PROCESS FOR FORMING THIN FILM OF OXIDE SUPERCONDUCTOR

Abstract: Complex cpds. comprise an organic cpd. (1) having a structure which acts as a ligand and an alkaline earth metal (2). In the organic cpd. (1) three or six protons are substd. by halogen atoms (3). (1) is specified to be an acetylacetone. The alkaline earth metal (2) is specified to be Ba or Sr. The halogen atom (3) is specified to be F or Cl. The process for forming a thin film of an oxide superconductor comprises (i) mixing together the gas of the complex cpds., a gas of an organometallic cpd. of a transition metal and/or its halide, (ii) adding oxygen to establish a predetermined oxygen partial pressure in the mixt., (iii) thermally decomposing this mixt. so as to deposit a film on a base. The transition metal is specified to be at least one of Cu, Ni and Ag. During thermal decompsn. the activation energy of the reaction is supplied by heating the base or irradiating it with light.

Description: BACKGROUND OF THE INVENTION Field of the Invention This invention relates to a process for producing a superconducting thin oxide film. The superconducting thin films are utilized in various devices, such as high speed computers, wiring thereof and superconducting photosensitive devices. Among the known processes for producing a superconducting thin film is a sputtering process. In producing a thin film, such as a thin oxide film composed of lanthanoids, alkali earth metals and copper, by this process it is necessary to produce a sputtering target by mixing Ln₂O₃, Ln being yttrium, scandium or lanthanoids, SrCO₃ or BaCO₃ and CuO in a variety of mixing ratios, heating the mixture in air for several hours at a temperature of 700 to 1000°C, pressure molding the mixture and calcining the molded product for several hours at a temperature ranging from 700 to 1000°C. Hence, a prolonged time is involved in producing the target by this process. When the target thus produced is used for preparing the thin film, the composition of the thin film and that of the target coincide with each other only on rare occasions since the sputtering yield differs from one element to another. In addition, in preparing the thin oxide films of various compositions for trial, it is necessary to produce a number of targets of various compositions by costly and time- and labor- consuming operations. It is also extremely difficult with the sputtering process to add a variety of impurities, such as F or Ag, thought to be helpful in improving superconductor film characteristics, that is, elevating the critical temperature (Tc) or stabilizing the film quality. It is also necessary with his process to set the vacuum so as to be not higher than 0.133 mbar (10-1 Torr) for producing the thin film, which means that the efficiency in preparing the film is poor and a painstaking operation is required for device maintenance. There is also known a metal organic chemical vapor deposition (MOCVD) process, according to which gases of a plurality of species of organometal compounds are introduced into a tubular reactor and metal compounds evolved by a gas phase reaction are stacked on a substrate maintained in a heated state in the reactor to produce a thin film. It is possible with this process to control the concentration ratio of the reactants in the reaction gases and crystallinity of the reaction product by changing the film forming conditions, such as the flow rate of the reaction gases, gas flow mode or the substrate temperature. Hence, the problems inherent in the sputtering process may possibly be eliminated by application of the MOCVD process. However, when the conventional MOCVD process is applied directly, a number of problems are necessarily presented in forming superconducting thin films of metal oxides. In preparing superconducting thin films of metal oxides with the conventional MOCVD process, the following problems are presented. i) In general, the gases of organometal compounds are extremely labile in oxygen as it is inflammable and ready to be cracked upon contacting with oxygen. Thus, when oxygen is introduced into the reaction system, they may be exploded or undergo premature reaction on or outside the substrate. ii) A majority of organometal compounds of the elements of the group IIIa or alkali earth metals exist as the solid at or around room temperature, so that a sufficient vapor pressure cannot be realized in a ordinary liquid or hot air heating type constant temperature vessel. iii) The organometal compounds of the lanthanoid series are liable to be condensed on the