Barium strontium .beta.-diketonates, processes for producing the same and processes for producing barium strontium-containing oxide dielectric films with the use of the same

BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to barium strontium .beta.-diketonates, processes for producing the same and processes for producing barium strontium-containing oxide dielectric films by the chemical vapor deposition method (hereinafter referred to simply as the CVD method) with the use of the same.
2. Description of the Prior Art
Investigations are in progress on (Ba,Sr)TiO.sub.3 films (hereinafter referred to simply as BST films) having high dielectric constants and ferroelectric (Sr,Ba)Nb.sub.2 O.sub.6 films (hereinafter referred to simply as SBN films) as DRAM capacitors usable in the generation of gigabit techniques and the CVD method excellent in mass productivity and step coverage properties is highly expected to be useful in forming these films. However, these films are three-component systems, which makes it difficult to regulate the compositional ratio Ba:Sr:Ti. This difficulty is partly caused by the fact that there has been known no Ba and Sr compounds usable as a CVD feedstock which is in the form of a liquid being excellent in the controllability in supply, has a sufficient vapor pressure and shows a high heat stability at the source temperature.
At the present time, investigations are in progress mainly on barium .beta.-diketonates, in particular, barium bis(dipivaloylmethanate) [hereinafter referred to simply as Ba(dpm).sub.2 ] as the barium compound, and strontium .beta.-diketonates, in particular, strontium bis(dipivaloylmethanate) [hereinafter referred to simply as Sr(dpm).sub.2 ] as the strontium compound. These compounds have melting points in the range of 200 to 220.degree. C. and vapor pressures at 200.degree. C. of about 0.01 Torr.
It is much convenient to control the supply system from two sources compared with the case of the supply from three sources. Although the source number can be lessened by using as one source a single compound containing both of two components Ba and Sr, no such compound has been known hitherto. It is anticipated that a metal .beta.-diketonate composed of two different elements might be formed as in the case of a double alkoxide formed from two metal alkoxides of different elements which are liable to undergo association with each other. However, there has never been reported in public so far that such a molecule is formed. J. E. Schwarberg, R. E. Sievers and R. W. Moshier [Anal. Chem., 42, 1828 (1970)] reported that when a mixture of Ca(dpm).sub.2 with Sr(dpm).sub.2 was subjected to gas chromatography at 250.degree. C., only one peak was observed and this peak showed a retention time different from those of Ca(dpm).sub.2 and Sr(dpm).sub.2 chromatographed individually; that thus Ca(dpm).sub.2 could not be separated from Sr(dpm).sub.2 by gas chromatography; and CaSr(dpm).sub.3.sup.+ was observed in the mass spectrum of a fraction obtained by melting Ca(dpm).sub.2 together with Sr(dpm).sub.2 and recovering by evaporation. Based on these facts, they estimated that Ca(dpm).sub.2 would react with Sr(dpm).sub.2 in the course of the gas chromatography to thereby form a composite complex CaSr(dpm).sub.4 with a heterogenous elemental nucleus.
[Ca(dpm).sub.2 ].sub.2 +[Sr(dpm).sub.2 ].sub.2 =2CaSr(dpm).sub.4.
However, the identification of CaSr(dpm).sub.4 and measurement of its physical properties are insufficient and still at the level of estimation. As a matter of course, no description on (Ba,Sr).sub.1 (dpm).sub.2 is given therein.
SUMMARY OF THE INVENTION
One of the problems to be solved by the present invention is to disclose novel one-source compounds each containing Ba and Sr at a specified ratio and being useful as a substitute for two-source compounds composed of a Ba compound and a Sr compound in the formation of BST films or SBN films by the CVD method. Still another problem is to provide processes for producing these novel compounds. Still another problem is to provide processes for producing barium strontium-containing oxide dielectric films by the CVD method with the use of these novel compounds.

BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows the FD-MS chart of Ba (dpm).sub.2, more particularly, (Ba.sub.0.999 Sr.sub.0.001) (dpm).sub.2.
FIG. 2 shows the FD-MS chart of Sr(dpm).sub.2, more particularly, (Ba.sub.0.003 Sr.sub.0.997) (dpm).sub.2.
