WO2011083647A1 - CIBLE DE PULVÉRISATION CATHODIQUE Cu-Ga, PROCÉDÉ DE FABRICATION DE CETTE CIBLE, COUCHE ABSORBANT LA LUMIÈRE AINSI QUE CELLULE SOLAIRE METTANT EN OEUVRE CETTE COUCHE ABSORBANT LA LUMIÈRE - Google Patents

CIBLE DE PULVÉRISATION CATHODIQUE Cu-Ga, PROCÉDÉ DE FABRICATION DE CETTE CIBLE, COUCHE ABSORBANT LA LUMIÈRE AINSI QUE CELLULE SOLAIRE METTANT EN OEUVRE CETTE COUCHE ABSORBANT LA LUMIÈRE Download PDF

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WO2011083647A1
WO2011083647A1 PCT/JP2010/071661 JP2010071661W WO2011083647A1 WO 2011083647 A1 WO2011083647 A1 WO 2011083647A1 JP 2010071661 W JP2010071661 W JP 2010071661W WO 2011083647 A1 WO2011083647 A1 WO 2011083647A1
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Prior art keywords
target
alkali metal
cigs
sputtering target
film
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PCT/JP2010/071661
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English (en)
Japanese (ja)
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正克 生澤
英生 高見
友哉 田村
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Jx日鉱日石金属株式会社
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Priority to JP2011548934A priority Critical patent/JP5877510B2/ja
Publication of WO2011083647A1 publication Critical patent/WO2011083647A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/02—Making non-ferrous alloys by melting
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
    • C23C14/3414—Metallurgical or chemical aspects of target preparation, e.g. casting, powder metallurgy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
    • H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
    • H01L31/0264—Inorganic materials
    • H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
    • H01L31/0322—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising only AIBIIICVI chalcopyrite compounds, e.g. Cu In Se2, Cu Ga Se2, Cu In Ga Se2
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/541—CuInSe2 material PV cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a Cu—Ga based sputtering target used in the preparation of a Cu—In—Ga—Se (hereinafter referred to as CIGS) quaternary thin film which is a light absorption layer of a thin film solar cell layer.
  • the present invention relates to a method for producing a Cu—Ga based sputtering target, a light absorption layer produced from the Cu—Ga based sputtering target, and a CIGS solar cell using the light absorption layer.
  • a vapor deposition method and a selenization method are known as a manufacturing method of the CIGS layer which is the light absorption layer.
  • Solar cells manufactured by vapor deposition have the advantages of high conversion efficiency, but have the disadvantages of low film formation speed, high cost, and low productivity.
  • the selenization method is suitable for industrial mass production, but after producing a laminated film of In and Cu—Ga, heat treatment is performed in a hydrogenated selenium atmosphere gas to selenize Cu, In, and Ga to obtain CIGS.
  • heat treatment is performed in a hydrogenated selenium atmosphere gas to selenize Cu, In, and Ga to obtain CIGS.
  • the CIGS-based alloy sintered body can be used as a sputtering target and direct-current (DC) sputtering with a high film forming speed and excellent productivity is possible, the bulk resistance of the CIGS-based alloy sintered body is usually several Since it is relatively high at 10 ⁇ or more, abnormal discharge such as arcing is likely to occur, and there is a problem of generation of particles on the film and deterioration of film quality.
  • Patent Document 1 a method of supplying from Na-containing soda lime glass (Patent Document 1), a method of providing an alkali metal-containing layer on a back electrode by a wet method (Patent Document 2), A method in which an alkali metal-containing layer is provided on a precursor by a wet method (Patent Document 3), a method in which an alkali metal-containing layer is provided on a back electrode by a dry method (Patent Document 4), There is one in which an alkali metal is added before or after film formation (Patent Document 5).
  • the temperature controllable range during selenization is very narrow, and it is difficult to control proper diffusion of Na within the above temperature range.
