TW201139720A - Metal alkoxide compound and method for producing metal-containing thin membrane using said compound - Google Patents

Metal alkoxide compound and method for producing metal-containing thin membrane using said compound Download PDF

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TW201139720A
TW201139720A TW100100716A TW100100716A TW201139720A TW 201139720 A TW201139720 A TW 201139720A TW 100100716 A TW100100716 A TW 100100716A TW 100100716 A TW100100716 A TW 100100716A TW 201139720 A TW201139720 A TW 201139720A
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Taiwan
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metal
compound
film
formula
gold
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TW100100716A
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Chinese (zh)
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Takumi Kadota
Chihiro Hasegawa
Hiroshi Nihei
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Ube Industries
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    • H—ELECTRICITY
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    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
    • H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
    • H01L21/02263—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase
    • H01L21/02271—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition
    • C—CHEMISTRY; METALLURGY
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    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/28—Titanium compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C31/02—Monohydroxylic acyclic alcohols
    • C07C31/125—Monohydroxylic acyclic alcohols containing five to twenty-two carbon atoms
    • 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
    • C07F7/003—Compounds containing elements of Groups 4 or 14 of the Periodic Table without C-Metal linkages
    • 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
    • C23C16/06—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 metallic material
    • C23C16/18—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 metallic material from metallo-organic 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
    • H01L21/02172—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides
    • H01L21/02175—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides characterised by the metal
    • H01L21/02181—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides characterised by the metal the material containing hafnium, e.g. HfO2
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
    • H01L21/02172—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides
    • H01L21/02175—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides characterised by the metal
    • H01L21/02186—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides characterised by the metal the material containing titanium, e.g. TiO2
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
    • H01L21/02172—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides
    • H01L21/02175—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides characterised by the metal
    • H01L21/02189—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides characterised by the metal the material containing zirconium, e.g. ZrO2
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10B—ELECTRONIC MEMORY DEVICES
    • H10B99/00—Subject matter not provided for in other groups of this subclass
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    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L28/00—Passive two-terminal components without a potential-jump or surface barrier for integrated circuits; Details thereof; Multistep manufacturing processes therefor
    • H01L28/40—Capacitors

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
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  • Chemical Vapour Deposition (AREA)

Abstract

This invention relates to a metal alkoxide compound expressed by formula (1) (in the formula, M represents zirconium, hafnium or titanium. 4 R's can be the same or different and each independently represents a straight-chain or branched alkyl group with the carbon atom number of 2 to 6), and a method for producing a metal-containing thin membrane by chemical vapor deposition (CVD) using the compound.

Description

201139720 六、發明說明： 【發明所屬之技術領域】 本發明侧於形成含錯、給或鈦_時所可使用氧 ^物、^秘化合物姐氧鈦化合物。本發日収利職氧錯化人 氧铪化合物姐氧鈦化合物，提供—種藉由化學氣相沈^ 法(Chemical Vapor Deposition法；以下稱為CVD法）、以及原子 iS(^riUyer Dep°sitkm法；以下稱為ALD法)而製造含金 【先前技術】 =來伴隨DRAM所代表的半導體記憶體以及元件的細微 巧，兩；丨電材料之含鍅、铪或鈦薄膜於電容器領域受人矚目。 ^重==的對於齡钱容^、絕賴钱子材湘途進行 伯η 3 給或鈦薄膜之製造方法，例如可舉出_法或凝膠法。 $ 優異_簡勻性、成份控制、其量紐之觀點，採 CVD^·或疋ALD法之製造係成為現今的主流。 習知揭示的鍅化合物’例如有：四氣化錯(例如參考非專 ^ j、石肖酸鍅(例如參考非專利文獻乃等無機 Ϊ非專利文獻3)、肆(1^甲基-2-_^"如 二考^專利文獻4)、肆(二甲基胺乙氧)錯(例如參考非專利文獻 物、·肆Ϊ丁稀_2_氧)錯(例如參考專利文獻υ等烧氧錯化合 ’一料乙基甲基胺}錯(例如參考非專利文獻胺錯化合物； 人‘二雔甲酿甲烧)樹例如參考非專利文獻乃等&二酉同基鍅化 二^基甲氧錯(例如參考非專利文獻8以及 .獻2)荨％戊二稀鍅化合物。再者，亦可舉出二異丙氧 甲基庚二酮酸鍅(zirc〇nium版〇卿〇xy以敝_邮 ePtanedi〇nate)等(例如參考專利文獻3)。 又’銓化合物，例如有：二甲基雙(曱基環戊二烯)給(例如參 201139720 考專利文獻4)。再者，關於給化合物及欽化合物，可舉出將具有 烷氧烷曱基的β-二酮基與烷氧基作為配位子之铪錯合物以及&錯 合物(例如參考專利文獻5)。 曰 [習知技術文獻] [專利文獻1]日本特開2008-69135號公報 [專利文獻2]曰本特開2009-108402號公報 [專利文獻3]曰本特開2009-073858號公報 [專利文獻4]日本特表2009-516078號公報 [專利文獻5]日本特開2007-31283號公報 [非專利文獻 1] Journal of the Electrochemical Society，vol 155 (9), H633 (2008) ’ · ’ [非專利文獻 2]Joumal of the Electrochemical Society，vol.147， (9), 3472 (2000) ， ， [非專利文獻 3]Chemistry of Materials, vol.14,1269 (2002) [非專利文獻 4]Journal of the Electrochemical Society，vol. 151, (5), C283 (2004) ’ ’ [非專利文獻 5]Joumal of the Electrochemical Society, vol.149， (1), C23 (2002) ’ ’ [非專利文獻 6]Joumal of the Electrochemical Society，vol. 156， (1),H71 (2009) [非專利文獻 7]Joumal of the Electrochemical Society, vol.152， (7), C498 (2005) [非專利文獻 8]ECS transactions，Vol.ll，（7)，113 (20〇7) 【發明内容】 [發明所欲解決的問題] 一般而言’ CVD法或ALD法所使用的金屬化合物之物性需 具有高蒸氣壓，且為低熔點(更理想之樣態為在室溫下為液狀或氣 體狀）。 201139720 假設在使用低蒸氣壓的金屬化合物之情況下，由於需要將填 充化合物的容器、輸送化合物的配管等保持於高溫，因而在耗費 高能源之同時，會因為設備全體成為高溫規格而產生成本高額化 的問題。 另一方面，在使用高熔點的金屬化合物之情況下，通常金屬 化合物的供給會不穩定，而難於穩定製造目標之含金屬薄膜。再 者，若配管等之保溫不完善，會造成配管内堵塞，因而產生在維 修耗費大量的時間之問題。 根據以上觀點’探討至今為止所報導的金屬化合物，可發現： 由於無機金屬化合物或β-二酮基金屬化合物皆為低蒸氣壓，同時 為南溶點’故不能解決前述問題。 相對於此，金屬烧氧化合物或金屬醯胺化合物中，揭示幾個 具有高蒸氣壓的金屬化合物，可藉由超過四配位的多牙配位體化 或多聚化而可達成高沸點或高熔點。 該等金屬化合物中，尤以達成單體化的化合物，亦即，呈有 尚蒸氣壓及低熔點的金屬化合物較為理想。然而，該等金屬彳/匕合 ，之熱穩定性皆低’其合成時或製造金屬細時會有分解的σ 題，甚至會因分解而混入雜質的碳這些問題產生。 詳言之，本發明係解決前述問題，提供一 具有低舰、高蒸氣壓，對於熱的敎性佳，同時藉^ 法及 ALD法而適於製造含金屬薄膜。且，本^ 屬烧氧化合物之含金㈣歡製造綠騎从、—種利用献 [解決問題之技術手段] 本發明係關於以下事項。 1.一種金屬烷氧化合物，以通式表示. [化 1] ,、’ 201139720201139720 VI. Description of the Invention: [Technical Field to Which the Invention Is Applicable] The present invention can be used to form an oxygen-containing compound, an oxygen compound, or a titanium compound. The oxygen-degraded human oxonium compound, the oxygen-oxygen compound, is provided by the chemical vapor deposition method (Chemical Vapor Deposition method; hereinafter referred to as CVD method) and the atomic iS (^riUyer Dep°). Sitkm method; hereinafter referred to as ALD method) to manufacture gold-containing [previous technology] = to accompany the semiconductor memory represented by DRAM and the subtleness of components, two; tantalum, niobium or titanium film containing tantalum electric material is subject to capacitor field People are eye-catching. ^Weighing == For the age of money, and the method of manufacturing the titanium film or the titanium film, for example, a method or a gel method. $ Excellent _ simplification, composition control, its quantitative point of view, the manufacturing system using CVD ^ · or 疋 ALD method has become the mainstream today. The ruthenium compound disclosed by the prior art is, for example, a four gasification error (for example, reference non-specific, bismuth sulphate (for example, refer to Non-Patent Document, etc.), 肆(1^methyl-2) -_^" as in the second test ^ patent document 4), 肆 (dimethylamine ethoxy) error (for example, refer to non-patent literature, 肆Ϊ丁稀_2_oxygen) wrong (for example, refer to the patent literature υ, etc. Burning oxygen mis-synthesis 'single ethyl methylamine} is wrong (for example, refer to the non-patent literature, amine-missing compound; human 'two-breasted nail-burning) tree, for example, refer to the non-patent literature, etc. & ^ methoxy methine (for example, refer to Non-Patent Document 8 and 2) 荨% pentane sulphate compound. Further, diisopropyloxymethyl pimelonate bismuth (zirc〇nium version 〇 亦可) 〇 敝 敝 邮 邮 邮 邮 邮 邮 邮 邮 邮 邮 邮 邮 邮 邮 邮 邮 邮 邮 邮 邮 邮 邮 邮 邮 邮 邮 邮 邮 邮 邮 邮 邮 邮 邮 邮 邮 邮 邮 邮 。 。 。 。 。 。 。 。 。 。 。 。 。. Further, examples of the compound and the compound include a ruthenium complex which has a β-diketone group having an alkoxyalkyl group and an alkoxy group as a ligand, and a complex compound (for example). Japanese Laid-Open Patent Publication No. 2008-108135 [Patent Document 2] JP-A-2009-108402 [Patent Document 3] 曰本特开2009 [Patent Document 4] Japanese Patent Publication No. 2009-516078 [Patent Document 5] JP-A-2007-31283 [Non-Patent Document 1] Journal of the Electrochemical Society, vol 155 (9), H633 ( 2008) '·' [Non-Patent Document 2] Joumal of the Electrochemical Society, vol. 147, (9), 3472 (2000), , [Non-Patent Document 3] Chemistry of Materials, vol. 14, 1269 (2002) [ Non-Patent Document 4] Journal of the Electrochemical Society, vol. 151, (5), C283 (2004) ' ' [Non-Patent Document 5] Joumal of the Electrochemical Society, vol. 149, (1), C23 (2002) ' [Non-Patent Document 6] Joumal of the Electrochemical Society, vol. 156, (1), H71 (2009) [Non-Patent Document 7] Joumal of the Electrochemical Society, vol. 152, (7), C498 (2005) [ Non-Patent Document 8] ECS transactions, Vol. ll, (7), 113 (20〇7) [Summary of the Invention] [Invented Problem to be Solved] Generally, the physical properties of the metal compound used in the CVD method or the ALD method are required to have a high vapor pressure and a low melting point (more preferably, a liquid or gas phase at room temperature). 201139720 It is assumed that when a metal compound having a low vapor pressure is used, it is necessary to maintain a high temperature of the container for filling the compound and the pipe for transporting the compound, and the cost is high because the entire device becomes a high temperature specification. Problem. On the other hand, in the case of using a metal compound having a high melting point, the supply of the metal compound is usually unstable, and it is difficult to stably manufacture the target metal-containing film. Further, if the insulation of the piping or the like is not perfect, the piping is clogged, which causes a problem that a large amount of time is spent on maintenance. From the above viewpoints, it has been found that the metal compound reported so far can be found that the above problems cannot be solved because both the inorganic metal compound or the β-diketone metal compound have a low vapor pressure and are both a south melting point. In contrast, in a metal alkoxide compound or a metal guanamine compound, several metal compounds having a high vapor pressure are disclosed, and a high boiling point or a high boiling point can be achieved by multidentate ligandization or multimerization of more than four coordination sites. High melting point. Among these metal compounds, a compound which achieves merization, that is, a metal compound having a vapor pressure and a low melting point is preferable. However, these metal ruthenium/rutheniums have low thermal stability, and there is a problem that they are decomposed during synthesis or when the metal is finely formed, and even carbon which is contaminated by impurities is decomposed. In particular, the present invention solves the aforementioned problems and provides a low-ship, high vapor pressure, good thermal conductivity, and is suitable for the production of a metal-containing film by the method of ALD and ALD. Further, the present invention relates to the following matters: the gold-containing oxygen-supplementing compound (four) is produced by the green rider and the use of the seed. [Technical means for solving the problem] The present invention relates to the following matters. A metal alkoxy compound represented by the formula. [Chem. 1] , , ' 201139720

