A functional superconductive photoelectric device

Abstract: A first type of functional superconductive photo-electric device of the invention is constituted with a superconductive thin film (5) having a photo-conductive effect located between two electrodes (6), and converting from a normally conducting state to a superconductive state in response to a light irradiation thereto, wherein the superconductive thin film (5) is formed of a compound semiconductor of Pb chalcogenide added with Pb and/or In more than its stoicheometry, such as Pb 1-x Sn x Te+In, so as to generate its precipitations. A second type of the functional superconductive photoelectric device of the invention is constituted with a photo-conductive material (21;31) formed of Pb 1-x Sn x Te filled in a gap between two superconductive electrodes (22a,22b;32a,32b), wherein the gap width (d) is shorter than 500 times of a coherence length of the super-conductivity. In either type of the invention, when a infrared light is irradiated onto the photo-conductive region (5,21;31) at a predetermined temperature, the coherence length of the superconductivity is extended so as to convert its normally conducting state to superconductive state. On ON/OFF of irradiation of a light shorter than 0.8 µm, Pb 1-x Sn x Te without In switches between the normally-conducting/superconducting states. With In addition, the material persistently converts the state from normally conducting state to the superconductive state.

Description: The present invention relates to a photoelectric device utilizing a superconducting transition temperature enhancement effect caused by a light irradiation thereto. More particularly, it relates to a superconducting photoelectric device which can be employed as a high speed light switch device, a photo detector or a light memory device. In recent years, the higher speed computer systems have been required, the higher speed of switching devices and memory devices have been required. As a high speed device to meet these requirements, there has been developed a superconductive transistor employing a Josephson junction. Switching operation of this transistor is carried out by electrically injecting electrons or positive holes into a semiconductor region located between superconductive regions. Accordingly,- it takes some time for the electrons or the positive holes to be injected thereto, resulting in a limit of its speed enhancement. Moreover, there has been proposed a superconductive photo-transistor which switches between its superconductive state and its normally conducting state in response to a light irradiation thereto, such as disclosed in Japanese Unexamined Patent Publication Sho 64-65884 or 63-239877. However, there has never been accomplished yet a superconductive device which switches from a normally conducting state to a superconductive state in response to a light irradiation thereto, that is logically reverse to that of the prior art device. Physics Letters, A, vol. 71A, no. 5,6,28 May 1979, pages 471-472, describes a photosensitive granular superconductor using CdS as the barrier between two superconducting electrodes. CdS is deposited on top of a discontinuous layer of In which after deposition of a second CdS film forms In islands. The critical temperature of the resulting composite material is enhanced by illumination of the film. The channels between the In islands are filled with CdS which produces Josephson coupling between the islands. Materials Science Forum Vols. 38-41 (1989), pages 531-536, discloses photoexcitation mechanism of electrons in narrow gap semiconductors doped with amphoteric deep impurities. There is discussed the influence of Sn referred to the value "X". "X" is referred to Pb for example. Single crystals of Pb 1-x Sn x Te grown by a vapor transport method are doped with indium (at 1 %) using an isothermal annealing. From Japanese Journal of Applied Physics, Supplements, vol. 26-31987, pages 1345 - 1346, superconductivity of lead chalcogenides with Pb inclusion is known as such. From Physical Review Letters, vol. 20, no. 23, 3 June 1968, pages 1286-1289, it is known that, if two conductors are separated by a sufficiently thin, evaporated CdS film, the observed tunnel current through the CdS film may be modulated by exposing the sample to a light source. If both conductors are metals in the superconducting state, it is possible to switch the CdS into a resistanceless state, the Josephson state, by exposing it to a light source. In Solid State Communication, vol. 76, no. 1, July 1990, pages 31-34, the electrical resistivity and the Hall coefficient of 1% In doped Pb 1-x Sn x Te (X=0.25) films with Pb precipitates are measured in the range of 1.5K<T<300K. In these films, the