Bi oxide superconductors

Abstract: A substance which has a Cu-O plane containing crystal structure in its unit cell and which is called a Bi oxide superconductor consisting essentially of Bi, Sr, Ca, Cu, and O. Not only part of Bi but also part of Sr and/or Ca of the Bi oxide superconductor is substituted for Pb and rare earth elements (RE), respectively. The Pb substitution relaxes the structural modulation which is closely related to superconductivity of the Bi oxide superconductor and the RE substitution controls its carrier concentration. Accordingly, superconducting properties such as transition temperature and critical current density can be improved remarkably. In addition, not only oxide superconductors with excellent superconductivity can be prepared in a low oxygen content but also the surface condition of the prepared superconductors is stable.

Description: This invention relates to Bi oxide superconductors. Oxide superconductors have recently been considered a potential as a high transition temperature (Tc) superconductor. Among them, a so-called Bi oxide superconductor consisting essentially of Bi-(Sr,Ca)-Cu-O exhibits an extremely high Tc with comparatively good stability to external environment such as moisture. In addition, its untoxic property incontradistinction with Tl oxide superconductors is an advantage that makes its industrial applicability still higher. It is known that the Bi oxide superconductor comes in three types depending on the length of the c-axis: 24 Å phase (Tc = about 8K); 30 Å phase (Tc = about 80K); and 36 Å phase (Tc = about 110K). These three types of Bi oxide superconductors are known to have one, two, and three planes, each plane consisting of copper and oxygen ions (Cu-O plane) per unit cell, respectively. Tl oxide superconductors represented by a formula: Tl m Ba₂Ca n-1 Cu n O y (where m is 1 or 2; n is the number of Cu-O planes per unit cell which is 1, 2, or 3), has a crystal structure substantially identical to that of the above Bi oxide superconductors, and are reported to have a Tc of about 20K with n = 1. Also, a Tc of about 90K with n = 2 and a Tc of about 120K with n = 3 have been reported. As revealed by these examples, it has been said that the number of Cu-O planes per unit cell intimately correlates with the Tc in the oxide superconductors and that the larger the number is, the higher the Tc becomes. However, the latest research reports that the above correlation is not always strictly applied and that higher Tcs could be obtained with smaller number of Cu-O planes by changing the carrier concentration in the superconductive material. For example, it is known that TlBa₂CuO₆, one of the Tl oxide superconductors, which has only one Cu-O plane per unit cell, exhibits a variation in Tc from 0 to 90K depending on the oxygen content. A similar phenomenon has been observed in the Bi oxide superconductors. It has been reported that Bi₂Sr₂CuO₆ (24 Å phase) exhibits an improvement of the Tc from 8 to about 20K by controlling the carrier concentration while substituting part of Sr for a rare earth element such as Nd. However, the maximum Tc thus obtained, being quite low compared to that of the TlBa₂CuO₆ superconductor, must be improved. It has also been revealed that the Tc value can be improved on Bi oxide superconductors of 30 Å phase represented by Bi₂(Sr,Ca)Cu₂O₈ by controlling the carrier concentration through substitution of part of Sr and/or Ca for rare earth elements. However, since the rate of Tc improvement is small in this system, further efforts in increasing the Tc are strongly called for. Generally, oxide superconductors of simpler structure can be formed more easily. To obtain a superconductor in the form of thin films by such method as a sputtering method, a simple crystal structure, particularly simple in the c-axis direction in case of Bi oxide superconductors, allows easier formation. From the viewpoint of reproducibility, the best Bi oxide superconductors is of Bi₂Sr₂CuO₆ system whose lattice constant in the c-axis direction is smallest, followed by Bi oxide superconductors of Bi₂(Sr,Ca)₃Cu₂O₈ system. Thus, high quality, high Tc Bi oxide