Bi-Sr-Ca-Cu-O system superconducting thin film and method of forming the same

Abstract: A method of forming a Bi-Sr-Ca-Cu-O system (Bi₂Sr₂CaCu₂O x ) superconducting thin film in which two half-unit cells constitute a Perovskite structure layer, characterized in that Sr and Bi, which are present between said half-unit cells, are each deposited without oxidation by using an MBE process or MO-MBE process with an atomic layer controlling level ability. A critical current density of the Bi-Sr-Ca-Cu-O system superconducting thin film is not significantly reduced.

Description: The present invention relates to an oxide high-temperature superconductor, and more particularly, to a Bi-Sr-Ca-Cu-O system superconducting thin film and a method of forming the same. Attempts have been made to apply superconductors to devices or wirings by using superconduction properties (e.g., zero electric-conductivity). However, since a critical temperature (Tc) of the superconductors is very low, they can be used only in liquid helium (He). Recently developed oxide superconductors have a relatively high Tc, so that they can be used in liquid nitrogen (N). Furthermore, an oxide high-temperature superconducting film can be formed by depositing oxide on a substrate under an atomic layer control, and such a film formation is attempted and studied (cf., Tomoji KAWAI: "Design and Synthesis of High Tc Superconducting Superlattice by Successive Deposition Method", Bulletin of the Japan Institute of Metals, Vol. 29, N0. 9 (1990), pp. 733-739, and J. N. Eckstein et al., "Epitaxial growth of high-temperature superconducting thin films", J. Vac. Sci. Technol. B7 (2), 1989, pp. 319-323). In contrast to metal superconductors, the oxide high-temperature superconductors have a problem that its coherent length (ξc) in the C-axis direction is remarkably short. For example, it is presumed that the coherent lengths of a Y-Ba-C-O system oxide and a Bi-Sr-Ca-Cu-O system oxide are about 0.3 nm and 0.1 - 0.2 nm, respectively, and thus these coherent lengths are very small compared with coherent lengths of the metal superconductors (e.g., 100 nm of Pb and 40 nm of Nb). Therefore, when a magnetic field is applied on the oxide superconductor in the C-axis direction, the critical temperature Tc is remarkable lowered. In Bi system oxide superconducting films (e.g., Bi₂Sr₂Ca n-1 CU n O x ), BiO layers partitioning Perovskite structure layer serve as an electron-shielding (blocking) layer, and electrons of CuO₂ layers certainly functioning as superconductivity can scarcely pass through the BiO layer, whereby the coherent length (ξc) of Bi-Sr-Ca-Cu-O system oxide shortens. If the number (m) of CuO₂ layers in a half-unit cell of the Perovskite structure layer is increased, the coherent length can elongate. However, when the number (m) of the CuO₂ layers is 4 or more, the critical temperature falls, and at m = 5 it becomes 10 K or less (namely, such an oxide superconducting film necessitates a helium cooling). An object of the present invention is to provide a Bi-Sr-Ca-Cu-O system oxide superconducting thin film of which a critical current does not lower under an increasing magnetic field without decreasing the critical temperature. Another object of the present invention is to provide a method of forming the above-mentioned Bi-Sr-Ca-Cu-O system oxide superconducting thin film. The above-mentioned and other objects of the present invention are attained by providing a Bi-Sr-Ca-Cu-O system superconducting thin film in which two half-unit cells constitute a Perovskite structure layer, characterized in that a substantially metallic Sr atomic layer and two substantially metallic Bi atomic layers lie between CuO atomic layers of said half-unit cells. According to the present invention, a method of forming the above-mentioned Bi-Sr-Ca-Cu-O system superconducting thin film is characterized in that Sr and Bi, which are present between the half-unit cells, are each deposited without oxidation by using a molecular-beam epitaxy (MBE) or a metal organic molecular-beam epitaxy (MO-MBE) process with an atomic layer controlling level ability. When the Bi-Sr-Ca-Cu-O system superconducting thin film is formed on a substrate under atomic layer control conditions, Sr and Bi, which are present between the half-unit cells, are each deposited as they are without oxidation, so that Bi is not substantially oxidized (i.e., Bi is slightly oxidized to form BiO 1-x , wherein x is 0.1 to 0.3). Such a substantially metallic Bi atomic layer (the BiO 1-x ) has a smaller electron-shielding ability. Therefore, electrons of the CuO₂ layers can easily flow through the Bi (BiO 1-x ) layer, which will certainly make the coherent length of the oxide superconducting thin film longer. As a result, a critical electric current density of the obtained thin film does not substantially deteriorate (decrease) within a magnetic field. Preferably, a single Sr atomic layer and two Bi atomic layers are formed between CuO atomic layers of the half-unit cells. Preferably, a superconducting thin film of the Bi₂Sr₂CaCu₂O x (2-2-1-2) system is provided. For a better understanding of the invention, and to show how the same may be carried into effect, reference will now be made, by way of example, to the accompanying drawings, in which:- Fig. 1 is a schematic view of a conventional MBE apparatus; Fig. 2 is a schematic sectional view of a Bi-Sr-Ca-Cu-O system superconducting thin film formed on a substrate under an atomic layer control condition in accordance with a method of the present invention; and Fig. 3 is a graph showing a relationship between a critical current density of Bi-Sr-Ca-Cu-O system superconducting thin films and a magnetic field intensity. Referring to Fig. 1, a conventional MBE apparatus comprises a vacuum (growth) chamber 1, a substrate holder 2 with a heater, Knudsen cells 4 to 7 for Bi, Sr, Ca and Cu, respectively, and an electron cyclotron resonance (ECR) device 8 for generating oxygen plasma. The MBE apparatus is provided with a quadrupole mass spectrometer (QMS) 9, a reflection high-energy electron diffraction (RHEED) screen 10, an electron gun 11 for RHEED and a thickness monitor 12 of a quartz oscillator. A substrate (of MgO or SrTiO₃) 3 is set on the holder 2. A Bi-Sr-Ca-Cu-O system superconducting thin film is formed (deposited) on the substrate 3 as follows. The vacuum chamber 1 is evacuated to attain a vacuum pressure (oxygen partial pressure) of 2.66 X 10⁻³ to 1.06 X 10⁻² Pa (2 X 10⁻⁵ to 8 X 10⁻⁵ Torr), and the substrate (MgO single crystalline plate) 3 is heated at a temperature of 600 to 800°C. As shown in Fig. 2, two BiO atomic layers are deposited on the substrate 3 by allowing a bismuth beam from the cell 4 to impinge on the substrate 3 and simultaneously by feeding an oxygen plasma beam from the ECR device 8 to the substrate 3. Maintaining the oxygen plasma beam, a strontium beam from the cell 5, a copper beam from the cell 7, a calcium beam from the cell 6, and the copper beam from the cell 7 are in sequence fed deposit a SrO atomic layer, a CuO atomic layer, a CaO atomic layer and a CuO atomic layer on the substrate 3. Thus, a half-unit cell of Bi₂Sr₂CaCu₂O x (2-2-1-2) is formed. In this case, the Bi Knudsen cell 4, Sr Knudsen cell 5, Ca Knudsen cell 6 and Cu Knudsen cell 7 are heated at 700°C, 740°C, 550°C and 1080°C, respectively. The ECR device 8 has a microwave power of 100 W and an accelerated voltage of 0.5 kV, and a substrate bias voltage is 0.5 kV. Next, an operation of the ECR device 8 and the feeding of oxygen are stopped. A Sr atomic layer and two Bi atomic layers are deposited without oxidation in sequence on the CuO atomic layer by bombarding of the Sr and Bi beams, as shown in Fig. 2. Thereafter, the ECR device 8 reoperates to generate an oxygen plasma beam, and a copper beam from the cell 7, a calcium beam from the cell 6, a copper beam from the cell 7, a strontium beam from the cell 5, and the bismuth beam from the cell 4 are in sequence fed to deposit a CuO atomic layer, a CaO atomic layer and a CuO atomic layer, a SrO atomic layer, and two BiO atomic layers, as shown in Fig. 2. Thus, another half-unit cell of Bi₂Sr₂CaCu₂O x is formed resulting in the formation of one unit Perovskite structure layer of Bi₂Sr₂CaCu₂O x (2-2-1-2). Such a successive deposition process is repeated to form a multilayer thin film of Bi₂Sr₂CaCu₂O x . The obtained Bi-Sr-Ca-Cu-O system superconducting thin film is cooled at 77 K by using liquid nitrogen, and a critical current density (Jc, A/cm²) of the film is measured by varying a magnetic field intensity B (T) to obtain results indicated with a solid line in Fig. 3. As a comparative example, a conventional type Bi-Sr-Ca-Cu-O system superconducting thin film is formed in accordance with the above-mentioned successive deposition process, except that the interruption of the ECR device operation and oxygen feeding is not performed. In this case, elements of all the molecular beams are oxidized with the oxygen plasma to deposit oxide layers only. A critical current density (Jc) of the thin film is measured under the same conditions to obtain results indicated with a broken line in Fig. 3. As it is clear from Fig. 3, the Bi-Sr-Ca-Cu-O system superconducting thin film according to the present invention has a superior critical current property that is substantially uneffected by a magnetic field compared with the conventional type Bi-Sr-Ca-Cu-O system superconducting thin film. According to the present invention, the Bi and Sr between the half-unit cells are deposited without oxidation to form the Bi (BiO 1-x ) atomic layer which takes the place of a conventional BiO atomic layer and has a smaller electron-shielding ability to elongate the coherent length (ξc). Therefore, although the critical current density of a conventional Bi-Sr-Ca-Cu-O system superconducting thin film is significantly reduced while increasing the magnetic field intensity, that of the Bi-Sr-Ca-Cu-O system superconducting thin film of the present invention is not significantly reduced. It will be obvious that the present invention is not restricted to the above-mentioned embodiments and that many variations are possible for persons skilled in the art without departing from the scope of the invention.

