TW200940553A

TW200940553A - Diruthenium complex and material and method for chemical vapor deposition

Info

Publication number: TW200940553A
Application number: TW97135559A
Authority: TW
Inventors: Tatsuya Sakai; Sanshiro Komiya; Naofumi Nomura
Original assignee: Jsr Corp
Priority date: 2008-03-17
Filing date: 2008-09-17
Publication date: 2009-10-01
Also published as: KR20100126387A; KR101526633B1; TWI422590B; WO2009116191A1

Abstract

This invention provides a diruthenium complex such as tetra ([mu]-formate) diruthenium (II, II) or tetra ([mu]-formate) (dihydrate) diruthenium (II, II), a material for chemical vapor deposition, comprising the complex, and a method for forming a ruthenium film by chemical vapor deposition using the material.

Description

200940553 九、發明說明【發明所屬之技術領域】本發明係關於一種新穎二釕錯合物，化學氣相成長材料及化學氣相成長方法。 ‘ 【先前技術】於DRAM(動態隨機存取記億體）中所代表之半導體裝 0 置，伴隨著其高積體化與細微化，有必要改變構成裝置之各種金屬膜、金屬氧化膜之材料。尤其，於半導體裝置內之多層配線用途要求有對導電性金屬膜的改良，而朝向變換爲新的導電性高的銅配線發展。於提高此銅配線之導電性目的而言，雖於多層配線之層間絕緣膜使用低介電率材料（低-k材料），但此低介電率材料中所含之氧原子容易進入銅配線中而產生其導電性降低的問題。因此，就防止來自低介電率材料之氧移動之目〇的而言，探討有於低介電率材料與銅配線間形成障壁膜之技術。作爲此障壁膜之用途’作爲來自介電體層之氧難以進入之材料以及可易於藉乾蝕刻加工之材料，金屬釕備受矚目。再者’以電鍍法包埋上述銅配線之鑲嵌成膜法中，自同時滿足上述障壁膜及電鍍成長膜兩者角色之目的觀之 ’金屬釕備受矚目（參考電子材料2003年11月號PP47-49以及 Jpn. J. Appl. Phys·，Vol. 43, No. 6A(2004) PP3315-3319)。又，即使於半導體裝置之電容中，作爲如氧化鋁、五 -5- 200940553 氧化鉅、氧化鈴、鈦酸鋇.緦（B S Τ)般之高介電率材料之電極材料，金屬釕由於其高的耐氧化性極高的導電性而備受矚目（參考特開2003-100909號公報）。上述金屬釕膜之形成，以往大多使用濺鍍法進行，但近幾年來對應於更細微化構造或薄膜化、量產性，而對化學氣相成長法進行探討（參考特開2003-318258號公報，特開2002-161367號公報及特表2002-523634號公報）。然而’以一般化學氣相成長法所形成之金屬膜其微結晶集合狀態鬆散等而表面形態不良，作爲解決上述形態問題之方法，已對使用雙（二特戊醯基甲酸酯）釕或二環戊釕、雙（烷基環戊二烯基）釕作爲化學氣相成長材料進行探討 (參考特開平06-283438號公報、特開平1 1 -3 5 5 89號公報以及特開2002- 1 1 4795號公報）。又於製造步驟中使用該等化學氣相成長材料時，由其製造條件安定之目的而言亦要求材料之良好保存安定性。然而，既有的釕或雙（烷基環戊二烯基）釕等，因空氣混入等而於短時間內引起材料氧化，產生性能劣化，其結果，所成膜之釕導電性降低，而有其保存安定性及於空氣中穩定操作性之問題。又’若於化學氣相成長材料使用保存安定性良好之雙（二特戊醯基甲酸酯）釕等，則所成膜之釕膜中雜質多，有無法獲得良好品質釕膜的問題。作爲解決上述問題之方法’已對具有其他羰基化合物或二烯化合物配位體之釕化合物、使用釕（11)價之化合物進行探討（參考特開2002-2 121 1 2號公報、特開2003-342286號公報以及特開 200940553 2〇06-241557號公報），但各化合物之保存安疋性與成膜後之釕膜中低雜質殘留兩者難以並存，故仍有問題。【發明內容】本發明有鑑於上述問題點，目的在於提供一種可獲得保存安定性優異，且殘留雜質少之良好品質釕膜之新穎二釕錯合物、化學氣相成長材料及使用化學氣相成長材料形成釕膜之簡易方法。本發明之其他目的及優點將由下列說明可清楚了解。依據本發明’本發明之上述目的及優點可藉下列第〜目的達成’即一種以下式（1)表示之二釕錯合物及由其辑合物組成之化學氣相成長材料：BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel diterpene complex, a chemical vapor grown material, and a chemical vapor growth method. [Prior Art] In the semiconductor device represented by DRAM (Dynamic Random Access Memory), it is necessary to change various metal films and metal oxide films constituting the device with its high integration and miniaturization. material. In particular, in the case of multilayer wiring in a semiconductor device, improvement of the conductive metal film is required, and the copper wiring which is converted into a new high conductivity is developed. For the purpose of improving the conductivity of the copper wiring, although a low dielectric material (low-k material) is used for the interlayer insulating film of the multilayer wiring, the oxygen atoms contained in the low dielectric material easily enter the copper wiring. In the middle, there is a problem that the conductivity thereof is lowered. Therefore, in order to prevent the movement of oxygen from a low dielectric material, a technique of forming a barrier film between a low dielectric material and a copper wiring has been discussed. As a use of the barrier film, as a material which is hard to enter from the dielectric layer and a material which can be easily dried and etched, metal is attracting attention. In addition, in the inlaid film forming method in which the above-mentioned copper wiring is embedded by electroplating, the 'metal 钌钌 ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( PP47-49 and Jpn. J. Appl. Phys., Vol. 43, No. 6A (2004) PP3315-3319). Further, even in the capacitance of the semiconductor device, as an electrode material of a high dielectric material such as alumina, pentaha-5-200940553 oxidized giant, oxidized bell, barium titanate (BS), metal ruthenium High electrical conductivity with high oxidation resistance is attracting attention (refer to Japanese Laid-Open Patent Publication No. 2003-100909). The formation of the above-mentioned metal ruthenium film has been conventionally carried out by a sputtering method. However, in recent years, the chemical vapor phase growth method has been studied in response to a finer structure, thin film formation, and mass productivity (refer to Japanese Patent Laid-Open No. 2003-318258 Japanese Patent Laid-Open Publication No. 2002-161367 and No. 2002-523634. However, the metal film formed by the general chemical vapor phase growth method has a fine crystal aggregate state and a poor surface morphology, and as a method for solving the above-mentioned morphological problem, bis(di-p-amyl phthalate) ruthenium or Dicyclopentanyl pentazide and bis(alkylcyclopentadienyl) fluorene are discussed as chemical vapor-grown materials (refer to Japanese Laid-Open Patent Publication No. Hei 06-283438, Japanese Patent Application Laid-Open No. Hei No. Hei No. Hei No. Hei. Bulletin 1 1 4795). When these chemical vapor-grown materials are used in the production steps, the preservation stability of the materials is also required for the purpose of stable production conditions. However, the existing ruthenium or bis(alkylcyclopentadienyl) ruthenium or the like causes oxidation of the material in a short time due to air incorporation, and the like, and the performance is deteriorated. As a result, the conductivity of the film is lowered. It has problems of preserving stability and stable operation in the air. Further, when a chemical vapor-grown material is used, such as bis(di-p-amyl phthalate) oxime which has good storage stability, there are many impurities in the ruthenium film formed, and there is a problem that a good quality ruthenium film cannot be obtained. As a method for solving the above problems, a ruthenium compound having another carbonyl compound or a diene compound ligand and a compound having a ruthenium (11) value have been examined (refer to JP-A-2002-2 121 1 2, JP-A-2003). In addition, it is difficult to coexist with both the storage stability of each compound and the low impurity residue in the ruthenium film after film formation, and there is still a problem. SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and an object thereof is to provide a novel bismuth complex, a chemical vapor grown material, and a chemical vapor phase which are excellent in storage stability and have a good quality ruthenium film with little residual impurities. A simple method of growing a enamel film. Other objects and advantages of the present invention will be apparent from the following description. According to the present invention, the above objects and advantages of the present invention can be achieved by the following first object, that is, a diterpene complex represented by the following formula (1) and a chemical vapor grown material composed of the same:

GG

YY

X 200940553 1〜1〇之烴基、碳數1〜10之鹵化烴基或碳數丨〜“之院氧基，且X及Y各獨立爲水、碳數1〜10之酮化合物、碳數卜⑺ 之醚化合物、碳數1~10之酯化合物、碳數之腈化合物依據本發明，本發明之上述目的及優點可藉由下列第一目的而達成，即一種以下述式（2)表示之二纟了錯合物及由該錯合物組成之化學氣相成長材料：X 200940553 1~1〇 of a hydrocarbon group, a halogenated hydrocarbon group having a carbon number of 1 to 10 or a carbon number of 院~"", and each of X and Y is independently a water, a ketone compound having a carbon number of 1 to 10, and a carbon number (7) The ether compound, the ester compound having 1 to 10 carbon atoms, and the nitrile compound having a carbon number. According to the present invention, the above objects and advantages of the present invention can be attained by the following first object, that is, a formula represented by the following formula (2) The complex and the chemical vapor grown material composed of the complex are obtained:

