TW200526802A - Metal complex having BETA-diketonato ligand and method for producing metal-containing thin film - Google Patents

Abstract

Disclosed is a novel beta-diketonato metal complex which can be advantageously used in a method wherein a metal thin film is produced by CVD, which represented by the following formula: (1) (wherein X represents a silyl ether group having a specific structure; Y represents the above-mentioned silyl ether group or an alkyl group; Z represents a hydrogen atom or an alkyl group; M represents Lu, Ir, Pd, Ni, V, Ti, Zr, Hf, Al, Ga, In, Sn, Pb, Zn, Mn, It, Cr, Mg, Co, Fe or Ag; and n represents the valence of the metal atom M.)

Description

200526802 (1) IX. Description of the invention [Technical field to which the invention belongs] The present invention relates to novel metal complexes having a / 3-diketone ligand 'and chemical vapor deposition using the metal complexes Method (CVD method) A method for manufacturing a metal thin film such as a metal thin film or a metal oxide thin film. [Previous technology] A thin film of noble metals such as ruthenium or iridium belonging to the Group V111 metal or its oxide film has been reviewed as a material for forming thin-film electrodes of semiconductor memories such as DRAM and FeRAM. This is because the noble metal has excellent electrical characteristics when used as a material for electrode formation. In addition, the use of a thin film of palladium or nickel for the purpose of 'increasing the density of copper cores on copper wirings used in silicon semiconductors' has been reviewed, as well as improving the adhesion between copper wirings and their underlying layers. The manufacturing method of the metal thin film can use the PVD method and the CVD method, but with the trend of miniaturization of the device in the future, it is better to use the c V D method to form a uniform thin film. Therefore, a suitable raw material compound is required. A known CVD method for forming a thin film containing ruthenium, iridium, palladium or nickel, such as a / 3-diketone complex of each metal. However, the θ-diketone complex of ruthenium, iridium, palladium, and nickel has a high melting point. Therefore, when feeding raw materials in a CVD apparatus, the piping may be blocked, so there is a doubt as a metal raw material for the CVD method. Also, the film formation speed of the CVD method is small, which is disadvantageous for the target film production surface. Patent Document 1 has proposed a ruthenium complex or an iridium complex of 2,2,6-trimethyl-3,5-heptanedione or 2,6-monomethyl-3,5-heptanedione. This -5- 200526802 (2) complex has a lower melting point, but the melting point of any complex is higher than l 10 or higher. Therefore, it is suspected as a metal raw material for the CVD method. Patent Document 2 has proposed a ruthenium complex containing a B-diketone having a large carbon number alkyl group as a ligand. The complex is a liquid at room temperature, so it can solve the problem of piping plugs in the CVD device, but the film formation speed of the ruthenium film is the same as that of the previous three Diketo) ruthenium complex, so the productivity of ruthenium film cannot be solved industrially. Patent Documents 3 and 4 have proposed that, in order to improve the homogenization of the formed thin film, a compound of tris (2,4-octanedionate) ruthenium complex (formula 1) and tris (2,4-octane) Method for separation of cis-trans isomers of dicopper) iridium complex. Ruthenium complexes have been proposed to be different from cyclopentadienyl ruthenium complexes of stone-diketone groups. Patent Documents 5 to 7 describe bis (ethylcyclopentadienyl) ruthenium complexes which are liquid at room temperature. However, the ruthenium complex is an organic metal and is sensitive to water, so the process of synthesis and post-treatment is complicated. In addition, when starting from a commercially available trivalent ruthenium chloride as a starting material, the target bis (ethylcyclopentadienyl) ruthenium complex is a divalent compound, so a reduction reaction is required and a reducing metal Zinc, etc., there are doubts about mass production by industrial manufacturing methods. The fabrication of palladium films by CVD using palladium complexes has not been previously reviewed. Patent Document 8 describes an example of producing a palladium film using bis (2,2,7-trimethyl-3,5-octanedionate) palladium complex in supercritical ethane, but in supercritical ethane, The response is not practical. Non-patent document 1 describes that a bis (cyclopentadienyl) nickel complex -6-200526802 (3) A nickel thin film is produced by the C V D method. However, the complex is solid (melting point: 7 3) ○ Therefore, the fields of semiconductors, electronic parts, and optical materials have begun to use vanadium thin films as thin film materials. Vanadium-containing thin film manufacturing methods such as coating thermal decomposition method, PVD method, and CVD method. However, in terms of composition control and the tendency of device miniaturization in the future, it is better to use CVD method to easily produce uniform thin films. Starting compound. It is known that when a vanadium-containing thin film is produced by a CVD method, the vanadium source used is a complex of an alkoxy metal such as VO (OEth), but the complex of an alkoxy metal is easily generated in the presence of only water Decomposition and deterioration, and it is difficult to keep it. Patent Document 9 has disclosed that using V (dpm) 3 (the dpm is 2,2,6,6-tetramethyl 3,5-heptanedione) Diketone complex. Because the V (dpm) 3 complex does not contain an alkoxy metal, it is stable in the presence of water, but its melting point is too high for 15 5 t, so it may block the CVD device when supplying raw materials. It is suspected that it will be used as a raw material for the production of thin films by CVD method. Began to review the use of thin films containing oxides of metal elements such as titanium, chromium or lead belonging to Group IVA of the periodic table as semiconductors, electronic parts, and optical parts. Materials in the field, especially in recent years, have been developed to use hafnium oxide as the entrance and exit insulating film of transistors. Manufacturing methods of thin films containing this element, such as coating thermal decomposition method, PVD method, or CVD method, Correspondence of miniaturization of semiconductor devices is best known by CVD 200526802 (4) raw materials for manufacturing thin films containing group IVA metal elements by CVD method, such as T i (Ο E t) 4-like alkoxy metal, or alkoxy-containing metal described in patent documents 丨 〇 ～ 〖2 And A-diketometal complexes. The metal complexes contain metal alkoxylates, so they may decompose and deteriorate in the presence of water only, and there is a problem of water management in the solvent during storage or synthesis. In addition, among the complexes described in the above patent documents, except for some titanium complexes, almost all titanium complexes, zirconium complexes, and donor complexes are solid at room temperature. Piping may be blocked when conveying the raw material, so there is a concern as a raw material for the CVD method. Patent Document 13 has disclosed that Hf (dpm) 4 (the dpm is 2, 2, 6, 6-tetramethyl) without containing oxymetal. -3,5_heptanedionate) complex. The complex is more stable in water, etc., but the melting point is too high at 3 1 5 ° C, so there will be problems with piping blockage when supplying raw materials, and the same Questions on raw materials for the CVD method. Therefore, a review was started to include metals such as boron, aluminum, gallium, and indium belonging to the group IIIB or their chemical compounds. Material films are used as materials in the fields of semiconductors, electronic parts, and optical parts. For example, review of functional films for electronic devices such as aluminum oxide films as the entrance and exit insulation films of semiconductor memory, and indium oxide films for transparent electrode films. Manufacture methods of thin films containing this metal, such as coating thermal decomposition method, PVD method, and CVD method, but in terms of the group or controllability of the film and the tendency of future device miniaturization, the CVD method is easy to produce uniform thin films. For the production of thin film containing Group IIIB metal by CVD method, such as trialkyl aluminum, trimethyl gallium and other trialkyl metal complexes for compound semiconductor, but only exist The complex under moisture and air has undergone drastic deterioration, -8-200526802 (5), and it is pyrophoric and difficult to handle. In addition, Al (dpm) 3 (dpm is 2,2,6,6-tetramethyl 3,5-heptanone ketone) -diketonyl complex can be used as the entrance and exit insulation of semiconductor memory The film is used to form alumina thin film, but the Al (dpm) 3 complex is a solid with a melting point of 26 5 ° C. Therefore, when the raw material is supplied, the pipe may be blocked in the CVD device, which is difficult to use as a raw material for CVD film formation. In addition, Patent Document 14 and Patent Document 15 have disclosed that an aluminum complex containing an alkoxy metal in the molecule, but the alkoxy metal-containing complex in the presence of only moisture will also decompose and deteriorate, which has a storage problem. . Patent Document 16 has proposed an alkylaluminum halide, but similarly, it undergoes severe deterioration only under moisture and air, and is pyrophoric and difficult to handle. For boron, gallium, and indium in Group IIIB metals other