superconducting transition occurs below 6K because of the proximity effect by Pb grains. By exposure to light, a large photoconductivity excited from In impurity enhances the superconducting transition temperature. The enhancement will be understood by considering that the coherence length of superconductivity in semiconducting region is extended by the photo-carriers. It is the object of the present invention to provide a superconductive photoelectric device utilizing a rise in superconducting transition temperature caused by photo-carriers. The object is solved by the features of claim 1 and claim 5, respectively. Claims 2 to 4 and claims 6 to 10 comprise further developments of the invention. The invention will now be described with reference to the accompanying drawings, wherein like numerals refer to like parts throughout. In the drawings Figs. 1(a) and (b) schematically illustrate an operation principle of the functional superconductive photoelectric device according to the present invention; Fig. 2 is a perspective view of an example of a structure of the functional superconductive photoelectric device according to the present invention; Fig. 3 is a graph showing characteristic curves of the Fig. 2 device; Fig. 4 is a graph showing low temperature part of the Fig. 3 characteristic curves, in an expanded scale; Fig. 5 shows a principle circuit diagram employing the device of the present invention in its switching circuit; Figs. 6(a) and (b) show input-output waveforms in Fig. 5 circuit; and Figs. 7 and 8 show cross-sectional views of other functional devices of the present invention. The present invention is based on a principle that in a photo-conductive material filled in a gap between closely located superconductive regions, a light irradiation thereto causes coherence length of the superconductivity to extend so that the photo-conductive gap is bridged by the superconductive regions. In this principle, grain of the lead doped in the compound semiconductor of PbSnTe functions as a superconductive material and the PbSnTe semiconductor functions as a photo-conductive material. Figs. 1(a) and (b) show a model of the above-described function principle. In the Fig. 1(a) structure, grains, i.e. precipitations, of the doped Pb are spatially distributing like stepping stones in a thin film 1 formed of Pb 1-x Sn x Te or Pb 1-x Sn x Te+In semiconductor. In a normally conducting state where no light is irradiated to compound semiconductor thin film 1, superconducting region of the Pb grains pass over Josephson junction between the Pb grain and Pb 1-x Sn x Te+In semiconductor, so as to penetrate into the semiconductor region 1 as indicated with shaded area 3. Then, however, the coherence length of the Pb is not long enough to connect the Pb grains by the superconductive regions. On the other hand, when a light is irradiated onto compound semiconductor thin film 1, photo carriers generated in the Pb 1-x Sn x Te /In semiconductor cause an extend of the coherence length of the Pb from each of the Pb grains. Consequently, the shaded areas indicating the superconducting state expand so as to be continuous with each other as shown in Fig. 1(b), so that the whole compound semiconductor thin film 1 becomes superconductive. Accordingly, thus provided persistent superconductivity allows to provide a photo memory device. Fig. 2 shows an example of a practical structure of the functional superconductive photoelectric device according to the present invention. A substrate 4 is formed of barium-fluoride (BaF 2 ) measuring 1 mm x 5 mm, for example. Other materials, such as magnesium oxide (MgO), semi-insulative gallium-arsenide (GaAs) or silicon (Si), can be employed for the substrate material, in place of the BaF 2 . At first, a photo-conductive ternary semiconductor, such as Pb 1-x Sn x Te, as a superconductive thin film 5, is deposited upon substrate 4 as thick as typically 1 µm by a hot wall method. Next, electrodes 6a and 6b typically formed of gold (Au) or indium (In) are provided on both the ends of compound semiconductor thin film 5. Thus, a functional superconductive photoelectric device is fabricated. Other methods, such as vacuum deposition, liquid phase epitaxial grow method, molecular beam epitaxy (MBE) or metal organic chemical vapor deposition (MOCVD), may be employed for fabricating compound semiconductor thin film 5, in stead of the hot wall method. According to the measurements, by present inventors, of the switch function and the memory function of thus fabricated superconductive photoelectric device where a constant current source (not shown in the figures) is connected to electrodes 6a and 6b as well as a light is irradiated onto photo-conductive thin film 5 at very low