Method of manufacturing a compound semiconductor thin film on a substrate

The present invention relates to a method of manufacturing a compound semiconductor thin film by the thermal decomposition of a metal organic compound and a solar cell using the above thin film. An organic solvent solution of the metal organic compound containing at least one metal-sulfur bond is pulverized into fine particles by an ultrasonic vibration method or by a spray injection method and the obtained fine particles or gaseous metal organic compound are thermally decomposed by contacting them on the heated surface of a thin film forming substrate and thus a compound semiconductor metal sulfide thin film is formed on the thin film forming substrate. With this method, a compound semiconductor thin film of large surface area with uniform quality can be manufactured at low manufacturing cost with good reproducibility. These metal sulfide thin films are of high purity, high density and high quality and thus can be used for various photo-electronic devices.

BACKGROUND OF THE INVENTION
 This invention relates to a method of manufacturing a compound
 semiconductor thin film of a metal sulfide for photoelectric devices or
 solar cells, and solar cells using the compound semiconductor thin film as
 an n-type semiconductor layer.
 Compound semiconductor thin films consisting of metal sulfides, such as
 cadmium sulfide (CdS), zinc sulfide (ZnS), lead sulfide (PbS), copper
 sulfide (CuS), mercury sulfide (HgS) and so on, are extensively used for
 photoelectric device materials in the photoelectric device industry. For
 example, a CdS thin film has been used to construct a photo-conductive
 sensor and a photo-filter by utilizing the change of its electric
 resistance caused by the irradiation of light on an optical filter. Also,
 CdS/CdTe system compound semiconductor solar cells comprised of the thin
 films of CdS and CdTe have been commercialized.
 Many of these compound semiconductor thin films are manufactured by a
 sputtering method or a vacuum evaporation method, in which source
 materials are evaporated under reduced pressure and thin films are formed
 on a substrate. By using any of these methods, the desired thin film
 properties for photoelectric device materials can be obtained. However,
 since these methods have to be conducted in a vacuum chamber, they are not
 suitable for a high-speed continuous deposition of thin films with large
 surface area and with uniform thickness. If the investment for enabling
 the large scale deposition of thin films by any these method were made,
 the amount for this large and complex equipment would be prohibitively
 high.
 The chemical bath deposition method is a method with which compound
 semiconductor thin films of large surface area can be more inexpensively
 manufactured than by the above methods. For example, for manufacturing CdS
 thin film, a substrate is immersed in an aqueous solution containing both
 cadmium-containing compound such as cadmium acetate and sulfur-containing
 compound such as thiourea, and a CdS layer is deposited on the substrate.
 When the CdS layer is heat treated, it becomes dense and thus a CdS thin
 film is formed.
 With this method, a CdS thin film of large surface area can be
 manufactured, but the obtained CdS thin film is not uniform and the
 process lacks in reproducibility since the CdS layer cannot be uniformly
 deposited.
 As another method of depositing a thin film, Pyrosol process, based on the
 pyrolysis of an aerosol produced by ultrasonic spraying method, has been
 reported (Thin Solid Films. vol. 77. pp. 81-90(1981) ). This research is
 mainly directed to the deposition of metal oxides (In.sub.2 O.sub.3,
 Fe.sub.2 O.sub.3, SnO.sub.2 etc.) on a glass substrate by the pyrolysis
 using a metal organic compound as a source material.
 In this report, it is described that the deposition of other materials such
 as metal sulfides is also possible by the above-mentioned method. But,
 concerning the deposition of the metal sulfides such as CdS, it is only
 abstractly described that two (2) compounds, providing the metal and the
 sulfur respectively, are needed as source materials for such coating.
 Furthermore, this method of the deposition of the metal sulfides is
 considered to have various disadvantages, such as that it is very
 difficult to select these two source materials having the same thermal
 decomposition temperature and that it is very difficult to control the
 concentration of the provided metal and sulfur at the constant ratio.
 The printing and sintering method has been proposed with which compound
 semiconductor thin films of large surface area and with uniform thickness
 can be continuously manufactured by using inexpensive equipment with good
 reproducibility. In this method, a paste is prepared by dispersing fine
 particles of a compound semiconductor and then the paste is coated on a
 substrate in the form of a film by a screen printing method, dried and
 sintered in the furnace on a continuous moving belt.
 With this method, it is also possible to perform patterning during thin
 film formation. Consequently, this method is now practically used for the
 manufacture of CdS/CdTe system compound semiconductor solar cells which
 are comprised of the sintered thin films of CdS and CdTe (Japanese Patent
 Publication No. Sho 56-28386).
 In this case, a CdS thin film is manufactured by the following process.
 First, a paste is prepared by dispersing fine particles of CdS, added with
 cadmium chloride (CdCl.sub.2) as a reducing agent of the melting point, in
 a dispersing solvent such as propylene glycol and then the paste is coated
 on a substrate, dried and sintered and thus the Cds thin film is
 manufactured. However, this method has the following disadvantages.
 Since the required sintering temperature is as high as about 700.degree.
 C., a conventional inexpensive soda lime glass plate cannot be used as a
 substrate, it is necessary to use a substrate having both a high heat
 resistance and chemical stability, such as a ceramic sheet of alumina of
 high purity or a barium borosilicate glass, both of which are known as
 very expensive materials. It is not suitable for high speed mass
 production, since the sintering period required is often more than two (2)
 hours.
 Moreover, the sintering has to be performed in an inert gas atmosphere,
 such as in nitrogen gas, and by accommodating a dried substrate in an
 expensive ceramic case in order to suppress the quick evaporation of
 CdCl.sub.2. Additionally, since a source material of CdS powder can only
 be pulverized into fine particles of 2 to 4 .mu.m, it is not possible to
 manufacture a film of thinner than 2 to 4 .mu.m, which is a diameter of
 pulverized CdS fine particles. Normally, CdS film as per manufactured by
 this method has a thickness of 20 to 60 .mu.m. Its surface is often
 irregular and has a number of void spaces inside of the film.
 Consequently, it is not possible to obtain a thin film of uniform quality.
 Since a compound semiconductor thin film which is manufactured by the
 printing and sintering method is relatively thick with a number of void
 spaces insides, it has a low light transmittance. Consequently, when this
 thin film is used as an n-type semiconductor layer of a solar cell, the
 solar cell cannot have an acceptable photoelectric conversion efficiency.
