Josephson device

Abstract: A Josephson device comprises a substrate, a lower superconductive layer, a tunneling layer and an upper superconductive layer which are laminated in this order, wherein the lower and upper superconductive layers each comprise a bismuth-copper-containing oxide superconductor and the tunneling layer comprises a bismuth-­ containing oxide. The bismuth-containing oxide is selected from an insulator compound, a normally conductive compound and a compound having a smaller critical current or a lower critical temperature that of the bismuth-copper-containing oxide superconductor. Both of the bismuth-copper-containing oxide superconductor and the bismuth-containing oxide have layer-lattice composite perovskite structures.

Description: The present invention relates to a Josephson device using a bismuth-based oxide superconductor and which is capable of being operated at a relatively high temperature. A Josephson junction is formed of two superconductive layers separated by a very thin insulating layer and has been proposed for use as a high-speed switching device for use e.g. in computers because of the tunneling effect which is produced at the junction region. A typical method for forming a Josephson junction involves forming a lead thin film followed by formation of a very thin oxide film on the surface of the lead thin film, the oxide film typically having a thickness of 30Å, after which another lead thin film is deposited thereon (see "CHODENDO (Superconduction)" edited by Japan Physics Society, p.147). Several measurements have been reported concerning the Josephson effect in oxide superconductors having a high superconductive transition temperature. Superconductors having a high superconductive transition temperature have mainly been of the point contact type, but such junctions cannot provide devices that can be put into practical use e.g. in highly integrated circuits. Amongst the devices in which an oxide superconductor is used, sandwich-type junctions based on lead have the disadvantage that it is difficult to form an insulating layer of thin and uniform thickness. Devices in which the insulating layer is of non-uniform thickness do not exhibit good characteristics and suffer from the disadvantage that the crystallizability of the superconductive layer may be significantly worsened if the insulating layer is of a material having a different crystal structure from the superconductor, again resulting in poor device characteristics. The present invention provides a Josephson device having the features set out in claim 1. Forms of this Josephson device do not suffer from the problems of non-uniformity and crystal structure of the superconductive layer, and provide a Josephson device having superior characteristics. The bismuth-based superconductor present in the above Josephson devices is less subject to atmospheric deterioration and contributes to the improved characteristics of the device. A paper by H. Kroger et al, Applied Physics Letters, Vol. 39, No. 3, 1 August 1981 pages 280-282 discloses a Josephson device comprising a substrate having a lower superconductive layer, a tunneling layer and an upper superconductive layer laminated on it. However, the superconductive layers are of niobium based material, whereas the layers in the present Josephson device are of bismuth based materials. A paper by M. G. Blamire, Journal of Physics D: Applied Physics, Vol. 20, No. 10, 14 October 1987 at pages 1330-1335 discloses a Josephson device formed by lower and upper superconductive layers made of YBa₂Cu₃O 7-X and a tunneling layer made of Y₂O₃. In a preferred embodiment, the present invention provides a Josephson device comprising a substrate, a lower superconductive layer, a tunneling layer and an upper superconductive layer which are laminated in this order, wherein: the lower and upper superconductive layers each comprise a bismuth-copper-containing oxide superconductor represented by the formula: {(Bi 1-b C b )₂O₂}(Cu 1-a B a ) 2+n A 3+n O (12+3n)-x wherein A represents at least one element selected from the elemental group consisting of Group Ia, IIa, IIIa and IVb elements of the periodic table; B represents at least one element selected from the elemental group consisting of Group Ib, IVa, Va, VIa and VIIIa elements; C represents at least one element selected