R5、R6、R7及R8各獨立爲氫原子、氟原子、碳數 1〜10之烴基、碳數1~1〇之鹵化烴基或碳數1~1〇之烷氧基。依據本發明，本發明之上述目的及優點可藉由下列第三目的而達成，即一種釕膜之形成方法，係由上述化學氣手目$長材料藉由化學氣相成長法所形成者。【實施方式】 -8- 200940553 以下，就本發明加以詳細說明。作爲本發明之化學氣相成長材料有用之新穎二釕錯合物係分別以上述式（1)及下述式（2)表示。上述式（1)中，Rl、R2、R3及R4各獨立爲氫原子、氟原子、碳數1~1〇之烴基、碳數1〜10之鹵化烴基或碳數1~1〇之烷氧基。其中，碳數1〜10之烴基較好爲碳數1〜7之烴基，其具體例可舉例爲例如甲基、乙基、正丙基、異丙基、正丁基、異丁基、第三丁基、新戊基、正己基、環己基、苯基、苄基、甲基苯基。又碳數1〜10之鹵化烴基較好爲碳數1〜6之鹵化烴基。其具體例可舉例爲例如氯甲基、二氯甲基、三氯甲基、氟甲基、二氟甲基、三氟甲基、2.2.2-三氟-乙基、五氟乙基、全氟丙基、全氟丁基、全氟己基、五氟苯基。又碳數1〜10之烷氧基較好爲碳數1~6之烷氧基，其具體例可舉例爲例如甲氧基、乙氧基、正丙氧基、異丙氧基、正丁氧基、異丁氧基、第三丁氧基、正己氧基、苯氧基。Rl、R2、R3及R4較佳之例可舉例爲例如氫原子、Μ原子、甲基、乙基、異丙基、第三丁基、新戊基、三氟甲基、五氟乙基、2.2.2-三氟-乙基、全氟己基、甲氧基、乙氧基、第三丁氧基。又，上述式（1)中，X及Υ各獨立爲水、碳數1〜10之 .酮化合物、碳數1〜10之醚化合物、碳數1~1〇之酯化合物、碳數1〜6之腈化合物。其中’碳數1~1〇之酮化合物較好爲碳數1〜7之酮化合物，其具體例可舉例爲例如丙酮、2-丁酮、3-甲基-2-丁酮、2-戊酮、頻那酮（Pinacolone)、3-戊 -9- 200940553 酮、3-己酮、2-庚酮。碳數1~1〇之醚化合物較好爲碳數 1~6之醚化合物，其具體例舉例爲二甲基醚、甲基乙基醚、二乙基醚、四氫呋喃、二噁烷、二丙基醚。碳數1〜10之酯化合物較好爲碳數1〜7之酯化合物，其具體例可舉例爲 • 乙酸甲酯、乙酸乙酯、乙酸丙酯、乙酸丁酯、乙酸戊酯 - (pentyl acetate)、乙酸戊酯（amyl acetate)、丙酸甲酯、丙酸乙酯、碳酸二甲酯、碳酸二乙酯。碳數1〜6之腈化合物 ^ 之具體例可舉例爲乙腈、丙腈。X及Y之較佳例可舉例爲水、丙酮、2 -丁酮、乙酸甲酯、丙酸甲酯、碳酸二甲酯、二甲基醚、二乙基醚、四氫呋喃、二噁烷、乙腈。上述式（2)中，R5、R6、R7及R8各獨立爲氫原子、氟原子、碳數卜10之烴基、碳數1〜10之齒化烴基或碳數1〜10 之烷氧基。其中，碳數1〜10之烴基較好爲碳數1〜7之烴基，其具體例可舉例爲例如甲基、乙基、正丙基、異丙基、正丁基、異丁基、第三丁基、新戊基、正己基、環己基、 φ 苯基、苄基、甲基苯基。又碳數1~10之鹵化烴基較好爲碳數1〜6之鹵化烴基。其具體例可舉例爲例如氯甲基、二氯甲基、三氯甲基、氟甲基、二氟甲基、三氟甲基、2.2.2-' 三氟-乙基、五氟乙基、全氟丙基、全氟丁基、全氟己基 ' 、五氟苯基。又碳數1〜1〇之烷氧基較好爲碳數1〜6之烷氧基，其具體例可舉例爲例如甲氧基、乙氧基、正丙氧基、異丙氧基、正丁氧基、異丁氧基、第三丁氧基、正己氧基、苯氧基。R5、R6、R7及R8較佳之例可舉例爲例如氫原子、氟原子、甲基、乙基、異丙基、第三丁基、新戊基、 -10- 200940553 單氟甲基、三氟甲基、五氟乙基、2.2.2-三氟-乙基、全氟己基、甲氧基、乙氧基、第三丁氧基。以上述式（1)及式（2)表示之化合物之合成法可參考D.R5, R6, R7 and R8 each independently represent a hydrogen atom, a fluorine atom, a hydrocarbon group having 1 to 10 carbon atoms, a halogenated hydrocarbon group having 1 to 1 carbon number, or an alkoxy group having 1 to 1 carbon number. According to the present invention, the above objects and advantages of the present invention can be attained by the third object of the present invention, which is a method for forming a ruthenium film formed by a chemical vapor phase growth method. [Embodiment] -8- 200940553 Hereinafter, the present invention will be described in detail. The novel diterpene complexes which are useful as the chemical vapor-grown growth material of the present invention are represented by the above formula (1) and the following formula (2). In the above formula (1), R1, R2, R3 and R4 each independently represent a hydrogen atom, a fluorine atom, a hydrocarbon group having 1 to 1 carbon number, a halogenated hydrocarbon group having 1 to 10 carbon atoms or an alkoxy group having 1 to 1 carbon number. base. The hydrocarbon group having 1 to 10 carbon atoms is preferably a hydrocarbon group having 1 to 7 carbon atoms, and specific examples thereof include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, and the like. Tributyl, neopentyl, n-hexyl, cyclohexyl, phenyl, benzyl, methylphenyl. Further, the halogenated hydrocarbon group having 1 to 10 carbon atoms is preferably a halogenated hydrocarbon group having 1 to 6 carbon atoms. Specific examples thereof include, for example, chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, 2.2.2-trifluoro-ethyl, pentafluoroethyl, Perfluoropropyl, perfluorobutyl, perfluorohexyl, pentafluorophenyl. Further, the alkoxy group having 1 to 10 carbon atoms is preferably an alkoxy group having 1 to 6 carbon atoms, and specific examples thereof include, for example, a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, and a n-butyl group. Oxyl, isobutoxy, tert-butoxy, n-hexyloxy, phenoxy. Preferred examples of R1, R2, R3 and R4 are exemplified by, for example, a hydrogen atom, a halogen atom, a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, a neopentyl group, a trifluoromethyl group, a pentafluoroethyl group, and 2.2. .2-Trifluoro-ethyl, perfluorohexyl, methoxy, ethoxy, tert-butoxy. Further, in the above formula (1), X and hydrazine are each independently water, a ketone compound having a carbon number of 1 to 10, an ether compound having a carbon number of 1 to 10, an ester compound having a carbon number of 1 to 1 Å, and a carbon number of 1 to 1. 6 nitrile compound. The ketone compound having a carbon number of 1 to 1 is preferably a ketone compound having 1 to 7 carbon atoms, and specific examples thereof include, for example, acetone, 2-butanone, 3-methyl-2-butanone, and 2-pentane. Ketone, Pinacolone, 3-pent-9- 200940553 ketone, 3-hexanone, 2-heptanone. The ether compound having 1 to 1 carbon atoms is preferably an ether compound having 1 to 6 carbon atoms, and specific examples thereof are dimethyl ether, methyl ethyl ether, diethyl ether, tetrahydrofuran, dioxane, and dipropylene. Ether. The ester compound having 1 to 10 carbon atoms is preferably an ester compound having 1 to 7 carbon atoms, and specific examples thereof include methyl acetate, ethyl acetate, propyl acetate, butyl acetate, and pentyl acetate. ), amyl acetate, methyl propionate, ethyl propionate, dimethyl carbonate, diethyl carbonate. Specific examples of the nitrile compound ^ having 1 to 6 carbon atoms are exemplified by acetonitrile and propionitrile. Preferred examples of X and Y are exemplified by water, acetone, 2-butanone, methyl acetate, methyl propionate, dimethyl carbonate, dimethyl ether, diethyl ether, tetrahydrofuran, dioxane, acetonitrile. . In the above formula (2), R5, R6, R7 and R8 each independently represent a hydrogen atom, a fluorine atom, a hydrocarbon group of carbon number 10, a toothed hydrocarbon group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms. The hydrocarbon group having 1 to 10 carbon atoms is preferably a hydrocarbon group having 1 to 7 carbon atoms, and specific examples thereof include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, and the like. Tributyl, neopentyl, n-hexyl, cyclohexyl, φ phenyl, benzyl, methylphenyl. Further, the halogenated hydrocarbon group having 1 to 10 carbon atoms is preferably a halogenated hydrocarbon group having 1 to 6 carbon atoms. Specific examples thereof may, for example, be chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, 2.2.2-'trifluoro-ethyl, pentafluoroethyl , perfluoropropyl, perfluorobutyl, perfluorohexyl', pentafluorophenyl. Further, the alkoxy group having 1 to 1 carbon atom is preferably an alkoxy group having 1 to 6 carbon atoms, and specific examples thereof include, for example, a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, and a positive electrode. Butoxy, isobutoxy, tert-butoxy, n-hexyloxy, phenoxy. Preferred examples of R5, R6, R7 and R8 are exemplified by, for example, a hydrogen atom, a fluorine atom, a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, a neopentyl group, -10-200940553 monofluoromethyl group, and a trifluoro group. Methyl, pentafluoroethyl, 2.2.2-trifluoro-ethyl, perfluorohexyl, methoxy, ethoxy, tert-butoxy. The synthesis method of the compound represented by the above formula (1) and formula (2) can be referred to D.

Rose and G· Wilkinson, J. Chem. Soc_ (A), 1791，（1 970)及 A.J. Lindsay and G. Wilkinson, J. Chem. Soc. Dalton Trans., 2321，（ 1 98 5)。Rose and G. Wilkinson, J. Chem. Soc_ (A), 1791, (1 970) and A.J. Lindsay and G. Wilkinson, J. Chem. Soc. Dalton Trans., 2321, (1 98 5).

❹ 以上述式（1)表示之二釕錯合物之具體例可舉例爲例如下列者：四（"-甲酸酯）（2-水合物）二釕（II,II)、四（/z-甲酸酯）二（丙酮）二釕（11,11)、四（"·甲酸酯）二（2 -丁酮）二釕（π，π) 、四（/Z-甲酸酯）二（二甲基醚）二釕（ΙΙ，Π)、四（以-甲酸酯）二（二乙基醚）二釕（II，II)、四（μ-甲酸酯）二（四氫呋喃）二釕（11，11)、四（//-甲酸酯）二（碳酸二甲酯）二釕（11，11)、四（ # -甲酸酯）二（乙酸甲酯）二釕（11，11)、四（# -甲酸酯）二（丙酸甲酯）二釕（11，11)、四（/ζ-甲酸酯）二（乙腈）二釕（Η,Η)、四（β-乙酸酯）（2-水合物）二釕（II，II)、四（//-乙酸酯）二（丙酮）二釕（II，II)、四（y-乙酸酯）二（2_ 丁酮）二釕（II，II) 、四（//-乙酸酯）二（二甲基醚）二釕（ΙΙ，Π)、四（#-乙酸酯）二（二乙基醚）二釕（π，π)、四（# -乙酸酯）二（四氫呋喃）二釕（11，11)、四（//-乙酸酯）二（碳酸二甲酯）二釕（π，^)、四（乙酸酯）二（乙酸甲酯）二釕（II，II)、四（"_乙酸酯）二（丙酸甲酯）二釕（II，II)、四（"-乙酸酯）二（乙腈）二釕（11,11)、四（y-丙酸酯）（2-水合物）二釕（II,II)、四（//-丙酸酯）二（丙酮）二釕（II，II)、四（"-丙酸酯）二（2-丁酮）二釕（II，II) -11 - 200940553 、四（#-丙酸酯）二（二甲基醚）二釕（IIJI)、四（//•丙酸酯）一（一乙基醚）二釕（II，II)、四（β_丙酸酯）二（四氫呋喃）二釕（11，11)、四（以_丙酸酯）二（碳酸二甲酯）二釕…，⑴、四（ # -丙酸酯）一（丙酸甲酯）二釕（π，π)、四（# _丙酸酯）二（乙腈）二釕（ΙΙ，ΙΙ)、Specific examples of the diterpene complex represented by the above formula (1) can be exemplified by, for example, the following: tetrakis ("-formate) (2-hydrate) diterpene (II, II), tetra (/ Z-formate) bis(acetone)difluorene (11,11), tetra (".formate) bis(2-butanone)difluorene (π,π), tetra (/Z-formate) Di(dimethyl ether) diterpene (ΙΙ, Π), tetra (or-formate) bis(diethyl ether) ruthenium (II, II), tetra (μ-formate) bis (tetrahydrofuran) Diterpenes (11,11), tetrakis (//-formate) bis (dimethyl carbonate) diterpene (11,11), tetra (#-formate) bis(methyl acetate) diterpene ( 11,11), tetrakis (#-formate) bis(methyl propionate) diterpene (11,11), tetrakis(/indole-formate) di(acetonitrile)dioxime (Η,Η), four (β-acetate) (2-hydrate) diterpene (II, II), tetra (//-acetate) di(acetone) diterpene (II, II), tetra (y-acetate) Di(2-butanone) diterpene (II, II), tetrakis (//-acetate) bis(dimethyl ether) diterpene (ΙΙ, Π), tetra (#-acetate) two (two Diethyl ether) π), tetra (#-acetate) bis(tetrahydrofuran)difluorene (11,11), tetrakis (//-acetate) bis(dimethyl carbonate) diterpene (π,^), four (b) Acid ester) bis (methyl acetate) diterpene (II, II), tetra ("-acetate) bis (methyl propionate) diterpene (II, II), tetra ("-acetate) Di(acetonitrile) diterpene (11,11), tetrakis (y-propionate) (2-hydrate) diterpene (II, II), tetrakis (//-propionate) di(acetone) dioxime ( II, II), tetra ("-propionate) bis(2-butanone) diterpene (II, II) -11 - 200940553, tetra (#-propionate) bis(dimethyl ether) diterpenoid (IIJI), tetrakis (//•propionate) mono(monoethyl ether) diterpene (II, II), tetra (β-propionate) bis(tetrahydrofuran) dioxime (11,11), four ( _propionate) bis (dimethyl carbonate) diterpene..., (1), tetra (#-propionate)-(methyl propionate) diterpene (π, π), tetra (# _ propionate) Di(acetonitrile) diterpene (ΙΙ, ΙΙ),

