Films of high Tc oxide superconductors and method for making the same

Abstract: Superconducting transition metal oxide films are provided which exhibit very high onsets of superconductivity and superconductivity at temperatures in excess of 40°K. These films are produced by vapour deposition processes using pure metal sources for the metals in the superconducting compositions, where the metals include multi-valent nonmagnetic transition metals, rare earth elements, and/or rare earth-like alkaline earth elements. The substrate is exposed to oxygen during vapour deposition and, offer formation of the film, ambient followed by a least one annealing step in an oxygen ambient and slow cooling over several hours to room temperature. The substrates chosen are not critical as long as they are not adversely reactive with the super conducting oxide film. Transition metals include Cu, Ni, Ti, and V, while the rare earth-like elements include Y, Ca, Ba, and Sr.

Description: This invention relates to films of high T c oxide superconductors and methods for making them, and more particularly to such film structures and methods where the oxide superconductors exhibit superconductivity at temperatures greater than 40K. Superconductors of many types are known in the prior art, including both elemental metals and compounds of various types, such as oxides. The recent technical breakthrough reported by Bednorz and Muller in Z. Phys. B, 64 , 189 (1984) was the first major improvement in a superconducting material in the last decade, wherein the critical transition temperature T c at which the material becomes superconducting, was increased substantially. Bednorz and Muller described copper oxide material including a rare earth element, or rare earth-like element, where the rare earth element could be substituted for by an alkaline earth element such as Ca, Ba or Sr. The work of Bednorz and Muller has led to intensive investigations in many laboratories in order to develop materials having still higher T c . For the most part, these high T c oxide superconductors consist of compounds of La, Sr, Cu, and 0, or Y, Ba, Cu, and 0. In particular, copending European patent application No. 88101321.3 describes a high T c oxide superconductor that is a single phase bulk superconductor having the general formula A 1±x M 2±x Cu 3 O y Where A is Y or a combination of Y, La, Lu, Sc or Yb; M is Ba, or a combination of Ba, Sr or Ca; x is between 0 and 0.5 and y is sufficient to satisfy the valence demands of the material. A particularly preferred single phase composition described in that copending application is Y Ba 2 Cu 3 O y . For many applications, it is necessary to be able to provide the superconducting material in film form, i.e, in a range of thin films (for example, about 1000 Angstroms) to thick films (for example, in excess of 1 micron). Heretofore, there has been no reported satisfactory way to provide films of these new high T c oxide superconductors where the film must exhibit superconductivity at temperatures in excess of 40K. Accordingly, it is a primary object of the present invention to provide a process in accordance with claim 1 of making films of high T c oxide superconductors having supercondtivity at temperatures in excess of 40K. The production of films of transition metal oxide superconductors exhibiting superconductivity at temperatures in excess of 40K, where the films are continuous and smooth, and exhibit compositional uniformity over usable areas is described. The production of continuous, smooth copper oxide superconductive films exhibiting superconductivity at temperature in excess of 40K, where the films exhibit a perovskite-like structure is described. The production of transition metal oxide superconductive films including a rare earth element or a rare earth-like element, where the films exhibit superconductivity at temperatures greater than 40K described. The films produced by this invention are oxide superconductors exhibiting superconductivity at temperatures in excess of 40K, the films being smooth and continuous and exhibiting substantial compositional uniformity. In particular, the films are comprised of copper oxides containing a superconducting phase, and typically including a rare earth element or rare earth-like element as claimed. These rare earth like elemente include Y, Se, and La. The transition metal is the multi-valent, non-magnetic element Cu. Cu provides unique superconducting films exhibiting essentially zero resistance at temperatures in excess of 77K, the boiling point of liquid nitrogen. The copper oxide based films produced by this invention exhibit exceptionally high temperatures for the onset of superconductivity at extremely elevated temperatures, in addition to being continuous, smooth, and of excellent compositional uniformity. The Cu oxide films are therefor considered to be unique examples of this class of films, as are the processes for making them. Typically, the films are characterised by a perovskite-like crystalline structure, such as those described in more detail by C. Michel and B Raveau in Dde Chimie Minerale, 21. p. 407 (1984). These films are formed by a vapour deposition process in which multiple metal sources are used, pure metal being vaporised from each of these sources. Vapours of the pure metal travel to the substrate which is exposed to an oxygen ambient. A