from rare earth elements; and O ≦ b < 1, O ≦ a < 1, -1 < n ≦ 10, and x > 0; and the tunneling layer comprises a bismuth-containing oxide represented by the formula: {(Bi 1-b C b )₂O₂}²⁺{Bi 1-a B a )₂(Ti 1-a A a )₃O₁₀} n ²⁻ wherein C represents at least one element selected from rare earth elements; B represents at least one element selected from the group consisting of Ca, Na, K, Ba, Sr, Pb and Pr; A represents at least one element selected from the group consisting of Nb, Ta, Fe, Sn and Ga; and O ≦ b < 1, O ≦ a < 1, and 1 ≦ n ≦ 5. In another embodiment, the present invention also provides a Josephson device, comprising a substrate, a lower superconductive layer, a tunneling layer and an upper superconductive layer which are laminated in this order, wherein; the lower and upper superconductive layers each comprise a bismuth-copper-containing oxide superconductor represented by the formula: {(Bi 1-b C b )₂O₂}(Cu 1-a B a ) 2+n A 3+n O (12+3n)-x wherein A represents at least one element selected from the elemental group consisting of Group Ia, IIa, IIIa and IVb elements of the periodic table; B represents at least one element selected from the elemental group consisting of Group Ib, IVa, Va, VIa and VIIIa elements; C represents at least one element selected from rare earth elements; and O ≦ b < 1, O ≦ a < 1, -1 < n ≦ 10, and x > 0; and the tunneling layer comprises a bismuth-containing oxide represented by the formula: Bi₂Sr₂LnCu₂O y wherein Ln represents at least one element selected from the group consisting of Y and lanthanides; and 7 ≦ y ≦ 9. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 illustrates an example of the Josephson device of the present invention; Fig. 2 illustrates a state wherein a bismuth-copper-containing oxide superconductor film is formed on a substrate; Fig. 3 illustrates a state wherein a Bi₄Ti₃O₁₂ film is formed on the bismuth-copper-containing oxide superconductor film; Fig. 4 illustrates a state wherein another bismuth-copper-containing oxide superconductor film is further formed on the Bi₄Ti₃O₁₂ insulating film; Fig. 5 illustrates a state wherein a part of the laminated films is removed to form an electrode; and Fig. 6 diagramatically shows current-voltage characteristics of a Josephson device obtained by the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS In a Josephson device comprising a substrate, a lower superconductive layer, a tunneling layer and an upper superconductive layer which are laminated in this order, the present inventors found, as a result of intensive studies, that a bismuth-copper-containing oxide superconductor having a layer-lattice composite perovskite structure may be used as the lower and upper oxide superconductive layers, and a bismuth layer-lattice compound having the similar layer-lattice composite perovskite structure may be used as the tunneling layer, thereby making it possible to prepare a Josephson device with a good crystallizability of superconductive layers and also form a thin and uniform tunneling layer, thus providing a Josephson device having good characteristics. Further, the use of bismuth-copper containing oxide superconductor has made it possible to provide a Josephson device that can sufficiently operate at temperatures not lower than the liquid nitrogen temperature and is particularly superior in moisture resistance, thermal resistance and so forth. In the present invention, the bismuth-copper-containing oxide superconductor preferably usable in the lower and upper oxide superconductive layers includes materials represented by the general formula (I): {(Bi 1-b C b )₂O₂}(Cu 1-a B a ) 2+n A 3+n O (12+3n)-x (I) wherein A represents at least one element selected from the elemental group consisting of Group Ia, IIa, IIIa and IVb elements of the periodic table; B represents at least one element selected from the elemental group consisting of Group Ib, IVa, Va, VIa and VIIIa elements; C represents at least one element selected from rare earth elements; and O ≦ b < 1, O ≦ a < 1, -1 < n ≦ 10, and x > 0; and having as its crystal structure the layer-lattice structure such that a perovskite-like layer is positioned between {(Bi 1-b C b )₂O₂}²⁺ layers (0 ≦ b < 1). Of the materials represented by the above Formula (I), particularly preferred are those represented by the following formula: Bi₂(Sr,Ca)₃Cu₂O x (7 ≦ x 