白石中之M表示錯、給或鈦’ 4個R可相同亦可相異，各 一立’並代表碳原子數2〜6的直鏈或分支狀之烷基。 化合物二種含金顧膜之製造方法，係利用前述1記載之金屬烧氧 1化學1^目沈積法的含金屬薄膜之製造方法，以前述 作為金屬供氧化合物或前述1記載之金狀氧化合物的溶液 七化學氣相沈積法的含金屬薄敵攸方法，該製y 化合物的:iit金祕氧化合物或前述1記載之金屬烧氧 七用化學氣相沈積&的含金屬薄膜之製造方法，該抑 仆1物ί載之金屬烧氧化合物或前述1記載之金屬烧氧 化σ物的液與氮氣源。 、6·—^利用化學氣相沈積法的含金屬薄膜之製造方法，該製全 i記載之金屬烧氧化合物或前述1記載之金屬烧氧 化合物的洛液與惰性氣體。 喊=任—項减之利用化學氣概積法的含金屬薄 膜之h方法，其中該金狀氧化合物的溶液之溶劑 脂 肪族烴類、芳香族烴類及醚類所構成的群中之至 [發明之效果] 根^發明，於形成含金屬薄膜時，可提供—種有用的金屈 烧氧化δ物。本發明的金姐氧化合物具有低缝及高某氣壓， 對於熱的穩亦佳，尤舦_ CVD法或勘法而製造含金 屬薄膜。再者’利用該金屬烷氧化合物，藉由cv 可以良好的成膜特性製造含金屬薄膜。 或 会M in the white stone indicates a wrong, giving or titanium '4 R' may be the same or different, and each represents a straight or branched alkyl group having 2 to 6 carbon atoms. The method for producing a gold-containing film of the compound is a method for producing a metal-containing film by the metal-burning oxygen 1 chemical deposition method described in the above 1, and the metal oxygen-supplying compound or the gold-oxygen described in the above 1 Solution of Compounds Seven chemical vapor deposition method of metal-containing thin enemies, the preparation of the y compound: iit gold oxy-compound or the metal-containing film of the above-mentioned metal sulphur oxide seven chemical vapor deposition & The method is a liquid aerobic compound of the servant or a liquid and a nitrogen source of the metal oxidized sigma described in the above. And a method for producing a metal-containing thin film by a chemical vapor deposition method, the metal alkoxide compound described in the above, or the metal liquid and the inert gas of the metal aerobic compound described in the above. Shouting = 任 - 减 减 减 减 减 减 减 减 减 减 减 减 减 减 减 减 减 减 减 减 减 减 减 减 减 减 减 减 减 减 减 减 减 减 减 减 减 减 减 减 减 减 减 减 减 减 减EFFECTS OF THE INVENTION According to the invention, in the formation of a metal-containing film, a useful gold-baked oxidized δ substance can be provided. The gold sulphur compound of the present invention has a low slit and a high gas pressure, and is excellent in heat stability, and a metal-containing film is produced by a CVD method or a survey method. Further, by using the metal alkoxide, a metal-containing thin film can be produced by cv with good film forming properties. Or will