FIG. 3 shows the FD-MS chart of the second fraction, more particularly (Ba.sub.0.003 Sr.sub.0.523) (dpm).sub.2.
FIG. 4 shows the TG-DTA chart of the second fraction.

DESCRIPTION OF THE PREFERRED EMBODIMENTS
The present inventors have conducted for a long time studies on the synthesis of organometallic compounds and the CVD method with the use of the same. To solve the problems as described above, they first individually synthesized Ba(dpm).sub.2 and Sr(dpm).sub.2 compounds. Then each compound was subjected to high-vacuum distillation and the melting point and vapor pressure thereof were measured. The vapor pressure was measured by the gas saturation method wherein porous ceramic particles were impregnated with the compound in a molten state to thereby support the compound on the particles. Next, Sr(dpm).sub.2 and Ba were reacted with dipivaloylmethane (hereinafter referred to simply as dmpH) to give a molar ratio of Ba(dpm).sub.2 to Sr(dpm).sub.2 of 1:1, followed by high-vacuum distillation to recover the distillate in three fractions, i.e., the first, second and third fractions (Example 1). The melting point of each fraction was measured and the composition [Ba, Sr, (dpm)] thereof was analyzed. Further, the evaporation properties were examined by TG-DTA. As a result, it was found out that the obtained product was highly favorable as a CVD feedstock. The results of the FD-MS (field desorption-mass spectroscopy) analysis on these fractions as the molecular species indicated that the obtained product was not a mere mixture but a novel compound mainly comprising (Ba,Sr).sub.3 (dpm).sub.6 [including Ba.sub.2 Sr(dpm).sub.6 and BaSr.sub.2 (dpm).sub.6 ].
Starting with the novel compound in the form of a liquid at 200.degree. C., an attempt has been made to form BST films. That is, a carrier gas is bubbled thereinto and thus the (Ba,Sr) component is supplied into a CVD apparatus. As a result, it has been found out that excellent films can be obtained constantly thereby. The present invention has been thus completed. Therefore, the present invention has made it possible to produce the novel compound (Ba,Sr).sub.3 (dpm).sub.6 which contains as a single source the (Ba,Sr) component for producing barium strontium-containing oxide dielectric films by the CVD method and can be supplied in the form of a liquid.
The novel compounds according to the present invention are barium strontium .beta.-diketonates, namely, .beta.-disketonates containing at least one barium atom and at least one strontium atom in the molecule formed by association.
Examples of the .beta.-diketonates are listed in Table 1.
TABLE 1______________________________________Abbrevi- Chemical ation Formula Name______________________________________thd or --C.sub.11 H.sub.19 O.sub.2 2,2,6,6-tetramethyl-3,5-heptanedionate dpm (commonly called "dipivaloylmethanate") tod --C.sub.11 H.sub.19 O.sub.2 2,2,7-trimethyl -3,5-octanedionate tmhpd --C.sub.10 H.sub.17 O.sub.2 2,2,6-trimethyl-3,5-heptanediona te dmhpd or --C.sub.9 H.sub.15 O.sub.2 2,6-dimethyl-3,5-heptanedionate dim (commonly called "diisobutyryl methanate") --C.sub.9 H.sub.15 O.sub.2 2,2-dimethyl-3, 5-heptanedionate tmod --C.sub.12 H.sub.21 O.sub.2 2,2,6,6-tetramethyl-3,5-octanedi onate______________________________________
Next, the most commonly employed dpm system will be described by way of example.
The Ba(dpm).sub.2 and Sr(dpm).sub.2 synthesized by the present inventors by reacting dipivaloylmethane with barium or strontium followed by high-vacuum distillation existed as trimers, i.e., Ba.sub.3 (dpm).sub.6 and Sr.sub.3 (dpm).sub.6 in benzene solution, as well as in vapor phase according to the results of the FD-MS analysis (cf. FIG.1).
The results of the identification of a product corresponding to (Ba,Sr).sub.1 (dpm).sub.2, which has an atomic ratio of Ba:Sr of about 1 and is produced by the production process according to the present invention and the method as will be described in Example 1, will be now described.
