JP2001200367A - Metallic complex composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a metallic complex composition capable of stably depositing a uniform lead titanate zirconate series thin film by one liquid and to provide a method for producing a lead titanate zirconate series thin film using the metallic complex composition. SOLUTION: This metallic complex composition is composed of a a metal- containing compound containing, load, a metal-containing compound containing zirconium and a complex of a β-diketone compound and the clycolate of titanium expressed by the following general formula (I) (wherein R1 and R2 are an alkyl group or a cyccloalkyl group which may independently be substituted by 1 to 10C halogen atoms or may have an ether bond; and R3 is 2 to 18C direct chain or branch alkylene group).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a metal complex composition, and more particularly, to a metal complex composition used as a raw material of a lead zirconate titanate-based thin film formed by a CVD (chemical vapor deposition) method. And a method for producing a lead zirconate titanate-based thin film using the metal complex composition.

[0002]

2. Description of the Related Art Lead zirconate titanate (PZT) is a ferroelectric material having a very high dielectric constant and good hysteresis characteristics, and utilizes this high dielectric constant. Highly integrated DRAM (dynamic random access memory) and FeRAM (ferro random access memory) utilizing the hysteresis characteristics of ferroelectric materials have been actively developed.

In applying this PZT to an actual device, a PZT-based thin film can be formed by a sol-gel method, a sputtering method, a CVD (Chemical Vapor Deposition) method, or the like. CV in terms of step coverage and uniformity
Method D is the most excellent film forming method.

As a gas phase source in the CVD method, an alkyl compound, an alkoxide compound or a complex with a β-diketone compound of a metal element constituting a metal oxide is used. The metal complex of β-diketone has good volatility and excellent reactivity because the bond is weak due to a coordination bond, and is useful as a gas phase source for the CVD method. Pivaloyl methanate, hexafluoroacetylacetonate, pentafluoropropanoyl pivaloyl methanate and the like are known.

Conventionally, a lead-containing compound, a zirconium-containing compound, and a titanium-containing compound, which are raw materials for a PZT-based thin film, are each provided with three raw material containers, which are separately gasified and then mixed in a gaseous state to form a reaction phase. (For example, Japanese Unexamined Patent Application Publication No.
-76778). However, in such a method, the apparatus becomes complicated, and it is desired that the raw material source of lead, zirconium and titanium be one liquid. For the purpose of solving such a problem, for example, Japanese Patent Application Laid-Open No. 10-298762
Japanese Patent Application Laid-Open Publication No. H11-163840 proposes that a raw material source of zirconium and titanium is dissolved in tetrahydrofuran to make one solution. However, even with this method, stable volatilization cannot be obtained with the combinations known so far, and uniform PZ
T-based thin films have not yet been obtained.

Accordingly, an object of the present invention is to provide a single solution stably,
An object of the present invention is to provide a metal complex composition capable of forming a uniform lead zirconate titanate-based thin film and a method for producing a lead zirconate titanate-based thin film using the metal complex composition.

[0007]

Means for Solving the Problems As a result of repeated studies, the present inventors have found that the use of a metal-containing compound containing lead, a metal-containing compound containing zirconium, and a specific titanium complex compound makes it possible to stabilize one liquid. The present inventors have found a metal complex composition capable of forming a good PZT-based thin film, and have reached the present invention.

That is, the present invention is characterized by comprising a metal-containing compound containing lead, a metal-containing compound containing zirconium, and a complex of a β-diketone compound represented by the following general formula (I) and a glycolate of titanium. And a metal complex composition.

[0009]

Embedded image (Wherein, R ₁ and R ₂ each independently represent 1 carbon atom)
Represents an alkyl group or a cycloalkyl group which may be substituted with a halogen atom of 10 to 10 or has an ether bond, and R ₃ represents a linear or branched alkylene group having 2 to 18 carbon atoms)

[0010] The present invention also provides a lead zirconate titanate comprising chemically vapor-depositing lead, zirconium and titanium or an oxide thereof on a substrate using the above metal complex composition. It is intended to provide a method for producing a system thin film.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, preferred embodiments of the metal complex composition of the present invention will be described in detail.

