TW201821431A - Compound, raw material for forming thin film, raw material for forming thin film for use in atomic layer deposition method, andmethod for manufacturing thin film - Google Patents

Compound, raw material for forming thin film, raw material for forming thin film for use in atomic layer deposition method, andmethod for manufacturing thin film Download PDF

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TW201821431A
TW201821431A TW106135404A TW106135404A TW201821431A TW 201821431 A TW201821431 A TW 201821431A TW 106135404 A TW106135404 A TW 106135404A TW 106135404 A TW106135404 A TW 106135404A TW 201821431 A TW201821431 A TW 201821431A
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thin film
raw material
compound
film
forming
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TWI801355B (en
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佐藤宏樹
和田仙二
齋藤昭夫
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日商Ａｄｅｋａ股份有限公司
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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
    • C—CHEMISTRY; METALLURGY
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    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F17/00—Metallocenes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/28—Titanium compounds
    • 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
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40—Oxides

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  • Organic Chemistry (AREA)
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  • Condensed Matter Physics & Semiconductors (AREA)
  • Manufacturing & Machinery (AREA)
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  • Formation Of Insulating Films (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

A thin-film-forming raw material which comprises a compound represented by general formula (1) (wherein R1 to R6 each independently represent a hydrogen atom or a linear or branched C1-4 alkyl group; R7, R8, and R9 each represent a linear or branched C1-4 alkyl group; and M1 represents a zirconium or titanium atom). It is preferable that one of R1 to R5 be a methyl group and the remaining four be hydrogen atoms. It is preferable that R6 and R7 be each a methyl or ethyl group. It is preferable that R8 and R9 be each a methyl or ethyl group.

Description

化合物、薄膜形成用原料、原子層堆積法用之薄膜形成用原料及薄膜之製造方法Compound, raw material for thin film formation, raw material for thin film formation for atomic layer deposition method, and manufacturing method of thin film

[0001] 本發明係關於新穎之化合物、含有該化合物而成之薄膜形成用原料、使用該薄膜形成用原料之薄膜之製造方法。又，本發明係關於新穎之原子層堆積法用之薄膜形成用原料及使用該薄膜形成用原料之薄膜之製造方法。[0001] The present invention relates to a novel compound, a raw material for forming a thin film containing the compound, and a method for producing a thin film using the raw material for forming a thin film. The present invention relates to a novel raw material for forming a thin film for an atomic layer deposition method and a method for producing a thin film using the raw material for forming a thin film.

[0002] 含有鋯原子、鈦原子或鉿原子之薄膜，係作為高介電材料電容器、強介電材料電容器、閘極絕緣膜、阻隔膜等之電子零件之電子構件，或作為光波導、光開關、光放大器等之光通信用裝置之光學構件使用。 　　[0003] 作為上述之薄膜之製造法，雖可列舉濺鍍法、離子鍍法、塗佈熱分解法或溶膠凝膠法等之MOD法、化學氣相成長法等，但由於具有組成控制性、段差被覆性優異、適合量產化、可混合集成等多項優點，包含化學氣相成長法(以下有時亦記載為CVD法)或原子層堆積法(以下有時亦記載為ALD法)為最合適之製造過程。 　　[0004] 作為化學氣相成長法所使用之金屬供給源，雖已大量報告有各式各樣的原料，但例如非專利文獻1中，作為鈦或鋯之ALD法用原料，揭示有肆(1-二甲基胺基-2-甲基-2-丙氧基)鋯或肆(1-二甲基胺基-2-甲基-2-丙氧基)鈦。惟，藉由非專利文獻1所揭示之化合物由於為黏性非常高之液體，故輸送性不良，生產性有問題。 　　[0005] 又，專利文獻1中，作為ALD法用原料，揭示有烷基環戊二烯基(二烷基胺基)鈦。惟，使用藉由專利文獻1所揭示之化合物進行成膜時，導致有膜中之殘留碳含量增多的問題。 ［先前技術文獻］ ［專利文獻］ 　　[0006] 　　[專利文獻1]日本特表2010-539709號公報 ［非專利文獻］ 　　[0007] 　　[非專利文獻1]ECS Transactions(2009)、 25(4、Atomic layer Deposition Applications 5)、209-216[0002] Films containing zirconium atoms, titanium atoms, or hafnium atoms are electronic components used as electronic components of high-dielectric material capacitors, ferroelectric material capacitors, gate insulating films, barrier films, etc., or as optical waveguides, light Optical components of optical communication devices such as switches and optical amplifiers. [0003] Examples of the method for producing the above thin film include a MOD method such as a sputtering method, an ion plating method, a coating thermal decomposition method, a sol-gel method, and a chemical vapor growth method. , Excellent step coverage, suitable for mass production, and hybrid integration, including chemical vapor growth method (hereinafter sometimes referred to as CVD method) or atomic layer deposition method (hereinafter sometimes referred to as ALD method) are The most suitable manufacturing process. [0004] Although various raw materials have been reported in large quantities as metal supply sources used in the chemical vapor growth method, for example, in Non-Patent Document 1, as a raw material for the ALD method of titanium or zirconium, it has been disclosed ( 1-dimethylamino-2-methyl-2-propoxy) zirconium or titanium (1-dimethylamino-2-methyl-2-propoxy) titanium. However, since the compound disclosed in Non-Patent Document 1 is a highly viscous liquid, it has poor transportability and productivity problems. [0005] Further, in Patent Document 1, as a raw material for an ALD method, an alkylcyclopentadienyl (dialkylamino) titanium is disclosed. However, when a film is formed using the compound disclosed in Patent Document 1, there is a problem that the residual carbon content in the film increases. [Prior Art Documents] [Patent Documents] [0006] [Patent Literature 1] Japanese Patent Publication No. 2010-539709 [Non-Patent Literature] [0007] [Non-Patent Literature 1] ECS Transactions (2009), 25 (4, Atomic layer Deposition Applications 5), 209-216

［發明欲解決之課題］ 　　[0008] 正尋求使化學氣相成長用原料等氣化，於基質表面形成含有金屬之薄膜時，可製造蒸氣壓高，熔點低，且高品質之含有金屬之薄膜的薄膜形成用原料。以往所知之薄膜形成用原料中，並未有顯示如此物性者。其中，為了提昇生產性，由於有必要提高薄膜形成用原料之輸送性，已強烈尋求熔點低且黏度低之材料。又，由於已知以ALD法製造之薄膜較以MOCVD法製造之薄膜有較高品質，期望可用ALD法製造含有金屬之薄膜，可解決上述課題之薄膜形成用原料。 ［用以解決課題之手段］ 　　[0009] 本發明者等經努力研究的結果，發現特定之化合物可解決上述課題，而完成本發明。又，本發明者等發現含有特定之化合物之原子層堆積法用之薄膜形成用原料可解決上述課題，而達成本發明。 　　[0010] 本發明係提供下述一般式(1)表示之化合物。 　　[0011][0012] (式中，R1 ～R6 分別獨立表示氫或碳原子數1～4之直鏈或分支狀之烷基，R7 、R8 及R9 表示碳原子數1～4之直鏈或分支狀之烷基，M1 表示鋯或鈦)。 　　[0013] 又，本發明係提供一種原子層堆積法用之薄膜形成用原料，其係含有下述一般式(2)表示之化合物而成。 　　[0014][0015] (式中，R11 ～R16 分別獨立表示氫或碳原子數1～4之直鏈或分支狀之烷基，R17 、R18 及R19 表示碳原子數1～4之直鏈或分支狀之烷基，M2 表示鋯、鉿或鈦)。 ［發明的效果］ 　　[0016] 根據本發明，可得到蒸氣壓高，藉由常壓30℃或稍微加溫成為液體，且黏度低之化合物。該化合物特別適合作為用以形成藉由CVD法或ALD法等之方法的含有金屬之薄膜所使用之薄膜形成用原料。又，根據本發明，可得到可形成高品質之含有金屬之薄膜的原子層堆積法用之薄膜形成用原料。[Problems to be Solved by the Invention] [0008] It is seeking to vaporize raw materials for chemical vapor growth, and to form a metal-containing film on the surface of a substrate, to produce a high-quality metal-containing film having a high vapor pressure, a low melting point, and the like. Raw materials for film formation. None of the conventionally known raw materials for forming a thin film exhibits such physical properties. Among them, in order to improve productivity, since it is necessary to improve the transportability of raw materials for film formation, materials with low melting points and low viscosity have been strongly sought. In addition, since a thin film manufactured by the ALD method is known to have higher quality than a thin film manufactured by the MOCVD method, it is expected that a metal-containing thin film can be manufactured by the ALD method, and a raw material for thin film formation that can solve the above-mentioned problems. [Means to Solve the Problem] [0009] As a result of diligent research, the present inventors discovered that a specific compound can solve the above-mentioned problems, and completed the present invention. In addition, the present inventors have found that the raw materials for thin film formation for the atomic layer deposition method containing a specific compound can solve the above-mentioned problems and achieve the present invention. [0010] The present invention provides a compound represented by the following general formula (1). [0011] [Wherein R 1 to R 6 each independently represent hydrogen or a linear or branched alkyl group having 1 to 4 carbon atoms, and R 7 , R 8 and R 9 each represent a straight group having 1 to 4 carbon atoms A chain or branched alkyl group, M 1 represents zirconium or titanium). [0013] The present invention also provides a raw material for forming a thin film for an atomic layer deposition method, which comprises a compound represented by the following general formula (2). [0014] [Wherein R 11 to R 16 each independently represent hydrogen or a linear or branched alkyl group having 1 to 4 carbon atoms, and R 17 , R 18 and R 19 each represent a straight group having 1 to 4 carbon atoms Chain or branched alkyl, M 2 represents zirconium, hafnium or titanium). [Effects of the Invention] According to the present invention, a compound having a high vapor pressure, which becomes a liquid at a normal pressure of 30 ° C or a slight warming, and a low viscosity can be obtained. This compound is particularly suitable as a raw material for forming a thin film for forming a metal-containing thin film by a method such as a CVD method or an ALD method. In addition, according to the present invention, a raw material for forming a thin film for an atomic layer deposition method capable of forming a high-quality metal-containing thin film can be obtained.