superconductive thin films will be prepared with satisfactory reproducibility only if the Tc of Bi₂Sr₂CuO₆ and Bi₂(Sr,Ca)₃Cu₂O₈ are improved. From this standpoint, further improvements in Tc superconductivity of the Bi superconductors are strongly demanded. By the way, to obtain a long conductor using the above described Bi oxide superconductors, attempts have been made to prepare a desired wire or tape by using a superconductive powder to fill, e.g., a metal coated tube, drawing it to a predetermined diameter and shape, and then subjecting it to a thermal treatment in an oxygen containing atmosphere. Since a material for the metal coated tube must have not only good conductivity but also high oxygen content during the preparation and thermal treatment of the Bi oxide superconductor, excellent oxygen permeability is also required. In addition, the thermal treatment at high temperatures require that the material be stabile with respect to the Bi oxide superconductor. From the above points, noble metals such as silver are often used as materials for the metal coated tube. However, the noble metals are not only expensive but also of poor mechanical properties in forming, e.g., a superconductive magnet. Copper and copper alloys which are inexpensive and have satisfactory mechanical properties are, on the other hand, susceptible to oxidation during thermal treatment in an oxygen containing atmosphere. The insufficient oxygen supply to the oxide superconductor in addition to their oxidation prevents copper and copper alloys from serving as materials suitable for obtaining the desired superconductivity. To this end, there is a strong demand for development of the Bi oxide superconductors that exhibit excellent superconducting properties even at a sufficiently low oxygen content in a thermal treatment to reduce deterioration of the metal coated tube materials such as copper and copper alloys. Such a demand also applies not only to the preparation of superconductive wires and tapes but also to the preparation of superconductive elements by laminating an oxide superconductive thin film and a metal thin film one upon the other. A superconductive compound comprising Pb 2+x , Bi x2 , Sr 2+x3 , Tr 1-y Ca y Cu₃O 8+δ where x₁+x₂+x₃ = 0, -1 ≤ x₁ ≤ 1 0 < x₂ ≤ 1, -1 ≤ x₃ ≤ 1, 0 < y ≤ 1, 0 ≤ δ ≤ 0.25 and Tr is a rare earth element is disclosed in W0-A-90/08740. A superconductive compound comprising Bi, Pb, Ca, Sr, Y, Cu and 0 is described in Physica C, vol. 165, No. 1, pages 55-61. A superconductive compound comprising Br₂ (Sr 1-x Ln x )₂ Cu 1+n 0y where Ln is a rare earth element is known from Japanese Journal of Applied Physics, Vol. 27, No. 9, pages L1620-L1622. It is therefore an object of the invention to provide a Bi oxide superconductor whose Tc is further improved by increasing the Tc improvement rate while controlling the carrier concentration of the Bi oxide superconductor. Another object of the invention is to provide a Bi oxide superconductor that exhibits excellent superconductivity even after a thermal treatment carried out in an atmosphere having a sufficiently low oxygen content. The Bi oxide superconductor of the invention comprises: a composition of Bi, Pb, Sr, RE, and Cu in an atomic ratio of 2-x : x : a-s : s : b, wherein RE is at least one element selected from the group consisting of Nd, Pr, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu and Y, a is 1.8 or more and 2.2 or less, b is 0.8 or more and 1.2 or less, s is 0.01 or more and 0.3 or less, x is 0.2 or more and 1 or less, and x > s. That is, the Bi oxide superconductor according to the invention is an improvement in superconducting properties such as Tc by not only controlling the carrier concentration through substitution of parts of Sr and/or Ca in its 24 Å phase, 30 Å phase, or 36 Å phase for RE elements, but also relaxing the structural modulation having an intimate correlation with its Tc through substitution of part of Bi for Pb. The crystal structure of the Bi oxide superconductor has a peculiar structural modulation that has an intimate correlation with its Tc. Thus, the Bi oxide superconductor of the invention has its carrier