TWI403606B - Raw material, and a method of manufacturing a thin film of film-forming zinc compound - Google Patents

Raw material, and a method of manufacturing a thin film of film-forming zinc compound Download PDF

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TWI403606B
TWI403606B TW96134725A TW96134725A TWI403606B TW I403606 B TWI403606 B TW I403606B TW 96134725 A TW96134725 A TW 96134725A TW 96134725 A TW96134725 A TW 96134725A TW I403606 B TWI403606 B TW I403606B
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film
raw material
zinc
compound
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TW96134725A
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TW200839027A (en
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Shinichi Tanaka
Atsushi Sakurai
Naoki Yamada
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Adeka Corp
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    • 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
    • C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
    • C07F3/06—Zinc 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)
  • Inorganic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
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  • Engineering & Computer Science (AREA)
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  • Metallurgy (AREA)
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Abstract

A raw material for forming a thin film, comprising a zinc compound represented by the general formula (1). (1) wherein R<SUP>1</SUP> represents an alkyl group having 1 to 4 carbon atoms; R<SUP>2</SUP> and R<SUP>3</SUP> independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; R<SUP>4</SUP> represents an alkyl group having 1 to 4 carbon atoms; R<SUP>5</SUP> represents an alkyl group having 1 to 4 carbon atoms or -CH<SUB>2</SUB>-CH<SUB>2</SUB>-NR<SUP>6</SUP>R<SUP>7</SUP>; R<SUP>6</SUP> and R<SUP>7</SUP> independently represent an alkyl group having 1 to 4 carbon atoms; X represents an oxygen atom or a nitrogen atom; and m represents a number of 0 when X represents an oxygen atom and represents a number of 1 when X represents a nitrogen atom.

Description

薄膜形成用原料、薄膜之製造方法及鋅化合物Raw material for film formation, method for producing film, and zinc compound

本發明係有關一種含有具特定構造之鋅化合物之薄膜形成用原料、使用該原料之薄膜之製造方法、及使用於薄膜形成用原料之新穎鋅化合物。The present invention relates to a raw material for forming a film containing a zinc compound having a specific structure, a method for producing a film using the raw material, and a novel zinc compound used for a raw material for forming a film.

含鋅之薄膜，具有光學特性、電氣特性、觸媒活性等各種特性，已被使用作為電子零件或光學零件之部件。The zinc-containing film has various characteristics such as optical characteristics, electrical characteristics, and catalytic activity, and has been used as a component of an electronic component or an optical component.

作為上述薄膜之製造方法，可例舉火燄堆積法、濺鍍法、離子植入法、塗布熱分解法或溶膠－凝膠等之MOD法、化學氣相生長法等，其中，包含ALD(原子層沉積)之化學氣相生長法(以下有時稱為CVD法)因具有組成控制性、階差被覆性優異、適於量產化、可作混成積體等的許多優點，故為最適宜的製造程序。Examples of the method for producing the film include a flame deposition method, a sputtering method, an ion implantation method, a coating thermal decomposition method, an MOD method such as a sol-gel method, a chemical vapor deposition method, and the like, and include ALD (Atom). The chemical vapor deposition method (hereinafter sometimes referred to as CVD method) of the layer deposition method is excellent in composition controllability, excellent in step coverage, suitable for mass production, and can be used as a mixed product. Manufacturing process.

有關CVD法，作為對薄膜供給鋅原子之前驅體，基於安定性及安全性層面的考量，β－二酮錯體已被廣泛研討。例如，專利文獻1、2，曾揭示一種使用二(戊烷－2,4－二酮)鋅錯合物之CVD，非專利文獻1中，曾報告一種使用二(2,2,6,6－四甲基庚烷－3,5－二酮)鋅錯合物之方法。專利文獻3，曾揭示於25℃下為液體之二(β－二酮)鋅的二(辛烷－2,4－二酮)鋅錯合物、二(2,2－二甲基－6－乙基癸－3,5－二酮)鋅錯合物。Regarding the CVD method, as a precursor for supplying a zinc atom to a film, a β-diketone complex has been extensively studied based on considerations of stability and safety. For example, Patent Documents 1 and 2 disclose a CVD using a bis(pentane-2,4-dione) zinc complex, and in Non-Patent Document 1, a use of two (2, 2, 6, 6) has been reported. A method of -tetramethylheptane-3,5-dione) zinc complex. Patent Document 3 discloses a bis(octane-2,4-dione)zinc complex and a bis(2,2-dimethyl-6) which are liquid bis(β-diketone) zinc at 25 ° C. -ethylguanidin-3,5-dione) zinc complex.

適於用在CVD法之原料的化合物(前驅體)，其被要求的性質是在薄膜堆積時，易於進行由氧化等之化學反應形成薄膜。上述鋅之β－二酮錯體為安定化合物，在CVD製程之供給層面上雖屬優異，但薄膜堆積時之反應性則未必令人滿意。A compound (precursor) suitable for use in a raw material of a CVD method is required to form a film by chemical reaction such as oxidation at the time of film deposition. The above-mentioned zinc β-diketone complex is a stable compound, and although it is excellent in the supply level of the CVD process, the reactivity at the time of film deposition is not necessarily satisfactory.

又，非專利文獻2、3中開示利用CVD法使用烷基鋅烷氧化物製造氧化鋅薄膜；作為其具體之化合物，開示有MeZn(OPri )、EtZn(OPri )、MeZn(OBut )。此等烷基鋅烷氧化物，據記載與二烷基鋅相較，其為安定且易於處理。Further, Non-Patent Documents 2 and 3 disclose that a zinc oxide thin film is produced by an CVD method using an alkyl zinc alkoxide; and as a specific compound thereof, MeZn(OPr i ), EtZn(OPr i ), MeZn(OBu t ) are disclosed. . These alkyl zinc alkoxides are described as being stable and easy to handle compared to dialkyl zinc.

然而，此處所記載之烷基鋅烷氧化物，為熔點高之固體，揮發性也不充分，作為薄膜形成用原料，特別是CVD用原料，未必定令人滿意。However, the alkyl zinc alkoxide described herein is a solid having a high melting point and is not sufficiently volatile, and is not necessarily satisfactory as a raw material for film formation, particularly a raw material for CVD.

另，非專利文獻4中，曾揭示RZnO．C2 H4 ．NMe2 三分子會聚成之(RZnO．C2 H4 ．NMe2 )3 (R＝Me、Et)，及MeZnOCH2 ．CH2 OMe四分子會聚成之(MeZnOCH2 ．CH2 OMe)4 ，但並未揭示將其作為薄膜形成用原料使用。Further, in Non-Patent Document 4, RZnO has been disclosed. C 2 H 4 . NMe 2 tri-molecular convergence (RZnO.C 2 H 4 .NMe 2 ) 3 (R=Me, Et), and MeZnOCH 2 . CH 2 OMe converge to four molecules of (MeZnOCH 2 .CH 2 OMe) 4 , but does not disclose its use as a raw material for film formation.

專利文獻1：日本專利特公平6－64738號公報(特別是請求項9)專利文獻2：日本專利特開2003－236376號公報(特別是實施例)專利文獻3：日本專利特開2005－350423號公報(特別是請求項1~6)Patent Document 1: Japanese Patent Publication No. Hei 6-64738 (particularly, claim 9) Patent Document 2: Japanese Patent Laid-Open Publication No. 2003-236376 (particularly, an example) Patent Document 3: Japanese Patent Laid-Open No. 2005-350423 Bulletin (especially Requests 1~6)

非專利文獻1：Microelectron.Eng.,29(1－4),169－72(1995)非專利文獻2：J.MATER.CHEM.,1994,4(8),1249－1253非專利文獻3：Electrochemical Society Proceedings Volume 2003－08 1123－1130非專利文獻4：J.Chem.Soc.(A),1966,1064－1069Non-Patent Document 1: Microelectron. Eng., 29(1-4), 169-72 (1995) Non-Patent Document 2: J. MATER. CHEM., 1994, 4(8), 1249-1253 Non-Patent Document 3: Electrochemical Society Proceedings Volume 2003-08 1123-1130 Non-Patent Document 4: J. Chem. Soc. (A), 1966, 1064-1069

本發明所欲解決的課題是，對於供給鋅至薄膜之前驅體，賦予適當之反應性及揮發性等之性質，特別是賦予適於CVD法中利用氧化製造薄膜時之反應性及揮發性等之性質。The problem to be solved by the present invention is to impart appropriate reactivity and volatility to a zinc-to-film precursor, and particularly to impart reactivity and volatility when a film is produced by oxidation in a CVD method. Nature.