6 - S 201139720 【實施方式] 本發明的金屬烧氧化合物係如該 Μ袅示4生、队屮力4* , , %八'^)所不。5亥通式（1)中， f似可相同亦可相異，各自互為獨立，並 代表石反原子數2〜㈣直鏈或分支狀之烧基，_理彳 ΞϊίΓ'ΐΓ鏈或分支狀之烷基，最理想之樣態'為碳㉟ 的直鏈或分支狀之烷基。R，例如為乙基、正丙基、異丙基、正丁 基、異丁基、第二丁基、戊基、己基，而較理想之樣態為乙基、 正丙基、異丙基。由於4俯R為相同的化合物較容易合成，故較 為理想。 本發明的金屬烷氧化合物之具體例，例如可舉出式(2)至式(1〇) 所示的化合物。再者，式(2)至式(10)中，Μ表示錯·、铪或鈦。 [化2] 〜6 - S 201139720 [Embodiment] The metal alkoxy compound of the present invention is as shown in the figure 4, the force 4*, and the %8'. In the general formula (1), f may be the same or different, each being independent of each other, and representing a stone anti-atomic number 2 to (four) linear or branched burning base, _ 彳Ξϊ 彳Ξϊ Γ ΐΓ ΐΓ chain or branch The alkyl group, the most preferred form, is a linear or branched alkyl group of carbon 35. R, for example, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, pentyl, hexyl, and the preferred form is ethyl, n-propyl, isopropyl . Since 4 is the same compound as R, it is easier to synthesize, so it is more desirable. Specific examples of the metal alkoxide compound of the present invention include compounds represented by the formula (2) to the formula (1). Further, in the formulae (2) to (10), Μ represents erbium, yttrium or titanium. [Chemical 2] ~

7 ⑼ ⑼ (10) 201139720 反應ΐΓίϊ金屬絲化合物錄考公知法，藉由烧氧交換 烷氣化人你I0法，為了形成含金屬薄膜而t要令金屬 牛，你|Γ I化，而作為令本發明的金屬烧氧化合物氣化之方 官而二可^用將金屬烧氧化合物本身填充或輸送至氣化 (例如可舉出己ΐ’、ΐΓ=金屬烷氧化合物稀釋罐 辰己燒、乙基環己烧、辛炫等脂肪族烴類； 液，用Ϊί，’四氫吱喃、二頂等_等)之溶液，以輸送 液體用泵導人氣化室而氣化的方法(溶液法）。 β上成膜對象物上蒸鍵含金屬薄膜的方法，可以公知的CVD法 人物…入法^行，例如可使用：在常壓或是減壓下，將金屬烧氧化 入氧蝴例如’氧氣、臭氧等)或與氮氣源(例如，氨氣、 同時’亦或是交互加熱的基板上，而蒸鏡含金屬薄膜的方法。 ^ ’ ^可使用：送人無性職體(例如，氬氣、統)同時加熱 板上，而蒸鍍含金屬薄臈的方法。又，亦可使用：以電漿cVD 法蒸鍍含金屬薄膜的方法。 使用氧氣蒸鑛含金屬薄膜時，對於全氣體量的含氧氣比例， 較理想之樣態為0.1〜99容量％，而更理想之樣態為〇 5〜％容量％。 ，用本發明之金屬烧氧化合物對含金屬薄膜進行蒸錄時，關 於”蒸鑛條件’例如’反應系内的壓力，較理想之樣態為 :Pa〜2〇〇kPa’而更理想之樣態為1〇Pa〜11〇kPa;成膜對象物溫度， 較理，之樣態為15〇〜7G〇t：，.而更理想之樣態為2GG〜6GG°C ;令金 屬烧氧化合物氣化的溫度，較理想之樣態為2〇〜25〇c>c，而相 之樣態為40〜2〇〇。(：。 心 、再者，本案發明的含金屬薄膜之製造方法之較理想樣態係如 以下所述。 一、（1)利，本案發明的金屬烷氧化合物或金屬烷氧化合物之溶劑 洛液與氧氣源(尤以氧氣、臭氧較為理想），藉由CVD法及 法而製造含金屬薄膜。7 (9) (9) (10) 201139720 Reaction ΐΓ ϊ ϊ ϊ ϊ ϊ ϊ ϊ ϊ ϊ ϊ ϊ ϊ ϊ ϊ ϊ ϊ ϊ ϊ ϊ ϊ ϊ ϊ ϊ ϊ ϊ ϊ ϊ ϊ ϊ ϊ ϊ ϊ ϊ ϊ ϊ ϊ ϊ ϊ ϊ ϊ ϊ ϊ ϊ ϊ ϊ ϊ ϊ ϊ ϊ ϊ ϊ ϊ The gasification of the metal aerobic compound of the present invention may be carried out by filling or transporting the metal alkoxide compound to gasification (for example, hexanol, hydrazine = metal alkoxide compound dilution tank, Ethyl cyclohexanone, octyl alcohol and other aliphatic hydrocarbons; liquid, using a solution of Ϊί, 'tetrahydrofuran, Erding, etc., to vaporize the liquid to be pumped into the gasification chamber (solution law). A method of vapor-bonding a metal thin film on a film formation object on β can be carried out by a known method of CVD. For example, it can be used to oxidize a metal into an oxygen butterfly such as 'oxygen at normal pressure or reduced pressure. , ozone, etc.) or with a nitrogen source (for example, ammonia, at the same time - or on a substrate that is heated alternately, while the vapor mirror contains a metal film. ^ ' ^ can be used: to give people an asexual body (for example, argon Gas, system) simultaneously heating the plate, and vapor deposition method containing metal thin ruthenium. Also, it can also be used: a method of vapor-depositing a metal-containing film by plasma cVD method. When using oxygen to vaporize metal-containing film, for whole gas The ratio of the oxygen content is preferably from 0.1 to 99% by volume, and more preferably from 5% to 5% by volume. When the metal-containing film is steamed by the metal alkoxide of the present invention, Regarding the "steaming conditions" such as the pressure in the reaction system, the preferred state is Pa~2〇〇kPa', and more ideally, the state is 1〇Pa~11〇kPa; the temperature of the film formation object is Rational, the state is 15〇~7G〇t:,. And the more ideal form is 2GG~6GG°C; The temperature at which the oxygenating compound is vaporized is preferably 2〇~25〇c>c, and the phase is 40~2〇〇. (:. Heart, again, the metal-containing film of the invention) The preferred embodiment of the manufacturing method is as follows. 1. (1) Lee, the solvent of the metal alkoxide or metal alkoxide of the invention, and the source of oxygen (especially oxygen and ozone), A metal-containing thin film is produced by a CVD method and a method.