In conclusion, this product was not a mixture of Ba.sub.3 (dpm).sub.6 with Sr.sub.3 (dpm).sub.6 but a mixture of a novel compound Ba.sub.2 Sr(dpm).sub.6 with another novel compound BaSr.sub.2 (dpm).sub.6.
Now, the identification will be described in detail.
Procedure for the Identification of the Product Corresponding to (Ba,Sr).sub.1 (dpm).sub.2 Having an Atomic Ratio of Ba:Sr of about 1
The product was subjected to high-vacuum simple distillation at 0.02 Torr and the distillate was divided into the first, second and third fractions. In this case, little still residue was observed.
Two samples were taken from each fraction and the Ba and Sr contents were analyzed. Table 2 shows the results.
TABLE 2______________________________________Analytical data on the composition of high- vacuum simple distillation fraction dpm Molar ratio Fraction Sam- Ba Sr (wt. Atomic ratio dpm/ (wt. %) ple (wt. %) (wt. %) %)* Ba:Sr (Ba + sr)______________________________________1st (32) 1 13.6 9.36 77.0 0.480:0.520 2.04 2 13.6 9.51 76.9 0.477:0.523 2.02 2nd (36) 1 14.0 9.75 76.3 0.478:0.522 1.95 2 13.8 9.68 76.5 0.476:0.524 1.98 3rd (32) 1 14.1 9.53 76.4 0.486:0.514 1.97 2 14.2 9.50 76.3 0.488:0.512 1.97 Average 0.481:0.519 1.99______________________________________ *calculated by taking dpm(wt. %) as 100 - (Ba + Sr).
As Table 2 shows, the compositions of the all fractions agreed with each other within the scope of analytical errors, which suggests that the composition of the product was the same throughout the evaporation.
Next, the molecular weight of each fraction was determined by the cryoscopic method with the use of benzene.
TABLE 3______________________________________Results on the molecular weight determination of high-vacuum simple distillation fraction Fraction M.w. Sample (g) Benzene (g) .DELTA.T (.degree. C.)______________________________________1st 1.3403 19.9 0.264 1310 2nd 1.6691 20.1 0.263 1610 3rd 1.2138 20.2 0.197 1560______________________________________
Although the data were somewhat scattered, the molecular weights ranged from 1,300 to 1,600. The molecular weights of the estimated trimers are as follows:
Ba.sub.3 (dpm).sub.6 : 1512
Ba.sub.2 Sr(dpm).sub.6 : 1462
BaSr.sub.2 (dpm).sub.6 : 1412
Sr.sub.3 (dpm).sub.6 : 1362.
Thus, the product was highly likely one composed of these compounds.
Next, molecular species were measured to determine whether the above fractions were a mere mixture of the known compound Ba.sub.3 (dpm).sub.6 with another known compound Sr.sub.3 (dpm).sub.6 or a mixture of a novel compound Ba.sub.2 Sr(dpm).sub.6 with another novel compound BaSr.sub.2 (dpm).sub.6, etc. The FD-MS analysis was employed in the measurement.
In electron impact-MS (EI-MS) or chemical ionization-MS (CI-MS), it is sometimes observed that only small molecular ion peaks or even no peak can be observed due to the occurrence of a number of fragment ions. In contrast thereto, the FD-MS analysis employed herein has an advantage that molecular ion peaks can be easily observed.
Instrument MS: JEOL SX-102.
Ionization method: FD
ion polarity: +
emitter: carbon
emitter current: 0-40 mA.
Measurement conditions
accelerating voltage: 8 kV
range: m/z=0-2000
scanning speed: 15 sec/decade.
Sample and Result:
The FD-MS data of Ba(dpm).sub.2, more particularly, (Ba.sub.0.999 Sr.sub.0.001) (dpm).sub.2 are shown in FIG. 1.
The FD-MS data of Sr(dpm).sub.2, more particularly, (Ba.sub.0.003 Sr.sub.0.997) (dpm).sub.2 are shown in FIG. 2.