 Recently, another method of manufacturing a compound semiconductor thin
 film of a metal sulfide is proposed in which a metal organic compound
 containing at least one metal-sulfur bond is thermally decomposed. This
 method is advantageous in that an inexpensive soda lime glass plate can be
 used as a thin film forming substrate since film forming temperature is
 lower than that required for the sintering in the printing and sintering
 method.
 Example of the concrete method of manufacturing the thin film by using this
 method is as follows. First, the metal organic compound layer is formed on
 a substrate and then a thin film of a metal sulfide is formed on the
 substrate by thermally decomposing the metal organic compound in an inert
 gas atmosphere or in a mixed gas atmosphere of an inert gas and hydrogen
 sulfide(H.sub.2 S) (Japanese Laid-Open Patent Publication Nos. Sho
 61-166979 and Sho 61-166978).
 However, this method has various disadvantages such as the metal organic
 compound is not completely decomposed in the inert gas atmosphere and as a
 result, black organic ingredients containing carbon or carbon compound
 remain in the thin film as performed.
 In order to solve the above problem, another concrete method is proposed
 with which a solution of the metal organic compound is coated on the
 substrate by, for example, spin coating method and a metal sulfide thin
 film is formed on the substrate by thermally decomposing the metal organic
 compound in oxygen containing atmosphere. (Japanese Laid-Open Patent
 Publication No. Sho 62-146276).
 Another concrete method is proposed with which an organic solvent solution
 of the metal organic compound, the solution having a viscosity of a
 specified range, is coated on the substrate by a printing method, dried
 and a metal sulfide thin film is formed on the substrate by thermally
 decomposing the metal organic compound. (Japanese Laid-Open Patent
 Publication No. Hei 8-316247).
 However, any of these two (2) concrete methods have various disadvantages,
 such as it is very difficult to uniformly coat a solution of the metal
 organic compound on the substrate of large surface area and thus it was
 not possible for a metal sulfide thin film with large surface area and
 with uniform thickness to be manufactured in an industrial scale.
 In these two methods, it is aimed to manufacture a thin film of high purity
 with few residual ingredients by sufficiently oxidizing the metal organic
 compound during the thermal decomposition in oxygen containing atmosphere
 and thus removing all ingredients other than metal and sulfur by
 vaporization of the ingredients.
 However, it was very difficult to manufacture a thin film of acceptable
 high purity since it is difficult to completely oxidize and thermally
 decompose the whole metal organic compound especially which is present in
 the proximity of the surface of the substrate among the coated layer of
 the organic solvent solution. It was often the case that some amount of
 impurities remained.
 In addition to these methods, another concrete method of manufacturing a
 compound semiconductor thin film by thermal decomposition is proposed with
 which a paste containing the metal organic compound containing at least
 one metal-sulfur bond is coated on a source substrate and the metal
 organic compound is vaporized by heating the source substrate. Then, the
 gaseous metal organic compound is thermally decomposed by contacting the
 gaseous metal organic compound at the heated surface of a thin film
 forming substrate which is placed opposite to the proximity of the source
 substrate, and a metal sulfide thin film is formed on the thin film
 forming substrate. (Japanese Laid-Open Patent Publication Nos. Hei 9-74065
 and Hei 10-4206 and U.S. Pat. No. 5,714,391).
 However, this method has various disadvantages, such as manufacturing cost
 of the thin film is very expensive since the source substrate is necessary
 in addition to the thin film forming substrate and also a complicated
 coating process of the paste on the source substrate is necessary.
 Moreover, it is difficult to uniformly contact the gaseous metal organic
 compound at the surface of the thin film forming substrate and to supply
 the center part of the surface of the thin film forming substrate with
 sufficient amount of oxygen. Consequently, it was difficult to manufacture
 the thin film with uniform thickness, high purity and large surface area
 by this method.
 BRIEF SUMMARY OF THE INVENTION
 An object of the present invention is to provide an industrial method of
 manufacturing a compound semiconductor thin film of a metal sulfide with
 large surface area, uniform quality, high density and high purity at low
 manufacturing cost with acceptable reproducibility.
 Another object of the present invention is to provide a solar cell with
 both low manufacturing cost and high photoelectric conversion efficiency
 by constructing the solar cell by using the compound semiconductor thin
 film which is manufactured by the above-mentioned method.
 A method of manufacturing a compound semiconductor thin film according to
 the present invention comprises the steps of pulverizing an organic
 solvent solution of a metal organic compound containing at least one
 metal-sulfur bond into fine particles, thermally decomposing the obtained
 fine particles by contacting them at the surface of a heated thin film
 forming substrate and thus forming a compound semiconductor thin film of a
 metal sulfide on the substrate.
 Another method of manufacturing a compound semiconductor thin film
 according to the present invention comprises the steps of pulverizing an
 organic solvent solution of a metal organic compound containing at least
 one metal-sulfur bond into fine particles, vaporizing the organic solvent
 by heating the fine particles, vaporizing the metal organic compound into
 gaseous bodies by heating further, thermally decomposing the obtained
 gaseous metal organic compound by contacting the gaseous metal organic
 compound at the surface of a heated thin film forming substrate, and thus
 forming a compound semiconductor thin film of a metal sulfide on the
 substrate.
 Solar cells according to the present invention are compound semiconductor
 solar cells by using a compound semiconductor metal sulfide thin film, the
 thin film being manufactured by the method of the present invention, as an
 n-type semiconductor layer.
 While the novel features of the invention are set forth particularly in the
 appended claims, the invention, both as to organization and content, will
 be better understood and appreciated, along with other objects and
 features thereof, from the following detailed description taken in
 conjunction with the drawings.

DETAILED DESCRIPTION OF THE INVENTION
 The present invention makes the use of advantages of the method for
 manufacturing a metal sulfide thin film by thermal decomposition methods
 and solves above-mentioned various problems involved in the conventional
 methods.
 In a method of manufacturing a compound semiconductor thin film according
 to the present invention, first an organic solvent solution of a metal
 organic compound containing at least one metal-sulfur bond is pulverized
 into fine particles and the obtained fine particles are contacted at the
 surface of a thin film forming substrate which is heated to the
 temperature higher than the thermal decomposition temperature of the metal
 organic compound.
 In this way, the metal organic compound contained in the fine particles is
 thermally decomposed at the surface of the substrate or at its proximity,
 and thus a compound semiconductor metal sulfide thin film is formed on the
 surface of the substrate.