本發明人等一再研討的結果，發現具有特定構造之鋅化合物可解決上述課題，終而完成本發明。As a result of repeated studies by the present inventors, it has been found that a zinc compound having a specific structure can solve the above problems, and the present invention has been completed.

亦即，本發明藉由提供一種含有下述通式(1)所示之鋅化合物之薄膜形成用原料而解決上述課題： (式中，R1 表示碳數1~4之烷基，R2 及R3 分別獨立地表示氫原子或碳數1~4之烷基，R4 表示碳數1~4之烷基，R5 表示碳數1~4之烷基或－CH2 －CH2 －NR6 R7 ，R6 及R7 表示碳數1~4之烷基，X表氧原子或氮原子，m於X為氧原子時為0，X為氮原子時為1)。In other words, the present invention solves the above problems by providing a raw material for forming a thin film containing a zinc compound represented by the following formula (1): (wherein R 1 represents an alkyl group having 1 to 4 carbon atoms, and R 2 and R 3 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; and R 4 represents an alkyl group having 1 to 4 carbon atoms; 5 represents an alkyl group having 1 to 4 carbon atoms or -CH 2 -CH 2 -NR 6 R 7 , and R 6 and R 7 represent an alkyl group having 1 to 4 carbon atoms, an oxygen atom or a nitrogen atom of X, and m is X. When the oxygen atom is 0, when X is a nitrogen atom, it is 1).

又，本發明另提供一種薄膜之製造方法，其係將含有上述薄膜形成用原料氣化所得之鋅化合物的蒸氣導入基體上，令其分解及/或化學反應而在該基體上形成薄膜。Furthermore, the present invention provides a method for producing a film by introducing a vapor of a zinc compound obtained by vaporizing the raw material for forming a film into a substrate, and decomposing and/or chemically reacting to form a film on the substrate.

此外，本發明又提供一種上述通式(1)中，R2 及R3 之至少任一者為碳數1~4之烷基之新穎鋅化合物。Further, the present invention provides a novel zinc compound of the above formula (1) wherein at least one of R 2 and R 3 is an alkyl group having 1 to 4 carbon atoms.

根據本發明，係提供一種具有適當反應性及揮發性等之性質的薄膜形成用原料作為CVD用原料。According to the present invention, a raw material for forming a film having properties such as appropriate reactivity and volatility is provided as a raw material for CVD.

又，本發明之薄膜形成用原料中所含之鋅化合物，隨著其構造其熔點或揮發性有所不同，故選擇適用於薄膜形成製程之薄膜形成用原料即可。Further, the zinc compound contained in the raw material for forming a film of the present invention may have a different melting point or volatility depending on the structure thereof, and therefore a material for forming a film suitable for the film formation process may be selected.

本發明之薄膜形成用原料中所用之上述通式(1)所示之鋅化合物，作為薄膜之前驅體具有適當之反應性，特別適於利用氧化形成薄膜。The zinc compound represented by the above formula (1) used in the raw material for forming a film of the present invention has appropriate reactivity as a film precursor, and is particularly suitable for forming a film by oxidation.

又，該化合物中，R2 及R3 之至少任一者為碳數1~4之烷基之化合物為新穎化合物。另，本發明有關之上述通式(1)所示之鋅化合物，有時具有立體異構性，有時X或NR6 R7 分子內配位形成環構造，且有分子彼此間會聚形成會聚體之情況。Further, in the compound, a compound in which at least one of R 2 and R 3 is an alkyl group having 1 to 4 carbon atoms is a novel compound. Further, the zinc compound represented by the above formula (1) according to the present invention sometimes has stereoisomerism, and sometimes X or NR 6 R 7 intramolecularly coordinates to form a ring structure, and molecules converge to form a convergence. The situation of the body.

例如，作為本發明有關之上述通式(1)所示之鋅化合物之會聚狀態，例如2分子會聚之例可舉例如下述通式(1－1)或(1－2)所示之構造，3分子會聚之例可舉例如下述通式(1－3)所示之構造。For example, as a polymerization state of the zinc compound represented by the above formula (1) according to the present invention, for example, a structure in which two molecules are concentrated may be, for example, a structure represented by the following formula (1-1) or (1-2). For example, the structure of the three molecules can be condensed, for example, the structure represented by the following formula (1-3).

(式中，R1 ~R5 、X及m係與上述通式(1)中所示者相同)。 (wherein R 1 to R 5 , X and m are the same as those shown in the above formula (1)).

本發明之鋅化合物，並不因此等異構物、配位體、會聚體而有所區別，可包含任一種形式。以下，茲以無分子內配位、會聚之形態代表加以例示。The zinc compound of the present invention is not distinguished by such an isomer, a ligand or a convergent, and may be contained in any form. Hereinafter, it is exemplified by a form of no intramolecular coordination or convergence.

上述通式(1)中，作為R1 ~R7 所示之碳數1~4之烷基，其可舉實例為甲基、乙基、丙基、異丙基、丁基、第二丁基、第三丁基、異丁基。In the above formula (1), the alkyl group having 1 to 4 carbon atoms represented by R 1 to R 7 may, for example, be a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group or a second group. Base, tert-butyl, isobutyl.

作為本發明之通式(1)所示之鋅化合物的具體例，可舉例如以下所示之化合物No.1~No.36。Specific examples of the zinc compound represented by the formula (1) of the present invention include the following compounds No. 1 to No. 36.

此等化合物中，上述通式(1)中，R2 及R3 之至少一者為碳數1~4之烷基之鋅化合物(上述具體例中，化合物No.7~No.15、No.22~No.30、No.32、No.33、No.35及No.36)為本發明之新穎鋅化合物。此等新穎之鋅化合物中，較佳的是，上述通式(1)中，X為氮原子、R4 為甲基或乙基、R5 為甲基或－CH2 －CH2 －NR6 R7 、R6 及R7 為甲基或乙基之鋅化合物(上述具體例中的化合物No.22~No.26、No.28~No.30、No.32、No.33、No.35及No.36)。In the above-mentioned compound, at least one of R 2 and R 3 in the above formula (1) is a zinc compound having an alkyl group having 1 to 4 carbon atoms (in the above specific example, the compound No. 7 to No. 15 and No. .22~No.30, No.32, No.33, No.35 and No.36) are novel zinc compounds of the present invention. Among these novel zinc compounds, it is preferred that, in the above formula (1), X is a nitrogen atom, R 4 is a methyl group or an ethyl group, R 5 is a methyl group or -CH 2 -CH 2 -NR 6 R 7 , R 6 and R 7 are a zinc compound of a methyl group or an ethyl group (Compound Nos. 22 to No. 26, No. 28 to No. 30, No. 32, No. 33, No. in the above specific examples). 35 and No. 36).

又，上述通式(1)所示之鋅化合物，隨著其構造其熔點或揮發性有所不同，故在作為薄膜形成用原料使用時，選擇具有適用於薄膜形成製程之熔點或揮發性的構造的鋅化合物使用即可。Further, since the zinc compound represented by the above formula (1) has a different melting point or volatility depending on its structure, when it is used as a raw material for film formation, it is selected to have a melting point or a volatility suitable for the film formation process. The zinc compound of the structure can be used.

上述通式(1)所示之鋅化合物，其程度上雖有差異，但均為具有可使用於所有CVD製程之揮發性的化合物。作為CVD用原料，較佳的是易揮發者、雖為固體但熔點低者(120℃以下)或室溫下為液體者。又，上述鋅化合物為易揮發者、雖為固體但熔點低者(120℃以下)或室溫下為液體者、或是對於有機溶劑溶解性大者，亦為較佳之MOD用原料。The zinc compounds represented by the above formula (1) are all different in degree, but all have compounds which can be used for the volatility of all CVD processes. As a raw material for CVD, those which are volatile, solid, but low in melting point (120 ° C or lower) or liquid at room temperature are preferred. Further, the zinc compound is a volatile material, and although it is solid, but has a low melting point (120 ° C or lower) or a liquid at room temperature, or a large solubility in an organic solvent, it is also a preferred raw material for MOD.