concentration controlled by substituting part of Sr and/or Ca for RE and has its structural modulation relaxed by substituting part of Bi for Pb. Accordingly, the rate of Tc improvement which has been kept low presumably due to structural modulation can be increased, thereby leading to significant Tc improvements. Substitution of alkali earth elements for rare earth elements contributes not only to increasing Tc but also to providing a small dispersion of a normal conductive phase in the superconductor. This has been verified by the fact that the volume fraction of a diamagnetic susceptibility of the superconductor is slightly decreased during such substitution. The dispersed normal conductor phase serves as a pinning site which pins an incident quantum magnetic flux under a high magnetic field, thereby allowing the critical current density to be also improved. The Bi oxide superconductor according to the invention has an advantage of being prepared at a low oxygen content or in the atmosphere of an inert gas such as pure argon. That is, no active oxygen ions need to be supplied when obtaining the Bi oxide superconductor, even in thin film form or for device fabrication. It is assumed that this is because substitution for Pb and RE element or elements contributes to eliminating superfluous oxygen in a BiO layer that is unstable (weak affinity) in the Bi oxide superconductor and because oxygen in the remaining site has a strong affinity. Therefore, such metal materials as copper and copper alloys that have conventionally been considered unusable due to oxidation or insufficient supply of oxygen to the oxide superconductor during the thermal treatment in the oxygen atmosphere may be used as a coated tube material. The use of these materials even opens the way to obtaining excellent superconducting properties through thermal treatments in an inert gas atmosphere or vacuum. For the same reason, the oxygen contained in the Bi oxide superconductor that has been prepared is stable, and thus no insulator layer such as AgO will be formed on the interface even when an Ag film is deposited thereon as an electrode. This means that the composition of the superconductor adjacent to its surface is uniform up to the interface, thereby advantageously contributing not only to eliminating interface resistance of the electrode but also to forming proximity-effect-based elements. The following Bi oxide superconductor is in accordance with the invention. An oxide superconductor having a composition substantially containing Bi, Pb, Sr, RE, and Cu in an atomic ratio of 2-x : x : a-s : s : b (where 1.8 ≦ a ≦ 2.2; 0.8 ≦ b ≦ 1.2; 0.01 ≦ s ≦ 0.3; and 0.2 ≦ x ≦ 1; with x>s) and a crystal structure of at least one Cu-O plane per unit cell. A more specific exemplary composition of the above oxide superconductor is represented by the following chemical formula (I). Bi 2-x Pb x Sr 2-s RE s CuO₆ ... ... (I) The numeral of oxygen in the above formula (I) is not necessarily the stoichiometric ratio and may be more or less than the ratio by small amount. The preferred numeral of oxygen is between the ratio + 0.2 and the ratio - 0.2. Here the reason why the amount of Bi/Pb substitution is limited to a range from about 0.2 to about 1 for each chemical formula is as follows. The amount x of substitution for Pb below 0.2 does not provide sufficient relaxation of the structural modulation, while x being in excess of 1 makes it difficult to prepare a single phase Bi oxide superconductor. Thus, the preferred amount of Bi/Pb substitution, or x, is between 0.2 and 0.6. The reason for limiting the amount of substitution of Sr and/or Ca for RE to a range from about 0.01 to about 0.3 in (1), from about 0.01 to about 0.3 in (2), and from about 0.01 to about 0.4 in (3) for each chemical formula is as follows. Amounts of substitution for RE below each minimum do not provide satisfactory effects of carrier concentration adjustment while those above each maximum excessively reduce the carrier concentration, thereby disadvantageously decreasing Tc. The preferred minimum amouts of substitution for RE are 0.05 respectively. The amount of substitution of Sr and/or