 When the above-mentioned method of manufacturing according to the present
 invention is used, the organic solvent solution of the metal organic
 compound is uniformly contacted at the surface of the substrate in the
 form of fine particles, and thus the metal organic compound is thermally
 decomposed uniformly on the whole part of the surface.
 As a result, a metal sulfide thin film of large surface area with uniform
 thickness can be formed. Since the metal organic compound is thermally
 decomposed in the form of fine particles, it is decomposed without
 remaining any ingredients which are not decomposed. In this way, a metal
 sulfide thin film of high density, high purity and high light
 transmittance is formed without containing any residual ingredients
 insides such as carbon. Moreover, since these thin films can be formed in
 the air by using an inexpensive equipment, a metal sulfide thin film at
 low manufacturing cost can be obtained.
 In another method of manufacturing a compound semiconductor thin film
 according to the present invention, first an organic solvent solution of a
 metal organic compound containing at least one metal-sulfur bond is
 pulverized into fine particles and the obtained fine particles are heated
 to the temperature which is close to the boiling point of the organic
 solvent, and also which is not higher than the melting point or the
 sublimation point of the metal organic compound. In this way, only the
 organic solvent in the fine particles is vaporized and the metal organic
 compound is separated from the organic solvent solution.
 Next the fine particles of the metal organic compound in a solid state are
 heated to the temperature of higher than the boiling point or the
 sublimation point of the metal organic compound but of below the thermal
 decomposition temperature and are vaporized into gaseous bodies via liquid
 state or by direct sublimation.
 When the obtained gaseous metal organic compound is contacted at the
 surface of a thin film forming substrate which is heated to the
 temperature higher than the thermal decomposition temperature of the metal
 organic compound and the metal organic compound is thermally decomposed, a
 compound semiconductor metal sulfide film is formed on the surface of the
 substrate.
 In this method, the gaseous metal organic compound, which means molecules
 of the metal organic compound, is contacted at the surface of the
 substrate. Consequently, the metal organic compound is thermally
 decomposed on the whole part of the surface more uniformly and more
 completely than in the above-mentioned first method. As a result, a
 compound semiconductor thin film of large surface area with more uniform
 thickness and higher purity than that formed in the first method is
 manufactured.
 In addition, compared with the first method, in which the fine particles of
 the organic solvent solution of the metal organic compound are contacted
 at the surface of the substrate, the gaseous metal organic compound is
 contacted at the surface of the substrate in this method. Therefore, the
 temperature of the surface of the substrate little decreases by the
 contact.
 Consequently, it is possible to control the temperature of thermal
 decomposition reaction of the metal organic compound more precisely than
 in the first method, and thus, in this method, a compound semiconductor
 thin film of high density and of high quality is manufactured, in which
 metal sulfide molecules are regularly arranged on the substrate.
 The organic solvent solution of the metal organic compound is preferred to
 be pulverized into fine particles by an ultrasonic vibration method or by
 a spray injection method.
 When the ultrasonic vibration method is used for pulverization into fine
 particles, it is easy to control the average diameter of fine particles by
 suitably adjusting the frequency of the ultrasonic vibration according to
 the properties of the organic solvent solution of the metal organic
 compound.
 When the average diameter of the fine particles is controlled to be within
 a suitable range, it becomes possible to quickly vaporize both the organic
 solvent and the metal organic compound contained in the fine particles,
 before the fine particles reach the heated surface of the substrate.
 Consequently, it becomes possible to thermally decomposes themetal organic
 compound more uniformly on the whole surface than when the average
 diameter is not suitably controlled. In this way, it becomes possible to
 form a compound semiconductor thin film with uniform and high quality. In
 order to achieve the above, it is preferred to control the average
 diameter of the fine particles of the metal organic compound to be in a
 range of 1 to 20 .mu.m.
 When the average diameter is below 1 .mu.m, thermal decomposition reaction
 is liable to occur before the metal organic compound reaches the surface
 of the substrate. Consequently, it is difficult to form a metal sulfide
 thin film of acceptable quality on the substrate. When the average
 diameter is over 20 .mu.m, the metal organic compound is not uniformly
 decomposed on the surface of the substrate. Consequently, it is difficult
 to form a metal sulfide thin film of uniform quality on the substrate.
 The above mentioned average diameter (D) of the fine particles is expressed
 by the following formula:
EQU D=.SIGMA.nd.sup.3 /.SIGMA.nd.sup.2
 where n is a number of fine particles which are present in each range
 obtained by dividing the range between largest diameter and smallest
 diameter by a factor of 10, d is a median value of diameters in respective
 divided range.
 Particle sizes of the obtained the fine particles can be measured by using
 a Laser method. In this method, particle sizes or particle size
 distribution can be measured from diffraction images which are formed by
 the interference of Laser lights which are scattered by the edges of fine
 particles which are present in the path of Laser lights.
 The average diameter of the fine particles which are produced by the
 ultrasonic vibration mainly depends on the frequency of the ultrasonic
 vibration. However, it also depends on both the specific gravity and the
 surface tension of the organic solvent solution of the metal organic
 compound.
 For example, in case of the toluene solution in which cadmium dibutyl
 dithiocarbamate is dissolved at the concentration of 17 to 20 wt % and
 with a viscosity of the solution being 0.85 to 0.95 centipoise (cP), it is
 possible to pulverize the toluene solution into the preferred range of 1
 to 20 .mu.m of the average diameter, when a frequency of the ultrasonic
 vibration is controlled to be in a range of 10 kHz to 3 MHz.
 When the frequency of the ultrasonic vibration is over 3 MHz, the average
 diameter of fine particles becomes below 1 .mu.m. When the frequency of
 the ultrasonic vibration is below 10 kHz, the average diameter of the fine
 particles becomes over 20 .mu.m.
 A spray injection method is another preferred method of pulverization into
 fine particles of the organic solvent solution of the metal organic
 compound. This method is advantageous in that the organic solvent solution
 can be pulverized into the fine particle by using inexpensive equipment.
 In addition, it is possible to pulverize the organic solvent solution of
 the metal organic compound with higher concentration and with higher
 viscosity by this method than by the ultrasonic vibration method.
 Consequently, it is advantageous that a compound semiconductor thin film
 can be formed in higher speed by using this method than by using the
 ultrasonic vibration method.
 When the organic solvent solution of the metal organic compound is
 pulverized into the fine particles by the spray injection method, it is
 also preferred to control the average diameter of the fine particles to be
 in a range of 1 to 20 .mu.m by the same reasons as in case of the
 pulverization by the ultrasonic vibration method.