9). The bismuth layer-lattice compound used as the tunneling layer in the present invention preferably includes materials represented by the general formula (II): {(Bi 1-b C b )₂O₂}²⁺{Bi 1-a B a )₂(Ti 1-a A a )₃O₁₀} n ²⁻ (II) wherein C represents at least one element selected from rare earth elements; B represents at least one element selected from the group consisting of Ca, Na, K, Ba, Sr, Pb and Pr; A represents at least one element selected from the group consisting of Nb, Ta, Fe, Sn and Ga; and O ≦ b < 1, O ≦ a < 1, and 1 ≦ n ≦ 5; or those represented by the following formula (III): Bi₂Sr₂LnCu₂O y (III) wherein Ln represents at least one element selected from the group consisting of Y and lanthanides; and 7 ≦ y ≦ 9. As the bismuth layer-lattice compound used as the tunneling layer, an insulator compound, a normally conductive compound or a compound having a smaller critical current or a lower critical temperature than that of the above bismuth-copper-containing oxide superconductor is used. In particular, of the materials represented by the general-formulas (II) and (III); (II) - 1) Bi₄Ti₃O₁₂ - 2) Bi₂PbFeTi 1.5 Sn 1.5 Oy (7 ≦ y ≦ 9) (III) - 1) Bi₂Sr₂YCu₂Oy (7 ≦ y ≦ 9) are preferably used in the present invention. The bismuth-copper-containing oxide superconductor and bismuth layer-lattice compound as exemplified above are similar to each other in crystal structure. More specifically, the bismuth-copper-containing oxide superconductor of the above formula (I), used as the upper and lower superconductive layers in the present invention, is found to be rhombic as a result of X-ray diffraction data, having the lattice constant of a = 5.4 Å, b = 27.0 Å (=5 x a), and c = 30.8 Å. The bismuth layer-lattice compound of the above formula (II) and (III), used as the joining layer, is also found to be rhombic, having the lattice constant of a = 5.5 Å, b = 5.4 Å, and c = 30.2 Å. When such Josephson device is prepared by using the superconductive layers and the tunneling layer having such crystal structure, there may occur no misfit between the layers because of the similar lattice constants in the both, so that a Josephson device with good characteristics can be obtained. The good characteristics herein mentioned refer to characteristics such as millimeter-wave response and magnetic response. This crystal structure is a layer-lattice composite perovskite structure, so that the film formation can be readily controlled and the uniform and thin layer can be formed as desired. A good Josephson effect attributable to this crystal structure can be well exhibited when all the upper and lower superconductive layers and the tunneling layer have the similar lattice constants. As a result of the measurement of the current-voltage characteristics of the Josephson device constituted according to the present invention, the device shows the characteristics as shown in Fig. 6, from which there is found a superior Josephson effect that the amount of current little changes until the voltage reaches a value higher than a given value and the current abruptly changes when the voltage is decreased to a value lower than a given value. The Josephson device of the present invention can be prepared according to conventional methods. More specifically, it can be prepared by sputtering or vacuum deposition, which can achieve compositional control, as well as by CVD. The upper and lower superconductive layers of the Josephson device of the present invention may each preferably have a layer thickness of from 200 nm (2,000 Å) to 500 nm (5,000 Å); and the tunneling layer has a layer thickness of from 1 to 50 nm (10 Å to 500 Å). As the substrate on which these layers are laminated, preferably used are, for example MgO (100) singlecrystals and SrTiO₃ singlecrystals. EXAMPLES The present invention will now be described below in greater detail by giving Examples. Example 1 A Josephson junction, as illustrated in Fig. 1, was formed in the following manner. In Fig. 1, the numeral 1 denotes a substrate made of MgO; 2, sputter films comprising a bismuth-copper-containing oxide superconductor; 3, a bismuth layer-lattice compound film; and 4, an electrode. First, using as a target a sintered material composed of 1 bismuth, 1 strontium, 1 calcium and 2 copper, a superconductive layer 2 was formed with a thickness of 300 nm (3,000 Å) on the