inner wall of the tabular reactor since the vapor pressure of these compounds is significantly lower than that of the organometal compounds adapted for application to semiconductors. iv) For preparing oxide superconductors, it is necessary to use an elevated substrate temperature. Object and Summary of the Invention It is therefore a principal object of the present invention to obviate the above deficiencies and to provide a process for preparing a superconducting thin film of a metal oxide with the MOCVD process. In accordance with the present invention, there is provided a process for preparing a superconducting thin oxide film comprising the steps of mixing a gas of at least one organometal compound of an alkali earth metal, a gas of at least one organometal compound of a group IIIa element and/or a halogenide thereof, and a gas of at least one organometal compound of a transistion metal and/or a halogenide thereof, with an inert gas, to form a gas mixture; mixing an oxygen-containing gas to said gas mixture to produce a gas mixture having a predetermined oxygen partial pressure not less than 67 mbar (50 Torr) and not higher than 400 mbar (300 Torr); and thermally decomposing said gas mixture having the predetermined oxygen partial pressure on a substrate to produce a thin film of a super conducting oxide on said substrate. It is preferred that the transition metal includes one or more of Cu, Ni and Ag. It is also preferred that the energy for activating the reaction be afforded by heating the substrate or by irradiating the substrate with light rays. It is furthermore preferred that the molar ratio of various metals in said gas of the group IIIa element: alkali earth metal: transition metal be equal to 1 : 0.1 to 100 : 0.01 to 40, the oxygen partial pressure be not less than 67 mbar (50 Torr) and not higher than 400 mbar (300 Torr) and the substrate temperature be not less than 450°C and not higher than 950°C. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a diagrammatic view showing a device used for forming a superconducting thin film of the present invention. Fig. 2 is a chart showing the temperature dependency of the electrical resistance of the thin film prepared in the examples of the present invention. Fig. 3 is a chart showing the temperature dependency of the electrical resistance for the case in which the substrate is heat-treated after the supply of a gas of the organometal compound is terminated in the Examples of the present invention. DESCRIPTION OF THE INVENTION The present invention will be explained in detail herein below. For forming a superconductor on a substrate as a thin film, it is of utmost importance that the respective elements making up the superconductor be supplied to the vicinity of the substrate with a predetermined concentration ratio. To this end, the selection of the organic compounds of the respective elements, oxygen partial pressure and the substrate temperature represent critical factors. This finding has led to fulfillment of the present invention. As a result of our eager studies and researches into the organic compounds of the alkali earth metals utilizable in the aforementioned MOCVD process, the present inventors have found a novel method for forming a thin film of an oxide superconductor. The organic compounds of the alkali earth metals may include those in which the alkali earth metal is Ba or Sr and the organic compound is acetylacetone or cyclopentadiene, such as, for example, dicyclopentadiene barium, diacetylacetone barium, dipentadiene strontium and diacetylacetone strontium. The vaporization temperatures for these compounds are: 480°C for Ba(C₅H₅)2; 250°C for Ba(C₅H₇O₂)₂; 450°C for Sr(C₅H₅)₂; and 240°C for Sr(C₅H₇O₂)₂. In preparing superconducting thin films, the organic compounds and/or the halogenides of the IIIa group elements of the Periodic Table and organic compounds and/or halogenides of transition metals are employed besides the aforementioned organic compounds of the alkali earth metals. As the organic compounds of the IIIa group elements, those in which one or more Y, Sc and lanthanoids are used as the IIIa group elements and cyclopentadiene and acetylacetone are used as the organic compounds, are preferred. Halogenides and above all fluorides thereof may also be employed. Examples of these compounds include tricyclopentadiene yttrium, Ln(C₅H₅)₃, such as tricyclopentadiene lanthanum, where Ln stands for Y, Sc or lanthanoids, or Ln (trifluoroacetylacetone)₃. As the organic compounds of transition metals, those in which one or more Cu, Ni