❹ 四（// -單氟乙酸酯）（2-水合物）二釕（ΙΙ，Π)、四（β ·單氟乙酸酯）二（丙酮）二釕（ΙΙ，Π)、四（#_單氟乙酸酯）（二2_ 丁酮）—釘（II，II)、四（〆-單氟乙酸醋）二（二甲醚）二金了 (11，11)、四（//-單氟乙酸酯）二（二乙醚）二釕（π，π)、四單m乙酸酯）二（四氫呋喃）二釕（ΙΙ，Π)、四（/ζ -單氟乙酸酯）一（碳酸一甲酯）二釕（II，II)、四（y _單氟乙酸酯）二（單氟乙酸一甲酯）一釕（II，II)、四（以-單氟乙酸酯）二（乙腈）二釕 (11,11)、四（V -三氟甲基乙酸酯）（2-水合物）二釕（Π，Π)、四（ β -三氟甲基乙酸酯）二（丙酮）二釕（ΙΙ，Π)、四-三氟甲基乙酸酯）（二2-丁酮）二釕（II，II)、四（V -三氟甲基乙酸酯）二 (二甲醚）二釕（11,11)、四（//-三氟甲基乙酸酯）二（二乙醚）二釕（II，II)、四（//-三氟甲基乙酸酯）二（四氫呋喃）二釕 (Π，ΙΙ)、四（y -三氟甲基乙酸酯）二（碳酸二甲酯）二釕（ΙΙ，Π) 、四（//-三氟甲基乙酸酯）二（三氟甲基乙酸二甲酯）二釕 (11,11)、四（以-三氟甲基乙酸酯）二（乙腈）二釕（11,11)、四（Μ ·四氟乙基乙酸酯）（2 -水合物）二釕（II，II)、四（ Μ -四氟乙基乙酸酯）二（丙酮）二釕（II，II)、四-四氟乙基乙酸酯）（二2-丁酮）二釕（II，II)、四（"-四氟乙基乙酸酯）二 -12- 200940553 (二甲醚）二釕（II，II)、四（#-四氟乙基乙酸酯）二（二乙醚）二釕（11，11)、四（//-四氟乙基乙酸酯）二（四氫呋喃）二釕 (11.11) 、四（/Z -四氟乙基乙酸酯）二（碳酸二甲酯）二釕（11,11) 、四（// -四氟乙基乙酸酯）二（四氟乙基乙酸二甲酯）二釕 (11.11) 、四（#-四氟乙基乙酸酯）二（乙腈）二釕（II，11)、四（#-甲氧基乙酸酯）（2-水合物）二釕（11，11)、四（//- 甲氧基乙酸酯）二（丙酮）二釕（II，II)、四（#-甲氧基乙酸酯 )(二2-丁酮）二釕（II,II)、四（//-甲氧基乙酸酯）二（二甲醚）二釕（II，II)、四（//-甲氧基乙酸酯）二（二乙醚）二釕（II，II) 、四（/Z-甲氧基乙酸酯）二（四氫呋喃）二釕（II,II)、四（//-甲氧基乙酸酯）二（碳酸二甲酯）二釕（11,11)、四（//-甲氧基乙酸酯）二（甲氧基乙酸二甲酯）二釕（II,II)、四（#-甲氧基乙酸酯）二（乙腈）二釕（11,11)、四（/Z-乙氧基乙酸酯）（2-水合物）二釕（II ,11)、四（//-乙氧基乙酸酯）二（丙酮）二釕（II,II)、四（//-乙氧基乙酸酯 )(二2-丁酮）二釕（II，II)、四（#-乙氧基乙酸酯）二（二甲醚）二釕（II，II)、四（#-乙氧基乙酸酯）二（二乙醚）二釕（II,II) 、四（//-乙氧基乙酸酯）二（四氫呋喃）二釕（II，II)、四（#-乙氧基乙酸酯）二（碳酸二甲酯）二釕（II,II)、四（/Z-乙氧基乙酸酯）二（乙氧基乙酸二甲酯）二釕（II,II)、四（#-乙氧基乙酸酯）二（乙腈）二釕（ΙΙ，Π)。該等中較佳者爲下列：四（//-甲酸酯）二（丙酮）二釕（11，11)、四（/2-甲酸酯）二（二乙醚）二釕（II，II)、四（/Z-甲酸酯）二（四氫呋喃）二釕 -13- 200940553 (11,11)、四 U-甲酸酯）二（乙腈）二釕（ΙΙ，Π)、四U -乙酸酯）二（丙酮）二釕（ΙΙ，ΙΙ)、四（V -乙酸酯）二（二乙醚）二釕（II，II)、四乙酸酯）二（四氫呋喃）二釕 (ΙΙ，ΙΙ)、四（；/ -乙酸酯）二（乙腈）二釕（ΙΙ，ΙΙ)、四（"-丙酸酯）二（丙酮）二釕（ΙΙ，Π)、四（#-丙酸酯）二（四氫呋喃）二釕（11,11)、四（μ-三氟甲基乙酸酯）二（丙酮）二釕（11，11)、四U-三氟甲基乙酸酯）二（二乙醚）二釕（II，II)、四（V-三氟甲基乙酸酯）二（四氫呋喃）二釕（II，Π)、四（//-三氟甲基乙酸酯）二（乙腈）二釕（ΙΙ，ΙΙ)、四（//-四氟乙基乙酸酯）二（丙酮）二釕（ΙΙ，Π)、四（/ζ-四氟乙基乙酸酯）二（二乙基醚）二釕（II，II)、四（Αί-四氟乙基乙酸酯）二（四氫呋喃）二釕（11，11)、四（//-四氟乙基乙酸酯）二（乙腈）二釕（ΙΙ，ΙΙ)、四（//-甲氧基乙酸酯）二（丙酮）二釕（11，11)、四（//-甲氧基乙酸酯）二（四氫呋喃）二釕（II,II)、四（//-甲氧基乙酸酯）二（乙腈）二釕（11,11)。以上述式（2)表示之二釕錯合物之具體例可舉例爲例如下列者：四（μ -甲酸酯）二釕（Π，ΙΙ)、四（Μ -乙酸酯）二釕（11,11) 、四（#-丙酸酯）二釕（11，11)、四（#-單氟乙酸酯）二釕 (ΙΙ，Π)、四（#-三氟甲基乙酸酯）二釕（11,11)、四（"-五氟乙基乙酸酯）二釕（ΙΙ，ΙΙ)、四（Μ-甲氧基乙酸酯）二釕（ΙΙ，ΙΙ) 、四（/ζ-乙氧基乙酸酯）二釕（Π，π)。 -14- 200940553 該等中較佳者爲下列者：四（V -甲酸酯）二釕（II,II)、四（"-乙酸酯）二釕（11,11) 、四（〆-丙酸酯）二釕（II,II)、四（# -三氟甲基乙酸酯）二釕 (Π，ιι)、四（#-五氟乙基乙酸酯）二釕（ΙΙ，Π)、四（"-甲氧基乙酸酯）二釕（ΙΙ，ΙΙ)。 ' 該等化合物可單獨或混合兩種以上作爲化學氣相成長材料使用。較好爲以單獨一種類之化合物作爲化學氣相成 0 長材料使用。本發明之化學氣相成長方法係使用上述化學氣相成長材料。本發明之化學氣相成長方法除使用上述化學氣相成長材料外，亦可使用該等本身習知之方法，例如可如下列般實施。 (1 )使本發明之化學氣相成長材料氣化，接著（2)將所得氣體加熱，經熱分解且使釕堆積在基體上。而且，上述〇步驟U)中，即使伴隨著本發明之化學氣相成長材料之分解，本發明之效果亦不致於受到抵減。此處使用之基體可使用例如玻璃、矽半導體、石英、金屬、金屬氧化物、合成樹脂等適當材料，但較好爲可耐釕化合物熱分解步驟之熱分解溫度之材料。上述步驟（1)中’使釕化合物氣化之溫度較好爲 100〜3 50 °c，更好爲 120〜3 00°c。上述步驟（2)中，使釕化合物熱分解之溫度較好爲 180 〜450°C，更好爲 200 〜400°C，最好爲 250~400t。 -15- 200940553 本發明之化學氣相成長方法可在惰性氣體存在或不存在下，亦可在還原性氣體存在或不存在下之任一條件下實施。另外，亦可在惰性氣體及還原性氣體同時存在之條件下實施。該惰性氣體可舉例爲例如氮氣、Μ氣、氦氣等。又，還原性氣體可舉例爲例如氫、氨等。尤其’由降低成膜之釕膜中雜質之目的，較好同時存在該還原性氣體。同時存在還原性氣體時，氛圍氣體中之還原性氣體之比例較 ^ 好爲1〜70莫耳％，更好爲3〜40莫耳％。又本發明之化學氣相成長方法可在氧化性氣體共存下實施。其中之氧化性氣體可舉例爲例如氧、一氧化碳、一氧化氮等。本發明之化學氣相成長方法可在加壓下、常壓下及減壓下之任一條件下實施。而且，較好在常壓下或減壓下實施，更好在15,OOOPa以下之壓力下實施。本發明之釕錯合物及化學成長材料於空氣中保存難以 p 產生氧化等劣化其保存安定性優異。若置於市售實驗用密閉容器中且保持在冷暗場所中，尤其是使容器內之氛圍氣體變成惰性氛圍氣體，則在1 5天左右材料不會產生劣化。如上述般獲得之釕膜由後述之實施例可明顯看出，保存安定性優異，純度及導電性高，可適用於例如配線電極之障壁膜、電鍍成長膜、電容電極等。實施例以下以實施例具體說明本發明。 -16- 200940553 實施例1 四（/z -乙酸酯）二釕（Π，ΙΙ)之合成使用高壓釜在6atm氫氣下使2.02 10克三氯化釕•三水合物、0.0138克亞當斯（Adam’s)氧化鉑觸媒、25毫升甲醇攪拌3小時，獲得藍色溶液。攪拌結束後’進行過濾，移到經氮氣置換之修連克（Schlenk)瓶中，於其中添加2.3 5 80 克乙酸鋰，且進行加熱回流1 8小時。回流結束後’進行熱時過濾，以甲醇洗淨3次’在8 0 °C下真空乾燥’獲得 0.9207克四（//-乙酸酯）二釕之茶色粉末。產率54%。對此處所得之固體實施元素分析後’碳：2 1.9 1 % ’氫 :2.70%。又四（g -乙酸酯）二釕之理論値爲碳：21.92%，氫：2.76%。 IR(KBr，cm·1) : 293 6vw， 1 5 5 6 vs ’ 1 444vs ’ 1 3 5 2 s > 1046m，944w，691s，621 w > 581w。 ❹ 實施例2 四（V -三氟乙酸酯）二（丙酮）二釕（Π，ΙΙ)之合成在經氮氣置換之修連克瓶中注入0.9059克四（/Ζ -乙酸酯）二釕、1.696克三氟乙酸鈉、28毫升三氟乙酸、4毫升三氟乙酸酐，且加熱回流3天。回流結束後’進行過濾獲得深紅色溶液。真空餾除溶劑’以醚萃取。再度真空餾除，且使用丙酮進行再結晶，以己烷洗淨後’真空乾燥，獲得1.3517克四（# -三氟乙酸酯）二（丙酮）二釕之紅紫色固體 -17- 200940553 。產率6 5 %。對此處所得之固體實施元素分析後，碳：22.19%，氫 :1.62%。又四（"-三氟乙酸酯）二（丙酮）二釕之理論値爲碳：2 1 · 8 3 %，氫：1 · 5 7 %。 19F-NMR(CDC13) <5 -91.68(s，CCF3)。圖 1。 IR(KBr，cm_1) : 2928w，2918w，1681s，1 644s，1 l 95vs ，1167s， 859m， 777m， 736s， 552m， 529m 〇 ❹ 實施例3 四（y -五氟丙酸酯）二（丙酮）二釕（Π，Π)之合成在經氮氣置換之修連克瓶中注入100.4毫克四（#-乙酸酯）二釕、194.1毫克三氟丙酸鈉、3.6毫升五氟丙酸、0.4 毫升五氟丙酸酐，且加熱回流3天。回流結束後，進行過濾獲得深紅色溶液。真空餾除溶劑，以醚萃取。再度真空餾除，且使用丙酮/己烷進行再結晶，以己烷洗淨後，經 H 真空乾燥，獲得122.4毫克四（μ-五氟丙酸酯）二（丙酮）二釕之紅紫色固體。產率5 5 %。對此處所得之固體實施元素分析後’碳：22.56%，氫 :1·53%。又四（# -五氟丙酸酯）二（丙酮）二釕之理論値爲碳：22.28%，氫：1 .25%。 19F-NMR(CDC13) δ -78.62(s - 1 2 F ’ C F 3) ’ -1 4 0 _ 2 1 (s ’ 8 F ，CF2)。圖 2。 IR(KBr，cm-1) : 2932w，2866w，1 683 s，1 670sh，1 639s ，1438m ， 1333m ， 1227s ， 1192sh > 1165s ， 1036s ， 832m -18- 200940553 ，737m， 553m 〇以下實施例中，比電阻係藉由NAPS〇N公司製造之探針電阻率測定器，型號「RT-80/RG-80」測定。膜厚及膜密度係藉由Philips公司製造之斜入射X射線分析裝置，型號「X’ Pert MRD」測定。ESCA光譜係藉由曰本電子 (股）製造之型號「JPS80」測定。又密著性之評價係以JIS K-5400爲準，以棋盤格膠帶法進行。 ❹ 實施例4 (1).在氮氣中將0.05克實施例1中獲得之四（#-乙酸酯）二釕（II，II)計量置於石英製之船型容器中，設置於石英製反應容器中。在反應容器內氣流之下游方向側附近放置貼附熱氧化膜之矽晶圓，且在室溫下使氮氣以300毫升/分鐘之流量流過反應容器內部歷時20分鐘。隨後使氮氣以1〇〇毫升/分鐘之流量流過反應容器中，進而使系統內成爲 φ 13Pa，且將反應容器於400 °C加熱15分鐘。自船型容器產生霧氣，且設置於附近之石英基板上發現堆積物。霧氣產生結束後，終止減壓，使氮氣流入系統中回復壓力，接著於101.3kPa下使氮氣以200毫升/分鐘之流量流入，反應容器之溫度上升至42(TC，就此保持約1小時後，在基板上獲得具有金屬光澤之膜。該膜之膜厚爲92 0埃。測定該膜之ESCA光譜後，在2 80eV與284eV觀察到屬於Ru3d軌道之峰，完全未看到源自其他元素之峰可理解爲金屬釕。又，對該釕膜以4端子法測定電阻率爲35 # Ω cm -19- 200940553 。該膜之膜密度爲12.0 g/cm3。對此處形成之釕膜以棋盤格膠帶法評價與基板之密著性，完全未看到基板與釕膜之剝離。 (2).保存安定性之確認係以加熱加速試驗實施對空氣之劣化性檢討。將1克四（以-乙酸酯）二釕（Π，ΙΙ)置於50毫升容量之石英製三頸燒瓶中，且將容器整體加熱至50 °C，隨後在常壓下以3升/分鐘之流量通入空氣3小時，四（〆-乙酸酯）二釕（II，11)外觀上並無變化。隨後，使容器回復至室溫，以無水氮氣置換容器之內部，且以與上述（1)同樣之要領實施成膜，在基板上獲得具有金屬光澤之膜。該膜之膜厚爲920埃。測定該膜之ESCA光譜後，在2 80eV與284eV觀察到屬於11113(1軌道之峰，完全未看到源自其他元素之峰可理解爲金屬釕。又，對該釕膜以4端子法測定電阻率爲3 5 // Ω cm 。該膜之膜密度爲12.Og/cm3。對此處形成之釕膜以棋盤格膠帶法評價與基板之密著性，完全未看到基板與釕膜之剝離，以空氣暴露加熱試驗未觀察到釕金屬膜質之劣化。實施例5 (1).在氮氣中將0.05克實施例1中獲得之四（// -乙酸酯）二釕（II，II)計量置於石英製之船型容器中，設置於石英製反應容器中。在反應容器內氣流之下游方向側附近放置貼附熱氧化膜之矽晶圓，且在室溫下使氫氣•氮氣之混合氣體（氫氣含量3體積％)以300毫升/分鐘之流量流過反應容器 -20- 200940553 內部歷時20分鐘。隨後使氫氣•氮氣之混合氣體（氫氣含量3體積％)以100毫升/分鐘之流量流過反應容器中，進而使系統內成爲13Pa，且將反應容器於400 °C加熱15分鐘。自船型容器產生霧氣，且設置於附近之石英基板上發現堆積物。霧氣產生結束後，終止減壓，使氮氣流入系統中回復壓力，接著於1〇1_3 kPa下使氫氣•氮氣之混合氣體（氫氣含量3體積％)以2 0 0毫升/分鐘之流量流入，反應容器之溫度上升至420 °C，就此保持約1小時後，在基板上獲得具有金屬光澤之膜。該膜之膜厚爲900埃。測定該膜之ESCA光譜後，在2 80eV與284eV觀察到屬於Ru3dW道之峰，完全未看到源自其他元素之峰可理解爲金屬釕。又，對該釕膜以4端子法測定電阻率爲28 # Ω cm 。該膜之膜密度爲12.0g/cm3。對此處形成之釕膜以棋盤格膠帶法評價與基板之密著性，完全未看到基板與釕膜之剝離。 (2).保存安定性之確認係以加熱加速試驗實施對空氣之劣化性檢討。將1克四（A -乙酸酯）二釕（Π，Π)置於50毫升容量之石英製三頸燒瓶中，且將容器整體加熱至50 °C，隨後在常壓下以3升/分鐘之流量使空氣通過歷時3小時，四（//-乙酸酯）二釕（11,11)在外觀上並無變化。隨後，使容器恢復至室溫，以無水氮氣置換容器之內部，且以與上述 (1)同樣之要領實施成膜，在基板上獲得具有金屬光澤之膜。該膜之膜厚爲900埃。測定該膜之ESCA光譜後’在280eV與28 4eV觀察到 -21 - 200940553 屬於Ru3d軌道之峰，完全未看到源自其他元素之峰可理解爲金屬釕。又，對該釕膜以4端子法測定電阻率爲28 // Ω cm 。該膜之膜密度爲12.Og/cm3。對此處形成之釕膜以棋盤格膠帶法評價與基板之密著性，完全未看到基板與釕膜之剝離，以空氣暴露加熱試驗未觀察到釕金屬膜質之劣化。實施例6 (1).在氮氣中將0.05克實施例2中獲得之四（μ -三氟乙酸酯）二（丙酮）二釕（11,11)計量置於石英製之船型容器中，設置於石英製反應容器中。在反應容器內氣流之下游方向側附近放置貼附熱氧化膜之矽晶圓，且在室溫下使氮氣以 3 00毫升/分鐘之流量流過反應容器內部歷時20分鐘。隨後使氮氣以1〇〇毫升/分鐘之流量流過反應容器中，進而使系統內成爲13Pa，且將反應容器於400 °C加熱15分鐘。自船型容器產生霧氣，且設置於附近之石英基板上發現堆積物。霧氣產生結束後，終止減壓，使氮氣流入系統中回復壓力，接著於101.3kPa下使氮氣以200毫升/分鐘之流量流入，反應容器之溫度上升至40(TC，就此保持約1小時後，在基板上獲得具有金屬光澤之膜。該膜之膜厚爲900埃。測定該膜之ESCA光譜後，在280eV與284eV觀察到屬於11113(1軌道之峰，完全未看到源自其他元素之峰可理解爲金屬釕。又，對該釕膜以4端子法測定電阻率爲2 1 // Ω cm 。該膜之膜密度爲12.Og/cm3。對此處形成之釕膜以棋盤格膠帶法評價與基板之密著性，完全未看到基板與釕膜之 -22- 200940553 剝離。 (2).保存安定性之確認係以加熱加速試驗實施對空氣之劣化性檢討。將1克四（Μ -三氟乙酸酯）二（丙酮）二釕 (II,II)置於50毫升容量之石英製三頸燒瓶中，且將容器整體加熱至50 °C ’隨後在常壓下以3升/分鐘之流量使空氣通過歷時3小時’四（y-三氟乙酸酯）二（丙酮）二釕（Π，Π)在外觀上並無變化。隨後，使容器回復至室溫，以乾燥氮氣置換容器之內部，且以與上述（1)同樣之要領實施成膜，在基板上獲得具有金屬光澤之膜。該膜之膜厚爲900埃。測定該膜之ESCA光譜後，在280eV與284eV觀察到屬於11113£1軌道之峰，完全未看到源自其他元素之峰可理解爲金屬釕。又，對該釕膜以4端子法測定電阻率爲2 1 " Ω cm 。該膜之膜密度爲12.0 g/cm3。對此處形成之釕膜以棋盤格膠帶法評價與基板之密著性，完全未看到基板與釕膜之剝離，以空氣暴露加熱試驗未觀察到釕金屬膜質之劣化。 ❹ 實施例7 (1).在氮氣中將0.05克實施例2中獲得之四（μ -三氟乙酸酯）二（丙酮）二釕（ΙΙ，ΙΙ)計量置於石英製之船型容器中， ' 設置於石英製反應容器中。在反應容器內氣流之下游方向側附近放置貼附熱氧化膜之矽晶圓，且在室溫下使氫氣· 氮氣之混合氣體（氫氣含量3體積％)以3 00毫升/分鐘之流量流過反應容器內部歷時20分鐘。隨後使氫氣•氮氣之混合氣體（氫氣含量3體積％)以1〇〇毫升/分鐘之流量流過反應容 -23- 200940553 器中，進而使系統內成爲13Pa，且將反應容器於400 °C加熱15分鐘。自船型容器產生霧氣，且設置於附近之石英基板上發現堆積物。霧氣產生結束後，終止減壓，使氮氣流入系統中回復壓力，接著於101.3 kP a下使氫氣•氮氣之混合氣體（氫氣含量3體積％)以200毫升/分鐘之流量流入，反應容器之溫度上升至400°C，就此保持約1小時後，在基板上獲得具有金屬光澤之膜。該膜之膜厚爲8 70埃。測定該膜之ESCA光譜後，在2 80eV與284eV觀察到屬於Ru3d軌道之峰，完全未看到源自其他元素之峰可理解爲金屬釕。又，對該釕膜以4端子法測定電阻率爲1 8 " Ω cm 。該膜之膜密度爲12.0g/cm3。對此處形成之釕膜以棋盤格膠帶法評價與基板之密著性，完全未看到基板與釕膜之剝離。 (2).保存安定性之確認係以加熱加速試驗實施對空氣之劣化性檢討。將1克四（/2 -三氟乙酸酯）二（丙酮）二釕 (ΙΙ，Π)置於50毫升容量之石英製三頸燒瓶中，且將容器整體加熱至50°C，隨後在常壓下以3升/分鐘之流量使空氣通過歷時3小時，四（//-三氟乙酸酯）二（丙酮）二釕（II,II)在外觀上並無變化。隨後，使容器回復至室溫，以無水氮氣置換容器之內部，且以與上述（1)同樣之要領實施成膜’在基板上獲得具有金屬光澤之膜。