Process for preparing superconducting thin film formed of oxide superconductor material

Abstract: A process for preparing an oxide superconductor thin film which has a high crystalline, clean and excellent superconductive surface on a substrate by MBE. The MBE is effected under a condition that the substrate is heated and an oxidizing gas is locally supplied to the proximity of the substrate so that the pressure of the proximity of the substrate becomes 6 x 10⁻⁶ to 8 x 10⁻⁵ Torr at a background pressure.

Description: Background of the Invention Field of the invention The present invention relates to a process for preparing superconducting thin films, and more specifically to an improved MBE (Molecular Beam Epitaxy) process particularly for preparing superconducting thin films formed of an oxide material, which has a clean surface, high crystallinity and excellent superconducting properties. Description of related art Oxide superconductors have been considered to have higher critical temperatures than those of metal superconductors, and therefore to have high possibility of practical use. For example, Y-Ba-Cu-O type oxide superconductor has a critical temperature higher than 80 K and it is reported that Bi-Sr-Ca-Cu-O type oxide superconductor and Tl-Ba-Ca-Cu-O type oxide superconductor have critical temperatures higher than 100 K. The oxide superconductor has a crystalline anisotropy in superconducting characteristics, and in particular, its critical current density is maximum in a direction perpendicular to the c -axis of crystal lattice. Therefore, when the oxide superconductor is used, attention should be paid to the crystalline orientation. When applying the oxide superconductor to superconducting electronics including superconducting devices and superconducting integrated circuits, the oxide superconductor has to be used in the form of a thin film. When the oxide superconductor is in the form of a thin film, the above mentioned crystalline anisotropy of superconducting characteristics becomes more remarkable. In addition, to realize high performance superconducting devices and superconducting integrated circuits, two kind of superconducting current paths through one of which superconducting current flows parallel to the substrate and through the other of which superconducting current flows perpendicular to the substrate are necessary. For example, superconducting current flows through a superconducting electrode in the direction parallel to the substrate, and flows through an interlayer superconducting current path in the direction perpendicular to the substrate. Therefore, when applying the oxide superconductor to superconducting devices and superconducting integrated circuits, a c -axis oriented oxide superconductor thin film of which critical current density is maximum in the direction parallel to the substrate and an a -axis oriented (or b -axis orientated, abbreviated " a -axis oriented" hereinafter) oxide superconductor thin film of which critical current density is maximum in the direction perpendicular to the substrate should be prepared. The orientation of the oxide superconductor thin film is determined by the film deposition temperature. The film deposition temperature generally means the temperature of the substrate while the oxide superconductor thin film is deposited. An a -axis oriented oxide superconductor thin film can be deposited at the substrate temperature of the order of 50 to 100 °C lower than that of c -axis oriented oxide superconductor thin film. In order to manufacture superconducting devices and superconducting integrated circuits of multi-layer structure, it is necessary that an a -axis oriented oxide superconductor thin film is stacked on a c -axis oriented oxide superconductor thin film. When the oxide superconductor thin films are stacked, a clean upper surface and high crystallinity are required of the lower oxide superconductor thin film. If the upper surface of the lower oxide superconductor thin film is not clean and contaminants are deposited or oxide is formed on it, the stacked thin films may become physically and electrically discontinuous or an unnecessary weak link of the Josephson junction may be formed at the interface. The discontinuity and weak link have adverse effect on the operations of the superconducting device and the superconducting integrated circuit so that their performance becomes below the determined values or do not operate at all. The coherence length of the oxide superconductor is very short, therefore, special attention should be given to the contamination of the upper surface of the lower thin film. In order to clean the surface of the oxide superconductor thin film, in the prior art, the oxide superconductor thin film is heated under a high vacuum so as to vaporize the contaminants. However, oxygen of the crystalline oxide superconductor is unstable and easily escapes when the oxide superconductor