S 8 201139720 (2) 利用本案發明的金屬烧氧化合物或金屬烧氧化合物之溶劑 溶液與氣氣源(尤以氨氣、氮氣較為理想），藉由CVD法及ALD 法而製造含金屬薄膜。 (3) 利用本案發明的金屬烧氧化合物或金屬烧氧化合物之溶劑 溶液與惰性氣體(尤以氬氣、氦氣較為理想），藉由CVD法而製造 含金屬薄膜。· [實施例] 接著’舉出實施例而具體地說明本發明’但本發明的範圍並 非限定於此。 實施例l(M=Zr’R=異丙基;肆(2,4_二曱基_3_戊氧)鍅之合成(式 (4)的鍅化合物之合成)） ,在氬氣環境下，具備檟;拌設備及溫度計之内容積i〇〇mi的燒 瓶中_，加入肆(異丙氧)錯·異丙醇加成物5.11g(13.17mmol)以及 2’4-—甲基戊醇10.l2g(88.61mmol)，令液溫升溫至i70〇C為止， 將生成的異丙醇蒸餾去除，並於同溫度下反應30分鐘。反應結束 後’在減壓下將反應液濃縮，接著減壓蒸餾(15〇。 ， 透明液體之肆(2,4_二甲基各戍氧)錯5 73g(=f產 平，/9%)。 再者，肆(2,4-一曱基-3-戊氧)锆為以下物性值所示之新賴的化 合物。 、 h-NMi^CDa ’ δ(ρΡτη)); 〇.9〇(觀，d)、1.70(8H，m)、3.30(4H， 元素分析：C28H6G〇4zr 測定值 C : 60.5%、Η : 11.1%、Zr : 16.5% 理論值 C : 60.9%、Η : 11.0%、Zr : 16.5% 的結;银曱基_3伽之合成(式(2) 在氬氣環境下’具備擾拌設備及溫度計 瓶中，力认肆(異丙氧)錯·異丙醇域物㈣u.4fmm_t 9 201139720 曱基-3-，醇7.29g(71.36mmol)，令液溫升溫至17(rc為止，將生成 的^丙醇蒸餾去除，並於同溫度下反應3〇分鐘。反應結束後，在 減壓下將反應液濃縮，接著減壓蒸顧，17pa)濃縮物，得到 白色固體之肆(2-曱基-3-戊氧)結4.18g(分離生產率；74%)。 再者，肆(2-曱基-3-戊氧)鍅為以下物性值所示之新穎的化合 物。 ^H-NMF^CDCb，δ(ρριη)) ; 〇.92(36H，m)、1.50(81-1，m)、 1.66(4H，m)、3·29(4Η，q) 元素分析：C24H5204Zr 測定值 C : 58.3%、H : 10.4%、Zr : 18.4% 理♦值 C ·· 58.1%、H : 10.6%、Zr : 18.4% 的錯正祕；肆(2·甲基·3七讓之合成(式⑶ 在氬氣環境下，具備攪拌設備及溫度計之内容積丨⑻ml的燒 瓶中，加入肆(異丙氧)鍅•異丙醇加成物屯^畝丨丨15mm〇l)以及2_ 甲基-3-己醇9.17g(78.91mmol)，令液溫升溫至2〇〇t：為止，將生成 的異丙醇⑧顧去除’並於同溫度下反應3〇分鐘。反應結束後，在 減壓下將反應液濃縮，接著減壓蒸饀(15〇°c，i2Pa)濃縮物，得到 低黏性的透明液體之肆(2-曱基-3-己氧)錯4.20g(分離生產率；68 再者，肆(2-曱基-3-己氧)錯為以下物性值所示之新穎的化合 物。 . 、 σ 'H-NMR^DC^ « 6(ppm)) ； 0.68(36H > m) > 1.35(12H > m) ^ 1.57(8H，m)、3.60(4H，q) 元素分析：C28H6()04Zr 測定值 C :60.7%、H·· 11.3%、Zr:16.5% 理論值 C : 60.9%、H : 11.0%、Zr : 16.5% 實施例4〜6及比較例1〜5(熱穩定性之比較！） 實施例1〜3所得之式(2)〜(4)的本發明之錯化合物與作為比較 201139720 之合成的式(11)〜(15)之锆化合物，為了確認各自的熱穩定性，對 於經過一次蒸顧的各化合物進行再蒸顧，而確認其回收率。其結 果示於表1。化合物的結構以下述式表示。但是，式中之Μ代表 鍅(Zr)。 [化3]S 8 201139720 (2) A metal-containing thin film is produced by a CVD method and an ALD method using a solvent solution of a metal aerobic compound or a metal oxide compound of the present invention and an air gas source (especially ammonia gas or nitrogen gas). (3) A metal-containing thin film is produced by a CVD method using a solvent solution of a metal alkoxide compound or a metal oxide compound of the present invention and an inert gas (especially argon gas or helium gas). [Examples] Next, the present invention will be specifically described by way of Examples, but the scope of the present invention is not limited thereto. Example 1 (M=Zr'R=isopropyl; synthesis of ruthenium (2,4-didecyl_3_pentyloxy) oxime (synthesis of ruthenium compound of formula (4)), under argon atmosphere With 槚; mixing equipment and thermometer contents in the flask of i〇〇mi _, adding 肆 (isopropyl isopropoxide) wrong isopropyl alcohol adduct 5.11g (13.17mmol) and 2'4-methyl pentane The alcohol was 10.12 g (88.61 mmol), and the liquid temperature was raised to i70 〇C, and the resulting isopropyl alcohol was distilled off and reacted at the same temperature for 30 minutes. After the end of the reaction, the reaction solution was concentrated under reduced pressure, followed by distillation under reduced pressure (15 〇., 透明 (2,4-dimethyl oxime) of the clear liquid, 5 73 g (=f yield, /9%) Further, cerium (2,4-indenyl-3-pentyloxy)zirconium is a compound of the following properties as shown by the following physical property values: h-NMi^CDa 'δ(ρΡτη)); 〇.9〇 (View, d), 1.70 (8H, m), 3.30 (4H, Elemental analysis: C28H6G〇4zr Measured value C: 60.5%, Η: 11.1%, Zr: 16.5% Theoretical value C: 60.9%, Η: 11.0% , Zr : 16.5% of the knot; silver 曱 _ _ gamma synthesis (formula (2) under argon environment with a scrambler and thermometer bottle, force 肆 (isopropyl isopropoxide) wrong · isopropanol domain (4) u.4fmm_t 9 201139720 Mercapto-3-, alcohol 7.29g (71.36mmol), the liquid temperature is raised to 17 (rc), the resulting propanol is distilled off and reacted at the same temperature for 3 minutes. After completion, the reaction mixture was concentrated under reduced pressure, and then evaporated to dryness, and then evaporated to give a white solid (yield: 4-mercapto-3-pentyloxy). Further, hydrazine (2-indolyl-3-pentyloxy) hydrazine is a novel compound represented by the following physical property values. ^H- NMF^CDCb, δ(ρριη)) ; 〇.92(36H,m), 1.50(81-1,m), 1.66(4H,m),3·29(4Η,q) Elemental analysis: C24H5204Zr measured value C : 58.3%, H: 10.4%, Zr: 18.4% ♦ value C ·· 58.1%, H: 10.6%, Zr: 18.4% of the wrong secret; 肆 (2·methyl·3 seven let the synthesis (3) In an argon atmosphere, a flask equipped with a stirring device and a thermometer (8) ml is added with hydrazine (isopropoxy) hydrazine • isopropanol adduct 屯 ^ mu 丨丨 15 mm 〇 l) and 2 _ methyl - 9.17 g (78.91 mmol) of 3-hexanol, the liquid temperature was raised to 2 〇〇t:, and the generated isopropyl alcohol was removed and reacted at the same temperature for 3 minutes. After the reaction, the pressure was reduced. The reaction solution was concentrated, and then the concentrate was evaporated under reduced pressure (15 ° C, i.sub.2Pa) to obtain a low viscosity, viscous liquid (2-mercapto-3-hexyloxy), 4.20 g (separation productivity; 68 Further, fluorene (2-mercapto-3-hexyloxy) is a novel compound represented by the following physical property values: . σ 'H-NMR^DC^ « 6 (ppm)); 0.68 (36H > m > 1.35(12H > m) ^ 1.57(8H,m), 3.60(4H,q) Elemental analysis: C28H6()04Zr Measured value C: 60.7%, H·· 11.3%, Zr: 16.5% Theoretical value C: 60.9%, H: 11.0%, Zr: 16.5% Examples 4 to 6 and Comparative Examples 1 to 5 (comparison of thermal stability! The compound of the present invention of the formulas (2) to (4) obtained in Examples 1 to 3 and the zirconium compound of the formula (11) to (15) synthesized as a comparison of 201139720, in order to confirm the respective thermal stability, Each of the compounds which were once steamed was re-distilled to confirm the recovery rate. The results are shown in Table 1. The structure of the compound is represented by the following formula. However, the Μ in the formula represents 鍅(Zr). [Chemical 3]

(12) (2) (3) (4) (11)(12) (2) (3) (4) (11)

(15) [表1](15) [Table 1]

