WO2005035823A1

WO2005035823A1 - METAL COMPLEX HAVING β-DIKETONATO LIGAND AND METHOD FOR PRODUCING METAL-CONTAINING THIN FILM

Info

Publication number: WO2005035823A1
Application number: PCT/JP2004/015083
Authority: WO
Inventors: Takumi Kadota; Chihiro Hasegawa; Kouhei Watanuki
Original assignee: Ube Industries, Ltd.
Priority date: 2003-10-14
Filing date: 2004-10-13
Publication date: 2005-04-21
Also published as: TW200526802A; JPWO2005035823A1

Abstract

[PROBLEMS] Disclosed is a novel β-diketonato metal complex which can be advantageously used in a method wherein a metal thin film is produced by CVD. [MEANS FOR SOLVING PROBLEMS] Disclosed is a metal complex 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

Specification

TECHNICAL FIELD The present invention relates to a metal complex having a diketonato ligand and a method for producing a metal-containing thin film.

[0001] The present invention relates to a metal complex having a novel β-diketonato ligand and a metal complex such as a metal thin film or a metal oxide thin film formed by a chemical vapor deposition method (CVD method) using the metal complex. The present invention relates to a method for producing a thin film.

Background art

[0002] A thin film of a noble metal such as ruthenium or iridium belonging to Group VIII metal or an oxide thin film thereof has been studied as a material for forming a thin film electrode of a semiconductor memory such as DRAM or FeRAM. This is because these noble metals have excellent electrical properties as electrode forming materials. In addition, use of a thin film of noridium or nickel for improving the density of copper nucleation in copper wiring used for a silicon semiconductor and for improving the adhesion between the copper wiring and its base has been studied.

[0003] As a method of manufacturing these metal thin films, the ability to use the PVD method and the CVD method is taken into consideration. In view of the future tendency of device miniaturization, uniform thin films can be easily manufactured. It is necessary to provide a suitable raw material.

[0004] As a compound for forming a ruthenium, iridium, palladium or nickel-containing thin film by a CVD method, a j8-diketonato complex of each metal is known. However, since the j8-diketonato complex of ruthenium, iridium, palladium and nickel has a high melting point, there is a risk of clogging in the piping during the transport of the raw material in the CVD equipment, which is a problem as a metal raw material used in the CVD method. There is. In addition, there is also a problem in terms of productivity of the target thin film, which has a low deposition rate by the CVD method.

[0005] Patent Document 1 proposes a ruthenium complex of 2,2,6-trimethyl-3,5-heptanedione or 2,6-dimethyl-3,5-heptanedione, and an iridium complex. Although the complex has a relatively low melting point, the complex of V and deviation has a high melting point of 110 ° C. or more, which is a problem as a metal raw material used in the CVD method.

[0006] Patent Document 2 discloses that j8-diketone having a large number of carbon atoms and an alkyl group is used as a ligand. Ruthenium complexes have been proposed. Since this complex is liquid at room temperature, the problem of clogging the piping of CVD equipment can be solved, but the deposition rate of ruthenium film can be reduced by the conventional tris (2,2,6,6-tetramethyl-3,5 heptadionate). As with ruthenium complexes, the industrial productivity of ruthenium thin films remains problematic.

[0007] Patent Documents 3 and 4 disclose a tris (2,4-octanedionato) ruthenium complex (compound of the formula (I)) and a tris (2,4-ota A method for separating a cis-trans isomer of a (tandionato) iridium complex has been proposed.

As for the ruthenium complex, a ruthenium complex of a cyclopentagel group different from the j8-diketonato group has been proposed.

Patent Documents 5-7 describe bis (ethylcyclopentagel) ruthenium complexes which are liquid at room temperature. However, since this ruthenium complex is an organic metal, it is sensitive to moisture, and the operation during synthesis and post-treatment is complicated. In addition, when synthesizing a commercially available trivalent ruthenium chloride as a starting material, a reduction reaction is required because the target bis (ethylcyclopentagenenyl) ruthenium complex is divalent. This poses a problem when considering mass production as an industrial production method, such as using zinc metal as a reducing agent.

[0010] The production of palladium thin films by the CVD method using a radium complex has not been studied much. Patent Document 8 describes an example of palladium thin film production using a bis (2,2,7-trimethyl-3,5-tactadionato) palladium complex in supercritical ethane instead of the CVD method. Reaction in supercritical ethane, not practical.

Non-Patent Document 1 describes production of a nickel thin film by a CVD method using a bis (cyclopentagenenyl) nickel complex. However, this complex is a solid (melting point: 173 ° C).

[0012] Further, use of a vanadium-containing thin film as a thin film material in the fields of semiconductors, electronic components, optical materials, and the like has been studied. Methods for producing vanadium-containing thin films include coating pyrolysis, PVD, and CVD.However, in consideration of composition controllability and the tendency for device miniaturization in the future, the CVD method is easy to produce uniform thin films. Film formation is the preferred method, It is necessary to provide a suitable raw material.

When a vanadium-containing thin film is manufactured by a CVD method, it is known that a complex having an alkoxide group such as VO (OEt) is used as a vanadium source.

Three

A complex containing an alkoxide group is liable to undergo decomposition and deterioration due to the presence of a small amount of moisture, and has a problem that storage is difficult.

[0014] Patent Document 9 discloses that V (dpm) (where dpm is 2,2,6,6-tetramethyl 3,5-heptane

Three

Represents a dionato group. The use of an ι8-diketonato complex represented by This V (dpm) complex is stable in the presence of moisture because it does not contain alkoxides.

Three

However, when a raw material with a high melting point of 155 ° C is supplied, there is a risk of clogging of the piping in the CVD equipment, which is a problem as a raw material for thin film production by the CVD method.

[0015] Thin films containing oxides of metal elements such as titanium, zirconium, and hafnium belonging to Group IVA of the periodic table have been studied as materials in the fields of semiconductors, electronic components, optical components, and the like. In particular, in recent years, development of hafnium oxide has been promoted as a gate insulating film of a transistor. Methods for producing thin films containing these elements include coating pyrolysis, PVD, and CVD.However, in consideration of the composition controllability of film formation and the response to miniaturization of semiconductor devices, the CVD method is used. Is the most preferred method.

[0016] As a raw material for producing a thin film containing a Group IVA metal element by a CVD method, metal alcoholates such as Ti (0 Et) or described in Patent Documents 10 to 12 are used.

Four

Metal complexes containing alkoxide groups and β-diketonato groups are known!

[0017] Since all of the above metal complexes contain an alkoxide group, there is a concern that the metal complex may be decomposed and deteriorated due to the presence of a small amount of water, and the problem of water management in the solvent during storage or synthesis remains. In addition, most of the complexes described in the above patent documents except for some titanium complexes, most of the titanium complexes, zirconium complexes and hafnium complexes are solid at room temperature. There is a risk of clogging in the middle of the piping, which is a problem as a raw material in the CVD method.

Patent Document 13 discloses that Hf (dpm) containing no alkoxide group (where dpm is 2, 2, 6, 6

Four

-Representing a tetramethyl-3,5-heptanedionato group). Although this complex is relatively stable to moisture and the like, its melting point is as high as 315 ° C. There is a problem of clogging of the piping, which is also a problem as a raw material in the CVD method.

Thin films containing metals such as boron, aluminum, gallium, and indium, which are metals belonging to Group III elements, or compounds thereof are being studied as materials in the fields of semiconductors, electronic components, optical components, and the like. ing. For example, the use of an aluminum oxide film as a functional thin film for an electronic device such as a gate insulating film of a semiconductor memory has been studied, and an indium oxide film has been used as a transparent electrode film. Methods for producing thin films containing these metals include the coating pyrolysis method, PVD method, and CVD method.However, considering the composition controllability of the thin film and the tendency for device miniaturization in the future, a uniform thin film can be produced. Easy! ヽ Film formation by the CVD method is a preferable method, and it is necessary to provide a suitable raw material.

[0020] As a raw material for producing a thin film containing a Group III metal by the CVD method, there are trialkylmetal complexes such as trimethylaluminum and trimethylgallium used for the production of compound semiconductors. It has the drawback that it deteriorates violently due to the presence of air and air, and is difficult to handle due to its ignitability. On the other hand, Al (dpm) (dpm is 2,

Three

Alkali (dpm) complex is a solid with a melting point of 265 ° C. | 8-diketonatoluminum-dum complex represented by 2,6,6-tetramethyl 3,5-heptanedionato group) ,material

Three

There is a risk of clogging of the piping inside the CVD equipment during supply, which is a problem as a raw material for thin film production by the CVD method. Patent Documents 14 and 15 disclose an aluminum complex containing an alkoxide group in the molecule.However, the complex containing the alkoxide group is also degraded and deteriorated by the presence of a small amount of water. However, there is a problem with its preservability. Further, Patent Literature 16 proposes an alkylaluminum hydride. However, like the trialkylaluminum, this complex is severely deteriorated by a small amount of moisture or air, and is difficult to handle because of its ignitability. At present, few Group III metals other than aluminum, such as boron, gallium and indium, have been developed except for trialkyl metal complexes, and j8-diketonato complexes of these metals, for example, tris (acetylacetonato) indium Complexes, such as In (dpm), are solids with a high melting point,

Three

This is a problem as a raw material for producing a thin film.