上述通式(1)所示之鋅化合物中，R2 及R3 為氫原子、X為氧原子、R4 為甲基者(上述具體例中之化合物No.1~No.6)，具有雖為固體但熔點低或室溫下為液體之特徵。例如，化合物No.1及No.2具有室溫下為液體之特徵。In the zinc compound represented by the above formula (1), R 2 and R 3 are a hydrogen atom, X is an oxygen atom, and R 4 is a methyl group (compound No. 1 to No. 6 in the above specific examples). It is solid but has a low melting point or a liquid at room temperature. For example, Compound No. 1 and No. 2 are characterized by being liquid at room temperature.

又，上式(1)所示之鋅化合物中，R2 及R3 之至少一者為碳數1~4之烷基者(上述具體例中，為化合物No.7~No.15、No.22~No.30、No.32、No.33、No.35及No.36)，與兩者均為氫原子者相較，具有易揮發之特徵。Further, in the zinc compound represented by the above formula (1), at least one of R 2 and R 3 is an alkyl group having 1 to 4 carbon atoms (in the above specific examples, the compound No. 7 to No. 15 and No. .22 to No. 30, No. 32, No. 33, No. 35, and No. 36) are characterized by being relatively volatile as compared with those in which both are hydrogen atoms.

又，上述通式(1)所示之鋅化合物中，X為氮原子者(上述具體例中，為化合物No.16~No.36)，與X為氧原子者相較，具有易揮發之特徵。Further, among the zinc compounds represented by the above formula (1), X is a nitrogen atom (in the above specific examples, it is a compound No. 16 to No. 36), and is more volatile than X which is an oxygen atom. feature.

又，上述通式(1)所示之鋅化合物中，X為氮原子、R5 為－CH2 －CH2 －NR6 R7 者(上述具體例中，為化合物No.31~No.36)，具有熔點特別低(100℃以下)之特徵。Further, in the zinc compound represented by the above formula (1), X is a nitrogen atom and R 5 is -CH 2 -CH 2 -NR 6 R 7 (in the above specific examples, the compound No. 31 to No. 36) It has a characteristic that the melting point is particularly low (below 100 ° C).

又，上述通式(1)所示之鋅化合物中，R1 為甲基或乙基者(上述具體例中，為化合物No.1、No.2、No.7~No.17、No.22~No.36)，具有易揮發之特徵。Further, in the zinc compound represented by the above formula (1), R 1 is a methyl group or an ethyl group (in the above specific examples, the compound No. 1, No. 2, No. 7 to No. 17, No. 22~No.36), with volatile characteristics.

本發明之上述通式(1)所示之鋅化合物，其製造方法並無特別限制，可應用習知之反應進行製造。作為其製造方法，可舉例如使(R1 )2 Zn所示之二烷基鋅與HO－CR2 R3 CH2 XR4 (R5 )m 所示之醇反應之方法。The method for producing the zinc compound represented by the above formula (1) of the present invention is not particularly limited, and it can be produced by a conventional reaction. As a method for producing the same, for example, a method of reacting a dialkylzinc represented by (R 1 ) 2 Zn with an alcohol represented by HO-CR 2 R 3 CH 2 XR 4 (R 5 ) m can be mentioned.

本發明之薄膜形成用原料，係指將上述通式(1)所示之鋅化合物作為薄膜之前驅體者，其形態可依據應用該薄膜形成用原料之薄膜的製造方法(例如，塗佈熱分解法或溶膠一凝膠等之MOD法、包含ALD法之CVD法)適當地選擇。本發明之薄膜形成用原料，基於其物性之故，作為具有令鋅化合物氣化之製程的CVD原料特別有用。The raw material for forming a film of the present invention refers to a zinc compound represented by the above formula (1) as a film precursor, and the form thereof can be determined according to a method for producing a film using the film forming material (for example, coating heat). The decomposition method, the MOD method such as a sol-gel, and the CVD method including the ALD method are appropriately selected. The raw material for film formation of the present invention is particularly useful as a CVD raw material having a process for vaporizing a zinc compound based on its physical properties.

本發明之薄膜形成用原料為化學氣相生長(CVD)用原料時，其形態可依使用之CVD法之輸送供給方法等的方法而適當選擇。When the raw material for film formation of the present invention is a raw material for chemical vapor deposition (CVD), the form thereof can be appropriately selected according to a method such as a transport supply method using a CVD method.

作為上述輸送供給方法，包含氣體輸送法及液體輸送法。氣體輸送法係藉由將CVD用原料在原料容器中加熱及/或減壓予以氣化，並因應必要與所用之氬、氮、氦等之載體氣體一起導入堆積反應部；液體輸送法係將CVD用原料以液體或溶液的狀態輸送至氣化室，於該氣化室進行加熱及/或減壓予以氣化，再導入堆積反應部。氣體輸送法時，上述通式(1)所示之鋅化合物係就此成為CVD用原料，於液體輸送法時，上述通式(1)所示之鋅化合物係就此或將該鋅化合物溶於有機溶劑而成之溶液成為CVD用原料。The above-described transport and supply method includes a gas transport method and a liquid transport method. The gas transport method is vaporized by heating and/or depressurizing the raw material for CVD in a raw material container, and is introduced into the deposition reaction portion together with the carrier gas such as argon, nitrogen or helium to be used; the liquid transport method will The raw material for CVD is sent to the vaporization chamber in the form of a liquid or a solution, and is heated and/or decompressed in the vaporization chamber to be vaporized, and then introduced into the deposition reaction portion. In the gas transport method, the zinc compound represented by the above formula (1) is used as a raw material for CVD, and in the liquid transport method, the zinc compound represented by the above formula (1) is dissolved or dissolved in the organic compound. The solvent-formed solution becomes a raw material for CVD.

又，製造多成分系薄膜時之多成分系CVD法中，有將CVD用原料各成分獨立地氣化供給之方法(以下稱為單一源法)，以及將多成分原料以預先期望之組成混合成之混合原料氣化供給之方法(以下稱為混合源法)。混合源法之情形下，上述通式(1)所示之金屬化合物單獨所構成之混合物、或在此等混合物中添加有機溶劑而成之混合溶液、上述通式(1)所示之金屬化合物與其它前驅體之混合物、或此等混合物中添加有機溶劑而成之混合溶液可作為CVD用原料。Further, in the multi-component CVD method for producing a multi-component thin film, there is a method of separately vaporizing and supplying each component of the CVD raw material (hereinafter referred to as a single source method), and mixing the multi-component raw material with a desired composition. A method of gasification supply of a mixed raw material (hereinafter referred to as a mixed source method). In the case of the mixed source method, a mixture of the metal compounds represented by the above formula (1), a mixed solution obtained by adding an organic solvent to the mixture, and a metal compound represented by the above formula (1) A mixed solution of a mixture with other precursors or an organic solvent added to the mixture can be used as a raw material for CVD.

上述CVD用原料中所使用之有機溶劑並無特殊限制，可使用習知一般之有機溶劑。作為該有機溶劑，例如可舉例如乙酸乙酯、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、嗎啉、乙二醇二甲醚、二甘醇二甲醚、三乙二醇二甲醚、二丁醚、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、1,4－二氰基苯等之具有氰基之烴類；吡啶、二甲基吡啶。其等基於溶質之溶解性、使用溫度與沸點、引火點之關係等，係以單獨或兩種以上之混合溶劑使用。使用此等有機溶劑時，該有機溶劑中之前驅體成分的合計量宜為0.01~2.0莫耳/升，特別好的是0.05~1.0莫耳/升。The organic solvent used in the raw material for CVD is not particularly limited, and a conventional organic solvent can be used. Examples of the organic solvent include acetates such as ethyl acetate, butyl acetate, and methoxyethyl acetate; tetrahydrofuran, tetrahydropyran, morpholine, ethylene glycol dimethyl ether, and diethylene glycol II. An ether such as methyl ether, triethylene glycol dimethyl ether, dibutyl ether or dioxane; methyl butyl ketone, methyl isobutyl ketone, ethyl butyl ketone, dipropyl ketone, diisobutyl butyl Ketones such as ketone, methyl amyl ketone, cyclohexanone, methylcyclohexanone; hexane, cyclohexane, methylcyclohexane, dimethylcyclohexane, ethylcyclohexane, g Hydrocarbons such as alkane, octane, toluene, xylene, etc.; 1-cyanopropane, 1-cyanobutane, 1-cyanohexane, cyanocyclohexane, cyanobenzene, 1,3-dicyandi Hydrocarbon having a cyano group such as propane, 1,4-dicyanobutane, 1,6-dicyanohexane, 1,4-dicyanocyclohexane or 1,4-dicyanobenzene ; pyridine, lutidine. These are used alone or in combination of two or more kinds based on the solubility of the solute, the relationship between the use temperature and the boiling point, and the ignition point. When such an organic solvent is used, the total amount of the precursor components in the organic solvent is preferably from 0.01 to 2.0 mol/liter, particularly preferably from 0.05 to 1.0 mol/liter.