surface reaction occurs forming a metal oxide film on the substrate. In order to enhance this surface reaction, the substrates are usually heated. An annealing step in an oxygen environment is then carried out to satisfy valence and stoichiometry requirements. Afterwards the annealed materials are slowly cooled to produce superconducting films. The use of separate metal sources provides control of the process while the oxygen ambient during vapor transport is used to insure that the growing films are stable. The post-anneal step in an oxygen environment ensures that sufficient oxygen is present to satisfy valence and stoichiometry requirements, as well as to obtain the proper phase for high T c superconducting. As previously noted, this invention relates to transition metal oxides containing a superconducting phase that exhibits superconductivity at temperatures in excess of 40K, and more particularly to films of these materials and to processes for making these films. The invention is specifically directed to films which are superconducting at temperatures in excess of 40K, at the designation "high T c " films being used to indicate this property. In this manner, a distinction is clearly made between the films of this invention and the superconducting ceramic films known in the art, such as Ba-Pb-Bi-0 films and Li-Ti-0 films. These previously known films are also oxide superconductors, but have very low transition temperatures, typically below about 13K. The Ba-Pb-Bi0 (BPB) composition is a perovskite-type oxide superconductor while Li-Ti-0 (LTO) oxide superconductors are spinel-type oxides. The preparation of BPB oxide films was first described by L R Gilbert et al. in Thin Solid Films, 54, pp. 129-136, (1978). These films were prepared by sputtering using mixed oxide targets produced by sintering and pressing together powders of barium, bismuth, and lead oxides. Sputtered films were amorphous and became metallic and superconducting (in most cases) upon annealing. Films were annealed both in air and in oxygen. A defect model based on barium vacancies and an equal number of oxygen vacancies was postulated for the superconducting behaviour of these films. In a subsequent article I.R. Gilbert et al described resputtering effects in the BPB perovskites. This article is I.R.Gilbert et al. J. Vac. Sci. Technol,. 17 (1), p. 389. Jan/Feb 1980. Subsequent to the work of Gilbert et al. M. Suzuki and co-workers further developed techniques for forming films of BPB. In their work, they produced superconducting thin films using high partial pressures of oxygen in their sputtering apparatus, where the sputtering targets were dense mixtures of Ba, Pb, and Bi oxides. Sputtering from pure metal targets was not suggested. A post-anneal step in an oxygen environment was used to obtain superconducting films having a perovskite-type structure. Both cooled and heated substrates were utilised. These processing conditions of Suzuki et al are described in the following references: 1. M. Suzuki et al, Japanese Journal of Applied Physics, vol. 19 No. 5 pp. 1231-1234, May 1980. 2. M. Suzuki, J, Appl. Phys., 53 (3) p. 1622. March 1982. In addition to the processing techniques developed by Suzuki et al to provide films of these oxide superconductors, their research has been extended to the utilisation of the superconducting oxide films in devices, such as tunnel junctions. References generally describing the devices and their characteristics are the following: 1. M. Suzuki et al. Japanese Journal of Applied Physics, Vol. 21 No. 7. p. 1437, July 1982. 2. M. Suzuki et al, Proceedings of the 13th Conference on Solid State Devices, Tokyo, 1981; Japanese Journal of Applied Physics, Voi. 21, (1982) supplement 21-1, pp. 313-318. Reference 2 describes Josephson Tunnel Devices fabricated from both BPB and LTO thin films. Accordingly the present invention provides a process of making films of superconductive material exhibiting superconductivity at temperatures in excess of 40K, as defined in claim 1. The film containing the copper oxide phase contains a rare earth element, and also contains an alkaline earth element as claimed. The film of superconductive oxide suitably has a thickness less than about 1 x 10 -6 m (10,000 angstroms). In one suitable embodiment of the present invention the superconducting film produced contains a rare earth or rare earth-like element and an alkaline earth element, the ratio of the rare earth element and alkaline rare earth element to the transition metal element being approximately 1:1. Suitable rare earth-like elements contained in the superconducting film are selected from the group consisting of Y, Sc, and La. The superconducting film produced by the present invention preferably exhibits a perovskite-like crystallographic structure. A suitable superconducting film produced within the scope of the present invention contains Y, Ba, and Cu; aptly wherein the ratio (Y, Ba) :Cu is approximately 1:1. In a further suitable embodiment of the present invention the produced superconducting film has a nominal composition Y 1 Ba 2 Cu 3 O y where y is sufficient to satisfy the valence and stoichimetry demands of the material. In a preferred embodiment the present invention produces a superconducting structure comprising, in combination, a substrate and a film of superconductive material formed on the substrate, in