 The metal organic compounds applicable to the present invention are these
 compounds containing at least one metal-sulfur bond, the metal being at
 least one metal selected from the group consisting of cadmium (Cd), zinc
 (Zn), copper (Cu), lead (Pb) and mercury (Hg).
 The type of such metal organic compounds as applicable to the present
 invention can be metal mercaptide, metal thioate, metal dithioate, metal
 thiocarbonate, metal dithiocarbonate, metal trithiocarbonate, metal
 thiocarbamate, metal dithiocarbamate, and so on.
 The metal organic compounds containing carbon and nitrogen, in addition to
 sulfur and metal, are preferably applicable to the present invention. When
 the metal organic compound contains both carbon and nitrogen, a metal
 sulfide thin film formed by the thermal decomposition of the metal organic
 compound especially strongly sticks to the surface of the substrate and
 also densely deposited on the surface. Consequently, a metal sulfide thin
 film with higher quality can be formed. More especially, when the metal
 thiocarbamate or metal dithiocarbamate is used, a metal sulfide thin film
 with very high quality can be formed.
 Many of above-mentioned metal organic compounds are thermally decomposed
 below 500.degree. C. and metal sulfides are produced. Consequently, in the
 present invention, a substrate material can be selected from wider variety
 of materials than in the conventional printing and sintering method. For
 example, these inexpensive materials with relatively low heat resistance,
 such as soda lime glass or low alkaline borosilicate glass, can be used as
 the substrate material.
 When cadmium organic compounds are used out of the above-mentioned metal
 organic compounds, since they have the thermal decomposition temperature
 of 300 to 350.degree. C., the surface temperature of the CdS thin film
 forming substrate is preferred to be kept in a range of 300 to 500.degree.
 C.
 When the surface temperature of the substrate is within the above range,
 the cadmium organic compound can be thermally decomposed in high
 efficiency. Consequently, it becomes possible to form a CdS thin film with
 high quality in a short period and with high yield rate.
 When the surface temperature of the substrate is below 300.degree. C., the
 cadmium organic compound is difficult to be thermally decomposed on the
 surface of the substrate. Consequently, a CdS thin film is difficult to be
 formed. When the surface temperature is over 500.degree. C., the cadmium
 organic compound is thermally decomposed very rapidly. Consequently, it is
 difficult to form a CdS thin film with uniform and high quality.
 Organic solvents for dissolving the metal organic compounds as applicable
 to the present invention can be the one selected from the group consisting
 of 1-methyl-2-pyrrolidone, xylene, toluene, .gamma.-butyrolactone,
 tetralin, dimethyl formamide, dimethyl sulfoxide, chloroform, and
 alcohols, such as methyl alcohol, ethyl alcohol and multi-valent alcohols.
 The mixed solvent consisting of more than two (2) kinds of the above
 solvents can also be used. For example, a mixed solvent of
 1-methyl-2-pyrrolidone and methyl alcohol at the mol ratio of 8:2 can be
 used as a solvent for dissolving cadmium dibenzyl dithiocarbamate. A mixed
 solvent of 1-methyl-2-pyrrolidone and butyl alcohol at the mol ratio of
 6:4 can be used as a solvent for dissolving cadmium thiobenzoate.
 When these organic solvents are used, the above metal organic compounds can
 be dissolved in the solutions in a high concentration, and therefore a
 compound semiconductor thin film can be formed at high speed.
 Moreover, since the metal sulfide thin film which is manufactured using the
 method of the present invention has high quality and high light
 transmittance, the solar cells which are constructed by using the above
 metal sulfide thin film as an n-type semiconductor layer show high
 photoelectric conversion efficiency.
 An example of the solar cell according to the present invention can be
 constructed as follows;
 A transparent conductive film consisting of such metal oxide as tin oxide
 (SnO.sub.2), indium-tin oxide (ITO) or zinc oxide is formed on one side
 surface of the transparent substrate such as glass plate. A compound
 semiconductor metal sulfide thin film is formed on the transparent
 conductive film by the method of the present invention, as an n-type
 semiconductor layer. Then, on the n-type semiconductor layer, a cadmium
 telluride (CdTe) thin film is formed as a p-type semiconductor layer, and
 thus a p-n junction is constructed.
 After that, a current collector is formed on the p-type semiconductor film,
 and a positive electrode is formed which is electrically connected with
 the current collector. Finally, a negative electrode which is electrically
 connected with the n-type semiconductor layer is formed. In this way, a
 compound semiconductor solar cell can be constructed.
 Another example of the solar cell according to the present invention can be
 constructed as follows;
 A positive electrode is formed on a substrate which has both electric
 conductivity and heat resistance, and a CdTe or copper-indium-selenide
 (Cu--In--Se, CIS) thin film is formed on the positive electrode as a
 p-type semiconductor layer. Then, a compound semiconductor metal sulfide
 thin film is formed on the p-type semiconductor layer by the method of
 present invention, as an n-type semiconductor layer, and thus a p-n
 junction is constructed. Finally, a negative electrode is formed which is
 electrically connected with the n-type semiconductor layer. In this way, a
 compound semiconductor solar cell can be constructed.
 In this case, the substrates which have both electric conductivity and heat
 resistance include a copper plate, or a sheet of copper, iron, stainless
 steel, aluminum or an insulating sheet which are plated with copper,
 silver, platinum, palladium or molybdenum on one side surface of the
 sheets.
 Details of the equipment for manufacturing a compound semiconductor thin
 film according to the present invention are described below by referring
 to the attached drawings of FIG. 1, FIG. 2 and FIG. 3.
 FIG. 1 shows an example of the equipment for manufacturing a compound
 semiconductor thin film according to the present invention.
 A transparent conductive film 2 is formed on one side surface of a
 substrate 1 which has high heat resistance. The substrate 1 is placed on a
 heater 10 and it is heated to the temperature at which a metal organic
 compound is thermally decomposed. A compound semiconductor thin film 3 is
 formed on the transparent conductive film 2.
 A vessel 4 is placed at a separate place from the substrate 1, and it is
 filled with an organic solvent solution 9 of the metal organic compound. A
 tube which is stretched from a carrier gas inlet 7 is connected to the
 upper empty space of the vessel 4. An ultrasonic vibration device 5 is
 placed at the bottom of the vessel 4. The vessel 4 and the substrate 1 are
 connected together by a tube 8. The end portion of the tube 8 of the
 substrate side is enlarged to the width which can just cover the substrate
 1.