  • the film quality may change during exposure to the atmosphere after film formation, and peeling may occur. There was also a problem that the equipment cost was very high.
  • the precipitation of the alkali metal compound is preferably carried out by sputtering or vapor deposition.
  • Mixed targets with In x Se y can be used, as well as metal-alkali metal mixed targets such as Cu / Na, Cu—Ga / Na or In / Na ”(Patent Document 4 and (See paragraph [0027] of Patent Document 6).
  • Patent Document 7 discloses forming a light absorption layer of a solar cell in which a film is formed by co-evaporation with other component elements using an alkali metal compound as an evaporation source (paragraph [0019] of the same document. ] And FIG. 1). In this case as well, similarly to Patent Document 4 and Patent Document 6, there is a problem in that component fluctuation occurs if adjustment (components and vapor deposition conditions) with other vapor deposition materials is not sufficiently performed.
  • Non-Patent Document 1 discloses a method of manufacturing a CIGS quaternary alloy sputtering target that has been subjected to HIP treatment after powder production by mechanical alloy serving as a nanopowder material, and characteristics of the target.
  • the characteristics of the CIGS quaternary alloy sputtering target obtained by this production method although there is a qualitative description that the density is high, no specific density value is disclosed.
  • oxygen concentration is high from using nano powder, the oxygen concentration of a sintered compact is not clarified at all.
  • expensive nanopowder is used as a raw material, it is unsuitable as a solar cell material that requires low cost.
  • Non-Patent Document 2 discloses a sintered body having a composition of Cu (In 0.8 Ga 0.2 ) Se 2 , a density of 5.5 g / cm 3 , and a relative density of 97%. Is disclosed. However, as the manufacturing method, there is only a description that the originally synthesized raw material powder is sintered by the hot press method, and a specific manufacturing method is not clearly described. Moreover, it does not describe about the bulk resistance of the obtained sintered compact.
  • JP 2004-47917 A Japanese Patent No. 3876440 Japanese Patent Laid-Open No. 2006-210424 Japanese Patent No. 4022577 Japanese Patent No. 3311873 JP 2007-266626 A JP-A-8-102546
  • the present invention eliminates the need to separately prepare a Na-containing layer or a Na diffusion blocking layer from a substrate when manufacturing a CIGS solar cell, and can make the alkali metal concentration in the CIGS layer relatively uniform. It is an object of the present invention to provide a Cu—Ga-based target, a method for producing the target, a light absorption layer produced from the target, and a CIGS solar cell using the light absorption layer.
  • the inventors of the present invention have used a Cu-Ga film obtained by sputtering using Cu-Ga added with an alkali metal as a sputtering target.
  • the CIGS layer absorbs light even after the subsequent selenization because the alkali metal concentration distribution in the CIGS film is significantly improved compared to the concentration distribution by conventional diffusion. It discovered that the conversion efficiency of the solar cell used as a layer improved. Further, it has been found that by adding an alkali metal, bulk resistance can be reduced, and abnormal discharge is suppressed during sputtering. The present invention is based on this finding.
  • the present invention 1.
  • the ratio of the number of gallium (Ga) atoms to the total number of gallium (Ga) and copper (Cu) atoms (Ga / (Ga + Cu)) is 0.2 to 0.6 and contains an alkali metal.
  • Cu—Ga based sputtering target characterized 2.
  • the present invention also provides: 5.
  • the ratio of the number of gallium (Ga) atoms to the total number of gallium (Ga) and copper (Cu) atoms is 0.2 to 0.6 and Cu— containing an alkali metal.
  • a Ga-based sputtering target is manufactured by sintering, Li 2 O, Na 2 O, K 2 O, Li 2 S, Na 2 S, K 2 S, and Li 2 Se are used as compounds for adding an alkali metal.
  • the present invention also provides: 6).