In the above general formula (I), R ₁ and R ₂ are β-
An alkyl group having 1 to 10 carbon atoms derived from a diketone compound, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, sec-pentyl, tert-pentyl , Hexyl, isohexyl, heptyl, isoheptyl, octyl, isooctyl, tertiary octyl, nonyl,
Examples thereof include linear or branched groups such as isononyl, decyl, and isodecyl. These may be substituted with a halogen atom such as fluorine, chlorine and bromine. Examples of these halogenated alkyl groups include monofluoromethyl, difluoromethyl, trifluoromethyl, monochloromethyl, dichloromethyl and trichloromethyl. , 1,
1,2-trifluoroethyl, perfluoroethyl, perfluorohexyl and the like can be mentioned. Further, those having an ether bond may be used.Examples of the alkyl group having an ether bond include methoxyethyl, ethoxyethyl, butoxyethyl, alkoxyalkyl such as methoxyethoxyethyl, ethoxyethoxyethyl, butoxyethoxyethyl, And groups such as alkoxyalkoxyalkyl such as 2- (2-methoxyethoxy) -1,1-dimethylethyl.

Examples of these β-diketone compounds include pentane-2,4-dione, octane-2,4-dione, 2-methylheptane-3,5-dione and 5-methylheptane-2,4-dione. , 3-methyldecane-4,
6-dione, 2,2,6-trimethyloctane-3,5
-Dione, 2,6-dimethyloctane-3,5-dione, 3-methylnonane-4,6-dione, 6-methyloctane-3,5-dione, 2,2,6,6-tetramethylheptane-3 , 5-dione, 2,7-dimethylnonane-4,6-dione, 2,2-dimethyldecane-3,5-
Dione, 2,2-dimethyl-6-ethyldecane-3,5
-Dione, 2,2,6,6-tetramethyl-7-oxanonane-3,5-dione, 2,2,6-trimethyl-
8,11-oxadodecane-3,5-dione, 2,2
6,6-tetramethyl-8,11-oxadodecane-
3,5-dione, 1,1,1-trifluoropentane-
2,4-dione, 2,2-dimethyl-6,6,6-trifluorohexane-3,5-dione, 1,1,1,5
5,5-hexafluoropentane-2,4-dione,
1,3-bis (trifluoromethyl) propane-1,3
-Dione, 1,3-bis (perfluorohexyl) propane-1,3-dione and the like.

Further, the compound having 2 to 18 carbon atoms represented by R ₃
Is a group provided by a glycol (that is, a residue obtained by removing two OH groups of a glycol). Examples of the glycol include 1, 2
-Ethanediol, 1,2-propanediol, 1,3
-Propanediol, 1,3-dimethyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2-ethyl-2-butyl -1,3-propanediol, 1-methyl-1,3-propanediol, 2-methyl-1,3-propanediol and the like.
3-propanediol and an alkyl-substituted product thereof are preferred for further improving the effects of the present invention.

The titanium complex compound represented by the above general formula (I) of the present invention is not limited with respect to the production method. For example, 1 mol of tetraisopropoxytitanium (TIPT) and β-diketone It can be obtained by subjecting 2 mol of the compound to a reflux deisopropanol reaction in an aliphatic hydrocarbon solvent, followed by further adding 1 mol of glycol and reacting.

The compound represented by the general formula (I) used in the present invention is more specifically represented by the following [Chemical Formula 3]
Compound No. shown in [Formula 14] 1 to 12 and the like. However, the present invention is not limited by these compounds.

[0017]

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[0018]

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[0019]

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[0020]

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[0021]

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[0022]

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[0023]

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[0024]

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[0025]

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[0026]

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[0027]

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[0028]

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As the lead-containing metal-containing compound and zirconium-containing metal-containing compound used in the present invention, conventionally known compounds can be used, and there is no particular limitation. , Glycolate, β-diketonate or a complex thereof can be used. Examples of alcohols that can provide alcoholates include lower alcohols such as methanol, ethanol, propanol, and butanol, and glycols that can provide glycolates include the glycols exemplified above, and β-diketones. Examples of the compound include the β-diketone compounds exemplified above.