than aluminum, under the current situation, almost no other than trialkyl metal complexes have been developed, and the / 3-diketone complexes of this metal, such as tri ( Ethyl acetone) indium complexes, indium (dpm) complexes, etc. are high melting point solids, so it is difficult to use them as raw materials for CVD film formation. In addition, we began reviewing the use of tin and miscellaneous oxide films belonging to Group IVB metals as raw materials in the fields of semiconductors and electronic parts, and the use of Group IVB metal oxides in tin oxide, tin oxide indium oxide (I TO), etc. Transparent conductive film or oxide ferroelectric film of BTS (barium, titanium, tin oxide, PZT (lead, chromium, titanium oxide), etc.) The method for manufacturing the group IVB metal-containing film is, for example, coating heat Decomposition method, PVD method, and CVD method, but in terms of composition control and the tendency of device miniaturization in the future, it is better to form a uniform thin film by CVD method. Therefore, a suitable raw material compound is required. A raw material for a thin film of a group metal element is a / 5-diketo metal complex. For example, Sn (AcAc) 2 (The AcAc 200526802 (6) is an acetamidoacetone). However, the S η is wrong. The compound is extremely sensitive to water, so there is a problem of water management during synthesis or storage (Patent Document 17). Patent Document 18 has described that the tetramethyl group having a Sn-C bond is directly bonded to the alkyl group by Sη. Base tin (Sh (CH3) 4) is used as a raw material for BTS thin films of oxide-based ferroelectrics. Although Sn (CH3) 4 can avoid the problem of decomposition of the above-mentioned 10,000-diketone complexes due to moisture, the characteristics of the BTS film obtained by using Sn (dpm) 2 are relatively poor. The reason is that Sn and Sn-C bond between alkyl groups is too strong for co-bonding, so it is more difficult to break Sn-C bond than Sn (dpm) 2 complex with Sn-0-C bond. Similarly, dibutyltin with Sn-C bond Diacetate and the tin complex of (CH3) 2Sn (dPm) 2 shown in Patent Document 19 also have the same problem. Moreover, Pd (dmp) 2 (Patent Document 20), double (1, 3-diphenyl-1,3-propionedionate) lead (Patent Document 21) and other / 3-diketo lead complexes, but these are high-melting solids, so they are formed by CVD. When filming, it is feared to block the piping supplied to the raw material system in the CVD device, which is difficult to use as a raw material for the CVD method. In recent years, there are many zinc compounds, manganese compounds, and yttrium compounds for raw materials in the fields of semiconductors and electronic parts Research and development. Among them, zinc compounds have been used in transparent conductive films and surface acoustic wave devices such as solar cells and liquid crystal display devices, and manganese compounds have been used in electrochromic devices or Using a thermistor element that has a large resistivity change and temperature decomposition energy to temperature, it also uses yttrium compounds for indium oxide-based high-temperature superconductor materials. In the method of manufacturing a thin film incorporating the metal atom, it is easy to The CVD method for producing uniform thin films has the best film formation, so a suitable raw material compound is required. It is known that the CVD method is used to produce a thin film containing zinc atoms, manganese atoms, and indium atoms. 200526802 (acac = ethenylacetone), Zn (dpm) (dpm = bis (2,2,6,6-tetramethyl-3,5-heptanedione, Mn (acac) 2, Mn ( acac)) 3, Mn (dpm) 3 Y (dpm) 3 Y (tod) 3 (tod) 3 (tod = bis (2,2,6,6-tetramethyl 3,5-octane diacetate)) Iso-dione complexes are metal complexes of ligands. For example, a method for producing a zinc-containing film using a zinc complex is known, for example, a method for producing a zinc oxide film by a plasma CVD method using Z n (dpm) 2 (for example, refer to Patent Documents 22 and 23), and a thermal CVD method using Zn (acac) 2 Method for producing fresh oxide film (Patent Document 24). However, at room temperature, any zinc complex is solid and has a high melting point. Therefore, when the film is formed by the CVD method, the pipes for supplying raw materials in the CVD device may be blocked, which is not suitable for industrial CVD film forming materials. A known method for producing a manganese film using a manganese complex is a method for producing a manganese oxide film by a CVD method using Mn (acaC) 3 (Non-Patent Document 2). However, the manganese complex is a solid at normal temperature and has a problem of high melting point. For example, it is known to use an indium complex to produce an indium-containing thin film. For example, Y (todh is a method for manufacturing an indium oxide film by a CVD method (Patent Document 25). However, the manganese complex is a solid at normal temperature and has a high melting point. There are many research and development projects concerning chromium compounds and magnesium compounds as raw materials in the fields of semiconductors and electronic parts. Among them, the use of chromium compounds on the surface of glass or steel plates for optical fiber lasers has been investigated. Also, the magnesium film is used as a protective film on the dielectric glass layer of the plasma display panel. In the method for manufacturing a thin film containing the metal atom, the CVD method which is easy to manufacture a uniform thin film is most popular, so the demand is Suitable raw material compounds are 200526802 (8). Raw materials for producing Cr or Mg-containing films by CVD are known, for example, Cr (acac) 3 (acac = acetamidoacetone), Cr (dpm) 3 (dpm = 2,2,6,6-tetramethyl-3,5-heptanedione), Mg (acaC) 2, ^^ (Hour 111) 2 and other cold-diketone groups as coordination Metal complexes, or metal complexes using carbonyl groups such as Cr (CO) 6 as the ligand, with MgCp2 (Cp = ring Metal complexes such as pentadienyl) as ligands. It is known to use chromium complexes to produce chromium-containing thin films. For example, Cr (dpm) 3 is used to produce chromium oxide films by plasma CVD. Method (Patent Documents 26 and 27), or a method of coating a steel sheet with chromium using Cr (CO) 6 (Patent Document 28). It is also known to use Mg (acac) for the production of a magnesium-containing film using a magnesium complex. 2. Mg (dpm) 2 or MgCp2 is a method for manufacturing magnesium oxide film by thermal CVD method or plasma CVD method (Patent Documents 27, 29). However, any metal complex is solid at normal temperature and has a high melting point. Therefore, when the film is formed by the CVD method, the piping for supplying the raw materials in the CVD device may be blocked, which is not suitable for the raw materials for manufacturing thin films by the industrial CVD method. In addition, it is described in Patent Document 30 that the silane group -A copper complex of a diketone group as a ligand. Patent Document 1: Japanese Patent Application Laid-Open No. 9-4 9 0 81 Patent Literature 2: Japanese Patent Application Laid-Open No. 2000-2 1 2 7 4 Document 3: Japanese Unexamined Patent Publication No. 2 0 3-5 5 2 9 4 Patent Document 4: Japanese Unexamined Patent Publication No. 2 0 3-6 4 0 1 1 1- 3 5 5 8 9 Patent Document 6: JP 2 0 0 2-1 0 5 0 9 Patent Publication 200526802 (9) Patent Document 7: JP 2 00 3-5 5 3 90 Patent Document 8: U.S. Patent 5 7 8 9027 Patent Document 9: JP 2003-49269 Patent Document 10: JP 200 1 -2003 67 Patent Document 1 1: JP 2002-6964 Patent Document 1 12: JP 2002-69027 Patent Document 13: JP 2002-2 494 5 Patent Document 14: JP 200 1 -2 1 4268 9 Patent Document 15: JP 2 0 0 3- 3 4 8 6 8 Patent Document 16: JP 9- 1 2 5 8 1 Patent Document 17: JP 6-23 4779 Patent Document 18: JP 9-249 9 73 Patent Document 19 : Japanese Patent Application Laid-open No. 7-2 5 8 8 Patent Literature 20: Japanese Patent Application Laid-Open No. 2002- 1 5 5 00 8 Patent Literature 21: Japanese Patent Application Laid-open No. 2003-226664 Patent Literature 2 2: Japanese Patent Application Laid-Open No. 2 0 0 0- 2 7 3 6 3 Patent Document 23: JP 2 0 3-8 9 8 7 Patent Document 24: JP 2003-3 1 846 Patent Document 25: JP 9-22 8 04 Publication No. 9 Patent Document 26: JP-A-Hei 6-92647 Patent Document 27: Japanese Patent Application Laid-Open No. 1 1-3 665 Patent Literature 28: Japanese Patent Application Laid-Open No. 2-661 71 Patent Literature 29: Japanese Patent Application Laid-Open No. 1 0-26995 Japanese Patent Publication No. 30: WO 03 / 064437A1 report 200526802 (10) Non-Patent Literature 1: Electrochemical and Solid-State letters, 5 (6) C 6 4-C 6 6 (2 0 0 2) Non-Patent Literature 2: J. Electrochemical Society, 142 (9), 3137 (1995) [Summary of the Invention] Problem to be Solved by the Invention The object of the present invention is to provide ruthenium, iridium, palladium, nickel, vanadium, titanium, chromium, copper, aluminum, gallium, indium, tin, zinc, zinc, copper A novel complex of selected metal atoms in the copper, copper, chromium, magnesium, iron, iron, and silver groups. In addition, it provides a complex with a low melting point, excellent stability in the air, and excellent film-forming properties, and is suitable for forming metal-containing films such as metal thin films or metal oxide thin films by applying the CVD method. Means for Solving the Problems The present inventors have found that the above-mentioned problem can be solved by using a metal complex having a / 3-diketo group having a sulphonic ether bond as the ligand, and the present invention has been completed. The present invention is the following formula (1) The metal complex shown:

-14-200526802 (11) [In the formula (1), X is a silyl ether group shown in the following (2), Y is a silyl ether group shown in the following (2), or a straight chain having a carbon number of 丨 to 8 Or branched alkyl; Z is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and M is ruthenium, iridium, palladium, nickel, vanadium, titanium, zirconium, aluminum, aluminum, indium, tin, f □ , Zinc, bell, stilbene, complex, magnesium, Ming, iron, and silver group selected metal atom, η is the valence of the metal atom shown by M (for example 2, 3, 4),

Rb (2) -Ra-〇-Si-Rc

V (In formula (2), Ra is a linear or branched alkylene group having 1 to 5 carbon atoms, and Rb, Re, and Rd are each independently a linear or branched alkyl group having 1 to 5 carbon atoms. )] In addition, the present invention is a metal complex containing a silane alkyl group represented by the following formula (3); S-diketone as a coordination group (the metal is ruthenium, iridium, palladium, nickel, vanadium , Selected from the group consisting of titanium, zirconium, lead, aluminum, gallium, indium, tin, lead, zinc, manganese, yttrium, chromium, magnesium, cobalt, iron, and silver). -15- (3) 200526802 (12)

[In the formula (3), X is a silyl ether group represented by the following (2), Y is a silyl ether group represented by the following (2), or a linear or branched alkyl group having 1 to 8 carbon atoms, Z is a gas atom or a carbon atom having 1 to 4 carbon atoms.

Rb / c -Ra-0-Si-R (2)

\ d R

(In formula (2), Ra is a linear or branched alkylene group having 1 to 5 carbon atoms, and Rb, 1 ^ and Rd are each independently a linear or branched alkyl group having 1 to 5 carbon atoms. )]. Further, Y is preferably a linear or branched alkyl group having 1 to 8 carbon atoms, and Z is preferably a hydrogen atom. Y is particularly preferably a straight or branched alkyl group having 1 to 4 carbon atoms. Ra is particularly preferably a dimethyl methyl group, and Rb, Re, and Rd are particularly preferably a linear alkyl group having 1 to 3 carbon atoms. base. In the present invention, after the metal complex of the above formula (1) or the metal complex having an A-diketone group having a silyl ether group represented by the above formula (3) as a ligand is vaporized, This vaporized metal complex is thermally decomposed and deposited on a substrate-16-200526802 (13) to produce a metal-containing thin film. Furthermore, since the thermal decomposition of the vaporized metal complex occurs in the presence of oxygen, a metal oxide thin film can be formed on the substrate. The effect of fapon is compared with the previously known metal complexes. In addition to the excellent stability and low melting point of the metal complexes of the present invention, the film-forming speed of metal-containing films is faster, so various metals can be efficiently produced industrially film. Best Mode for Carrying Out the Invention The present invention will be described in detail below. The present invention is used as a complex of a metal complex, and has a styrenic ether group; specific examples of the 8-diketone are the following compounds.

The / 3-diketone can be subjected to acid treatment of the resulting product 'after reacting a silylated organic acid ester with a ketone in the presence of a base', followed by isolation or purification by a known method such as distillation or column chromatography. Got. The metal / 3-monoketo complex containing the 10,000-diketone compound as a ligand can be obtained by a known method of reacting a diketone with a metal salt in the presence of a base. The method for purifying the metal complex obtained by the reaction may be a column chromatography method or a distillation method. A metal complex containing an A-diketone complex having a sulphonic acid group -17- 200526802 (14) An example is shown below. In the following formulas, M 2 + is a divalent metal ion (for example, Ni 2 H, Pd2 +, Sn2 +, Pb2 +, Zn2 +, Mg2 +, Co2 +, Ag2 +), and M3 + is a trivalent metal ion (for example, Lu3 +, Ir3 +, V3 +, Al3 + , B3 +, Ga3 +, In3 +, Mn3 +, Y3 +, Cr3 +, Fe3 +), and M4 + is a tetravalent metal ion (for example, Hf4 +, Zr4 +, Ti4 +).

In the CVD method, it is necessary to vaporize a raw material compound for forming a thin film, but the method used in the present invention to vaporize a metal complex containing a / 3-diketone complex having a silane ether group may be: The complex itself is poured into or transported to -18-200526802 (15) Gasification chamber, or the complex is subjected to a suitable solvent (such as hexane, octane, methylcyclohexane or Aliphatic hydrocarbons such as ethyl cyclohexane; aromatic hydrocarbons such as toluene; ethers such as tetrahydrofuran or dibutyl ether) are introduced into the gasification chamber for gasification, that is, the solution method. The substrate can be distilled using a known CVD method. That is, a method of contacting a metal complex vapor of the present invention with a heated substrate under reduced pressure or in the presence of an inert gas to thermally decompose it to precipitate a metal thin film, or a method of depositing a metal thin film in the presence of a reducing gas such as hydrogen, or A method of depositing an oxide film of the element under an oxidizing gas such as oxygen, or a method of depositing a nitride film of the element under a nitrogen-containing alkaline gas such as ammonia. In addition, a plasma CVD method can be used to deposit a thin metal film. When a metal thin film is formed from the metal complex containing a silane alkyl-dione complex by the vapor deposition method, the vapor deposition conditions can be as follows. That is, the pressure in the reaction system is preferably IPa to 200 kPa, more preferably 10 Pa to 110 kPa, the substrate temperature is preferably 50 to 700 ° C, and more preferably 100 to 500 ° C. The metal complex The gasification temperature is preferably 50 to 25. (:, More preferably 90 to 200 ° C. When the metal oxide film is formed using an oxidizing gas such as oxygen, the content of the oxidizing gas to the total gas amount is preferably 10 to 90% by volume, and more preferably 20 to 70. Capacity%. When a reducing gas such as hydrogen is used for vapor deposition of a metal complex, the content of the reducing gas to the total gas content is preferably 10 to 95% by volume, and more preferably 30 to 90% by volume. When a nitrogen-containing test gas such as ammonia is used for the metal complex, the content of the nitrogen-containing alkaline gas to the total gas content is preferably 10 to 95% by volume, and more preferably 20 to 90% by volume. -200526802 (16) [Embodiment] [Example 1] Synthesis of 2,6-monomethyl_2_ (trimethylsilyloxybubble 3,% heptanedione (Called soph)