  • the Cu—Ga based target contains an alkali metal
  • the uniformity of the alkali metal concentration in the film obtained by sputtering the target can be improved, and the alkali metal in the CIGS film can be improved. Therefore, the conversion efficiency of the solar cell using the CIGS layer as a light absorption layer is improved. Further, by adding an alkali metal to the sputtering target, the bulk resistance can be reduced, and an excellent effect can be obtained in that abnormal discharge can be suppressed during sputtering.
  • the ratio of the number of Ga atoms to the total number of Ga and Cu atoms is 0.2 to 0.6. This is because the band gap of the CIGS film made of Cu—Ga having a composition in this range is appropriate in relation to the sunlight spectrum, and improves the conversion efficiency of the CIGS solar cell using the CIGS film.
  • CIGS is a quaternary alloy composed of copper (Cu), indium (In), gallium (Ga), and selenium (Se), and its composition is CuIn 1-x Ga x Se 2-y (where x, y Are respectively represented by an atomic ratio), and the composition ranges are 0 ⁇ x ⁇ 0.5 and 0 ⁇ y ⁇ 0.04.
  • the CIGS based film does not contain Ga and becomes a CIS film. Its band gap is 1.04 eV, but the most suitable solar cell band gap in relation to sunlight is 1.4 eV. Therefore, since the band gap is too small, the voltage of the solar cell is not sufficiently high, and the conversion efficiency does not increase.
  • the band gap is 1.42 eV, and the conversion efficiency can be made relatively high.
  • the atomic ratio of Ga exceeds 0.6, the band gap further increases, so that the energy necessary for generating electrons becomes too high, and the current of the solar cell cannot be increased.
  • the conversion efficiency tends to decrease. Therefore, an appropriate range of the Ga atom number ratio is (Ga / (Ga + In)) of 0.2 to 0.6.
  • the Cu—Ga based sputtering target of the present invention is characterized by containing an alkali metal.
  • the present invention is not described as a Cu-Ga sputtering target, but a Cu-Ga-based sputtering target and a system are described so that the main component of the sputtering target is composed of Cu and Ga, but also includes an alkali metal. It means that.
  • Alkali metals bring about effects such as an increase in crystal grain size and an increase in carrier concentration at the time of CIGS film production, and are effective in improving the conversion efficiency of CIGS solar cells.
  • the alkali metal is also referred to as Ia element in the periodic table, but in the present invention, hydrogen is not included in the alkali metal. This is because a means for effectively adding hydrogen is difficult, and it is not recognized that it is effective for the expression of effective electrical and structural characteristics.
  • an alkali metal it is considered that the alkali metal, which is a monovalent element, is substituted with a trivalent lattice position, thereby releasing holes and improving conductivity. Therefore, any element can be effective as long as it is an alkali metal, and Li, Na, and K are desirable from the viewpoint of ease of use and cost of the compound. In particular, Na is desirable from the viewpoints of expression of effects and ease of use of compounds.
  • these metals are highly reactive with elemental elements, and are particularly dangerous due to violent reaction with water, so it is desirable to add them in the form of a compound containing these elements. Therefore, Li 2 O, Na 2 O, K 2 O, Li 2 S, Na 2 S, K 2 S, Li 2 Se, Na 2 Se, K 2 Se, etc., which are easily available as compounds and are relatively inexpensive, are desirable. .
  • Se is a constituent material in CIGS, and therefore, it is more desirable because there is no concern of generating lattice defects or other composition materials.
  • the concentration of alkali metal has a correlation with conductivity and crystallinity, and is desirably 10 16 to 10 18 cm ⁇ 3 .
  • the alkali metal concentration is less than 10 16 cm ⁇ 3 , when the CIGS film is formed, the conductivity is sufficiently low and appropriate conductivity cannot be obtained, so the effect of adding an alkali metal is not sufficient, while the alkali metal concentration is Even if it exceeds 10 18 cm ⁇ 3 , the effect is saturated and the relative density of the target decreases.