Of these metal complex compounds containing lead or zirconium, the use of a compound represented by the following general formula (II) is preferred because a more stable metal complex composition can be obtained.

[0031]

Embedded image (In the formula, M represents Pb or Zr, R ₄ , R ₅ and R ₆ each independently represent the same group as R ₁ and R _2, and R ₇ represents a straight chain having 2 to 18 carbon atoms or Represents a branched alkylene group, and when M is Pb, l + m + n / 2 is 2
And l and m represent 0, 1 or 2, and n is 0 or 1.
And when M is Zr, l + m + n / 2 is 4, 1 and m represent 0, 1, 2, 3, or 4, and n is 0,
Represents 1 or 2)

Examples of the metal-containing compound containing lead include 4-ethyl lead, lead bis (acetylacetonate),
Lead bis (2,2,6,6-tetramethylheptane-3,
5-dionate), lead bis (1-methoxy-1,1,1,2)
5,5-tetramethylhexane-2,4-dionate), lead bis (1,1,1-trifluoropentane-
2,4-dionate), lead bis (1,1,1-trifluoro-5,5-dimethylhexane-2,4-dionate), lead bis (1,1,1,5,5,5-hexafluoro) Pentane-2,4-dionate), lead bis (1,3-
Diperfluorohexylpropane-1,3-dionate). Examples of the metal-containing compound containing zirconium include, for example, zirconium tetrakis (tertiary butanat), zirconium tetrakis (n-butanato), and zirconium tetrakis (isopropanate). ),
Zirconium tetrakis (acetylacetonate), zirconium tetrakis (2,2,6,6-tetramethylheptane-3,5-dionate), zirconium tetrakis (1-methoxy-1,1,5,5-tetramethylhexane-2) , 4-dionate), zirconium tetrakis (1,1,1-trifluoropentane-2,4-dionate), zirconium tetrakis (1,1,1-trifluoro-5,5-dimethylhexane-2,4-dionate) ), Zirconium tetrakis (1,1,1,5,
5,5-hexafluoropentane-2,4-dionate), zirconium tetrakis (1,3-diperfluorohexylpropane-1,3-dionate), zirconium bis (2,2,6,6-tetramethylheptane-
3,5-dionate) bis (isopropanate), zirconium bis (2,2,6,6-tetramethylheptane-3,5-dionate) -2-methyl-2,4-pentanglycolate and the like. Can be

In the metal complex composition of the present invention, the metal complex compound containing lead, the metal complex compound containing zirconium and the compound represented by the above general formula (I) are mixed at any ratio according to the purpose. Usually, the ratio is such that 1 to 4 mol of the lead-containing metal complex compound and 0.5 to 2 mol of the zirconium-containing metal complex compound are added to 1 mol of the compound represented by the general formula (I). In particular, a ratio of 1.5 to 3 mol of the lead-containing metal complex compound and 0.8 to 1.5 mol of the zirconium-containing metal complex compound per 1 mol of the compound represented by the above general formula (I). used.

Among the CVD methods according to the present invention, solution CVD
Although the organic solvent used in the case of the method is not particularly limited, for example, methanol, ethanol,
-Alcohols such as propanol (IPA) and n-butanol; acetates such as ethyl acetate, butyl acetate and methoxyethyl acetate; ether alcohols such as methyl cellosolve, ethyl cellosolve, butyl cellosolve and diethylene glycol monomethyl ether; tetrahydrofuran; glyme; Ethers such as diglyme, triglyme and dibutyl ether, ketones such as methyl butyl ketone, methyl isobutyl ketone, ethyl butyl ketone, dipropyl ketone, diisobutyl ketone, methyl amyl ketone, cyclohexanone and methyl cyclohexanone, hexane, cyclohexane, heptane, octane ,
Examples include hydrocarbons such as toluene and xylene, which are appropriately selected depending on the solubility of the solute, the relationship between the operating temperature and the boiling point, the flash point, and the like.Especially, ethers such as tetrahydrofuran, glyme, and diglyme stabilize the complex. And is preferably used.