Next, tin and lead oxide thin films belonging to Group IVB metals are used in fields such as semiconductors and electronic components. Investigations are being made on materials such as transparent conductive thin films such as tin oxide and tin-doped indium oxide (ITO), BTS (barium, titanium, tin oxide), PZT (lead, zirconium, and titanium oxide). ), Etc. A Group IVB metal oxide is used for the ferroelectric film. Methods for producing thin films containing Group IVB metals include coating pyrolysis, PVD, and CVD.However, in consideration of composition controllability and future trends in device miniaturization, uniform thin films can be produced. The preferred method is to form a film by the easy CVD method, and it is necessary to provide a suitable raw material.

As a raw material for producing a thin film containing a Group IVB metal element by a CVD method, a β-diketonato metal complex may be mentioned. For example, Sn (AcAc) (where Ac Ac is an acetyl-acetonato group

2

), Sn (dpm) (dpm is bis (2,2,6,6-tetramethyl-3,5-heptandio)

2

Represents a nato group). These Sn complexes are extremely sensitive to moisture and have a problem of moisture management during synthesis or storage (Patent Document 17). In Patent Document 18, tetramethyltin having a Sn—C bond in which an alkyl group is directly bonded to Sn (denoted as Sn (CH 2)) is used as a raw material for producing a BTS thin film that is an oxide-based ferroelectric substance. Although there is a description to use,

3 4

Can avoid the problem of decomposition by water like the above j8-diketonato complex.

3 4

However, compared to the use of Sn (dpm), the resulting BTS film is inferior in characteristics. this is,

2

It is considered that the Sn—C bond between Sn and the alkyl group has a strong covalent bond, so that the Sn—C bond is less likely to be decomposed than the Sn (dpm) complex having the Sn—O—C bond. . Likewise

2

And dibutyltin diacetate having a Sn—C bond and described in Patent Document 19 (CH 2)

3 2

A similar problem exists with tin complexes such as Sn (dpm).

2

[0023] On the other hand, as for the lead complex, Pb (dmp) (Patent Document 20) or bis (1,3-diphen-

2

There have been proposals for the use of j8-diketonato lead complexes, such as ru 1,3-propanedionato) lead (Patent Document 21), but these are all solids with a high melting point. There is a risk of clogging of the piping in the raw material supply system in the CVD equipment, which is a problem as a raw material for thin film production by the CVD method.

[0024] In recent years, many researches and developments have been made on zinc compounds, manganese compounds, and yttrium compounds as materials in the fields of semiconductors, electronic components, and the like. Zinc-based composites are used as transparent conductive films such as solar cells and liquid crystal display devices, and as surface acoustic wave devices. Compounds have been used and studied as thermistor elements, which take advantage of the fact that they have high resistance to temperature change and resistance change with temperature, and yttrium compounds as materials for copper oxide-based high-temperature superconductors. hand! / As a method for producing a thin film containing these metal atoms, a uniform thin film can be easily produced, and film formation by a CVD method has been most actively employed. You.

[0025] Raw materials for producing a thin film containing zinc, manganese, and yttrium atoms by the CVD method include, for example, Zn (acac) (acac = acetyl acetonato group), Zn (dpm) (dpm

twenty two

= Bis (2,2,6,6-tetramethyl-3,5 heptadionato group)), Mn (acac), Mn (ac

2 ac), Mn (dpm), Y (dpm), Y (tod) (tod = bis (2,2,6,6-tetramethyl-1,3,5

3 3 3 3

Metal complexes having a β-diketonato group as a ligand such as an octane dionato group)) are known! / Pull [0026] As a production example of a zinc-containing thin film using a zinc complex, for example, Zn (dpm) is used. hand

(2) A method for producing a zinc oxide film by a plasma CVD method (see, for example, Patent Documents 22 and 23), and a method for producing a zinc oxide film by a thermal CVD method using Zn ( _acac ).

2

The method (Patent Document 24) is known. However, since all zinc complexes are solid at room temperature and have a high melting point, there is a risk of clogging of the piping in the raw material supply system in the CVD apparatus during film formation by the CVD method. Not suitable as a raw material for thin film production.

As an example of the production of a manganese-containing thin film using a manganese complex, for example, Mn (acac)

A method for producing a manganese oxide film by a CVD method using the above method is known (Non-Patent Document 2). However, this manganese complex, like the zinc complex, has a problem that it is solid at room temperature and has a high melting point.

[0028] Examples of the production of an yttrium-containing thin film using an yttrium complex include, for example, Y (tod)

A method of manufacturing an yttrium oxide film by a CVD method using No. 3 is known (Patent Document 25). However, this yttrium complex, like the zinc complex, is solid at room temperature and has a high V ヽ melting point!

Many researches and developments have been made on chromium compounds and magnesium compounds as materials in the fields of semiconductors, electronic components and the like. Chromium compounds for optical fiber lasers The use and study of magnesium compounds for the production of glass and the coating of steel sheet surfaces, and the use of magnesium compounds as protective films on dielectric glass layers of plasma display panels have been conducted. As a method of producing a thin film containing these metal atoms, a uniform thin film can be easily produced! The film formation by the cVD method is most actively employed, and a suitable raw material is required. I have.

[0030] The chromium atom CVD by the CVD method is used as a raw material for producing a thin film containing a magnesium atom, such as Cr (acac) (acac = acetyl acetonato group), Cr (dpm) (dpm = 2, 2, 6, 6—te

3 3 -Diketonato such as tramethyl-3,5-heptanedionato group), Mg (acac), Mg (dpm)

twenty two

Complex with a carbonyl group as a ligand, metal complex with a carboxy group such as Cr (CO) as a ligand

6

Cyclopentajenyl groups such as MgCp (Cp cyclopentagenenyl group) and ligands

2

Are known metal complexes!

[0031] An example of the production of a chromium-containing thin film using a chromium complex is a plasma using Cr (dpm).

Three

Method of manufacturing chromium oxide film by CVD method (Patent Documents 26 and 27) and using Cr (CO)

A method of coating a steel sheet with chromium (Patent Document 28) is known. Examples of the production of a magnesium-containing thin film using a magnesium complex include Mg (acac), Mg (dpm) and

22.Manufacture magnesium oxide films by thermal CVD or plasma CVD using MgCp.

2

A known method is known (Patent Documents 27 and 29). However, since all metal complexes are solid at room temperature and have a high melting point, there is a risk of clogging of the piping in the raw material supply system in the CVD equipment during film formation by the CVD method. It is not suitable as a raw material for thin film production by the method.

A copper complex having β-diketonate having a silyl ether bond as a ligand is described in Patent Document 30.

Patent Document 1: JP-A-949081

Patent Document 2: JP-A-2000-212744

Patent Document 3: JP-A-2003-55294

Patent Document 4: JP 2003-64019 A

Patent Document 5: JP-A-11 35589

Patent Document 6: JP-A-2002-105091 Patent Document 7: JP-A-2003-55390

Patent Document 8: US Patent No. 5789027

Patent Document 9: JP-A-2003-49269

Patent Document 10: Japanese Patent Application Laid-Open No. 2001-200367

Patent Document 11: Japanese Patent Application Laid-Open No. 2002-69641

Patent Document 12: Japanese Patent Application Laid-Open No. 2002-69027

Patent Document 13: Japanese Patent Application Laid-Open No. 2002-249455

Patent Document 14: JP 2001-2142689 A

Patent Document 15: JP-A-2003-34868

Patent Document 16: JP-A-9-12581

Patent Document 17: JP-A-6-234779

Patent Document 18: JP-A-9-249973

Patent Document 19: JP-A-7-25886

Patent Document 20: JP-A-2002-155008

Patent Document 21: JP-A-2003-226664

Patent Document 22: JP-A-2000-273636

Patent Document 23: JP-A-2003-89875

Patent Document 24: JP 2003-31846 A

Patent Document 25: JP-A-9-228049

Patent Document 26: JP-A-6-92647

Patent Document 27: JP-A-11 3665

Patent Document 28: JP-A-2-66171

Patent Document 29: JP-A-10-269952

Patent Document 30: WO 03Z064437A1 Nonfret

Non-patent document 1: Electrochemical and Solid-State letters, 5 (6) C64- C66 (2002) Non-patent document 2: J. Electrochemical Society, 142 (9), 3137 (1995)

Disclosure of the invention

Problems the invention is trying to solve [0034] The present invention relates to ruthenium, iridium, palladium, nickel, vanadium, titanium, zirconium, hafnium, aluminum, gallium, indium, tin, lead, zinc, manganese, yttrium, chromium, magnesium, cobalt, iron, and It is an object of the present invention to provide a novel complex of a metal atom selected from the group consisting of silver. In addition, because of its low melting point, excellent stability in air, and excellent film-forming properties, it is suitable for forming metal-containing thin films such as metal thin films or metal oxide thin films by CVD. The purpose is to provide

Means for solving the problem

The present inventor has proposed a metal complex having β-diketonate having a silyl ether bond as a ligand.