  • the alkali metal concentration can be analyzed by various analysis methods.
  • the alkali metal concentration in the Cu—Ga based target can be analyzed by a method such as ICP analysis, and the alkali metal concentration in the Cu—Ga based film and its film thickness.
  • the direction distribution can be obtained by SIMS analysis or the like.
  • the relative density of the Cu—Ga based sputtering target of the present invention is 97% or more, preferably 98% or more, more preferably 99.1% or more.
  • the relative density is a ratio of values obtained by dividing the actual absolute density of the sintered compact target by the theoretical density of the target having the composition. If the relative density of the target is low, there are many internal vacancies in the target, so splashing and abnormal discharge starting from the periphery of the vacancies are likely to occur when the internal vacancies are exposed during sputtering. Particle generation increases, which contributes to a decrease in conversion efficiency of CIGS solar cells. Further, the unevenness of the target surface proceeds at an early stage, and abnormal discharge or the like starting from surface protrusions (nodules) is likely to occur. Therefore, the relative density of the target is desirably at least 97% or more.
  • the target of the present invention can be produced, for example, as follows. After weighing each raw material of Cu, Ga and alkali metal compound so as to have a predetermined composition ratio, they are put in a crucible and heated to about 50 to 200 ° C. higher than the melting point in a heating furnace pressurized to about 0.5 MPa atmospheric pressure. The mixed raw material is dissolved, held for about 1 hour, cooled, and the primary synthetic raw material is taken out. This primary synthetic raw material is pulverized to obtain a fine powder raw material. Examples of the pulverization method include mechanical pulverization, gas atomization method, water atomization method and the like, and any method is possible.
  • the appropriate hot press conditions vary depending on the Ga concentration. For example, when the Ga concentration is 30 at%, the temperature is 600 to 700 ° C. and the pressure is about 30 to 40 MPa. A suitable holding time is about 1 to 3 hours, a suitable cooling rate is 5 ° C./min or more, and a pressure applied to a suitable mixed raw material powder is 30 to 40 MPa. It is possible to improve the density of the Cu—Ga based target under such hot pressing conditions.
  • the pre-pressure method in which pressure is applied first is more than the post-pressure method in which pressure is applied after the temperature is set to the maximum temperature. Since the raw material powder is crushed more finely before sintering, it is effective for increasing the sintering density.
  • the density of the prepared Cu—Ga-based sintered body can be analyzed by the Archimedes method, the Ga concentration by the ICP analysis method, and the alkali metal concentration by the GDMS method.
  • the Cu—Ga based sintered body is machined to a target of, for example, a diameter of 6 inches and a thickness of 6 mm.
  • This target is bonded to a backing plate as a brazing material, and a sputtering target / backing plate assembly is obtained.
  • a Cu—Ga-based film can be obtained by sputtering using this target / backing plate assembly.
  • each component of the solar cell other than this portion uses a conventional method.
  • Can be produced That is, after sputtering a molybdenum electrode on a glass substrate, after sputter deposition of In, after sputter deposition of an alkali metal-containing CuGa target, the laminated film portion of In and alkali metal-containing CuGa is selenized with selenium hydride.
  • an alkali metal-containing CIGS film can be formed to produce a light absorption layer.
  • a solar cell using an alkali metal-containing CIGS layer can be produced by further wet-forming CdS on the CIGS layer and forming ZnO as a buffer layer and aluminum-added ZnO as a transparent conductive film. .
  • Example 1 Cu raw material and Ga raw material were weighed so that the ratio of the number of Ga atoms was 0.3 and the concentration of Na 2 Se was 10 17 cm ⁇ 3 , put in a carbon crucible, and heated by applying 0.5 Mpa of argon After melting at 1000 ° C. in a furnace, the synthetic raw material was taken out after cooling at a cooling rate of 5 to 10 ° C./min.