In the CVD method, a stabilizer of a metal compound [compound represented by the above general formula (I)] and / or a stabilization of a solution are added to a raw material or a raw material solution, including a solution CVD method. A nucleophilic reagent may be used as an agent. Examples of the stabilizer include glyme, diglyme,
Ethylene glycol ethers such as triglyme and tetraglyme, 18-crown-6, dicyclohexyl-
Crown ethers such as 18-crown-6, 24-crown-8, dicyclohexyl-24-crown-8, dibenzo-24-crown-8, ethylenediamine,
N, N'-tetramethylethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, 1,1,
4,7,7-pentamethyldiethylenetriamine, 1,
Polyamines such as 1,4,7,10,10-hexamethyltriethylenetetramine; cyclic polyamines such as cyclam and cyclen; β-ketoesters such as methyl acetoacetate, ethyl acetoacetate and 2-methoxyethyl acetoacetate Acetylacetone, dipivaloylmethane, and β-diketones as exemplified above.

These stabilizers are used in an amount of 0.1 mol to 10 mol, preferably 1 to 4 mol, per 1 mol of the solute metal compound.

The CVD method used to manufacture the PZT thin film according to the present invention includes, for example, thermal CVD, plasma CV
D, a method such as photo-CVD, etc., can be mentioned, but there is no particular limitation as long as it is a CVD method generally employed in a CVD apparatus.

The PZT-based thin film obtained by the CVD method may be subjected to an annealing treatment if necessary.

As a method for producing a PZT thin film, a metal complex compound comprising a lead-containing metal complex compound, a zirconium-containing metal complex compound and a compound represented by the above general formula (I) is used to form a PZT thin film on a substrate. , Lead, zirconium and titanium or oxides thereof are preferably grown by chemical vapor deposition.

Here, examples of the substrate include a silicon wafer, ceramics, and glass.

When the above-described lead zirconate titanate is subjected to chemical vapor deposition, first, the raw material composition is vaporized and introduced onto the substrate, and then the raw material compound is decomposed on the substrate.
Lead, zirconium and titanium or their oxides are grown on the thin film. In the step of vaporizing, to prevent decomposition of the raw material compound, 10,000 Pa or less,
In particular, it is preferable to vaporize under a reduced pressure of 5000 Pa or less at a decomposition temperature or less. Further, it is preferable that the substrate is heated in advance to a temperature higher than the decomposition temperature of the raw material compound, preferably higher than 250 ° C., more preferably higher than 350 ° C.

The PZT thin film according to the present invention is, for example, a DRA using a thin film capacitor using a high-ferroelectric substance.
It is used for applications such as capacitor electrodes of memory devices such as M and FeRAM.

[0043]

The present invention will be specifically described below with reference to Synthesis Examples and Examples of the compound represented by the general formula (I), but the present invention is not limited by these Synthesis Examples and Examples. is not. In the following synthesis examples, “%” is based on weight.

Synthesis Example 1 (Synthesis of Compound No. 1) 71 g (0.25 mol) of TIPT and 92 g (0.5 mol) of dipivaloylmethane (DPM) were refluxed in 1000 ml of xylene at 60 ° C. for 2 hours. After isopropanol removal, 19 g of 1,3-propanediol
(0.25 mol), and the mixture was refluxed at 140 ° C. for 3 hours to remove isopropanol. The solvent was removed under reduced pressure to obtain 120 g (yield 98%) of a brown glassy solid having a purity of 92% by liquid chromatography (hereinafter, referred to as LC). In a differential thermogravimetric analysis of the obtained glassy solid under a nitrogen gas flow, a temperature increasing rate was 10 ° C./min, and a weight reduction starting temperature at 1 atm was 224 ° C. Heating and melting glassy solid 157
Purification by distillation at １６163 ° C./1.5 mmHg and LC purity 1
105 g (86% yield) of a 00% brown glassy solid was obtained.

The titanium content of the obtained compound was 9.8.
It was 0%. In addition, the following infrared absorption spectrum (I
R) It was identified as the target from the analysis results.