[0018] 本發明之化合物係上述一般式(1)表示者，適合作為具有CVD法等之氣化步驟之薄膜製造方法的前驅物者，亦可使用ALD法形成薄膜。本發明之化合物係於常壓30℃或稍微加溫成為液體，且黏度低之化合物。由於熔點低且黏度低之化合物輸送性良好，適合作為具有CVD法等之氣化步驟之薄膜製造方法的前驅物。 　　[0019] 在上述一般式(1)，作為R1 ～R9 表示之碳原子數1～4之直鏈或分支狀之烷基，例如可列舉甲基、乙基、丙基、異丙基、丁基、異丁基、第2丁基、第3丁基等。 　　[0020] 從化合物之熔點低的觀點來看，在上述一般式(1)，以R1 ～R5 為氫或甲基之化合物較佳，以R1 ～R5 全部為氫或R1 ～R5 當中之一個為甲基且殘留之4個為氫之化合物特佳。從化合物之熔點低且蒸氣壓高的觀點來看，在上述一般式(1)，R6 較佳為氫、1級之烷基或2級之烷基之化合物，更佳為甲基、乙基、丙基或異丙基之化合物，特佳為甲基、乙基或丙基之化合物。從化合物之熔點低且蒸氣壓高的觀點來看，在上述一般式(1)，R7 較佳為1級之烷基或2級之烷基之化合物，更佳為甲基、乙基、丙基或異丙基之化合物，特佳為甲基、乙基或丙基之化合物。在上述一般式(1)，R6 及R7 為甲基或乙基之化合物，由於熔點低且蒸氣壓高，故較佳。在上述一般式(1)，R8 及R9 較佳為1級之烷基之化合物，更佳為甲基、乙基或丙基之化合物，特佳為甲基或乙基之化合物。藉由未伴隨氣化步驟之MOD法之薄膜的製造方法時，R1 ～R9 可藉由對於所使用溶劑之溶解性、薄膜形成反應等適當選擇。 　　[0021] 在上述一般式(1)，作為M1 為鋯之化合物的較佳具體例，例如可列舉下述化合物No.1～No.18。尚，在下述化合物No.1～No.18，「Me」表示甲基，「Et」表示乙基。 　　[0022][0023][0024] 在上述一般式(1)，作為M1 為鈦之化合物的較佳具體例，例如可列舉下述化合物No.19～No.36。尚，在下述化合物No.19～No.36，「Me」表示甲基，「Et」表示乙基。 　　[0025][0026][0027] 本發明之化合物並未因其製造方法而有特別限制，應用周知之反應進行製造。上述一般式(1)表示之化合物當中，製造M1 為鋯之化合物時，例如將肆(二烷基胺基)鋯作為出發原料，使此環戊二烯或烷基環戊二烯反應後，可藉由使對應之構造的二烷基胺基醇進行反應製得。製造M1 為鈦之化合物時，作為出發原料，除了使用肆(烷基胺基)鈦等之外，可用與上述之製造方法相同之方法製得。 　　[0028] 所謂本發明之薄膜形成用原料，係將上述所說明之本發明之化合物作為薄膜之前驅物，其形態因適用該薄膜形成用原料之製造過程而有所不同。例如製造僅包含鋯原子或鈦原子之薄膜時，本發明之薄膜形成用原料並未含有上述化合物以外之金屬化合物。另外，製造包含2種以上之金屬及/或類金屬之薄膜時，本發明之薄膜形成用原料除了上述化合物，含有包含所期望金屬之化合物及/或包含類金屬之化合物(以下亦稱為其他前驅物)。本發明之薄膜形成用原料如後述，可進一步含有有機溶劑及/或親核試劑。本發明之薄膜形成用原料如上述說明，由於前驅物之化合物之物性適合CVD法、ALD法，尤其是作為化學氣相成長用原料(以下有時亦稱為CVD用原料)有用。 　　[0029] 本發明之薄膜形成用原料為化學氣相成長用原料時，其形態係藉由所使用之CVD法的輸送供給方法等之手法適當選擇者。 　　[0030] 作為上述之輸送供給方法，有藉由將CVD用原料於儲存該原料之容器(以下有時亦只記載為原料容器)中進行加熱及/或減壓，使其氣化而成為蒸氣，與如有必要使用之氬、氮、氦等之載體氣體一起，將該蒸氣對設置基質之成膜腔室內(以下有時亦記載為堆積反應部)導入之氣體輸送法、藉由將CVD用原料以液體或溶液之狀態輸送至氣化室，於氣化室進行加熱及/或減壓使其氣化而成為蒸氣，將該蒸氣對成膜腔室內導入之液體輸送法。氣體輸送法的情況，可將上述一般式(1)表示之化合物本身作為CVD用原料。液體輸送法的情況，可將上述一般式(1)表示之化合物本身或可將該化合物溶解於有機溶劑之溶液作為CVD用原料。此等之CVD用原料可進一步包含其他前驅物或親核試劑等。 　　[0031] 又，多成分系之CVD法中，有將CVD用原料以各成分獨立進行氣化、供給之方法(以下有時亦記載為單一來源法)、與預先將多成分原料以所期望之組成混合之混合原料進行氣化、供給之方法(以下有時亦記載為混合來源法(Cocktail source method))。混合來源法的情況，可將本發明之化合物與其他前驅物的混合物或將該混合物溶解於有機溶劑之混合溶液作為CVD用原料。此混合物或混合溶液可進一步包含親核試劑等。 　　[0032] 作為上述之有機溶劑，並未特別限制，可使用周知一般的有機溶劑。作為該有機溶劑，例如可列舉乙酸乙酯、乙酸丁酯、乙酸甲氧基乙酯等之乙酸酯類；四氫呋喃、四氫吡喃、乙二醇二甲基醚、二乙二醇二甲基醚、三乙二醇二甲基醚、二丁基醚、二噁烷等之醚類；甲基丁基酮、甲基異丁基酮、乙基丁基酮、二丙基酮、二異丁基酮、甲基戊基酮、環己酮、甲基環己酮等之酮類；己烷、環己烷、甲基環己烷、二甲基環己烷、乙基環己烷、庚烷、辛烷、甲苯、二甲苯等之烴類；1-氰基丙烷、1-氰基丁烷、1-氰基己烷、氰基環己烷、氰基苯、1,3-二氰基丙烷、1,4-二氰基丁烷、1,6-二氰基己烷、1,4-二氰基環己烷、1,4-二氰基苯等具有氰基之烴類；吡啶、二甲基砒啶(Lutidine)等。此等之有機溶劑因溶質的溶解性、使用溫度與沸點、閃燃點的關係等，可單獨使用，或混合二種以上使用。使用此等之有機溶劑時，將前驅物溶解於有機溶劑之溶液之在CVD用原料中之前驅物整體的量以成為0.01～2.0莫耳/升較佳，尤其是以成為0.05～1.0莫耳/升特佳。所謂前驅物整體的量，係指本發明之薄膜形成用原料未含有本發明之化合物以外之金屬化合物及類金屬化合物時，為本發明之化合物的量，本發明之薄膜形成用原料除了該化合物之外，含有包含其他金屬之化合物及/或包含類金屬之化合物(其他前驅物)時，為本發明之化合物及其他前驅物的合計量。 　　[0033] 又，多成分系之CVD法的情況中，作為與本發明之化合物一起使用之其他前驅物，並未特別限制，可使用CVD用原料所使用之周知一般的前驅物。 　　[0034] 作為上述之其他前驅物，可列舉選自由氫化物、氫氧化物、鹵素化物、疊氮化物、烷基、烯基、環烷基、芳基、炔基、胺基、二烷基胺基烷基、單烷基胺基、二烷基胺基、二胺、二(矽烷基-烷基)胺基、二(烷基-矽烷基)胺基、二矽烷基胺基、烷氧基、烷氧基烷基、醯肼、磷化物、腈、二烷基胺基烷氧基、烷氧基烷基二烷基胺基、矽烷氧基、雙酮基(Diketonate)、環戊二烯基、矽烷基、吡唑特(Pyrazolate)、胍化物(Guanidinate)、磷醯胍酸根(Phosphoguanidinate)、脒鹽(Amidinate)、酮亞胺鹽(Ketoiminate)、二酮胺(Diketiminate)、具有將羰基及磷脒鹽(Phosphoamidinate)作為配位子之化合物所組成群組中之一種或二種以上之矽或金屬的化合物。 　　[0035] 作為前驅物的金屬種，可列舉鎂、鈣、鍶、鋇、鐳、鈧、鋯、鈦、鉿、釔、釩、鈮、鉭、錳、鐵、鉻、鉬、鎢、鋨、釕、鈷、銠、銥、鎳、鈀、鉑、銅、銀、金、鋅、鋁、鎵、銦、鍺、錫、鉛、銻、鉍、釔、鑭、鈰、鐠、釹、鉕、釤、銪、釓、鋱、鏑、鈥、鉺、銩、鐿。 　　[0036] 上述之其他前驅物，在該發明所屬之技術範圍係周知者，其製造方法亦為周知。列舉製造方法之一例，例如使用醇化合物作為有機配位子時，藉由使先前所敘述之金屬的無機鹽或其水合物、與該醇化合物的鹼金屬烷氧化物進行反應，可製造前驅物。於此作為金屬的無機鹽或其水合物，可列舉金屬的鹵素化物、硝酸鹽等，作為鹼金屬烷氧化物，可列舉鈉烷氧化物、鋰烷氧化物、鉀烷氧化物等。 　　[0037] 上述之其他前驅物為單一來源法的情況時，較佳為本發明之化合物、與類似熱及/或氧化分解之舉動的化合物，混合來源法的情況時，除了類似熱及/或氧化分解之舉動之外，以混合時不引起因化學反應等導致變質者較佳。 　　[0038] 又，本發明之薄膜形成用原料中，如有必要，為了賦予本發明之化合物及其他前驅物的穩定性，亦可含有親核試劑。作為該親核試劑，可列舉甘醇二甲醚、二甘醇二甲醚、三甘醇二甲醚、四甘醇二甲醚等之乙二醇醚類、18-冠(Crown)-6、二環己基-18-冠-6、24-冠-8、二環己基-24-冠-8、二苯并-24-冠-8等之冠醚類、乙二胺、N,N,N’N’-四甲基乙二胺、二乙烯三胺、三乙烯四胺、四乙烯五胺、五乙烯六胺、1,1,4,7,7-五甲基二乙烯三胺、1,1,4,7,10,10-六甲基三乙烯四胺、三乙氧基三乙烯胺等之多胺類、1,4,7,11-四氮雜環十四烷(Cyclam)、環烯(Cyclene)等之環狀多胺類、吡啶、吡咯烷、哌啶、嗎啉、N-甲基吡咯烷、N-甲基哌啶、N-甲基嗎啉、四氫呋喃、四氫吡喃、1,4-二噁烷、噁唑、噻唑、硫雜環戊烷(Oxathiolane)等之雜環化合物類、乙醯乙酸甲酯、乙醯乙酸乙酯、乙醯乙酸-2-甲氧基乙酯等之β-酮酯類或乙醯丙酮、2,4-己烷二酮、2,4-庚烷二酮、3,5-庚烷二酮、雙三甲基乙醯基甲烷(Dipivaloylmethane)等之β-二酮類，此等之親核試劑的使用量，相對於前驅物整體的量1莫耳較佳為0.1莫耳～10莫耳的範圍，更佳為1～4莫耳。 　　[0039] 本發明之薄膜形成用原料中，盡可能使其不包含構成該原料之成分以外的雜質金屬元素分、雜質氯等之雜質鹵素分及雜質有機分。雜質金屬元素分較佳為每一元素為100ppb以下，更佳為10ppb以下，以總量較佳為1ppm以下，更佳為100ppb以下。尤其是作為LSI之閘極絕緣膜、閘極膜、阻隔層使用時，必須減少對所得之薄膜有電氣特性影響之鹼金屬元素及鹼土類金屬元素的含量。雜質鹵素分較佳為100ppm以下，更佳為10ppm以下，最佳為1ppm以下。雜質有機分，以總量較佳為500ppm以下，更佳為50ppm以下，最佳為10ppm以下。又，由於水分成為在化學氣相成長用原料中的粒子產生，或在薄膜形成中之粒子產生的原因，故針對前驅物、有機溶劑及親核試劑，為了減低個別的水分，使用時盡可能提早去除水分較佳。前驅物、有機溶劑及親核試劑個別的水分量較佳為10ppm以下，更佳為1ppm以下。 　　[0040] 又，本發明之薄膜形成用原料為了減低或防止所形成薄膜的粒子汚染，以盡可能使其不包含粒子較佳。具體而言，藉由於液相的光散射式液中粒子檢測器之粒子測定中，大於0.3μm之粒子的數目於液相1mL中為100個以下較佳，大於0.2μm之粒子的數目於液相1mL中為1000個以下更佳，大於0.2μm之粒子的數目於液相1mL中為100個以下最佳。 　　[0041] 作為使用本發明之薄膜形成用原料，製造薄膜之本發明之薄膜的製造方法，有藉由將使本發明之薄膜形成用原料氣化之蒸氣，及如有必要所使用之反應性氣體，導入設置基質之成膜腔室內，其次，於基質上使前驅物進行分解及/或化學反應，將含有金屬之薄膜成長於基質表面，使其堆積之CVD法。對於原料之輸送供給方法、堆積方法、製造條件、製造裝置等，並未特別受到限制，可使用周知一般之條件及方法。 　　[0042] 作為上述如有必要所使用之反應性氣體，例如作為氧化性者，可列舉氧、臭氧、二氧化氮、一氧化氮、水蒸氣、過氧化氫、甲酸、乙酸、乙酸酐等，作為還原性者可列舉氫，又，作為製造氮化物者，可列舉單烷基胺、二烷基胺、三烷基胺、伸烷基二胺等之有機胺化合物、肼、氨等，此等可使用1種或2種以上。此等當中，由於本發明之薄膜形成用原料與臭氧的反應性良好，作為反應性氣體，使用1種時，較佳為使用臭氧，作為反應性氣體，使用2種以上之混合氣體時，較佳為至少包含臭氧。 　　[0043] 又，作為上述之輸送供給方法，可列舉前述之氣體輸送法、液體輸送法、單一來源法、混合來源法等。 　　[0044] 又，作為上述之堆積方法，可列舉將原料氣體或原料氣體與反應性氣體僅由熱使其反應，而堆積薄膜之熱CVD、使用熱與電漿之電漿CVD、使用熱與光之光CVD、使用熱、光及電漿之光電漿CVD、將CVD之堆積反應分成基本過程，以分子級別進行階段性堆積之ALD。 　　[0045] 作為上述基質的材質，例如可列舉矽；氮化矽、氮化鈦、氮化鉭、氧化鈦、氮化鈦、氧化釕、氧化鋯、氧化鉿、氧化鑭等之陶瓷；玻璃；金屬釕等之金屬。作為基質的形狀，可列舉板狀、球狀、纖維狀、鱗片狀。基質表面可為平面，可成為溝槽構造等之三次元構造。 　　[0046] 又，作為上述之製造條件，可列舉反應溫度(基質溫度)、反應壓力、堆積速度等。對於反應溫度，充分反應本發明之化合物的溫度較佳為100℃以上，更佳為150℃～400℃，特佳為200℃～350℃。又，反應壓力於熱CVD或光CVD時，較佳為大氣壓～10Pa，使用電漿時，較佳為2000Pa～10Pa。 　　又，堆積速度可由原料的供給條件(氣化溫度、氣化壓力)、反應溫度、反應壓力來控制。由於堆積速度快時，有所得之薄膜的特性惡化的情況，慢時有生產性產生問題的情況，故較佳為0.01～100nm/分鐘，更佳為1～50nm/分鐘。又，ALD法時，以能得到所期望膜厚的方式以循環的次數控制。 　　[0047] 作為上述之製造條件，可進一步列舉使薄膜形成用原料氣化成為蒸氣時之溫度或壓力。使薄膜形成用原料氣化成為蒸氣的步驟，可於原料容器內進行，可於氣化室內進行。任一種情況下，以本發明之薄膜形成用原料於0～150℃蒸發較佳。又，於原料容器內或氣化室內使薄膜形成用原料氣化成為蒸氣時，以原料容器內之壓力及氣化室內之壓力皆為1～10000Pa較佳。 　　[0048] 本發明之薄膜的製造方法採用ALD法，除了由上述之輸送供給方法，使薄膜形成用原料氣化成為蒸氣，將該蒸氣導入成膜腔室內之原料導入步驟之外，可具有：由該蒸氣中之上述化合物於上述基質的表面形成前驅物薄膜之前驅物薄膜成膜步驟、排氣未反應之化合物氣體之排氣步驟及使該前驅物薄膜與反應性氣體進行化學反應，而於該基質的表面，形成含有金屬之薄膜的含金屬之薄膜形成步驟。 　　[0049] 於以下，對於上述之各步驟，詳細說明形成金屬氧化物薄膜的情況。將金屬氧化物薄膜由ALD法形成時，首先，進行於前述說明之原料導入步驟。將薄膜形成用原料成為蒸氣時較佳之溫度或壓力係與於上述說明者相同。其次，由導入堆積反應部之化合物，使前驅物薄膜成膜於基質表面(前驅物薄膜成膜步驟)。此時，加熱基質或加熱堆積反應部，可加入熱。於此步驟成膜之前驅物薄膜，係從本發明之化合物所生成之薄膜，或本發明之化合物的一部分進行分解及/或反應所生成之薄膜，與目的之金屬氧化物薄膜具有不同之組成。進行本步驟時之基質溫度，較佳為室溫～500℃，更佳為150～350℃。進行本步驟時之系統(成膜腔室內)的壓力較佳為1～10000Pa，更佳為10～1000Pa。 　　[0050] 其次，從堆積反應部，排氣未反應之化合物氣體或副產物之氣體(排氣步驟)。未反應之化合物氣體或副產物之氣體，雖然理想為從堆積反應部完全排氣，但並非一定要完全排氣。作為排氣方法，可列舉由氮、氦、氬等之惰性氣體掃氣(Purge)系統內之方法、藉由減壓系統內進行排氣之方法、組合此等方法之方法等。減壓時之減壓度較佳為0.01～300Pa，更佳為0.01～100Pa。 　　[0051] 其次，導入氧化性氣體於堆積反應部，由該氧化性氣體之作用或氧化性氣體及熱之作用，從先前之前驅物薄膜成膜步驟得到之前驅物薄膜形成金屬氧化物薄膜(含金屬氧化物之薄膜形成步驟)。本步驟中使熱產生作用時之溫度，較佳為室溫～500℃，更佳為150～350℃。進行本步驟時之系統(成膜腔室內)的壓力較佳為1～10000Pa，更佳為10～1000Pa。本發明之化合物與氧化性氣體的反應性良好，可得到殘留碳含量少且高品質之金屬氧化物薄膜。 　　[0052] 本發明之薄膜的製造方法中，如上述採用ALD法時，可將藉由由上述之原料導入步驟、前驅物薄膜成膜步驟、排氣步驟及含金屬氧化物之薄膜形成步驟所構成之一連串操作之薄膜堆積作為1循環，可將此循環重複多次直到得到必要膜厚的薄膜為止。此情況下，進行1循環後，與上述排氣步驟同樣進行，從堆積反應部排氣未反應之化合物氣體及反應性氣體(形成金屬氧化物薄膜時為氧化性氣體)，進而排氣副成之氣體後，以進行下一個循環較佳。 　　[0053] 又，藉由金屬氧化物薄膜之ALD法之形成中，可施加電漿、光、電壓等之能量，可使用觸媒。施加該能量之時期及使用觸媒之時期並未特別限定，例如可在原料導入步驟之化合物氣體導入時、在前驅物薄膜成膜步驟或含金屬氧化物之薄膜形成步驟之加溫時、在排氣步驟之系統內的排氣時、在含金屬氧化物之薄膜形成步驟之氧化性氣體導入時，亦可於上述之各步驟之間。 　　[0054] 又，本發明之薄膜的製造方法中，薄膜堆積之後，為了得到更良好之電氣特性，可於惰性環境下、氧化性環境下或還原性環境下進行退火處理，有必要段差嵌入時，可設置回流步驟。此時之溫度為200～1000℃，較佳為250～500℃。 　　[0055] 使用本發明之薄膜形成用原料製造薄膜之裝置，可使用周知之化學氣相成長法用裝置。作為具體裝置之例，可列舉可將如圖1之前驅物以起泡供給進行之裝置或如圖2具有氣化室之裝置。又，如圖3及圖4可列舉對於反應性氣體進行電漿處理之裝置。並不限於如圖1～圖4之單片式裝置，亦可使用使用批量爐之可多片同時處理之裝置。 　　[0056] 含有使用本發明之薄膜形成用原料所製造之金屬的薄膜，已被使用在切削工具、電子材料用之配線或電極，例如可使用在半導體記憶體材料或鋰空氣電池用之電極等。 　　[0057] 本發明之原子層堆積法用之薄膜形成用原料，係含有下述一般式(2)表示之化合物者。 　　[0058][0059] (式中，R11 ～R16 分別獨立表示氫或碳原子數1～4之直鏈或分支狀之烷基，R17 、R18 及R19 表示碳原子數1～4之直鏈或分支狀之烷基，M2 表示鋯、鉿或鈦)。 　　[0060] 在上述一般式(2)，作為R11 ～R19 表示之碳原子數1～4之直鏈或分支狀之烷基，例如可列舉甲基、乙基、丙基、異丙基、丁基、異丁基、第2丁基、第3丁基等。 　　[0061] 從化合物之熔點低的觀點來看，在上述一般式(2)，以R11 ～R15 為氫或甲基之化合物較佳，以R11 ～R15 全部為氫或R11 ～R15 當中之一個為甲基且殘留之4個為氫之化合物特佳。從化合物之熔點低且蒸氣壓高的觀點來看，在上述一般式(2)，R16 較佳為氫、1級之烷基或2級之烷基之化合物，更佳為甲基、乙基、丙基或異丙基之化合物，特佳為甲基、乙基或丙基之化合物。從化合物之熔點低且蒸氣壓高的觀點來看，在上述一般式(2)，R17 較佳為1級之烷基或2級之烷基之化合物，更佳為甲基、乙基、丙基或異丙基之化合物，特佳為甲基、乙基或丙基之化合物。在上述一般式(2)，R16 及R17 為甲基或乙基之化合物由於熔點低且蒸氣壓高故較佳。在上述一般式(2)，以R18 及R19 為1級之烷基之化合物較佳，更佳為甲基、乙基或丙基之化合物，特佳為甲基或乙基之化合物。 　　[0062] 作為上述一般式(2)表示之化合物之較佳具體例，除了可列舉上述之化合物No.1～36之外，在上述一般式(2)，作為M2 為鉿之化合物，亦可列舉下述化合物No.37～No.54。尚，在下述化合物No.37～No.54，「Me」表示甲基，「Et」表示乙基。 　　[0063][0064][0065] 本發明之原子層堆積法用之薄膜形成用原料所使用之化合物並未因其製造方法而有特別限制，應用周知之反應進行製造。上述一般式(2)表示之化合物當中，製造M2 為鋯或鈦之化合物時，可用上述之方法製得。製造M2 為鉿之化合物時，作為出發原料，除了使用肆(烷基胺基)鉿等之外，可用與上述之製造方法相同之方法製得。 　　[0066] 本發明之原子層堆積法用之薄膜形成用原料(以下有時亦稱為ALD用原料)的形態，可藉由所使用之ALD法的輸送供給方法等之手法適當選擇。 　　[0067] 作為上述之輸送供給方法，有藉由將ALD用原料於儲存該原料之容器(以下有時亦只記載為原料容器)中進行加熱及/或減壓，使其氣化而成為蒸氣，如有必要使用之氬、氮、氦等之載體氣體一起，將該蒸氣對設置基質之堆積反應部導入之氣體輸送法、藉由將ALD用原料以液體或溶液之狀態輸送至氣化室，於氣化室進行加熱及/或減壓使其氣化而成為蒸氣，將該蒸氣對成膜腔室內導入之液體輸送法。氣體輸送法的情況，可將上述一般式(2)表示之化合物本身作為ALD用原料。液體輸送法的情況，可將上述一般式(2)表示之化合物本身或可將該化合物溶解於有機溶劑之溶液作為ALD用原料。此等之ALD用原料可進一步包含親核試劑等。 　　[0068] 作為上述之有機溶劑，並未特別限制，可使用周知一般的有機溶劑。作為該有機溶劑，例如可列舉乙酸乙酯、乙酸丁酯、乙酸甲氧基乙酯等之乙酸酯類；四氫呋喃、四氫吡喃、乙二醇二甲基醚、二乙二醇二甲基醚、三乙二醇二甲基醚、二丁基醚、二噁烷等之醚類；甲基丁基酮、甲基異丁基酮、乙基丁基酮、二丙基酮、二異丁基酮、甲基戊基酮、環己酮、甲基環己酮等之酮類；己烷、環己烷、甲基環己烷、二甲基環己烷、乙基環己烷、庚烷、辛烷、甲苯、二甲苯等之烴類；1-氰基丙烷、1-氰基丁烷、1-氰基己烷、氰基環己烷、氰基苯、1,3-二氰基丙烷、1,4-二氰基丁烷、1,6-二氰基己烷、1,4-二氰基環己烷、1,4-二氰基苯等具有氰基之烴類；吡啶、二甲基砒啶(Lutidine)等，此等之有機溶劑因溶質的溶解性、使用溫度與沸點、閃燃點的關係等，可單獨使用，或混合二種以上使用。使用此等之有機溶劑時，將上述一般式(2)表示之化合物溶解於有機溶劑之溶液之在ALD用原料中之上述一般式(2)表示之化合物的量以成為0.01～2.0莫耳/升較佳，以成為0.05～1.0莫耳/升特佳。 　　[0069] 又，原子層堆積法用之薄膜形成用原料中，如有必要，為了賦予本發明之化合物的穩定性，亦可含有親核試劑。作為該親核試劑，可列舉甘醇二甲醚、二甘醇二甲醚、三甘醇二甲醚、四甘醇二甲醚等之乙二醇醚類、18-冠(Crown)-6、二環己基-18-冠-6、24-冠-8、二環己基-24-冠-8、二苯并-24-冠-8等之冠醚類、乙二胺、N,N’-四甲基乙二胺、二乙烯三胺、三乙烯四胺、四乙烯五胺、五乙烯六胺、1,1,4,7,7-五甲基二乙烯三胺、1,1,4,7,10,10-六甲基三乙烯四胺、三乙氧基三乙烯胺等之多胺類、1,4,7,11-四氮雜環十四烷(Cyclam)、環烯(Cyclene)等之環狀多胺類、吡啶、吡咯烷、哌啶、嗎啉、N-甲基吡咯烷、N-甲基哌啶、N-甲基嗎啉、四氫呋喃、四氫吡喃、1,4-二噁烷、噁唑、噻唑、硫雜環戊烷(Oxathiolane)等之雜環化合物類、乙醯乙酸甲酯、乙醯乙酸乙酯、乙醯乙酸-2-甲氧基乙酯等之β-酮酯類或乙醯丙酮、2,4-己烷二酮、2,4-庚烷二酮、3,5-庚烷二酮、雙三甲基乙醯基甲烷(Dipivaloylmethane)等之β-二酮類。此等之親核試劑的使用量，相對於上述一般式(2)表示之化合物的量1莫耳較佳為0.1莫耳～10莫耳的範圍，更佳為1～4莫耳。 　　[0070] 本發明之原子層堆積法用之薄膜形成用原料中，盡可能使其不包含構成該原料之成分以外的雜質金屬元素分、雜質氯等之雜質鹵素分及雜質有機分。雜質金屬元素分較佳為每一元素為100ppb以下，更佳為10ppb以下，以總量較佳為1ppm以下，更佳為100ppb以下。尤其是作為LSI之閘極絕緣膜、閘極膜、阻隔層使用時，必須減少對所得之薄膜有電氣特性影響之鹼金屬元素及鹼土類金屬元素的含量。雜質鹵素分較佳為100ppm以下，更佳為10ppm以下，最佳為1ppm以下。雜質有機分，以總量較佳為500ppm以下，更佳為50ppm以下，最佳為10ppm以下。又，由於水分成為在化學氣相成長用原料中的粒子產生，或在薄膜形成中之粒子產生的原因，故針對上述一般式(2)表示之化合物、有機溶劑及親核試劑，為了減低個別的水分，使用時盡可能提早去除水分較佳。上述一般式(2)表示之化合物、有機溶劑及親核試劑個別的水分量較佳為10ppm以下，更佳為1ppm以下。 　　[0071] 又，本發明之原子層堆積法用之薄膜形成用原料為了減低或防止所形成薄膜的粒子汚染，以盡可能使其不包含粒子較佳。具體而言，藉由於液相的光散射式液中粒子檢測器之粒子測定中，大於0.3μm之粒子的數目於液相1mL中為100個以下較佳，大於0.2μm之粒子的數目於液相1mL中為1000個以下更佳，大於0.2μm之粒子的數目於液相1mL中為100個以下最佳。 　　[0072] 作為使用本發明之原子層堆積法用之薄膜形成用原料，藉由ALD法製造薄膜之本發明之薄膜的製造方法，並未特別受到限制，可使用上述之周知一般的條件及方法。 　　[0073] 作為藉由ALD法之薄膜之製造時所使用之反應性氣體，例如作為氧化性者，可列舉氧、臭氧、二氧化氮、一氧化氮、水蒸氣、過氧化氫、甲酸、乙酸、乙酸酐等，作為還原性者可列舉氫，又，作為製造氮化物者，可列舉單烷基胺、二烷基胺、三烷基胺、伸烷基二胺等之有機胺化合物、肼、氨等，此等可使用1種或2種以上。此等當中，本發明之原子堆積法用之薄膜形成用原料由於與臭氧的反應性良好，作為反應性氣體，使用1種時，較佳為使用臭氧，作為反應性氣體，使用2種以上之混合氣體時，較佳為至少包含臭氧。 　　[0074] 又，作為藉由ALD法之薄膜之製造時之輸送供給方法，可列舉前述之氣體輸送法、液體輸送法、單一來源法、混合來源法等。 　　[0075] 作為藉由ALD法之薄膜之製造所使用之基質的材質，例如可列舉矽；氮化矽、氮化鈦、氮化鉭、氧化鈦、氮化鈦、氧化釕、氧化鋯、氧化鉿、氧化鑭等之陶瓷；玻璃；金屬釕等之金屬。作為基質的形狀，可列舉板狀、球狀、纖維狀、鱗片狀。基質表面可為平面，可成為溝槽構造等之三次元構造。 　　[0076] 又，作為上述之製造條件，可列舉反應溫度(基質溫度)、堆積速度等。對於反應溫度，充分反應上述一般式(2)表示之化合物的溫度較佳為100℃以上，更佳為150℃～400℃，特佳為150℃～350℃。又，堆積速度可由原料的供給條件(氣化溫度、氣化壓力)、反應溫度、反應壓力來控制。由於堆積速度快時，有所得之薄膜的特性惡化的情況，慢時有生產性產生問題的情況，故較佳為0.01～0.1nm/循環。 　　[0077] 作為上述之製造條件，可進一步列舉使原子層堆積法用之薄膜形成用原料氣化成為蒸氣時之溫度或壓力。使原子層堆積法用之薄膜形成用原料氣化成為蒸氣的步驟，可於原料容器內進行，可於氣化室內進行。任一種情況下，以本發明之原子層堆積法用之薄膜形成用原料於0～150℃蒸發較佳。又，於原料容器內或氣化室內使原子層堆積法用之薄膜形成用原料氣化成為蒸氣時，以原料容器內之壓力及氣化室內之壓力皆為1～10000Pa較佳。 　　[0078] 本發明之薄膜的製造方法採用ALD法，除了由上述之輸送供給方法，使原子層堆積法用之薄膜形成用原料氣化成為蒸氣，將該蒸氣導入成膜腔室內之原料導入步驟之外，可具有：由該蒸氣中之上述一般式(2)表示之化合物於上述基質的表面形成前驅物薄膜之前驅物薄膜成膜步驟、排氣未反應之化合物氣體之排氣步驟及使該前驅物薄膜與反應性氣體進行化學反應，而於該基質的表面，形成含有金屬之薄膜的含金屬之薄膜形成步驟。 　　[0079] 於以下，對於上述之各步驟，為例詳細說明形成金屬氧化物薄膜的情況。將金屬氧化物薄膜由ALD法形成時，首先，進行於前述說明之原料導入步驟。