該膜之膜厚爲870埃。測定該膜之ESCA光譜後，在280eV與284eV觀察到屬於尺113(1軌道之峰，完全未看到源自其他元素之峰可理解爲金屬釕。又，對該釕膜以4端子法測定電阻率爲1 8 # Ω cm -24- 200940553 。該膜之膜密度爲12.0g/cm3。對此處形成之釕膜以棋盤格膠帶法評價與基板之密著性，完全未看到基板與釕膜之剝離，以空氣暴露加熱試驗未觀察到釕金屬膜質之劣化。實施例8 (1) .在氮氣中將0.05克實施例3中獲得之四（#-五氟丙酸酯）二（丙酮）二釕（II，II)計量置於石英製之船型容器中， ^ 設置於石英製反應容器中。在反應容器內氣流之下游方向側附近放置貼附熱氧化膜之矽晶圓，且在室溫下使氮氣以 3 00毫升/分鐘之流量流過反應容器內部歷時2 0分鐘。隨後使氮氣以100毫升/分鐘之流量流過反應容器中，進而使系統內成爲13Pa，且將反應容器於400 °C加熱15分鐘。自船型容器產生霧氣，且設置於附近之石英基板上發現堆積物。霧氣產生結束後，終止減壓，使氮氣流入系統中回復壓力，接著於101.3kPa下使氮氣以200毫升/分鐘之流量流入 Q ，反應容器之溫度上升至400°C，就此保持約1小時後，在基板上獲得具有金屬光澤之膜。該膜之膜厚爲600埃。測定該膜之ESCA光譜後，在2 80eV與284eV觀察到屬於Rum軌道之峰，完全未看到源自其他元素之峰可理解爲金屬釕。又’對該釕膜以4端子法測定電阻率爲1 6 // Ω cm 。該膜之膜密度爲12.0g/cm3。對此處形成之釕膜以棋盤格膠帶法評價與基板之密著性，完全未看到基板與釕膜之剝離。 (2) ·儲存安定性之確認係以加熱加速試驗實施對空氣 -25- 200940553 之劣化性檢討。將1克四（v-五氟丙酸酯）二（丙酮）二釕 (ΙΙ，Π)置於50毫升容量之石英製三頸燒瓶中，且將容器整體加熱至50 °C，隨後在常壓下以3升/分鐘之流量使空氣通過歷時3小時，四（# -五氟丙酸酯）二（丙酮）二釕（ΙΙ，Π)在外觀上並無變化。隨後，使容器回復至室溫，以乾燥氮氣置換容器之內部，且以與上述（1)同樣之要領實施成膜’在基板上獲得具有金屬光澤之膜。該膜之膜厚爲6 00埃。測定該膜之ESCA光譜後，在2 8 0eV與284eV觀察到屬於Ru3d軌道之峰，完全未看到源自其他元素之峰可理解爲金屬釕。又，對該釕膜以4端子法測定電阻率爲1 6 // Ω cm 。該膜之膜密度爲1 2.0g/cm3。對此處形成之釕膜以棋盤格膠帶法評價與基板之密著性’完全未看到基板與釕膜之剝離，以空氣暴露加熱試驗未觀察到釕金屬膜質之劣化。實施例9 (1).在氮氣中將〇·〇5克實施例3中獲得之四（μ -五氟丙酸酯）二（丙酮）二釕（II，II)計量置於石英製之船型容器中，設置於石英製反應容器中。在反應容器內氣流之下游方向側附近放置貼附熱氧化膜之矽晶圓，且在室溫下使氫氣· 氮氣之混合氣體（氫氣含量3體積％)以3〇〇毫升/分鐘之流量流過反應容器內部歷時20分鐘。隨後使氫氣•氮氣之混合氣體（氫氣含量3體積％)以1〇〇毫升/分鐘之流量流過反應容器中，進而使系統內成爲13Pa ’且將反應容器於400 °C加熱15分鐘。自船型容器產生霧氣’且設置於附近之石英基 -26- 200940553 板上發現堆積物。霧氣產生結束後，終止減壓，使氮氣流入系統中回復壓力，接著於101.3kPa下使氫氣•氮氣之混合氣體（氫氣含量3體積％)以2 00毫升/分鐘之流量流入，反應容器之溫度上升至400°C，就此保持約1小時後，在基板上獲得具有金屬光澤之膜。該膜之膜厚爲5 7 0埃。測定該膜之ESCA光譜後，在280eV與284eV觀察到屬於11113(1軌道之峰，完全未看到源自其他元素之峰可理解爲金屬釕。又，對該釕膜以4端子法測定電阻率爲2 1 " Ω cm 。該膜之膜密度爲12_0g/cm3。對此處形成之釕膜以棋盤格膠帶法評價與基板之密著性，完全未看到基板與釕膜之剝離。 (2).保存安定性之確認係以加熱加速試驗實施對空氣之劣化性檢討。將1克四（// -五氟丙酸酯）二（丙酮）二釕 (II,II)置於5〇毫升容量之石英製三頸燒瓶中，且將容器整體加熱至50°c，隨後在常壓下以3升/分鐘之流量使空氣通過歷時3小時’四（#-五氟丙酸酯）二（丙酮）二釕（π，ΐι)在外觀上並無變化。隨後，使容器回復至室溫，以無水氮氣置換容器之內部’且以與上述（1)同樣之要領實施成膜，在基板上獲得具有金屬光澤之膜。該膜之膜厚爲5 70埃。測定該膜之ESCA光譜後，在280eV與284eV觀察到屬於Ru3d軌道之峰，完全未看到源自其他元素之峰可理解爲金屬釕。又，對該釕膜以4端子法測定電阻率爲2 1 # Ω cm 。該膜之膜密度爲12.0g/cm3。對此處形成之釕膜以棋盤格膠帶法評價與基板之密著性，完全未看到基板與釕膜之 -27- 200940553 ，剝離，以空氣暴露加熱試驗未觀察到釕金屬膜質之劣化。比較例1 (1) .在氮氣中將0.01克市售雙（乙基環戊二烯基）釕計量置於石英製之船型容器中，設置於石英製反應容器中。在反應容器內氣流之下游方向側附近放置石英基板，且在室溫下使氧氣•氮氣之混合氣體（氧氣含量5體積％)以250 毫升/分鐘之流量流過反應容器內部歷時60分鐘。隨後使氧氣•氮氣之混合氣體（氧氣含量5體積％)以20毫升/分鐘之流量流過反應容器中，進而使系統內成爲1 l〇Pa，且將反應容器於3 50 °C加熱30分鐘。自船型容器產生霧氣，且設置於附近之石英基板上發現堆積物。霧氣產生結束後，終止減壓，使氮氣流入系統中恢復壓力，接著於101 .3kPa 下使氮氣以200毫升/分鐘之流量流入，就此保持約1小時後，在基板上獲得具有金屬光澤之膜。該膜之膜厚爲850 埃。測定該膜之ESCA光譜後，在280eV與284eV觀察到屬於Ru3d軌道之峰，完全未看到源自其他元素之峰可判定爲金屬釕。針對該釕膜以4端子法測定電阻率爲25 // Ω cm 。又，該膜之膜密度爲12.1 g/cm3。對此處形成之釕膜以棋盤格膠帶法評價與基板之密著性，完全未看到基板與釕膜之剝離。 (2) .對市售雙（乙基環戊二烯）釕，以與實施例1之（2) 相同，以加熱加速試驗實施對空氣之劣化性檢討。將1克雙（乙基環戊二烯）釕置於50毫升容量之石英製三頸燒瓶中 -28 - 200940553 ，且將容器整體加熱至50°C，隨後在常壓下以3升/分鐘之流量使空氣通過3小時。由此’本來是淺黃色透明液體狀之雙（乙基環戊二烯）釕之外觀變化成不透明之黃色液體狀。隨後，使容器回復至室溫，以無水氮氣置換容器之內部，且以與上述（1)同樣之要領實施成膜’在基板上獲得具有黑色金屬光澤之膜。該膜之膜厚爲30 0埃。測定該膜之ESCA光譜後’在280eV與284eV觀察到屬於Ru3d軌道之峰，完全未看到源自其他元素之峰可理解爲金屬釕。又’對該釕膜以4端子法測定電阻率後’爲 7 8 # Qcm並未顯示低導電率。該膜之膜密度爲10.8g/cm3。對此處形成之釕膜以棋盤格膠帶法評價與基板之密著性， 100個棋盤格釕膜中有80個釕膜剝離，釕膜質顯著下降。因此，雙（乙基環戊二烯）釕由空氣加熱試驗確定釕金屬膜質劣化。如上述，使用本發明之化學氣相成長材料時，可獲得長期保存安定性優異，且殘留之雜質少之良好品質釕膜。又，使用該化學氣相成長材料可以簡易方法形成釕膜。【圖式簡單說明】圖1爲實施例2中所得之四（μ -三氟乙酸酯）二（丙酮）二釕之19F_NMR光譜圖。圖2爲實施例3中所得之四（μ-五氟丙酸酯）二（丙酮）二釕之19F-NMR光譜圖。 -29-❹ tetra (//-monofluoroacetate) (2-hydrate) diterpene (ΙΙ, Π), tetra (β · monofluoroacetate) di (acetone) diterpene (ΙΙ, Π), four ( #_monofluoroacetate) (di-2-butanone)-nail (II, II), tetrakis(〆-monofluoroacetic acid vinegar) di(dimethyl ether) di gold (11,11), four (// -monofluoroacetate) bis(diethyl ether) dioxane (π, π), tetra-mono-m acetate) bis(tetrahydrofuran)dioxin (ΙΙ,Π), tetrakis(/ζ-monofluoroacetate) Monomethyl carbonate (II, II), tetrakis (y-monofluoroacetate) bis (monomethyl monofluoroacetate) monoterpene (II, II), tetra (mono-fluoroacetic acid) Ester) bis(acetonitrile) ruthenium (11,11), tetrakis(V-trifluoromethyl acetate) (2-hydrate) diterpene (Π, Π), tetra (β-trifluoromethylacetic acid) Ester) bis(acetone)dioxin (ΙΙ,Π), tetra-trifluoromethyl acetate) (di-2-butanone) diterpene (II, II), tetra (V-trifluoromethyl acetate) Di(dimethyl ether) dioxane (11,11), tetrakis (//-trifluoromethyl acetate) bis(diethyl ether) dioxane (II, II), tetrakis (//-trifluoromethyl) Acetate) II Hydrogenfuran) Diterpenes (Π,ΙΙ), Tetrakis(y-trifluoromethyl acetate) Di(dimethyl carbonate) Diterpenes (ΙΙ,Π), Tetrakis (//-Trifluoromethyl acetate) Di(trifluoromethylacetate dimethyl ester) dioxane (11,11), tetrakis(-trifluoromethyl acetate) di(acetonitrile)difluorene (11,11), tetrakis(tetrafluoro) Ethyl acetate) (2-hydrate) diterpene (II, II), tetrakis(Μ-tetrafluoroethyl acetate) di(acetone) diterpene (II, II), tetra-tetrafluoroethyl Acetate) (di-2-butanone) diterpene (II, II), tetra ("-tetrafluoroethyl acetate) di-12- 200940553 (dimethyl ether) diterpene (II, II), Tetraki(#-tetrafluoroethyl acetate) bis(diethyl ether) dioxane (11,11), tetrakis(//-tetrafluoroethyl acetate) bis(tetrahydrofuran)dioxin (11.11), four ( /Z-tetrafluoroethyl acetate) bis(dimethyl carbonate) dioxane (11,11), tetrakis(//-tetrafluoroethyl acetate) bis(tetrafluoroethyl acetate dimethyl ester) Diterpenes (11.11), tetrakis (#-tetrafluoroethyl acetate) di(acetonitrile) diterpene (II, 11), tetrakis (#-methoxyacetate) (2-hydrate) diterpene ( 11 11), tetrakis (//- methoxyacetate) di(acetone) diterpene (II, II), tetra (#-methoxyacetate) (di-2-butanone) diterpene (II, II), tetrakis (//-methoxyacetate) bis(dimethyl ether) diterpene (II, II), tetrakis (//-methoxyacetate) di(diethyl ether) dioxane (II , II), tetrakis (/Z-methoxyacetate) bis(tetrahydrofuran)dioxin (II, II), tetrakis (//-methoxyacetate) bis (dimethyl carbonate) diterpene ( 11,11), tetrakis (//-methoxyacetate) bis(methoxyacetic acid dimethyl ester) diterpene (II, II), tetra (#-methoxyacetate) di(acetonitrile) Diterpenes (11,11), tetrakis (/Z-ethoxyacetate) (2-hydrate) diterpene (II, 11), tetrakis (//-ethoxyacetate) di(acetone) Diterpenes (II, II), tetrakis (//-ethoxyacetate) (di-2-butanone) diterpene (II, II), tetra (#-ethoxy acetate) di (dimethyl Ether) Diterpenes (II, II), tetrakis (#-ethoxyacetate) bis(diethyl ether) dioxane (II, II), tetrakis (//-ethoxyacetate) bis (tetrahydrofuran) Diterpenoid (II, II), tetra (#-ethoxy acetate) di (carbonic acid) Methyl ester) Diterpenes (II, II), tetrakis (/Z-ethoxy acetate) bis (ethoxy dimethyl acetate) diterpene (II, II), tetra (#-ethoxy acetic acid Ester) bis(acetonitrile) diterpene (ΙΙ, Π). The preferred ones are as follows: tetrakis (//-formate) bis(acetone)dioxin (11,11), tetrakis(/2-formate)di(diethyl ether)dioxin (II, II) ), tetrakis (/Z-formate) bis(tetrahydrofuran)difluorene-13- 200940553 (11,11), tetra-U-formate) bis(acetonitrile) diterpene (ΙΙ,Π), four U-B Acid ester) di(acetone) diterpene (ΙΙ, ΙΙ), tetra (V-acetate) bis (diethyl ether) diterpene (II, II), tetraacetate) bis(tetrahydrofuran) dioxime (ΙΙ, ΙΙ), four (; / - acetate) bis (acetonitrile) diterpene (ΙΙ, ΙΙ), tetra ("-propionate) di (acetone) diterpene (ΙΙ, Π), four (#-C Acid ester) bis(tetrahydrofuran)difluorene (11,11), tetrakis (μ-trifluoromethyl acetate) di(acetone)dioxin (11,11), tetra-U-trifluoromethyl acetate) Di(diethyl ether) diterpene (II, II), tetra (V-trifluoromethyl acetate) di(tetrahydrofuran) diindole (II, fluorene), tetra (//-trifluoromethyl acetate) Di(acetonitrile) diterpene (ΙΙ, ΙΙ), tetrakis (//-tetrafluoroethyl acetate) di(acetone) diterpene (ΙΙ, Π), four (/ Ζ-tetrafluoroethyl acetate) bis(diethyl ether) ruthenium (II, II), tetrakis(Αί-tetrafluoroethyl acetate) bis(tetrahydrofuran) ruthenium (11,11), four (//-tetrafluoroethyl acetate) bis(acetonitrile) diterpene (ΙΙ, ΙΙ), tetrakis (//-methoxyacetate) di(acetone) dioxime (11,11), four ( //-Methoxyacetate) bis(tetrahydrofuran)dioxin (II, II), tetrakis (//-methoxyacetate) bis (acetonitrile) dioxime (11, 11). Specific examples of the diterpene complex represented by the above formula (2) can be exemplified by, for example, the following: tetra(μ-formate) dioxime (Π, ΙΙ), tetrakis(Μ-acetate) dioxime ( 11,11), tetra (#-propionate) diterpene (11,11), tetra (#-monofluoroacetate) diterpene (ΙΙ, Π), tetra (#-trifluoromethyl acetate) Diterpenoids (11,11), tetrakis ("-pentafluoroethyl acetate) diterpene (ΙΙ, ΙΙ), tetrakis(Μ-methoxyacetate) diterpene (ΙΙ, ΙΙ), four (/ζ-ethoxyacetate) diterpene (Π, π). -14- 200940553 The preferred ones are: (V-formate) diterpene (II, II), tetra ("-acetate) diterpene (11,11), tetra (〆 -propionate) Diterpenes (II, II), tetra (#-trifluoromethyl acetate) diterpene (Π, ιι), tetra (#-pentafluoroethyl acetate) diterpene (ΙΙ, Π), four ("-methoxyacetate) diterpene (ΙΙ, ΙΙ). 