In a 500 ml flask, 3.7 g (0.351 mol) of sodium ammonium sulphate was suspended in 200 ml of hexane: and then 2- (trimethylsilyloxy-2-methyl) was added. 26.7 g (0.140 mole) of methyl-propionate. 12 lg (0 Mi mole) of methyl-2-butanone was dropped into the resulting solution, and the reaction was performed while maintaining at 15 ° C, and it was found that the reaction solution produced Ammonia gas. After reacting at 15 C for 1 hour, the reaction solution was made weakly acidic with acetic acid. After washing the obtained layer with water, it was dried over sodium sulfate and then distilled (〖〇} / 8mmHg) to obtain the target substance. 18.8 g of 2,6-dimethyl_2_ (trimethylsilyloxy) _3,5-heptanedione (0.07 7 mol, yield 55%). The obtained compound was analyzed by NMR 'IR and MS simultaneously. J -NMRCCDCh): δ 0.14 (s, 9Η), 1.14 (d, 6Η), i.39 (s, 6Η), 2.44 ~ 2.50 (m, 0.85H), 2.64 ~ 2.69 (m, 0.15H), 3.77 ( s, 0.3H), 5.97 (s.0.85H), 15.51 (s, 0.85H). IR (cm-1): 2971, 1606 (br), 1253, 1199, 1045, 842 MS (m / e): 244 -20- 200526802 (17) [Example 2] Synthesis of tris (2,6 -dimethylformate) -(2- (trimethylsilyloxy) -3,5-heptanedione) ruthenium complex [R u (s oopd) 3] 1 0 0 m 1 In a flask, ruthenium chloride ( 111) 3 · 6.3 g (1 · 3.9 mmol) of 3 hydrate was dissolved in 30 ml of ethanol, and then 7 g (36.3 mmol) of 28% sodium methylate / methanol solution was added at room temperature. Stir for 30 minutes. Next, add 10 g of 2, 6-dimethyl-2- (trimethylsilyloxy) -3,5-heptanedione (4 0.9 mmol), and heat to 100 ° C in 30 minutes. . Methanol, ethanol and water were distilled off during heating. Thereafter, the temperature was raised to 180 ° C over 30 minutes, at which time the solution changed from dark brown to red. Subsequently, the temperature was returned to room temperature, and 100 ml of hexane was added, followed by filtration to obtain a red solution. It was washed with water, dried and concentrated to obtain a red liquid. Column chromatography (hexane / ethyl acetate = 9.5 / 0.5) to obtain the target orange-red liquid tris (2, 6-dimethyl-2-((trimethylsilyloxy) -3,5-heptane) Keto) ruthenium complex 2.72 g (3.3 mmol, yield 24%). The obtained compound was subjected to IR analysis, elemental analysis, and MS analysis. IR (cm-1): 2966, 1545, 1501, 1403, 1251, 1199, 1047, 890, 842. Analysis of C36H69〇9Si3Ru by Cholesterol Determination of C: 5 2 · 7%, Η: 8 · 2 0%, Ru: 1 2% theoretical 値 C: 5 2.0%, Η: 8.3 7%, Ru: 1 2.2% MS (m / e) determination 値: 8 3 1, 5 8 8, 1 3 1, 7, 3 theoretical 値 (Exact mass ): 831.33 200526802 (18) According to IR analysis, it is known that the peak of 16 0 6 -1 cm, which is unique to cold-diketones, disappears, and a peak of 1 5 4 5 c m_1, which is unique to diketones, appears instead. Therefore, the ruthenium complex is a novel substance. [Example 3] Synthesis of bis (2 '6-monomethyl-2- (dimethyllithium oxonoxy) -3,5-heptanedione) IG complex [Pd (sopd) 2] Hexane 100 m 1 was added to a 300 m 1 flask, and 1.2 g (30 mmol) of 60% sodium hydride was suspended, and then 2,6-dimethyl_2_ (trimethyl) was dripped under ice-cooling. Methylsilyloxy) -3,5-heptanedione 6.10 g (25.0 mmol), hydrogen was found to be produced. When hydrogen was generated, a solution prepared by dissolving 2.80 g (12.5 mmol) of palladium acetate in 30 ml of methylene chloride was added to the hexane solution, and after reacting at room temperature for 1 hour, 100 ml of water was added. After the organic layer was separated, it was washed with water, dried and concentrated to obtain an orange liquid. Column chromatography (hexane / ethyl acetate = 9.5 / 0.5) to obtain the target bis (2,6-dimethyl-2- (trimethylsilyloxy) -3,5-heptanedione as a yellow solid Compound) 5.40 g (9.10 mmol, 73% yield) of palladium complex. The obtained compound was subjected to IR analysis, elemental analysis, and MS analysis. Element analysis C24H46〇6Si2Pd Determination of 値 c: 4 8 · 3% Η Η ·· 7 · 90% 'P d: 1 8 ° / 〇Theoretical 値 C: 4 8 · 6%, Η: 7 · 8 2% 'P d: 1 7.9% MS (m / e)

Measurement 値: 592, 131, 73 Theoretical 値 (Exact mass): 5 92.1 9 Melting point · 9 5 ° C -22- 200526802 (19) According to IR analysis, it is known that '/ 3-a ketone specific 1 6 0 6 c The m-1 peak disappeared and a peak of 1 5 5 6 cm · 1 peculiar to the diketo group appeared instead, so the palladium complex was a novel substance. [Example 4] Synthesis of bis (2,6-dimethyl-2- (trimethylsilyloxy) _3,5-heptanedione) nickel complex [Ni (soph) 2] in a 100 ml flask After dissolving 5.0 g (20.0 mmol) of nickel acetate tetrahydrate in 3 5 ml of water, 2,6-dimethyl-2-(trimethylsilyloxy) -3,5 -A solution obtained by dissolving 9.90 g (40.6 mmol) of heptanedione in 40 ml of hexane was added to the aqueous solution. An aqueous sodium hydroxide solution (1.60 g of NaOH was dissolved in 10 ml of water) was added while stirring at room temperature, and then the reaction was performed at room temperature for 1 hour. Then add 10ml of 25% ammonia water to obtain a double-layer homogeneous solution and separate the liquid. After obtaining the hexane layer, wash with water, and then dry and concentrate to obtain the dark green liquid bis (2,6-dimethyl-2) of the object. -(Trimethylsilyloxy) -3,5-heptanedione) nickel complex 5.67 g (10. 4 millimoles, yield 5 2%). The obtained compound was subjected to IR analysis, elemental analysis, and MS analysis. IRCcnT1): 2963, 1579, 1508, 1413, 1252, 1195, 1050, 892, 841 Elemental analysis C24H46〇6Si2Ni Determination of 値 C: 5 2.3%, Η: 8 · 7.1%, Ni: 1 1% Theoretical 値 C : 5 2 · 8%, Η: 8 · 50%, Ni: 1 0.8% MS (m / e) Measurement 値: 5 4 5, 5 4 4, 1 3 1 '7 3 200526802 (20) Theoretical 値(Exact mass): 545.48 According to IR analysis, the 1 606CHT1 peak, which is unique to yS-diketone, disappeared, and a peak of 1 79 cm · 1, which is unique to diketone group, was replaced. Therefore, the nickel complex is a novel substance. [Example 5] Vapor deposition experiment (manufactured ruthenium thin film) The Ru (spd) 3 complex obtained in Example 2 was used to perform a vapor deposition test by a CVD method to evaluate film formation characteristics. In addition, a vapor deposition test was performed using a comparative tertiary (2,4-octanedionate) ruthenium complex. For the vapor deposition test, the apparatus shown in FIG. 1 was used. The Ru (sopd) 3 complex 20 placed in the vaporizer 3 (glass bottle) was heated and vaporized with a heater 1 0B, and then preheated with a preheater 1 0 A through mass flow adjustment 1 A The introduced ammonia gas exits the gasifier and is introduced into the reactor 4. The valve 6 in front of the vacuum pump is used to control the pressure in the reaction system to a certain pressure, and the pressure is monitored by the pressure gauge 5. The central part of the glass reactor is a structure that can be heated by a heater 10. The Rii (soPd) 3 complex introduced into the reactor was placed in the central part of the reactor, and then the surface of the vapor-deposited substrate 21 heated by a heater 10 to a certain temperature was thermally decomposed, and was placed on the substrate 21 The ruthenium metal was analyzed. The gas exhausted from the reactor 4 has a structure that is exhausted to the atmosphere through the gas condensing valve 7 and a vacuum pump. The substrate 21 to be vapor-deposited is a rectangular object of 7 mm × 40 mm. The deposition conditions and the characteristics of the obtained film are shown below. [Evaporation conditions] Gasification temperature: 1 5 (Γc -24- 200526802 (21) Substrate: Si02 / Si Substrate temperature: 3 5 0 ° c Mining time: 10 minutes Pressure in reaction system: 532Pa He Flow rate: 15ml / [Film characteristics] (1) When a film was formed using Rix (sopd) 3 complex as a raw material, it was confirmed that a RU film having a film thickness of 1000 nm was formed on the substrate (analyzed by XPS). (2) After the (2,4-octanedionate) ruthenium complex was formed as a raw material, almost no film was formed on the substrate. [Example 6] Vapor deposition experiment (made into a nickel film): The apparatus shown in FIG. 1 was used to The CVD method was used to perform a vapor deposition test on the Ni (sopd) 2 complex obtained in Example 4. After the Ni (sopd) 2 complex was poured into the gasifier 3, the gas of the gasifier was discharged with helium, And the hydrogen introduced into the reactor 4 through the mass flow regulator 1 B and the stop valve 2, and then the evaporation conditions were changed as shown below, and other methods were performed in the same manner as in Example 5. The evaporation conditions and the obtained film characteristics were as follows. [Deposition conditions] Gasification temperature: 2 0 (TC substrate: S i 0 2 / S i 200526802 (22)

Substrate temperature: 3 00 ° C Evaporation time: 30 minutes · Internal reaction pressure: 3 990Pa.