將原子層堆積法用之薄膜形成用原料成為蒸氣時較佳之溫度或壓力係與於上述說明者相同。其次，由導入堆積反應部之化合物，使前驅物薄膜成膜於基質表面(前驅物薄膜成膜步驟)。此時，加熱基質或加熱堆積反應部，可加入熱。於此步驟成膜之前驅物薄膜，係從上述一般式(2)表示之化合物所生成之薄膜，或上述一般式(2)表示之化合物的一部分進行分解及/或反應所生成之薄膜，與目的之金屬氧化物薄膜具有不同之組成。進行本步驟時之基質溫度，較佳為100～400℃，更佳為150～350℃。進行本步驟時之系統(成膜腔室內)的壓力較佳為1～10000Pa，更佳為10～1000Pa。 　　[0080] 其次，從堆積反應部，排氣未反應之化合物氣體或副產物之氣體(排氣步驟)。未反應之化合物氣體或副產物之氣體，雖然理想為從堆積反應部完全排氣，但並非一定要完全排氣。作為排氣方法，可列舉由氮、氦、氬等之惰性氣體掃氣系統內之方法、藉由減壓系統內進行排氣之方法、組合此等方法之方法等。減壓時之減壓度較佳為0.01～300Pa，更佳為0.01～100Pa。 　　[0081] 其次，導入氧化性氣體於堆積反應部，由該氧化性氣體之作用或氧化性氣體及熱之作用，從先前之前驅物薄膜成膜步驟得到之前驅物薄膜形成金屬氧化物薄膜(含金屬氧化物之薄膜形成步驟)。本步驟中使熱產生作用時之溫度，較佳為室溫～500℃，更佳為150～350℃。進行本步驟時之系統(成膜腔室內)的壓力較佳為1～10000Pa，更佳為10～1000Pa。由於上述一般式(2)表示之化合物與氧化性氣體的反應性良好，可得到殘留碳含量少之金屬氧化物薄膜。 　　[0082] 本發明之薄膜的製造方法中，如上述採用ALD法時，可將藉由由上述之原料導入步驟、前驅物薄膜成膜步驟、排氣步驟及含金屬氧化物之薄膜形成步驟所構成之一連串操作之薄膜堆積作為1循環，可將此循環重複多次直到得到必要膜厚的薄膜為止。此情況下，進行1循環後，與上述排氣步驟同樣進行，從堆積反應部排氣未反應之化合物氣體及反應性氣體(形成金屬氧化物薄膜時為氧化性氣體)，進而排氣副成之氣體後，以進行下一個循環較佳。 　　[0083] 又，藉由金屬氧化物薄膜之ALD法之形成中，可施加電漿、光、電壓等之能量，可使用觸媒。施加該能量之時期及使用觸媒之時期並未特別限定，例如可在原料導入步驟之化合物氣體導入時、在前驅物薄膜成膜步驟或含金屬氧化物之薄膜形成步驟之加溫時、在排氣步驟之系統內的排氣時、在含金屬氧化物之薄膜形成步驟之氧化性氣體導入時，亦可於上述之各步驟之間。 　　[0084] 又，本發明之薄膜的製造方法中，薄膜堆積之後，為了得到更良好之電氣特性，可於惰性環境下、氧化性環境下或還原性環境下進行退火處理，有必要段差嵌入時，可設置回流步驟。此時之溫度為200～1000℃，較佳為250～500℃。 　　[0085] 使用本發明之原子層堆積法用之薄膜形成用原料製造薄膜之裝置，可使用周知之化學氣相成長法用裝置。作為具體裝置之例，可列舉可將如圖1之前驅物以起泡供給進行之裝置或如圖2具有氣化室之裝置。又，如圖3及圖4可對於反應性氣體進行電漿處理之裝置。並不限於如圖1～圖4之單片式裝置，亦可使用使用批量爐之可多片同時處理之裝置。 　　[0086] 含有使用本發明之原子層堆積法用之薄膜形成用原料所製造之金屬的薄膜，已被使用在切削工具、電子材料用之配線或電極，例如可使用在半導體記憶體材料或鋰空氣電池用之電極等。 ［實施例］ 　　[0087] 以下，具有實施例及評價例更進一步詳細說明本發明。然而，本發明並非因以下之實施例等而受到任何限制者。 　　[0088] [實施例1]化合物No.4之製造 　　於2000mL4口燒瓶於Ar環境下冰浴肆(二甲基胺基)鋯230.0g與脫水甲苯1190g之混合溶液後，將環戊二烯113.7g由等壓滴下漏斗約耗費1小時滴下使其反應。接著，將1-(二甲基胺基)-2-甲基-2-丙醇201.5g由等壓滴下漏斗約耗費2小時滴下加入使其反應。滴下結束後，緩緩昇溫至室溫，進而繼續反應2小時。接著，於減壓下餾除溶劑後，分取減壓蒸餾67Pa/145～7℃之餾分，而得到312g之淡黃色液體之化合物No.4。 　　[0089] (分析值) (1)常壓TG-DTA 　　質量50%減少溫度：271℃(Ar流量：100mL/分鐘、昇溫：10℃/分鐘、樣品量：11.491mg) (2)元素分析(金屬分析：ICP-AES、CHN分析：CHN分析裝置) 　　鋯含量：20.05質量%(理論值：20.10質量%) 　　C：58.0質量%(理論值：58.23質量%)、H：7.9質量%(理論值：8.44質量%)、N：5.8質量%(理論值：6.17質量%) 　　[0090] [實施例2]化合物No.22之製造 　　於300mL4口燒瓶於Ar環境下冰浴肆(二甲基胺基)鈦19.3g與脫水甲苯118.9g之混合溶液後，將環戊二烯12.0g由等壓滴下漏斗約耗費30小時滴下使其反應。接著，將1-(二甲基胺基)-2-甲基-2-丙醇20.2g由等壓滴下漏斗約耗費1小時滴下加入使其反應。滴下結束後，緩緩昇溫至室溫，進而繼續反應2小時。接著，於減壓下餾除溶劑後，進行減壓蒸餾，而得到28.2g之淡黃色液體之化合物No.22。 　　[0091] (分析值) (1)常壓TG-DTA 　　質量50%減少溫度：272℃(Ar流量：100mL/分鐘、昇溫：10℃/分鐘、樣品量：10.421mg) (2)元素分析(金屬分析：ICP-AES、CHN分析：CHN分析裝置) 　　鈦含量：11.5質量%(理論值：11.67質量%) 　　C：64.1質量%(理論值：64.38質量%)、H：8.7質量%(理論值：9.33質量%)、N：6.1質量%(理論值：6.83質量%) 　　[0092] [製造例1]化合物No.40之製造 　　於300mL4口燒瓶於Ar環境下冰浴肆(二乙基胺基)鉿37.4g與脫水甲苯110.6g之混合溶液後，將環戊二烯11.1g由等壓滴下漏斗約耗費30小時滴下使其反應。接著，將1-(二甲基胺基)-2-甲基-2-丙醇18.8g由等壓滴下漏斗約耗費1小時滴下加入使其反應。滴下結束後，緩緩昇溫至室溫，進而繼續反應2小時。接著，於減壓下餾除溶劑後，分取減壓蒸餾60Pa/145～7℃之餾分，而得到34.5g之淡黃色液體之化合物No.40。 　　[0093] (分析值) (1)常壓TG-DTA 　　質量50%減少溫度：258℃(Ar流量：100mL/分鐘、昇溫：10℃/分鐘、樣品量：10.421mg) (2)元素分析(金屬分析：ICP-AES、CHN分析：CHN分析裝置) 　　鉿含量：32.9質量%(理論值：32.99質量%) 　　C：48.6質量%(理論值：48.84質量%)、H：6.7質量%(理論值：7.08質量%)、N：4.7質量%(理論值：5.18質量%) 　　[0094] [評價例1]鋯化合物之物性評價 　　針對化合物No.4、下述所示之比較化合物1及比較化合物2，藉由目視觀察在常壓30℃之各化合物的狀態。又，使用落球式黏度計(Anton Paar公司製、製品名：AMVn)，測定在30℃之黏度。又，針對比較化合物1及比較化合物2，使用TG-DTA，於常壓下測定重量減少50%時溫度(Ar流量：100mL/分鐘、昇溫：10℃/分鐘、比較化合物1之樣品量：13.064mg、比較化合物2之樣品量：12.485mg)。又，在惰性氣體環境下，準備於100℃～300℃為止每10℃之溫度分別進行1小時加熱處理之樣品，從上述加熱處理之溫度低的樣品，於常壓條件下依序進行TG-DTA測定(Ar流量：100mL/分鐘、昇溫：10℃/分鐘、測定溫度範圍：25℃～600℃)。將TG-DTA測定後之殘渣的量成為2質量%以上之最初樣品之上述加熱處理的溫度定為「熱分解溫度」。將結果示於表1。 　　[0095][0096][0097] 由上述表1，瞭解到化合物No.4、比較化合物1及比較化合物2皆為於常壓30℃的條件下，為液體之低熔點的化合物。又，瞭解到化合物No.4雖較比較化合物1於30℃之黏度更高，但作為化學氣相成長用原料為足夠之低黏度。熔點低且黏度低之薄膜形成用原料由於輸送性良好，故可提昇生產性之薄膜形成用原料。又，從常壓TG-DTA的結果來看，瞭解到化合物No.4作為化學氣相成長用原料，顯示充分之蒸氣壓，且具有非常高之熱穩定性。 　　[0098] [評價例2]鈦化合物之物性評價 　　針對化合物No.22、下述所示之比較化合物3，藉由目視觀察在常壓30℃之各化合物的狀態。針對固體化合物使用微小熔點測定裝置，測定熔點。又，針對比較化合物3，使用TG-DTA，測定於常壓下重量減少50%時的溫度(Ar流量：100mL/分鐘、昇溫：10℃/分鐘、樣品量：8.997mg)。將結果示於表2。 　　[0099][0100][0101] 由上述表2，瞭解到相對於比較化合物3為熔點75℃之化合物，化合物No.22於常壓30℃之條件下為液體之低熔點的化合物。熔點低之薄膜形成用原料由於輸送容易，故為可提昇生產性之薄膜形成用原料。又，從常壓TG-DTA的結果來看，瞭解到化合物No.22，雖較比較化合物3，減少50質量%時之溫度略高，但作為化學氣相成長用原料已顯示充分之蒸氣壓。 　　[0102] [實施例3]藉由ALD法之氧化鋯薄膜之製造 　　將化合物No.4作為化學氣相成長用原料，使用圖1所示之化學氣相成長用裝置，藉由以下之條件的ALD法，於矽基板上製造氧化鋯薄膜。針對所得之薄膜，進行藉由X光反射率法之膜厚測定、藉由X光繞射法及X光光電子分光法之薄膜構造及薄膜組成的確認時，膜厚為2～4nm，膜組成為氧化鋯(以藉由XPS分析之Zr4d峰值確認)，薄膜中之殘留碳含量較檢測下限即0.1atom%更少。每1循環所得之膜厚為0.02～0.04nm。 　　[0103] (條件) 　　反應溫度(基板溫度)；250℃、反應性氣體；臭氧 (步驟) 　　將由下述(1)～(4)所構成之一連串步驟作為1循環，重複100循環。 　　(1)將以原料容器加熱溫度：150℃、原料容器內壓力：80Pa以下的條件使其氣化之化學氣相成長用原料導入成膜腔室，系統壓力：於80Pa使其堆積10秒。 　　(2)藉由10秒之氬掃氣，去除未反應原料及副產物氣體。 　　(3)將反應性氣體導入成膜腔室，系統壓力：以80Pa使其反應10秒。 　　(4)藉由10秒之氬掃氣，去除未反應原料及副產物氣體。 　　[0104] [比較例3]藉由ALD法之氧化鋯薄膜之製造 　　將比較化合物2(Zr(DMAMP)4 )作為化學氣相成長用原料，使用圖1所示之化學氣相成長用裝置，藉由以下之條件的ALD法，於矽基板上製造氧化鋯薄膜。針對所得之薄膜，進行藉由X光反射率法之膜厚測定、藉由X光繞射法及X光光電子分光法之薄膜構造及薄膜組成的確認時，膜厚為1nm，膜組成為氧化鋯(以藉由XPS分析之Zr4d峰值確認)，薄膜中之殘留碳含量為5atom%。每1循環所得之膜厚為0.01nm。 　　[0105] (條件) 　　反應溫度(基板溫度)；280℃、反應性氣體；臭氧 (步驟) 　　將由下述(1)～(4)所構成之一連串步驟作為1循環，重複100循環。 　　(1)將以原料容器加熱溫度：150℃、原料容器內壓力：80Pa以下的條件使其氣化之化學氣相成長用原料導入成膜腔室，系統壓力：於80Pa使其堆積10秒。 　　(2)藉由10秒之氬掃氣，去除未反應原料及副產物氣體。 　　(3)將反應性氣體導入成膜腔室，系統壓力：以80Pa使其反應10秒。 　　(4)藉由10秒之氬掃氣，去除未反應原料及副產物氣體。 　　[0106] 由實施例3之結果，瞭解到藉由將本發明之化合物作為ALD法用薄膜形成用原料使用，可製得品質非常良好之氧化鋯薄膜。另外，由比較例3之結果，瞭解到將比較化合物2作為ALD法用薄膜形成用原料使用時，製造亦包含生產性且品質良好之氧化鋯薄膜有困難。 　　[0107] [實施例4] 藉由ALD法之氧化鈦薄膜之製造 　　將化合物No.22作為化學氣相成長用原料，使用圖1所示之化學氣相成長用裝置，由以下條件之ALD法，於矽基板上製造氧化鈦薄膜。對於所得之薄膜，進行藉由X光反射率法之膜厚測定、藉由X光繞射法及X光光電子分光法之薄膜構造及薄膜組成的確認時，膜厚為3～4nm，膜組成為氧化鈦(以藉由XPS分析之Ti3d峰值確認)，薄膜中之殘留碳含量較檢測下限之0.1atom%更少。每1循環所得之膜厚為0.03～0.04nm。 　　[0108] (條件) 　　反應溫度(基板溫度)；300℃、反應性氣體；臭氧 (步驟) 　　將由下述(1)～(4)所構成之一連串步驟作為1循環，重複100循環。 　　(1)將以原料容器加熱溫度：160℃、原料容器內壓力：80Pa以下的條件使其氣化之化學氣相成長用原料導入成膜腔室，系統壓力：於80Pa使其堆積10秒。 　　(2)藉由10秒之氬掃氣，去除未反應原料及副產物氣體。 　　(3)將反應性氣體導入成膜腔室，系統壓力：以80Pa使其反應10秒。 　　(4)藉由10秒之氬掃氣，去除未反應原料及副產物氣體。 　　[0109] [實施例5]藉由ALD法之氧化鉿薄膜之製造 　　將化合物No.40作為化學氣相成長用原料，使用圖1所示之化學氣相成長用裝置，由以下條件之ALD法，於矽基板上製造氧化鉿薄膜。對於所得之薄膜，進行藉由X光反射率法之膜厚測定、藉由X光繞射法及X光光電子分光法之薄膜構造及薄膜組成的確認時，膜厚為2～4nm，膜組成為氧化鉿(以藉由XPS分析之Hf4f峰值確認)，薄膜中之殘留碳含量較檢測下限之0.1atom%更少。每1循環所得之膜厚為0.02～0.04nm。 　　[0110] (條件) 　　反應溫度(基板溫度)；300℃、反應性氣體；臭氧 (步驟) 　　將由下述(1)～(4)所構成之一連串步驟作為1循環，重複100循環。 　　(1)將以原料容器加熱溫度：150℃、原料容器內壓力：80Pa以下的條件使其氣化之化學氣相成長用原料導入成膜腔室，系統壓力：於80Pa使其堆積10秒。 　　(2)藉由10秒之氬掃氣，去除未反應原料及副產物氣體。 　　(3)將反應性氣體導入成膜腔室，系統壓力：以80Pa使其反應10秒。 　　(4)藉由10秒之氬掃氣，去除未反應原料及副產物氣體。 　　[0111] 尚，本國際申請案，係根據2016年11月8日所申請之日本國專利申請第2016-218054號而主張優先權者，將此日本國專利申請之全內容援用於本國際申請案。[0018] The compound of the present invention is represented by the above general formula (1), and is suitable as a precursor of a thin film manufacturing method having a gasification step such as a CVD method, and the thin film can also be formed using an ALD method. The compound of the present invention is a compound having a low viscosity at a temperature of 30 ° C. or slightly warmed to a liquid. Since the compound having a low melting point and a low viscosity has good transportability, it is suitable as a precursor for a thin film manufacturing method having a gasification step such as a CVD method. [0019] In the above general formula (1), as R 1 ~ R 9 Examples of straight or branched alkyl groups having 1 to 4 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, second butyl, and third butyl Wait. [0020] From the viewpoint of the low melting point of the compound, in the general formula (1), R is 1 ~ R 5 Compounds which are hydrogen or methyl are preferred, with R 1 ~ R 5 All hydrogen or R 1 ~ R 5 Compounds in which one is methyl and the remaining four are hydrogen are particularly preferred. From the viewpoint of a compound having a low melting point and a high vapor pressure, in the general formula (1) above, R 6 Preferred is a compound of hydrogen, a grade 1 alkyl or a grade 2 alkyl, more preferably a methyl, ethyl, propyl or isopropyl compound, and particularly preferably a methyl, ethyl or propyl compound . From the viewpoint of a compound having a low melting point and a high vapor pressure, in the general formula (1) above, R 7 The compound of the first-order alkyl group or the second-order alkyl group is more preferable, and the compound of the methyl, ethyl, propyl, or isopropyl group is more preferable, and the compound of the methyl, ethyl, or propyl group is particularly preferable. In the above general formula (1), R 6 And R 7 Compounds which are methyl or ethyl are preferred because they have a low melting point and a high vapor pressure. In the above general formula (1), R 8 And R 9 Preferred is a compound of a grade 1 alkyl group, more preferred is a compound of methyl, ethyl or propyl, and particularly preferred is a compound of methyl or ethyl. In the case of a method for manufacturing a thin film by the MOD method without a gasification step, R 1 ~ R 9 It can be appropriately selected by the solubility of the solvent to be used, the film formation reaction, and the like. [0021] In the general formula (1), as M 1 Preferred specific examples of the compound that is zirconium include the following compounds No. 1 to No. 18, for example. In the following compounds No. 1 to No. 18, "Me" represents a methyl group, and "Et" represents an ethyl group. [0022] [0023] [0024] In the above general formula (1), as M 1 Preferable specific examples of the compound which is titanium include the following compounds No. 19 to No. 36. In the following compounds No. 19 to No. 36, "Me" represents a methyl group, and "Et" represents an ethyl group. [0025] [0026] [0027] The compound of the present invention is not particularly limited due to its production method, and is produced by a known reaction. Among the compounds represented by the above general formula (1), M is produced 1 When it is a compound of zirconium, for example, using (dialkylamino) zirconium as a starting material, after reacting this cyclopentadiene or alkylcyclopentadiene, a corresponding dialkylamino group can be formed by Alcohol is prepared by reaction. Manufacturing M 1 When it is a titanium compound, it can be produced by the same method as the above-mentioned production method except that titanium (alkylamino) titanium is used as a starting material. [0028] The raw material for forming a thin film of the present invention uses the compound of the present invention described above as a precursor of a thin film, and its form varies depending on the manufacturing process to which the raw material for thin film formation is applied. For example, when producing a thin film containing only zirconium atoms or titanium atoms, the raw material for forming a thin film of the present invention does not contain a metal compound other than the above compounds. In addition, when producing a thin film containing two or more metals and / or metalloids, the raw material for forming a thin film of the present invention contains, in addition to the above-mentioned compounds, a compound containing a desired metal and / or a compound containing a metalloid (hereinafter also referred to as other Precursor). The raw material for film formation according to the present invention may further contain an organic solvent and / or a nucleophile as described later. As described above, the raw material for forming a thin film of the present invention is suitable for the CVD method and the ALD method because the physical properties of the precursor compound are suitable, and it is particularly useful as a raw material for chemical vapor growth (hereinafter sometimes referred to as a raw material for CVD). [0029] When the raw material for forming a thin film of the present invention is a raw material for chemical vapor growth, its morphology is appropriately selected by a method such as a conveying and supplying method using a CVD method. [0030] As the above-mentioned conveying and supplying method, there is a method in which a raw material for CVD is heated and / or decompressed in a container storing the raw material (hereinafter