Thus, the present invention was found to be a compound that solved the above-mentioned problems, and the present invention was completed.

[0036] The present invention provides a metal complex represented by the following formula (1):

[0037] [Formula 1]

[In equation (1),

X represents a silyl ether group represented by the following (2),

Υ represents a silyl ether group represented by the following (2) or a straight-chain or branched alkyl group having 118 carbon atoms;

Ζ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,

、 Is ruthenium, iridium, palladium, nickel, vanadium, titanium, zirconium, hafnium, aluminum, gallium, indium, tin, lead, zinc, manganese, yttrium, chromium, magnesium, conoretto, iron, and Metal atom selected from the group consisting of silver Represents

n represents the valence of the metal atom represented by M (for example, 2, 3, 4);

[Formula 2]

(In the formula (2), R ^a represents a straight-chain or branched alkylene group having 115 carbon atoms, and R ^b and RR ^d each independently represent Represents a straight-chain or branched alkyl group having 1 to 5 carbon atoms).

The present invention also relates to a metal complex having a | 8-diketonato group having a silyl ether group represented by the following formula (3) as a ligand (where the metal is ruthenium, iridium, palladium, nickel, vanadium) , Titanium, zirconium, hafnium, aluminum, gallium, indium, tin, lead, zinc, manganese, yttrium, chromium, magnesium, conoreto, iron, and silver.

[0042] [Formula 3]

[In equation (3),

X represents a silyl ether group represented by the following (2),

Y is a silyl ether group represented by the following (2) or a straight chain having 118 carbon atoms. Or a branched alkyl group,

Z represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,

[0044] [Formula 4]

R ^b

R ^a — 0— Si / one R one (2)

R ^d

(In the formula (2), R ^a represents a linear or branched alkylene group having 115 carbon atoms, and R ^b and RR ^d each independently represent Represents a straight or branched alkyl group having 1 to 5 carbon atoms))].

It is preferable that Y is a linear or branched alkyl group having 18 to 18 carbon atoms, and Z is a hydrogen atom. In particular, Y is a straight-chain or branched alkyl group having 14 to 14 carbon atoms, ^Ra is a dimethylmethylene group, and R ^b and RR ^d are each a straight-chain or branched alkyl group having 13 to 13 carbon atoms. It is preferably an alkyl group.

The present invention also vaporizes a metal complex having the above-mentioned formula (1) or a metal complex having a β-diketonato group having a silyl ether group represented by the above-mentioned formula (3) as a ligand. There is also a method for producing a metal-containing thin film, which comprises thermally decomposing the deposited metal complex and depositing it on a substrate to form a metal-containing thin film.

[0048] By performing the thermal decomposition of the vaporized metal complex in the presence of oxygen, a metal oxide thin film can be formed on the substrate.

The invention's effect

[0049] The metal complex of the present invention has excellent stability and a low melting point as compared with the conventionally known corresponding metal complex, and also has a high deposition rate of the metal-containing thin film. It is effective for industrial production of various metal-containing thin films.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.

In the present invention, specific examples of β-diketones used as ligands of metal complexes and having a silyl ether group include the following compounds.

[0051] [Formula 5]

[0052] These diketones are obtained by reacting a silylated organic acid ester with a ketone in the presence of a base, adding an acid treatment to the product, and isolating the product by a purification means such as distillation or column chromatography. · It can be obtained by a conventionally known method for purification. These β-diketonato complexes of the metal having the | 8-diketone conjugate as a ligand can be obtained by a known method of reacting β-diketone with a salt of the metal in the presence of a base. The metal complex obtained by the reaction can be purified by a column chromatography method or a distillation method.

Examples of metal complexes containing a / 3 diketonato ligand having a silyl ether group are shown below. The Micromax ²⁺ in the lower SL each formula, the divalent metal ions ^{^{(eg, Ni 2+, Pd 2+, Sn}} Pb 2+, Zn Mg 2 +, Co 2+, Ag 2+) a, M ³⁺ Is a trivalent metal ion (e.g., Lu ³⁺ , Ir ³⁺ , V ³⁺ , Al ³⁺ , B ³⁺ , Ga ³⁺ , In ³⁺ , Mn ³⁺ , Y ³⁺ , Cr ³⁺ , Fe ³⁺ ), and M ⁴⁺ represents a tetravalent metal ion (eg, Hf ⁴⁺ , Zr ⁴⁺ , Ti ⁴⁺ ).

[0054] [Formula 6]

[0055] In the CVD method, it is necessary to vaporize a raw material compound for forming a thin film. The method of vaporizing a metal complex containing a β-diketonato ligand having a silyl ether group according to the present invention is as follows. A method in which the complex is charged or transported into a chamber and vaporized, or these complexes are converted into a suitable solvent (eg, an aliphatic hydrocarbon such as hexane, octane, methylcyclohexane, or ethylcyclohexane, an aromatic hydrocarbon such as toluene, Then, the solution diluted with tetrahydrofuran or ether such as dibutyl ether) is pumped by a liquid transfer pump. A so-called solution method in which the gas is introduced into a vaporization chamber and vaporized can be used.

For the vapor deposition on the substrate, a known CVD method can be used. That is, the metal complex vapor of the present invention is contact pyrolyzed with a heated substrate under a reduced pressure or in the presence of an inert gas to deposit a metal thin film, or the metal complex vapor is present in the presence of a reducing gas such as hydrogen. A method of depositing a thin film, or a method of depositing an oxidized thin film of the element under an oxidizing gas such as oxygen, and a method of depositing a nitride film of the element in the presence of a nitrogen-containing basic gas such as ammonia gas. For precipitation. Further, a method of depositing the metal-containing thin film by a plasma CVD method can also be used.

The following conditions can be mentioned as vapor deposition conditions when a metal-containing thin film is formed by vapor deposition using the metal complex containing a β-diketonato ligand having a silyl ether group of the present invention. The pressure in the reaction system is preferably lPa-200 kPa, more preferably lOPa-11 OkPa, the substrate temperature is preferably 50-700 ° C, more preferably 100-500 ° C, and the vaporization temperature of the metal complex. Is preferably 50-250 ° C, more preferably 90-200 ° C.

[0058] The content of the oxidizing gas in the formation of the metal oxidized thin film using an oxidizing gas such as oxygen is preferably 10 to 90% by volume, more preferably 20 to 90% by volume. — 70% by volume. When a reducing gas such as hydrogen is used for vapor deposition of the metal complex, the content ratio of the reducing gas to the total gas amount is preferably 10 to 95% by volume, more preferably 30 to 90% by volume. When a nitrogen-containing basic gas such as ammonia is used for vapor deposition of the metal complex, the content ratio of the nitrogen-containing basic gas to the total gas amount is preferably 10 to 95% by volume, and more preferably 20 to 90% by volume. .

Example

[Example 1]

Synthesis of 2, 6-dimethyl-2 (trimethylsilyloxy) 3,5-heptadione (β-diketone represented by the following formula, called sopd) [0060] [Formula 7]

[0061] In a 500-mL flask, 13.7 g (0.351 mol) of sodium amide was suspended in 200 mL of hexane, and 26.7 g of 2- (trimethylsilyloxy) -2-methyl-methyl propionate was added thereto. 40 mol) was added. To the solution was added dropwise 12. lg (0.141 mol) of 3-methyl-2-butanone, and the mixture was kept at 15 ° C. As the reaction progressed, ammonia gas was generated in the reaction liquid. After reacting at 15 ° C for 1 hour, the reaction solution was made weakly acidic with acetic acid. The obtained hexane layer was washed with water, dried over anhydrous sodium sulfate, and distilled (101 ° C, 8 mmHg) to remove the desired 2,6-dimethyl-2- (trimethylsilyloxy) -3,5-heptadione. 18.8 g (0.077 mol, yield 55%) were obtained.

[0062] The obtained compound was identified by NMR, IR, and MS.