化合物 初次蒸顧條件 再蒸餾回 收率 熔點 實施例4 2 140〇C/17Pa 回收99% .40°C 實施例5 4 150〇C/12Pa 回收98% 液體/室溫 比較例1 11 180〇C/15Pa 無法回收 180°C 實施例6 3 150〇C/12Pa 回收97% 液體/室溫 比較例2 13 200〇C/12Pa 無法回收 180°C 比較例3 12 180°C、190°C、 250〇C/15Pa 於各個溫度流出 無法回收 黏性液體〜 固體 比較例4 14 250〇C/30Pa 無法回收 200°C 比較例5 15 180〇C/9Pa 無法回收 180°C π 201139720 相對於式(11)〜(15)的錯化合物(比較例於 而無法回t本發_絲魏合嫩(2)〜(4齡化 ^留回收率為97〜99%，而可得知其熱穩定性佳。再者，本發p 氧鍅化合物’ T、論其分子量，均可錄溫度且低減壓度、，兀 因此’可得知其適於含鍅薄膜之製造。 ’、、、制 實施例7及比較例6(熱穩定性之比較2 ;加熱處理測 對於實施例1所得到的式(4)之錯化合物與肆(第三丁氧 專利文獻3的烷氧鍅化合物)進行熱穩定性之比較測試。° 境下將各自的化合物以25(TC加熱1〇小時後，對於熱處理之^ 氧錯化合物，雜kNMR峨察分解狀況，再者，進行 二 確認其回收率，比較各自的結果。結果示於表2。 …、 [表2] 化合物 熱處理前 實施 例7 比較 例6 4Compound initial steaming condition Re-distillation recovery Melting point Example 4 2 140 〇C/17Pa Recovery 99%. 40 °C Example 5 4 150 〇C/12Pa Recovery 98% Liquid/room temperature Comparative Example 1 11 180 〇C/ 15Pa Unrecoverable 180°C Example 6 3 150〇C/12Pa Recovery 97% Liquid/Room Comparative Example 2 13 200〇C/12Pa Unable to recover 180°C Comparative Example 3 12 180°C, 190°C, 250〇 C/15Pa can not recover viscous liquid at each temperature~ Solid Comparative Example 4 14 250〇C/30Pa Unrecoverable 200°C Comparative Example 5 15 180〇C/9Pa Unable to recover 180°C π 201139720 Relative to formula (11) ~ (15) of the wrong compound (comparative example can not be returned to the hair of the hair _ silk Wei Henen (2) ~ (4 years of aging retention retention rate of 97 to 99%, and it can be known that its thermal stability is good. Furthermore, the present p-oxoquinone compound 'T, the molecular weight thereof, can be recorded at a temperature and a low degree of decompression, so that it can be known to be suitable for the production of a ruthenium-containing film. ',,, and Example 7 And Comparative Example 6 (Comparison of thermal stability 2; heat treatment to measure the compound of the formula (4) obtained in Example 1 and hydrazine (the alkoxylation of the third butanol patent document 3) (Comparative test of thermal stability). After the respective compounds were heated at 25 °C for 1 hour, the decomposition of the compound was investigated for the heat-treated compound, and the k-NMR was observed. The results were compared and the results are shown in Table 2. [Table 2] Example 7 before compound heat treatment Comparative Example 6 4