may be simply referred to as a raw material container), and then vaporized into vapor. With a carrier gas such as argon, nitrogen, or helium, if necessary, the gas is transported by introducing the vapor into a film-forming chamber in which a substrate is installed (hereinafter sometimes referred to as a stacking reaction part), by CVD A liquid transport method in which a raw material is transferred to a gasification chamber in the state of a liquid or a solution, and the gasification chamber is heated and / or reduced in pressure to vaporize it into a vapor, and the vapor is introduced into a film forming chamber. In the case of the gas transport method, the compound itself represented by the general formula (1) can be used as a raw material for CVD. In the case of the liquid transport method, the compound represented by the general formula (1) itself or a solution in which the compound is dissolved in an organic solvent can be used as a raw material for CVD. These raw materials for CVD may further include other precursors or nucleophiles. [0031] In the multi-component CVD method, there are a method in which raw materials for CVD are independently vaporized and supplied with each component (hereinafter may also be referred to as a single source method), and a multi-component raw material is previously prepared in a desired manner. A method for gasifying and supplying a mixed raw material having a mixed composition (hereinafter sometimes referred to as a Cocktail source method). In the case of the mixed source method, a mixture of the compound of the present invention and other precursors or a mixed solution in which the mixture is dissolved in an organic solvent can be used as a raw material for CVD. This mixture or mixed solution may further contain a nucleophile and the like. [0032] The organic solvent is not particularly limited, and a well-known general organic solvent can be used. Examples of the organic solvent include acetates such as ethyl acetate, butyl acetate, and methoxyethyl acetate; tetrahydrofuran, tetrahydropyran, ethylene glycol dimethyl ether, and diethylene glycol dimethyl Ethers such as ether, triethylene glycol dimethyl ether, dibutyl ether, dioxane, etc .; methylbutyl ketone, methyl isobutyl ketone, ethyl butyl ketone, dipropyl ketone, diiso Ketones such as butyl ketone, methyl amyl ketone, cyclohexanone, methyl cyclohexanone; hexane, cyclohexane, methyl cyclohexane, dimethyl cyclohexane, ethyl cyclohexane, Hydrocarbons such as heptane, octane, toluene, xylene, etc .; 1-cyanopropane, 1-cyanobutane, 1-cyanohexane, cyanocyclohexane, cyanobenzene, 1,3-dioxane Hydrocarbons with cyano groups such as cyanopropane, 1,4-dicyanobutane, 1,6-dicyanohexane, 1,4-dicyanocyclohexane, 1,4-dicyanobenzene ; Pyridine, lutidine and the like. These organic solvents can be used alone or in combination of two or more due to the solubility of the solute, the relationship between the use temperature and the boiling point and the flash point. When using these organic solvents, it is preferable that the amount of the entire precursor in the CVD raw material solution in which the precursor is dissolved in the organic solvent is 0.01 to 2.0 mol / liter, especially 0.05 to 1.0 mol. / Literally excellent. The total amount of the precursor refers to the amount of the compound of the present invention when the film-forming raw material of the present invention does not contain a metal compound and a metal-like compound other than the compound of the present invention, and the film-forming raw material of the present invention excludes the compound. In addition, when a compound containing other metals and / or a metalloid-containing compound (other precursors) is contained, it is the total amount of the compound of the present invention and other precursors. [0033] In the case of the multi-component CVD method, the other precursors used together with the compound of the present invention are not particularly limited, and conventionally known precursors used for CVD raw materials can be used. [0034] Examples of the other precursors include those selected from the group consisting of hydrides, hydroxides, halides, azides, alkyl groups, alkenyl groups, cycloalkyl groups, aryl groups, alkynyl groups, amine groups, and dialkyl groups. Aminoalkyl, monoalkylamino, dialkylamino, diamine, bis (silyl-alkyl) amine, bis (alkyl-silyl) amine, disylamino, alkoxy Base, alkoxyalkyl, hydrazine, phosphide, nitrile, dialkylaminoalkoxy, alkoxyalkyldialkylamino, silyloxy, diketonate, cyclopentane Alkenyl, silane, Pyrazolate, Guanidinate, Phosphoguanidinate, Amidinate, Ketoiminate, Diketiminate, etc. One or two or more silicon or metal compounds in the group consisting of carbonyl and phosphoamidinate compounds as ligands. [0035] Examples of the metal species of the precursor include magnesium, calcium, strontium, barium, radium, hafnium, zirconium, titanium, hafnium, yttrium, vanadium, niobium, tantalum, manganese, iron, chromium, molybdenum, tungsten, rhenium, Ruthenium, cobalt, rhodium, iridium, nickel, palladium, platinum, copper, silver, gold, zinc, aluminum, gallium, indium, germanium, tin, lead, antimony, bismuth, yttrium, lanthanum, cerium, praseodymium, neodymium, thorium,钐, 铕, 釓, 鋱, 镝, 铒, 铒, 銩, 镱. [0036] The other precursors mentioned above are well known in the technical scope to which the invention belongs, and their manufacturing methods are also well known. As an example of a manufacturing method, for example, when an alcohol compound is used as an organic ligand, a precursor of an inorganic salt of a metal or a hydrate thereof and an alkali metal alkoxide of the alcohol compound can be reacted to produce a precursor. . Examples of the metal inorganic salt or hydrate thereof include metal halides and nitrates, and examples of the alkali metal alkoxide include sodium alkoxide, lithium alkoxide, and potassium alkoxide. [0037] When the other precursors mentioned above are single-source methods, the compounds of the present invention and compounds with similar thermal and / or oxidative decomposition behavior are preferred. In the case of mixed-source methods, except for similar thermal and / or In addition to the action of oxidative decomposition, those who do not cause deterioration due to chemical reactions or the like during mixing are preferred. [0038] The raw material for forming a thin film of the present invention may contain a nucleophile in order to impart stability to the compound of the present invention and other precursors, if necessary. Examples of the nucleophile include glycol ethers such as glycol dimethyl ether, diglyme, triglyme, and tetraglyme, 18-crown (Crown) -6 , Dicyclohexyl-18-crown-6, 24-crown-8, dicyclohexyl-24-crown-8, dibenzo-24-crown-8, crown ethers, ethylenediamine, N, N, N'N'-tetramethylethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexaamine, 1,1,4,7,7-pentamethyldiethylenetriamine, Polyamines such as 1,1,4,7,10,10-hexamethyltriethylenetetramine, triethoxytriethyleneamine, 1,4,7,11-tetraazacyclotetradecane (Cyclam ), Cyclic polyamines such as cyclone, pyridine, pyrrolidine, piperidine, morpholine, N-methylpyrrolidine, N-methylpiperidine, N-methylmorpholine, tetrahydrofuran, tetra Heteropyran, 1,4-dioxane, oxazole, thiazole, oxathiolane and other heterocyclic compounds, ethyl acetate, ethyl acetate, ethyl acetate-2- Β-ketoesters such as methoxyethyl or acetone, 2,4-hexanedione, 2,4-heptanedione, 3,5-heptanedione, bistrimethylacetone Β-diketones such as Dipivaloylmethane The amount of these nucleophiles used is preferably in the range of 0.1 to 10 mol, more preferably 1 to 4 mol, relative to the total amount of the precursor. [0039] The raw material for forming a thin film of the present invention does not contain, as much as possible, impurity halogen components such as impurity metal element components, impurity chlorine components, and impurity organic components other than components constituting the raw material. The impurity metal element content is preferably 100 ppb or less per element, more preferably 10 ppb or less, and the total amount is preferably 1 ppm or less, and more preferably 100 ppb or less. In particular, when used as a gate insulating film, a gate film, and a barrier layer of an LSI, it is necessary to reduce the content of alkali metal elements and alkaline earth metal elements that have an influence on the electrical characteristics of the obtained film. The impurity halogen content is preferably 100 ppm or less, more preferably 10 ppm or less, and most preferably 1 ppm or less. The total amount of impurities is preferably 500 ppm or less, more preferably 50 ppm or less, and most preferably 10 ppm or less. In addition, since moisture is the cause of particles in raw materials for chemical vapor growth or particles in film formation, in order to reduce individual moisture for precursors, organic solvents, and nucleophiles, it is necessary to use as little as possible during use. It is better to remove water early. The water content of each of the precursor, the organic solvent, and the nucleophile is preferably 10 ppm or less, and more preferably 1 ppm or less. [0040] In order to reduce or prevent particle contamination of the formed thin film, the raw material for forming a thin film of the present invention is preferable to contain no particles as much as possible. Specifically, the number of particles larger than 0.3 μm is preferably less than 100 in 1 mL of the liquid phase, and the number of particles larger than 0.2 μm is smaller than that in the liquid. The number of particles in 1 mL is preferably 1,000 or less, and the number of particles larger than 0.2 μm is preferably 100 or less in 1 mL of liquid phase. [0041] As a method for producing a thin film of the present invention using the raw material for forming a thin film of the present invention, there is a method for producing a thin film of the present invention by vaporizing a raw material for forming a thin film of the present invention, and using reactivity if necessary. The gas is introduced into the film-forming chamber in which the substrate is installed. Second, the precursor is decomposed and / or chemically reacted on the substrate, and a metal-containing film is grown on the surface of the substrate to accumulate the CVD method. There are no particular restrictions on the method of conveying and supplying raw materials, stacking methods, manufacturing conditions, manufacturing equipment, and the like, and well-known general conditions and methods can be used. [0042] Examples of the reactive gas used if necessary include, for example, oxidizing agents, such as oxygen, ozone, nitrogen dioxide, nitric oxide, water vapor, hydrogen peroxide, formic acid, acetic acid, acetic anhydride, and the like. Examples of reducing agents include hydrogen, and examples of those producing nitrides include organic amine compounds such as monoalkylamine, dialkylamine, trialkylamine, and alkylenediamine, hydrazine, and ammonia. Etc. One kind or two or more kinds can be used. Among these, since the raw material for forming a thin film of the present invention has good reactivity with ozone, when one kind of reactive gas is used, it is preferable to use ozone, and when two or more mixed gases are used as the reactive gas, Preferably, it contains at least ozone. [0043] Examples of the above-mentioned transportation and supply method include the aforementioned gas transportation method, liquid transportation method, single-source method, and