temperatures, temperature dependence of resistivity of the photo-conductive thin film 5 is obtained as hereinafter described. The characteristics is measured with a sample employing Pb 0.75 Sn 0.25 Te+In, where the ratio of PbSn:Te is 51:49 and the In content is 1 % of PbSn, for photo-conductive thin film 5; thus, the Pb content is beyond the stochiometry; PbSn:Te = 50:50. The measure data is shown in Fig. 3, where the ordinate indicates the resistance value in ohm and the abscissa indicates the device temperature in degree K. Fig. 4 shows very low temperature part of Fig. 3 curves in an expanded scale in order to provide easier comprehension of the lower temperature characteristics, where the ordinate is normalized by the resistance value at 8 degree K. In the figures, the solid line indicates dark state characteristic, when no light is irradiated thereto; the dotted line indicates the characteristics when an infrared light of wavelength spectrum having the peak at approximately 10 µm wave length is irradiated thereto from a 300 degrees K (i.e. room temperature) black body; and the chain line indicates the characteristic when a 1 µm wavelength infrared light of 10 µW/cm 2 strength is irradiated from a GaAs LED (light emitting diode) onto the photo-conductive thin film 5. As observed in Fig. 4, the electrical resistance value of the above-described devices falls off at the temperature below 8 degrees K by an infrared light irradiation thereto, as well as the superconducting transition temperature T c shifts towards higher temperature, that is, the superconducting state is realized at a higher temperature. For example, at the device temperature 2 degrees K, photo-conductive thin film 5 is in a normally conductive state in the dark state as indicated by curve 11 ; however, under an infrared light irradiation thereto from an LED, photo-conductive thin film 5 becomes superconductive having zero resistance value as indicated by curve 13, where it is observed that the resistance value shifts as much as range R off . At 3 degrees K, under the infrared light irradiation it is observed that the resistance value falls off by a little over 50 % as shown by range R off '. This phenomena is explained in the same way as that of Fig. 1, as follows. In the compound semiconductor as a superconductive thin film, each of precipitations of the doped impurities (Pb), or grains born from the precipitations, forms a Josephson junction with the semiconductor material, where electrons in the semiconductor material are excited by the light irradiation thereto so as to rapidly increase the carrier concentration, which then causes the extend of the coherence length of the superconductivity from the Pb grains so that the coherence length reaches the same degree as the thickness of the barrier of the Josephson junction. Consequently, it is supposed that the whole semiconductor region becomes superconductive. Though it is observed that an approximately 2 % addition of Pb by weight is effective to enhance the superconducting transition temperature under the light irradiation, an addition of 1 to several percents of Pb also provides good results. Moreover, in the above-cited compound semiconductor the carrier concentration does not decrease, but keeping the superconducting state even after the light irradiation from the LED is discontinued. This is supposed to be owing to the contribution of the added In as an impurity. Accordingly, this compound semiconductor possessing a persistent photo-conductivity characteristic can be employed as a light memory device. When a shorter wavelength light than 0.8 µm is irradiated onto above-cited Pb 1-x Sn x Te semiconductor without In addition, the material does not exhibit the persistently superconductive characteristic, accordingly, can be employed as a switching device between the normally conducting state and the superconducting state in response to the existence of the light irradiation thereto. Fig. 5 shows a basic circuit configuration employing the above-described functional photoelectric device as an optical switch. An electrode 6a at a one side of device 14 shown above in Fig. 2 is connected to a power source 15, and an electrode 6b at the other side as an output terminal is connected to a high impedance user's circuit 16. Functional photoelectric device 14 is mounted in a cooling dewer (not shown in the figure), shielded from light irradiation and kept at a predetermined temperature between 2 to 4 degrees K. An infrared light LED 17 is placed to face photo-conductive thin film 5, for inputting a signal light thereto. According to ON/OFF-switching of the LED, the resistance value of the photo-conductive thin film 5 varies so as to generate a high speed ON/OFF-switched