Zr(OtBu)4 透明液體 透明液體 熱處理後 透明液體 褐色液體 褐色固體 再蒸顧 回收率 回收98% 回收87% 熱處理前後 Ιί-NMR比車交 _ I 無變化 產生雜質 ^本發明之烷氧锆化合物(式(4)之鍅化合物)，熱處理後顏色亦無 4化，且H-NMR的光譜圖案亦無看到變化。再者，再蒗 回 收率亦達98%。 另一方面，肆(第三丁氧)鍅，熱處理後立即變色為褐色，再基 館的回收率亦低’而且，容器中殘留有蒸傭殘逢之褐色固體(分^ 物）。 根據前述而可得知本發明的烷氧鍅化合物對於熱具有高穩定 性。 “ 通常’ALD法中，重複對於基板的化合物吸附、與反應氣體(例 如，氧氣、臭氧)的反應而進行成膜。化合物對於該基板吸附時， 需要化合物於基板溫度下不會熱分解。本發明之烷氧鍅化合物(式 201139720 體展兄)下的；疋I"生冋故於基板上不會顯現熱分解，而可得4 採用ALD法非常適合。另-方面，由於觀察到辦第三丁 專利文獻3之烷氧锆化合物)於加熱處理測試中之變質、八 故於基板上易顯現熱分解，而可得知ALD法不合適、。^ ， 實施例8〜9(蒸鍍實驗；含锆薄膜之製造） 的絲Μ合物，根據 LVD法進订蒸鑛貫驗，並評鑑成膜特性。 評鑑測試巾.，係使關1所示的設備。在氣化 ，)中，院曰氧錄化，物20，係以加熱器·力口熱而氣化，並伴^ 出1QA所預熱後而導人的氦氣流 出乳化β 3。流出耽化益3的氣體’係與經由質量流量控制器m、 争止閥2而導人的氧氣同時導人反應器4。反應系内 空栗正面的閥6之開關而控既定壓力，並藉由壓 ，應器的中央部為可以加熱H 1GC加熱的結構。導人反應器；^ ^錯化合物，係設置於反應器内中央部，於加熱器iQc加^ ^溫度之被蒸錄板21的絲上氧倾讀，胁基板21上^ 出含鍅薄膜。流出反應器4的氣體，係經由分離哭7、直 為排氣至大氣中的結構。 班真工泵而成 传用Ϊ 3表^麵條敍紐結果⑽雜）。再者，被蒸鍍基板係 使用6mmx20mm尺寸的矩形物。 ---- -1 Zr成膜條件 —_____^特性 Zr化合物；（3) Zr化合物氣化溫度；7〇。〇 實施例8 He載體流量；i〇mi/min 膜厚；150nm 氧氣流量；50ml/min 基板材料；Si02/Si xps分析；氧化鍅 ---1 .基板溫廑；320°C ------ 13 201139720 反應系内壓力；3990Pa 蒸鍍時間；30分鐘 實施例9 Zr化合物；（4) Zr化合物氣化溫度；70°C He載體流量；lOml/min 氧氣流量；50ml/min 基板材料；Si02/Si 基板溫度；320°C 反應系内壓力；3990Pa 蒸鍍時間；30分鐘 膜厚；lOOnm XPS分析；氧化锆 結果可得知本發明之烷氧鍅化合物(式⑶及(4)的化合物），於 氧氣環境下係顯現優異的成膜特性。 實施例10(M=Hf，R=異丙基；肆(2,4-二曱基-3-戊氧)給之合成 (式(4)的铪化合物之合成)） 在氬氣環境下，具備攪拌設備及溫度計之内容積100ml的燒 瓶中加入肆(異丙氧）鈴·異丙醇加成物5.15g(l〇.84mmol)以及 2,4-二曱基戊醇10.00g(86 06mm〇1)，令液溫升溫至17〇。〇為止， 將生成的異丙醇蒸餾去除，並於同溫度下反應30分鐘。反應結束 士’在減壓下將反應液濃縮，接著減壓細(携。c，17Pa)濃縮物， Ϊ 的透明液體之肆(2,4_二甲基冬戊氧)給4.94g(分離生產 合物再者’肆(2,4_二甲基各戊氧)給為以下物性值所示之新穎的化 ^ ^-NMRCCDC^ > 5(ppm)) ； 〇.9〇(48H ^ d) > 1.7〇(8H, m) ^ 3.39(4H ^ 元素分析：C28H60O4Hf 測定值 C : 53.0%、H : 9.7%、Hf : 27 7% f 論值 C : 52.6%、H : 9.5%、Hf : 27.9% 實施例11(熱穩定性；加熱處理測試） 201139720 為了確認實施例10所得之式(4)的铪化合物(本發明) 性而進行再蒸餾，並確認其回收率。而且，在氬氣環境下以、 加熱10小時後，對於熱處理後之铪化合物，根據1h_n_ 分解狀況，再者，進行再蒸餾，並確認其回收率。 下所述。 不Ί尔如以 初次蒸餾；150〇C(17Pa) 再蒸餾回收率；99% 熱處理前；無色透明液體 熱處理後；無色透明液體 熱處理後的再蒸餾回收率；97% 熱處理後的1H-NMR(CDC13，δ(ρρηι));無變化 根據上述結果可知：本發明的金屬烷氧化合物具有優異的熱 穩定性’而且尤以藉由CVD法或是ALD法而製造含金屬:薄膜日寺 為有用的化合物。 、 實施例12(M=Ti，R=異丙基；肆(2,4_二曱基戊氧) (式(4)的鈦化合物之合成)） W σ成 ,在氬氣環境下，具備攪拌設備及溫度計之内容積i〇〇ml的燒 巧中’加入肆(異丙氧）鈦⑼㈣卩分腿吣以及2,4_二甲基 醇10.00g(86.06mmol)，令液溫升溫至170〇c為止，將生成^異丙 醇蒸餾去除，並於同溫度下反應3〇分鐘。反應結束後，在減壓下 將反應液濃縮，接著減壓蒸餾(16〇它，2ipa)濃縮物，得到無色透 明固體之肆(2,4-二甲基-3-戊氧)鈦6.50g(分離生產率；72.6%)。 再者，肆(2,4-二甲基-3-戊氧)鈦為以下物性值所示之新穎 合物。 、Zr(OtBu)4 transparent liquid transparent liquid heat-treated transparent liquid brown liquid brown solid re-steam recovery recovery 98% recovery 87% before and after heat treatment Ιί-NMR ratio car _ I no change produces impurities ^ alkoxy zirconium compound of the invention (The compound of the formula (4)), the color after heat treatment was also not changed, and the spectral pattern of H-NMR did not change. In addition, the yield was 98%. On the other hand, ruthenium (t-butoxide) ruthenium was discolored to brown immediately after heat treatment, and the recovery rate of the base was also low. Moreover, a brown solid (a fraction) of steaming residue remained in the container. From the foregoing, it can be understood that the alkoxyfluorene compound of the present invention has high stability to heat. "In the general ALD method, the compound is adsorbed on the substrate and reacted with a reaction gas (for example, oxygen or ozone) to form a film. When the compound is adsorbed on the substrate, the compound is not thermally decomposed at the substrate temperature. The invention is based on the alkoxy oxime compound (formula 201139720); 疋I" 冋 冋 于 于 于 于 于 基板 热 基板 基板 基板 基板 基板 基板 基板 基板 基板 基板 基板 基板 基板 基板 基板 基板 基板 基板 基板 基板 基板 基板 基板 基板 基板 基板 基板 基板 基板 基板 基板 基板The alkoxy zirconium compound of Japanese Patent No. 3) is deteriorated in the heat treatment test, and it is easy to exhibit thermal decomposition on the substrate, and it is known that the ALD method is not suitable, and Examples 8 to 9 (evaporation test) ; Μ 含 含 的 的 含 含 含 含 含 含 含 含 含 含 含 含 含 含 含 含 含 含 含 含 含 含 含 含 含 含 含 含 含 含 含 含 含 含 含 含 含 含 含 含 含 含 含In the middle, the hospital occupies the oxygen, and the object 20 is gasified by the heater and the heat of the mouth, and is accompanied by the enthalpy of the enthalpy of the enthalpy of the gas after the preheating of 1QA. 'The system is guided by the oxygen guided by the mass flow controller m and the valve 2 Reactor 4. The switch of the valve 6 on the front side of the empty chestnut in the reaction system controls the predetermined pressure, and the central part of the reactor is heated to heat the structure of H 1GC. The reactor is introduced; It is disposed in the central portion of the reactor, and the oxygen is poured on the wire of the vapor deposition plate 21 at the temperature of the heater iQc, and the ruthenium-containing film is formed on the substrate 21. The gas flowing out of the reactor 4 is crying through the separation. 7. The structure is directly exhausted to the atmosphere. The class of the pump is used to transfer the Ϊ 3 table ^ noodle nucleus results (10) miscellaneous. Moreover, the vapor-deposited substrate is a rectangular object of 6mm x 20mm size. --- - -1 Zr film forming conditions - _____^ characteristics Zr compound; (3) Zr compound gasification temperature; 7 〇. 〇 Example 8 He carrier flow rate; i 〇 mi / min film thickness; 150 nm oxygen flow rate; 50 ml / min substrate Material; SiO 2 /Si xps analysis; yttrium oxide -1 - substrate temperature enthalpy; 320 ° C ------ 13 201139720 reaction system pressure; 3990 Pa evaporation time; 30 minutes Example 9 Zr compound; Zr compound gasification temperature; 70 ° C He carrier flow rate; lOml / min oxygen flow rate; 50 ml / min substrate material; Si02 / Si base Plate temperature; 320 ° C reaction system pressure; 3990 Pa evaporation time; 30 minutes film thickness; 100 nm XPS analysis; zirconia results can be found in the alkoxy oxime compounds of the present invention (compounds of formula (3) and (4)) Excellent film-forming properties are exhibited in an oxygen atmosphere. Example 10 (M = Hf, R = isopropyl; hydrazine (2,4-dimercapto-3-pentyloxy)) (Formula (4) Synthesis of the compound)) In a argon atmosphere, a flask containing 100 ml of a stirring apparatus and a thermometer was charged with 5.10 g of isopropylidene oxide bello-isopropanol adduct (1〇.84 mmol) and 2,4 - 10.00 g of dinonylpentanol (86 06 mm 〇 1), and the temperature of the liquid was raised to 17 Torr. The resulting isopropyl alcohol was distilled off and reacted at the same temperature for 30 minutes. The reaction mixture was concentrated under reduced pressure, followed by a fine (c. The compound of the formula 肆(2,4-dimethylisopentyloxy) was given as the novel chemical property represented by the following physical property values ^ ^-NMRCCDC^ > 5 (ppm); 〇.9〇(48H ^ d) > 1.7〇(8H, m) ^ 3.39 (4H ^ Elemental analysis: C28H60O4Hf measured value C: 53.0%, H: 9.7%, Hf: 27 7% f Theoretical value C: 52.6%, H: 9.5%, Hf: 27.9% Example 11 (thermal stability; heat treatment test) 201139720 In order to confirm the hydrazine compound (present invention) property of the formula (4) obtained in Example 10, re-distillation was carried out, and the recovery rate was confirmed. After heating for 10 hours under an argon atmosphere, the ruthenium compound after the heat treatment was subjected to re-distillation according to the decomposition state of 1 h_n_, and the recovery rate was confirmed. The following is the case. C(17Pa) Re-distillation recovery rate; 99% before heat treatment; after heat treatment of colorless transparent liquid; re-distillation recovery after heat treatment of colorless transparent liquid; 97% 1H-NMR after heat treatment (CDC1 3, δ(ρρηι)); no change According to the above results, it can be seen that the metal alkoxide compound of the present invention has excellent thermal stability 'and in particular, the metal is produced by the CVD method or the ALD method: the film is useful for the temple. Compound 12, Example 12 (M=Ti, R=isopropyl; 肆(2,4-didecylpentyloxy) (synthesis of titanium compound of formula (4))) W σ, in an argon atmosphere Next, with the contents of a stirring device and a thermometer, i〇〇ml, add 肆 (isopropyl isopropoxide) titanium (9) (four) 卩 leg 吣 and 2,4 dimethyl alcohol 10.00g (86.06mmol), make liquid The temperature was raised to 170 ° C, and the resulting isopropanol was distilled off and reacted at the same temperature for 3 minutes. After the reaction was completed, the reaction liquid was concentrated under reduced pressure, followed by distillation under reduced pressure (16 Torr, 2ipa) Concentrate to give 6.50 g of ruthenium (2,4-dimethyl-3-pentyloxy)titanium as a colorless transparent solid (separation productivity; 72.6%). Further, ruthenium (2,4-dimethyl-3-) Pentylene oxide is a novel compound represented by the following physical property values.