The FD-MS data of the second fraction, more particularly (Ba.sub.0.477 Sr.sub.0.523) (dpm).sub.2 are shown in FIG. 3.
The FD-MS list of the second fraction is shown in Table 4.
TABLE 4______________________________________FD-MS list of the second fraction (Intensity has been normalized by taking m/z = 1413 as 100.) Ionic species m/z Intensity Sum of intensities______________________________________Sr(dpm).sub.2 452 15.08 453 12.42 454 41.49 455 14.72 456 6.17 89.88 Bd(dpm).sub.2 500 4.57 501 15.98 502 16.45 503 14.94 504 50.61 505 40.90 506 8.78 152.23 Sr.sub.2 (dpm).sub.4 905 4.41 906 18.13 907 18.62 908 36.17 909 31.29 910 15.93 911 4.06 128.61 SrBa(dpm).sub.4 954 3.87 955 8.08 956 19.98 957 16.71 958 31.97 959 29.71 960 23.64 961 9.60 133.56 Ba.sub.2 (dpm).sub.4 1004 1.95 1005 4.22 1006 12.67 1007 10.29 1008 12.19 1009 12.54 1010 7.77 61.63 Sr.sub.3 (dpm).sub.6 1358 6.64 1359 14.22 1360 23.07 1361 34.83 1362 40.93 1363 63.47 1364 47.30 1365 32.79 1366 14.01 1367 3.90 281.16 Sr.sub.2 Ba(dpm).sub.6 1406 6.33 1407 8.07 1408 23.42 1409 40.69 1410 43.30 1411 57.74 1412 80.09 1413 100.00 1414 68.46 1415 45.05 1416 19.33 1417 5.69 498.17 SrBa.sub.2 (dpm).sub.6 1454 1.49 1455 4.65 1456 7.54 1457 10.72 1458 21.88 1459 27.60 1460 33.78 1461 56.55 1462 56.19 1463 84.74 1464 57.68 1465 33.24 1466 18.63 1467 5.81 420.50 Ba.sub.3 (dpm).sub.6 1506 8.00 1507 6.14 1508 10.72 1509 10.87 1510 16.86 1511 15.05 1512 18.03 1513 22.47 1514 23.46 1515 12.68 144.28______________________________________
FIG. 1 shows the main molecule of Ba(dpm).sub.2 was Ba.sub.3 (dpm).sub.6 at around the m/z of 1512 while Sr as the trace impurity was in the form of Ba.sub.2 Sr(dpm).sub.6 observed at around the m/z of 1462. FIG. 2 shows that the main molecule of Sr(dpm).sub.2 was Sr.sub.3 (dpm).sub.6 observed at around the m/z of 1363 while Ba as the trace impurity was in the form of Ba.sub.2 Sr(dpm).sub.6 observed at around the m/z of 1413. These compounds were both trimers as anticipated based on the results of the molecular weight determination. FIG. 3 and Table 4 indicate that the second fraction was a mixture of Ba.sub.2 Sr(dpm).sub.6 with BaSr.sub.2 (dpm).sub.6 observed respectively at around the m/z of 1463 and around the m/z of 1413. Ba.sub.2 Sr(dpm).sub.6 and BaSr.sub.2 (dpm).sub.6 are both novel compounds which are diketonate molecules of trimers composed of two different elements. They are the compounds of the present invention. These two novel compounds are indicated as (Ba,Sr).sub.3 (dpm).sub.6.
The structures of these novel compounds Ba.sub.2 Sr(dpm).sub.6 and BaSr.sub.2 (dpm).sub.6 are still unknown. Supposing that they are in the most likely form of hexa dentate linear trimers, each compound has two molecular species consisting of three atoms, as follows:
Ba.sub.2 Sr(dpm).sub.6 : Ba--Ba--Sr and Ba--Sr--Ba.
BaSr.sub.2 (dpm).sub.6 : Ba--Sr--Sr and Sr--Ba--Sr.
The vapor pressures of these novel compounds are very close to each other, though seemingly not identical. Therefore, it can be thought that they can be regarded as substantially the same with each other as a CVD source.