 When the ultrasonic vibration device 5 is vibrated, the organic solvent
 solution 9 of the metal organic compound is pulverized into fine particles
 and upper empty space of the vessel 4 is filled with the fine particles.
 These fine particles are transported through the tube 8 by a carrier gas
 which is introduced from the carrier gas inlet 7 to the surface of the
 substrate 1, where they are injected. Then, the metal organic compound is
 thermally decomposed on the surface of the substrate 1 or at its
 proximity, and the compound semiconductor thin film 3 is formed on the
 transparent conductive film 2, which is formed in advance on the substrate
 1.
 FIG. 2 shows another example of the equipment for manufacturing a compound
 semiconductor thin film according to the present invention.
 A transparent conductive film 2 is formed on one side surface of a
 substrate 1 which has high heat resistance. The substrate 1 is placed on a
 heater 10 and it is heated to the temperature at which a metal organic
 compound is thermally decomposed. Facing to the substrate 1, a nozzle 12
 is placed, whose bottom part is provided with an injection outlet 6 of an
 organic solvent solution 9 of the metal organic compound. The nozzle 12 is
 also connected with a first tube which is stretched from a vessel 4 filled
 with the organic solvent solution 9 of the metal organic compound and with
 a second tube which is stretched from a carrier gas inlet 7.
 When a carrier gas is supplied from the carrier gas inlet 7 to the
 injection outlet 6, the organic solvent solution 9 of the metal organic
 compound in the vessel 4 is injected in the form of fine particles from
 the injection outlet 6. Then, injected fine particles contact at the
 surface of heated substrate 1 and are thermally decomposed on the surface
 of substrate 1 or at its proximity. In this way, produced metal sulfides
 deposit on the transparent conductive film 2 and a compound semiconductor
 thin film 3 is formed.
 FIG. 3 shows other example of the equipment for manufacturing a compound
 semiconductor thin film according to the present invention.
 A transparent conductive film 2 is formed on one side surface of a
 substrate 1 which has high heat resistance. The substrate 1 is placed on
 the heater 10 and it is heated to the temperature at which a metal organic
 compound is thermally decomposed. A compound semiconductor thin film 3 is
 formed on the transparent conductive film 2.
 A vessel 4 is placed at a separate place from the substrate 1, and it is
 filled with an organic solvent solution 9 of the metal organic compound. A
 tube which is stretched from a carrier gas inlet 7 is connected to the
 upper empty space of the vessel 4. An ultrasonic vibration device 5 is
 placed at the bottom of the vessel 4. The vessel 4 and the substrate 1 are
 connected together by a tube 8. The end portion of the tube 8 of the
 substrate side is enlarged to the width which can just cover the substrate
 1.
 In this enlarged portion, both a first heating zone 15, where the organic
 solvent is vaporized, and a second heating zone 16, where the metal
 organic compound is vaporized into gaseous bodies, are provided. Around
 the tube of the first heating zone 15, a heater 17 is provided which heats
 up the first heating zone 15. With this heater 17, a temperature of
 heating zone 15 is controlled to the temperature at which the organic
 solvent is vaporized. Around the tube of the second heating zone 16, a
 heater 18 is provided which heats up the second heating zone 16. With this
 heater 18, a temperature of the second heating zone 16 is controlled to
 the temperature at which the metal organic compound is vaporized into
 gaseous bodies.
 When the ultrasonic vibration device 5 is vibrated, the organic solvent
 solution 9 of the metal organic compound is pulverized into fine particles
 and upper empty space of the vessel 4 is filled with the fine particles.
 These fine particles are transported through a tube 8 by a carrier gas,
 which is introduced from the carrier gas inlet 7, to the first heating
 zone 15. At this first heating zone 15, mainly the organic solvent is
 vaporized and separated from the metal organic compound.
 When solid state fine particles of the metal organic compound reach the
 second heating zone 16, they are vaporized at this second heating zone.
 Then, the gaseous fine particles are injected on the surface of the
 substrate 1 which is heated up in advance and the metal organic compound
 is thermally decomposed on the surface of the substrate 1 or at its
 proximity. In this way, the compound semiconductor thin film 3 is formed
 on the transparent conductive thin film 2 which is formed in advance on
 the substrate 1.
 A temperature of the first heating zone 15 is preferred to be controlled to
 that which is close to the boiling point of the organic solvent used, and
 also which is not higher than the sublimation point or the melting point
 of the metal organic compound used.
 A temperature of the second heating zone 16 is preferred to be controlled
 to that which is close to the sublimation point or the boiling point of
 the metal organic compound used.
 When the temperatures of both the first heating zone 15 and the second
 heating zone 16 are controlled to the higher temperature than the thermal
 decomposition temperature of the metal organic compound used, the metal
 organic compound thermally decomposes before it reach the surface of the
 substrate 1. Consequently, it is not possible to effectively form the
 compound semiconductor thin film 3 on the transparent conductive film 2.
 In any of the above methods, the thermal decomposition reaction of the
 metal organic compound is preferred to be performed in oxygen containing
 atmosphere. Consequently, in addition to the air, a mixed gas of oxygen
 with inert gases such as nitrogen, argon, helium, and neon can be used.
 When the reaction furnace is filled with the air in advance only the inert
 gases can be used as the carrier gas.
 And in any case of the above methods, a variety of insulating or conductive
 substrate which has high heat resistance can arbitrarily be used as the
 thin film forming substrate, other than a conductive substrate which is
 prepared by forming a transparent conductive film on a insulating plate
 such as glass plate.
 The more details of the present invention are described below by referring
 to actual examples of the methods of manufacturing compound semiconductor
 thin films and the solar cells constructed by using the thin films
 manufactured by the above methods.
 EXAMPLE 1
 A compound semiconductor CdS thin film was formed by using the equipment
 which is shown in FIG. 1. A transparent conductive SnO.sub.2 film 2 was
 formed on one side surface of a substrate 1 consisting of a soda glass
 plate of 35.times.35 cm.sup.2 and used this as a thin film forming
 substrate. Cadmium dibenzyl dithiocarbamate was dissolved in
 1-methyl-2-pyrrolidone at the concentration of 2.0 mol/l. This solution
 was used as the organic solvent solution 9 of the metal organic compound.
 The viscosity of the solution 9 was about 50 cP.