'These compounds may be used singly or in combination of two or more kinds as chemical vapor grown materials. It is preferred to use a single compound as a chemical vapor phase to form a long material. The chemical vapor phase growth method of the present invention uses the above chemical vapor grown material. The chemical vapor phase growth method of the present invention may be carried out by using a conventionally known method in addition to the above chemical vapor grown material, and for example, it can be carried out as follows. (1) The chemical vapor-grown growth material of the present invention is vaporized, and then (2) the obtained gas is heated, thermally decomposed, and the ruthenium is deposited on the substrate. Further, in the above step U), even if the chemical vapor-grown growth material of the present invention is decomposed, the effects of the present invention are not impaired. As the substrate to be used herein, a suitable material such as glass, germanium semiconductor, quartz, metal, metal oxide, synthetic resin or the like can be used, but a material which is resistant to the thermal decomposition temperature of the thermal decomposition step of the hydrazine compound is preferable. The temperature at which the hydrazine compound is vaporized in the above step (1) is preferably from 100 to 3 50 ° C, more preferably from 120 to 30,000 ° C. In the above step (2), the temperature at which the ruthenium compound is thermally decomposed is preferably from 180 to 450 ° C, more preferably from 200 to 400 ° C, most preferably from 250 to 400 t. -15- 200940553 The chemical vapor phase growth method of the present invention can be carried out in the presence or absence of an inert gas or in the presence or absence of a reducing gas. Further, it may be carried out under the conditions in which an inert gas and a reducing gas are simultaneously present. The inert gas can be exemplified by, for example, nitrogen, helium, neon, or the like. Further, the reducing gas may, for example, be hydrogen, ammonia or the like. In particular, it is preferred that the reducing gas be present at the same time for the purpose of reducing impurities in the film of the film. When a reducing gas is present, the ratio of the reducing gas in the atmosphere is preferably from 1 to 70 mol%, more preferably from 3 to 40 mol%. Further, the chemical vapor phase growth method of the present invention can be carried out in the presence of an oxidizing gas. Among them, the oxidizing gas can be exemplified by, for example, oxygen, carbon monoxide, nitrogen monoxide or the like. The chemical vapor phase growth method of the present invention can be carried out under any conditions of pressure, atmospheric pressure and pressure reduction. Further, it is preferably carried out under normal pressure or under reduced pressure, and more preferably under a pressure of 1,500 OOPa. The ruthenium complex and the chemical growth material of the present invention are difficult to store in air, and are deteriorated in oxidation and the like, and are excellent in storage stability. If it is placed in a commercially available closed container and kept in a cool dark place, especially if the atmosphere in the container becomes an inert atmosphere, the material does not deteriorate in about 15 days. The ruthenium film obtained as described above is apparent from the examples described later, and has excellent storage stability, high purity and conductivity, and is applicable to, for example, a barrier film of a wiring electrode, a plating growth film, a capacitor electrode, and the like. EXAMPLES Hereinafter, the present invention will be specifically described by way of examples. -16- 200940553 Example 1 Synthesis of tetrakis (/z-acetate) dioxime (Π, ΙΙ) Using an autoclave to make 2.02 10 g of antimony trichloride • trihydrate, 0.018 g of Adams under 6 atm of hydrogen (Adam's The platinum oxide catalyst and 25 ml of methanol were stirred for 3 hours to obtain a blue solution. After the completion of the stirring, the mixture was filtered, transferred to a nitrogen-substituted Schlenk bottle, and 2.3 5 80 g of lithium acetate was added thereto, and heated under reflux for 18 hours. After the completion of the reflux, it was filtered while hot, and washed with methanol three times to dry under vacuum at 80 ° C to obtain 0.9207 g of a tan powder of tetrakis (//-acetate) dioxime. The yield was 54%. After performing elemental analysis on the solid obtained here, 'carbon: 21.9 1% 'hydrogen: 2.70%. The theoretical theory of four (g-acetate) diterpene is carbon: 21.92%, hydrogen: 2.76%. IR (KBr, cm·1): 293 6vw, 1 5 5 6 vs ' 1 444vs ' 1 3 5 2 s > 1046m, 944w, 691s, 621 w > 581w.实施 Example 2 Synthesis of tetrakis(V-trifluoroacetate) bis(acetone)dioxime (Π,ΙΙ) 0.9059 g of tetrakis(/Ζ-acetate) was injected into a Nitrix-replaced repair bottle.钌, 1.696 g of sodium trifluoroacetate, 28 ml of trifluoroacetic acid, 4 ml of trifluoroacetic anhydride, and heating under reflux for 3 days. After the end of the reflux, filtration was carried out to obtain a deep red solution. The vacuum distillation solvent was extracted with ether. The mixture was again evaporated in vacuo, and then recrystallised from acetone, washed with hexane and then dried in vacuo to give <RTI ID=0.0>>> The yield was 6 5 %. After performing elemental analysis on the solid obtained here, carbon: 22.19%, hydrogen: 1.62%. The theoretical enthalpy of the fourth ("-trifluoroacetate) bis(acetone) dioxime is carbon: 2 1 · 8 3 %, hydrogen: 1 · 5 7 %. 19F-NMR (CDC13) <5-91.68 (s, CCF3). figure 1. IR (KBr, cm_1): 2928w, 2918w, 1681s, 1 644s, 1 l 95vs, 1167s, 859m, 777m, 736s, 552m, 529m 实施 Example 3 Tetrakis(y-pentafluoropropionate) di(acetone) Synthesis of diterpene (Π, Π) Injected 100.4 mg of tetrakis (#-acetate) dioxime, 194.1 mg of sodium trifluoropropionate, 3.6 ml of pentafluoropropionic acid, 0.4 ml in a Nitrix-replaced repair bottle. Pentafluoropropionic anhydride was heated and refluxed for 3 days. After the reflux was completed, filtration was carried out to obtain a deep red solution. The solvent was evaporated in vacuo and extracted with ether. After vacuum distillation, it was recrystallized from acetone/hexane, washed with hexane, and dried in vacuo to give 122.4 mg of tetras(penta-pentafluoropropionate) bis(acetone) bismuth reddish purple solid. . The yield was 5 5 %. After performing elemental analysis on the solid obtained here, 'carbon: 22.56%, hydrogen: 1.53%. The theoretical theory of the four (#-pentafluoropropionate) di(acetone) dioxime is carbon: 22.28%, hydrogen: 1.25%. 19F-NMR (CDC13) δ -78.62 (s - 1 2 F ' C F 3) '1 - 1 4 0 _ 2 1 (s ' 8 F , CF 2 ). figure 2. IR (KBr, cm-1): 2932w, 2866w, 1 683 s, 1 670sh, 1 639s, 1438m, 1333m, 1227s, 1192sh > 1165s, 1036s, 832m -18- 200940553, 737m, 553m 〇 In the following examples The specific resistance was measured by a probe resistivity meter manufactured by NAPS Corporation, model number "RT-80/RG-80". The film thickness and film density were measured by an oblique incident X-ray analyzer manufactured by Philips, Model No. "X' Pert MRD". The ESCA spectrum was measured by the model "JPS80" manufactured by Sakamoto Electronics Co., Ltd. The evaluation of the adhesion was carried out by the checkerboard tape method based on JIS K-5400.实施 Example 4 (1). 