熔點：65〜75°C iH-NMRCCDCL，δ(ρριΏ)) ; 〇·93(48Η，m)、1.71(8H， 3.70(4Η，m) ’ 元素分析·· C28H6()〇4Ti 測定值 C : 66.3%、Η : 12.2%、Ti : 9,3% 15 201139720 理論值 C : 66.1%、Η : 11.9%、Ti : 9.4% 實施例13(M=Zr ’ R=異丙基；肆(2,4-二甲基各戊氧)錯之合成 (式(4)的锆化合物之合成)） 在氬氣環境下’具備攪拌設備及溫度計之内容積1〇〇ml的燒 瓶中，秤量四氣化锆4.02g(17.25mmol)以及甲基環己烷5〇〇11，於 水冷卻下滴加異丙胺12ml(140.08mmol)。接著滴加2,4_二甲基_3_ 戊醇12ml(85.61mmol)，使其反應1小時後，過濾反應液，並^農縮 遽液。減壓蒸顧(160°C，13Pa)濃縮物’而得到低黏性的透明液體 之肆(2,4-二曱基各戊氧)錯7.7lg(分離生產率；81.0%)。 實施例14(M=Zr，R=異丙基；肆(2,4-二甲基_3_戊氧)鍅之合成 (式(4)的锆化合物之合成)） 在氬氣環境下’具備撥拌設備及溫度計之内容積5〇ml的燒瓶 中’秤量四氯化錯4.12g(17.68mmol)以及甲基環己烧25m卜於水 冷卻下滴加第二丁胺13ml(128.51mmol)。滴加該溶液於放入2,4_ 二甲基-3-戊醇9.88g(85.03mmol)以及甲基環已烷25m丨之且備攪拌 設備及溫度計之内容積l〇0ml的燒瓶中，並使其反應丨^時。過 濾反應液，並濃縮濾、液。減壓蒸顧(16(TC，15Pa)濃縮物，而得到 低黏性的透明液體之肆(2,4-二甲基-3-戊氧)鍅8 〇5g(分離生產率； 82.5%)。 實施例l5(M=Zr，R=異丙基；肆(2,4_二曱基各戊氧)錯之合 (式(4)的锆化合物之合成)） 在氬氣環境下，具備授拌設備及溫度計之内容積1〇〇ml的燒 瓶中’秤量四氯化錯4.20g(18.02mmol)以及甲苯5〇m卜於水冷卻 下滴加第三丁胺23.5ml(224.91mmol)。接著滴加2,4-二曱基·3_戊醇 12ml(85.61mm〇l)，使其反應！小時後，過濾反應液，並濃縮濾液。 減壓蒸餾(16(TC ’ 10Pa)濃縮物，而得到低黏性的透明液體之^(2,4_ 二甲基-3-戊氧)錯7.69g(分離生產率；77.3%)。 ’ 實施例16(M=Zr，R=異丙基；肆(2,4_二甲基各戊氧)錯之合 (式(4)的锆化合物之合成)） 取Melting point: 65 to 75 ° C iH-NMRCCDCL, δ (ρριΏ); 〇 · 93 (48 Η, m), 1.71 (8H, 3.70 (4 Η, m) ' Elemental analysis · · C28H6() 〇 4Ti Measured value C: 66.3%, Η: 12.2%, Ti: 9,3% 15 201139720 Theoretical value C: 66.1%, Η: 11.9%, Ti: 9.4% Example 13 (M=Zr 'R=isopropyl; 肆(2, Synthesis of 4-dimethylperoxyl) (synthesis of zirconium compound of formula (4))) In an argon atmosphere, a flask equipped with a stirring apparatus and a thermometer, and a volume of 1 〇〇ml, was weighed and gasified. Zirconium 4.02g (17.25mmol) and methylcyclohexane 5〇〇11, 12ml (140.08mmol) of isopropylamine was added dropwise with water cooling, followed by dropwise addition of 2,4-dimethyl-3-butanol 12ml (85.61mmol) After reacting for 1 hour, the reaction solution was filtered, and the condensate was liquefied, and the concentrate was distilled under reduced pressure (160 ° C, 13 Pa) to obtain a low-viscosity transparent liquid 2 (2, 4- Indole pentyloxy) 7.7 lg (separation productivity; 81.0%). Example 14 (M = Zr, R = isopropyl; hydrazine (2,4-dimethyl-3- pentyloxy) hydrazine ( Synthesis of zirconium compound of formula (4))) In an argon atmosphere, 'with a mixing device and a thermometer containing 5 〇ml of the flask' An amount of 4.12 g (17.68 mmol) of tetrachlorinated tetrachloride and 25 ml of methylcyclohexane was added dropwise 13 ml (128.51 mmol) of second butylamine under water cooling. The solution was added dropwise to 2,4-dimethyl-3- - 9.80 g (85.03 mmol) of pentanol and 25 m of methylcyclohexane, and the contents of a stirring apparatus and a thermometer are placed in a 0 ml flask, and the reaction mixture is filtered. The reaction solution is filtered and concentrated. The liquid was evaporated under reduced pressure (16 (TC, 15 Pa) concentrate to obtain a low viscosity transparent liquid bismuth (2,4-dimethyl-3-pentyloxy) 鍅 8 〇 5 g (separation productivity; 82.5%) Example l5 (M=Zr, R=isopropyl; 肆(2,4-difluorenylpentyloxy)) (combination of zirconium compound of formula (4))) Under argon atmosphere, In a flask equipped with a mixing device and a thermometer, the volume of the mixture was adjusted to 4.20 g (18.02 mmol) and toluene 5 〇m, and the third butylamine (23.5 ml (224.91 mmol) was added dropwise with water cooling. Then, 12 ml (85.61 mm 〇l) of 2,4-dimercapto-3-pentanol was added dropwise and allowed to react. After the hour, the reaction liquid was filtered, and the filtrate was concentrated. And get a low viscosity transparent liquid ^(2,4_ dimethyl-3-pentyl) ) Wrong 7.69g (separated productivity; 77.3%). Example 16 (M=Zr, R=isopropyl; 肆(2,4-dimethylisopentyloxy)) (combination of zirconium compound of formula (4))