MgO substrate 1 according to rapid frequency magnetron sputtering (Fig. 2). The composition of the resulting film was analized according to a plasma emission spectroscopy to reveal that the film was composed of 2 bismuth, 1.48 strontium, 1.50 calcium, and 2.0 copper. The substrate temperature was set at 700°C, and the film formation was carried out in a mixed gas comprising argon and oxygen, at a gas pressure of 6.67 x 10⁻² mbar (5 x 10⁻² Torr) and an oxygen partial pressure of 6,67 x 10⁻³ mbar (5 x 10⁻³ Torr). After the above superconductive layer was formed, a heat treatment (under conditions of 840°C and 6 hrs in oxygen 1 atmospheric pressure) was carried out, followed by annealing at a rate of 3°C per minute. Next, on the resulting bismuth-copper-containing oxide superconductor film 2, the bismuth layer-lattice compound (Bi₄Ti₃O₁₂) layer 3 was formed as shown in Fig. 3. The film formation was carried out by ion beam deposition, where Bi₂O₃ was used as a starting material containing bismuth atoms and metallic titanium was used as a starting material containing titanium atoms. The substrate temperature was set at 200°C, oxygen gas was fed (9 to 10 mℓ/sec.), and the titanium component was ionized and accelerated at an accelerating voltage of 2 kV and an ionizing current of 100 mA. On the other hand, the vaporized substance generated from the starting material containing bismuth atoms was deposited by resistance heating. The bismuth and titanium components were deposited at a rate of from 2 to 3 Å/sec., and the resulting Bi₄Ti₃O₁₂ thin film 3 had been turned into a layer-lattice film with a thickness of 3 nm (30 Å). On this film, another bismuth-copper-containing oxide superconductor film 2 was formed by rapid frequency magnetron sputtering (Fig. 4). The film formation rate was set to 5 Å/sec., and the heat treatment as in the first layer film 1 was not carried out. The resulting film 2 had a film thickness of 240 nm (2,400 Å). Next, a part of the films was removed by argon ion milling to bring them into the state as shown in Fig. 5, followed by vacuum deposition of gold to form the electrode 4, thus forming the device of the present invention, as shown in Fig. 1. The critical temperature of superconductive films of this device was measured to find that it was 105 K. The current-voltage (I-V) characteristics of this Josephson device was measured at 60 K according to a four-terminal method. As a result, there were obtained the characteristics as shown in Fig. 6, and thus a good junction was seen to have been formed. Example 2 Example 1 was repeated to form a Josephson device of the present invention, except that the target material used in forming the bismuth-copper-containing oxide superconductor by sputtering was replaced with a material composed of 0.9 bismuth, 0.1 lead, 1 strontium, 1 calcium and 2 copper. After film formation, the composition of the film was analyzed by plasma emission spectroscopy, to find that the film comprised 2 bismuth, 1.0 lead, 3.0 strontium, 2.0 calcium and 5.0 copper in compositional ratio. The resulting device had a critical temperature of 92 K, and the I-V characteristics were measured at 60 K. As a result, there was obtained substantially the same results as Example 1. Example 3 Example 1 was repeated to form a Josephson device of the present invention, except that the target material used in forming the bismuth-copper-containing oxide superconductor by sputtering was replaced with a material composed of 1 bismuth, 1 strontium, 1 calcium, 1.8 copper and 0.2 titanium. After film formation, the composition of the film was analyzed by plasma emission spectroscopy, to find that the film comprised 1 bismuth, 1.5 strontium, 1.5 calcium, 1.5 copper and 0.5 titanium in compositional ratio. The resulting device had a critical temperature of 60 K. The I-V characteristics were measured at 20 K to find that there was obtained substantially the same results as Example 1. Example 4 The bismuth-copper-containing oxide superconductor was formed in the same manner as Example 1, and the material composed of 0.5 sodium, 4.5 bismuth and 4.0 titanium was used as the bismuth layer-lattice compound as an insulating layer. The film formation was carried out in the same manner as Example 1, according to ion beam deposition. Sodium, titanium and Bi₂O₃ were used as starting