was prepared by stirring for a minute. -30-201219408 (Synthesis Example 5) Preparation of a composition for forming an aluminum oxide film After adding 2.50 g of tris(talladium) ((C12H25)3A1), the total amount was changed by adding propylene glycol monomethyl ether acetate. lO.OOg, and a solution containing 25 mass% of tris(dodecyl)aluminum was prepared. Further, in the above solution 〇. 50 niL, a solution containing cyclopentadienyl titanium trichloride 20 pmol/g prepared in (Synthesis Example I-1) 16 μί, and a dimethyl polyxanthene-polyoxyalkylene group The copolymer (manufactured by Dow Corning Toray) 16PL was added under stirring at room temperature, and then the composition for forming an aluminum oxide film was prepared by stirring for 1 minute. (Synthesis Example 6) Preparation of a composition for forming an aluminum oxide film After adding 5.00 g of tris-butoxyaluminum, the total amount was changed to 10.〇〇g by adding propylene glycol monomethyl ether acetate, and the preparation was three. A composition for forming an aluminum oxide film of 50% by mass of sec-butoxy aluminum. (Synthesis Example 7) The composition for forming an aluminum oxide film was prepared by adding 4-methylanisole to 6.00 g of a complex of triethylamine and aluminum hydride to make the total amount to 10. 〇〇g. A solution of 60% by mass of a complex of triethylamine and aluminum hydride. Further, in a solution of 0.50 mL of the above solution, a solution of cyclohexadienyltitanium trichloride 20 mol/g prepared in (Synthesis Example 1-1) was added at room temperature with stirring, followed by stirring for 1 minute. Further, a composition for forming an aluminum oxide film is prepared. -31 - 201219408 (Synthesis Example B1) Preparation of a composition for forming an underlayer film bis(penta-2,4-dione)titanium(IV)diisopropyloxide 〇.3〇g and hydrazine (dimethylamine) The base 64 μm was placed in a 20 mL glass vessel, and propylene glycol monomethyl ether acetate was added thereto to make the total amount 18.00 g. After the mixture was thoroughly stirred, it was allowed to stand at room temperature for 2 hours. Then, this was filtered through a membrane filter (manufactured by Whatman Inc.) having a pore size of 聚μίί made of polytetrafluoroethylene to obtain a composition for forming an underlayer film. (Synthesis Example B-2) Preparation of a composition for forming an underlayer film propylene glycol monomethyl ether was added to 0.5 〇g of polydibutyl titanate to make the total amount 100.00 g. After the mixture was thoroughly stirred, it was allowed to stand at room temperature for 2 hours. Then, this membrane filter (manufactured by Whatman Inc.) having a pore size of μ·1 μm made of polytetrafluoroethylene was used to obtain a composition for forming an underlayer film. (Example 1) The ruthenium substrate was placed in a spin coater, and 1 mL of the composition for forming an underlayer film prepared in Synthesis (B-1) was dropped in a nitrogen atmosphere, and the rotation was performed at 3,000 rpm for 10 seconds. The clock rotates. The substrate was placed in a hot plate set at 150 ° C and heated for 25 minutes. The thickness of the underlying film is 5 nm. (a) The substrate was again placed in a spin coater under a nitrogen atmosphere, and the entire amount of the alumina-forming composition prepared in Synthesis (Example 1-3) was dropped, and rotated for 10 seconds at a rotation number of 800 rpm. . This substrate was heated in a hot plate at 150 ° C for 10 minutes in an atmospheric gas atmosphere in which the oxygen gas/nitrogen partial pressure ratio was adjusted to 1/99. -32-201219408 (b) Thereafter, the substrate was transferred to an atmospheric pressure gas atmosphere in which the oxygen gas/nitrogen partial pressure ratio was adjusted to 90/10, and then heated at 250 ° C for 30 minutes, and the surface of the substrate was covered with a pale yellow transparent film. The obtained film was analyzed by ESCA, and it was found that the film was an aluminum oxide film having a film thickness of 35 Onm. (Example 2) The surface of the substrate was coated with a pale yellow transparent film in the same manner as in Example 1 except that the composition for forming an aluminum oxide film was used as the composition for forming an aluminum oxide film. The obtained film was analyzed by ESC A, and it was found that the film was an aluminum oxide film having a film thickness of 290 η τη. (Example 