mixed-source method. [0044] Examples of the deposition method include thermal CVD for depositing a thin film, plasma CVD using heat and plasma, and thermal and plasma reaction using a raw gas or a raw gas and a reactive gas to react only with heat. Light CVD, photo-plasma CVD using heat, light, and plasma, CVD stacking reaction is divided into basic processes, and ALD is staged at the molecular level. [0045] Examples of the material of the substrate include silicon; ceramics such as silicon nitride, titanium nitride, tantalum nitride, titanium oxide, titanium nitride, ruthenium oxide, zirconia, hafnium oxide, and lanthanum oxide; glass; Metals such as ruthenium. Examples of the shape of the substrate include a plate shape, a spherical shape, a fibrous shape, and a scaly shape. The surface of the substrate may be planar and may be a three-dimensional structure such as a trench structure. [0046] Examples of the manufacturing conditions include a reaction temperature (substrate temperature), a reaction pressure, and a deposition rate. As for the reaction temperature, the temperature at which the compound of the present invention is fully reacted is preferably 100 ° C or higher, more preferably 150 ° C to 400 ° C, and particularly preferably 200 ° C to 350 ° C. When the reaction pressure is thermal CVD or photo CVD, it is preferably from atmospheric pressure to 10 Pa, and when plasma is used, it is preferably from 2000 Pa to 10 Pa. The deposition rate can be controlled by the supply conditions of the raw materials (gasification temperature, gasification pressure), reaction temperature, and reaction pressure. When the deposition speed is high, the characteristics of the obtained film may be deteriorated, and when the production speed is slow, there may be problems in productivity. Therefore, it is preferably 0.01 to 100 nm / minute, and more preferably 1 to 50 nm / minute. In the ALD method, the number of cycles is controlled so that a desired film thickness can be obtained. [0047] As the above-mentioned production conditions, a temperature or a pressure at the time of vaporizing the raw material for forming a thin film into vapor can be further mentioned. The step of vaporizing the film-forming raw material into vapor may be performed in a raw material container or may be performed in a gasification chamber. In either case, it is preferable that the raw material for forming a thin film of the present invention is evaporated at 0 to 150 ° C. When the raw material for film formation is vaporized into vapor in the raw material container or the gasification chamber, the pressure in the raw material container and the pressure in the gasification chamber are preferably 1 to 10,000 Pa. [0048] The thin film manufacturing method of the present invention adopts the ALD method. In addition to the above-mentioned conveying and supplying method, the raw material for thin film formation is vaporized into steam, and the raw material introducing step of introducing the steam into the film forming chamber may have: Forming a precursor film on the surface of the substrate from the aforementioned compound in the vapor, a precursor film forming step, an exhaust step of exhausting unreacted compound gas, and chemically reacting the precursor film with a reactive gas, and A metal-containing thin film forming step is formed on the surface of the substrate. [0049] Hereinafter, a case where a metal oxide thin film is formed will be described in detail for each of the steps described above. When the metal oxide thin film is formed by the ALD method, first, the raw material introduction step described above is performed. The preferred temperature or pressure when the film-forming raw material is vaporized is the same as that described above. Next, a precursor film is formed on the surface of the substrate from the compound introduced into the accumulation reaction part (precursor film formation step). In this case, heat may be added to the substrate by heating or accumulating the reaction portion. The precursor film before film formation in this step is a film formed from the compound of the present invention or a part of the compound of the present invention is decomposed and / or reacted, and has a different composition from the intended metal oxide film. . The substrate temperature during this step is preferably room temperature to 500 ° C, and more preferably 150 to 350 ° C. The pressure of the system (in the film-forming chamber) when performing this step is preferably 1 to 10,000 Pa, and more preferably 10 to 1000 Pa. [0050] Next, an unreacted compound gas or a by-product gas is exhausted from the accumulation reaction section (exhaust step). Although the unreacted compound gas or by-product gas is desirably completely exhausted from the accumulation reaction part, it is not necessarily exhausted completely. Examples of the exhaust method include a method in a purge system using an inert gas such as nitrogen, helium, and argon, a method in which exhaust is performed in a decompression system, and a method combining these methods. The degree of pressure reduction during the pressure reduction is preferably 0.01 to 300 Pa, and more preferably 0.01 to 100 Pa. [0051] Next, an oxidizing gas is introduced into the stacking reaction part, and the precursor film is obtained from the previous precursor film film forming step to form a metal oxide film by the action of the oxidizing gas or the effect of the oxidizing gas and heat ( Metal oxide-containing thin film forming step). The temperature at which heat is generated in this step is preferably room temperature to 500 ° C, and more preferably 150 to 350 ° C. The pressure of the system (in the film-forming chamber) when performing this step is preferably 1 to 10,000 Pa, and more preferably 10 to 1000 Pa. The compound of the present invention has good reactivity with an oxidizing gas, and can obtain a high-quality metal oxide thin film with a small residual carbon content. [0052] In the method for manufacturing a thin film of the present invention, when the ALD method is used as described above, the raw material introduction step, the precursor thin film forming step, the exhaust step, and the metal oxide-containing thin film forming step can be performed. As one cycle of the film deposition that constitutes a series of operations, this cycle can be repeated multiple times until a film with the necessary film thickness is obtained. In this case, after 1 cycle, it is performed in the same manner as the above-mentioned exhausting step. Unreacted compound gas and reactive gas (oxidizing gas when forming a metal oxide thin film) are exhausted from the deposition reaction part, and the exhaust gas is formed as a secondary After the gas, it is better to carry out the next cycle. [0053] In the formation of the metal oxide thin film by the ALD method, energy such as plasma, light, and voltage can be applied, and a catalyst can be used. The time when the energy is applied and the time when the catalyst is used are not particularly limited. For example, when the compound gas is introduced in the raw material introduction step, the precursor film formation step or the metal oxide-containing film formation step is heated, When exhausting the system in the exhausting step, or when introducing an oxidizing gas in the film forming step containing a metal oxide, it may be between the above steps. [0054] In the method for manufacturing a thin film of the present invention, after the film is deposited, in order to obtain better electrical characteristics, annealing treatment may be performed in an inert environment, an oxidizing environment, or a reducing environment. You can set the reflow step. The temperature at this time is 200 to 1000 ° C, preferably 250 to 500 ° C. [0055] As a device for manufacturing a thin film using the raw material for forming a thin film of the present invention, a well-known device for a chemical vapor growth method can be used. As an example of a specific device, there can be mentioned a device which can perform a precursor supply as shown in FIG. 1 by foaming supply or a device having a gasification chamber as shown in FIG. 2. Moreover, as shown in FIG. 3 and FIG. 4, the apparatus which plasma-processes a reactive gas is mentioned. It is not limited to the single-chip device as shown in FIGS. 1 to 4, and a device that can process multiple pieces simultaneously using a batch furnace can also be used. [0056] A thin film containing a metal produced using the raw material for forming a thin film of the present invention has been used in cutting tools and wirings or electrodes for electronic materials. For example, it can be used in semiconductor memory materials or electrodes for lithium-air batteries. . [0057] The raw material for forming a thin film used in the atomic layer deposition method of the present invention includes a compound represented by the following general formula (2). [0058] [Wherein, R 11 ~ R 16 Each independently represents hydrogen or a linear or branched alkyl group having 1 to 4 carbon atoms, R 17 , R 18 And R 19 Represents a linear or branched alkyl group having 1 to 4 carbon atoms, M 2 For zirconium, hafnium or titanium). [0060] In the above general formula (2), as R 11 ~ R 19 Examples of straight or branched alkyl groups having 1 to 4 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, second butyl, and third butyl Wait. [0061] From the viewpoint of a low melting point of the compound, in the general formula (2), R 11 ~ R 15 Compounds which are hydrogen or methyl are preferred, with R 11 ~ R 15 All hydrogen or R 11 ~ R 15 Compounds in which one is methyl and the remaining four are hydrogen are particularly preferred. From the viewpoint of a compound having a low melting point and a high vapor pressure, in the general formula (2) above, R 16 Preferred is a compound of hydrogen, a grade 1 alkyl or a grade 2 alkyl, more preferably a methyl, ethyl, propyl or isopropyl compound, and particularly preferably a methyl, ethyl or propyl compound . From the viewpoint of a compound having a low melting point and a high vapor pressure, in the general formula (2) above, R 17 The compound of the first-order alkyl group or the second-order alkyl group is more preferable, and the compound of the methyl, ethyl, propyl, or isopropyl group is more preferable, and the compound of the methyl, ethyl, or propyl group is particularly preferable. In the above general formula (2), R 16 And R 17 A compound which is a methyl group or an ethyl group is preferred because of its low melting point and high vapor pressure. In the above general formula (2), use R 18 And R 19 A compound of a class 1 alkyl group is preferred, a compound of methyl, ethyl or propyl is more preferred, and a compound of methyl or ethyl is particularly preferred. [0062] As a preferable specific example of the compound represented by the above general formula (2), in addition to the above-mentioned compound Nos. 1 to 36, in the above general formula (2), as M 2 The compound which is a hydrazone may also be the following compounds No. 37 to No. 54. In the following compounds No. 37 to No. 54, "Me" represents a methyl group, and "Et" represents an ethyl group. [0063] [0064] [0065] The compound used for the raw material for forming a thin film for the atomic layer deposition method of the present invention is not particularly limited due to its production method, and it is produced by a known reaction. Among the compounds