and Ag are used as the transition metals and acetylacetone and/or cyclopentadiene are used as the organic compounds, are preferred. Halogenides and above all fluorides thereof may also be employed. Examples of these compounds typically include diacetylacetone copper, ditrifluoroacetyleacetone copper and dihexafluoroacetylacetone copper. It is noted that Cu atoms in the oxides may be easily substituted by Ag atoms by introducing the gas of the Ag compounds. For such substitution, the gas of an organic compound of Cu and the gas of an organic compound of Ag, for example, may preferably be employed as a mixture which is adjusted so that the mixing ratio Ag/(Cu + Ag) is not higher than 0.8. The organic compounds of the alkali earth metals, organic compounds and/or halogenides of the IIIa group elements and the organic compounds and/or halogenides of the transition metals, described hereinabove, are gasified and mixed, the resulting mixture is thermally decomposed and formed into a thin film of the superconducting oxide of these metals on the substrate. When the elements other than one or more elements selected from the group consisting of the elements of the aforementioned lanthanoid series, one or more elements selected from the group consisting of Cu, Ni and Ag and one or more elements selected from the group consisting of the alkali earth metal elements, are added for improving the characteristics of the thin film of the oxide superconductor, these elements may be supplied as a gas of one or more organic compounds and/or one or more halogenides thereof. As the carrier gas for the organic compounds or halogenides of the above elements, referred to hereinafter as the feedstock gas, H₂, H₂ + Ar or N₂ is employed in the conventional MOCVD devices adapted for application to semiconductors. In the present invention, inert gases such as He, Ar and N₂ are employed. The oxygen-containing gas is discharged at a position closer to the substrate so that it is mixed with a gas of the organic compound in close proximity to the substrate. As the oxygen-containing gas, pure oxygen or oxygen diluted with an inert gas may be advantageously employed. At this time, an energy for activating the reaction is preferably supplied for oxidizing the gas of the organic compound and/or the halogenide of the feedstock material on the substrate. This may be accomplished by a heat energy evolved upon heating the substrate or a light energy evolved upon irradiating the substrate with light rays. When forming the superconducting thin film with the use of an organic compound of alkali earth metals, the operating conditions are preferably such that the molar ratio of the metals in the gas of the IIIa group element: alkali earth metal: transition metal is equal to 1 : 0.1 to 100 : 0.01 to 40, the oxygen partial pressure is not lower than 67 mbar (50 Torr) and not higher than 400 mbar (300 Torr) and the substrate temperature is not lower than 450°C and not higher than 950°C. With the operating conditions outside the above defined range, the superconducting phase may not be evolved, or may be evolved only in minor quantities. The process for forming the superconducting thin film of the present invention will now be explained by referring to Fig. 1. However, the present invention is not limited to the embodiment shown therein which is merely an exemplary device for practicing the invention. The gas of an organic compound of an alkali earth metal, the gas of an organic compound or halogenide of the IIIa group element and the gas of an organic compound or halogenide of the transition metal, are metered by gas flow meters 1a, 1b and 1c, respectively and supplied along with an inert gas to organometal compound bombes 2a, 2b and 2c, respectively, where they are heated by heating units 3a, 3b and 3c, respectively, before being supplied to and mixed in a tubular reactor 5 heated by a heating unit 8 Reference numeral 4 indicates a gas inlet pipe. A substrate 7 is held on a holder 9 at a position downstream of the reactor 5 and heated by a substrate heating unit 10. The reactor 5 is evacuated by an exhaust device 11, so that the gases of the organometal compounds are caused to flow in the form of a gas mixture from the bombes 2a, 2b and 2c towards the substrate 7. The oxygen-containing gas is metered in a flow meter 1d and supplied through a guide pipe 6 into the gas mixture in proximity to the upstream end of the substrate 7 so that a predetermined oxygen partial pressure is reached in the vicinity of the substrate 7. A thin film of a superconductor mainly