0.05 g of the (#-acetate) diterpene (II, II) obtained in Example 1 was metered in a vessel made of quartz in a nitrogen atmosphere, and set in a quartz reaction. In the container. A tantalum wafer to which a thermal oxide film was attached was placed in the vicinity of the downstream side of the gas flow in the reaction vessel, and nitrogen gas was allowed to flow through the inside of the reaction vessel at a flow rate of 300 ml/min for 20 minutes at room temperature. Subsequently, nitrogen gas was passed through the reaction vessel at a flow rate of 1 Torr/min, thereby making the inside of the system φ 13 Pa, and the reaction vessel was heated at 400 ° C for 15 minutes. The ship-type container generates mist and deposits are found on the nearby quartz substrate. After the completion of the mist generation, the pressure reduction was terminated, the nitrogen gas was introduced into the system to recover the pressure, and then nitrogen gas was flowed at a flow rate of 200 ml/min at 101.3 kPa, and the temperature of the reaction vessel was raised to 42 (TC, which was maintained for about 1 hour, A film having a metallic luster was obtained on the substrate. The film thickness of the film was 92 0 Å. After measuring the ESCA spectrum of the film, a peak belonging to the Ru3d orbital was observed at 2 80 eV and 284 eV, and no other element was observed. The peak can be understood as a metal ruthenium. Further, the ruthenium film is measured by a 4-terminal method with a resistivity of 35 # Ω cm -19- 200940553. The film density of the film is 12.0 g/cm3. The adhesion of the substrate to the substrate was evaluated by the cell tape method, and the peeling of the substrate and the ruthenium film was not observed at all. (2) The confirmation of the preservation stability was carried out by the heating acceleration test to carry out a review of the deterioration of the air. - Acetate) Diterpene (Π, ΙΙ) was placed in a 50 ml quartz three-necked flask, and the whole of the vessel was heated to 50 ° C, and then air was introduced at a flow rate of 3 liter / minute under normal pressure. 3 hours, four (〆-acetate) diterpenes (II, 11) There is no change in the above. Then, the container is returned to room temperature, the inside of the container is replaced with anhydrous nitrogen, and film formation is carried out in the same manner as in the above (1), and a film having a metallic luster is obtained on the substrate. The thickness was 920 angstroms. After measuring the ESCA spectrum of the film, it was observed that it was 11113 (1 orbital peak) at 2 80 eV and 284 eV, and the peak derived from other elements was not observed at all, which was understood to be metal ruthenium. The resistivity was measured by the 4-terminal method to be 3 5 // Ω cm. The film density of the film was 12.Og/cm3. The adhesion of the film formed here was evaluated by the checkerboard tape method and the adhesion to the substrate was not observed at all. To the peeling of the substrate from the ruthenium film, no deterioration of the ruthenium metal film quality was observed by the air exposure heating test. Example 5 (1). 0.05 g of the tetra(//-acetate) obtained in Example 1 was placed under nitrogen. The second (II, II) metering is placed in a quartz vessel and placed in a quartz reaction vessel. A silicon wafer with a thermal oxide film attached to the downstream side of the gas stream in the reaction vessel is placed at room temperature. Under a hydrogen/nitrogen mixed gas (hydrogen content of 3 vol%) to 30 A flow rate of 0 ml/min was passed through the reaction vessel -20-200940553 for 20 minutes. Then a mixture of hydrogen and nitrogen (hydrogen content of 3 vol%) was passed through the reaction vessel at a flow rate of 100 ml/min to further the system. The inside was 13 Pa, and the reaction vessel was heated at 400 ° C for 15 minutes. The mist was generated from the ship type container, and the deposit was found on the nearby quartz substrate. After the mist generation was completed, the pressure reduction was terminated, and the nitrogen gas was flowed into the system to restore the pressure. Then, a mixed gas of hydrogen and nitrogen (hydrogen content of 3 vol%) was flowed at a flow rate of 200 ml/min at 1〇1_3 kPa, and the temperature of the reaction vessel was raised to 420 ° C, and it was maintained for about 1 hour. A film having a metallic luster is obtained on the substrate. The film had a film thickness of 900 angstroms. After the ESCA spectrum of the film was measured, a peak belonging to the Ru3dW track was observed at 2 80 eV and 284 eV, and a peak derived from other elements was not observed at all as a metal ruthenium. Further, the resist film was measured by a 4-terminal method to have a resistivity of 28 # Ω cm . The film had a film density of 12.0 g/cm3. The enamel film formed here was evaluated for adhesion to the substrate by a checkerboard tape method, and peeling of the substrate and the ruthenium film was not observed at all. (2). Confirmation of preservation stability The air deterioration test was carried out by a heating acceleration test. One gram of tetrakis(A-acetate) diterpene (Π, Π) was placed in a 50-mL quartz three-necked flask, and the whole of the vessel was heated to 50 ° C, followed by 3 liters under normal pressure. The flow rate in minutes allowed the air to pass for 3 hours, and the tetrakis (//-acetate) diterpene (11, 11) did not change in appearance. Subsequently, the container was returned to room temperature, the inside of the container was replaced with anhydrous nitrogen, and film formation was carried out in the same manner as in the above (1), and a film having a metallic luster was obtained on the substrate. The film had a film thickness of 900 angstroms. After measuring the ESCA spectrum of the film, -21 - 200940553 was observed to be a peak of Ru3d orbital at 280 eV and 28 4eV, and a peak derived from other elements was not observed at all as a metal ruthenium. Further, the resistivity of the tantalum film was measured by a 4-terminal method to be 28 // Ω cm . The film had a film density of 12.0 g/cm3. The enamel film formed here was evaluated for adhesion to the substrate by a checkerboard tape method, and peeling of the substrate and the ruthenium film was not observed at all, and deterioration of the ruthenium metal film quality was not observed by the air exposure heating test. Example 6 (1). In a nitrogen gas, 0.05 g of the tetrakis (μ-trifluoroacetate) di(acetone) dioxime (11, 11) obtained in Example 2 was metered in a vessel made of quartz. It is placed in a quartz reaction vessel. A tantalum wafer to which a thermal oxide film was attached was placed in the vicinity of the downstream side of the gas flow in the reaction vessel, and nitrogen gas was allowed to flow through the inside of the reaction vessel at a flow rate of 300 ml/min for 20 minutes at room temperature. Subsequently, nitrogen gas was passed through the reaction vessel at a flow rate of 1 Torr/min, thereby making the inside of the system 13 Pa, and the reaction vessel was heated at 400 ° C for 15 minutes. A mist is generated from the ship-shaped container, and deposits are found on the quartz substrate in the vicinity. After the end of the mist generation, the pressure was reduced, the nitrogen gas was flowed into the system to restore the pressure, and then nitrogen gas was flowed at a flow rate of 200 ml/min at 101.3 kPa, and the temperature of the reaction vessel was raised to 40 (TC, and after about 1 hour, A film having a metallic luster was obtained on the substrate. The film thickness of the film was 900 angstrom. After measuring the ESCA spectrum of the film, it was observed to be 11113 (1 orbital peak) at 280 eV and 284 eV, and no other elements were observed at all. The peak can be understood as a metal ruthenium. Further, the resistivity of the ruthenium film measured by a 4-terminal method is 2 1 // Ω cm. The film density of the film is 12.Og/cm 3 . The ruthenium film formed here is in a checkerboard The tape method was used to evaluate the adhesion to the substrate, and the peeling of the substrate and the ruthenium film -22-200940553 was not observed at all. (2) The confirmation of the preservation stability was carried out by the heating acceleration test to carry out a review of the deterioration of the air. Tetrakis(Μ-trifluoroacetate) bis(acetone)dioxin (II, II) was placed in a 50 ml quartz three-necked flask, and the whole of the vessel was heated to 50 ° C. Then, under normal pressure, 3 liters / minute flow allows air to pass for 3 hours 'four (y-trifluoroethyl) The ester) di(acetone) dioxime (Π, Π) did not change in appearance. Subsequently, the vessel was returned to room temperature, the inside of the vessel was replaced with dry nitrogen, and film formation was carried out in the same manner as in the above (1). A film having a metallic luster was obtained on the substrate. The film thickness of the film was 900 angstroms. After measuring the ESCA spectrum of the film, a peak of 11113 £1 orbit was observed at 280 eV and 284 eV, and no other elements were observed. The peak can be understood as a metal ruthenium. Further, the ruthenium film is measured by a 4-terminal method with a resistivity of 2 1 " Ω cm . The film density of the film is 12.0 g/cm 3 . The ruthenium film formed here is in a checkerboard The adhesion between the substrate and the ruthenium film was not observed by the tape method, and no deterioration of the ruthenium metal film was observed by the air exposure heating test. 