thin film is heated under a high vacuum. If some amount of oxygen escapes from the crystalline oxide superconductor, the critical temperature of the oxide superconductor is lowered or the oxide superconductor loses its superconductivity. Therefore, the oxide superconductor thin film which is used as a lower layer of a stacked multi-layer structure is required to have a clean outermost surface, high crystallinity and excellent superconducting characteristics. The present applicant's earlier patent applications EP-A-0 412 007 and EP-A-0 426 570 describe processes for preparing thin films of oxide superconducting material such as YBa 2 Cu 3 O 7-x on a substrate, using molecular beam epitaxy. In these processes, a jet of oxidizing gas was directed onto a substrate located in a chamber, while metallic ions were evaporated from K-cell evaporation sources also located in the chamber. In the processes described in EP-A-0 412 007, the oxidizing gas was a mixed gas including oxygen. In the processes described in EP-A-0 426 570, the oxidizing gas was oxygen. In certain examples described in these documents, the reaction chamber was evacuated to a pressure of 6.66 x 10 -4 Pa (5 x 10 -6 Torr). In one example described in EP-A-0 412 007, the reaction chamber was evacuated to a pressure of 1.066 x 10 -3 Pa (8 x 10 -6 Torr) during a process for formation of a thin film of Bi 2 Sr 2 Ca 2 Cu 3 O 7-x . SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a process for preparing an oxide superconductor thin film which has a clean upper surface, high crystallinity and excellent superconducting characteristics, which has overcome the above mentioned defects of the conventional ones. The above and other objects of the present invention are achieved in accordance with the present invention by a process for preparing a thin film formed of an oxide superconductor on a substrate by MBE characterized in that said MBE is conducted using an MBE apparatus comprising a first sub-chamber in which a plurality of evaporation sources are positioned and a second sub-chamber in which said substrate is positioned, said first and second sub-chambers being separated by a partition wall having an opening, wherein said substrate is heated and an oxidizing gas is locally supplied to the proximity of said substrate so that the pressure of said second sub-chamber becomes 7.998 x 10 -4 to 1.0664 x 10 -2 Pa (6 x 10 -6 to 8 x 10 -5 Torr) while the pressure of said first sub-chamber is maintained lower than 1.333 x 10 -7 Pa (1 x 10 -9 Torr). In the process in accordance with the present invention, the MBE is effected at a background pressure lower than 1.333 x 10 -7 Pa (1 x 10 -9 Torr). This quite low background pressure means that there is no leak nor any gas generation in the vacuum chamber of the MBE apparatus. Therefore, no contaminant, for example hydrocarbons and metal carbides, is deposited on the oxide superconductor prepared by the process in accordance with the present invention. In a preferred embodiment, the oxidizing gas is selected from the group consisting of O 2 including 5 to 70 volume percent O 3 , N 2 O and NO 2 . These gases have higher oxidizing power than pure O 2 and it is favorable for preparing an oxide superconductor thin film by the MBE. According to one preferable embodiment of the present invention, the substrate is cooled down to room temperature after the oxide superconductor thin film was deposited, in the atmosphere in which the oxide superconductor thin film was deposited. While the substrate is cooled down, the oxide superconductor crystal system of the thin film is transformed from a tetragonal system to an orthorhombic system. At this stage, the oxide superconductor thin film should be in the oxidizing atmosphere, in order to get excellent superconducting characteristics. In one preferred embodiment, the MBE is effected while the oxidizing gas is struck onto a deposition surface of the substrate. By this, the pressure of the oxidizing gas on the deposition surface of the substrate was further elevated. In a preferred embodiment, the oxide superconductor is formed of a high-T c (high critical temperature) oxide superconductor, particularly, formed of a high-T c copper-oxide type compound oxide superconductor for example a Y-Ba-Cu-O type compound oxide superconductor material, a Bi-Sr-Ca-Cu-O type compound oxide superconductor material, and a Tl-Ba-Ca-Cu-O type compound oxide superconductor material. In the case of Y 1 Ba 2 Cu 3 O 7-δ oxide superconductor, the MBE is preferably effected at a substrate temperature of 650 to 730 °C by using metal yttrium, metal barium and metal copper as evaporation sources. It is more preferable that the MBE is effected at a substrate temperature of 700 °C. If the substrate temperature is lower than 650 °C, the obtained Y 1 Ba 2 Cu 3 O 7-δ oxide superconductor thin film is constituted of polycrystals which includes c -axis orientated