The physical properties of (Ba,Sr).sub.3 (dpm).sub.6 according to the present invention were measured. By way of example, use was made, as the samples for the measurement, of the above fractions (Ba.sub.0.48 Sr.sub.0.52) (dpm).sub.2.
(1) Melting Point
Each sample was introduced into a glass capillary and its melting point was measured with the naked eye:
first fraction: 160.degree. C.
second fraction: 160.degree. C.
third fraction: 160.degree. C.
(2) Liquid Density
1.1 g/cm.sup.3 (180.degree. C.)
(3) Vapor Pressure
method: gas saturation method.
Porous ceramic grains were impregnated with a sample in a molten state and then packed into a glass cylinder. A carrier gas Ar was fed into the cylinder from the bottom thereof and Ar and the vaporized sample were introduced from the top into a cooling tube. After trapping, the Ba and Sr contents were analyzed. The measurement was effected under the total pressure of 10 Torr at 200.degree. C. The vapor pressure in terms of a monomer was determined for convenience's sake.
Vapor pressure at 200.degree. C. (in terms of monomer): 0.02 Torr.
The first, second and third fractions showed the same vapor pressure.
(4) Kinematic Viscosity
The kinematic viscosity of the second fraction was measured by using a glass capillary viscometer (Cannon-Fenske Model).
87.3 cSt (centistokes)/180.degree. C.
44.9 cSt/200.degree. C.
23.8 cSt/220.degree. C.
(5) TG-DTA
Measurement conditions: sample weight: 16.53 mg
atmosphere: Ar 1 atm
temperature rise rate: 10.0
deg/min.
FIG. 4 shows the data of the second fraction. Other fractions gave similar results.
As FIG. 4 clearly shows, the weight loss in TG began at about 240.degree. C. The weight loss reached 50% and 93% respectively at 400.degree. C. and 440.degree. C. No clear-cut melting point was observed in DTA. This is seemingly because the sample was a mixture of compounds having various structures.
(6) Solubility
Solubility in toluene (g/100 ml toluene, 20.degree. C.):
first fraction: 13
second fraction: 15
third fraction: 20.
The solubility of each single component will be given below by way of reference:
Ba(dpm).sub.2 : 2
Sr(dpm).sub.2 : 145.
(7) Heat Stability
5 g of the second fraction was introduced into a SUS32 tube (Ar atmosphere) followed by sealing up. After keeping in an oil bath at 200.degree. C. for 10 days, it was taken out therefrom and analyzed by TG-DTA. As a result, no change was observed.
The present invention further relates to processes for producing the compounds of the present invention at a high mass productivity.
The first process comprises reacting barium and strontium with a .beta.-diketone in a solvent, removing the solvent and then purifying and recovering the product by high-vacuum distillation to thereby give barium strontium .beta.-diketonate. It will suffice when the barium and strontium are supplied at a ratio corresponding to the target Ba:Sr ratio. As the solvent, it is preferable to use oxygen-free and dried hydrocarbons such as toluene. The reaction temperature is the boiling point of the solvent. That is, the reaction is effected under reflux. The reaction time varies depending on the surface areas and surface activities of the metals. In general, it ranges from several hours to several days. When specified amounts of the metals are consumed in the reaction, the solvent is removed and the product is purified and recovered by high-vacuum distillation. It is not desirable to effect purification by recrystallization, since the purified product is liable to be contaminated with solvent molecules, unreacted .beta.-diketone and less volatile organic matters.
The second process comprises reacting barium with a .beta.-diketone in a solution of strontium .beta.-diketonate, removing the solvent and then purifying and recovering the product by high-vacuum distillation to thereby give barium strontium .beta.-diketonate. As the solvent, it is preferable to use hydrocarbons such as toluene. The reaction temperature is the boiling point of the solvent. That is, the reaction is effected under reflux. The .beta.-diketone is supplied preferably in excess at the equivalence point to the barium. Unless it is employed in excess, the reaction proceeds slowly and thus it takes a very long time to complete the reaction. The reaction time ranges from several hours to several tens of hours.