represented by the general formula (2) above, M is produced 2 When it is a compound of zirconium or titanium, it can be obtained by the method described above. Manufacturing M 2 When it is a compound of amidine, it can be produced by the same method as the above-mentioned production method, except that a (alkylamino) amidine is used as a starting material. [0066] The form of the raw material for forming a thin film (hereinafter sometimes referred to as a raw material for ALD) used in the atomic layer deposition method of the present invention can be appropriately selected by a method such as a transport and supply method of the ALD method used. [0067] As the above-mentioned conveying and supplying method, there is a method in which a raw material for ALD is heated and / or decompressed in a container (hereinafter sometimes referred to only as a raw material container) storing the raw material, and is then vaporized to become a vapor. If necessary, the carrier gas such as argon, nitrogen, and helium is used together, and the vapor is introduced into the deposition reaction part of the substrate by a gas transportation method, and the raw material for ALD is transferred to the gasification chamber in a liquid or solution state. In a liquid conveying method of heating and / or decompression in a gasification chamber to vaporize it into a vapor, and introducing the vapor into a film forming chamber. In the case of the gas transport method, the compound represented by the general formula (2) itself can be used as a raw material for ALD. In the case of the liquid transport method, the compound represented by the general formula (2) itself or a solution in which the compound can be dissolved in an organic solvent can be used as a raw material for ALD. These raw materials for ALD may further include a nucleophile and the like. [0068] The organic solvent is not particularly limited, and a well-known general organic solvent can be used. Examples of the organic solvent include acetates such as ethyl acetate, butyl acetate, and methoxyethyl acetate; tetrahydrofuran, tetrahydropyran, ethylene glycol dimethyl ether, and diethylene glycol dimethyl Ethers such as ether, triethylene glycol dimethyl ether, dibutyl ether, dioxane, etc .; methylbutyl ketone, methyl isobutyl ketone, ethyl butyl ketone, dipropyl ketone, diiso Ketones such as butyl ketone, methyl amyl ketone, cyclohexanone, methyl cyclohexanone; hexane, cyclohexane, methyl cyclohexane, dimethyl cyclohexane, ethyl cyclohexane, Hydrocarbons such as heptane, octane, toluene, xylene, etc .; 1-cyanopropane, 1-cyanobutane, 1-cyanohexane, cyanocyclohexane, cyanobenzene, 1,3-dioxane Hydrocarbons with cyano groups such as cyanopropane, 1,4-dicyanobutane, 1,6-dicyanohexane, 1,4-dicyanocyclohexane, 1,4-dicyanobenzene ; Pyridine, lutidine and the like. These organic solvents can be used alone or in combination of two or more due to the solubility of the solute, the relationship between the use temperature and the boiling point and the flash point. When these organic solvents are used, the amount of the compound represented by the general formula (2) in the raw material for ALD in which the compound represented by the general formula (2) is dissolved in a solution of the organic solvent is 0.01 to 2.0 mol / Liter is preferably 0.05 to 1.0 mol / liter. [0069] The raw material for forming a thin film used in the atomic layer deposition method may contain a nucleophile in order to impart stability to the compound of the present invention, if necessary. Examples of the nucleophile include glycol ethers such as glycol dimethyl ether, diglyme, triglyme, and tetraglyme, 18-crown (Crown) -6 Crown ethers, dicyclohexyl-18-crown-6, 24-crown-8, dicyclohexyl-24-crown-8, dibenzo-24-crown-8, ethylenediamine, N, N ' -Tetramethylethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexaamine, 1,1,4,7,7-pentamethyldiethylenetriamine, 1,1, Polyamines such as 4,7,10,10-hexamethyltriethylenetetramine, triethoxytrivinylamine, 1,4,7,11-tetraazacyclotetradecane (Cyclam), cycloolefins (Cyclene) and other cyclic polyamines, pyridine, pyrrolidine, piperidine, morpholine, N-methylpyrrolidine, N-methylpiperidine, N-methylmorpholine, tetrahydrofuran, tetrahydropyran, Heterocyclic compounds such as 1,4-dioxane, oxazole, thiazole, and oxathiolane, methyl ethyl acetate, ethyl ethyl acetate, ethyl 2-methoxyethyl Β-ketoesters such as esters or acetoacetone, 2,4-hexanedione, 2,4-heptanedione, 3,5-heptanedione, bistrimethylacetamidomethane (Dipivaloylmethane Β-diketones The amount of these nucleophiles used is preferably in the range of 0.1 to 10 mol, more preferably 1 to 4 mol, relative to the amount of the compound represented by the general formula (2). [0070] As far as possible, the raw materials for forming a thin film for the atomic layer deposition method of the present invention do not contain impurities such as impurity metal elements other than components constituting the raw materials, impurity halogens such as impurities chlorine, and impurities organic components. The impurity metal element content is preferably 100 ppb or less per element, more preferably 10 ppb or less, and the total amount is preferably 1 ppm or less, and more preferably 100 ppb or less. In particular, when used as a gate insulating film, a gate film, and a barrier layer of an LSI, it is necessary to reduce the content of alkali metal elements and alkaline earth metal elements that have an influence on the electrical characteristics of the obtained film. The impurity halogen content is preferably 100 ppm or less, more preferably 10 ppm or less, and most preferably 1 ppm or less. The total amount of impurities is preferably 500 ppm or less, more preferably 50 ppm or less, and most preferably 10 ppm or less. In addition, since moisture causes particles in raw materials for chemical vapor growth or particles in film formation, the compounds, organic solvents, and nucleophiles represented by the general formula (2) described above are used to reduce individual It is better to remove the water as early as possible when using it. The water content of each of the compound represented by the general formula (2), the organic solvent, and the nucleophile is preferably 10 ppm or less, and more preferably 1 ppm or less. [0071] In order to reduce or prevent particle contamination of the formed thin film, the raw material for thin film formation used in the atomic layer deposition method of the present invention is preferable so as not to contain particles as much as possible. Specifically, the number of particles larger than 0.3 μm is preferably less than 100 in 1 mL of the liquid phase, and the number of particles larger than 0.2 μm is smaller than that in the liquid. The number of particles in 1 mL is preferably 1,000 or less, and the number of particles larger than 0.2 μm is preferably 100 or less in 1 mL of liquid phase. [0072] As a raw material for forming a thin film using the atomic layer deposition method of the present invention, the method of producing the thin film of the present invention by which an ALD method is used to produce the thin film is not particularly limited, and the above-mentioned known general conditions and methods can be used . [0073] Examples of the reactive gas used in the production of the thin film by the ALD method include oxygen, ozone, nitrogen dioxide, nitric oxide, water vapor, hydrogen peroxide, formic acid, and acetic acid. And acetic anhydride. Examples of reducing agents include hydrogen, and examples of nitrides include organic amine compounds such as monoalkylamines, dialkylamines, trialkylamines, and alkylene diamines, and hydrazine. , Ammonia, etc. These may be used singly or in combination of two or more. Among these, since the raw material for film formation used in the atomic deposition method of the present invention has good reactivity with ozone, when one kind of reactive gas is used, it is preferable to use ozone, and as the reactive gas, two or more kinds of When the gas is mixed, it is preferable to include at least ozone. [0074] Examples of the conveyance and supply method at the time of manufacturing a thin film by the ALD method include the aforementioned gas transportation method, liquid transportation method, single-source method, and mixed-source method. [0075] Examples of the material of the substrate used in the production of the thin film by the ALD method include silicon; silicon nitride, titanium nitride, tantalum nitride, titanium oxide, titanium nitride, ruthenium oxide, zirconia, and oxide Ceramics such as rhenium and lanthanum oxide; glass; metals such as ruthenium. Examples of the shape of the substrate include a plate shape, a spherical shape, a fibrous shape, and a scaly shape. The surface of the substrate may be planar and may be a three-dimensional structure such as a trench structure. [0076] Examples of the manufacturing conditions include a reaction temperature (substrate temperature), a deposition rate, and the like. As for the reaction temperature, the temperature at which the compound represented by the general formula (2) is sufficiently reacted is preferably 100 ° C or higher, more preferably 150 ° C to 400 ° C, and particularly preferably 150 ° C to 350 ° C. The deposition rate can be controlled by the supply conditions of the raw materials (gasification temperature, gasification pressure), reaction temperature, and reaction pressure. When the deposition speed is high, the characteristics of the obtained film may be deteriorated, and when the production speed is slow, problems may occur in productivity, so it is preferably 0.01 to 0.1 nm / cycle. [0077] As the above-mentioned production conditions, the temperature or pressure at the time of vaporizing the raw material for forming a thin film used in the atomic layer deposition method into vapor can be further mentioned. The step of vaporizing the raw material for forming a thin film used in the atomic layer deposition method into a vapor may be performed in a raw material container or in a gasification chamber. In either case, it is preferable that the raw material for forming a thin film used in the atomic layer deposition method of the present invention is evaporated at 0 to 150 ° C. When the raw material for the film formation for the atomic layer deposition method is vaporized in the raw material container or the gasification chamber into vapor, the pressure in the raw material container and the pressure in the gasification chamber are preferably 1 to 10,000 Pa. [0078] The thin film manufacturing method of the present invention adopts the ALD method. In addition to the above-mentioned transportation and supply method, the raw material for thin film formation used in the atomic layer deposition method is vaporized into vapor, and the raw material introduction step of introducing the vapor into the film forming chamber is performed. In addition, the method may include a step of forming a precursor film on the surface of the substrate from a compound represented by the general formula (2) in the vapor, a step of forming a precursor film, a step of exhausting an unreacted compound gas, and The precursor film performs a chemical reaction with a reactive gas, and a metal-containing thin film forming step is formed on the surface of the substrate. [0079] Hereinafter, for each of the steps described above, the case of forming a metal oxide thin film will be described in detail as an example. When the metal oxide thin film is formed by