NMR (CDCl): δ 0.14 (s, 9H), 1.14 (d, 6H), 1.39 (s, 6H), 2.44

Three

One 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

[Example 2]

Synthesis of tris (2,6 dimethyl-2- (trimethylsilyloxy) -3,5 heptanedionato) luteum complex [Ru (sopd)]:

Three

3. 63 g (13.9 mm monole) of Shiojiri Noleteium (III) 3 water was added to a 100 mL flask and dissolved in 30 mL of ethanol. At room temperature, 7 g (36.3 mmol) of a 28% sodium methylate Z methanol solution was added, and the mixture was stirred at room temperature for 30 minutes. Thereafter, 10 g (40.9 millimonole) of 2,6 dimethyl-2 (trimethinolesilyloxy) 3,5-heptandiene was added to the mixture, and the mixture was heated to 100 ° C with 30 minutes of power. During the heating, methanol, ethanol and water were distilled off. Then the temperature The temperature was raised to 180 ° C over 30 minutes. At that point, the solution turned from dark brown to red. Thereafter, the temperature was returned to room temperature, 100 mL of hexane was added, and the mixture was filtered to obtain a red solution. After washing with water, drying and concentration were performed to obtain a red liquid. 2.72 g of the target compound, orange-red liquid tris (2,6-dimethyl-2- (trimethylsilyloxy) -3,5-heptanedionato) ruthenium complex, was obtained by column chromatography (hexane / ethyl acetate = 9.5 / 0.5) (3.3 mmol, yield: 24%).

[0064] The obtained i-danied product was identified by IR analysis, elemental analysis, and MS analysis.

IR (cm ^-1 ): 2966, 1545, 1501, 1403, 1251, 1199, 1047, 890, 842 Elemental analysis: CH OSiRu

36 69 9 3

Measured value C: 52.7%, H: 8.20%, Ru: 12%

Theoretical value C: 52.0%, H: 8.37%, Ru: 12.2%

MS (m / e)

Measured values: 831, 588, 131, 73

Theoretical value (Exact mass): 831.33

[0065] In the IR analysis, disappeared peaks of j8- diketone specific 1606Cm- ^1, diketonato group specific peak 1545 cm ¹ has appeared instead. This ruthenium complex is a new substance

[Example 3]

Synthesis of bis (2,6-dimethyl-2- (trimethylsilyloxy) -3,5-heptanedionato) palladium complex [Pd (sopd)]:

2

In a 300 mL flask, 160 mL of hexane was taken, and 1.2 g (30 mimol) of 60% hydrogen chloride was suspended. 6.10 g (25.0 mmol) of 2,6-dimethyl-2- (trimethylsilyloxy) -3,5-heptanedione was added dropwise to the suspension under ice cooling. Hydrogen generation was observed. When the generation of hydrogen had ceased, a solution of 2.80 g (12.5 mmol) of palladium acetate dissolved in 30 mL of methylene chloride was added to the hexane solution. After reacting at room temperature for 1 hour, 100 mL of water was added, the organic layer was separated, washed with water, dried and concentrated to obtain an orange liquid. By column chromatography (hexane Z ethyl acetate = 9.5 / 0.5), the target substance, a yellow solid, bis (2,6-dimethyl-2- (trimethylsilyloxy) -3,5-heptanedi (Onato) palladium complex 5.40 g (9.10 mmol, yield: 73%) was obtained.

[0067] Identification of the obtained i-danied product was performed by IR analysis, elemental analysis, and MS analysis.

IR (cm ^-1 ): 2964, 1556, 1504, 1405, 1252, 1198, 1038, 890, 841 Elemental analysis: CH OSiPd

24 46 6 2

Measured value C: 48.3%, H: 7.90%, Pd: 18%

Theoretical value C: 48.6%, H: 7.82%, Pd: 17.9%

MS (m / e)

Measured values: 592, 131, 73

Theoretical value (Exact mass): 592.19

Melting point: 95 ° C

[0068] In the IR analysis, it disappeared peaks of j8- diketone specific 1606Cm- ^1, diketonato specific peak 1556 ¹ has appeared instead. This palladium complex is a novel substance.

[Example 4]

Synthesis of bis (2,6-dimethyl-2- (trimethylsilyloxy) -3,5-heptanedionato) nickel complex [Ni (sopd)]:

2

An aqueous solution of 5.00 g (20.0 mmol) of nickel acetate tetrahydrate dissolved in 35 mL of water in a 100 mL flask was charged with 9.90 g (40.6 mmol) of 2,6-dimethyl-2- (trimethylsilyloxy) -3,5-heptanedion. ) Was dissolved in 40 mL of hexane. An aqueous sodium hydroxide solution (60 g of NaOH was dissolved in 10 mL of water) was reacted at room temperature for 1 hour while stirring at room temperature. Thereafter, 10 mL of 25% aqueous ammonia was added to make the two layers into a uniform liquid. After that, a hexane layer was obtained by liquid separation, washed with water, dried and concentrated to obtain a blue-green liquid. This was distilled (185 ° C, 0.3 torr) to obtain 5.67 g (10 .6) of a dark green liquid, bis (2,6-dimethyl-2- (trimethylsilyloxy) -3,5-heptanedionato) nickel complex, which was the target substance. 4 mmol, yield: 52%).

[0070] Identification of the obtained i-danied product was performed by IR analysis, elemental analysis, and MS analysis.

IR (cm ^-1 ): 2963, 1579, 1508, 1413, 1252, 1195, 1050, 892, 841 Elemental analysis: CH OSiNi

24 46 6 2

Measured value C: 52.3%, H: 8.71%, Ni: ll% Theoretical value C: 52.8%, H: 8.50%, Ni: 10.8%

MS (m / e)

Measurements: 545, 544, 131, 73

Exact mass: 545.48

[0071] In the IR analysis, disappeared peaks of j8- diketone specific 1606Cm- ^1, diketonato group specific peak 1579Cm ¹ has appeared instead. This nickel complex is a novel substance.

[Example 5]

Deposition experiment (production of ruthenium thin film):

Using the Ru (sopd) complex obtained in Example 2, a deposition test was performed by a CVD method.

Three

The film forming characteristics were evaluated. For comparison, a vapor deposition test using a tris (2,4-octanedionato) ruthenium complex was performed.

The apparatus shown in FIG. 1 was used for the vapor deposition test. The Ru (sopd) complex 20 in the vaporizer 3 (glass ampoule) is heated by the heater 10B and vaporized, and the mass flow controller 1A

Three

After passing through the helium gas introduced after preheating in the preheater 10A, the gas leaves the vaporizer and is introduced into the reactor 4. The pressure in the reaction system is controlled to a predetermined pressure by opening and closing a valve 6 in front of a vacuum pump, and monitored by a pressure gauge 5. The center of the glass reactor has a structure that can be heated with a heater at 10C. The Ru (sopd) complex introduced into the reactor

Three

The thermal decomposition is performed on the surface of the substrate 21 to be deposited, which is set at the center of the reactor and heated to a predetermined temperature by the heater 10C, and ruthenium metal is deposited on the substrate 21. The gas exiting the reactor 4 is exhausted into the atmosphere via a trap 7 and a vacuum pump. As the substrate 21 to be deposited, a rectangular substrate having a size of 7 mm × 40 mm was used.

The deposition conditions and the characteristics of the obtained film are shown below.

[0073] [Evaporation conditions]

Evaporation temperature: 150 ° C

Substrate: SiO / Si

2

Substrate temperature: 350 ° C

Deposition time: 10 minutes

Reaction system pressure: 532Pa He flow rate: 15mLZ min

C film characteristics]

(1) As a result of the film formation operation using the Ru (sopd) complex as a raw material, a lOOnm-thick Ru film (

Three

XPS analysis) was formed!

(2) Even after the film formation operation using the tris (2,4-octanedionato) ruthenium complex as a raw material, almost no film formation was observed on the substrate.

[Example 6]

Deposition experiment (production of nickel thin film):

The Ni (sopd) complex obtained in Example 4 was subjected to a CVD method using the apparatus shown in FIG.

2

Was carried out. Vaporizer 3 is filled with Ni (sopd) complex and converted to helium gas.

2

Except that the gas exiting the entrainer was introduced into the reactor 4 together with the hydrogen gas introduced via the mass flow controller 1B and the stop valve 2, and the deposition conditions were changed as follows. Vapor deposition was performed in the same manner as in 5.

[Deposition conditions]

Evaporation temperature: 200 ° C

Substrate: SiO / Si

2

Substrate temperature: 300 ° C

Deposition time: 30 minutes

Reaction system pressure: 3990Pa

H

2 flow rate: 480mLZ min

He flow rate: 80mLZ min

C film characteristics]

As a result of the film formation operation using the Ni (sopd) complex as a raw material, a 50 nm thick Ni film (XPS

2

Analysis) was formed.