(Results of IR Analysis) The absorption peak was shown below. ^{3448cm -1, 3415cm -1, 3382cm -1} , 2960cm -1, 2867cm -1, 2362cm -1, 2329cm -1, 1575cm -1, 1533cm -1, 1502cm -1, 1457cm -1, 1382cm -1, 1355cm - ¹ , 1292 cm ^-1 , 1224 cm ^-1 , 1174 cm ^-1 , 1145 cm ^-1 , 1087 cm ^-1 , 962 cm ^-1 , 873 cm ^-1 , 767 cm ^-1 , 621 cm ^-1 , 507 cm ^-1 , 476 cm ^-1 , 437 cm ^-1 432 cm ^-1 , 408 cm ^-1

[Synthesis Example 2] (Synthesis of Compound No. 2) Except that 1,3-propanediol in Synthesis Example 1 was replaced with 26 g (0.25 mol) of 2,2-dimethyl-1,3-propanediol. Is Synthesis Example 1
Brown glassy solid 12 with an LC purity of 93%
6 g (98% yield) was obtained. In the differential thermogravimetric analysis of the obtained glassy solid under a nitrogen gas flow, the temperature at which the weight loss started at 1 atm was 247 ° C. The glassy solid was heated and melted, and purified by distillation at 170 to 175 ° C / 1.6 mmHg to obtain 114 g (88% yield) of a brown glassy solid having an LC purity of 100%.

The titanium content of the obtained compound was 9.2.
7%. Further, it was identified as the target substance from the following IR analysis results.

(Results of IR Analysis) The following absorption peaks were shown. ^{3434cm -1, 2960cm -1, 2871cm -1} , 2833cm -1, 1645cm -1, 1577cm -1, 1562cm -1, 1537cm -1, 1504cm -1, 1461cm -1, 1380cm -1, 1357cm -1, 1294cm - ^{1, 1226cm -1, 1174cm -1,} 1145cm -1, 1089cm -1, 1016cm -1, 968cm -1, 873cm -1, 796cm -1, 690cm -1, 649cm -1, 626cm -1, 578cm -1, 511 cm ^-1 , 441 cm ^-1 , 403 cm ^-1

[Synthesis Example 3] (Synthesis of Compound No. 3) 29.5 g (0.25 mol) of 1,3-propanediol of Synthesis Example 1 was 2-ethyl-2-methyl-1,3-propanediol. In the same manner as in Synthesis Example 1 except for replacing the above, 131 g (yield 99%) of a brown glassy solid having an LC purity of 94% was obtained. In the differential thermogravimetric analysis under a nitrogen stream of the obtained glassy solid, the temperature at which the weight loss started at 1 atm was 244 ° C. The glassy solid was heated and melted, and purified by distillation at 162 to 168 ° C./1.2 mmHg to obtain a brown glassy solid having an LC purity of 100%.
g (93% yield).

The titanium content of the obtained compound was 9.0.
2%. Further, it was identified as the target substance from the following IR analysis results.

(Results of IR Analysis) The absorption peak was shown below. ^{3482cm -1, 3452cm -1, 2962cm -1} , 2873cm -1, 2364cm -1, 2333cm -1, 1575cm -1, 1535cm -1, 1502cm -1, 1457cm -1, 1382cm -1, 1355cm -1, 1294cm - ¹ , 1224 cm ^-1 , 1176 cm ^-1 , 1145 cm ^-1 , 1089 cm ^-1 , 1031 cm ^-1 , 966 cm ^-1 , 873 cm ^-1 , 792 cm ^-1 , 651 cm ^-1 , 624 cm ^-1 , 584 cm ^-1 , 507 cm ^-1 , 476 cm ^-1 , 439 cm ^-1 , 406 cm ^-1 ,

Synthesis Example 4 (Synthesis of Compound No. 4) Except that 1,3-propanediol in Synthesis Example 1 was replaced with 33 g (0.25 mol) of 2,2-diethyl-1,3-propanediol. Is Synthesis Example 1
A brown glassy solid 13 having an LC purity of 92%
3 g (98% yield) were obtained. The weight start temperature at 1 atm in the differential thermogravimetric analysis of the obtained glassy solid under a nitrogen stream was 250 ° C. The glassy solid is heated and melted, and purified by distillation at 172 to 180 ° C./1.5 mmHg to obtain L
125 g of a brown glassy solid having a C purity of 100% (yield 92
%).