The third process comprises reacting strontium .beta.-diketonate with barium .beta.-diketonate optionally in a solvent, removing the solvent, if any, and then purifying and recovering the product by high-vacuum distillation to thereby give barium strontium .beta.-diketonate. As the solvent, if employed, it is preferable to select toluene, etc. The reaction is effected at the boiling point of the solvent under reflux for one to several days. When no solvent is used, a strontium .beta.-diketonate powder is mixed with a barium .beta.-diketonate powder and then the resultant mixture is maintained at 220 to 230.degree. C. for several hours to one day to thereby perform the reaction in a molten state.
The present invention further provides a process for producing barium strontium-containing oxide dielectric films by the chemical vapor deposition method which comprises bringing a heated substrate into contact with barium strontium .beta.-diketonate.
Examples of the barium strontium-containing oxide dielectric films include BST films and SBN films. The Ba:Sr ratio of the feedstock barium strontium .beta.-diketonate is determined depending on the Ba:Sr ratio of the desired film composition. Although the Ba:Sr ratio of the feedstock may be the same as that of the desired film composition, it should be somewhat modified in some cases depending on the CVD conditions.
The barium strontium .beta.-diketonate to be used as the feedstock in the CVD method is in the form of a liquid, since it has been heated to 180 to 230.degree. C. under reduced pressure. After bubbling a carrier gas into this liquid, it is combined with other oxide feedstock gas while maintaining at an appropriate temperature by heating so as to prevent the gas from condensation. Then the mixture is introduced into a CVD chamber, where it is mixed with an oxidative gas such as O.sub.2 or N.sub.2 O and thermally decomposed on a substrate heated to 500 to 700.degree. C. to thereby give a composite oxide film.
As the second method of supply, use can be made of a supporting/evaporation system. In this system, the feedstock liquid is supported on porous ceramic grains by impregnation and then packed into a cylinder. After heating to 180 to 230.degree. C., a carrier gas is fed into the layer. Then the saturated vapor of barium strontium .beta.-diketonate is taken out and introduced into a CVD chamber. This supporting/evaporation system has an advantage that since the liquid is held in the pores and thus the vapor-liquid interfacial area is enlarged, the saturated vapor can be readily obtained while gas pressure loss is lessened. It is preferred that the source bubbler and the supporting/evaporation cylinder are operated under a pressure as low as 10 to 150 Torr. This is because a number of feedstock materials can be evaporated together at a low carrier gas flow rate and a trace amount of gas impurities formed by thermal decomposition, etc. can be discharged from the cylinder thereby, thus minimizing the degradation of the source.
As the third method of supply, use can be made of a system which comprises dissolving the barium strontium .beta.-diketonate feedstock in THF, etc. followed by flash evaporation.
In the case of a BST film, a gas such as Ti(OiPr).sub.4 or Ti(OiPr).sub.2 (dpm).sub.2 is used as a TiO.sub.2 source. Since the Ba:Sr ratio of the film is determined depending on the Ba:Sr ratio of the barium strontium .beta.-diketonate source, the appropriate (Ba+Sr)/Ti ratio of the film may be achieved by regulating the gas supply from the TiO.sub.2 source.
In general, the thermal CVD is effected at a substrate temperature of 500 to 700.degree. C. under a pressure of 0.1 to 10 Torr with the use of O.sub.2 or N.sub.2 O as the oxidative gas.
In addition to the thermal CVD method, use may be made of the ECR-plasma CVD method, the laser CVD method, etc. in the present invention.
In the case of an SBN film, a gas such as Nb(OEt).sub.5 is used as an Nb.sub.2 O.sub.5 source. Since the Ba:Sr ratio of the film is determined depending on the Ba:Sr ratio of the barium strontium .beta.-diketonate source, the appropriate (Ba+Sr)/Nb ratio of the film may be achieved by regulating the gas supply from the Nb.sub.2 O.sub.5 source.
In general, the heat CVD is effected at a substrate temperature of 500 to 700.degree. C. under a pressure of 1 to 100 Torr with the use of O.sub.2 or N.sub.2 O as the oxidative gas.