Claims: A Bi-Sr-Ca-Cu-O system superconducting thin film in which two half-unit cells constitute a Perovskite structure layer, characterized in that a substantially metallic Sr atomic layer and two substantially metallic Bi atomic layers lie between CuO atomic layers of said half-unit cells. A superconducting thin film according to claim 1, wherein said superconducting thin film is of Bi₂Sr₂CaCu₂O x (2-2-1-2). A method of forming a Bi-Sr-Ca-Cu-O system superconducting thin film according to claim 1 in which two half-unit cells constitute a Perovskite structure layer, characterized in that Sr and Bi, which are present between said half-unit cells, are each deposited without oxidation by using a molecular-beam expitaxy (MBE) or a metal-organic molecular-beam epitaxy (MO-MBE) process with an atomic layer controlling level ability. A method according to claim 3, wherein a single Sr atomic layer and two Bi atomic layer are formed between CuO atomic layers of said half-unit cells.

Inventors: OTANI SEIGEN C O FUJITSU LIMIT, OTANI, SEIGEN, C/O FUJITSU LIMITED
Applicants: FUJITSU LTD, FUJITSU LIMITED
Application year: 1992
Main classification: C30B23
IPC codes: C01B13, H01B13, H01L39, C30B25, C01G1, C01G29, C30B23, H01B12