accordance with the process of claim 1. Suitably the superconducting film has the properties of a superconducting onset temperature in excess of 90K and a substantially zero resistive state at temperatures in excess of 70K. Preferably the superconducting film of the preferred embodiment contains Y and Ba, and is a copper oxide superconducting film. In a further preferred embodiment of the present invention the produced superconducting structure comprises in combination a substrate, and a superconducting film deposited on the substrate, the superconducting film exhibiting the onset of superconductivity at temperatures in excess of 90K and further exhibiting a substantially zero resistance state at temperatures in excess of 70K, said superconducting film being continuous and comprised of a film exhibiting a perovskite-like crystalline structure. The transition metal is copper. Preferably the method of the present invention further includes the step of annealing said as-deposited oxide film in an inert gas environment prior to annealin said oxide film in an oxygen environment. The process for making films is particularly suitable where the substrate is comprised of a refractory oxide Preferably the annealing step of the method of the invention includes a first annealing step at a first temperature and a second annealing step at a higher temperature. Preferably three metal sources are utilised to provide vapours of three metals, said three metals including said transition metal, a rare earth element or rare earth-like element, and an alkaline earth element; in particular the three metals are Y, Ba and Cu, there being three separate sources for these three elements. Aptly the substrate is heated during deposition and the formation of the transition metal oxide film on the substrate. Suitably the ratio in the film of (Y,Ba):Cu is about 1: 1. A further preferred embodiment of the present invention comprises a structure exhibiting a high superconductivity T c , said structure including a substrate, and a film formed on said substrate, said film being a superconductive oxide film having the property of substantially zero resistance at temperatures in excess of about 70K and being comprised of a nonmagnetic multi-valent transition metal oxide phase. Suitably the film exhibits a crystalline perovskite-like structure. A particularly preferred film is one wherein the transition metal oxide is copper oxide. In order to illustrate the process of the present invention and provide technical background information several examples will be given which are not all embodiments of the present invention, followed by a discussion of the various processing steps. EXAMPLES Y-Ba copper-oxide superconductive films were produced having high T c . Compositions having the nominal composition YBaCu 2 O 4 , not being an embodiment of the present and YBa 2 Cu 3 O y were formed. The value of y is chosen to provide satisfaction of the valence and stoichiometry requirements of the composition and can be, for instance, y = 8. A vacuum deposition system was used, having three 10kV electron beam heated sources. The deposition rate could be controlled over the range of 0.1 - 1 nm/sec, and substrate temperature could be varied from -100 to 700°C. The substrate composition can vary, and generally consisted of sapphire wafers commercially available with both c and a-axis orientation. Plates of MgO were also used as substrates, both with <110> and <001> orientations. In general, only small differences were found in the final films among the above mentioned substrates. The three electron guns were filled with the desired three metals, Y, Ba, Cu, and the evaporation rates were adjusted to give the nominal desired composition at the substrate plane. It was initially found that films made at room temperature in a high vacuum were often unstable upon removal to room ambient and generally were not superconducting. In order to avoid the deterioration of the films and to obtain stable films at room ambient, the films were deposited in a partial pressure of oxygen with a pressure up to 0.13 Pa (10 -3 torr). The substrate temperatures were elevated typically to about 450°C. Films between 0.1 and 1 micron were grown. The ac resistance versus temperature data for these films were taken using four terminal pressure contacts while susceptibility measurements were made using a SQUID magnetometer. The applied current was kept small during the resistance versus temperature measurements, typically around 1 microamp, while smaller currents were also used. These films showed a strong Meissner effect. The as-deposited films were dark and of high resistance. These as-deposited films did not generally go superconducting. When annealed at high temperature (about 900°C) in oxygen, the films became metallic and generally were superconducting. Knowledge of the chemical composition proved to be of great value in adjusting vapour deposition rates, substrate temperature and background pressure. The Y-based films exhibited high T c behaviour. For example, a film of composition Y 0.75 Ba 1.35 Cu 3 O 7.7 (not being an embodiment of the invention) experienced an onset of superconductivity at about 97°K and superconducting behaviour at about 50K. There was some microscopic evidence for the existance of a second phase in these films. The films have a nearly complete Meissner effect