composed of oxides of the alkali earth metals, IIIa group elements and the transition elements, evolved upon thermal decomposition from the respective organometallic gases, is formed on the substrate 7. An example of the reaction taking place with the use of Ln(C₅H₅)₃, Cu(acac)₂ and Ba(acac)₂ may be expressed by the formula 2Ln(C₅H₅)₃ + 4Ba(acac)₂ + 6Cu(acac)₂ + 102O₂→ 2LnBa₂Cu₃O₇ + 130CO₂ + 85H₂O where acac denotes acetylacetone. In the above reaction, an organic compound of Sr, for example, may be used in place of the organic compound of Ba. In this manner, a (Ln 1-x Sr x )CuO 4-y type superconducting thin film is produced. Examples The present invention will be explained with reference to certain illustrative Examples. Example 1 Using the device shown in Fig. 1, and also using an Ar gas as the carrier gas, SrTiO₃ as the substrate, a gas of dicyclopentadiene barium as a gas of the organometal compound of the alkali earth metal, a gas of tricyclopentadiene yttrium gas as a gas of the organometal compound of the group IIIa element and a gas of diacetylacetone copper as an organometal compound of the transition metal, these gases were mixed in various mixing ratios to produce gas mixtures. Then, using these gas mixtures as the feedstock gases, thin films were formed on the substrate at the oxygen partial pressure of 266 mbar (200 Torr) and the substrate temperature of 600°C. The relation between the thin film products and the mixing ratios of the feedstock gases is shown in Table 1, wherein each of the gas mixing ratios is expressed in terms of the concentration ratio of the various elements in each gas mixture. The products were identified by X-ray diffraction. In the above table, circle marks indicate superconductivity, brackets indicate that the products in the brackets exist in minor quantities and double brackets indicate that the products in the double brackets exist in trace quantities. Example 2 Using a device similar to that shown in Example 1, and also using a gas mixture of di(cyclopentadiene) barium, tri (cyclopentadiene)yttrium and diacetylacetone copper as the feedstock gas, the molar ratio of the elements Y, Ba and Cu in each gas mixture was set so that Y : Ba : Cu = 1 : 10 : 0.1 and the oxygen partial pressure was set so as to be equal to 266 mbar (200 Torr). The relation between the substrate temperature and the thin film products under these conditions are shown in Table 2. Example 3 Using a device similar to that shown in Example 1, and also using a gas mixture of di(cyclopentadiene) barium, tri (cyclopentadiene)yttrium and diacetylacetone copper as the feedstock gas, the molar ratio of the elements Y, Ba and Cu in each gas mixture was set so that Y : Ba : Cu = 1 : 10 : 0.1 and the substrate temperature was set so as to be equal to 700°C. The relation between the oxygen partial pressure and the film products is shown in Table 3. substrate temperature (C°) products superconductivity 300 CuO 400 CuO, Y₂O₃ 500 YBa₂Cu₃O₇, (CuO), (Y₂O₃) ○ 600 YBa₂Cu₃O₇, (Y₂O₃), (BaCO₃) ○ 700 YBa₂Cu₃O₇, ((Y₂O₃)), ((BaCO₃)) ○ 800 YBa₂Cu₃O₇, ((Y₂O₃)), ((BaCO₃)) ○ strength lowered oxygen partial pressure (mbar) products superconductivity 133 ( 10 Torr) (CuO), (Cu₂O) (YBa₂Cu₃O₇), (Y₂O₃) 66.50 ( 50 Torr) YBa₂Cu₃O₇ ○ 133 (100 Torr) YBa₂Cu₃O₇ ○ 266 (200 Torr) YBa₂Cu₃O₇, ((Y₂O₃)), ((BaCO₃)) ○ 400 (300 Torr) YBa₂Cu₃O₇, ((Y₂O₃)), (BaCO₃) ○ In the above tables, circle marks indicate superconductivity, brackets indicate that the products in the brackets exist in minor quantities and double brackets indicate that the products in the double brackets exist in trace quantities. The circle marks indicate superconductivity. Example 4 Using the device shown in Fig. 1 and also using an Ar gas as the carrier gas and SrTiO₃ as the substrate, the molar ratio of the elements Ln, Ba and Cu in the feedstock gas Ln : Ba : Cu was changed within the range of from 1 : 0.1 0.1 to 1 : 40 : 40, wherein the ratio is normalized with Ln being set to unity. The oxygen pressure and the substrate temperature were also changed in the range of from 0.13 to 400 mbar (0.1 to 300 Torr) and in the range of from 300 to 900°C, respectively. The temperature dependency of the electrical resistance of the so-prepared thin film is shown in Fig. 3. The electrical resistance started to be decreased abruptly in the vicinity of 30K and was reduced almost to zero at 18K. After formation of the film, the supply of the feedstock material was terminated and the film was heat-treated for several hours at the oxygen-containing gas of 1010.3 mbar (760 Torr) and the