WO2013172252A1 - ALLIAGE POUR UNE COUCHE ABSORBANT LA LUMIÈRE AJOUTÉE AU SODIUM (Na), PROCÉDÉ PERMETTANT DE PRODUIRE CE DERNIER ET CELLULE SOLAIRE - Google Patents

ALLIAGE POUR UNE COUCHE ABSORBANT LA LUMIÈRE AJOUTÉE AU SODIUM (Na), PROCÉDÉ PERMETTANT DE PRODUIRE CE DERNIER ET CELLULE SOLAIRE Download PDF

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WO2013172252A1
WO2013172252A1 PCT/JP2013/063085 JP2013063085W WO2013172252A1 WO 2013172252 A1 WO2013172252 A1 WO 2013172252A1 JP 2013063085 W JP2013063085 W JP 2013063085W WO 2013172252 A1 WO2013172252 A1 WO 2013172252A1
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alloy
light absorption
manufacturing
producing
cig
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PCT/JP2013/063085
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Japanese (ja)
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賢二 吉野
章 永岡
俊和 広瀬
三香 山下
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株式会社 日本マイクロニクス
国立大学法人宮崎大学
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Priority to JP2014515590A priority Critical patent/JP5963852B2/ja
Priority to CN201380025411.XA priority patent/CN104303266B/zh
Publication of WO2013172252A1 publication Critical patent/WO2013172252A1/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
    • C23C14/0623—Sulfides, selenides or tellurides
    • 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
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02518—Deposited layers
    • H01L21/02521—Materials
    • H01L21/02568—Chalcogenide semiconducting materials not being oxides, e.g. ternary compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02518—Deposited layers
    • H01L21/0257—Doping during depositing
    • H01L21/02573—Conductivity type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02518—Deposited layers
    • H01L21/02587—Structure
    • H01L21/0259—Microstructure
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02612—Formation types
    • H01L21/02614—Transformation of metal, e.g. oxidation, nitridation
    • 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
    • H01L31/04—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 adapted as photovoltaic [PV] conversion devices
    • H01L31/06—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 adapted as photovoltaic [PV] conversion devices characterised by potential barriers
    • H01L31/072—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 adapted as photovoltaic [PV] conversion devices characterised by potential barriers the potential barriers being only of the PN heterojunction type
    • H01L31/0749—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 adapted as photovoltaic [PV] conversion devices characterised by potential barriers the potential barriers being only of the PN heterojunction type including a AIBIIICVI compound, e.g. CdS/CulnSe2 [CIS] heterojunction solar 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
    • 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

  • Solar cells are roughly classified into three types: silicon-based, compound-based, and organic-based, and silicon is the most widely used. Recently, compound-based solar cells are thin and have little change over time. Is expected to increase, and development is progressing.
  • silicon copper (hereinafter referred to as Cu), indium (hereinafter referred to as In), gallium (hereinafter referred to as Ga), selenium (hereinafter referred to as Se), sulfur (hereinafter referred to as S).
  • a group I-III-VI group 2 compound called chalcopyrite is used as a group I-III-VI group 2 compound called chalcopyrite.
  • Typical examples include copper indium diselenide CuInSe 2 (hereinafter referred to as CIS), copper indium diselenide / gallium Cu (In, Ga) Se 2 (hereinafter referred to as CIGS), and diselene / copper indium sulfide / gallium Cu. (In, Ga) (S, Se) 2 (hereinafter referred to as CIGSS) (see Patent Document 1).
  • Chalcopyrite type compound semiconductors have the characteristics of becoming both p-type and n-type semiconductors, are direct transition semiconductors, have excellent light absorption characteristics, and the forbidden band width is 3.5 eV of aluminum sulfide copper CuAlS 2 . It covers a wide wavelength range of 0.8 eV of tellurium indium copper CuInTe 2 and can produce light emitting and receiving elements from the infrared region to the ultraviolet region.
  • a polycrystalline CIGS solar cell is reported to have a conversion efficiency of 20.3% by taking advantage of excellent light absorption characteristics (see Non-Patent Document 1).
  • M.M. A solar cell in which a CIGS film is formed after depositing a Na 2 O 2 film on a substrate due to a small resistance value of a CIGS film deposited on a glass containing a Na component by Ruckh et al. Has an energy conversion efficiency of Na 2 It was shown to improve about 2% of solar cells without depositing O 2 film. In addition, it has been reported that the energy conversion efficiency, which usually depends largely on the Cu / In ratio, is constant regardless of the Cu / In ratio (see Non-Patent Document 4).
  • the energy conversion efficiency is improved as compared with the case of using another substrate, but it is difficult to control stably, resulting in variations in characteristics.
  • substrate which does not contain Na it is necessary to diffuse Na into a light absorption layer, and the various methods shown below are proposed.