the ALD method, first, the raw material introduction step described above is performed. The preferable temperature or pressure when the raw material for forming a thin film for the atomic layer deposition method is steam is the same as that described above. Next, a precursor film is formed on the surface of the substrate from the compound introduced into the accumulation reaction part (precursor film formation step). In this case, heat may be added to the substrate by heating or accumulating the reaction portion. The precursor film before film formation in this step is a thin film generated from the compound represented by the general formula (2), or a part of the compound represented by the general formula (2), which is decomposed and / or reacted, and The intended metal oxide films have different compositions. The substrate temperature during this step is preferably 100 to 400 ° C, and more preferably 150 to 350 ° C. The pressure of the system (in the film-forming chamber) when performing this step is preferably 1 to 10,000 Pa, and more preferably 10 to 1000 Pa. [0080] Next, unreacted compound gas or by-product gas is exhausted from the accumulation reaction section (exhaust step). Although the unreacted compound gas or by-product gas is desirably completely exhausted from the accumulation reaction part, it is not necessarily exhausted completely. Examples of the exhausting method include a method of scavenging a system with an inert gas such as nitrogen, helium, and argon, a method of performing exhaustion in a decompression system, and a method of combining these methods. The degree of pressure reduction during the pressure reduction is preferably 0.01 to 300 Pa, and more preferably 0.01 to 100 Pa. [0081] Next, an oxidizing gas is introduced into the deposition reaction part, and the precursor film is obtained from the previous precursor film film forming step to form a metal oxide film by the action of the oxidizing gas or the effect of the oxidizing gas and heat ( Metal oxide-containing thin film forming step). The temperature at which heat is generated in this step is preferably room temperature to 500 ° C, and more preferably 150 to 350 ° C. The pressure of the system (in the film-forming chamber) when performing this step is preferably 1 to 10,000 Pa, and more preferably 10 to 1000 Pa. Since the compound represented by the general formula (2) has good reactivity with an oxidizing gas, a metal oxide thin film having a small residual carbon content can be obtained. [0082] In the thin film manufacturing method of the present invention, when the ALD method is used as described above, the raw material introduction step, the precursor thin film forming step, the exhaust step, and the metal oxide-containing thin film forming step can be performed by As one cycle of the film deposition that constitutes a series of operations, this cycle can be repeated multiple times until a film with the necessary film thickness is obtained. In this case, after 1 cycle, it is performed in the same manner as the above-mentioned exhausting step. Unreacted compound gas and reactive gas (oxidizing gas when forming a metal oxide film) are exhausted from the deposition reaction part, and the exhaust gas is formed as a by-product. After the gas, it is better to carry out the next cycle. [0083] In the formation of the metal oxide thin film by the ALD method, energy such as plasma, light, and voltage can be applied, and a catalyst can be used. The time when the energy is applied and the time when the catalyst is used are not particularly limited. For example, when the compound gas is introduced in the raw material introduction step, the precursor film formation step or the metal oxide-containing film formation step is heated, When exhausting the system in the exhausting step, or when introducing an oxidizing gas in the film forming step containing a metal oxide, it may be between the above steps. [0084] In the method for manufacturing a thin film of the present invention, after the thin film is deposited, in order to obtain better electrical characteristics, annealing treatment may be performed in an inert environment, an oxidizing environment, or a reducing environment. You can set the reflow step. The temperature at this time is 200 to 1000 ° C, preferably 250 to 500 ° C. [0085] A well-known chemical vapor growth method can be used as a device for manufacturing a thin film using the raw material for film formation for the atomic layer deposition method of the present invention. As an example of a specific device, there can be mentioned a device which can perform a precursor supply as shown in FIG. 1 by foaming supply or a device having a gasification chamber as shown in FIG. 2. Moreover, as shown in FIG. 3 and FIG. 4, the apparatus which can perform plasma processing with respect to a reactive gas. It is not limited to the single-chip device as shown in FIGS. 1 to 4, and a device that can process multiple pieces simultaneously using a batch furnace can also be used. [0086] A thin film containing a metal produced using the raw material for forming a thin film for the atomic layer deposition method of the present invention has been used in cutting tools and wirings or electrodes for electronic materials. For example, it can be used in semiconductor memory materials or lithium. Electrodes for air batteries. [Examples] [0087] Hereinafter, the present invention will be described in more detail with examples and evaluation examples. However, the present invention is not limited in any way by the following examples and the like. [Example 1] Production of Compound No. 4 In a 2000 mL 4-neck flask, a mixed solution of 230.0 g of zirconium (dimethylamino) zirconium and 1190 g of dehydrated toluene in an Ar environment, cyclopentadiene 113.7 It takes about 1 hour to drop g from an isostatic dropping funnel to make it react. Next, 201.5 g of 1- (dimethylamino) -2-methyl-2-propanol was added dropwise from an isobaric dropping funnel over a period of about 2 hours, and reacted. After completion of the dropping, the temperature was gradually raised to room temperature, and the reaction was continued for 2 hours. Next, after distilling off the solvent under reduced pressure, a fraction of 67 Pa / 145 to 7 ° C was fractionated under reduced pressure to obtain 312 g of compound No. 4 as a pale yellow liquid. (Analytical value) (1) 50% mass reduction of atmospheric pressure TG-DTA temperature: 271 ° C (Ar flow rate: 100 mL / min, temperature increase: 10 ° C / min, sample amount: 11.491 mg) (2) Elemental analysis ( Metal analysis: ICP-AES, CHN analysis: CHN analysis device) Zirconium content: 20.05% by mass (theoretical value: 20.10% by mass) C: 58.0% by mass (theoretical value: 58.23% by mass), H: 7.9% by mass (theoretical value) : 8.44% by mass), N: 5.8% by mass (theoretical value: 6.17% by mass) [Example 2] Production of Compound No. 22 in a 300 mL 4-necked flask under an Ar environment in an ice bath (dimethylamino group) ) After a mixed solution of 19.3 g of titanium and 118.9 g of dehydrated toluene, 12.0 g of cyclopentadiene was dropped from an isostatic dropping funnel for about 30 hours to react. Next, 20.2 g of 1- (dimethylamino) -2-methyl-2-propanol was added dropwise from an isostatic dropping funnel over a period of about 1 hour and reacted. After completion of the dropping, the temperature was gradually raised to room temperature, and the reaction was continued for 2 hours. Next, after distilling off the solvent under reduced pressure, distillation under reduced pressure was performed to obtain 28.2 g of Compound No. 22 as a pale yellow liquid. (Analytical value) (1) 50% reduction in atmospheric pressure TG-DTA mass: 272 ° C (Ar flow rate: 100 mL / min, temperature increase: 10 ° C / min, sample amount: 10.421 mg) (2) Elemental analysis ( Metal analysis: ICP-AES, CHN analysis: CHN analysis device) Titanium content: 11.5% by mass (theoretical value: 11.67% by mass) C: 64.1% by mass (theoretical value: 64.38% by mass), H: 8.7% by mass (theoretical value) : 9.33% by mass), N: 6.1% by mass (theoretical value: 6.83% by mass) [Production Example 1] Production of Compound No. 40 in a 300 mL 4-necked flask under an Ar environment in an ice bath (diethylamine group) ) After mixing a mixed solution of 37.4 g and 110.6 g of dehydrated toluene, 11.1 g of cyclopentadiene was dropped from an isostatic dropping funnel for about 30 hours to react. Next, 18.8 g of 1- (dimethylamino) -2-methyl-2-propanol was added dropwise from an isostatic dropping funnel over about 1 hour and reacted. After completion of the dropping, the temperature was gradually raised to room temperature, and the reaction was continued for 2 hours. Next, after distilling off the solvent under reduced pressure, a fraction of 60 Pa / 145 to 7 ° C was fractionated under reduced pressure to obtain 34.5 g of Compound No. 40 as a pale yellow liquid. (Analytical value) (1) 50% reduction in atmospheric pressure TG-DTA mass: 258 ° C (Ar flow rate: 100 mL / min, temperature increase: 10 ° C / min, sample amount: 10.421 mg) (2) Elemental analysis ( Metal analysis: ICP-AES, CHN analysis: CHN analysis device) Thorium content: 32.9% by mass (theoretical value: 32.99% by mass) C: 48.6% by mass (theoretical value: 48.84% by mass), H: 6.7% by mass (theoretical value) : 7.08% by mass), N: 4.7% by mass (theoretical value: 5.18% by mass) [0094] [Evaluation Example 1] Evaluation of Physical Properties of Zirconium Compound For Compound No. 4, Comparative Compound 1 and Comparative Compound 2 shown below The state of each compound at 30 ° C under normal pressure was visually observed. The viscosity was measured at 30 ° C. using a falling ball viscosity meter (manufactured by Anton Paar, product name: AMVn). For Comparative Compound 1 and Comparative Compound 2, the temperature at which the weight was reduced by 50% using TG-DTA was measured at normal pressure (Ar flow rate: 100 mL / min, temperature increase: 10 ° C / min, sample amount of Comparative Compound 1: 13.064 mg, sample amount of comparative compound 2: 12.485 mg). In addition, in an inert gas environment, prepare samples that are heat-treated at a temperature of 100 ° C to 300 ° C for 1 hour at a temperature of 10 ° C. From the samples with a low temperature of the heat treatment, TG- DTA measurement (Ar flow rate: 100 mL / min, temperature increase: 10 ° C / min, measurement temperature range: 25 ° C to 600 ° C). The temperature of the above-mentioned heat treatment of the initial sample in which the amount of the residue after the TG-DTA measurement was 2% by mass or more was defined as the "thermal decomposition temperature". The results are shown in Table 1. [0095] [0096] [0097] From Table 1 above, it is understood that compound No. 4, comparative compound 1 and comparative compound 2 are all compounds having a low melting point under the condition of normal pressure of 30 ° C. It was also found that although Compound No. 4 had a higher viscosity at 30 ° C than Comparative Compound 1, it had a sufficiently low viscosity as a raw material for chemical vapor growth. The raw material for film formation having a low melting point and a low viscosity can improve the productivity of the raw material for film formation due to its good transportability. From the results of atmospheric pressure TG-DTA, it was found that compound No. 4, as a raw material for chemical vapor growth, shows sufficient vapor pressure and has very high thermal stability. [Evaluation