又，使用單一源法或混合源法之多成分系CVD法中，與本發明之上述通式(1)所示鋅化合物一起使用之其他前驅體並無特殊限制，可使用CVD原料中所用之習知一般前驅體。Further, in the multi-component CVD method using a single source method or a mixed source method, the other precursor used together with the zinc compound represented by the above formula (1) of the present invention is not particularly limited, and a CVD material can be used. Conventional general precursors.

作為上述其他前驅體，可舉例選自使用由醇化合物、二醇化合物、β－二酮化合物、環戊二烯化合物、有機胺化合物等之作為有機配位基團使用之化合物所組成組群之一種或兩種以上，與矽、硼、磷及金屬之化合物。作為金屬物種，可舉例如鋰、鈉、鉀、銣、銫等之1族元素，鈹、鎂、鈣、鍶、鋇等之2族元素，鈧、釔、鑭系元素(鑭、鈰、鐠、釹、鉕、釤、銪、釓、鋱、鏑、鈥、鉺、銩、鐿、鎦)、放射性元素等之3族元素，鈦、鋯、鉿之4族元素，釩、鈮、鉭之5族元素，鉻、鉬、鎢之6族元素，錳、鎝、錸之7族元素、鐵、釕、鋨之8族元素，鈷、銠、銥之9族元素，鎳、鈀，鉑之10族元素，銅、銀、金之11族元素，鎘、汞之12族元素，鋁、鎵、銦、鉈之13族元素，鍺、錫、鉛之14族元素，砷、銻、鉍之15族元素，針之16族元素。As the other precursor, it is exemplified by a group consisting of a compound which is used as an organic coordinating group such as an alcohol compound, a diol compound, a β-diketone compound, a cyclopentadiene compound, an organic amine compound or the like. One or two or more compounds with cerium, boron, phosphorus and metals. Examples of the metal species include a group 1 element such as lithium, sodium, potassium, rubidium, and cesium, and a group 2 element such as strontium, magnesium, calcium, strontium, barium, etc., lanthanum, cerium, and lanthanide elements (镧, 铈, 鐠, 钕, 鉕, 钐, 铕, 釓, 鋱, 镝, 鈥, 铒, 銩, 镱, 镏), radioactive elements, etc., group 3 elements of titanium, zirconium, hafnium, vanadium, niobium, tantalum Group 5 elements, 6 elements of chromium, molybdenum and tungsten, group 7 elements of manganese, lanthanum and cerium, group 8 elements of iron, lanthanum and cerium, group 9 elements of cobalt, lanthanum and cerium, nickel, palladium, platinum Group 10 elements, elements of copper, silver and gold, group 12 elements of cadmium and mercury, group 13 elements of aluminum, gallium, indium and antimony, 14 elements of antimony, tin and lead, arsenic, antimony and antimony Group 15 elements, 16 elements of the needle.

上述其他之前驅體，若為單一源法之情形，宜為熱分解及/或氧化分解之舉動類似的化合物，若為混合源法之情形，除了熱分解及/或氧化分解之舉動類似以外，宜為混合時不會引起化學反應導致之變質者。In the case of the single source method, the above-mentioned other precursors are preferably compounds which are similar to thermal decomposition and/or oxidative decomposition. In the case of the mixed source method, in addition to the actions of thermal decomposition and/or oxidative decomposition, It should be a mixture that does not cause chemical reactions when mixing.

又，本發明之CVD用原料中，因應必要，為賦予本發明鋅化合物及其他前驅體之安定性，可含有親核性試劑。作為該親核性試劑，可舉例如乙二醇二甲醚、二甘醇二甲醚、三乙二醇二甲醚、四乙二醇二甲醚等之乙二醇醚類，18－冠醚－6、二環己基－18－冠醚－6、24－冠醚－8、二環己基－24－冠醚－8、二苯并－24－冠醚－8等之冠醚類，乙二胺、N,N'－四甲基乙二胺、二伸乙基三胺、三伸乙基四胺、四伸乙基五胺、五伸乙基六胺、1,1,4,7,7－五甲基二伸乙基三胺、1,1,4,7,10,10－六甲基三伸乙基四胺、三乙氧基三伸乙基胺等之多胺類，四氮雜環十四烷、四氮雜環十二烷等之環狀多胺類，吡啶、吡咯啶、哌啶、嗎啉、N－甲基吡咯啶、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、氧雜硫雜環戊烷等之雜環化合物類，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，或乙醯基丙酮、2,4－己烷二酮、2,4－庚烷二酮、3,5－庚烷二酮、二特戊醯基甲烷等之β－二酮類。此等安定劑之使用量，相對前驅體1莫耳係使用0.1－10莫耳之範圍，宜使用1－4莫耳。Further, the raw material for CVD of the present invention may contain a nucleophilic reagent for imparting stability to the zinc compound of the present invention and other precursors as necessary. Examples of the nucleophilic reagent include glycol ethers such as ethylene glycol dimethyl ether, diglyme, triethylene glycol dimethyl ether, and tetraethylene glycol dimethyl ether, and 18-crown. Crown ethers such as ether-6, dicyclohexyl-18-crown-6, 24-crown-8, dicyclohexyl-24-crown-8, dibenzo-24-crown-8, etc. Diamine, N,N'-tetramethylethylenediamine, di-ethyltriamine, tri-ethyltetramine, tetra-ethylpentamine, penta-ethylhexamine, 1,1,4,7 a polyamine such as 7-pentamethyldiethylideneamine, 1,1,4,7,10,10-hexamethyltriethylamine, triethoxytriethylamine, or the like, Cyclic polyamines such as tetraazacyclotetradecane and tetraazacyclododecane, pyridine, pyrrolidine, piperidine, morpholine, N-methylpyrrolidine, N-methylpiperidine, N- Heterocyclic compounds such as methylmorpholine, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, oxazole, thiazole, oxathiolane, ethyl acetacetate, ethyl acetate a β-ketoester such as acetoxyacetic acid-2-methoxyethyl ester, or acetonitrile, 2,4-hexanedione, 2,4-heptanedione, 3, A β-diketone such as 5-heptanedione or dip-amyl methane. The amount of such stabilizers used is in the range of 0.1 to 10 moles relative to the precursor 1 mole, and preferably 1-4 moles.

本發明之薄膜形成用原料，應儘量不含構成其之成分以外之雜質金屬元素成分、雜質氯等之雜質鹵素、雜質有機成分。雜質金屬元素成分就各元素宜為100 ppb以下，更好為10 ppb以下，總量宜為1 ppm以下，更好為100 ppb以下。雜質有機成分總量宜為500 ppm以下，更好為50 ppm以下，特別好的是10 ppm以下。又，水分會成為CVD原料中的粒子或源自CVD法之粒子發生的原因，因此，就金屬化合物、有機溶劑、親核試劑，為使各自之水分降低，在使用時最好預先盡可能除去水分。水分量宜為10 ppm以下，更好的是1 ppm以下。The raw material for forming a film of the present invention should contain as much as possible an impurity-containing metal element component other than the constituents thereof, an impurity halogen such as impurity chlorine, and an impurity organic component. The impurity metal element component is preferably 100 ppb or less, more preferably 10 ppb or less, and the total amount is preferably 1 ppm or less, more preferably 100 ppb or less. The total amount of the impurity organic component is preferably 500 ppm or less, more preferably 50 ppm or less, and particularly preferably 10 ppm or less. Further, since water causes particles in the CVD raw material or particles derived from the CVD method to occur, the metal compound, the organic solvent, and the nucleophilic reagent are preferably removed as much as possible in order to reduce the water content. Moisture. The water content should be 10 ppm or less, more preferably 1 ppm or less.