EXAMPLE 1
Production of Barium Strontium .beta.-diketonate (Ba.sub.0.48 Sr.sub.0.52) (dpm).sub.2
A 500 ml four-necked flask provided with a reflux condenser, a thermometer and stirring blades was vacuum purged with argon. Then 350 ml of toluene was fed thereinto followed by the supply of 40.3 g (89 mmol) of Sr(dpm).sub.2, 65.6 g (356 mmol) of dipivaloylmethane dpmH and 12.2 g (89 mmol) of a metallic barium piece. The resultant mixture was heated with stirring. When it reacted under reflux for 8 hours, the metal piece disappeared. Next, the solvent and the unreacted dpmH components were distilled off under reduced pressure. The residue was further treated at 170.degree. C. under 0.05 Torr to thereby distill off the dissolved dpmH remaining in a small amount. A 65 g portion of the residue was transferred to a high-vacuum distillation apparatus, where it was distilled by heating at an oil bath temperature of 220.degree. C. under 0.02 Torr to give 19.5 g of the first fraction, 21.7 g of the second fraction and 19.2 g of the third fraction. These three fraction were each in the form of a pale yellow solid at room temperature. The identification thereof and the measurement of their physical properties were performed by the methods described above.
EXAMPLE 2
Production of Barium Strontium .beta.-diketonate (Ba.sub.0.49 Sr.sub.0.51) (dpm).sub.2
A 500 ml four-necked flask provided with a reflux condenser, a thermometer and stirring blades was vacuum purged with argon. Then 400 ml of toluene was fed thereinto followed by the supply of 14.94 g (29.7 mmol) of Ba(dpm).sub.2 and 13.80 g (30.4 mmol) of Sr(dpm).sub.2. The resultant mixture was stirred at 20.degree. C. for 8 hours but the Ba(dpm).sub.2 was not dissolved at all. Next, the mixture was maintained under the reflux of toluene for 24 hours. As a result, the reactants were completely dissolved and turned slightly yellow and transparent. After distilling off the solvent, the residue was subjected to high-vacuum distillation at an oil bath temperature of 220.degree. C. under 0.02 Torr to give 25 g of a pale yellow distillate, which was (Ba.sub.0.49 Sr.sub.0.51) (dpm).sub.2 with a Ba:Sr ratio of 0.49:0.51, having a melting point of 160.degree. C. and TG-DTA data similar to those given in FIG. 4.
EXAMPLE 3
Production of Barium Strontium .beta.-diketonate (Ba.sub.0.49 Sr.sub.0.51) (dpm).sub.2
A high-vacuum distillation still made of Pyrex was vacuum purged with argon. Then 24.60 g (48.8 mmol) of Ba(dpm).sub.2 and 22.75 g (50.1 mmol) of Sr(dpm).sub.2 were supplied thereinto. The still was heated in an oil bath at 220.degree. C. for 6 hours to give a yellow and transparent liquid. Next, it was subjected to high-vacuum distillation at an oil bath temperature of 220.degree. C. under 0.02 Torr to give 42 g of a pale yellow distillate, which was (Ba.sub.0.49 Sr.sub.0.51) (dpm).sub.2 with a Ba:Sr ratio of 0.49:0.51, having a melting point of 160.degree. C. and TG-DTA data similar to those given in FIG. 4.
EXAMPLE 4
Production of Barium Strontium .beta.-diketonate (Ba.sub.0.51 Sr.sub.0.49) (dpm).sub.2
A 500 ml four-necked flask provided with a reflux condenser, a thermometer and stirring blades was vacuum purged with argon. Then 400 ml of toluene was fed thereinto followed by the successive supply of 38.0 g (206 mmol) of dipivaloylmethane dpmH and 3.80 g (27.7 mmol) of a Ba piece and 2.33 g (26.6 mmol) of an Sr piece. After heating the resultant mixture under reflux, the metal pieces disappeared. Next, the solvent and the unreacted dpmH were distilled off under reduced pressure. The residue was further subjected to high-vacuum distillation at an oil bath temperature of 220.degree. C. under 0.02 Torr to give 24 g of a pale yellow distillate which was (Ba.sub.0.51,Sr.sub.0.49) (dpm).sub.2 with a Ba:Sr ratio of 0.51:0.49, and showing TG-DTA data similar to those given in FIG. 4.