signal in user's circuit 16. LED 17 may be replaced with an output end of an optical fiber transmission line connected to a distant signal source. More practically, a plurality of light switch devices 14 can be combined so as to constitute a light logic circuit common for the user's circuit. An input-ouput characteristics of light switch device 14 is shown in Figs. 6, where in response to the input signal (i.e. the ON/OFF of the signal light) shown in Fig. 6(a) from signal source 18 an output signal shown in Fig. 6 (b) appears at output terminal 66 of the device 14. At an input light signal OFF-state, photo-conductive thin film 5 being at a normally conducting state keeps the output signal at V n level; on the contrary, at an input light signal ON-state, photo-conductive thin film 5 being converted to a superconductive state makes the output terminal rapidly rise to a superconductive level V s which is close to the power source voltage. Therefore, a threshold level V th provided in advance in the user's circuit, between these two voltages, allows detection of the output signal component. As is apparent from the principle described above, the present invention utilizes a proximity effect caused from the light excitation of the superconductive grains (Pb) added in the photo-conductive semiconductor; therefore, the material having the photo-conductive effect is not limited only to the above-recited PbSnTe; but also other semi-insulative materials (having a low carrier concentration), in which high carrier mobility as well as long life time of the carrier are accomplished, can provide a similar functional photoelectric device based on the same principle. Compound semiconductors, such as the above-recited Pb 1-x Sn x Te as well as other lead chalcogenides, such as PbCdTe (lead-cadnium-tellurium), PbSTe (lead-sulphor-tellurium) or PbSSe (lead-sulphor-selenium), possess a narrow band gap as well as a high carrier mobility, therefore, are suitable for a device which rapidly respond particularly to an infrared light. A III-V group high resistance material in which the high resistivity is accomplished with GaAs doped with chrome (Cr), highly purified GaAs, or indium-phosphorus (InP) doped with iron (Fe) may be employed as the switching device by being added with the superconductive grains. A II-VI group compound semiconductor, such as cadmium-tellurium (CdTe), mercury-cadmium-tellurium (HgCdTe) or cadmium-sulphur (CdS) may also alternatively employed thereto. Even in the above-cited case where GaAs or InP is employed, the persistently conductive photo-conductivity can be accomplished by introducing a DX center thereto. The above-described photo-conductive superconductive thin film can be considered that Josephson junctions are formed between the semiconductor base material and each of the countless superconductive grains. Therefore, even if the above-cited superconductive grains do not exist, a functional photoelectric device having the same function can be accomplished based on the same principle, when a particular structure of the superconductive electrodes is employed as described below. Fig. 7 shows a preferred embodiment of the case. A superconductive film 22 formed of, for example, neodymium-cerium-strontium-copper (NdCeSrCuO) is first deposited on a substrate 23. Next, a part of this film is removed to form a fine gap having a width d, by which two superconductive electrodes 22a and 22b are separated from each other. Next, a photo-conductive thin film 21 formed of PbSnTe doped with In to accomplish a high resistance is deposited to fill at least the gap between two superconductive electrodes 22a and 22b, so as to fabricate a functional superconductive photo-electric device. The gap width d is particularly chosen to be below 500 times of the coherence length of the superconductivity, in consideration that the extended coherence length of the superconductivity becomes continuous with each other excited by the light irradiation. For the case where PbSnTe is employed, the coherence length in a dark state is approximately 3 nm (30 angstrom.). Therefore, the gap width d is chosen to be 0.5 µm. Electrode terminals (not shown in the figure) are provided to both the superconductive electrodes 22a and 22b, to which a constant current source is connected to measure the characteristics. The device of this configuration also exhibits the switching characteristic as well as the memory effect. As an example of configurations, the structure shown in Fig. 8 is also effective. A photo-conductive film 31 formed of compound semiconductor of lead chalcogenide is coated uniformly upon a substrate 33, over which the same superconductive film 32 as described above is then formed. Next, a gap having the