From the results of Examples 5 and 6, the / 3 diketonato complex of the present invention having a silyl ether group was

It is important to have excellent film-forming properties as compared with conventionally known materials.

[Example 7] Synthesis of tris (2,6-dimethyl-2- (trimethylsilyloxy) -3,5-heptanedionato) vanadium complex (V (sopd)):

Three

5.20 g (33.1 mm monole) of Shii-Dani Nonadium (III) was placed in a 300 mL flask, and dissolved in 50 mL of ethanol. At room temperature, 22 g (114.1 mmol) of a 28% sodium methylate Z methanol solution was added, and the mixture was stirred at room temperature for 10 minutes. Thereafter, 24.3 g (99.4 mmol) of 2,6-dimethyl-2- (trimethylsilyloxy) -3,5-heptanedione was added, and the mixture was stirred at room temperature for 30 minutes. Thereafter, 50 mL of hexane was added to the mixture, and 80 mL of water was added to the mixture, followed by liquid separation to obtain a brown solution. After washing with water, drying and concentration were performed to obtain a brown liquid. By column chromatography (hexane Z-ethyl acetate = 9.5 / 0.5), the desired brown liquid tris (2,6-dimethyl-2- (trimethylsilyloxy) -3,5-heptanedionate) was obtained. 10.6 g (13.6 mmol, yield: 41%) of the vanadium complex were obtained.

[0078] Identification of the obtained i-bonded product was performed by IR analysis, elemental analysis, and MS analysis.

IR (cm ^-1 ): 2966, 1560, 1506, 1409, 1252, 1198, 1048, 890, 842 Elemental analysis: CHO Si V

36 69 9 3

Measured value C: 55.0%, H: 8.85%, V: 6.5%

Theoretical value C: 55.4%, H: 8.90%, V: 6.5%

MS (m / e)

Measurements: 780, 537, 131, 73

Theoretical value (Exact mass): 780. 37

[0079] In the IR analysis, disappeared peaks of j8- diketone specific 1606Cm- ^1, diketonato group specific peak 1560 cm ¹ has appeared instead. This vanadium complex is a new substance

[Example 8]

Deposition experiment (production of vanadium oxide thin film):

Using the vanadium complex obtained in Example 7, a deposition test was performed by a CVD method to evaluate film formation characteristics.

The apparatus shown in Fig. 1 was used for the evaluation test. The vanadium complex 20 placed in the vaporizer 3 (glass ampule) is heated by the heater 10B and vaporized, and the mass flow controller 1A After passing through the preheater 10A, the gas leaves the vaporizer accompanying the helium gas introduced after preheating. The gas exiting the vaporizer 3 is introduced into the reactor 4 together with the oxygen gas introduced via the mass flow controller 1B and the stop valve 2. The pressure in the reaction system is controlled to a predetermined pressure by opening and closing a valve 6 in front of a vacuum pump, and monitored by a pressure gauge 5. The central part of the glass reactor has a structure that can be heated by a heater 10C. The vanadium complex introduced into the reactor is oxidized and thermally decomposed on the surface of the substrate 21 to be deposited, which is set in the center of the reactor and heated to a predetermined temperature by the heater 10C, and a vanadium oxide film is formed on the substrate 21. Precipitates. The gas exiting the reactor 4 is exhausted into the atmosphere via a trap 7 and a vacuum pump.

[0081] The deposition conditions and the characteristics of the deposited film are shown below. As the substrate to be deposited, a rectangular substrate having a size of 7 mm × 40 mm was used.

[0082] [Evaporation conditions]

Evaporation temperature: 150 ° C

Substrate: SiO / Si

2

Substrate temperature: 400 ° C

Deposition time: 15 minutes

Reaction system pressure: 1330Pa

O 2 flow rate: lOmLZ min

He flow rate: 15mLZ min

C film characteristics]

As a result of the film formation operation, it was confirmed that a 30 nm-thick oxide vanadium film (by XPS analysis) was formed on the substrate. That is, it can be understood that a uniform oxide vanadium thin film could be formed by using the vanadium complex of the present invention as a raw material.

[Example 9]

Synthesis of tetrakis (2,6-dimethyl-2- (trimethylsilyloxy) -3,5-heptanedionato) hafium complex (Hf (sopd)):

Four

In a 50 mL flask, 1.60 g (4.46 mm monole) of hafnium tetraethoxide Hf (OEt)

Four

And 2,6-dimethyl-2- (trimethylsilyloxy) -3,5-heptanedione 5 mmol), and the temperature was gradually increased to 220 ° C over 2 hours. During that time, about 1 mL of ethanol was distilled off from the reaction system. Thereafter, the mixture was concentrated at 120 ° C. 40 Pa for about 1 hour, and 80 mL of hexane was added at room temperature. After filtering off the insoluble matter, the hexane layer was washed with water, dried and concentrated, and distilled (240 ° C., 67 Pa) to obtain 3.0 g (2.60 mmol, yield: 58%) of the target substance as a pale yellow solid. Got.

[0084] The obtained i-danied product was identified by IR analysis, elemental analysis, and MS analysis.

IR (cm ^-1 ): 2967, 1586, 1540, 1509, 1440, 1252, 1199, 1047, 892, 841 Elemental analysis: CHO Si Hf

48 92 12 4

Measured value C: 50.3%, H: 8.10%, Hf: 15.5%

Theoretical value C: 50.0%, H: 8.05%, Hf: 15.5%

MS (m / e)

Measurements: 998, 909, 131, 73

Exact mass: 1152. 51

Melting point: 68 ° C

[0085] In the IR analysis, the peak at 1606cm- ¹ peculiar to j8-diketone disappeared, and a peak at 1586cm- ¹ peculiar to diketonato groups appeared instead. This hafnium complex is a new substance

[Example 10]

Deposition experiment (production of hafnium oxide thin film)

Using the Hf (sopd) complex obtained in Example 9, a deposition test by the CVD method was performed.

Four

The method was performed by the method described in 8, and the film formation characteristics were evaluated.

[0087] The deposition conditions and the characteristics of the deposited film are shown below. As the substrate to be deposited, a rectangular substrate having a size of 7 mm × 40 mm was used.

[0088] [Evaporation conditions]

Evaporation temperature: 200 ° C

Substrate: SiO / Si

2

Substrate temperature: 400 ° C

Deposition time: 30 minutes Reaction system pressure: 5320Pa

O flow rate: 40mLZ

2 minutes

He flow rate: 60mLZ min

C film characteristics]

As a result of the film formation operation, it was confirmed that a hafnium oxide film having a thickness of 30 nm (by XPS analysis) was formed on the substrate. That is, it can be seen that a uniform vanadium oxide thin film could be formed by using the hafnium complex of the present invention as a raw material.

[Example 11]

Synthesis of tris (2,6-dimethyl-2- (trimethylsilyloxy) -3,5-heptanedionato) aluminum-complex (Al (sopd)):

Three

5.60 g (34.5 mmol) of aluminum triethoxide and 31.3 g (128.1 mmol) of 2,6-dimethyl-2- (trimethylsilyloxy) -3,5-heptanedione were placed in a 200 mL flask. The temperature was gradually increased to 170 ° C. over 1 hour. During that time, 6 mL of ethanol was distilled off from the reaction system. Thereafter, the mixture was concentrated at 120 ° C. and 40 Pa for about 1 hour, and then 80 mL of hexane was added at room temperature. After filtering off the insoluble matter, the hexane layer was washed with water, dried and concentrated to obtain a brown liquid. By distillation and purification (190 ° C, Z53Pa), 9.25 g (12.2 mmol, yield) of the target yellow liquid tris (2,6-dimethyl-2- (trimethylsilyloxy) -3,5-heptandionato) aluminum complex was obtained. Rate: 35%).

[0090] The identification of the obtained i-danied product was performed by IR analysis, elemental analysis, and MS analysis.

IR (cm " ¹ ): 2966, 1584, 1543, 1511, 1452, 1418, 1252, 1200, 1048, 891, 841

Elemental analysis: C H O Si Al

36 69 9 3

Measured value C: 57.8%, H: 9.21%, Al: 3.6%

Theoretical value C: 57.1%, H: 9.19%, Al: 3.6%

MS (m / e)

Measurements: 756, 625, 513

Theoretical value (Exact mass): 756. 41

[0091] In the IR analysis, the peak at 1606 cm- ¹ unique to j8-diketone disappeared, and instead, the diketonato A group-specific peak of 1584 cm ¹ appears. This aluminum complex is a new substance.