 The solution 9 was poured in the vessel 4 and was pulverized into fine
 particles with average particle diameter of 6 .mu.m, by using the
 ultrasonic vibration with a frequency of 2 MHz. Since the thermal
 decomposition temperature of cadmium dibenzyl dithiocarbamate is about
 340.degree. C., the temperature of the surface of the substrate 1 was
 controlled to be at 400.degree. C. Air was used as the carrier gas and the
 compound semiconductor CdS thin film 3 was formed on the transparent
 conductive film 2. Necessary time period for forming the CdS thin film 3
 was 210 sec.
 The obtained CdS thin film was analyzed by X ray photo-electronic
 spectroscopy method. When the amount of residual carbon inside the thin
 film, which often causes a reduction of light transmittance, was measured
 on the obtained thin film, only a trace (below 1 atom %) was found and
 thus the obtained thin film was proved to be of high purity.
 The obtained CdS film was divided into nine (9) equal portions as shown in
 FIG. 4 and a film thickness in each portion was measured. Results are
 shown in Table 1.
 TABLE 1
 Thickness of thin film
 Portion No. (.Arrow-up bold.)
 1 500
 2 520
 3 540
 4 510
 5 520
 6 540
 7 510
 8 520
 9 530
 As shown in Table 1, the thickness of the obtained CdS thin film controlled
 to be in a small range of 500 to 540 anstrom.
 EXAMPLE 2
 A compound semiconductor CdS thin film was formed by using the equipment
 which is shown in FIG. 3. The substrate 1 and the conductive film 2 was
 prepared in the same way as in Example 1. Cadmium dibenzil dithiocarbamate
 was dissolved in xylene at the concentration of 2.0 mol/l. This solution
 was used as the organic solvent solution 9 of the metal organic compound.
 The viscosity of the solution 9 was about 50 cP.
 The solution 9 was poured in the vessel 4 and was pulverized into the fine
 particles with average particle diameter of 6 .mu.m by using an ultrasonic
 vibration with a frequency of 2 MHz. The temperature of first heating zone
 15 was controlled to be about 150.degree. C., the temperature of second
 heating zone was controlled to be about 300.degree. C. and the temperature
 of the surface of the substrate 1 was controlled to be 400.degree. C.
 In this condition, a compound semiconductor CdS thin film 3 was formed on
 the transparent conductive film 2 by using air as the carrier gas. The
 above respective temperatures were chosen based on the facts that the
 boiling point of xylene is 138.degree. C., the melting point, the boiling
 point, and the thermal decomposition temperature of cadmium dibenzyl
 dithiocarbamate are 195.degree. C., about 300.degree. C. and about
 350.degree. C. respectively. Necessary time period for forming the CdS
 thin film was 180 sec.
 When the amount of residual carbon inside the film was measured on the
 obtained thin film in the same way as used in Example 1, it was not
 detected at all. Consequently, the obtained thin film was proved to be of
 higher purity than the one obtained in Example 1.
 The obtained CdS thin film was divided into nine (9) equal portions as
 shown in FIG. 4 and a film thickness in each portion was measured. Results
 are shown in Table 2.
 TABLE 2
 Thickness of thin film
 portion No. (.Arrow-up bold.)
 1 510
 2 520
 3 510
 4 510
 5 510
 6 510
 7 520
 8 500
 9 510
 As shown in Table 2, the thickness of the obtained CdS thin film was
 controlled to be in a small range of 500 to 520 angstrom. It means that
 the thickness of the obtained CdS thin film was controlled to be in a
 narrower range than that obtained in Example 1.
 COMATIVE EXAMPLE 1
 A Cds thin film was formed on the same thin film forming substrate as used
 in Example 1 by using conventional vacuum evaporation method. A pellet was
 prepared by molding CdS powder of high purity and used as a target. The
 distance between the target and the substrate was adjusted to be 100 mm
 and the Cds thin film was formed at the condition of 10.sup.-6 Torr and
 350.degree. C.
 The obtained CdS thin film was divided into nine (9) equal portions as
 shown in FIG. 4 and a film thickness in each portion was measured. Results
 are shown in Table 3.
 TABLE 3
 Thickness of thin film
 Portion No. (.Arrow-up bold.)
 1 500
 2 550
 3 550
 4 580
 5 600
 6 520
 7 510
 8 550
 9 510
 As shown in Table 3, the thickness of the obtained CdS thin film widely
 dispersed in a range of 500-600 angstrom. It means that the Cds thin films
 which are obtained in Example 1 and Example 2 have more uniform film
 thickness than that obtained in Comparative Example 1.
 COMATIVE EXAMPLE 2
 A Cds thin film was formed on the same thin film forming substrate as used
 in Example 1 by using a conventional thermal decomposition method of the
 metal organic compound. In this method, an organic solvent solution of the
 metal organic compound is coated on the substrate, dried and then
 thermally decomposed to form the CdS thin film on the SnO.sub.2
 transparent conductive film.
 Cadmium dibenzyl thiocarbamate was dissolved in 1-methyl-2-pyrrolidone at
 the concentration of 0.4 mol/l. The viscosity of this solution was about
 10 cP. The solution was coated by roll-coater on the SnO.sub.2 film which
 was formed on the substrate. Then, it was dried at 150.degree. C. and
 thermally decomposed for 120 sec. at 450.degree. C. in air. In this way,
 the CdS thin film was formed on the SnO.sub.2 film.
 When the amount of residual carbon inside the film was measured on the
 obtained CdS thin film in the same way as used in Example 1, it was found
 to be 6 to 9 atom %. It means that higher amount of impurities are
 contained in this thin film than in the thin films obtained in Example 1
 and Example 2, respectively.
 The obtained CdS thin film was divided into nine (9) equal portions as
 shown in FIG. 4 and a film thickness in each portion was measured. Results
 are shown in Table 4.
 TABLE 4
 Thickness of thin film
 Portion No. (.Arrow-up bold.)
 1 500
 2 540
 3 500
 4 580
 5 570
 6 580
 7 510
 8 550
 9 520
 As shown in Table 4, the thickness of the obtained CdS thin film widely
 dispersed in a range of 500 to 580 angstrom. It means that the Cds thin
 films which are obtained in Example 1 and Example 2 have more uniform film
 thickness than that obtained in Comparative Example 2.
 EXAMPLE 3
 Cds thin films were formed in the same way as in Example 1, using various
 cadmium organic compounds which are shown in Table 5. When the obtained
 CdS thin films were analyzed by X ray photo-electronic spectroscopy, it
 was found that the condition of cadmium-sulfur bond in the thin films was
 the same as the condition of cadmium-sulfur bond in a single crystal of
 CdS.