实施 Example 7 (1). 0.05 g was carried out in nitrogen gas. The tetrakis (μ-trifluoroacetate) di(acetone) dioxime (ΙΙ, ΙΙ) obtained in Example 2 was metered in a vessel made of quartz, and was placed in a reaction vessel made of quartz. A twin crystal attached with a thermal oxide film is placed near the downstream side And a mixed gas of hydrogen and nitrogen (hydrogen content of 3 vol%) was allowed to flow through the inside of the reaction vessel at a flow rate of 300 ml/min for 20 minutes at room temperature. Then, a mixed gas of hydrogen and nitrogen (hydrogen content of 3 volumes) was used. %) Flowed through the reaction volume -23-200940553 at a flow rate of 1 〇〇 ml/min, thereby making the inside of the system 13 Pa, and heating the reaction vessel at 400 ° C for 15 minutes. The mist was generated from the ship type container and was set at Deposits were found on the nearby quartz substrate. After the mist was generated, the decompression was terminated, and the nitrogen gas was introduced into the system to restore the pressure. Then, a mixed gas of hydrogen and nitrogen (hydrogen content of 3 vol%) was made at 200 ml/min at 101.3 kPa. After a minute flow rate, the temperature of the reaction vessel was raised to 400 ° C, and after maintaining for about 1 hour, a film having a metallic luster was obtained on the substrate. The film had a film thickness of 8,70 angstroms. After the ESCA spectrum of the film was measured, a peak belonging to the Ru3d orbital was observed at 2 80 eV and 284 eV, and a peak derived from other elements was not observed at all as a metal ruthenium. Further, the resistivity of the tantalum film was measured by a four-terminal method to be 1 8 " Ω cm . The film had a film density of 12.0 g/cm3. The enamel film formed here was evaluated for adhesion to the substrate by a checkerboard tape method, and peeling of the substrate and the ruthenium film was not observed at all. (2). Confirmation of preservation stability The air deterioration test was carried out by a heating acceleration test. 1 gram of tetrakis(/2-trifluoroacetate) bis(acetone) ruthenium (ΙΙ, Π) was placed in a 50 ml volume quartz three-necked flask, and the whole of the vessel was heated to 50 ° C, followed by Air was passed at a flow rate of 3 liters/min under normal pressure for 3 hours, and tetrakis(//-trifluoroacetate) bis(acetone)dioxin (II, II) did not change in appearance. Subsequently, the container was returned to room temperature, and the inside of the container was replaced with anhydrous nitrogen, and film formation was carried out in the same manner as in the above (1) to obtain a film having a metallic luster on the substrate. The film had a film thickness of 870 angstroms. After measuring the ESCA spectrum of the film, it was observed at 280 eV and 284 eV that it was a ruler 113 (a peak of one orbital, and a peak derived from other elements was not observed at all) as a metal ruthenium. Further, the ruthenium film was measured by a 4-terminal method. The resistivity was 1 8 # Ω cm -24- 200940553. The film density of the film was 12.0 g/cm3. The adhesion of the film formed here was evaluated by the checkerboard tape method, and the substrate was not observed at all. Peeling of the enamel film, no deterioration of the ruthenium metal film was observed by the air exposure heating test. Example 8 (1) 0.05 g of the tetrakis (#-pentafluoropropionate) II obtained in Example 3 was placed in nitrogen ( Acetone) Diterpenes (II, II) are metered in a vessel made of quartz, ^ is placed in a quartz reaction vessel, and a crucible wafer to which a thermal oxide film is attached is placed in the vicinity of the downstream side of the gas flow in the reaction vessel, and Nitrogen gas was passed through the inside of the reaction vessel at a flow rate of 300 ml/min for 20 minutes at room temperature. Then, nitrogen gas was passed through the reaction vessel at a flow rate of 100 ml/min, thereby making the system 13 Pa and reacting. The container is heated at 400 ° C for 15 minutes. Produced from a ship type container Gas, and deposits were found on the nearby quartz substrate. After the mist generation was completed, the pressure was reduced, the nitrogen gas was flowed into the system to restore the pressure, and then nitrogen gas was flowed into the Q at a flow rate of 200 ml/min at 101.3 kPa. The temperature was raised to 400 ° C, and after maintaining for about 1 hour, a film having a metallic luster was obtained on the substrate. The film thickness of the film was 600 Å. After measuring the ESCA spectrum of the film, it was observed at 2 80 eV and 284 eV. The peak of the Rum orbital, the peak derived from other elements is not understood to be a metal ruthenium. The resistivity of the ruthenium film measured by the 4-terminal method is 1 6 // Ω cm. The film density of the film is 12.0 g. /cm3. The adhesion of the tantalum film formed here to the substrate was evaluated by the checkerboard tape method, and the peeling of the substrate and the tantalum film was not observed at all. (2) The confirmation of the storage stability was carried out by the heating acceleration test. Deterioration review of air-25-200940553. Place 1 gram of tetrakis (v-pentafluoropropionate) di(acetone) ruthenium (ΙΙ, Π) in a 50 ml quartz three-necked flask and place the container Heating to 50 °C overall, followed by 3 liters at atmospheric pressure The flow rate of /min makes the air pass for 3 hours, and the four (#-pentafluoropropionate) di(acetone) diterpene (ΙΙ, Π) does not change in appearance. Then, the container is returned to room temperature to dry. The inside of the container was replaced with nitrogen, and film formation was carried out in the same manner as in the above (1). A film having a metallic luster was obtained on the substrate. The film thickness of the film was 600 angstroms. After measuring the ESCA spectrum of the film, at 2 A peak belonging to the Ru3d orbital was observed at 80eV and 284eV, and a peak derived from other elements was not observed at all as a metal ruthenium. Further, the resistivity of the tantalum film was measured by a four-terminal method to be 1 6 // Ω cm . The film had a film density of 1 2.0 g/cm3. The enamel film formed here was evaluated for adhesion to the substrate by a checkerboard tape method. The peeling of the substrate and the ruthenium film was not observed at all, and deterioration of the ruthenium metal film quality was not observed by the air exposure heating test. Example 9 (1). 