又，本發明之薄膜形成用原料，為降低或防止製造之薄膜之粒子污染，以液相利用光散射式液中粒子檢測器的粒子測定中，大於0.3 μm之粒子數目宜在100個以下，更好的是大於0.2 μm之粒子數目在液相1 ml中為1000個以下，又更好的是大於0.2 μm之粒子數目在液相1 ml中為1000個以下，100個以下更好。Further, in the raw material for forming a film of the present invention, in order to reduce or prevent particle contamination of the produced film, in the measurement of particles in a liquid phase using a light scattering liquid particle detector, the number of particles larger than 0.3 μm is preferably 100 or less. More preferably, the number of particles larger than 0.2 μm is 1000 or less in the liquid phase 1 ml, and more preferably, the number of particles larger than 0.2 μm is 1000 or less in the liquid phase 1 ml, and more preferably 100 or less.

本發明薄膜之製造方法，係指將本發明之上述通式(1)所示之鋅化合物、因應必要使用之其他前驅體氣化成之蒸氣、及因應必要使用之反應性氣體導入至基板上，其次，使前驅體在基板上分解及/或反應，令薄膜在基板上生長、堆積之CVD法。有關原料之輸送方法、堆積方法、製造條件，製造裝置等，並無特殊限制，可使用週知之一般條件、方法。The method for producing a film of the present invention refers to a method in which a zinc compound represented by the above formula (1) of the present invention, a vapor which is vaporized by other precursors to be used, and a reactive gas which is used as necessary are introduced onto a substrate. Next, a CVD method in which a precursor is decomposed and/or reacted on a substrate to grow and deposit a film on a substrate. The method of transporting the raw materials, the method of stacking, the conditions of manufacture, the manufacturing apparatus, and the like are not particularly limited, and well-known general conditions and methods can be used.

上述因應必要使用之反應性氣體，例如作為氧化性者可舉例如氧、臭氧、二氧化氮、一氧化氮、水蒸氣、過氧化氫、甲酸、乙酸、無水乙酸等；作為還原性者可舉例如氫；作為製造氮化物者，可舉例如單烷胺、二烷胺、三烷胺、伸烷二胺等之有機胺化合物、聯胺、氨等；作為製造硫化物者，可舉例如硫化氫。The reactive gas to be used in the above-mentioned manner, for example, as an oxidizing agent, may, for example, be oxygen, ozone, nitrogen dioxide, nitrogen monoxide, water vapor, hydrogen peroxide, formic acid, acetic acid, anhydrous acetic acid or the like; as a reducing person, for example Examples of the material for producing the nitride include an organic amine compound such as a monoalkylamine, a dialkylamine, a trialkylamine or a stretched diamine, a hydrazine, an ammonia, etc., and examples of the sulfide to be produced include, for example, vulcanization. hydrogen.

又，作為上述輸送供給方法，可舉例如上述之氣體輸送法、液體輸送法、單一源法、混合源法等。Further, examples of the transport and supply method include the above-described gas transport method, liquid transport method, single source method, mixed source method, and the like.

又，作為上述之堆積方法，可舉例如將原料氣體或原料氣體與反應性氣體只藉熱促其反應而令薄膜堆積之熱CVD，使用熱與電漿之電漿CVD，使用熱與光之光CVD，使用光與電漿之光電漿CVD，以及將CVD之堆積反應分為各簡單過程，以分子程度階段性進行堆積之ALD(Atomic Layer Deposition)。Further, as the above-mentioned deposition method, for example, thermal CVD in which a raw material gas or a source gas and a reactive gas are reacted by heat to cause deposition of a thin film, plasma CVD using heat and plasma, and heat and light are used. Photo CVD, photo-plasma CVD using light and plasma, and ALD (Atomic Layer Deposition) in which the deposition reaction of CVD is divided into simple processes and stacked at a molecular level.

又，作為上述之製造條件，可舉例如反應溫度(基板溫度)、反應壓力、堆積速度等。就反應溫度而言，宜在本發明之上述化合物可充分反應之溫度160℃以上，更好的是在250℃~800℃。另，反應壓力宜為大氣壓~10 Pa，更好的是大氣壓~100 Pa。堆積方法與反應壓力之組合可為任意，可舉例如減壓熱CVD、減壓電漿CVD、減壓光CVD、減壓光電漿CVD、大氣壓熱CVD、大氣壓電漿CVD、大氣壓光CVD、大氣壓光電漿CVD。堆積速度可隨原料之供給條件(氣化溫度、氣化壓力)、反應溫度、反應壓力而控制。堆積速度若大則所獲得之薄膜特性有劣化之情形，堆積速度若小則有生產性之問題，因此宜為0.5~5000 nm/分鐘，更好的是1~1000 nm/分鐘。又，採用ALD時，可控制循環次數而獲得所期望之膜厚。Further, examples of the production conditions described above include a reaction temperature (substrate temperature), a reaction pressure, a deposition rate, and the like. The reaction temperature is preferably a temperature at which the above-mentioned compound of the present invention can be sufficiently reacted at 160 ° C or higher, more preferably at 250 ° C to 800 ° C. Further, the reaction pressure is preferably from atmospheric pressure to 10 Pa, more preferably from atmospheric pressure to 100 Pa. The combination of the deposition method and the reaction pressure may be any, and examples thereof include reduced pressure thermal CVD, reduced pressure plasma CVD, reduced pressure photo CVD, reduced pressure photo CVD CVD, atmospheric pressure thermal CVD, atmospheric piezoelectric CVD, atmospheric pressure photo CVD, and atmospheric pressure. Photoelectric CVD. The stacking speed can be controlled depending on the supply conditions (gasification temperature, vaporization pressure), reaction temperature, and reaction pressure of the raw materials. If the deposition speed is large, the film characteristics obtained may be deteriorated. If the deposition rate is small, there is a problem of productivity. Therefore, it is preferably 0.5 to 5000 nm/min, more preferably 1 to 1000 nm/min. Further, when ALD is employed, the desired number of film thicknesses can be obtained by controlling the number of cycles.

又，本發明薄膜之製造方法中，薄膜堆積後，為獲得更好之電氣特性，可進行退火處理，有必要掩埋階差時，可設置溢流步驟。此時之溫度為500~1200℃，宜為600~1000℃。Further, in the method for producing a film of the present invention, after the film is deposited, in order to obtain better electrical characteristics, annealing treatment can be performed, and when it is necessary to bury the step, an overflow step can be provided. The temperature at this time is 500 to 1200 ° C, preferably 600 to 1000 ° C.

使用本發明之薄膜形成用原料之本發明薄膜之製造方法所製造的薄膜，藉由適當選擇其他成分之前驅體、反應性氣體及製造條件，可形成金屬、合金、硫化物、氧化物陶瓷、氮化物陶瓷、玻璃等之所期望種類的薄膜。有關製造之薄膜種類，例如可舉例如鋅、ZnSe、氧化鋅、硫化鋅、鋅－銦複合氧化物、添加鋰之氧化鋅、添加鋅之鐵氧體、鉛－鋅複合氧化物、鉛－鋅－鈮複合氧化物、鉍－鋅－鈮複合氧化物、鋇－鋅－鉭複合氧化物、錫－鋅複合氧化物，至於此等薄膜之用途，可舉例如透明導電體、發光體、螢光體、光觸媒、磁性體、導電體、高介電體、強介電體、壓電體、微波介電體、光波導路、光放大器、光開關、電磁波屏蔽件、太陽電池等等。A film produced by the method for producing a film of the present invention using the raw material for forming a film of the present invention can form a metal, an alloy, a sulfide, an oxide ceramic, or the like by appropriately selecting a precursor of the other component, a reactive gas, and a production condition. A desired type of film of nitride ceramics, glass, or the like. Examples of the film to be produced include, for example, zinc, ZnSe, zinc oxide, zinc sulfide, zinc-indium composite oxide, lithium-added zinc oxide, zinc-added ferrite, lead-zinc composite oxide, and lead-zinc. - cerium composite oxide, cerium-zinc-cerium composite oxide, cerium-zinc-cerium composite oxide, tin-zinc composite oxide, and the use of such a thin film, for example, a transparent conductor, an illuminant, and a fluorescent Body, photocatalyst, magnetic body, electric conductor, high dielectric body, ferroelectric body, piezoelectric body, microwave dielectric body, optical waveguide, optical amplifier, optical switch, electromagnetic wave shield, solar cell, and the like.