EXAMPLE 5
Production of BST Film by the CVD Method
During the embodiment of the CVD method, the whole feedstock container and thermal decomposition reactor systems were maintained under 10 Torr.
A feedstock container 1 packed with 40 g of (Ba.sub.0.49 Sr.sub.0.51) (dpm).sub.2 was introduced into a thermostatic chamber at 200.degree. C. and a carrier gas Ar was bubbled thereinto at 20 sccm. (Ba.sub.0.49 Sr.sub.0.51) (dpm).sub.2 evaporated with it and the mixture was fed into the thermal decomposition reactor via a gas mixer. Separately, 30 g of Ti(OiPr).sub.2 was supported on porous ceramic grains, which were then packed into another feedstock container 2. Then it was introduced into a thermostatic chamber at 125.degree. C. and a carrier gas Ar was supplied thereinto at 30 sccm. Ti(OiPr).sub.4 sublimated together with this gas and the mixture was fed into the thermal decomposition reactor via a gas mixer. At the same time, an oxygen gas was introduced into the thermal decomposition reactor at 50 sccm. The thermal decomposition reactor had been provided therein with a Pt/SiO.sub.2 /Si substrate heated to 550.degree. C. The (Ba.sub.0.49 Sr.sub.0.51) (dpm).sub.2 and Ti(OiPr).sub.2 (dpm).sub.2 underwent oxidative decomposition on this substrate and thus a BST film of 60 nm thickness was formed after 20 minutes. The result of XRD analysis indicated that this film had a perovskite structure. When this film was dissolved and the metal contents were analyzed by ICP emission spectroscopy, it was found out that the Ba:Sr:Ti ratio was 0.49:0.51:1.02.
EXAMPLE 6
Production of SBN Film by the CVD Method
During the embodiment of the CVD method, the whole feedstock container and thermal decomposition reactor systems were maintained under 10 Torr.
A feedstock container 1 packed with 40 g of (Ba.sub.0.49 Sr.sub.0.51) (dpm).sub.2 was introduced into a thermostatic chamber at 210.degree. C. and a carrier gas Ar was bubbled thereinto at 20 sccm. (Ba.sub.0.49 Sr.sub.0.51) (dpm).sub.2 evaporated with it and the mixture was fed into the thermal decomposition reactor via a gas mixer. Separately, another feedstock container 2 packed with 40 g of Nb(OEt).sub.5 was introduced into a thermostatic chamber at 125.degree. C. and a carrier gas Ar was supplied thereinto at 20 sccm. Nb(OEt).sub.5 evaporated with it and the mixture was fed into the thermal decomposition reactor via a gas mixer. At the same time, an oxygen gas was introduced into the thermal decomposition reactor at 40 sccm. The thermal decomposition reactor had been provided therein with a quartz substrate heated to 600.degree. C. The (Ba.sub.0.49 Sr.sub.0.51) (dpm).sub.2 and Nb(OEt).sub.5 underwent oxidative decomposition on this substrate and thus an SBN film of 80 nm thickness was formed after 20 minutes. The result of XRD analysis indicated that this film had a tetragonal tungsten bronze structure. When this film was dissolved and the metal contents were analyzed by ICP emission spectroscopy, it was found out that the Ba:Sr:Nb ratio was 0.49:0.51:2.07.
Because of having a melting point of 160.degree. C., being in the form of a liquid and having enough pressure at 200.degree. C., the barium strontium .beta.-diketonates, [Ba.sub.2 Sr(dpm).sub.6 and BaSr.sub.2 (dpm).sub.6 ] according to the present invention can be quantitatively supplied by gas bubbling or by evaporation from a porous carrier as a feedstock in the CVD method while maintaining a constant Ba/Sr ratio. Thus, barium strontium-containing oxide dielectric films can be produced at a high reproducibility by thermal decomposition on a substrate in an oxidative atmosphere.

Barium strontium .beta.-diketonates, processes for producing the same and processes for producing barium strontium-containing oxide dielectric films with the use of the same

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