3) The surface of the substrate was coated with a pale yellow transparent film in the same manner as in Example 1 except that the composition for forming an aluminum oxide film was used as the composition for forming an aluminum oxide film. The obtained film was analyzed by ESC, and it was found that the film was an aluminum oxide film having a film thickness of 260 nm. (Example 4) Metallic copper was formed into a film by sputtering on a tantalum substrate. The thickness is 5 nm. (a) The substrate was again placed in a spin coater under a nitrogen atmosphere, and the entire amount of the composition for forming an aluminum oxide film prepared in (Synthesis Example 4) was dropped, and rotated at a number of revolutions of 600 rpm for 10 seconds. The substrate was heated on a hot plate at 150 ° C for 5 minutes. (b) After that, the substrate is transferred to an atmospheric pressure gas atmosphere of adjusted oxygen gas/nitrogen partial pressure ratio -33-201219408 = 90/10, and then heated at 250 ° C for 30 minutes. The substrate surface is covered with a pale yellow transparent film. . The obtained film was subjected to ESCA analysis. This film was found to be an aluminum oxide film having a film thickness of 340 nm. (Example 5) The ruthenium substrate was placed in a spin coater 'dropped under a nitrogen gas atmosphere' (composition example B-2), and the underlying film-forming composition 1 mL ' was rotated at 3,000 rpm for 10 seconds. Rotate. The substrate was placed in a hot plate set at 200 ° C and heated for 10 minutes. The thickness of the underlying film is 5 nm. (a) The substrate was placed in a spin coater under a nitrogen atmosphere, and the entire amount of the composition for forming an aluminum oxide film prepared in Synthesis (Example 5) was dropped, and rotated at a number of revolutions of 600 rpm for 10 seconds. The substrate was heated on a hot plate at 150 ° C for 5 minutes. (b) Thereafter, the substrate was transferred to an atmospheric gas atmosphere in which the oxygen gas/nitrogen partial pressure ratio was adjusted to 90/10, and then heated at 250 ° C for 30 minutes, and the surface of the substrate was covered with a pale yellow transparent film. The obtained film was analyzed by ESCA to find that the film was an aluminum oxide film having a film thickness of 320 nm. (Example 6) The surface of the substrate was coated with a pale yellow transparent film, except that the composition for forming an alumina film was used in the same manner as in Example 5 except that the composition for forming an alumina prepared by (Synthesis Example 6) was used. The obtained film was analyzed by ESCA to find that the film was an alumina film having a film thickness of 310 nm. -34-201219408 (Comparative Example 1) The ruthenium substrate was placed in a spin coater, and 1 mL of the composition for forming an underlayer film prepared in Synthesis (B-1) was dropped in a nitrogen atmosphere, and the number of rotations was 3,000 rpm. Perform a 10 second rotation. The substrate was placed in a hot plate set at 150 ° C and heated for 25 minutes. The thickness of the underlying film was 5 nm. (a) The substrate was placed in a spin coater under a nitrogen atmosphere, and the entire amount of the alumina-forming composition prepared in Synthesis (Example 7) was dropped, and rotated at 600 rpm for 10 seconds. The substrate was heated on a hot plate at 150 ° C for 5 minutes. (b) Thereafter, the substrate was transferred to an atmospheric gas atmosphere in which the oxygen gas/nitrogen partial pressure ratio was adjusted to 90/10, and then heated at 250 ° C for 30 minutes, and the surface of the substrate was covered with a pale yellow transparent film. The obtained film was analyzed by ESCA, and it was found that the film had a film thickness of 290 nm and the upper portion of 170 nm was an aluminum oxide film, but the lower layer portion of 120 nm was a film of mixed metal aluminum and aluminum oxide. -35-

Claims (1)