Example 2] Evaluation of Physical Properties of Titanium Compound Regarding Compound No. 22 and Comparative Compound 3 shown below, the state of each compound at 30 ° C. under normal pressure was visually observed. For a solid compound, a melting point was measured using a minute melting point measuring device. For Comparative Compound 3, the temperature at which the weight was reduced by 50% at normal pressure using TG-DTA (Ar flow rate: 100 mL / min, temperature increase: 10 ° C./min, sample amount: 8.997 mg) was measured. The results are shown in Table 2. [0099] [0100] [0101] From Table 2 above, it is understood that the compound No. 22 is a liquid low-melting compound at a temperature of 30 ° C. compared to the compound having a melting point of 75 ° C. compared to Comparative Compound 3. Since the raw material for forming a thin film having a low melting point is easy to transport, it is a raw material for forming a film that can improve productivity. Furthermore, from the results of atmospheric pressure TG-DTA, it was found that the compound No. 22 had a slightly higher temperature at a 50% reduction in mass than the comparative compound 3, but it had shown sufficient vapor pressure as a raw material for chemical vapor growth. . [Example 3] Production of zirconia thin film by ALD method Using compound No. 4 as a raw material for chemical vapor phase growth, using a chemical vapor growth device shown in FIG. 1 under the following conditions The ALD method is used to fabricate a zirconia film on a silicon substrate. For the obtained thin film, when the film thickness was measured by the X-ray reflectance method, and the film structure and the film composition were confirmed by the X-ray diffraction method and the X-ray photoelectron spectroscopy method, the film thickness was 2 to 4 nm. It becomes zirconia (confirmed by the peak of Zr4d by XPS analysis), and the residual carbon content in the film is less than the lower limit of detection, which is 0.1 atom%. The film thickness obtained per cycle is 0.02 to 0.04 nm. (Condition) Reaction temperature (substrate temperature); 250 ° C., reactive gas; ozone (step) A series of steps consisting of the following (1) to (4) was taken as one cycle, and 100 cycles were repeated. (1) The raw material for chemical vapor growth is vaporized under the conditions of heating temperature of the raw material container: 150 ° C., pressure in the raw material container: 80 Pa or less, and is introduced into a film forming chamber, and the system pressure is set at 80 Pa for 10 seconds. (2) Unreacted raw materials and by-product gases are removed by a 10 second argon sweep. (3) A reactive gas is introduced into the film forming chamber, and the system pressure is: reacted at 80 Pa for 10 seconds. (4) Remove unreacted raw materials and by-product gases by argon scavenging for 10 seconds. [Comparative Example 3] Comparative Compound 2 (Zr (DMAMP) 4 ) As a raw material for chemical vapor growth, a chemical vapor growth apparatus shown in FIG. 1 was used, and a zirconia thin film was produced on a silicon substrate by an ALD method under the following conditions. For the obtained thin film, when the film thickness was measured by the X-ray reflectance method, and the film structure and the film composition were confirmed by the X-ray diffraction method and the X-ray photoelectron spectroscopy method, the film thickness was 1 nm and the film composition was oxidized. Zirconium (confirmed by the peak of Zr4d analyzed by XPS), the residual carbon content in the film was 5 atom%. The film thickness obtained every 1 cycle was 0.01 nm. [Condition] Reaction temperature (substrate temperature); 280 ° C, reactive gas; ozone (step) A series of steps consisting of the following (1) to (4) is taken as one cycle, and 100 cycles are repeated. (1) The raw material for chemical vapor growth is vaporized under the conditions of heating temperature of the raw material container: 150 ° C., pressure in the raw material container: 80 Pa or less, and is introduced into a film forming chamber. (2) Unreacted raw materials and by-product gases are removed by a 10 second argon sweep. (3) A reactive gas is introduced into the film forming chamber, and the system pressure is: reacted at 80 Pa for 10 seconds. (4) Remove unreacted raw materials and by-product gases by argon scavenging for 10 seconds. [0106] From the results of Example 3, it was found that by using the compound of the present invention as a raw material for forming a thin film for an ALD method, a zirconia thin film having a very good quality can be obtained. In addition, from the results of Comparative Example 3, it was found that when the comparative compound 2 was used as a raw material for forming a thin film for an ALD method, it was difficult to produce a high-quality zirconia thin film including productivity. [Example 4] Compound No. 22 was used as a raw material for chemical vapor growth by the production of a titanium oxide thin film by the ALD method, and the chemical vapor growth device shown in FIG. 1 was used, and the following conditions were used for the ALD method: , Manufacture a titanium oxide film on a silicon substrate. For the obtained thin film, when the film thickness was measured by the X-ray reflectance method, and the film structure and the film composition were confirmed by the X-ray diffraction method and the X-ray photoelectron spectroscopy method, the film thickness was 3 to 4 nm. It becomes titanium oxide (confirmed by the peak of Ti3d by XPS analysis), and the residual carbon content in the film is less than the lower limit of detection of 0.1 atom. The film thickness obtained per cycle is 0.03 to 0.04 nm. [Condition] Reaction temperature (substrate temperature); 300 ° C, reactive gas; ozone (step) A series of steps consisting of the following (1) to (4) is taken as one cycle, and 100 cycles are repeated. (1) The raw material for chemical vapor growth was vaporized under the conditions that the raw material container heating temperature: 160 ° C. and the pressure inside the raw material container: 80 Pa or less were introduced into a film forming chamber, and the system pressure was set at 80 Pa for 10 seconds. (2) Unreacted raw materials and by-product gases are removed by a 10 second argon sweep. (3) A reactive gas is introduced into the film forming chamber, and the system pressure is: reacted at 80 Pa for 10 seconds. (4) Remove unreacted raw materials and by-product gases by argon scavenging for 10 seconds. [Example 5] Production of ytterbium oxide thin film by ALD method Using compound No. 40 as a raw material for chemical vapor growth, using the apparatus for chemical vapor growth shown in FIG. 1, the ALD method under the following conditions was used. , A hafnium oxide film is fabricated on a silicon substrate. For the obtained thin film, when the film thickness was measured by the X-ray reflectance method, and the film structure and the film composition were confirmed by the X-ray diffraction method and the X-ray photoelectron spectroscopy method, the film thickness was 2 to 4 nm. It became thorium oxide (confirmed by the peak of Hf4f by XPS analysis), and the residual carbon content in the film was less than 0.1 atom% of the lower detection limit. The film thickness obtained per cycle is 0.02 to 0.04 nm. [Condition] Reaction temperature (substrate temperature); 300 ° C, reactive gas; ozone (step) A series of steps consisting of the following (1) to (4) is taken as one cycle, and 100 cycles are repeated. (1) The raw material for chemical vapor growth is vaporized under the conditions of heating temperature of the raw material container: 150 ° C., pressure in the raw material container: 80 Pa or less, and is introduced into a film forming chamber, and the system pressure is set at 80 Pa for 10 seconds. (2) Unreacted raw materials and by-product gases are removed by a 10 second argon sweep. (3) A reactive gas is introduced into the film forming chamber, and the system pressure is: reacted at 80 Pa for 10 seconds. (4) Remove unreacted raw materials and by-product gases by argon scavenging for 10 seconds. [0111] Still, this international application claims priority based on Japanese Patent Application No. 2016-218054 filed on November 8, 2016, and applies the entire contents of this Japanese patent application to this International Application. case.

[0017] 　　[圖1]圖1係表示有關本發明之薄膜之製造方法所使用之化學氣相成長用裝置之一例的概要圖。 　　[圖2]圖2係表示有關本發明之薄膜之製造方法所使用之化學氣相成長用裝置之另一例的概要圖。 　　[圖3]圖3係表示有關本發明之薄膜之製造方法所使用之化學氣相成長用裝置之另一例的概要圖。 　　[圖4]圖4係表示有關本發明之薄膜之製造方法所使用之化學氣相成長用裝置之另一例的概要圖。[0017] FIG. 1 is a schematic diagram showing an example of a chemical vapor growth apparatus used in a method for producing a thin film according to the present invention. [Fig. 2] Fig. 2 is a schematic diagram showing another example of a chemical vapor growth apparatus used in the method for producing a thin film of the present invention. [Fig. 3] Fig. 3 is a schematic diagram showing another example of a chemical vapor growth apparatus used in the method for producing a thin film according to the present invention. [Fig. 4] Fig. 4 is a schematic diagram showing another example of a chemical vapor growth apparatus used in the method for producing a thin film of the present invention.

Claims (5)

一種下述一般式(1)表示之化合物，(式中，R1 ～R6 分別獨立表示氫或碳原子數1～4之直鏈或分支狀之烷基，R7 、R8 及R9 表示碳原子數1～4之直鏈或分支狀之烷基，M1 表示鋯或鈦)。A compound represented by the following general formula (1), (In the formula, R 1 to R 6 each independently represent hydrogen or a linear or branched alkyl group having 1 to 4 carbon atoms, and R 7 , R 8, and R 9 each represent a linear or branched chain having 1 to 4 carbon atoms. Alkyl group, M 1 represents zirconium or titanium). 一種薄膜形成用原料，其係含有如請求項1所記載之化合物而成。A raw material for forming a thin film comprising the compound described in claim 1. 一種薄膜之製造方法，其係將含有使如請求項2所記載之薄膜形成用原料氣化所得之化合物的蒸氣，導入設置有基質之成膜腔室內，再使該化合物分解及/或化學反應，而於該基質的表面形成含有鋯原子或鈦原子之薄膜。A method for manufacturing a thin film, which comprises introducing a vapor containing a compound obtained by vaporizing a raw material for forming a thin film according to claim 2, into a film forming chamber provided with a substrate, and decomposing and / or chemically reacting the compound A thin film containing zirconium atoms or titanium atoms is formed on the surface of the substrate. 一種原子層堆積法用之薄膜形成用原料，其係含有下述一般式(2)表示之化合物而成，(式中，R11 ～R16 分別獨立表示氫或碳原子數1～4之直鏈或分支狀之烷基，R17 、R18 及R19 表示碳原子數1～4之直鏈或分支狀之烷基，M2 表示鋯、鉿或鈦)。A raw material for forming a thin film for an atomic layer deposition method, comprising a compound represented by the following general formula (2), (In the formula, R 11 to R 16 each independently represent hydrogen or a linear or branched alkyl group having 1 to 4 carbon atoms, and R 17 , R 18 and R 19 each represent a straight chain or branched carbon group having 1 to 4 carbon atoms. Alkyl group, M 2 represents zirconium, hafnium or titanium). 一種薄膜之製造方法，其係將含有使如請求項4所記載之薄膜形成用原料氣化所得之化合物的蒸氣，導入設置有基質之成膜腔室內，藉由原子層堆積法，而於該基質的表面形成含有選自鋯原子、鉿原子及鈦原子中之至少一種原子的薄膜。A method for producing a thin film, which comprises introducing a vapor containing a compound obtained by vaporizing a raw material for forming a thin film as described in claim 4, into a film-forming chamber provided with a substrate, and applying an atomic layer deposition method thereon. A thin film containing at least one atom selected from the group consisting of zirconium atoms, hafnium atoms, and titanium atoms is formed on the surface of the substrate.
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