Ca for RE is from 0.1 to 0.15 in (1) as a value s, from 0.1 to 0.2 in (2) as a value m, and from 0.1 to 0.3 in (3) as a value n. Preferred modes of substitution of (Sr, Ca) for RE of the Bi oxide superconductors in (2) and (3) are as follows. In substituting Sr, at least one element is selected from the group consisting of La, Nd, Dy, Eu, and Sm. In substituting part of Ca, at least one element is selected from the group consisting of Nd, Pr, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, and Y. Both Sr and Ca or only one of them may be substituted. The Bi oxide superconductor of the invention may be prepared by, e.g., the following methods. (a) To prepare it in the form of sintered bodies, single elements such as Bi, Pb (Sr,Ca), RE, and Cu and compounds thereof such as carbonates and oxides thereof are mixed at a predetermined mole fraction. A raw composition is prepared by mixing the starting materials, i.e., the above elements, so that the atomic ratio of formula (I) will be satisfied. As long as the atomic ratio of the starting material is within the above described range, the advantage of the invention will be provided. A tolerance of 10% is provided depending on the preparation condition. Then, the above raw composition is tentatively fired in an oxygen atmosphere as necessary, subjected to a thermal treatment at 700 to 900°C in an inert gas atmosphere including or not including oxygen, and finally sintered. (b) To prepare it in the form of thin films, a Bi oxide superconductive thin film is formed by a vapor deposition method, a sputtering method, a cluster ion beam method, a molecular beam epitaxy (MBE) method, a chemical vapor deposition method, and the like, using the sintered body obtained by method (a) or the above starting materials. The superconductive wire or tape using the Bi oxide superconductor of the invention may be prepared by, e.g., the following methods. A Bi oxide superconductor is prepared as in method (a) and then a Bi oxide superconductive powder is prepared by pulverizing the prepared superconductor. The preferred oxide superconductor is the Bi oxide superconductor prepared by (2) from a stability viewpoint. The Bi oxide superconductive powder is then used to fill and seal a metal coated tube. A metal coated tube material should be selected so that its mechanical strength, conductivity (required as a stable material), and costs will be appropriate. From the above considerations, copper or a copper alloy such as a copper-nickel alloy are preferred. Stainless tubes may also be applicable. In using the metal coated tubes described above, it is preferable to form a layer made of a noble metal such as silver and gold over an inner peripheral surface, or a surface of contact with the oxide superconductor. This is to prevent interaction between the oxide superconductor and the tube coating material during thermal treatment, thereby allowing excellent superconductivity to be obtained. The metal coated tube having the above noble metal layer may be prepared by, e.g., a mechanical forming method in which a thin silver tube is inserted into the coated metal and drawn; a thin film forming method such as a plating method; or a liquid coating method. Thereafter, the metal coated tube which has been filled by the Bi oxide superconductive powder is processed into a desired wire or tape shape by, e.g., a surface reducing or wire drawing process, subjected to a thermal treatment for property improvement to obtain the desired superconductive wire or tape. The thermal treatment should preferably be carried out in the atmosphere of an inert gas such as nitrogen or argon, or in a vacuum to prevent deterioration of the metal coated tube. The superconductive wire or tape using the Bi oxide superconductor of the invention exhibits excellent superconductivity even during the thermal treatment in the above-described atmosphere. For example, for a metal coated tube consisting, e.g., of copper or a copper alloy, it is preferable to limit the oxygen content in the atmosphere below 1000 ppm, although this also depends on the thermal treatment temperature, which is preferably adjusted to about 750 to 