  • One is to produce a CIGS light absorption layer by forming a back electrode on a substrate, forming a precursor film on the back electrode, and heat-treating it in a selenium (Se) or sulfur (S) atmosphere.
  • the group Ia element alkali metal
  • the Ia group element of the substrate diffuses into the light absorption layer during the heat treatment, and then the film thickness of the back electrode The film quality is optimized and the amount of diffusion is controlled (see Patent Document 2).
  • the light absorption layer includes a group Ia in order to improve energy conversion efficiency.
  • the back electrode is dipped in an aqueous solution containing an alkali metal and then dried.
  • an alkali layer on top see Patent Document 3).
  • a manufacturing method of a chalcopyrite thin film solar cell includes a first step of forming a precursor containing In, Cu, and Ga metal elements on a back electrode layer formed on a substrate, A second step of attaching a sodium molybdate-containing aqueous solution to the precursor, a selenization step of performing heat treatment in an H 2 Se gas atmosphere on the substrate that has undergone both the first and second steps, and transmitting light.
  • the molybdenum atom in the sodium molybdate has a catalytic function peculiar to transition metals.
  • the selenization reaction is promoted from the surface of the light absorption layer, thereby improving the crystallinity.
  • sodium molybdate (Na 2 MoO 4 ) has a higher decomposition rate than the conventionally used sodium tetraborate hydrate, and the adhesion rate of sodium atoms to the surface of the light-absorbing layer is increased, resulting in good efficiency.
  • concentration of the solution attached to the light absorption layer for promoting crystallization can be kept low, and as a result, the occurrence of spotted spots due to the adhesion unevenness of the aqueous solution can be suppressed (see Patent Document 4). .
  • a solar cell having a back electrode, a chalcopyrite absorption layer, and a front electrode on a substrate, selected from Na, potassium (K) and lithium (Li) before or during manufacture of the absorption layer.
  • Elemental compounds are added by doping and the additional diffusion of alkali metal ions from the substrate into the absorption layer during the manufacturing process is prevented by placing a diffusion blocking layer between the substrate and the absorption layer, thereby There is also a method of adjusting a desired concentration determined by doping of the element in the completed absorption layer (see Patent Document 5).
  • a method of forming a Na component layer on the Mo metal layer to be the back electrode by vapor deposition or sputtering, and further forming a laminated precursor such as an In layer and a Cu—Ga layer Since it has hygroscopicity, it may deteriorate during exposure to the atmosphere after film formation, and peeling may occur in the layer.
  • the method of adding a compound of an element selected from Na, potassium (K) and lithium (Li) by doping before or during the production of the absorption layer has a problem that the production process is complicated.
  • the diffusion of Na to the CIGS film or the CIGSS film as the light absorption layer can be controlled with high accuracy, and the manufacturing method is also simple. It aims at providing the manufacturing method of the sputtering target by the alloy for optical absorption layers, the alloy for optical absorption layers, and the solar cell using the sputtering target for optical absorption layers.
  • the present invention is an alloy for a light absorption layer used as a light absorption layer material for solar cell production, in which a group Ia element is added to copper, indium, gallium, and selenium.
  • a group Ia element is added to copper, indium, gallium, and selenium.
  • the alloy for a light absorption layer according to the present invention is manufactured by crystallizing copper, indium, gallium, selenium, and a compound composed of Group Ia and Group VIa elements at a high temperature.
  • the reason why the compound is composed of Group Ia and Group VIa elements is that an alkali metal composed only of Group Ia elements such as Li, Na, and K reacts violently with moisture and oxygen.
  • the light absorbing layer alloy according to the present invention is a light absorbing layer alloy obtained by further adding sulfur to copper, indium, gallium, selenium, and group Ia elements.
  • This light-absorbing layer alloy is manufactured by crystallizing copper, indium, gallium, selenium, sulfur, and a compound comprising Group Ia and Group VIa elements at a high temperature.
  • the reason why the compound is composed of Group Ia and Group VIa elements is that an alkali metal composed only of Group Ia elements such as Li, Na, and K reacts violently with moisture and oxygen.
  • the compound consisting of Group Ia and Group VIa elements is sodium selenide, Group Ia Na diffuses into the CIGS crystal or CIGSS crystal and develops the Na effect, and the CIGS quaternary alloy or CIGSS ternary element as the Group VIa element
  • Se which is a component of the system alloy, there is an effect of filling Se vacancies in CIGS or CIGSS.
  • Copper sulfide, indium, gallium, selenium, and the light absorbing layer alloy in which sulfur is further added to the group Ia element may be sodium sulfide.
  • the Ia group Na diffuses into the CIGSS crystal and develops the Na effect.
  • S as the component of the CIGSS ternary alloy as the VIa group element, there is an effect of filling the S vacancies in the CIGSS.