The titanium content of the obtained compound was 8.7.
9%. Further, it was identified as the target substance from the following IR analysis results.

(Results of IR Analysis) The absorption peaks are shown below. ^{3444cm -1, 2962cm -1, 2929cm -1} , 2875cm -1, 2362cm -1, 2333cm -1, 1575cm -1, 1535cm -1, 1502cm -1, 1459cm -1, 1382cm -1, 1355cm -1, 1292cm - ^{1, 1224cm -1, 1174cm -1,} 1145cm -1, 1091cm -1, 968cm -1, 933cm -1, 871cm -1, 790cm -1, 738cm -1, 659cm -1, 622cm -1, 584cm -1, 549 cm ^-1 , 505 cm ^-1 , 472 cm ^-1

Synthesis Example 5 (Synthesis of Compound No. 7) The 1,3-propanediol of Synthesis Example 1 was replaced with 26 g of 2,4-pentanediol (0.25 g).
Mol), 126 g (yield 98%) of a pale yellow transparent liquid having an LC purity of 96% was obtained in the same manner as in Synthesis Example 1. In the differential thermogravimetric analysis of the obtained glassy solid under a nitrogen stream, the temperature at which the weight loss started at 1 atm was 217 ° C. 130-132 ° C / 0.2mmHg
Purified by distillation in a light yellow transparent liquid 12 with an LC purity of 100%
0 g (93% yield) was obtained.

The titanium content of the obtained compound was 8.8.
1%. Further, it was identified as the target substance from the following IR analysis results.

(Results of IR Analysis) The absorption peak was shown below. ^{2964cm -1, 2931cm -1, 2866cm -1} , 1561cm -1, 1538cm -1, 1502cm -1, 1458cm -1, 1383cm -1, 1357cm -1, 1295cm -1, 1223cm -1, 1147cm -1, 1078cm - ¹ , 1043 cm ^-1 , 971 cm ^-1 , 945 cm ^-1 , 871 cm ^-1 , 796 cm ^-1 , 762 cm ^-1 , 627 cm ^-1 , 597 cm ^-1 , 551 cm ^-1 , 506 cm ^-1 , 481 cm ^-1 , 434 cm ^-1 411 cm ^-1

[Synthesis Example 6] (Synthesis of Compound No. 8) The 1,3-propanediol of Synthesis Example 1 was replaced with 2-methyl-2,4-pentanediol 2
Synthesis Example 1 except that 9.5 g (0.25 mol) was replaced.
130 g of a colorless transparent liquid having an LC purity of 96%
(98% yield). In the differential thermogravimetric analysis under a nitrogen stream of the obtained compound, the temperature at which weight loss started at 1 atm was 220 ° C. 134 to 13 by heating and melting the liquid
Purification by distillation at 5 ° C / 0.2mmHg and LC purity 100%
This gave 121 g of a colorless transparent liquid (yield 91%).

The titanium content of the obtained compound was 8.7.
9%. Further, it was identified as the target substance from the following IR analysis results.

(Results of IR Analysis) The following absorption peaks were shown. ^{2964cm -1, 2927cm -1, 2865cm -1} , 1560cm -1, 1537cm -1, 1502cm -1, 1457cm -1, 1382cm -1, 1357cm -1, 1294cm -1, 1222cm -1, 1147cm -1, 1078cm - ^{1, 1045cm -1, 972cm -1,} 945cm -1, 871cm -1, 796cm -1, 761cm -1, 626cm -1, 597cm -1, 549cm -1, 505cm -1, 480cm -1, 432cm -1, 410cm ^-1

[Comparative Synthesis Example] 71 g of TIPT (0.25
Mol) and 92 g (0.5 mol) of DPM
Isopropanol was refluxed at 60 ° C. for 2 hours in 0 ml, and then recrystallized from hexane to give a white crystal 1 having an LC purity of 100%.
09 g (82% yield) was obtained. In the differential thermogravimetric analysis under a nitrogen stream of the obtained crystal, the temperature at which the weight loss started at 1 atm was 202 ° C.