 When the obtained CdS thin films were analyzed by X ray diffraction method,
 reflection peaks which are ascribed to (002) face were observed, and thus
 the obtained CdS thin films were identified to be constructed from
 hexagonal CdS crystals.
 Furthermore, when Cd organic compounds which contain carbon and nitrogen,
 such as Cd diethyl dithiocarbamate, Cd dibutyl dithiocarbamate, Cd
 dibenzyl dithiocarbamate, and Cd thiocarbamate, were used as the source
 material, the peaks of (002) face of the obtained CdS thin films were
 sharper and their half-width were smaller than that of the other obtained
 CdS thin films. It proves that the above CdS thin films obtained from the
 Cd organic compounds containing carbon and nitrogen are especially highly
 crystallized and very dense.
 Transmission spectrum of the obtained CdS thin films was measured by
 spectrophotometer, and the optical band-gaps as shown in Table 5 were
 obtained.
 TABLE 5
 Type of Cd organic Temp. of Optical band-gap
 compound substrate (.degree. C.) (eV)
 Cadmium diethyl 400 2.42
 dithiocarbamate
 Cadmium dibutyl 400 2.40
 dithiocarbamate
 Cadmium dibenzyl 400 2.44
 dithiocarbamate
 Cadmium 400 2.44
 thiocarbamate
 Cadmium thioate 400 2.43
 Cadmium dithioate 400 2.44
 Cadmium 400 2.44
 thiocarbonate
 Cadmium 400 2.43
 dithiocarbonate
 Cadmium 400 2.42
 trithiocarbonate
 Cadmium mercaptide 400 2.44
 As shown in Table 5, optical band-gaps of the obtained CdS thin films were
 in a range of 2.40 to 2.44 eV. These values are nearly the same value as
 2.42 eV, which is a standard value of CdS single crystal. It proves that
 the obtained CdS thin films were films of high quality with few lattice
 defects.
 EXAMPLE 4
 CdS thin films were formed in the same way as in Example 2, by using
 various cadmium organic compounds which are shown in Table 6. When the
 obtained CdS thin films were analyzed by X ray photo-electronic
 spectroscopy, it was found that the condition of cadmium-sulfur bond in
 the thin films was the same as the condition of cadmium-sulfur bond in a
 single crystal of CdS.
 When the obtained CdS thin films were analyzed by X ray diffraction method,
 reflection peaks which are ascribed to (002) face were observed, and thus
 the obtained CdS thin films were identified to be constructed from
 hexagonal CdS crystals.
 Furthermore, when Cd organic compounds which contain carbon and nitrogen,
 such as Cd diethyl dithiocarbamate, Cd dibutyl dithiocarbamate, Cd
 dibenzyl dithiocarbamate, and Cd thiocarbamate, were used as the source
 material, the peaks of (002) face of the obtained CdS thin films were
 sharper and their half-width were smaller than that of the other obtained
 CdS thin films. It proves that the above CdS thin films obtained from the
 Cd organic compounds containing carbon and nitrogen are especially highly
 crystallized and very dense.
 The optical band-gaps of the obtained CdS thin films were measured in the
 same way as in Example 3. Results are shown in Table 6.
 TABLE 6
 Type of Cd organic Temp. of Optical
 Compound substrate (.degree. C.) Band-gap (eV)
 Cadmium diethyl 400 2.42
 dithiocarbamate
 Cadmium dibutyl 400 2.40
 dithiocarbamate
 Cadmium dibenzyl 400 2.44
 dithiocarbamate
 Cadmium 400 2.44
 thiocarbamate
 Cadmium mercaptide 400 2.44
 Cadmium thioate 400 2.43
 Cadmium dithioate 400 2.44
 Cadmium 400 2.44
 thiocarbonate
 Cadmium 400 2.43
 dithiocarbonate
 Cadmium 400 2.42
 trithiocarbonate
 Cadmium isopropyl 400 2.40
 xanthogenate
 Cadmium 400 2.43
 thiobenzoate
 As shown in Table 6, optical band-gaps of the obtained CdS thin films were
 in a range of 2.40 to 2.44 eV. These values are nearly the same value as a
 standard value of CdS. It proves that the obtained CdS thin films were
 films of high quality with few lattice defects.
 EXAMPLE 5
 A CdS thin film 3 was formed by using the equipment which is shown in FIG.
 2. The substrate 1 and the transparent conductive SnO.sub.2 film 2 were
 prepared in the same way as in Example 1. Cadmium thiobenzoate was
 dissolved in 1-methyl-2-pyrrolidone at the concentration of 0.5 mol/l.
 This solution was used as the organic solvent solution 9 of the metal
 organic compound. The viscosity of the solution 9 was about 50 cP.
 The solution 9 was poured in the vessel 4 in FIG. 2. Air was provided from
 the carrier gas inlet 7 and the fine particles of the solution 9 were
 injected from the injection outlet 6 of the nozzle 12 on the surface of
 the substrate 1 which was heated at 400.degree. C. The CdS thin film 3 was
 thus formed on the SnO.sub.2 film 2.
 When the obtained CdS thin film was analyzed in the same way as in Example
 3, it was found that the condition of cadmium-sulfur bond in the CdS thin
 film was the same as that in CdS single crystal and that the CdS thin film
 was constructed from hexagonal CdS crystals. Consequently, the CdS thin
 film was identified to be a film of high quality with few lattice defects.
 EXAMPLE 6
 Compound semiconductor thin films consisting of various kinds of metal
 sulfides were formed in the same way as in Example 1, by using various
 kinds of metal organic compounds other than that of cadmium, as shown in
 Table 7.
 The temperature of the surface of the thin film forming substrate was
 properly adjusted according to the thermal decomposition temperature of
 the metal organic compound. Optical band-gaps of the obtained metal
 sulfide thin films were measured in the same way as in Example 3. Results
 are shown in Table 7.
 TABLE 7
 Temp. of Optical
 Type of metal Produced substrate band-gap
 organic compound sulfide (.degree. C.) (eV)
 Copper diethyl CuS 380 1.40
 dithiocarbamate
 Zinc diethyl ZnS 500 3.60
 dithiocarbamate
 Mercury diethyl HgS 330 1.80
 dithiocarbamate
 Lead diethyl PbS 550 0.38
 dithiocarbamate
 As shown in Table 7, optical band-gaps which were measured on the obtained
 metal sulfide thin films were nearly the same as the standard values of
 respective metal sulfides. It proves that all obtained metal sulfide thin
 films are of high quality with few lattice defects.