5 g of 〇·〇 5 g of the (IV-pentafluoropropionate) di(acetone) dioxime (II, II) obtained in Example 3 was placed in a quartz vessel. The container is placed in a quartz reaction vessel. A silicon wafer to which a thermal oxide film is attached is placed in the vicinity of the downstream side of the gas flow in the reaction vessel, and a mixed gas of hydrogen and nitrogen (hydrogen content of 3 vol%) is flowed at a flow rate of 3 〇〇ml/min at room temperature. The inside of the reaction vessel lasted for 20 minutes. Subsequently, a mixed gas of hydrogen and nitrogen (hydrogen content of 3 vol%) was passed through the reaction vessel at a flow rate of 1 Torr/min, thereby making the inside of the system 13 Pa' and heating the reaction vessel at 400 °C for 15 minutes. A deposit was found on the quartz-based -26-200940553 plate generated from the ship-type container. After the completion of the mist generation, the pressure reduction was terminated, and the nitrogen gas was introduced into the system to recover the pressure, and then a hydrogen gas/nitrogen gas mixture (hydrogen content: 3 vol%) was flowed at a flow rate of 200 ml/min at a flow rate of 200 ml/min at a reaction vessel temperature of 101.3 kPa. After rising to 400 ° C, the film having a metallic luster was obtained on the substrate after about 1 hour. The film thickness of the film was 570 angstroms. After measuring the ESCA spectrum of the film, a peak belonging to 11113 (1 orbital peak) was observed at 280 eV and 284 eV, and a peak derived from other elements was not observed at all, which was understood to be a metal ruthenium. Further, the ruthenium film was measured by a 4-terminal method. The rate was 2 1 " Ω cm. The film density of the film was 12_0 g/cm 3 . The adhesion of the ruthenium film formed here to the substrate was evaluated by a checkerboard tape method, and no peeling of the substrate and the ruthenium film was observed at all. (2). Confirmation of preservation stability The air deterioration test was carried out by heating acceleration test. 1 gram of tetrakis(//pentafluoropropionate) di(acetone) ruthenium (II, II) was placed at 5 〇ml volume in a three-necked quartz flask, and heat the whole container to 50 ° C, then pass the air at a flow rate of 3 liters / minute under normal pressure for 3 hours 'tetra (#-pentafluoropropionate) The bis(acetone) ruthenium (π, ΐι) did not change in appearance. Subsequently, the container was returned to room temperature, and the inside of the container was replaced with anhydrous nitrogen, and film formation was carried out in the same manner as in the above (1). A film having a metallic luster was obtained on the substrate. The film thickness of the film was 5 70 angstroms. The ESCA spectrum of the film was measured. A peak belonging to the Ru3d orbital was observed at 280 eV and 284 eV, and a peak derived from other elements was not observed as a metal ruthenium. Further, the resistivity of the ruthenium film measured by a 4-terminal method was 2 1 # Ω cm. The film density of the film was 12.0 g/cm3. The adhesion of the film formed here was evaluated by the checkerboard tape method, and the substrate and the enamel film were not observed at all. -27-200940553, peeling, heating by air exposure No deterioration of the ruthenium metal film quality was observed in the test. Comparative Example 1 (1) 0.01 g of commercially available bis(ethylcyclopentadienyl) ruthenium was placed in a ship made of quartz in a nitrogen atmosphere, and was set in quartz. In the reaction vessel, a quartz substrate is placed in the vicinity of the downstream side of the gas flow in the reaction vessel, and a mixed gas of oxygen and nitrogen (oxygen content of 5 vol%) is allowed to flow through the inside of the reaction vessel at a flow rate of 250 ml/min at room temperature. 60 minutes. Then, a mixed gas of oxygen and nitrogen (oxygen content of 5 vol%) was flowed through the reaction vessel at a flow rate of 20 ml/min, thereby making the inside of the system 1 l〇Pa, and the reaction vessel was at 3 50 °C. Heat for 30 minutes. Self-ship The container generates mist, and deposits are found on the nearby quartz substrate. After the mist is generated, the pressure is reduced, the nitrogen gas flows into the system to restore the pressure, and then nitrogen gas is flowed at a flow rate of 200 ml/min at 101.3 kPa. After maintaining for about 1 hour, a film having a metallic luster was obtained on the substrate. The film thickness of the film was 850 angstroms. After measuring the ESCA spectrum of the film, a peak belonging to the Ru3d orbital was observed at 280 eV and 284 eV, and was not seen at all. The peak derived from other elements can be determined as a metal ruthenium. The resistivity of the ruthenium film measured by the 4-terminal method is 25 // Ω cm . Further, the film had a film density of 12.1 g/cm3. The enamel film formed here was evaluated for adhesion to the substrate by a checkerboard tape method, and no peeling of the substrate and the ruthenium film was observed at all. (2) The commercially available bis(ethylcyclopentadienyl) hydrazine was subjected to the heat acceleration test to carry out a review of the deterioration of air by the same procedure as in the second embodiment (2). 1 g of bis(ethylcyclopentadienyl) hydrazine was placed in a 50 ml quartz three-necked flask -28 - 200940553, and the whole of the vessel was heated to 50 ° C, followed by 3 liters / min under normal pressure. The flow allows the air to pass for 3 hours. Thus, the appearance of bis(ethylcyclopentadiene) which is originally a pale yellow transparent liquid changes to an opaque yellow liquid. Subsequently, the container was returned to room temperature, and the inside of the container was replaced with anhydrous nitrogen, and film formation was carried out in the same manner as in the above (1). A film having a black metallic luster was obtained on the substrate. The film thickness of the film was 30 Å. After the ESCA spectrum of the film was measured, a peak belonging to the Ru3d orbital was observed at 280 eV and 284 eV, and no peak derived from other elements was observed to be a metal ruthenium. Further, after the resistivity was measured by the 4-terminal method, the film was 7 8 # Qcm and showed no low conductivity. The film had a film density of 10.8 g/cm3. The enamel film formed here was evaluated for adhesion to the substrate by a checkerboard tape method, and 80 enamel films were peeled off in 100 checkerboard enamel films, and the enamel film was remarkably lowered. Therefore, bis(ethylcyclopentadienyl) ruthenium was determined by air heating test to determine the deterioration of the ruthenium metal film. As described above, when the chemical vapor-grown growth material of the present invention is used, a good quality tantalum film which is excellent in long-term storage stability and has few residual impurities can be obtained. Further, the ruthenium film can be formed by a simple method using the chemical vapor grown material. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a 19F-NMR spectrum chart of tetrakis(μ-trifluoroacetate) bis(acetone) dioxime obtained in Example 2. Fig. 2 is a 19F-NMR spectrum chart of tetrakis(μ-pentafluoropropionate) di(acetone) dioxime obtained in Example 3. -29-

Claims

200940553 X. Patent application scope I A diterpene complex represented by the following formula (1)

R1, R2, R3 and R4 are independently a hydrogen atom, a fluorine atom, a hydrocarbon group having 1 to 10 carbon atoms, a halogenated hydrocarbon group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, and each of X and γ is independently water. A ketone compound having 1 to 1 carbon atom, an ether compound having 1 to 10 carbon atoms, an ester compound having 1 to 1 carbon number, and a nitrile compound having a carbon number. 2. - a diterpene complex represented by the following formula (2), -30- 200940553 ❹

R5, R6, R7 and R8 are each independently a hydrogen atom, a fluorine atom, a hydrocarbon group having a carbon number of 10, a halogenated hydrocarbon group having 1 to 1 carbon number, or an alkoxy group having a carbon number of 10. 3. A chemical vapor-grown growth material characterized by the composition of the second aspect of the patent application. A chemical vapor-grown material characterized by a staple compound of the second item of the patent application. A method for forming a ruthenium film, which is characterized in that the chemical vapor grown material of the third or fourth aspect of the patent application is formed by a chemical vapor phase growth method. -31 -