materials. The deposition was carried out under the above compositional ratio while heating the substrate at a temperature of 600°C and feeding oxygen gas at a rate of from 10 to 20 mℓ/min. The deposition rate was each set to be from 0.5 to 3 Å/sec. and the film had a thickness of 3 nm (30 Å). Other procedures followed those in Example 1 to form a Josephson device of the present invention. The resulting device showed substantially the same results for both the critical temperature and I-V characteristics. Example 5 A Josephson junction, as illustrated in Fig. 1, was formed in the following manner. In Fig. 1, the numeral 1 denotes a substrate made of MgO; 2, a lower superconductive layer; 3, an insulating film; 4, an upper superconductive layer; and 5, an electrode. First, using as a target a sintered material composed of 1 bismuth, 1 strontium, 1 calcium and 2 copper, a bismuth-copper-containing oxide superconductor film was formed on the MgO substrate as a lower superconductive layer with a thickness of 300 nm (3,000 Å) according to rapid frequency magnetron sputtering (Fig. 2). The composition of the resulting film was analized according to plasma emission spectroscopy to reveal that the film had the compositional ratio of Bi₂Sr 1.48 Ca 1.50 Cu 2.03 O x . The substrate was heated to a temperature of 700°C, and the film formation was carried out in a mixed gas comprising Ar and O₂, at a gas pressure of 6,67 x 10⁻² mbar (5 x 10⁻² Torr) and an O₂ partial pressure of 6,67 x 10⁻³ mbar (5 x 10⁻³ Torr). After this film was formed, a heat treatment (under conditions of 840°C and 6 hrs in O₂ 1 atmospheric pressure) was carried out, followed by annealing at a rate of 3°C per minute. Next, on the resulting lower superconductive layer, the insulating film (Bi₂Sr₂YCu₂O y ) was formed as shown in Fig. 3. The film formation was carried out by ion beam deposition, where Bi₂O₃ and SrO were used as starting materials containing Bi and Sr atoms, and Y and Cu were used as starting materials containing Y and Cu atoms. The substrate was heated to a temperature of 200°C, oxygen gas was fed (9 to 10 mℓ/sec.), and the Y and Cu components were ionized and accelerated at an accelerating voltage of 2 kV and an ionizing current of 100 mA. On the other hand, the vaporized substances generated from the starting materials containing Bi and Sr atoms was deposited by resistance heating. The deposition was carried out at a rate of from 1 to 2 Å/sec., and the resulting Bi₂Sr₂YCu₂O y thin film had a thickness of 3 nm (30 Å). On this film, another bismuth-copper-containing oxide superconductor film was formed as an upper superconductive layer by rapid frequency magnetron sputtering (Fig. 4). The film formation rate was set at 5 Å/sec., and the heat treatment as in the lower superconductive layer film 1 was not carried out. The resulting film 2 had a thickness of 240 nm (2,400 Å). Next, a part of the films was removed by Ar ion milling to bring them into the state as shown in Fig. 5, followed by vacuum deposition of Au to form the electrode, thus forming the junction as shown in Fig. 1. The critical temperature of this device was measured to find that it was 80 K. The current-voltage characteristics of this Josephson junction was measured at 60 K according to a four-terminal method. As a result, there were obtained the characteristics as shown in Fig. 6, and thus a good junction was seen to have been formed. Example 6 The bismuth-copper-containing oxide superconductor was formed in the same manner as Example 1, and the material composed of 2 bismuth, 1 lead, 1 iron, 1.5 titanium, 1.5 tin and 7 oxygen was used as the bismuth layer-lattice compound as an insulating layer. The film formation was carried out in the same manner as Example 1, according to ion beam deposition. Lead, iron, titanium, tin and Bi₂O₃ were used as starting materials. The deposition was carried out under the above compositional ratio while heating the substrate at a temperature of 600°C and feeding oxygen gas at a rate of from 10 to 20 mℓ/min. The deposition rate was each set to be from 0.5 to 3 Å/sec. and the film had a thickness of 3 nm (30 Å). Other procedures followed those in Example 1 to form a Josephson device of the present invention. The resulting device showed substantially the same results for both the critical temperature and I-V characteristics.