201219408 七、申請專利範圍： 1. 一種氧化鋁膜形成用組成物，其特徵係含有具有 碳數1〜12之1價有機基的鋁化合物及有機溶劑。 2. 如請求項1記載之氧化鋁膜形成用組成物，其中， 前述鋁化合物爲由下述式（1-1)所表示的化合物、 下述式（1-2)所表示的化合物、下述式（1-3)所表示的 化合物、含有下述式（I-4)所表示的構造單元之化合物 、及含有下述式（1-5)所表示的構造單元之化合物所選 出之至少一種， A.lZxmR 3-mLn ( 1 — 1) (上述式（1-1)中’ Z1爲氫原子或鹵素原子，R1各自獨 立爲碳數1〜12之1價有機基，L爲配位基，m爲0〜2之整數 ，η爲0〜2之整數） 【化1】201219408 VII. Patent Application Range: 1. A composition for forming an aluminum oxide film, which comprises an aluminum compound having a monovalent organic group having 1 to 12 carbon atoms and an organic solvent. 2. The composition for forming an aluminum oxide film according to claim 1, wherein the aluminum compound is a compound represented by the following formula (1-1), a compound represented by the following formula (1-2), and The compound represented by the formula (1-3), the compound containing the structural unit represented by the following formula (I-4), and the compound containing the structural unit represented by the following formula (1-5) are selected at least A. lZxmR 3-mLn (1 - 1) (In the above formula (1-1), 'Z1 is a hydrogen atom or a halogen atom, and R1 is independently a monovalent organic group having a carbon number of 1 to 12, and L is a coordination group. Base, m is an integer of 0 to 2, and η is an integer of 0 to 2) R ‘ Κ- RZ (上述式（1-2)中，R2各自獨立，爲氫原子、鹵素原子 或碳數1〜12之1價有機基，R3各自獨立，爲碳數ι〜12之1 價有機基） 【化2】R ' Κ- RZ (In the above formula (1-2), R2 is independently a hydrogen atom, a halogen atom or a monovalent organic group having a carbon number of 1 to 12, and each of R 3 is independently a carbon number of 1 to 12; Organic base) -36- 201219408 (上述式（1-3)中’ R4各自獨立爲碳數之1價有機 基，Z2爲氫原子或g素原子） 【化3】 Vs RS-Ak R5-36- 201219408 (In the above formula (1-3), R4 is independently a monovalent organic group having a carbon number, and Z2 is a hydrogen atom or a g atom.) 3 Vs RS-Ak R5 (1-4) (上述式（1-4)中，R5及R6各自獨立，爲碳數1〜12之1 價有機基） 【化4】 R7 -|-ΑΙ-04- (1-5) (上述式（1-5)中，R7各自獨立，爲碳數1〜12之1價有 機基）。 3. 如請求項1或2記載之氧化鋁膜形成用組成物，其 中，前述氧化鋁膜形成用組成物含有鈦化合物。 4. 一種氧化鋁膜形成方法，其特徵係含有下述（a) 及（b )之步驟： (a)在基體上塗佈含有具有碳數1〜12之1價有機基 的鋁化合物及有機溶劑的氧化鋁膜形成用組成物，形成塗 膜之步驟 -37- 201219408 (b)在氧化性氣體存在下、對前述塗膜進行選自加 熱及光照射之至少一種處理，形成氧化鋁膜之步驟。 5. 如請求項4記載之氧化鋁膜形成方法，其中，前述 鋁化合物爲下述式（1-1)所表示的化合物， A1Z (1-1) (上述式（1-1)中，Ζι爲氫原子或鹵素原子，Rl各自獨 立爲碳數1〜12之1價有機基，L爲配位基，m爲〇〜2之整數 ，η爲0〜2之整數）^ 6. 如請求項4或5記載之氧化鋁膜形成方法，其中， 前述步驟（b)之氣體中氧化性氣體之濃度爲1〜1〇〇莫耳％ 〇 7. 如請求項4〜6中任1項記載之氧化鋁膜形成方法， 其中’前述氧化性氣體爲水蒸氣、氧或臭氧。 8. 如請求項4〜7中任1項記載之氧化鋁膜形成方法 ’其中’以使在前述步驟（b)該氧化鋁膜具有2 OOnrn以 上膜厚之方式’在前述步驟（a)塗佈氧化鋁膜形成用組 成物。 -38- 201219408 四 指定代表圖： (一） 本案指定代表圖為：無 (二） 本代表圖之元件代表符號簡單說明：無 201219408 五 本案若有化學式時，請揭示最能顯示發明特徵的化學 式：無(1-4) (In the above formula (1-4), R5 and R6 are each independently, and are a monovalent organic group having a carbon number of 1 to 12) [Chemical 4] R7 -|-ΑΙ-04- (1-5) (In the above formula (1-5), R7 is each independently and is a monovalent organic group having 1 to 12 carbon atoms). 3. The composition for forming an aluminum oxide film according to claim 1 or 2, wherein the composition for forming an aluminum oxide film contains a titanium compound. 4. A method for forming an aluminum oxide film, comprising the steps of (a) and (b) below: (a) coating an aluminum compound having a monovalent organic group having a carbon number of 1 to 12 on an organic substrate and organic Step of forming a coating film of a solvent for forming an aluminum oxide film - 37 - 201219408 (b) performing at least one treatment selected from the group consisting of heating and light irradiation in the presence of an oxidizing gas to form an aluminum oxide film step. 5. The method for forming an aluminum oxide film according to claim 4, wherein the aluminum compound is a compound represented by the following formula (1-1), A1Z (1-1) (in the above formula (1-1), Ζι Is a hydrogen atom or a halogen atom, R1 is each independently a monovalent organic group having a carbon number of 1 to 12, L is a ligand, m is an integer of 〇~2, and η is an integer of 0 to 2) ^ 6. The method for forming an aluminum oxide film according to 4 or 5, wherein the concentration of the oxidizing gas in the gas of the step (b) is 1 to 1 〇〇 mol% 〇 7. as recited in any one of claims 4 to 6. A method for forming an aluminum oxide film, wherein 'the aforementioned oxidizing gas is water vapor, oxygen or ozone. 8. The method for forming an aluminum oxide film according to any one of claims 4 to 7 wherein 'they' is coated in the aforementioned step (a) such that the aluminum oxide film has a film thickness of 2 OOnrn or more in the above step (b) A composition for forming an aluminum oxide film. -38- 201219408 Four designated representatives: (1) The representative representative of the case is: None (2) The representative symbol of the representative figure is a simple description: No 201219408 If there is a chemical formula in the case, please disclose the chemical formula that best shows the characteristics of the invention. :no
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