He flow rate: 80 ml / min [Film characteristics] When a film was formed using a Ni (sopd) 2 complex as a raw material, it was confirmed that a Ni film having a film thickness of 50 nm was formed on the substrate (analyzed by XPS). φ From the results of Examples 5 and 6, it is known that the Θ-diketone complex of the present invention having a silane-based ether group has superior film-forming properties as compared with previously known materials. [Example 7] Synthesis of tris (2,6-dimethyl-2- (trimethylsilyloxy) -3,5-heptanedione) palladium complex (VcS0Pd) 3) Chlorination 5.20 g (33.1 mmol) of palladium (III) was placed in a 300 ml flask. After dissolving in 50 ml of ethanol, 22 g (l 14.1 mmol) of 28% sodium methylate / methanol solution was added at room temperature. Stir for another 10 minutes. Next, 24.3 g (99.4 mmol) of 2,6-dimethyl-2- (trimethylsilyloxy) -3,5-heptanedione was added, and after stirring at room temperature for 30 minutes, 50 ml of hexane was added, and then 80 ml of water was added for liquid separation to obtain a brown solution. It was washed with water, dried and concentrated to obtain a brown liquid. Column chromatography (hexane / ethyl acetate = 9.5 / 0.5) to obtain the target product as a brown liquid tris (2,6-dimethyl-2- (trimethylsilyloxy) -3,5-heptanedione Compound) palladium complex 10.6 (13.6 millimoles, 41% yield). -26- 1048 200526802 (23) IR analysis, elemental analysis and MS analysis of the obtained compounds IR (cm): 2966, 1560, 1506, 1409, 1252, 1198,

, 890, 842 Elemental analysis C36H69〇9Si3V Determination of 値 C: 55. 0%, Η: 8. 85%, V: 6.5% Theoretical 値 C: 5 5 · 4%, Η: 8 · 90% , V: 6.5% MS (m / e) Determination of 値: 780, 537, 131, 73 EXact mass: 7 8 0.3 7 According to IR analysis, the unique peak of stone-dione disappears and appears instead. The diketo group has a unique peak of 15 60CHT1, so the palladium is a novel substance. [Example 8] Vapor deposition experiment (manufacturing a palladium oxide film) The palladium complex obtained in Example 7 was used to conduct a CVD method to evaluate the film formation characteristics. The evaluation test used the apparatus shown in FIG. The heater 10B enters the palladium complex 20 of the gasifier 3 (glass ampoule). After heating and gasification, the mass gas regulator 1A is used to preheat the ammonia gasifier introduced by the preheater 10A. The gas discharged from the gasifier 3 is introduced into the reactor 4 together with the oxygen introduced through the mass flow regulator 1 B check valve 2. The pressure in the reaction system is controlled to a certain pressure by using the front 6 switch of the vacuum pump, and monitored by the meter 5. The central part of the glass reactor is a structure that can be heated by the heater 10 ℃, and the plating test will be followed by the discharge and stop valve pressure heating -27- 200526802 (24). After the palladium complex introduced into the reactor was placed in the center of the reactor, the surface of the vapor-deposited substrate 21 heated to a certain temperature by a heater 10C was thermally decomposed by oxidation, and a palladium oxide film was deposited on the substrate 21. The gas discharged from the reactor 4 is exhausted to the atmosphere through the gas condensing valve 7 and the vacuum pump. The vapor deposition conditions and the characteristics of the vapor-deposited film are shown below. The substrate to be vapor-deposited was a rectangular object of 7 mm x 40 mm. [Evaporation conditions] Gasification temperature: 150 ° C Substrate: Si02 / Si Substrate temperature: 400 ° c Evaporation time: 15 minutes Pressure in the reaction system: 1 3 3 0Pa 〇2 Flow rate: 1 〇m 1 / He flow rate: 15 ml / min [Film characteristics] As a result of the film formation operation, it was confirmed that a palladium oxide film having a film thickness of 3 Onm was formed on the substrate (analyzed by XP S). That is, when the palladium complex of the present invention is used as a raw material, a uniform palladium oxide film can be formed. [Example 9] Synthesis of tetrakis (2,6-dimethyl-2- (trimethylsilyloxy) _3,5-heptadienyl) donor complex (Hf (soopd) 4) 200526802 (25) 41.60 g (4.46 mmol) of tetraethoxylate (DEt) and 2.50 g of 2,6-dimethyl-2- (dimethyl-5-oxenyloxy) -3,5-heptanedione will be given (22.5 millimoles) was placed in a 50 ml flask, and the temperature was gradually raised to 22 (rc) in 2 hours. During this time, about 1 ml of ethanol was distilled off from the reaction system. After concentration at 120 ° C / 40 Pa for about 1 hour, 80 ml of hexane was added at room temperature. After filtering the insoluble component, the hexane layer was washed with water, dried and concentrated, followed by distillation to obtain 3.0 g (2.60 mmol, 58%) of the target substance as a pale yellow solid. IR analysis, elemental analysis and MS analysis. IRCcnT1): 2967, 1586, 1540, 1509, 1440, 1252, 1199, 1047, 892, 841 Elemental analysis C48H92012 Si4Hf Determination of 値 C: 5 0.3%,%: 8.0.1 0 %, H f: 15. 5% Theoretical 値 C: 5 0.0%, Η: 8.0 5%, H f: 15. 5 0 / 〇MS (m / e) determination 値: 9 9 8, 9 0 9 , 1 3 1, 7 3 Exact mass: 1 1 52.5 1

Melting point: 6 8 ° C According to IR analysis, the MOScnr1 peak, which is unique to / 3-diketone, disappears, and instead, a 158 8CHT1 peak, which is unique to diketone, appears. Therefore, the complex is a novel substance. [Example 10] Evaporation experiment (manufacture of rhenium oxide film) The Hf (sopd) 4 complex obtained in Example 9 was used to perform CVD by the same method as in -29-200526802 (26) Example 8 Test 'and evaluate film formation characteristics. The vapor deposition conditions and the characteristics of the vapor-deposited film are shown below. The substrate to be vapor-deposited; ^ 7mmx40mm rectangular. [Deposition conditions] Gasification temperature: 200 ° C Substrate: Si02 / Si Substrate temperature: 400 ° C Evaporation time: 30 minutes Pressure in the reaction system: 5 3 20Pa 〇2 flow rate: 40ml / min He flow rate: 60ml / min [Film characteristics] As a result of the film formation operation, it was confirmed that an oxide film having a film thickness of 30 nm was formed on the substrate (analyzed by XP S). That is, using the complex of the present invention as a raw material, Nichiji, a uniform oxidation film can be obtained. [Example 1 1] Synthesis of tris (2,6-dimethyl-2- (trimethylsilyloxy) -3,5-heptanedione) aluminum complex (A 1 (s oopd) 3) 5.60 g (34.5 mmol) of aluminum triethoxide and 31.3 g (128.1 mmol) of 2,6-dimethyl-2- (trimethylsiloxy) -3,5-heptanedione ) Put into a 200ml flask and slowly raise the temperature to 1 70 ° C over 1 hour. In the meantime, it was seen that 6ml of ethanol was distilled off from the -30-200526802 (27) reaction system. After concentration at 120 ° C / 40Pa for about 1 hour, 80 ml of hexane was added at room temperature. After filtering the insoluble components, the hexane layer was washed with water, dried, and concentrated to obtain a brown liquid. Purified by distillation (1 90 ° C / 53P a) to obtain the target product as a yellow liquid tris (2,6-dimethyl-2- (trimethylsilyloxy) -3,5-heptanedione) Aluminum complex 9.25 g (12.2 millimoles, 35% yield). The obtained compound was subjected to IR analysis, elemental analysis, and MS analysis. IR (cm-1): 2966, 1 5 8 4, 1 5 43, 15 11, 1 452, 14 18, 1252, 1200, 1048, 891, 841. Element analysis C36H69〇9Si3Al Determination of C: 5 7.8%, Tritium: 9.2 1%, A1: 3.6% Theoretical Tritium: 57.1%, Tritium: 9 · 19%, A1: 3.6% MS (m / e) Determination Tritium: 7 5 6, 6 2 5 , 5 1 3 Theoretical mass (Exact mass): 756.41 According to IR analysis, the peak of 1 6 0 6 c ηΓ, which is unique to / 3-diketone, will disappear, and the peak of 1 5 84 cm · !, which is unique to diketone, will appear instead. Therefore, the lead complex is a novel substance. [Example 12] Di (2,6-dimethyl-2- (trimethylsilyloxy) · 3,5-heptanedione) indium complex (I n (s oopd) 3) Drop 2,6-dimethyl_2_ (trimethylsilyloxy) -3,5 · heptanes at 15.0 § (63.4 mmol) into a 1001) flask at 0 ° C. 28% of sodium methylate / -31-200526802 (28) 1 2 g (6.2 2 mmol) of methanol solution, and then drop indium chloride tetrahydrate 6 · 0 4 g (2 0 · 6 millimolar) indium chloride solution obtained by dissolving in methanol 5 mi. After stirring for 30 minutes at 0 ° C, hexane / water was added at room temperature (1: post-separation · liquid ', then the hexane layer was washed with water, dried and concentrated to obtain a pale yellow liquid. This liquid was purified by distillation (218 ° C / 59 Pa) to obtain the target product as a pale yellow liquid tris (2, 6-dimethyl-2- (trimethylsilyloxy) _3,5-heptanedione) indium complex 12.2 g (14.4 Millimolar, yield 70%). IR analysis, elemental analysis, and MS analysis of the obtained compounds. IR (c πΓ 1): 2 9 6 6, 1 5 7 0, 1 5 1 0, 1 4 2 7 , 1 2 5 2, 1 1 9 8, 10 47, 890, 841 Elemental analysis C36H69〇9Si3In Determination of 値 C: 5 1.8%, Η: 8. 18%, I η: 1 3.6% theoretical 値C: 5 1.2%, Η: 8 · 23%, I η: 1 3.6% MS (m / e) determination 値: 846, 830, 713, 601, 131, 73 Theoretical 値 (Exact mass): 844.33 _ According to IR analysis, the peak ΙόΟόεηΓ1, which is unique to diketones, will disappear, and a peak 1 5 70cm · 1, which is unique to diketones, will appear instead. Therefore, the indium complex is a novel substance. [Example 1 3]. Synthesis III ( 2,6-dimethyl-2- (trimethylsilyloxy) -3,5-heptane Hexyl) gallium complex (Ga (sopd) 3) 〇t: the following 2,6-dimethyl-2- (trimethylsilyloxy) -3,5-heptane-32- 200526802 ( 29) 14.0 g (5 7.3 mmol) of ketone was dropped into a 28% sodium methylate / methanol solution in a 100 ml flask (10.86 g (56.3 mmol)), and 3.15 g of gallium chloride was added dropwise. (17.9. Millimolar) dissolve 15nU of methanol in a gallium chloride solution. Stir down for 30 minutes. 'Add hexane / water (1: i) at room temperature to 100ml. After separation, wash the courtyard layer with water' After drying and concentrating, a light yellow liquid was obtained. The liquid was distilled and refined (196 ° C. 4 1Pa) to obtain the target product as a light yellow liquid tris (2,6_dimethyl_ 2-(trimethylsilyloxy). ) -3,5 -heptanedionyl) gallium complex 10.4 @ (13.0 mmol, 73% yield). The obtained compound was analyzed by IR analysis, element analysis and MS analysis. IR (c πΓ 1): 2 9 6 6, 1 5 7 5, 1 5 4 2, 1 5 1 2, 1 4 3 6, 1 4 0 4, 1 2 5 3, 1199, 1047, 891, 841. Analysis of C36H69. 9Si3Ga determination 値 C ·· 5 4 · 4 ° / 〇, Η ·· 8.58%, G a ·· 8.7% theoretical 値 C ·· 5 4.1%, Η: 8.6 9% G a: 7.7 2% MS (m / e) Determination of 値: 800, 798, 669, 667, 555, 483, 131, 73 φ Theoretical 値 (Exact mass): 798.35 According to IR analysis, / 5-dione The unique peak of 16 0 6 cm _ 1 will disappear, and the unique peak of 1 5 7 5 cm_1 will appear instead. Therefore, the gallium complex is a novel substance. [Example 1 4]. Evaporation experiment (manufacturing aluminum oxide film, indium oxide film, and gallium oxide film): The Al (sopd) 3 complex obtained in Example 11 was used, Example-33-200526802 (30 ) The In (sopd) 3 complex obtained in 12 and the Ga (sopd) 3 complex obtained in Example 13 were subjected to a vapor deposition test by the CVD method in the same manner as in Example 8 and the film formation characteristics were evaluated. The vapor deposition conditions and the characteristics of the vapor-deposited film are shown below. The substrate to be vapor-deposited was a rectangular object of 7 mm x 40 mm. [Production of aluminum oxide film] [Evaporation conditions] Gasification temperature: 180 ° C Substrate: Si02 / Si Substrate temperature: 350 ° C Deposition time: 30 minutes Pressure in the reaction system: 2660Pa 〇2 Flow rate: 10 ml / min He flow rate: 15 m 1 / min [film characteristics] As a result of the film formation operation, it was confirmed that an aluminum oxide film having a film thickness of 30 nm was formed on the substrate (analyzed by XP S). That is, when the aluminum complex of the present invention is used as a raw material, a uniform alumina film can be formed. [Manufacture of indium oxide film] [Steaming conditions]