substrate temperature of 600°C to 800°C. As shown in Fig. 4, the resistance started to be decreased in the vicinity of 35K and was lowered to almost zero at 23K thus indicating an improvement in the critical temperature Tc. When an organic compound having its ligand substituted by a fluoride, such as La(trifluoroacetylacetone)₃, is employed, part of the oxygen of the oxide film is substituted by fluorine. In this manner, the critical temperature Tc of the film has been improved by about several K degrees. Example 5 Using the same device as that in Example 1 and also using La(C₅H₅)₃, Cu(C₅H₇O₂)₂ and Sr(C₅H₅)₂ as the organic compounds, thin films were formed under various operating conditions. The relation between the film products and the film forming conditions is shown in Table 4. It is seen from the above results that, for producing a superconductive film having a composition of La 1-x Sr x CuO 4 , the reaction is preferably conducted under a higher oxygen partial pressure and a higher substrate temperature for a smaller ratio of La : Sr : Cu and under a lower oxygen partial pressure and a higher substrate temperature for a larger ratio of La : Sr : Cu. For improving the critical temperature, the film may be doped with Ag. To this end, the low melting silver compound, such as Ag₂CO₃ having melting point of 218°C or Ag₂O having melting point of 100°C, is heated and vaporized for mixing Ag into the reaction gas and thereby adding Ag to the product. Upon measurement with an X-ray microanalyzer, it has been demonstrated that the silver Ag thus added to the thin film is uniformly distributed at the overall film surface. It may be seen from this that the present process guarantees an unpartialized and uniform distribution of impurities and represents a process for addition of impurities which is more favorable than the conventional process for preparing superconductive materials, such as the sputtering process or the solid phase reaction process. It is noted that the device shown in Fig. 1 is merely illustrative and the present invention may be practiced using any other device than that shown in Fig 1. INDUSTRIAL APPLICABILITY When a mixture of a gas of tan organic compound of an alkali earth metal, a gas of an organic compound of a group IIIa element and/or a halogenide thereof and a gas of an organic compound of a transition metal and/or a halogenide thereof is reacted under a prescribed condition with an oxygen-containing gas discharged in the vicinity of the substrate, a thin superconducting film is readily formed on the substrate in accordance with the MOCVD process.

Claims: A process for preparing a superconducting thin oxide film comprising the steps of mixing a gas of at least one organometal compound of an alkali earth metal, a gas of at least one organometal compound of a group IIIa element and/or a halogenide thereof, and a gas of at least one organometal compound of a transition metal and/or a halogenide thereof, with an inert gas, to form a gas mixture; mixing an oxygen-containing gas to said gas mixture to produce a gas mixture having a predetermined oxygen partial presssure not less than 67 mbar (50 Torr) and not higher than 400 mbar (300 Torr) ; and thermally decomposing said gas mixture having the predetermined oxygen partial pressure on a substrate to produce a thin film of a super conducting oxide on said substrate. The process according to Claim 1 wherein said transition metal is at least one metal selected from the group consisting of Cu, Ni and Ag. The process according to Claim 2 wherein an energy for activating a reaction is supplied during said thermal decomposition of said gas mixture having said predetermined oxygen partial pressure on the substrate. The process according to Claim 3 wherein the energy for activating a reaction is supplied by heating the substrate or by irradiating the substrate with light rays. The process according to Claim 4 wherein the molar ratio of the various metals in said gas of a group IIIa element: alkali earth metal: transition metal is equal to 1: 0.1 to 100 : 0.01 to 40, the oxygen partial pressure is not less than 67 mbar (50 Torr) and not higher than 400 mbar (300 Torr) and the substrate temperature is not less than 450°C and not higher than 950°C.

Inventors: TAKAHASHI M KAWASAKI STEEL COR, UMINO H KAWASAKI STEEL CORP TE, TAKAHASHI, M KAWASAKI STEEL CORP TECHRESEAR DIV, UMINO, H KAWASAKI STEEL CORP TECHNICAL RESEAR DIV
Applicants: KAWASAKI STEEL CO, KAWASAKI STEEL CORPORATION
Application year: 1988
Main classification: H01B13
IPC codes: H01L39, C23C16