S 16 201139720 在氬氣環境下’具備攪拌設備及溫度計之内容積l〇〇ml的燒 瓶中’秤量四氣化銼4.20g(18 02mm〇1)以及甲苯5〇m卜於水冷卻 下滴加二乙胺16 5ml(157 92mm〇1)。接著滴加2,4_二甲基·>戊醇 12mip5’61mmd)，使其反應1小時後’過滤反應液，並濃縮濾液。 減壓蒸餾(160°c，lipa)濃縮物，而得到低黏性的淡黃色透明液體 之肆(2,4_二甲基冬戊氧)結7J6g(分離生產率；76 7%)。 、實施例17(M=Zr，R=異丙基；肆(2,4_二曱基_3_戊氧)鍅之合成 (式(4)的鍅化合物之合成)） 在氬氣環境下，具備授拌設備及溫度計之内容積l〇〇ml的燒 瓶中:秤量四氯化錯4.20g(18 02mmol)以及曱苯50此，俾使系= 成-10°c以下’且滴加二乙胺16 0ml(153 13mm〇1)。接著滴加2,4_ 二曱基-3-戊醇i2ml(85.61mm〇l)，使其反應丨小時後，過濾反^ 液，並濃縮濾液。減a蒸餾(i6(tc，11Pa)濃縮物，而得到低黏;^ 的透，液體之肆(2,4_二甲基各戊氧)鍅7 92§(分離生產率；79·。 列18(M=Zr，R=異丙基；肆(2,4_二甲基各戊氧)鍅之合成 (式(4)的錯化合物之合成)） 在氬氣環境下，具備攪拌設備及溫度計之内容積l〇0ml的笋 瓶中:秤量四氯化錯4_20g(18.02mm〇l)以及曱苯5_，俾使系= 成-i〇c以下，且滴加二甲胺1161g(257.54mm〇1)。接著滴加2、4 ί甲f12ml(85.61mm〇1)，使其反應1小時後，過滤反應 液並浪縮濾液。減壓蒸餾(16(rc，llpa)濃縮物，而得 的透，液體之肆(2,4_二甲基各戊氧〕錯頂以分離生產率;％ : 貫施例19(M=Hf，R=異丙基；肆(2 4_二甲基_3_戊 (綱的铪化合物之合成)） A氧)铪之合成 由在’具備設備及溫度計之内容積觸ml的燒 升泣，四氯化姶5.〇3g(15.71mm〇1)以及甲苯5〇11^，於水A卻 :滴加第三丁胺l〇ml(95.71mmol)。接著滴加2,4-二甲a:3戍7醇 減小時後，過遽反應液，並^縮遽液。 賴滅(170 C ’ 19.Pa)祕物，而得到低黏性的透明液體之肆似_ 201139720 二甲基各戊氧)銓3.5〇g(分離生產率；34 9%)。 實施例2〇(从，，異丙基；肆(2 4_二〇 (式(4)的鈦化合物之合成)） 土 戍乳)鈦之合成 在氬氣環境下，具備撥拌設備及溫度計之藉 瓶令’量四氯化鈦5·咏(3G施職ί)以及f苯編】， 下滴加第二丁胺16ml(153.13mm〇l)。接著滴加2 4_二甲基^ 液減聖G顧(160 C ’ 17Pa)濃縮物，而得到透明固體之肆(2,4_二 曱基_3·戊氧)鈦Olg(分離生產率；56.2%)。 [產業上利用性] -根據本發明，特別是藉由CVD法或是ALD法，可提供一種 令含金屬薄膜形成時有用的金屬烷氧化合物。又，亦可提供—種 利用該金屬烷氧化合物而製造含金屬薄膜的方法。 【圖式簡單說明】 [圖1 ]實施例中使用的蒸鐵設備之構成示意圖。 【主要元件符號說明】 1 停止閥 1A 質量流量控制器 1B 質量流量控制器 1C 質量流量控制器 2 停止閥 3 氣化器 4 反應器 5 壓力計 6 閥 7 分離器 8 停止閥 201139720 10A 預熱器 10B 氣化器加熱器 IOC 反應器加熱器 20 金屬烷氧化合物 21 基板 19S 16 201139720 In an argon atmosphere, 'with a stirring device and a thermometer, the contents of a volume of l〇〇ml in the flask' weighing four gasification 锉 4.20g (18 02mm 〇 1) and toluene 5 〇 m 卜 drop under water cooling Diethylamine 16 5 ml (157 92 mm 〇 1). Then, 2,4-dimethyl·>pentanol 12mip5'61mmd) was added dropwise, and after reacting for 1 hour, the reaction liquid was filtered, and the filtrate was concentrated. The concentrate was distilled under reduced pressure (160 ° C, lipa) to give a low-viscosity pale yellow transparent liquid of ruthenium (2,4-dimethyl winter pentoxide) 7 J 6 g (separation productivity; 76 7%). Example 17 (M=Zr, R=isopropyl; synthesis of ruthenium (2,4-didecyl_3_pentyloxy) oxime (synthesis of ruthenium compound of formula (4))) under argon atmosphere In the flask with the contents of the mixing equipment and the thermometer, weighed 4.20g (18 02mmol) and the benzene 50, and the 系 系 = = -10 °c below and add two Ethylamine 16 0 ml (153 13 mm 〇 1). Then, 2,4-dimercapto-3-pentanol i2 ml (85.61 mm 〇l) was added dropwise, and after reacting for a few hours, the reaction solution was filtered, and the filtrate was concentrated. Subtract a distillation (i6 (tc, 11Pa) concentrate to obtain a low viscosity; ^ permeable, liquid bismuth (2,4 dimethyl pentyloxy) 鍅 7 92§ (separation productivity; 79 · column 18 (M=Zr, R=isopropyl; synthesis of ruthenium (2,4-dimethylisopentyloxy) ruthenium (synthesis of the wrong compound of formula (4))) Under argon atmosphere, equipped with stirring equipment and thermometer The contents of the product l l0ml of bamboo shoots: weighing four chlorinated wrong 4_20g (18.02mm 〇 l) and benzene benzene 5_, 俾 系 = = - i 〇 c below, and adding dimethylamine 1161g (257.54mm 〇 1). Then, 2,4 甲A f12ml (85.61mm〇1) was added dropwise, and after reacting for 1 hour, the reaction solution was filtered and the filtrate was shaken, and the concentrate was distilled under reduced pressure (16 (rc, llpa)). Permeability, liquid enthalpy (2,4-dimethyl pentoxide) is topped to separate productivity; %: Example 19 (M=Hf, R=isopropyl; 肆(2 4_ dimethyl_3) The synthesis of 氧 ( (the synthesis of 铪 铪 ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) 5〇11^, in water A: add tributylamine l〇ml (95.71mmol) dropwise, then add 2,4-dimethyl a:3戍7 alcohol to reduce the time, after The reaction solution, and the sputum sputum. The sputum (170 C ' 19.Pa) secrets, and the low viscosity of the transparent liquid is similar to _ 201139720 dimethyl pentoxide 铨 3.5 〇 g (separation productivity; 34 9%). Example 2 从 (from, isopropyl; 肆 (2 4 〇 〇 (synthesis of titanium compound of formula (4))) 戍 戍) synthesis of titanium in argon atmosphere, Mixing the equipment and the thermometer to make a bottle of 'Titanium Tetrachloride 5·咏 (3G Shi ί) and f Benzene), add the second butylamine 16ml (153.13mm〇l), then add 2 4 _Dimethyl^ liquid minus St. G Gu (160 C '17Pa) concentrate, to obtain a transparent solid ruthenium (2,4-didecyl-3-3 pentyloxy) titanium Olg (separation productivity; 56.2%). Industrial Applicability] - According to the present invention, in particular, a metal alkoxide which is useful for forming a metal-containing film can be provided by a CVD method or an ALD method. Further, it is also possible to provide a metal alkoxide compound. A method for producing a metal-containing film. [Simplified description of the drawings] [Fig. 1] Schematic diagram of the structure of the iron-ironing device used in the embodiment. [Explanation of main component symbols] 1 Stop valve 1A mass flow control 1B Mass flow controller 1C Mass flow controller 2 Stop valve 3 Gasifier 4 Reactor 5 Pressure gauge 6 Valve 7 Separator 8 Stop valve 201139720 10A Preheater 10B Gasifier heater IOC Reactor heater 20 Metal alkane Oxygen compound 21 substrate 19

Claims (1)

201139720 七'申請專利範圍： 1.一種金屬烷氧化合物，以通式(1)表示； [化1]201139720 Seven' patent application scope: 1. A metal alkoxy compound represented by the general formula (1); [Chemical 1] 式中之Μ表示鍅、姶或鈦，4個R可相同亦可相異，各自互 為獨立’並代表碳原子數2〜6的直鏈或分支狀之烷基。 2. —種利用化學氣相沈積法之含金屬薄膜之製造方法，係使用申請 專利範圍第1項之金屬燒氧化合物或申請專利範圍第^項之金^ 烷氧化合物的溶液作為金屬供給源。 申奴糊化學氣概積法之含金屬薄膜之 專利範圍第1項之金狀氧化合物或申請 專利辄圍第1項之金屬燒氧化合物的溶液與氧氣源。 i如專=圍第2項之利用化學氣相沈積法之含金屬薄膜之 lie方去，係使用申請專利範圍第丨項之金 2由 專利1(1圍第1項之金屬燒氧化合物的溶液與氮氣源。σ 2 °月 辦金屬薄膜之 專利範㈣1狀金魏^合偏合物或申請 6.如申請專利範圍第2至5項中任一項 金屬_之製造方法，射該金敎' 目沈積法之含 自於脂肪族烴類、芳香族烴細類所構選 20In the formula, Μ represents ruthenium, osmium or titanium, and four R groups may be the same or different, each independently of each other and represent a linear or branched alkyl group having 2 to 6 carbon atoms. 2. A method for producing a metal-containing film by chemical vapor deposition, using a metal alkoxide compound of the first application of the patent scope or a solution of a gold alkoxide compound of the patent application scope as a metal supply source . The metal oxide film of the Shennu paste chemical gas accumulation method. The gold oxide compound of the patent range No. 1 or the solution and the oxygen source of the metal aerobic compound of the first paragraph of the patent. i, for example, the second part of the chemical vapor deposition method using the metal film of the lie side, the use of the patent scope of the second paragraph of the gold 2 by the patent 1 (1 surrounding the first item of the metal aerobic compound Solution and nitrogen source. σ 2 ° monthly patent film of metal film (4) 1 type gold Wei conjugate or application 6. If the metal of any of the scope of the patent range 2 to 5, the method of shooting敎' The method of sedimentation is based on the selection of aliphatic hydrocarbons and aromatic hydrocarbons.
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