Gasification temperature: 190 ° C 200526802 (31) Substrate: Si02 / Si Substrate temperature: 3 5 0 ° c · Evaporation time min. Pressure in the reaction system: 2660Pa 〇2 flow rate: 1 〇m 1 / minH e flow rate: 15 m 1 / min [film characteristics] φ As a result of the film formation operation, it was confirmed that an indium oxide film having a film thickness of 40 nm was formed on the substrate (analyzed by XP S). That is, when the indium complex of the present invention is used as a raw material, a uniform indium oxide thin film can be formed. [Production of gallium oxide film] [Evaporation conditions] Gasification temperature: 1 8 Ot Substrate: Si02 / Si # Substrate temperature: 3 5 0 ° C Evaporation time: 30 minutes Pressure in the reaction system: 2660Pa 〇2 Flow rate: 1 〇 m 1 / min

He flow rate: 15ml / min · [Film characteristics] As a result of film formation operation, it was confirmed that an oxygen film having a thickness of 3 Onm was formed on the substrate -35- 200526802 (32) Gallium film (analyzed by XPS). That is, when the gallium complex of the present invention is used as a raw material, a uniform gallium oxide thin film can be formed. [Example 1 5] Synthesis of bis (2,6-dimethyl-2- (trimethylsilyloxy) -3,5-heptadienyl) tin complex using A-diketone 2, 6-Dimethyl-2- (trimethylsiloxy) -3,5-heptanone 20. (^ (81.8 mmol)) was placed in a 201111 flask, and 28% sodium methylate was added. / Methanol solution 1 3 g (6 7.4 mmol). After stirring at room temperature for 30 minutes, SnCl 2 6.3 0 g (33.2 mmol) / ethanol (30 m 1) solution was added dropwise at room temperature. A white sink source was generated. The suspension solution was concentrated, and then 50 m of hexane was added to remove solids. The washed layer was washed and dried to obtain a yellow liquid. After distillation (1 44 ° C / 15Pa), Yellow liquid bis (2,6_dimethyl (trimethylpyridyloxy) -3,5-heptanedione) tin complex 6.3 g (10.4 mmol, yield 3 1 %). The obtained compound was subjected to IR analysis, elemental analysis, and MS analysis. IR (c πΓ 1): 2 9 6 6, 1 5 7 0, 1 5 0 7, 1 4 0 4, 1 3 7 0, 1 2 5 2, 1 1 9 7, 1047, 889, 841 Elemental analysis C24H4606 Si2Sn Determination of 値 C: 4 7.2%, Η: 7.8 8%, S η : 19% theoretical 値 C: 47.6%, Η: 7.66%, S η: 19.6% MS (m / e) determination 値: 6 0 6, 3 6 3 200526802 (33) theoretical 値 (Exact mass): 606.19 According to IR analysis, the peak 1 606CHT1, which is unique to cold-diketones, will disappear, and a peak 1, 15 70cm-1, which is unique to diketones, will appear, so the tin complex is a novel substance. Example 16] Vapor deposition experiment (manufacturing of tin oxide film): Using the Sn (sopd) 2 complex obtained in Example 17, a CVD method was used in the same manner as in Example 8 to perform a vapor deposition test and evaluate the film formation characteristics. The plating conditions and the characteristics of the vapor-deposited film are shown below. The substrate to be vapor-deposited is a rectangular object of 70 mm x 40 mm. [Production of tin oxide film] [Evaporation conditions]