crystals and a -axis orientated crystals. On the contrary, if the substrate temperature exceeds 730 °C, metal copper molecules are not oxidized so that the Y 1 Ba 2 Cu 3 O 7-δ oxide superconductor can not obtained. The above evaporation sources are preferably set to K cells. It is preferable that the temperature of the K cell of the metal yttrium is 1150 to 1350 °C, more preferably 1220 °C, the temperature of the K cell of the metal barium is 570 to 640 °C, more preferably 620 °C, and the temperature of the K cell of the metal copper is 950 to 1090 °C, more preferably 1000 °C. The temperatures of the K cells are determined by the geometric arrangement of the MBE apparatus and the material which constitutes the crucibles. In addition, the substrate can be formed from an insulating substrate, preferably an oxide single crystalline substrate such as MgO, SrTiO 3 , CdNdAlO 4 , etc. These substrate materials are very effective in forming or growing a crystalline film having a high degree of crystallinity. The above and other objects, features and advantages of the present invention will be apparent from the following description of preferred embodiments of the invention with reference to the accompanying drawings. Brief Description of the Drawings Figure 1 is a diagrammatic sectional view of a film deposition apparatus which can be used for carrying out the process in accordance with the present invention; Figure 2 is a LEED (Low Energy Electron Diffraction) image of an oxide superconductor thin film prepared by the process in accordance with the present invention; Figures 3 and 4 are XPS (X-ray Photoelectron Spectroscopy) spectra of an oxide superconductor thin film prepared by the process in accordance with the present invention. Description of the Preferred embodiments Referring to Figure 1 there is shown a diagrammatic sectional view of a film deposition apparatus which can be used for carrying out the process in accordance with the present invention. The film deposition apparatus shown basically includes a vacuum chamber 2 provided with a main evacuating apparatus 1, at least one K (Knudsen's) cell and at least one electron beam gun 11 provided at the bottom of the vacuum chamber 2, and a sample holder 5 provided at the top of the vacuum chamber 2 for holding a substrate 4 on which a film is to be deposited. The sample holder 5 is associated with a heater 5a for heating the substrate. In addition, the vacuum chamber 2 is also provided with a port 10 for exchanging a sample, a liquid nitrogen shroud 6 for forming a cold trap around an evaporation source of the K cell, and a RHEED (Reflecting High Energy Electron Diffraction) device 8 for observing the thin film roughness during the deposition. In front of the substrate held by the sample holder, a shutter 9 is located for controlling a deposition time during the deposition process. The K cell 3 and the electron beam gun 11 are provided with an openable shutter 19. In addition, a gas supplying apparatus 7 is provided so as to introduce an oxidizing gas such as O 2 , O 3 , NO 2 , N 2 O, etc. in the proximity of the substrate 4 held by the sample holder 5, so that the oxidizing gas can be supplied to form an oxygen-enriched atmosphere in the proximity of the substrate 4 in order to oxidize the metal molecular beams incoming from the evaporation source in the course of the film deposition. Furthermore, the film deposition apparatus additionally includes a partition wall 21 for dividing the vacuum chamber 2 into a first sub-chamber 2A which is constituted of a lower portion of the vacuum chamber defined below the partition wall 21 and which is coupled to the K cell 3, the electron beam gun 11 and the main evacuating apparatus 1, and a second sub-chamber 2B which is constituted of an upper portion of the vacuum chamber defined above the partition wall 21 and in which sample holder 5 is located. The partition wall 21 includes a through opening 23 formed at a center thereof. The position of the opening 23 is determined to ensure that a beam emitted from K cell 3 and the electron beam gun 11 toward the substrate 4 is not obstructed by the partition wall 21. In addition, the size of the opening 23 is determined to enable restricted molecular flows between the first sub-chamber 2A and the second sub-chamber 2B so that a pressure difference can be created between the first sub-chamber 2A and the second sub-chamber 2B when the opening 23 is open. Therefore, the partition wall 21 having the through opening 23 constitutes a vacuum impedance. A gate valve 22 is provided on the partition wall 21 for hermetically closing the opening 23 of the partition wall 21, so as to completely shut off the molecular flows between the first sub-chamber 2A and the second sub-chamber 2B when the gate valve 22 is closed. The opening and closing of this gate valve 22 is controlled from the outside of the film deposition apparatus by means which