above-described width d is formed on a part of the superconductive film 32 so as to provide two superconductive electrodes 32a and 32b. It is apparent that a protective insulation film transparent to the input light may be further provided upon thus configurated device. As described above, according to the present invention a functional device, operatable at a higher speed than the conventional switching devices and memory devices employing prior art electrical signals, are achieved. Therefore, a compact as well as high speed logic device can be accomplished by combining the functional superconductive photoelectric device of the present invention with a light IC (integrated circuit). Moreover, its light-responding feature allows an application in a light detection apparatus handling an infrared light. More particularly, a device, accomplishing a characteristic that a normally conducting state is switched to a superconductive stated in response to a light irradiation according to the present invention, allows to constitute various high speed logic circuits by being combined with a conventional device having a logically contrary characteristic that the superconductive state is converted to a normally conducting state in response to a light irradiation. The many features and advantages of the invention are apparent from the detailed specification and thus, it is intended by the appended claims to cover all such features and advantages of the methods which fall within scope of the following claims. Further, since numerous modifications and changes will readily occur to those skilled in the art, it is not detailed to limit the invention and accordingly, all suitable modifications are equivalents may be resorted to, falling within the scope of the following claims.

Claims: A superconductive photoelectric device, constituted with a photo-conductive thin film (5) located between two superconducting electrodes (6, 6a, 6b), said photo-conductive thin film (5) converting from a normally conducting state to a superconductive state in response to a light irradiation thereto, is characterized in that : said photo-conductive thin film (5) is formed of a compound semiconductor of lead chalcogenide added with lead (Pb) or with lead (Pb) and indium (In) so excessive over stoichiometry as to precipitate grains of said lead or of said lead and indium, respectively, therein. A superconductive photoelectric device as recited in claim 1, characterized in that : said photo-conductive thin film (5) is formed of lead-tin-tellurium (PBSnTe), whereby said superconducting state caused from said light irradiation is continued even after said light irradiation is discontinued. A superconductive photoelectric device as recited in claim 2, wherein said photo-conductive thin film (5) is formed of lead-tin-tellurium Pb 1-x Sn x Te added with indium In as an impurity. A superconductive photoelectric device as recited in claim 3, wherein the value of x is substantially 0.25. A superconductive photoelectric device, constituted with a photo-conductive region (21) filling the gap between two superconductive regions (22a, 22b), said photoconductive film converting from a normally conducting state to a superconductive state in response to light radiation thereto, is characterized in that : said photo-conductive region is formed of a compound semiconductor of lead chalcogenide added with lead or indium and that the gap width between said superconductive regions (22a, 22b) is shorter than 500 times of the coherence length of the superconductive material of said superconductive regions. A superconductive photoelectric device as recited in claim 5, characterized in that : said photo-conductive region is formed of PbSnTe. A superconductive photoelectric device as recited in claim 5, characterized in that : said compound semiconductor photo-conductive region, added with lead or indium, is formed of a III-V group. A superconductive photoelectric device as recited in claim 7, wherein said III-V group compound semiconductor comprises gallium-arsenide (GaAs) and indium-phosphorus (InP). A superconductive photoelectric device as recited in claim 5, characterized in that : said compound semiconductor photo-conductive region, added with lead or indium, is formed of a II-VI group. A superconductive photoelectric device as recited in claim 9, wherein said II-VI group compound semiconductor comprises cadmium-tellurium (CdTe), mercury-cadmium-tellurium (HgCdTe) and cadmium-sulphor (CdS).

Inventors: MURASE KAZUO, OHTSUKI OSAMU, SHINOHARA KOJI, TAKAOKA SADAO, MURASE, KAZUO, OHTSUKI, OSAMU, SHINOHARA, KOJI, TAKAOKA, SADAO
Applicants: FUJITSU LTD, FUJITSU LIMITED
Application year: 1991
Main classification: H01L39
IPC codes: H01L39, H01L31