實施例Example

以下，茲以實施例、評價例及比較例對本發明更詳細加以說明。惟本發明不受以下實施例等之任何限制。Hereinafter, the present invention will be described in more detail by way of examples, evaluation examples and comparative examples. However, the present invention is not limited by the following examples and the like.

[實施例1]化合物No.15之製造[Example 1] Production of Compound No. 15

在以乾燥氬氣置換之反應燒瓶內饋入二乙基鋅1.0 mol/升之己烷溶液50 ml，於常溫下於其中緩慢滴入3－乙氧基甲基－2,4－二甲基－3－戊醇8.77 g與己烷50 ml之混合物。而後，在維持氬氣氛圍下於常溫下終夜攪拌。而後進行脫溶劑，獲得白色固體9.7 g。就所得之固體進行以下分析，確認其為目的物。50 ml of a 1.0 mol/liter hexane solution of diethyl zinc was fed into a reaction flask which was replaced with dry argon gas, and 3-ethoxymethyl-2,4-dimethyl group was slowly dropped thereto at normal temperature. A mixture of 8.77 g of 3-pentanol and 50 ml of hexane. Then, the mixture was stirred overnight at room temperature under an argon atmosphere. Then, the solvent was removed to obtain 9.7 g of a white solid. The obtained solid was subjected to the following analysis to confirm that it was the intended product.

(分析)(1)元素分析(CHN：CHN分析儀、金屬分析：ICP)碳49.5質量%(理論值53.8%)、氫9.2質量%(理論值9.8%)、鋅24.3%質量(理論值24.3%)(2)1 H－NMR(溶劑：重苯)圖1中表示其光譜圖。(Analysis) (1) Elemental analysis (CHN: CHN analyzer, metal analysis: ICP) carbon 49.5 mass% (theoretical value 53.8%), hydrogen 9.2 mass% (theoretical value 9.8%), zinc 24.3% mass (theoretical value 24.3) %) (2) 1 H-NMR (solvent: heavy benzene) The spectrum thereof is shown in FIG.

[實施例2]化合物No.23之製造[Example 2] Production of Compound No. 23

在以乾燥氬氣置換之反應燒瓶內饋入二甲基鋅1.0 mol/升之己烷溶液50 ml，於常溫下於其中緩慢滴入1－二甲胺基－2－甲基－2－丙醇5.86 g與己烷50 ml之混合物。而後，在維持氬氣氛圍下於常溫下終夜攪拌。而後進行脫溶劑，獲得白色固體6.9 g。就所得之固體進行以下分析，確認其為目的物。50 ml of dimethyl zinc 1.0 mol/liter hexane solution was fed into a reaction flask which was replaced with dry argon gas, and 1-dimethylamino-2-methyl-2-propene was slowly added dropwise thereto at normal temperature. A mixture of 5.86 g of alcohol and 50 ml of hexane. Then, the mixture was stirred overnight at room temperature under an argon atmosphere. Then, the solvent was removed to obtain 6.9 g of a white solid. The obtained solid was subjected to the following analysis to confirm that it was the intended product.

(分析)(1)元素分析(CHN：CHN分析儀、金屬分析：ICP)碳42.7質量%(理論值42.77%)、氫8.5質量%(理論值8.72%)、氮6.7質量%(理論值7.12%)、鋅31.5%質量(理論值33.25%)(2)1 H－NMR(溶劑：重苯)圖2中表示其光譜圖。(Analysis) (1) Elemental analysis (CHN: CHN analyzer, metal analysis: ICP) carbon 42.7 mass% (theoretical value 42.77%), hydrogen 8.50 mass% (theoretical value 8.72%), nitrogen 6.7% by mass (theoretical value 7.12) %), zinc 31.5% by mass (theoretical value 33.25%) (2) 1 H-NMR (solvent: heavy benzene) The spectrogram is shown in FIG.

[實施例3]化合物No.24之製造[Example 3] Production of Compound No. 24

在以乾燥氬氣置換之反應燒瓶內饋入二乙基鋅1.0 mol/升之己烷溶液50 ml，於常溫下於其中緩慢滴入1－二甲胺基－2－丙醇5.16 g與己烷50 ml之混合物。而後，在維持氬氣氛圍下於常溫下終夜攪拌。而後進行脫溶劑，獲得透明固體7.7 g。就所得之固體進行以下分析，確認其為目的物。50 ml of a 1.0 mol/liter hexane solution of diethyl zinc was fed into a reaction flask which was replaced with dry argon gas, and 1-dimethylamino-2-propanol 5.16 g was slowly added dropwise thereto at room temperature. A mixture of 50 ml of alkane. Then, the mixture was stirred overnight at room temperature under an argon atmosphere. Then, solvent removal was carried out to obtain 7.7 g of a transparent solid. The obtained solid was subjected to the following analysis to confirm that it was the intended product.

(分析)(1)元素分析(CHN：CHN分析儀、金屬分析：ICP)碳42.7質量%(理論值42.77%)、氫8.5質量%(理論值8.72%)、氮6.8質量%(理論值7.12%)、鋅32.0%質量(理論值33.25%)(2)1 H－NMR(溶劑：重苯)圖3中表示其光譜圖。(Analysis) (1) Elemental analysis (CHN: CHN analyzer, metal analysis: ICP) Carbon 42.7 mass% (theoretical value 42.77%), hydrogen 8.5% by mass (theoretical value 8.72%), nitrogen 6.8% by mass (theoretical value 7.12) %), zinc 32.0% by mass (theoretical value 33.25%) (2) 1 H-NMR (solvent: heavy benzene) The spectrum thereof is shown in FIG.

[實施例4]化合物No.25之製造[Example 4] Production of Compound No. 25

在以乾燥氬氣置換之反應燒瓶內饋入二乙基鋅1.0 mol/升之己烷溶液50 ml，於常溫下於其中緩慢滴入1－二甲胺基－2－甲基－2－丙醇5.86 g與己烷50 ml之混合物。而後，在維持氬氣氛圍下於常溫下終夜攪拌。而後進行脫溶劑，獲得白色固體7.3 g。就所得之固體進行以下分析，確認其為目的物。50 ml of a 1.0 mol/liter hexane solution of diethyl zinc was fed into a reaction flask which was replaced with dry argon gas, and 1-dimethylamino-2-methyl-2-prop was slowly added dropwise thereto at normal temperature. A mixture of 5.86 g of alcohol and 50 ml of hexane. Then, the mixture was stirred overnight at room temperature under an argon atmosphere. Then, the solvent was removed to obtain 7.3 g of a white solid. The obtained solid was subjected to the following analysis to confirm that it was the intended product.

(分析)(1)元素分析(CHN：CHN分析儀、金屬分析：ICP)碳44.9質量%(理論值45.6%)、氫8.7質量%(理論值9.1%)、氮6.2質量%(理論值6.6%)、鋅30.3%質量(理論值31.0%)(2)1 H－NMR(溶劑：重苯)圖4中表示其光譜圖。(Analysis) (1) Elemental analysis (CHN: CHN analyzer, metal analysis: ICP) carbon 44.9 mass% (theoretical value 45.6%), hydrogen 8.7% by mass (theoretical value 9.1%), nitrogen 6.2 mass% (theoretical value 6.6) %), zinc 30.3% by mass (theoretical value 31.0%) (2) 1 H-NMR (solvent: heavy benzene) The spectrum of Figure 4 is shown.

[實施例5]化合物No.33之製造[Example 5] Production of Compound No. 33

在以乾燥氬氣置換之反應燒瓶內饋入二甲基鋅1.0 mol/升之己烷溶液50 ml，於常溫下於其中緩慢滴入1－[(2－二甲胺基－乙基)－甲胺基]－2－甲基－2－丙醇8.72 g與己烷50 ml之混合物。滴入終了後，在維持氬氣氛圍下於常溫下終夜攪拌。而後進行脫己烷溶劑，就殘渣進行減壓蒸餾，自0.4 Torr/137℃之餾份獲得白色固體11.3 g。就所得之物質進行以下分析，確認其為目的物。50 ml of dimethyl zinc 1.0 mol/liter hexane solution was fed into a reaction flask which was replaced with dry argon gas, and 1-[(2-dimethylamino-ethyl)- was slowly added dropwise thereto at normal temperature. A mixture of 8.72 g of methylamino]-2-methyl-2-propanol and 50 ml of hexane. After the completion of the dropwise addition, the mixture was stirred overnight at room temperature under an argon atmosphere. Then, a solvent for dehexane removal was carried out, and the residue was subjected to distillation under reduced pressure to obtain 11.3 g of a white solid from a fraction of 0.4 Torr / 137 °C. The obtained material was subjected to the following analysis to confirm that it was the intended product.