are not shown. In addition , an auxiliary evacuating apparatus 20 is coupled to the second sub-chamber 2B for evacuating the second sub-chamber 2B to an ultra-high vacuum when the gate valve 22 is closed. The auxiliary evacuating apparatus 20 is constituted of a cryopump. On the other hand, the main evacuating apparatus 1 is constituted of a diffusion pump. Example A thin film of Y 1 Ba 2 Cu 3 O 7-δ oxide superconductor was prepared by using the-apparatus of Figure 1. First, an MgO (100) substrate 4 was set in the sample holder 5, and metal yttrium, metal barium and metal copper were set in three K cells 3 as evaporation sources. Thereafter, the chamber 2 was closed and the gate valve 22 was opened. The vacuum chamber 2 was evacuated by the main evacuating apparatus 1 and the auxiliary evacuating apparatus 20 to an ultra-high vacuum of which the pressure was lower than 1.333 x 10 -7 Pa (1 x 10 -9 Torr) in which background pressure the film deposition by the MBE process was available. Succeedingly, O 2 gas including 8 volume percent O 3 was supplied from the gas supplying device 7 so that the pressure in the second chamber 2B became 6.665 x 10 -3 Pa (5 x 10 -5 Torr). As mentioned above, the vacuum chamber 2 was provided with the vacuum impedance (the partition wall 21 having the through opening 23), a pressure difference of about one digit or more was created between the first sub-chamber 2A and the second sub-chamber 2B. In addition, the oxidizing gas jetted from the gas supplying device 7 was struck onto a deposition surface of the substrate, the pressure of the oxidizing gas on the deposition surface of the substrate was further elevated. Then, the substrate 4 was heated by the heater 5a to a temperature of 700 °C. The K cell 3 of metal yttrium was heated to a temperature of 1220 °C, the K cell 3 of metal barium was heated to a temperature of 620 °C and the K cell 3 of metal copper was heated to a temperature of 1000 °C. When molecular beams had become stably generated from the evaporation sources, the shutters 9 and 19 were opened so as to start deposition of the oxide superconductor thin film onto the substrate 4. At this time, a surface roughness of this deposited film was observed by the RHEED device. The oxide superconductor thin film was grown up to a thickness of 90 nanometers at a deposition rate of 1 nanometer/minute. The deposition rate is preferably 0.5 to 2 nanometers/minute. When the oxide superconductor thin film has reached a thickness of 90 nanometers, the substrate 4 was cooled down to the room temperature. While the substrate 4 was cooled down, it was maintained in the condition in which the oxide superconductor thin film was deposited. After the oxide superconductor thin film was obtained, crystal structure and surface condition of the oxide superconductor thin film was evaluated by LEED and XPS without exposing the oxide superconductor thin film to the air. It became clear that the oxide superconductor thin film was a c -axis orientated Y 1 Ba 2 Cu 3 O 7-δ oxide superconductor thin film. The results are shown in Figures 2 to 4. Figure 2 shows a LEED image of the oxide superconductor thin film prepared by the above process in accordance with the present invention. In Figure 2, some spots are observed. This reveals the fact that the oxide superconductor thin film has a crystalline surface. Figures 3 and 4 show XPS spectra of the oxide superconductor thin film prepared by the above process in accordance with the present invention. Figure 3 shows XPS spectra in a range in which 3p peak of yttrium and a peak of C can be observed. In Figure 3, no peak of C can be observed. Therefore, there is no composition of C which is a contaminant on the surface of the oxide superconductor thin film prepared by the above process in accordance with the present invention and the surface is clean. Figure 4 shows XPS spectra in a range in which peaks of Cu can be observed. In Figure 4, intensive satellite peaks of Cu can be observed. This reveals the fact that the surface of the oxide superconductor thin film prepared by the above process in accordance with the present invention has excellent superconductivity. As explained above, an oxide superconductor thin film which has an excellent surface condition can be obtained without any post-deposition treatment by the process in accordance with the present invention. The oxide superconductor thin film prepared by the process in accordance with the present invention has a high crystalline, clean and excellent superconductive surface. Therefore, the oxide superconductor thin film is suitable for a lower layer of stacked films. The invention has thus been shown and described with reference to the specific embodiments. However, it should be noted that the present invention is in no way limited to the details of the illustrated structures but converts and modifications may be made within the scope of the appended claims.