  • this synthetic raw material is put into a carbon crucible of a water atomizer and melted at 1000 ° C. Then, while dropping the molten liquid, 10 Mpa of high-pressure water is injected into the dropped liquid to obtain a Cu—Ga mixed fine powder. Got. The mixed fine powder was filtered and then dried at 120 ° C. to obtain a mixed fine powder raw material.
  • the mixed fine powder raw material was heated from room temperature to 650 ° C. at a temperature increase rate of 5 ° C./min as a hot press condition, held at 650 ° C. for 2 hours, and a pressure of 35 Mpa was applied. Thereafter, the sintered body was taken out after cooling at a temperature drop rate of 5 ° C./min.
  • the relative density of the obtained Cu—Ga based sintered body was 99.9%.
  • This sintered body was processed into a disk shape having a diameter of 6 inches and a thickness of 6 mm to produce a sputtering target.
  • a glass of Corning 1737 having a diameter of 4 inches and a thickness of 0.7 mm was used as a substrate, and an In target was sputtered onto the glass substrate to obtain a film thickness of 1 ⁇ m.
  • the CuGa-based sputtering target prepared above is sputtered under the conditions of sputtering power of direct current (DC) 1000 W, atmospheric gas of argon, gas flow rate of 50 sccm, and sputtering pressure of 0.5 Pa, and the film thickness is 1 ⁇ m.
  • a film was prepared.
  • the produced In and Cu—Ga-based laminated film was placed in a furnace, and a selenization process was performed for 1 hour at a furnace temperature of 500 ° C. while supplying a hydrogen selenide gas.
  • the resistivity of the film taken out was measured by the film thickness and the four probe method, and the resistivity of the film was determined to be 3.1 ⁇ cm.
  • the results are shown in Table 1. As is clear from the above, good values for achieving the object of the present invention are shown.
  • Example 2 to Example 5 The ratio of the number of Ga atoms, Ga / (Ga + Cu), was 0.2 in Example 2, 0.4 in Example 3, 0.5 in Example 4, and 0.6 in Example 5. Other than that was the same conditions as Example 1, and produced the sintered compact and the thin film. The results of the properties of the sintered body and the thin film are also shown in Table 1.
  • Example 2 the relative density of the sintered body target was 99.8%, the CIGS film resistivity was 3.1 ⁇ cm, and in Example 3, the relative density of the sintered body target was 98.8. %, CIGS film resistivity 3.3 ⁇ cm, in Example 4, the relative density of the sintered body target was 98.6%, CIGS film resistivity 3.4 ⁇ cm, in Example 5, the relative density of the sintered body target was 97 0.8% and CIGS film resistivity of 3.2 ⁇ cm, both of which showed good values for achieving the object of the present invention.
  • Example 6 A sintered body and a thin film were prepared under the same conditions as in Example 1 except that the compounds for adding the alkali metal were changed to those described in Table 1 respectively. That is, Example 6 uses Na 2 O as the alkali metal compound, Example 7 uses Na 2 S as the alkali metal compound, Example 8 uses Li 2 Se as the alkali metal compound, In Example 9, K 2 Se was used as the alkali metal compound.
  • Table 1 The results of the properties of the sintered body and the thin film are also shown in Table 1.
  • Example 6 the relative density of the sintered body target was 99.2%, the CIGS film resistivity was 3.9 ⁇ cm, and in Example 7, the relative density of the sintered body target was 99.4. %, CIGS film resistivity 3.6 ⁇ cm, in Example 8, the relative density of the sintered body target was 99.1%, CIGS film resistivity 3.8 ⁇ cm, in Example 9, the relative density of the sintered body target was 98 0.9%, and CIGS film resistivity was 3.7 ⁇ cm, both of which showed good values for achieving the object of the present invention.