(分析)(1)元素分析(CHN：CHN分析儀、金屬分析：ICP)碳46.6質量%(理論值47.35%)、氫9.1質量%(理論值9.54%)、氮10.8質量%(理論值11.04%)、鋅25.5%質量(理論值25.77%)(2)1 H－NMR(溶劑：重苯)圖5中表示其光譜圖。(Analysis) (1) Elemental analysis (CHN: CHN analyzer, metal analysis: ICP) Carbon 46.6 mass% (theoretical value 47.35%), hydrogen 9.1 mass% (theoretical value 9.54%), nitrogen 10.8 mass% (theoretical value 11.04) %), 25.5% by mass of zinc (theoretical value 25.77%) (2) 1 H-NMR (solvent: heavy benzene) The spectrum thereof is shown in FIG.

[實施例6]化合物No.36之製造[Example 6] Production of Compound No. 36

在以乾燥氬氣置換之反應燒瓶內饋入二乙基鋅1.0 mol/升之己烷溶液150 ml，於常溫下於其中緩慢滴入1－[(2－二甲胺基－乙基)－甲胺基]－2－甲基－2－丙醇26.14 g與己烷80 ml之混合物。滴入終了後，在維持氬氣氛圍下於常溫下終夜攪拌。而後進行脫己烷溶劑，就殘渣進行減壓蒸餾，自0.37 Torr/143℃之餾份獲得白色固體3.8 g。就所得之固體進行以下分析，確認其為目的物。150 ml of a 1.0 mol/liter hexane solution of diethyl zinc was fed into a reaction flask which was replaced with dry argon gas, and 1-[(2-dimethylamino-ethyl)- was slowly added dropwise thereto at normal temperature. A mixture of 26.14 g of methylamino]-2-methyl-2-propanol and 80 ml of hexane. After the completion of the dropwise addition, the mixture was stirred overnight at room temperature under an argon atmosphere. Then, a solvent for dehexane removal was carried out, and the residue was subjected to distillation under reduced pressure to obtain 3.8 g of a white solid from a fraction of 0.37 Torr / 143 °C. The obtained solid was subjected to the following analysis to confirm that it was the intended product.

(分析)(1)元素分析(CHN：CHN分析儀、金屬分析：ICP)碳48.5質量%(理論值49.3%)、氫9.3質量%(理論值9.8%)、氮9.8質量%(理論值10.5%)、鋅24.1%質量(理論值24.4%)(2)1 H－NMR(溶劑：重苯)圖6中表示其光譜圖。(Analysis) (1) Elemental analysis (CHN: CHN analyzer, metal analysis: ICP) Carbon 48.5 mass% (theoretical value 49.3%), hydrogen 9.3 mass% (theoretical value 9.8%), nitrogen 9.8 mass% (theoretical value 10.5) %), zinc 24.1% by mass (theoretical value 24.4%) (2) 1 H-NMR (solvent: heavy benzene) The spectrum thereof is shown in Fig. 6.

[評估例1]液體或低熔點鋅化合物之評估[Evaluation Example 1] Evaluation of liquid or low melting point zinc compound

針對液體或因熔點較低之故，自液體變化成氣體之相變化容易的鋅化合物，即化合物No.2、No.15、No.33、No.36、二(辛烷－2,4－二酮)鋅錯合物(比較化合物1)、二(2,2－二甲基－6－乙基－癸烷－3,5－二酮)鋅錯合物(比較化合物2)，採用將系固定於一定壓力，測定液面附近之蒸氣溫度的方法進行評估。改變系之壓力測定4點蒸氣溫度，以庫拉吉斯－庫拉派龍法作圖，獲得蒸氣壓之算式，算出120℃、150℃之蒸氣壓。又，測定條件為氧100 ml/min、升溫速度為10℃/min，利用表1中所示之樣本量之TG測定，評估氧化分解性。以在500℃下之殘餘部分為ZnO，以相對於試料全部為氧化物時之理論值比例(%)進行評估。結果如表1所示。A zinc compound which is easy to change from a liquid to a gas phase due to a liquid or a lower melting point, that is, Compound No. 2, No. 15, No. 33, No. 36, and di(octane-2, 4-) Diketo)zinc complex (Comparative Compound 1), bis(2,2-dimethyl-6-ethyl-decane-3,5-dione) zinc complex (Comparative Compound 2), It is evaluated by a method of fixing the pressure at a certain pressure and measuring the vapor temperature near the liquid surface. The pressure of the system was measured to determine the vapor pressure at 4 o'clock, and the vapor pressure was calculated by the Kurajis-Kurapai method, and the vapor pressure at 120 ° C and 150 ° C was calculated. Further, the measurement conditions were oxygen 100 ml/min, and the temperature increase rate was 10 ° C/min, and the oxidative decomposition property was evaluated by the TG measurement of the sample amount shown in Table 1. The residual portion at 500 ° C was ZnO, and the ratio (%) of the theoretical value when the sample was all oxide was evaluated. The results are shown in Table 1.

由上述結果可確認，作為本發明鋅化合物之化合物No.2、No.15、No.33及No.36，較之比較化合物1及2，蒸氣壓大、且氧化分解性良好。From the above results, it was confirmed that Compound No. 2, No. 15, No. 33, and No. 36, which are zinc compounds of the present invention, have a larger vapor pressure and better oxidative decomposition properties than Comparative Compounds 1 and 2.

[評估例2]固體鋅化合物之評估[Evaluation Example 2] Evaluation of solid zinc compound

測定化合物No.23、No.24及No.25以及CH3 －CH2 －Zn－OCH(CH3 )2 (比較化合物3)之TG－DTA。又，測定條件為氬100 ml/min、升溫速度為10℃/min，測定樣本量如表2中所記載。50℃減量溫度示於表2。TG-DTA of Compound No. 23, No. 24 and No. 25 and CH 3 -CH 2 -Zn-OCH(CH 3 ) 2 (Comparative Compound 3) was measured. Further, the measurement conditions were argon 100 ml/min, and the temperature increase rate was 10 ° C/min, and the sample amount was measured as shown in Table 2. The 50 ° C reduction temperature is shown in Table 2.

由表2可確認，作為本發明之鋅化合物的化合物No.23、No.24及No.25，較之比較化合物3，揮發性良好、且惰性氛圍下之熱安定性良好。As is clear from Table 2, the compounds No. 23, No. 24, and No. 25 which are zinc compounds of the present invention have good volatility and good thermal stability in an inert atmosphere as compared with the comparative compound 3.

[實施例7]氧化鋅薄膜之製造1[Example 7] Production of zinc oxide film 1

使用圖7所示之CVD裝置，在藍寶石基板上，以下述條件製造氧化鋅薄膜。就製造之薄膜，以螢光X射線確認其膜厚及膜組成。A zinc oxide thin film was produced on the sapphire substrate under the following conditions using a CVD apparatus shown in FIG. The film thickness and film composition of the manufactured film were confirmed by fluorescent X-ray.

(製造條件)鋅CVD原料：化合物No.2、原料溫度：120℃、原料壓力：500~1000 Pa、載體氣體：氬150 sccm、氧化氣體：氧1000 sccm、反應壓力：600 Pa、反應溫度(基板溫度)：500℃、成膜時間：60分鐘(Production conditions) Zinc CVD raw material: Compound No. 2, raw material temperature: 120 ° C, raw material pressure: 500 to 1000 Pa, carrier gas: argon 150 sccm, oxidizing gas: oxygen 1000 sccm, reaction pressure: 600 Pa, reaction temperature ( Substrate temperature): 500 ° C, film formation time: 60 minutes

(結果)膜厚：496 nm，膜組成：氧化鋅(Result) Film thickness: 496 nm, film composition: zinc oxide

[實施例8]氧化鋅薄膜之製造2[Example 8] Production of zinc oxide film 2

使用圖7所示之CVD裝置，在藍寶石基板上，以下述條件製造氧化鋅薄膜。就製造之薄膜，以螢光X射線確認其膜厚及膜組成。A zinc oxide thin film was produced on the sapphire substrate under the following conditions using a CVD apparatus shown in FIG. The film thickness and film composition of the manufactured film were confirmed by fluorescent X-ray.