Claims: A process for preparing a thin film formed of an oxide superconductor on a substrate by MBE, characterized in that said MBE is conducted using an MBE apparatus comprising a first sub-chamber (2A) in which a plurality of evaporation sources are positioned and a second sub-chamber (2B) in which said substrate is positioned, said first and second sub-chambers being separated by a partition wall (21) having an opening (23), wherein said substrate is heated and an oxidizing gas is locally supplied to the proximity of said substrate so that the pressure of said second sub-chamber (2B) becomes 7.998 x 10 -4 to 1.0664 x 10 -2 Pa (6 x 10 -6 to 8 x 10 -5 Torr) while the pressure of said first sub-chamber (2A) is maintained lower than 1.333 x 10 -7 Pa (1 x 10 -9 Torr). A process as claimed in claim 1, characterized in that said oxidizing gas is selected from the group consisting of O 2 including 5 to 70 volume percent O 3 , N 2 O and NO 2 . A process as claimed in claim 1 or 2, characterized in that said substrate is cooled down to room temperature after the oxide superconductor thin film has been deposited, in the atmosphere in which the oxide superconductor thin film was deposited. A process as claimed in any one of claims 1 to 3, characterized in that the MBE is conducted while the oxidizing gas is struck onto a deposition surface of said substrate so as to raise the pressure at the deposition surface of said substrate. A process as claimed in any one of claims 1 to 4, characterized in that said superconductor is Y 1 Ba 2 Cu 3 O 7-δ oxide superconductor. A process as claimed in claim 5, characterized in that said MBE is conducted at a substrate temperature 650 to 730 °C. A process as claimed in claim 6, characterized in that said MBE is conducted at a substrate temperature 700 °C. A process as claimed in any one of claims 5 to 7, characterized in that said MBE is conducted using metal yttrium, metal barium and metal copper as evaporation sources. A process as claimed in claim 8, characterized in that the metal yttrium, the metal barium and the metal copper are set to K cells. A process as claimed in claim 9, characterized in that said MBE is conducted at a temperature of the K cell of the metal yttrium of 1150 to 1350 °C, at a temperature of the K cell of the metal barium of 570 to 640 °C and at a temperature of the K cell of the metal copper of 950 to 1090 °C. A process as claimed in claim 10, characterized in that said MBE is conducted at a temperature of the K cell of the metal yttrium of 1220 °C, at a temperature of the K cell of the metal barium of 620 °C and at a temperature of the K cell of the metal copper of 1000 °C.

Inventors: NAKAMURA TAKAO, NAKAMURA, TAKAO, Nakamura, Takao, c/o Osaka Works of Sumitomo
Applicants: SUMITOMO ELECTRIC INDUSTRIES, SUMITOMO ELECTRIC INDUSTRIES, LTD.
Application year: 1993
Main classification: C04B35
IPC codes: C30B23, H01L39, C23C14