showing a susceptibility of about 0.5 of 1/4# Additional Y-Ba films were grown having an onset of superconductivity at about 97K and exhibiting superconductivity at temperatures in excess of 77K. These films had a nominal composition Y 0.87 Ba 1.53 CU 3 O 9-y EXAMPLE The process of this invention can also be applied to other high T c oxide superconductors. For example, films containing La, Sr, Cu, and O which are not embodiments of the present invention can be obtained by this technique. In this case, the three electron guns are filled with La, Sr, and Cu. The general steps of the process are then the same as that described with respect to the preceding example except that there are some variations in the annealing steps. These variations will be described in the following discussion. DISCUSSION OF PROCESS STEPS A key feature of the present process uses vapour streams of the metals to be utilised in the film. Substantially pure metal sources are used, rather than oxide sources which previously have been used to sputter low T c oxide superconductors (see Suzuki et al above). Codeposition of these three metals occurs onto a heated substrate, there being an oxygen ambient so that oxygen will simultaneously arrive at the substrate for a surface reaction to form the oxide film. Those of skill in the art will recognise that other techniques can be used to provide the necessary oxygen ambient (e.g an oxygen ion beam, a jet of oxygen, etc). In the applicants' experimentation, t has been found necessary to provide oxygen in orde r to stabilise the growing films. Without the oxygen ambient, the films were unstable upon removal to room ambient and generally were not superconducting. They were not uniform in appearance or deposition as confirmed by x-ray data. However, some of the proper structure was present on the films. Consequently, in order to avoid deterioration of the films and to obtain stable films at room ambient, a partial oxygen pressure was used. Generally, high temperatures are required to provide the perovskite phases necessary to obtain superconductivity. For example, for bulk materials a sintering step in excess of about 900°C is required. However, such temperatures cannot be used when pure metals are vapour deposited, as many of these pure metals have melting points which are less than these high temperatures. This is particularly true for the alkaline earth )elements. Thus, in a vacuum environment these metals would boil off, leading to excess deficiencies of the metals in the growing film. Typically, in order to obtain the proper phase high temperatures are required but such high temperatures cannot be used in the film deposition apparatus. Therefore, complete in-situ oxidation is not readily obtained and, for this reason, subsequent annealing steps are used. These annealing steps are tailored in accordance with the composition of the film that is grown and the amount of oxygen incorporated into the growing film. Typically, the annealing step is used to insure that a proper amount of oxygen is present and/or to obtain the right phase for superconductivity. For example, a 2-step anneal is used for superconducting oxides containing La and Sr which are not embodiments of present invention if there is not a composition of the present claim 1. For these films, a first anneal at about 400°C in a pure oxygen environment is used. This anneal is for approximately 6-30 minutes. It is then followed by a second annealing step at about 700°C in pure oxygen, again for about 6-30 minutes. The first low temperature anneal adds oxygen to the film, while the second higher temperature anneal is used to produce the proper phase for superconductivity. In these La-Sr films, if the annealing temperature is greater than about 550°C, the films will start to lose oxygen. However, an anneal at temperatures greater than this is necessary to provide the proper perovskite phase for superconductivity. Therefore, a two-step approach is used where the first annealing step at about 400°C enables additional oxygen to be incorporated while the second annealing step at about 700°C allows the formation of the proper superconducting phase, even though some oxygen will be lost. Y-Ba films, as deposited, exhibit characteristics between insulating and metal properties. Their room temperature resistance is in the megaohm range for films typically about 4·10 -7 m (4000 Angstroms). Thus, an intermediate annealing step is not required since these films contain enough oxygen, in contrast with as-deposited La-Sr films which have a room temperature resistance of only about 5-10 ohms. Y-Ba films can be annealed directly at high temperature (about 900°C) in an oxygen atmosphere for a few minutes. They are then slowly cooled (about 3 hours) to room temperature. In an alternative step, the Y-Ba films are first heated to about 900°C in a 100% He atmosphere. The presence of He performs mixing in order to eliminate compositional non-uniformities which may be present in the film, which makes the films more homogeneous. This is followed by an anneal in 100% oxygen for a few minutes at about 900°C. As noted above, the cooling step after annealing is generally done slowly over a period of several hours to room temperature. It appears to be particularly important to provide very slow cooling over the first few hundred degrees. During this cooling, the oxygen