[Example 12]

Synthesis of tris (2,6 dimethyl-2- (trimethylsilyloxy) -3,5 heptanedionato) indium complex (In (sopd)):

Three

In a lOOmL flask, 15.5g of 2,6-dimethyl-2- (trimethylsilyloxy) 3,5 heptanedione was added to 12g (62.2mmol) of a 28% methanol solution of sodium methylate Z at 0 ° C. 63.4 mmol) was added dropwise. Thereafter, a solution of indium chloride in which 6.04 g (20.6 mmol) of indium chloride tetrahydrate was dissolved in 15 mL of methanol was added dropwise. After stirring at 0 ° C for 30 minutes, 100 mL of hexane Z water (1: 1) was added at room temperature. After liquid separation, the hexane layer was washed with water, dried and concentrated to obtain a pale yellow liquid. By distilling and purifying the liquid (218 ° C., 59 Pa), the target substance, a pale yellow liquid, tris (2,6 dimethyl-2 (trimethylsilyloxy) -3,5 heptadionato) indium complex, 12.2 g (14.4 Mmol, yield: 70%)

[0093] The obtained i-danied product was identified by IR analysis, elemental analysis, and MS analysis.

IR (cm ^-1 ): 2966, 1570, 1510, 1427, 1252, 1198, 1047, 890, 841 Elemental analysis: CHO Si In

36 69 9 3

Measured value C: 51.8%, H: 8.18%, In: 13.6%

Theoretical value C: 51.2%, H: 8.23%, In: 13.6%

MS (m / e)

Measurements: 846, 830, 713, 601, 131, 73

Theoretical value (Exact mass): 844. 33

[0094] In the IR analysis, disappeared peaks of j8- diketone specific 1606Cm- ^1, diketonato group specific peak 1570 cm ¹ has appeared instead. This indium complex is a new substance

[Example 13]

Synthesis of tris (2,6 dimethyl-2 (trimethylsilyloxy) -3,5 heptanedionato) gallium complex (Ga (sopd)): In a lOOmL flask, add 28% Na !! ゥ Mumetilate / Methanol solution to 10.86 g (56.3 mimol) at 0 ° C at 2,6 dimethyl-2- (trimethylsilyloxy) 3,5- Heptanedione 14.Og (57.3 mmol) was added dropwise. Thereafter, a gallium chloride solution obtained by dissolving 3.15 g (17.9 mmol) of salt gallium in 15 mL of methanol was added dropwise. After stirring at 0 ° C for 30 minutes, 100 mL of hexane Z water (1: 1) was added at room temperature. After liquid separation, the hexane layer was washed with water, dried and concentrated to obtain a pale yellow liquid. The liquid was purified by distillation (196 ° C., 41 Pa) to obtain 10.4 g (13.0 g) of the target substance, a pale yellow liquid, tris (2,6 dimethyl-2 (trimethylsilyloxy) -3,5-heptanedionato) gallium complex. Mmol, yield: 73%).

[0096] Identification of the obtained i-danied product was performed by IR analysis, elemental analysis, and MS analysis.

IR (cm ^-1 ): 2966, 1575, 1542, 1512, 1436, 1404, 1253, 1199, 1047, 891, 841

Elemental analysis: C H O Si Ga

36 69 9 3

Measured value C: 54.4%, H: 8.58%, Ga: 8.7%

Theoretical value C: 54.1%, H: 8.69%, Ga: 7.72%

MS (m / e)

Measurements: 800, 798, 669, 667, 555, 483, 131, 73

Theoretical value (Exact mass): 798.35

[0097] In the IR analysis, disappeared peaks of j8- diketone specific 1606Cm- ^1, diketonato group specific peak 1575 cm ¹ has appeared instead. This gallium complex is a novel substance.

[Example 14]

Vapor deposition experiments (production of aluminum oxide film, indium oxide film, and gallium oxide film): Al (sopd) complex obtained in Example 11, In (sopd) complex obtained in Example 12 And then

3 3 Using the Ga (sopd) complex obtained in Example 13,

Three

The film formation characteristics were evaluated by the method described in Example 8.

[0099] The deposition conditions and the characteristics of the deposited film are shown below. As the substrate to be deposited, a rectangular substrate having a size of 7 mm × 40 mm was used.

[0100] [Production of aluminum oxide film]

[Evaporation conditions] Evaporation temperature: 180 ° C

Substrate: SiO / Si

2

Substrate temperature: 350 ° C

Deposition time: 30 minutes

Reaction system pressure: 2660Pa

O flow rate:

2 lOmLZ min

He flow rate: 15mLZ min

C film characteristics]

As a result of the film forming operation, it was confirmed that an aluminum oxide film having a thickness of 30 nm (by XPS analysis) was formed on the substrate. That is, by using the aluminum complex of the present invention as a raw material, it is contributing that a uniform oxide aluminum thin film could be formed.

[0101] [Production of indium oxide film]

[Evaporation conditions]

Evaporation temperature: 190 ° C

Substrate: SiO / Si

2

Substrate temperature: 350 ° C

Deposition time: 30 minutes

Reaction system pressure: 2660Pa

O 2 flow rate: lOmLZ min

He flow rate: 15mLZ min

C film characteristics]

As a result of the film formation operation, it was confirmed that a 40 nm-thick indium oxide film (by XPS analysis) was formed on the substrate. In other words, the use of the indium complex of the present invention as a raw material contributes to the ability to form a uniform indium oxide thin film.

[0102] [Manufacture of gallium oxide film]

[Evaporation conditions]

Evaporation temperature: 180 ° C

Substrate: SiO / Si Substrate temperature: 350 ° C

Deposition time: 30 minutes

Reaction system pressure: 2660Pa

O

2 flow rate: lOmLZ min

He flow rate: 15mLZ min

C film characteristics]

As a result of the film forming operation, it was confirmed that a 30 nm-thick oxidized gallium film (by XPS analysis) was formed on the substrate. That is, it can be seen that a uniform gallium oxide thin film could be formed by using the gallium complex of the present invention as a raw material.

[0103] [Example 15]

Synthesis of bis (2,6-dimethyl-2- (trimethylsilyloxy) -3,5-heptanedionato) tin complex (Sn (sopd)):

2

A 200 mL flask was charged with 20.0 g (81.8 mmol) of j8-diketone 2,6-dimethyl-2- (trimethylsilyloxy) -3,5-heptanedione, and 28% sodium methylate Z was added thereto. 13 g (67.4 mmol) of a methanol solution were added.

After stirring at room temperature for 30 minutes, SnCl 6.30 g (33.2 mmol) Z ethanol (30 mL)

2

The solution was added dropwise at room temperature. Upon precipitation, a white precipitate formed. After concentrating the suspension, 50 mL of hexane was added, and the solid was filtered off. The obtained hexane layer was washed with water, dried and concentrated to obtain a yellow liquid. By distillation purification (144 ° C, Z15Pa), 6.3 g (10.4 mmol, yield: bis (2,6-dimethyl-2- (trimethylsilyloxy) -3,5-heptanedionato) tin complex of yellow liquid, which is the target substance, was obtained. : 31%).

[0104] The obtained i-danied product was identified by IR analysis, elemental analysis, and MS analysis.

IR (cm ^-1 ): 2966, 1570, 1507, 1404, 1370, 1252, 1197, 1047, 889, 841 Elemental analysis: CHO Si Sn

24 46 6 2

Measured value C: 47.2%, H: 7.88%, Sn: 19%

Theoretical value C: 47.6%, H: 7.66%, Sn: 19.6%

MS (m / e)

Measurements: 606, 363 Theoretical value (Exact mass): 606.19

[0105] In the IR analysis, J8- diketone peak peculiar 1606Cm- ¹ disappears, and diketonato group specific peak 1570 cm ¹ is obtained instead. This tin complex is a novel substance.

[Example 16]

Deposition experiment (production of tin oxide film):

Using the Sn (sopd) complex obtained in Example 17, a deposition test by a CVD method was performed.

2

It carried out by the method described in Example 8, and evaluated the film-forming property.

[0107] The deposition conditions and the characteristics of the deposited film are shown below. As the substrate to be deposited, a rectangular substrate having a size of 7 mm × 40 mm was used.

[Manufacture of tin oxide film]

[Evaporation conditions]

Evaporation temperature: 190 ° C

Substrate: SiO / Si

2

Substrate temperature: 400 ° C

Deposition time: 30 minutes

Reaction system pressure: 5320Pa

O 2 flow rate: 40mLZ min

He flow rate: 60mLZ min

C film characteristics]

As a result of the film forming operation, it was confirmed that a 50 nm-thick oxidized tin film (by XPS analysis) was formed on the substrate. In other words, it can be seen that a uniform oxide tin thin film could be formed by using the tin complex of the present invention as a raw material.