Gasification temperature: 190 ° C Substrate: Si02 / Si # Substrate temperature · 400 ° C Evaporation time: 30 minutes Pressure in the reaction system: 5 3 2 0Pa 〇2 Flow rate: 4 0 m 1 / min H e Flow rate: 60 m 1 / min, [film characteristics] The result of the film formation operation was' on the substrate, it was confirmed that the film thickness was 5 Onm of oxygen-37- 200526802 (34) tin film (analyzed by XPs). That is, when the tin complex of the present invention is used as a raw material, a uniform tin oxide film can be formed. [EXAMPLE 17] Synthesis of bis (2,6-monomethyl-2-dimethylsandoloxy) _3,5-heptanedionyl) zinc (II) (Zn (sopd) 2) 2 8 % Sodium methoxide in methanol solution 17 · 6 g (9 1.0 mmol) was added to the internal volume of the thermometer and dropping funnel equipped with a sample disturbing device 2 0 0 m 1 in a flask, kept at 4 ° C 23.1 g (94.4 mmol) of 2,6-dimethyl-2-trimethylsilyloxy-3,5-heptanedione was slowly added dropwise at a temperature, and the mixture was stirred for another 30 minutes at the same temperature. Next, a solution prepared by dissolving 6.08 g (44.6 mmol) of zinc chloride (Π) in 120 ml of ethanol was added dropwise, and the mixture was reacted at room temperature for 1 hour under stirring. After the reaction was completed, 100 m 1 of the own courtyard and 100 m of water were added to the reaction solution to separate the organic layer. The organic layer was washed with water, dried over sodium sulfate, filtered, and the filtrate was concentrated. The concentrate (154 t, 24P a) was distilled under reduced pressure to obtain a pale yellow liquid bis (2,6-dimethyl-2-methyl). Silyloxy-3,5-heptanedione) zinc (11) 19.7§ (isolated yield 80%). Bis (2,6-dimethyl-2-trimethylsilyloxy-3,5-heptanedione) zinc (II) is a novel compound having the following physical properties. IR (neat (c irT 1): 2 9 6 6, 1 5 66, 1 5 09, 1410, 1 2 5 2, 1198 (/ 3 -dione-specific peak (1 606CHT1) will disappear and / 3 will appear _Diketone-specific peak (1 5 66CHT1)) Elemental analysis (C24H46〇6Si2Zn): Carbon: 52.9%, Hydrogen: 8.33%, 200526802 (35) Zinc: 1 1.3% (Theoretical 値: Carbon: 5 2.2%, hydrogen: 8.40%, zinc: 11.8%) MS (m / e): 5.50, 5 3 5, 419, 307 [Example 1 8] Synthesis of tris (2,6 -dimethylformate -2-(trimethyl sulphonyloxy) _3,5-heptanedionyl) manganese (III) (Mn (sopd) 3) A 28% solution of sodium methoxide in methanol 1 2.5 g (6 4.9 millimoles) Add a 200ml flask equipped with a stirring device, a thermometer and a dropping funnel, and slowly drip into 2,6-dimethyl-2-trimethylsilyloxy while maintaining the liquid temperature at 4 ° C. -3,5-heptanedione 17.0 g (69.6 millimoles), and then stirred at the same temperature for another 30 minutes. Manganese chloride (Π) tetrahydrate 6.0 · 6 g (3 0.6 millimoles) was added dropwise. The solution obtained by dissolving in 120 ml of ethanol was reacted with stirring at room temperature for 1 hour. After the reaction was completed, hexane 100 m 1 and water 100 m 1 were added to The organic layer was separated. The organic layer was washed with water and dried over sodium sulfate. After filtration, the filtrate was concentrated, and the concentrate (176t, 44Pa) was distilled under reduced pressure to obtain a dark brown liquid tris (2,6-dimethyl- 2- (trimethylsilyloxy) -3,5-heptanedione manganese (III) 2.73 g (isolated yield: 11%). Tris (2,6-dimethyl-2- 2- (Trimethylsilyloxy) -3,5-heptanedione manganese (III) is a novel compound having the following physical properties: IR (neat (cm'1): 2 9 6 7, 1 5 6 5, 1 4 9 9, 14 14, 1 2 5 2, 1197, 1046, 889, 841 (fluorene-dione-specific peak (1 606 cnT1) will disappear, and a / 3-diketopy-specific peak will appear (1 5 6 5 CHT1)) Elemental analysis (C36H 69 09 Si3Mn): Carbon: 55.6%, Hydrogen: 7.78% 200526802 (36), Meng · 7 · 〇% (Li δ 値 値. 5 ash · 5 5 · 1 %, Hydrogen: 7.86%, manganese: 7.0% MS (m / e): 784,541 [Example 19] Synthesis of tris (2,6-dimethyl-2-trimethylsilyloxy) 3,5_heptanedionyl) yttrium (III) (Y (sopd) 3) Add 26.0% (8 3.0 mmol) of 28% sodium methoxide in methanol solution with stirring Device The internal volume of the thermometer and the dropping funnel were 2,000 m 1 in a flask, and the solution was slowly dripped into the 2,6-dimethyl-2 -trimethyl-5Xinoxyloxy-3,5-while maintaining 4 ° C. After 22.0 g (90.0 mmol) of heptanedione, it was stirred for another 30 minutes at the same temperature. Next, 8.11 g (26. 7 mmol) of terbium chloride (111) hexahydrate was added dropwise to a solution of 160 ml of ethanol, and the reaction was carried out at room temperature with stirring for 1 hour. After the reaction was completed, hexane 100 m 1 and water 100 m 1 were added to separate the organic layer. After the organic layer was washed with water, dried over sodium sulfate, filtered, and the filtrate was concentrated, and the concentrate was distilled under reduced pressure (210 ° C, 73 Pa) to obtain a viscous yellow liquid (2,6-dimethyl- 1-g of 2-trimethylsuccinyloxy-3,5-heptanedione) gold ethyl (III) (55% yield). Tris (2,6-dimethyl · 2-trimethylsilyloxy-3,5-heptanedione) yttrium (III) is a novel compound having the following physical properties. IR (neat (cm'1): 2965, 1 5 8 5, 1 5 04, 1412, 125 1, 1196, 1048, 841 (The peak unique to cold dione (ΙόΟόοηΓ1) will disappear, and / 3-2 will appear Keto-specific peak (1 5 8 5 0: 1 ^ 1)) Elemental analysis (C36H69〇9Si3Y): Carbon: 52.3%, Hydrogen: 8.66%, 200526802 (37) Yttrium: 10.6% (Theoretical 値: Carbon: 52.8%, hydrogen: 8.49%, yttrium: 109% MS (m / e): 8 1 8, 77 5, 6 8 7, 5 99, 5 1 1, 3 97 '[Example 20] (Evaporation Experiment: Production of oxidized metal thin films) The metal complexes (zinc complexes (Zn (sopd) 2), manganese complexes (Mn (sopd) 3)) and yttrium complexes obtained in Examples 17 to 19 were used respectively. Y (soopd) 3)), the CVD method was used to perform the vapor deposition test in the same manner as described in Example 8, and the film formation characteristics were evaluated by φ. The vapor deposition conditions and the characteristics of the vapor deposition film are shown below. The substrate to be vapor-deposited It is a rectangular object of 7mmx40mm. [Production of zinc oxide film] [Deposition conditions]

Gasification temperature: 17 (TC substrate: Si02 / Si Φ substrate temperature: 4 0 0 t: evaporation time: 30 minutes pressure in the reaction system: 5 3 20Pa 〇2 flow rate: 40ml / min