atmosphere can be maintained. It has been noted that substrate heating appears to be important in order to provide good control of the relative amounts of the metal in the high T c superconductors of this invention. Generally the ratio of the rare earth element/alkaline earth element must be controlled reasonably well. For example the ratio La:Sr is usually about 1.8:0.2 (not being an embodiment of the invention). However, it is difficult to control alkaline earth elements as a vapour transporting species since they tend not to have a constant transport rate. In order to compensate for this, the substrate temperature is elevated. Generally, it is believed that the substrate temperature can be controlled to obtain the necessary reaction between the depositing metals and oxygen at the substrate. Epitaxy may be possible with the correct combinations of substrate temperature, metal transport rates etc. It has been observed that the substrate temperature during co-deposition of the metals comprising the superconducting oxide films can determine the relative amounts of these metals in the film. Rather than deposit on cooled or room temperature substrates, higher substrate temperatures were used. For example, at a substrate temperature 650°C in an oxygen ambient pressure of 0.13 Pa (10 -3 T) the La:Sr ratio was 1.75:0.04 (not being an embodiment of the invention). At a substrate temperature of 550°C in the same oxygen ambient a ratio of 1.9:0.31 was obtained (not being an embodiment of the invention). Thus, the substrate temperature can be used to smooth out variations in the deposition rate of various metals and allows good control of the rare earth element:alkaline earth element ratio. The substrate temperature is convenient to control and quite precisely adjustable. While several substrates have been mentioned, many others can be considered. Generally, it is preferable that the substrate be non-reactive with alkaline earth oxides of the type to be found in the superconducting films, since the alkaline earth materials are quite reactive. Refractory oxides are very favourable substrates, as are magnesium aluminium spinels, sapphire, and MgO. The particular orientation of the substrate does not appear to be critical. Further, the substrate need not have a planar, layer-like form, but can be in the shape of a wire or any type of irregular surface geometry. In the practice of this invention, films of transition metal superconducting oxide are formed exhibiting high T c and especially a T c in excess of liquid nitrogen temperatures. In the further practice of this invention, it is to be understood that the term film broadly encompasses a layer, coating, etc, that is formed (deposited or grown) on a surface of any composition, shape, etc. These films have wide-spread applications in the electric and electronics industry, including uses as transmission and circuit lines, device electrodes, sensitive detectors of electromagnetic fields, and in various optoelectronic devices. Specific immediate uses include applications in high field magnets, electromechanical devices, Josephson tunnel devices, and interconnect metallurgy on and between chips in order to improve speed and packaging density in the microelectronics industry.

Claims: A process of making a crystalline film exhibiting superconductivity at temperature in excess of 40K, the film being a single transition metal oxide phase having the general formula Y Ba 2 Cu 3 O y where y is sufficient to satisfy the valence demands of the material, said process including the steps of: employing an evaporation process to transport metal atoms from separate metal sources to a substrate; providing an oxygen ambient at said substrate while said metal atoms are arriving there at, said metal atoms and said oxygen reacting to form a transition metal oxide film on said substrate; annealing the as-deposited oxide film in an oxygen environment; and over several hours slowly cooling said annealed film to room temperature. A process as claimed in claim 1, wherein the evaporation process transports metal atoms from substantially pure metal sources to the substrate. A process as claimed in claim 1 or claim 2, where the annealing includes a first annealing step at a first temperature and a second annealing step at a higher temperature. A process as claimed in any of claims 1 to 3 wherein the film exhibits superconductivity at a transition temperature T c in excess of 70K. A process as claimed in any preceding claim, wherein said film is continuous and smooth. A process as claimed in any preceding claim, wherein said superconducting film has the properties of a superconducting onset temperature in excess of 90K and a substantially zero resistive state at temperatures in excess of 70K. A process as claimed in any preceding claim, wherein the superconducting film exhibits a perovskite-like crystalline structure.

Inventors: CHAUDHARI PRAVEEN, GAMBINO RICHARD JOSEPH, KOCH ROGER HILSEN, LACEY JAMES ANDREW, LAIBOWITZ ROBERT BENJAMIN, VIGGIANO JOSEPH MICHAEL, CHAUDHARI, PRAVEEN, GAMBINO, RICHARD JOSEPH, KOCH, ROGER HILSEN, LACEY, JAMES ANDREW, LAIBOWITZ, ROBERT BENJAMIN, VIGGIANO, JOSEPH MICHAEL, CHAUDHARI, PRAVEEN NMN
Applicants: IBM, INTERNATIONAL BUSINESS MACHINES CORPORATION
Application year: 1988
Main classification: H01L39
IPC codes: H01B12, C01G1, H01B13, H01L39, C30B29, C30B1, C01G3