(製造條件)鋅CVD原料：化合物No.33、原料溫度：120℃、原料壓力：500~1000 Pa、載體氣體：氬150 sccm、氧化氣體：氧1000 sccm、反應壓力：600 Pa、反應溫度(基板溫度)：500℃、成膜時間：60分鐘(Manufacturing conditions) Zinc CVD raw material: Compound No. 33, raw material temperature: 120 ° C, raw material pressure: 500 to 1000 Pa, carrier gas: argon 150 sccm, oxidizing gas: oxygen 1000 sccm, reaction pressure: 600 Pa, reaction temperature ( Substrate temperature): 500 ° C, film formation time: 60 minutes

(結果)膜厚：1325 nm，膜組成：氧化鋅(Result) Film thickness: 1325 nm, film composition: zinc oxide

[實施例9]氧化鋅薄膜之製造3[Example 9] Production of zinc oxide film 3

使用圖8所示之CVD裝置，在藍寶石基板上，以下述條件製造氧化鋅薄膜。就製造之薄膜，以螢光X射線確認其膜厚及膜組成。A zinc oxide thin film was produced on the sapphire substrate under the following conditions using a CVD apparatus shown in FIG. The film thickness and film composition of the manufactured film were confirmed by fluorescent X-ray.

(製造條件)鋅CVD原料：化合物No.23之0.25莫耳/kg之乙基環己烷溶液、原料流量：0.4 sccm、氣化室溫度：220℃、氣化室壓力：800 Pa、載體氣體：氬150 sccm、氧化氣體：氧1000 sccm、反應壓力：~800 Pa、反應溫度(基板溫度)：500℃、成膜時間：60分鐘(Manufacturing conditions) Zinc CVD raw material: 0.25 mol/kg ethylcyclohexane solution of Compound No. 23, raw material flow rate: 0.4 sccm, gasification chamber temperature: 220 ° C, gasification chamber pressure: 800 Pa, carrier gas : Argon 150 sccm, oxidizing gas: oxygen 1000 sccm, reaction pressure: ~800 Pa, reaction temperature (substrate temperature): 500 ° C, film formation time: 60 minutes

(結果)膜厚：1735 nm，膜組成：氧化鋅(Result) Film thickness: 1735 nm, film composition: zinc oxide

產業上之可利用性Industrial availability

本發明之新穎鋅化合物，可用作為具有氣化步驟之CVD法等之薄膜形成用原料，還可用於塗佈熱分解法或溶膠－凝膠法等MOD之薄膜形成用原料、有機合成觸媒、高分子化合物合成觸媒等等。The novel zinc compound of the present invention can be used as a raw material for film formation such as a CVD method having a gasification step, and can also be used for coating a film for forming a film such as a thermal decomposition method or a sol-gel method, or an organic synthesis catalyst. Polymer compound synthesis catalyst and the like.

圖1為實施例1所獲得之本發明鋅化合物(化合物No.15)之1 H－NMR光譜圖。Fig. 1 is a 1 H-NMR spectrum chart of the zinc compound (Compound No. 15) of the present invention obtained in Example 1.

圖2為實施例2所獲得之本發明鋅化合物(化合物No.23)之1 H－NMR光譜圖。Fig. 2 is a 1 H-NMR spectrum chart of the zinc compound (Compound No. 23) of the present invention obtained in Example 2.

圖3為實施例3所獲得之本發明鋅化合物(化合物No.24)之1 H－NMR光譜圖。Fig. 3 is a 1 H-NMR spectrum chart of the zinc compound (Compound No. 24) of the present invention obtained in Example 3.

圖4為實施例4所獲得之本發明鋅化合物(化合物No.25)之1 H－NMR光譜圖。Fig. 4 is a 1 H-NMR spectrum chart of the zinc compound (Compound No. 25) of the present invention obtained in Example 4.

圖5為實施例5所獲得之本發明鋅化合物(化合物No.33)之1 H－NMR光譜圖。Fig. 5 is a 1 H-NMR spectrum chart of the zinc compound (Compound No. 33) of the present invention obtained in Example 5.

圖6為實施例6所獲得之本發明鋅化合物(化合物No.36)之1 H－NMR光譜圖。Fig. 6 is a 1 H-NMR spectrum chart of the zinc compound (Compound No. 36) of the present invention obtained in Example 6.

圖7為實施例7及8中所使用之本發明薄膜之製造方法中所用的CVD裝置之概要圖。Fig. 7 is a schematic view showing a CVD apparatus used in the method for producing a film of the present invention used in Examples 7 and 8.

圖8為實施例9所使用之本發明薄膜之製造方法中所用的CVD裝置之概要圖。Fig. 8 is a schematic view showing a CVD apparatus used in the method for producing a film of the present invention used in Example 9.

(無元件符號說明)(no component symbol description)

Claims (9)

一種薄膜形成用原料，含有下述通式(1)所示之鋅化合物： (式中，R1 表示碳數1~4之烷基，R2 及R3 分別獨立地表示氫原子或碳數1~4之烷基，R4 表示碳數1~4之烷基，R5 表示碳數1~4之烷基或－CH2 －CH2 －NR6 R7 ，R6 及R7 表示碳數1~4之烷基，X表氧原子或氮原子，m於X為氧原子時為0，X為氮原子時為1)。A raw material for forming a film, comprising a zinc compound represented by the following formula (1): (wherein R 1 represents an alkyl group having 1 to 4 carbon atoms, and R 2 and R 3 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; and R 4 represents an alkyl group having 1 to 4 carbon atoms; 5 represents an alkyl group having 1 to 4 carbon atoms or -CH 2 -CH 2 -NR 6 R 7 , and R 6 and R 7 represent an alkyl group having 1 to 4 carbon atoms, an oxygen atom or a nitrogen atom of X, and m is X. When the oxygen atom is 0, when X is a nitrogen atom, it is 1). 如請求項1之薄膜形成用原料，其中上述通式(1)中，R2 及R3 為氫原子，X為氧原子，R4 為甲基。The raw material for film formation according to claim 1, wherein, in the above formula (1), R 2 and R 3 are a hydrogen atom, X is an oxygen atom, and R 4 is a methyl group. 如請求項1之薄膜形成用原料，其中上述通式(1)中，R2 及R3 中之至少任一者為碳數1~4之烷基。The raw material for film formation according to claim 1, wherein in the above formula (1), at least one of R 2 and R 3 is an alkyl group having 1 to 4 carbon atoms. 如請求項1或3之薄膜形成用原料，其中上述通式(1)中，X為氮原子。The raw material for film formation according to claim 1 or 3, wherein in the above formula (1), X is a nitrogen atom. 如請求項4之薄膜形成用原料，其中上述通式(1)中，R5 為－CH2 －CH2 －NR6 R7 。The raw material for film formation according to claim 4, wherein, in the above formula (1), R 5 is -CH 2 -CH 2 -NR 6 R 7 . 如請求項1之薄膜形成用原料，其中上述通式(1)中，R1 為甲基或乙基。The raw material for film formation according to claim 1, wherein in the above formula (1), R 1 is a methyl group or an ethyl group. 一種薄膜之製造方法，其係將請求項1~6中任一項之薄膜形成用原料氣化所得之含鋅化合物的蒸氣導入基體，令其分解及/或化學反應，在基體上形成薄膜。A method for producing a film by introducing a vapor of a zinc-containing compound obtained by vaporizing a raw material for forming a film according to any one of claims 1 to 6 into a substrate, decomposing and/or chemically reacting to form a film on the substrate. 一種鋅化合物，其係上述通式(1)中，R2 及R3 中之至少任一者為碳數1~4之烷基者。A zinc compound which is in the above formula (1), wherein at least one of R 2 and R 3 is an alkyl group having 1 to 4 carbon atoms. 如請求項8之鋅化合物，其係上述通式(1)中，X表示氮原子，R4 表示甲基或乙基，R5 表示甲基或－CH2 －CH2 －NR6 R7 ，R6 及R7 表示甲基或乙基者。The zinc compound of claim 8, which is in the above formula (1), X represents a nitrogen atom, R 4 represents a methyl group or an ethyl group, and R 5 represents a methyl group or -CH 2 -CH 2 -NR 6 R 7 , R 6 and R 7 represent a methyl group or an ethyl group.
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