[Example 17]

Synthesis of bis (2,6-dimethyl-2-trimethylsilyloxy 3,5-heptanedionato) zinc (II) (Zn (sopd))

2

In a 200 mL flask equipped with a stirrer, thermometer, and dropping funnel, 17.6 g (91.0 mmol) of a 28% sodium methoxide methanol solution was added, and the solution temperature was maintained at 4 ° C. 2,6-Dimethyl-2-trimethylsilyloxy 3,5-heptanedione 23.lg (94.4 mm Mol) was slowly added dropwise, followed by stirring at the same temperature for 30 minutes. Next, a solution prepared by dissolving 6.08 g (44.6 mmol) of Shiri-Zai (II) in 120 mL of ethanol was added dropwise, and the mixture was allowed to react at room temperature for 1 hour with stirring. After the reaction was completed, 100 mL of hexane and 100 mL of water were added to the reaction solution, and then the organic layer was separated. The organic layer was washed with water and dried over anhydrous sodium sulfate. After filtration, the filtrate was concentrated, and the concentrate was distilled under reduced pressure (154 ° C, 24 Pa) to give bis (2,6-dimethyl-2-trimethylsilyloxy 3,5-heptanedionato) zinc (as a pale yellow liquid). II) 19.7 g was obtained (isolation yield: 80%).

Bis (2,6-dimethyl-2-trimethylsilyloxy 3,5-heptanedionato) zinc (II) is a novel compound having the following physical properties.

[0110] IR (neat (cm ^-1 )): 2966, 1566, 1509, 1410, 1252, 1198

(The peak peculiar to j8 diketone (1606 cm disappeared and the peak peculiar to β-diketonate (15 66 cm " ¹ ) was observed)

Elemental analysis (C H O Si Zn): carbon: 52.9%, hydrogen: 8.33%, zinc: 11.3%

24 46 6 2

(Theoretical value: carbon: 52.2%, hydrogen: 8.40%, zinc: 11.8%)

MS (m / e): 550, 535, 419, 307

[Example 18]

Synthesis of tris (2,6-dimethyl-2-trimethylsilyloxy 3,5-heptanedionato) manganese (III) (Mn (sopd))

Three

In a 200-mL flask equipped with a stirrer, thermometer and dropping funnel, 12.5 g (64.9 mmol) of a 28% methanol solution of sodium methoxide was added, and the solution temperature was maintained at 4 ° C. Then, 2,6-dimethyl-2-trimethylsiloxy-3,5-heptanedione 17.Og (69.6 mmol) was slowly added dropwise, and the mixture was stirred at the same temperature for 30 minutes. Next, a solution prepared by dissolving 6.06 g (30.6 mmol) of Shimadani manganese (II) tetrahydrate in 120 mL of ethanol was added dropwise, and reacted at room temperature for 1 hour with stirring. After the reaction was completed, 100 mL of hexane and 100 mL of water were added to the reaction solution, and then the organic layer was separated. The organic layer was washed with water and dried over anhydrous sodium sulfate. After filtration, the filtrate was concentrated, and the concentrate was distilled under reduced pressure (176 ° C., 44 Pa) to give tris (2,6-dimethyl-2-trimethylsilyloxy 3,5-heptanedionato) manganese (III) as a black-brown liquid. 2. 73 g was obtained (isolation yield: 11%). Tris (2,6-dimethyl-2-trimethylsilyloxy 3,5-heptanedionato) manganese (III) is a novel compound having the following physical properties.

[0112] IR (neat (cm ^-1 )): 2967, 1565, 1499, 1414, 1252, 1197, 1046, 889, 841

(The peak peculiar to j8 diketone (1606 cm— disappeared and the peak peculiar to β-diketonate ( ¹ 65 cm ″ ¹ ) was observed)

Elemental analysis (C H O Si Mn): carbon: 55.6%, hydrogen: 7.78%, manganese: 7.0%

36 69 9 3

(Theoretical value: carbon: 55.1%, hydrogen: 7.86%, manganese: 7.0%)

MS (mZe): 784, 541

[Example 13]

Synthesis of tris (2,6-dimethyl-2-trimethylsilyloxy 3,5-heptanedionato) yttrium (III) (Y (sopd))

Three

In a 200-mL flask equipped with a stirrer, thermometer, and dropping funnel, 16.0 g (83.0 mmol) of a 28% sodium methoxide methanol solution was added, and the solution temperature was maintained at 4 ° C. Then, 22.0 g (90.0 mmol) of 2,6-dimethyl-2-trimethylsilyloxy 3,5-heptanedione was slowly added dropwise, followed by stirring at the same temperature for 30 minutes. Next, a solution prepared by dissolving 8.11 (26.7 mmol) of yttrium (III) chloride hexahydrate in 160 mL of ethanol was added dropwise, and the mixture was reacted at room temperature for 1 hour with stirring. After the reaction was completed, 100 mL of hexane and 100 mL of water were added to the reaction solution, and then the organic layer was separated. The organic layer was washed with water and dried over anhydrous sodium sulfate. After filtration, the filtrate is concentrated, and the concentrate is distilled under reduced pressure (210 ° C, 73 Pa) to obtain tris (2,6-dimethyl-2-trimethylsilyloxy 3,5-heptanedionato) yttrium as a viscous yellow liquid. (III) 12. Og was obtained (isolation yield: 55%).

Tris (2,6-dimethyl-2-trimethylsilyloxy 3,5-heptanedionato) yttrium (III) is a novel compound having the following physical properties.

[0114] IR (neat (cm ^-1 )): 2965, 1585, 1504, 1412, 1251, 1196, 1048, 841

(The peak peculiar to j8 diketone (1606 cm— disappeared and the peak peculiar to β-diketonate (15 85 cm ″ ¹ ) was observed)

Elemental analysis (C H O Si Y): carbon: 52.3%, hydrogen: 8.66%, yttrium: 10.6%

36 69 9 3

(Theoretical value: carbon: 52.8%, hydrogen: 8.49%, yttrium: 10.9%) MS (m / e): 818, 775, 687, 599, 511, 397

[Example 20]

(Evaporation experiment: Production of metal oxide thin film)

The metal complex (zinc complex (Zn (sopd)), manganese complex (Mn (

2

sopd)) and yttrium complex (Y (sopd))), respectively.

3 3

The test was performed by the method described in Example 8 to evaluate the film forming characteristics.

The deposition conditions and the characteristics of the deposited film are shown below. As the substrate to be deposited, a rectangular substrate having a size of 7 mm × 40 mm was used.

[Manufacture of zinc oxide film]

[Evaporation conditions]

Evaporation temperature: 170 ° C

Substrate: SiO / Si

2

Substrate temperature: 400 ° C

Deposition time: 30 minutes

Reaction system pressure: 5320Pa

O 2 flow rate: 40mLZ min

He flow rate: 60mLZ min

C film characteristics]

As a result of the film forming operation, it was confirmed that a 70 nm-thick oxidized zinc film (by XPS analysis) was formed on the substrate. In other words, the use of the zinc complex of the present invention as a raw material contributes to the formation of a uniform zinc oxide thin film.

[Manufacture of manganese oxide film]

[Evaporation conditions]

Evaporation temperature: 190 ° C

Substrate: SiO / Si

2

Substrate temperature: 400 ° C

Deposition time: 30 minutes

Reaction system pressure: 5320Pa O flow rate: 40mLZ min

2

He flow rate: 60mLZ min

C film characteristics]

As a result of the film forming operation, it was confirmed that a 50-nm-thick oxidized manganese film (by XPS analysis) was formed on the substrate. In other words, the use of the manganese complex of the present invention as a raw material contributes to a uniform manganese oxide thin film.

[Production of yttrium oxide film]

[Evaporation conditions]

Evaporation temperature: 200 ° C

Substrate: SiO / Si

2

Substrate temperature: 400 ° C

Deposition time: 30 minutes

Reaction system pressure: 5320Pa

O 2 flow rate: 40mLZ min

He flow rate: 60mLZ min

C film characteristics]

As a result of the film formation operation, it was confirmed that a 40 nm-thick yttrium oxide film (by XPS analysis) was formed on the substrate. In other words, the use of the yttrium complex of the present invention as a raw material contributes to the formation of a uniform yttrium oxide thin film.