Claims: A Josephson device, comprising a substrate, a lower superconductive layer, a tunneling layer and an upper superconductive layer which are laminated in this order, characterised in that said lower and upper superconductive layers each comprise a bismuth-copper-oxide superconductor having a layered perovskite structure and said tuneling layer comprises a bismuth oxide compound having a similar layered perovskite structure, the lattice constant of the lower superconductive layer, the upper superconductive layer and the tunneling layer being similar so that no misfit occurs when growing one layer on top of the other. A Josephson device according to claim 1, wherein said lower and upper superconductive layers each comprise a bismuth-copper-containing oxide superconductor represented by the formula: {(Bi 1-b C b )₂O₂} (Cu 1-a B a ) 2+n A 3+n O(12+3n)-x wherein: A represents at least one element selected from the elemental group consisting of Group Ia, IIa, IIIa and IVb elements of the periodic table; B represents at least one element selected from the elemental group consisting of Group Ib, IVa, Va, VIa and VIIIa elements; C represents at least one element selected from rare earth elements; and 0 ≦ b < 1, 0 ≦ a < 1, -1 < n ≦ 10, and x > 0; and said tunneling layer comprises a bismuth-containing oxide represented by the formula: {(Bi 1-b C b )₂O₂}²⁺{Bi 1-a B a )₂(Ti 1-a A a )₃O₁₀}²⁻ n wherein: C represents at least one element selected from rare earth elements; B represents at least one element selected from the group consisting of Ca, Na, K, Ba, Sr, Pb and Pr; A represents at least one element selected from the group consisting of Nb, Ta, Fe, Sn and Ga; and 0 ≦ b < 1, 0 ≦ a < 1, and 1 ≦ n ≦ 5. The Josephson device according to claim 1, wherein said bismuth-copper-containing oxide superconductor has a layer-lattice structure such that a perovskite-like layer is positioned between {(Bi 1-b C b )₂O₂}²⁺ layers. The Josephson device according to claim 1, 2 or 3, wherein said bismuth-copper-containing oxide superconductor comprises a superconductor constituted of elements comprising Bi, Sr, Ca, Cu and O. A Josephson device according to any preceding claim, wherein the tunneling layer comprises a bismuth-containing oxide represented by the formula: Bi₂Sr₂LnCu₂O Y wherein Ln represents at least one element selected from the group consisting of Y and lanthanides; and 7 ≦ y ≦ 9. The Josephson device according to any preceding claim, wherein said bismuth-containing oxide is selected from an insulator compound, a normally conductive compound, a compound having a smaller critical current than that of said bismuth-copper-containing oxide superconductor and a compound having a lower critical temperature than that of said bismuth-copper-containing oxide superconductor. The Josephson device according to any preceding claim, wherein said lower and upper superconductive layers each have a layer thickness of from 200 nm to 500 nm (2,000 Å to 5000 Å). The Josephson device according to any preceding claim, wherein said tunneling layer has a layer thickness of from 1 nm to 50 nm (10 Å to 500 Å). The Josephson device according to any preceding claim, wherein the substrate is a MgO(100) single crystal or a SrTiO₃ single crystal.

Inventors: KANEKO NORIO, KAWASAKI TAKEHIKO, NIIZUMA KIYOZUMI, TANAKA ATSUKO, YAMAMOTO KEISUKE, KANEKO, NORIO, KAWASAKI, TAKEHIKO, NIIZUMA, KIYOZUMI, TANAKA, ATSUKO, YAMAMOTO, KEISUKE
Applicants: CANON KK, CANON KABUSHIKI KAISHA
Application year: 1989
Main classification: H01L39
IPC codes: H01L39