The titanium content of the obtained compound was 8.9.
9%. Further, it was identified as the target substance from the following IR analysis results.

(Results of IR Analysis) The following absorption peaks were shown. ^{3741cm -1, 3407cm -1, 2996cm -1} , 2925cm -1, 2863cm -1, 1645cm -1, 1592cm -1, 1562cm -1, 1533cm -1, 1500cm -1, 1456cm -1, 1384cm -1, 1357cm - ^{1, 1326cm -1, 1294cm -1,} 1226cm -1, 1135cm -1, 997cm -1, 873cm -1, 850cm -1, 792cm -1, 761cm -1, 626cm -1, 584cm -1, 501cm -1, 453 cm ^-1 , 426 cm ^-1

[Examples 1-1 to 1-7 and Comparative Example 1-1]
~ 1-2] Metal complexes containing lead, zirconium and titanium
Each of the compositions in a hexane solution was prepared as shown in the following table.
1) Prepared at the compounding ratio (molar ratio) and desolvated.
It was evaluated by thermal analysis. The Pb (TH used here)
D)_Two, Pb (METHD) _Two, Zr (THD)_Fouras well as
Zr (METHD)_FourThe chemical structural formula of the following [Formula 16]
Shown in [Formula 19].

In the evaluation method, the temperature was raised from 30 ° C. to 600 ° C. at a rate of 10 ° C./min in an argon gas atmosphere at a pressure of 1333 Pa, and the temperature range showing a weight loss and the remaining amount of volatile at 300 ° C. were evaluated. The results are shown in Table 2 below.

[0067]

[Table 1]

[0068]

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[0069]

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[0070]

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[0071]

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[0072]

[Table 2]

According to the above example, in the complex composition comprising a complex of lead, zirconium and titanium, by using the specific titanium-containing complex compound used in the present invention as a titanium raw material, a one-step smooth volatilization loss curve can be obtained. draw,
Furthermore, since the volatile residue at 300 ° C is small, CV
It is easy to control the composition of the D film.

On the other hand, from the above comparative example, when a titanium-containing complex compound other than the specific titanium-containing complex compound used in the present invention is used as a titanium raw material, a multi-step volatile raw material polarity is drawn, and the volatile residue at 300 ° C. Because of the large amount, it is extremely difficult to control the composition of the CVD film.

[0075]

The metal complex composition of the present invention is excellent as a CVD material for producing a lead zirconate titanate-based thin film.

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Toshiya Kamimoto 7-35 Higashiogu, Arakawa-ku, Tokyo Asahi Denka Kogyo Co., Ltd. F-term (reference) 4H049 VN05 VP01 VQ21 VQ24 VQ85 VR43 VS21 VT40 VT44 VU24 VV02 VW35 4K030 AA11 BA01 BA18 BA22 BA42 BA46 LA01 LA15 5F058 BA11 BA20 BC03 BC04 BC20 BF02 BF27 BJ01

Claims (3)

[Claims] 1. A metal complex comprising a metal-containing compound containing lead, a metal-containing compound containing zirconium, and a complex of a β-diketone compound and a glycolate of titanium represented by the following general formula (I). Composition. Embedded image (Wherein, R ₁ and R ₂ each independently represent 1 carbon atom)
Represents an alkyl group or a cycloalkyl group which may be substituted with a halogen atom of 10 to 10 or has an ether bond, and R ₃ represents a linear or branched alkylene group having 2 to 18 carbon atoms) 2. The metal complex according to claim 1, wherein the metal-containing compound containing lead and the metal-containing compound containing zirconium are a complex or a complex with an alcoholate, a glycolate or a β-diketone compound. Composition. 3. A zirconate titanate, characterized in that lead, zirconium and titanium or their oxides are chemically vapor-grown on a substrate using the metal complex composition according to claim 1 or 2. Manufacturing method of lead-based thin film.