[Example 19]

Synthesis of tris (2,6-dimethyl-2-trimethylsilyloxy 3,5-heptanedionato) chromium (III) (Cr (sopd))

Three

In a 200-mL flask equipped with a stirrer, thermometer, and dropping funnel, 11.3 g (58.4 mmol) of a 28% sodium methoxide methanol solution was added, and the solution temperature was maintained at 2 ° C. Then, 14.7 g (60.2 mmol) of 2,6-dimethyl-2-trimethylsiloxy-3,5-heptanedione was slowly added dropwise, followed by stirring at the same temperature for 30 minutes. Next, a solution in which 5.10 g (19.2 mmol) of Shiridani chromium (III) hexahydrate was dissolved in 20 mL of methanol was added dropwise, and the mixture was reacted for 1 hour at room temperature without stirring. After completion of the reaction, the mixture was concentrated to remove methanol, and After 100 mL of hexane and 100 mL of water were removed, the organic layer was separated. The organic layer was washed with water and dried over anhydrous sodium sulfate. After filtration, the filtrate was concentrated, and the concentrate was distilled under reduced pressure (190 ° C, 51 Pa) to obtain tris (2,6-dimethyl-2-trimethylsilyloxy-3,5-heptanedionato) chromium (III) as a purple liquid. 2. Olg was obtained (isolation yield: 13%).

Tris (2,6-dimethyl-2-trimethylsilyloxy 3,5-heptanedionato) manganese (III) is a novel compound having the following physical properties.

[0120] IR (neat (cm ^-1 )): 2966, 1567, 1505, 1413, 1252, 1198, 1047, 841

(The peak peculiar to j8 diketone (1606 cm disappeared and the peak peculiar to β-diketonate (15 67 cm " ¹ ) was observed)

Elemental analysis (C H O Si Cr): carbon: 55.8%, hydrogen: 8.81%, chromium: 6.7%

36 69 9 3

(Theoretical value: carbon: 55.3%, hydrogen: 8.89%, manganese: 6.65%)

MS (m / e): 781, 538, 279, 205, 131, 73

[0121] [Example 22]

Synthesis of tris (2,6-dimethyl-2-trimethylsilyloxy 3,5-heptanedionato) magnesium (Π) (Mg (sopd))

Three

In a 200-mL flask equipped with a stirrer, thermometer, and dropping funnel, 2.00 g (34.3 mm monole) of magnesium hydroxide and 40 mL of 1,2-dimethoxyethane were added. Methyl-2-trimethylsilyloxy 3,5-heptanedione (17.3 g, 70.8 mmol) was slowly added dropwise, and the mixture was reacted at room temperature for 30 minutes with stirring. After completion of the reaction, the mixture was concentrated to remove 1,2-dimethoxyethane, and then 80 mL of methylene chloride was added to the concentrate. The concentrate was washed with water and dried over anhydrous sodium sulfate. After filtration, the filtrate is concentrated, and the concentrate is distilled under reduced pressure (220 ° C, 29 Pa) to obtain bis (2,6-dimethyl-2-trimethylsilyloxy-3,5-heptanedionato) magnesium as a viscous yellow liquid. (II) 9. Olg was obtained (isolation yield: 51%).

Bis (2,6-dimethyl-2-trimethylsilyloxy-3,5-heptanedionato) magnesium (II) is a novel compound having the following physical properties.

[0122] IR (neat (cm ^-1 )): 2964, 1588, 1506, 1435, 1251, 1195, 1049, 891, 841

(j8 Diketone specific peak (1606cm disappeared, β diketonate specific peak (15 88cm " ¹ ) was observed)

Elemental analysis (C H O Si Mg): carbon: 56.8%, hydrogen: 9.13%, magnesium: 4.8

24 46 6 2

%

(Theoretical value: carbon: 56.4%, hydrogen: 9.07%, magnesium: 4.76%)

MS (m / e): 510, 495, 379, 251, 131, 73

[Example 23]

(Evaporation experiment: Production of metal oxide thin film)

Metal complexes (chromium complex (Cr (sopd))) and magnesium complexes obtained in Examples 21 and 22

Three

(Mg (sopd)) and a vapor deposition test by the CVD method described in Example 8.

2

The method was performed according to the method, and the film forming characteristics were evaluated.

[0124] The deposition conditions and the characteristics of the deposited film are shown below. As the substrate to be deposited, a rectangular substrate having a size of 7 mm × 40 mm was used.

[Manufacture of chromic oxide film]

[Evaporation conditions]

Evaporation temperature: 190 ° C

Substrate: SiO / Si

2

Substrate temperature: 350 ° C

Deposition time: 30 minutes

Reaction system pressure: 3990Pa

O

2 flow rate: lOmLZ min

He flow rate: 15mLZ min

C film characteristics]

As a result of the film formation operation, it was confirmed that a 30-nm-thick chromium oxide film (by XPS analysis) was formed on the substrate. That is, it can be seen that a uniform chromium oxide thin film could be formed by using the chromium complex of the present invention as a raw material.

[Manufacture of magnesium oxide film]

[Evaporation conditions]

Evaporation temperature: 190 ° C Substrate: SiO / Si

2

Substrate temperature: 350 ° C

Deposition time: 30 minutes

Reaction system pressure: 3990Pa

O flow rate:

2 lOmLZ min

He flow rate: 15mLZ min

C film characteristics]

As a result of the film forming operation, it was confirmed that a 35 nm-thick oxidized magnesium film (by XPS analysis) was formed on the substrate. In other words, the use of the magnesium complex of the present invention as a raw material contributes to the ability to form a uniform magnesium oxide thin film.

Brief Description of Drawings

FIG. 1 is a diagram showing a configuration of a vapor deposition device.

Explanation of symbols

[0128] 3 vaporizer

4 Reactor

10B vaporizer heater

10C reactor heater

20 Raw material complex melt

21 substrate

Claims

Claims A metal complex represented by the following formula (1):

[In equation (1),

X represents a silyl ether group represented by the following (2),

Y represents a silyl ether group represented by the following (2) or a linear or branched alkyl group having 18 carbon atoms;

Z represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,

M is ruthenium, iridium, palladium, nickel, vanadium, titanium, zirconium, hafnium, aluminum, gallium, indium, tin, lead, zinc, manganese, yttrium, chromium, magnesium, conoreto, iron, and Represents a metal atom selected from the group consisting of silver,

n represents a valence of a metal atom represented by M;

[Formula 2]

(2)

(In the formula (2), Ra represents ^a linear or branched alkylene group having 115 carbon atoms, and R ^b and R \ R ^d each independently represent a carbon atom having 1 to 5 carbon atoms. Represents 15 linear or branched alkyl groups)].

[2] The metal complex according to claim 1, wherein Y is a linear or branched alkyl group having 118 carbon atoms, and Z is a hydrogen atom.

[3] Y is a linear or branched alkyl group having 14 to 14 carbon atoms, ^Ra is a dimethylmethylene group, and R ^b and RR ^d are both linear alkyl groups having 13 to 13 carbon atoms. The metal complex according to claim 2, which is:

[4] A metal complex having a β-diketonato group as a ligand to which a silyl ether group represented by the following formula (3) is attached (provided that the metal is ruthenium, iridium, metal, radium, nickel, vanadium, titanium, Zirconium, hafnium, aluminum, gallium, indium, tin, lead

, Zinc, manganese, yttrium, chromium, magnesium, cobalt, iron, and silver):

[Formula 3]

[In equation (3),

X represents a silyl ether group represented by the following (2),

Ζ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,

[Formula 4]

(In the formula (2), Ra represents ^a linear or branched alkylene group having 115 carbon atoms, and R ^b and RR ^d each independently represent a carbon atom having 115 carbon atoms. Represents a straight-chain or branched alkyl group))].

[5] The metal complex according to claim 4, wherein Y is a linear or branched alkyl group having 18 to 18 carbon atoms, and Z is a hydrogen atom.

[6] Y is a linear or branched alkyl group having 1 to 4 carbon atoms, ^Ra is a dimethylmethylene group, and R ^b and RR ^d are each a straight-chain alkyl group having 1 to 3 carbon atoms. 6. The metal complex according to claim 5, which is a group.

[7] The metal complex according to claim 1 is vaporized, and the vaporized metal complex is thermally decomposed.

And producing a metal-containing thin film by depositing the metal-containing thin film on a substrate.

[8] The method for producing a metal-containing thin film according to claim 7, comprising performing thermal decomposition of the vaporized metal complex in the presence of oxygen to form a metal oxide thin film on the substrate.

[9] The method for producing a metal-containing thin film according to claim 7, wherein the metal complex is vaporized together with a solvent.

[10] The method for producing a metal-containing thin film according to claim 9, wherein the solvent is an aliphatic hydrocarbon, an aromatic hydrocarbon or an ether.

[11] The metal complex according to claim 4 is vaporized, and the vaporized metal complex is thermally decomposed.

12. The method for producing a metal-containing thin film according to claim 9, comprising thermally decomposing the vaporized metal complex in the presence of oxygen to form a metal oxide thin film on the substrate. 12. The method for producing a metal-containing thin film according to claim 11, wherein the metal complex is vaporized together with a solvent. 14. The method for producing a metal-containing thin film according to claim 13, wherein the solvent is an aliphatic hydrocarbon, an aromatic hydrocarbon, or an ether.