He flow rate: 60ml / min, [film characteristics] As a result of the film formation operation, it was confirmed that an oxygen film with a film thickness of 70 nm was formed on the substrate -41-200526802 (38) Zinc film (analyzed by XP s). That is, when the zinc complex of the present invention is used as a raw material, a uniform zinc oxide thin film can be formed. [Manufacturing of manganese oxide film] [Steaming conditions] Gasification temperature: 190 ° C Substrate: S i 〇 2 / S i Substrate temperature: 400 ° C Evaporation time: 30 minutes Pressure in reaction system: 5320Pa 〇2 Flow rate: 40ml He flow rate: 60 ml / min [Film characteristics] As a result of the film formation operation, it was confirmed that a 5 Onm & manganese oxide film was formed on the substrate (analyzed by XP S). That is, when the manganese complex of the present invention is used as a raw material, a uniform oxide film can be formed. [Production of yttrium oxide film] [Evaporation conditions] Gasification temperature: 200 ° C Substrate: S i 0 2 / s i Substrate temperature: 4 0 0. (: -42- 200526802 (39) Evaporation time: 30 minutes Pressure in the reaction system: 5 3 20Pa 〇2 flow rate: 40ml / min He flow rate: 60ml / min [film characteristics] As a result of the film formation operation, It was confirmed that an yttrium oxide film having a film thickness of 40 nm was formed (analyzed by XPS). That is, when the yttrium complex of the present invention was used as a raw material, a uniform yttrium oxide film was formed. [Example 21] Synthesis of tris (2,6-dimethyl _2_trimethylsilyloxy-3,5-heptanedione) chromium (III) (Cr (Sopd) 3) 28% sodium methoxide in methanol 11.3 g (5 8.4 Millimoles) was added to a 200ml flask equipped with a stirring device, a thermometer and a dropping funnel, and 2,6-dimethyl-2-trimethylsilyloxy was slowly dropped into the flask while maintaining a liquid temperature of 2 ° C. After 14.7 g (60.2 mmol) of 3,5-heptanedione, stir at the same temperature for 30 minutes. Next, 5.10 g (19.2 mmol) of chromium (III) chloride hexahydrate was added dropwise to dissolve in 20 ml of methanol. The solution was stirred at room temperature for 1 hour under stirring. After the reaction was completed, methanol was concentrated and distilled off, and then 100 ml of hexane and 100 ml of water were added to the concentrate to separate the organic layer. After washing the organic layer with water, Sodium sulfate After drying, filtering and concentrating the filtrate, and distilling under reduced pressure (190 ° C, 51Pa), a purple liquid tris (2,6-dimethyl-2-trimethylsilyloxy-3,5-heptanedione) was obtained. ) Chromium (111) 2. Olg (13% yield) -43- 200526802 (40) Tris (2,6-dimethyl-2-trimethylsilyloxy-3,5-heptanedione Alkyl) manganese (III) is a novel compound with the following physical properties: IR (neat (cm_I) · 2966, 1 5 67, 1 5 0 5, 1413, 1 2 5 2 5 1 1 9 8, 1047, 841 (The peak unique to stone-diketone (1 606CHT1) will disappear, and the peak unique to / 3-diketo group (1 6 6 701 ^ 1) will appear) Elemental analysis (C36H69〇9Si3Cr): Carbon: 55.8 ° /. , Hydrogen: 8.81%, Chromium: 6.7% (Theoretical 値: Carbon: 55.3%, Hydrogen: 8.89%, Manganese: 6.65%) MS (m / e): 781, 5 3 8, 279, 205, 131, 73 [ Example 22 Synthesis of tris (2,6-dimethyl-2-trimethylsilyloxy-3,5-heptanedione) magnesium (III) (Mg (s0Pd) 3) Hydroxide 2.00g of magnesium (34.3 mmol) and 40ml of 1,2 · dimethoxyethane are added to a 200ml flask equipped with a stirring device, a thermometer and a dropping funnel, and then slowly dripped into 2,6-dimethylformamide 17.3 g (70.8 millimoles) of methyl-2-trimethylsilyloxy-3,5-heptanedione were reacted at room temperature with stirring for 30 minutes. After the reaction was completed, 1,2-dimethoxyethane was concentrated and removed, and 80 ml of dichloromethane was added to the concentrate. The concentrated solution was washed with water, dried over sodium sulfate, filtered, and the filtrate was concentrated, followed by distillation under reduced pressure (22 0 ° C, 2 9P a) to obtain a viscous yellow liquid bis (2,6 -dimethylformate). -2 -trimethylsilyloxy-3,5-heptanedione) magnesium (11) 9.01§ (51% yield). Bis (2,6-dimethyl-2-trimethylsilyloxy-3,5-heptanedione) magnesium (11) is a novel compound having the following physical properties. -44- 200526802 (41) IR (neat (cm_1): 2964, 1588, 1506, 1435, 1251 '1195, 1049, 891, 841 (yS-diketone-specific peak (ΙόόοπΓ1) will disappear, yS-diketone Gite-specific peak (1 5 8 8 5 CITT1) will appear) Elemental analysis (C24H4606 SiMg): Carbon: 56.8%, Hydrogen: 9.13%, Magnesium: 4.8% (Theoretical 値: Carbon: 5 6.4 8%, Hydrogen: 9.07 %, Magnesium: 4.76% MS (m / e) ··· 510, 495, 3 79, 251, 131, 73 [Example 23] (Evaporation Test: Production of Oxide Metal Film) Example 2 1 and 2 were used in each case The obtained metal complex (chromium complex (Cr (sopd) 3) and magnesium complex (Mg (sopd) 2)) were subjected to a vapor deposition test by the same method as in Example 8 by CVD method, and the film formation was evaluated. Characteristics. The vapor deposition conditions and the characteristics of the vapor-deposited film are as follows. The substrate to be vapor-deposited is a rectangular object of 7mmx40mm. [Manufacture of chromium oxide film] [Evaporation conditions] Gasification temperature: 19 (TC substrate: Si02 / Si substrate temperature: 350 ° C vapor deposition time: 30 minutes pressure in the reaction system: 3990Pa 〇2 flow rate: 10ml / min-45- 200526802 (42)

Flow rate of He: 15ml / min [Film characteristics] It was confirmed that an oxygen film having a thickness of 30 nm was formed on the substrate. The chromium complex of the present invention was used as a raw material. The result of the film formation operation was a chromium film (analyzed by XPS). That is, can form a uniform chromium oxide thin film. [Manufacturing of magnesium oxide film] [Deposition conditions] Vaporization temperature: 19 ° C Substrate: Si〇2 / Si Substrate temperature: 350 ° C Deposition time: 30 minutes Pressure in reaction system: 3 990Pa 〇2 flow rate : 10 m 1 / min. He flow rate: 15 ml / min. [Film characteristics] The result of the film formation operation was' the formation of a zinc oxide film with a film thickness of 3 5 nm (analyzed by Xp s) on the substrate was determined. When the magnesium complex is used as a raw material, a uniform magnesium oxide film can be formed. [Brief description of the drawings] FIG. 1 is a structural diagram of a vapor deposition device. -46- 200526802 (43) [Description of main component symbols] 1 A: Mass flow regulator 1 B: Mass flow regulator 2: Stop valve 3: Gasifier 4: Reactor 6: Valve 7: Condensate valve 10A: Preheater 1 〇B: Gasifier heater 10C: Reactor heater 2 0: Raw material complex solution 21: Substrate-47

Claims (1)

200526802 十 X. Scope of patent application 1. A metal complex, as shown in the following formula (1), [In formula (1), X is a silyl ether group represented by the following formula (2); Y is a silyl ether group represented by the following formula (2), or a straight or branched chain having 1 to 8 carbon atoms Alkyl group; Z is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; M is ruthenium, iridium, palladium, nickel, vanadium, titanium, chromium, aluminum, gallium, indium, tin, lead, zinc, manganese Yttrium, chromium, magnesium, cobalt, iron, and silver group selected metal atoms; η is the valence of the metal atom shown by M; Rb a / c -Ra ~ 0—Si—Rc (2) Rc (Formula ( In 2), Ra is a linear or branched alkylene group having 1 to 5 carbon atoms; Rb, 1 ^ and Rd are each independently a linear or branched alkyl group having 1 to 5 carbon atoms)]. 2. The metal complex according to item 1 of the scope of the patent application, wherein Y is a straight or branched chain alkyl group having 1 to 8 carbons and 48 to 200526802 carbon atoms, and Z is a hydrogen atom. 3. If the metal complex of item 2 of the patent application range, where Y is a linear or branched alkyl group having 1 to 4 carbon atoms, Ra is dimethyl methyl group, Rb, Re and Rd are all carbon A linear alkyl group having 1 to 3 atoms. 4. A metal complex, characterized in that the Θ-diketonyl group attached with a silane alkyl ether group represented by the following formula (3) is a coordination group, and the metal is ruthenium, iridium, palladium, nickel, vanadium, Titanium, zirconium, aluminum, gallium, indium, tin, lead, zinc, manganese, yttrium, chromium, magnesium, cobalt, iron and silver, [In formula (3), X is a silyl ether group represented by the following formula (2); γ is a silyl ether group represented by the following (2), or a linear or branched chain having 1 to 8 carbon atoms Alkyl; Z is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; Ra—O—Si—R (2) (In the formula (2), Ra is a linear or branched alkylene group having 1 to 5 carbon atoms; Rb -49- 200526802 (3) 'R / and Rd are each independently 1 to 6 carbon atoms 5's linear or branched alkyl group)]]. 5. The metal complex according to item 4 of the application, wherein Y is a linear or branched alkyl group having 1 to 8 carbon atoms, and Z is a hydrogen atom. 6. If the metal complex of item 5 of the patent application, where Y is a linear or branched alkyl group having 1 to 4 carbon atoms, Ra is particularly preferably dimethyl methyl, and Rb, Re and Rd are all It is a linear alkyl group having 1 to 3 carbon atoms. 7 · A method for manufacturing a metal-containing thin film, characterized in that, after vaporizing the metal complex as described in the first item of the patent application, the vaporized metal complex is thermally decomposed and deposited on a substrate, To produce a metal-containing film. 8. The method for manufacturing a metal-containing thin film according to item 7 of the scope of the patent application, wherein the metal complex that is vaporized in the presence of oxygen is thermally decomposed to form a metal oxide thin film on the substrate. 9 · The method for manufacturing a metal-containing thin film according to item 7 of the patent application, wherein the metal complex is vaporized simultaneously with the solvent. 10. The method for manufacturing a metal-containing thin film according to item 9 of the application, wherein the solvent is an aliphatic hydrocarbon, an aromatic hydrocarbon or an ether. 11. A method for manufacturing a metal-containing thin film, characterized in that after vaporizing a metal complex as described in item 4 of the patent application, the gasified metal complex is thermally decomposed and deposited on a substrate to generate Metal film. 1 2. The method of manufacturing a metal-containing thin film according to item 9 of the scope of the patent application, wherein the metal complex formed by vaporization is thermally decomposed in the presence of oxygen, and a metal oxide thin film is formed on the substrate. 13. The method for manufacturing a metal-containing thin film according to item 11 of the scope of patent application -50- 200526802 (4), wherein the metal complex is vaporized simultaneously with the solvent. 14. The method for manufacturing a metal-containing thin film according to item 13 of the application, wherein the solvent is an aliphatic hydrocarbon, an aromatic hydrocarbon or an ether. -51-