900°C. The thermal treatment under the above conditions provide satisfactory effects also in case of preparing, e.g., a coil even if it is carried out after winding the coil into a predetermined shape. According to the invention, the Bi oxide superconductor has not only its carrier concentration controlled but also its structural modulation relaxed, and this contributes to greatly improving its Tc. In addition, an increase in Tc of the Bi oxide superconductor whose structure is suitable for easy preparation, a stable preparation in a low oxygen content, a stable surface condition of the prepared superconductor, and the like provide an oxide superconductor that can be a strong potential as superconductive devices and superconductive wires and tapes. Moreover, the Bi oxide superconductor of the invention with its dispersed normal conductive phase acting as a pinning site provides improvements in critical current density. Embodiments of the invention will be described. [Example 1 and Comparative Example 1] The Bi oxide superconductive thin films represented by formula (I) was prepared by the MBE method as follows. A crucible accommodating Bi, Pb, Sr, RE (Nd, La, or Sm), and Cu, which were deposition sources, was arranged within a vacuum container of an MBE device, and an MgO substrate was set to a substrate holder and heated to about 400 to 500°C by a heater. Then, the vacuum container was first evacuated roughly to a high vacuum degree and then finely adjusted so that an oxygen atmosphere of about 1 x 10⁻³ Torr can be obtained therein. Under such condition, each deposition source was heated to a temperature commensurate with its evaporation temperature to start film formation, and the 1000 nm thick Bi oxide superconductive thin films of the compositions shown in Table 1 were produced. The MBE condition was adjusted so that the films of respective compositions can be prepared. The superconducting properties of the thus prepared Bi oxide superconductive thin films were evaluated by means of a dc four probe method and through magnetization measurement by a SQUID magnetometer. The result is also shown in Table 1. Further, when Meissner effect in 4.2 K of every thin film is measured, superconductivity in every thin film is confirmed. Exemplary films that were not Pb-substituted or were Pb-substituted by small amount were prepared for comparison purposes (Comparative Example 1). The data on these films are also shown in Table 1. No single phase thin film was produced when the amount x of substitution of Pb was greater than 1. Sample No. Composition T c Example 1 1 Bi 1.8 Pb 0.2 Sr 1.9 Nd 0.1 CuO₆ 40K 2 Bi 1.6 Pb 0.4 Sr 1.8 Nd 0.2 CuO₆ 50K 3 Bi 1.5 Pb 0.5 Sr 1.9 Nd 0.2 CuO₆ 55K 4 Bi 1.4 Pb 0.6 Sr 1.8 Nd 0.2 CuO₆ 60K 5 Bi 1.0 Pb 1.0 Sr 1.7 Nd 0.3 CuO₆ 80K 6 Bi 1.8 Pb 0.2 Sr 1.9 La 0.1 CuO₆ 42K 7 Bi 1.8 Pb 0.2 Sr 1.9 Sm 0.1 CuO₆ 40K 8 Bi 1.4 Pb 0.6 Sr 1.9 La 0.1 CuO₆ 57K Comparative example 1 1 Bi₂Sr₂CuO₆ 6K 2 Bi 1.9 Pb 0.1 Sr₂CuO₆ 10K

Claims: An oxide superconductor comprising: a composition of Bi, Pb, Sr, RE, and Cu in an atomic ratio of 2-x : x : a-s : s : b, wherein RE is at least one element selected from the group consisting of Nd, Pr, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu and Y, a is 1.8 or more and 2.2 or less, b is 0.8 or more and 1. 2 or less, s is 0.01 or more and 0.3 or less, x is 0.2 or more and 1 or less, and x > s. An oxide superconductor according to claim 1, wherein said oxide superconductor has a composition subtantially represented by the chemical formula of Bi 2-x Pb x Sr 2-s RE s CUO 6+δ , wherein δ is -0.2 or more and 0.2 or less. An oxide superconductor according to claim 1 or claim 2, wherein said oxide superconductor has a composition substantially represented by the chemical formula of Bi 2-x Pb x Sr 2-s RE s CuO₆.

Inventors: ANDO KEN, FUKUSHIMA NOBURU, NIU HIROMI, ANDO, KEN, FUKUSHIMA, NOBURU, NIU, HIROMI, ANDO, KEN, C/O INTELLECTUAL PROPERTY DIVISION, FUKUSHIMA, NOBURU, INTELLECTUAL PROPERTY DIVISION, NIU, HIROMI, C/O INTELLECTUAL PROPERTY DIVISION
Applicants: TOSHIBA KK, KABUSHIKI KAISHA TOSHIBA
Application year: 1990
Main classification: H01L39
IPC codes: H01L39, C04B35