 EXAMPLE 7
 CdS thin films were formed in the same way as in Example 1 and Example 2,
 and solar cells were constructed by using the CdS thin films respectively,
 as an n-type semiconductor layer. FIG. 5 is a sectional view of the solar
 cell.
 A transparent conductive thin film 22 was formed on one side surface of the
 glass plate 21 and a CdS thin film 23 of 500 angstrom thick was formed on
 the transparent conductive film 22 in the same way as in Example 1 or
 Example 2. This CdS thin film was used as a window layer and a CdTe thin
 film 24 of 5 .mu.m thick was formed on the CdS thin film 23 by using a
 proximity sublimation method. Then, a carbon electrode 25 was formed on
 the CdTe thin film 24. Finally, an Ag--In electrode 26 was formed on the
 CdS thin film 23 and on the carbon electrode 25 respectively, and thus the
 solar cell was constructed.
 IV characteristics of respective solar cells as per constructed were
 measured by using a solar simulator light of AM 1.5, 100 mV/cm.sup.2 at
 25.degree. C. In case of the solar cell which was constructed by using the
 CdS thin film formed in the same way as in Example 1, open circuit voltage
 was 820 mV, short circuit current density was 24.6 mA/cm.sup.2, maximum
 output power density was 14.6 mW/cm.sup.2, and photoelectric conversion
 efficiency was 14.6%.
 In case of the solar cell which was constructed by using the CdS thin film
 formed in the same way as in Example 2, open circuit voltage was 830 mV,
 short circuit current density was 24.7 mA/cm.sup.2, maximum output power
 density was 14.8 mW/Cm.sup.2 and photoelectric conversion efficiency was
 14.8%.
 These values are much higher than those of conventional solar cells. The
 reason why such excellent characteristics were obtained for these above
 solar cells seems to be as follows;
 First, photosensitivity at short wave length has increased since the
 obtained CdS thin film is very thin and dense without any void spaces.
 Second, short circuit current has increased since the obtained CdS thin
 film is of high purity, with little amount of residual ingredients such as
 carbon and thus the light transmittance is high in the whole wave length.
 COMATIVE EXAMPLE 3
 A CdS thin film was formed by the conventional printing and sintering
 method, and a solar cell was constructed by using CdS film as an n-type
 semiconductor layer. FIG. 6 is a sectional view of the solar cell. The CdS
 sintered film 27 of about 20 .mu.m thick was formed on the barium
 borosilicate glass plate 21 by the conventional screen printing and
 sintering method. A CdTe sintered film 28 was formed on the CdS sintered
 film 27. A carbon electrode 25 was formed on the CdTe sintered film 28.
 Then, an Ag--In electrode 26 was formed and thus the solar cell is
 constructed.
 IV characteristics of the solar cell as per constructed were measured in
 the same way as in Example 7. Results were as follows; Open circuit
 voltage was 750 mV, short circuit current density was 22.5 mA/cm.sup.2,
 maximum output power density was 11.3 mW/cm.sup.2, and photoelectric
 conversion efficiency was 11.3%.
 These values are much lower than those of the solar cells in Example 7. The
 reason why such inferior characteristics were obtained for the above solar
 cell seems to be mainly because the CdS sintered film 27 was as thick as
 about 20 .mu.m since the film was formed by the conventional printing and
 sintering method.
 COMATIVE EXAMPLE 4
 A CdS thin film was formed in the same way as Comparative Example 2 by
 using a conventional thermal decomposition method of the metal organic
 compound. A solar cell was constructed by using the CdS thin film and in
 the same way as in Example 7.
 IV characteristics of the solar cell as per constructed were measured in
 the same way as in Example 7. Results were as follows; Open circuit
 voltage was 810 mV, short circuit current density was 24.0 mA/cm.sup.2,
 maximum output power density was 13.9 mW/cm.sup.2 and photoelectric
 conversion efficiency was 13.9%. These values are lower than those of the
 solar cells in Example 7.
 The reason why such inferior characteristics were obtained for the above
 solar cell seems to be because the CdS thin film is not of high density
 and of high purity compared with the CdS thin films in Example 7.
 EXAMPLE 8
 A Cds thin film was formed according to the method of the present invention
 and copper-indium-solenide (CIS) solar cell was constructed by using the
 CdS thin film as an n-type semiconductor layer. FIG. 7 is a sectional view
 of the solar cell.
 A molybdenum electrode 32 was formed on one side surface of a soda lime
 glass plate 31 by using a conventional evaporation method. Then, a CIS
 film 33 was formed by a multi-element evaporation method using copper,
 indium and selenium as source materials, and thus a CdS thin film forming
 substrate was prepared. A temperature of the thin film forming substrate
 was controlled to be 350.degree. C. and a CdS thin film 34 was formed on
 the CIS thin film 33, in the same way as Example 2. Then, a zinc oxide
 film 35, a transparent electrode of ITO 36, and a magnesium fluoride film
 37 were successively formed, and thus the solar cell was constructed.
 IV characteristics of the solar cell as per constructed were measured in
 the same way as in Example 7. Results were as follows; Open circuit
 voltage was 550 mV, short circuit current density was 39.5 mA/cm.sup.2,
 and photoelectric conversion efficiency under the light source of 100
 mW/cm.sup.2 was 13.6%. These values prove that the above solar cell has
 excellent characteristics.
 In the above Example, the copper-indium-selenium film was used as a p-type
 semiconductor layer. It is also possible to use a
 copper-indium-germanium-selenium film.
 COMATIVE EXAMPLE 5
 A temperature of the surface of the thin film forming substrate was
 controlled to be 350.degree. C. and a CdS thin film was formed in the same
 way as in Comparative Example 2. A solar cell was constructed in the same
 way as in Example 8.
 IV characteristics of the solar cell as per constructed were measured in
 the same way as in Example 7. Results were as follows; Open circuit
 voltage was 530 mV, short circuit current density was 38.5 mA/cm.sup.2
 photoelectric conversion efficiency was 12.9%.
 It is understood that various other modifications will be apparent to and
 can be readily made by those skilled in the art without departing from the
 scope and spirit of this invention. Accordingly, it is not intended that
 the scope of the claims appended hereto be limited to the description as
 set forth herein, but rather that the claims be construed as encompassing
 all the features of patentable novelty that reside in the present
 invention, including all features that would be treated as equivalents
 thereof by those skilled in the art to which this invention pertains.