  • Example 10 A sintered body and a thin film were prepared under the same conditions as in Example 1 except that the alkali metal concentration was changed to that described in Table 1. That is, in Example 10, the alkali metal concentration was 2 ⁇ 10 16 cm ⁇ 3, and in Example 11, the alkali metal concentration was 8 ⁇ 10 17 cm ⁇ 3 .
  • the results of the properties of the sintered body and the thin film are also shown in Table 1.
  • Example 10 the relative density of the sintered body target was 97.8%, CIGS film resistivity was 4.7 ⁇ cm, and in Example 11, the relative density of the sintered body target was 99.5. %, CIGS film resistivity was 2.1 ⁇ cm, and all showed good values for achieving the object of the present invention.
  • Comparative Examples 1 and 2 A sintered body and a thin film were prepared under the same conditions as in Example 1 except that the alkali metal concentration was changed to that described in Table 1. That is, in Comparative Example 1, the alkali metal concentration was 2 ⁇ 10 15 cm ⁇ 3, and in Comparative Example 2, the alkali metal concentration was 8 ⁇ 10 19 cm ⁇ 3 . Comparative Example 1 has a low alkali metal concentration, while Comparative Example 2 has an alkali metal concentration that is too high, both of which are outside the conditions of the present invention. The results of the properties of the sintered body and the thin film are also shown in Table 1.
  • Comparative Example 1 As shown in Table 1 above, in Comparative Example 1, the relative density of the sintered compact target was 98.5%, and there was no particular problem, but the CIGS film resistivity was as high as 69.0 ⁇ cm, which was defective. In Comparative Example 2, the CIGS film resistivity was as good as 1.9 ⁇ cm, but the relative density of the sintered compact target decreased to 94.3%, which was a problem.
  • the uniformity of the alkali metal concentration in the film obtained by sputtering the target can be improved. Since the concentration distribution of the alkali metal is markedly improved as compared with the concentration distribution by the conventional diffusion, the conversion efficiency of the solar cell having the CIGS layer as the light absorption layer is improved. . Therefore, it is useful as a material for manufacturing CIGS solar cells.

Abstract

L'invention concerne un cible de pulvérisation cathodique Cu-Ga, se caractérisant en ce que le rapport entre le nombre d'atomes de gallium (Ga) et le nombre total d'atomes de gallium (Ga) et de cuivre (Cu) (Ga / (Ga + Cu)), est compris entre 0,2 et 0,6, et en ce qu'elle contient un métal alcalin. Plus spécifiquement, l'invention concerne une cible de pulvérisation cathodique Cu-Ga pour laquelle, lors de la fabrication d'une cellule solaire CIGS, la fabrication d'une couche bloquant la diffusion de Na partir d'une couche contenant du Na ou à partir du substrat entre autre n'est pas nécessaire, et pour laquelle la concentration du métal alcalin à l'intérieur de la couche CIGS est relativement uniforme. L'invention concerne également un procédé de fabrication de cette cible de pulvérisation, une couche absorbant la lumière fabriquée à partir de cette cible ainsi qu'une cellule solaire CIGS mettant en oeuvre cette couche absorbant la lumière.
PCT/JP2010/071661 2010-01-07 2010-12-03 CIBLE DE PULVÉRISATION CATHODIQUE Cu-Ga, PROCÉDÉ DE FABRICATION DE CETTE CIBLE, COUCHE ABSORBANT LA LUMIÈRE AINSI QUE CELLULE SOLAIRE METTANT EN OEUVRE CETTE COUCHE ABSORBANT LA LUMIÈRE WO2011083647A1 (fr)

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Cited By (14)

* Cited by examiner, † Cited by third party
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JP2011214140A (ja) * 2010-03-18 2011-10-27 Mitsubishi Materials Corp スパッタリングターゲット及びその製造方法
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JP2014015682A (ja) * 2013-08-02 2014-01-30 Sumitomo Metal Mining Co Ltd Ｃｕ−Ｇａ合金スパッタリングターゲット
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