  • a method for producing an alloy for a light absorption layer in which a group Ia element is added to copper, indium, gallium, and selenium is a first step of producing a CIG ternary alloy by crystallizing a compound containing copper, indium, and gallium at a high temperature. And a second step of producing a CIG ternary alloy powder by pulverizing the CIG ternary alloy, and mixing selenium and a compound composed of Group Ia and VIa elements into the pulverized CIG ternary alloy, and crystallizing at a high temperature. And a third step of manufacturing a CIGS quaternary alloy.
  • the temperature in the first step of producing the CIG ternary alloy and the third step of producing the CIGS quaternary alloy is 1000 to 1100 ° C., and is returned to room temperature after the completion of the first step of producing the CIG ternary alloy.
  • the CIG ternary alloy is pulverized to mix selenium and a compound composed of Group Ia and VIa elements.
  • the temperature in each of the first step for producing a CIG ternary alloy and the third step for producing a CIGS quaternary alloy the temperature is raised to 100 ° C. or less per hour, and the temperature of 1000 to 1100 ° C. is maintained for 6 hours or more. The temperature is controlled at a temperature of 100 ° C. or more per hour to return to room temperature.
  • the copper, indium and gallium in the first step of manufacturing the CIG ternary alloy are vacuum-encapsulated in the ampule, and the pulverized CIG ternary alloy, selenium and the third step of manufacturing the CIGS quaternary alloy
  • the compounds consisting of elements Ia and VIa are sealed in an ampoule in a vacuum.
  • a method for producing an alloy for a light absorption layer composed of copper, indium, gallium, selenium, sulfur and a group Ia element is obtained by crystallizing a compound containing copper, indium and gallium at a high temperature to form a CIG ternary alloy.
  • a third step of producing a CIGSS ternary alloy by crystallization at a high temperature is a method for producing an alloy for a light absorption layer composed of copper, indium, gallium, selenium, sulfur and a group Ia element.
  • a method for producing an alloy for a light absorption layer made of copper, indium, gallium, selenium, sulfur and a group Ia element is produced by crystallizing a compound containing copper, indium and gallium at a high temperature to produce a CIG ternary alloy.
  • a method for manufacturing an alloy for a light absorption layer comprising copper, indium, gallium, selenium, sulfur and a group Ia element wherein the temperature control is performed in one process, copper, indium, gallium, selenium, sulfur And the first step of vacuum-sealing sodium selenide in an ampoule, and the ampoule is first raised to 200 ° C. and maintained for a certain period of time, then heated to 1050 ° C. and maintained for a certain period of time, and then the electric furnace heater is stopped. And a second step of returning to room temperature.
  • the first step for producing a CIG ternary alloy and the third step for producing a CIGSS ternary alloy were mixed.
  • the raw material is vacuum sealed in an ampoule.
  • the ampoule used for manufacturing the light-absorbing layer alloy is preferably carbon-coated and quartz glass is used.
  • the light-absorbing layer alloy produced by the method for producing a light-absorbing layer alloy is sliced to produce a light-absorbing layer sputtering target.
  • Other manufacturing methods of the light-absorbing layer sputtering target include a powdering step of pulverizing and pulverizing the light-absorbing layer alloy manufactured by the manufacturing method of the light-absorbing layer alloy, and a powdered light-absorbing layer alloy.
  • a solar cell is manufactured by a manufacturing method including a thin film manufacturing process for forming a light absorption layer on a back electrode laminated on a substrate by sputtering using a sputtering target for a light absorption layer according to the present invention. can do.
  • a manufacturing method comprising a thin film manufacturing process for forming a light absorbing layer by vacuum deposition on a back electrode laminated on a substrate by a vacuum deposition apparatus using the sputtering target for the light absorbing layer.
  • a solar cell can be manufactured.
  • an alloy for a light absorption layer for forming a light absorption layer of a solar cell is crystallized by mixing a Group Ia element such as Na into a CIGS quaternary alloy or a CIGSS quinary alloy.
  • the composition ratio can be accurately controlled. Since this light absorbing layer alloy to which Na is added is used as a sputtering target in a sputtering apparatus and the light absorbing layer is formed by sputtering, uniform diffusion of a group Ia element such as sodium can be obtained.
  • the manufactured light absorption layer alloy may be used in a vacuum vapor deposition apparatus to form a light absorption layer by vacuum vapor deposition. Even in this case, uniform diffusion of a group Ia element such as Na can be obtained.
  • the film formation as the light absorption layer of the solar cell requires a special process. However, it is possible to manufacture a solar cell with high energy conversion efficiency for light energy at low cost.
  • the substrate does not contain Na element, alumina, alkali-free glass, stainless steel
  • a polymer film such as a polyimide film can be used.
  • a compound semiconductor used as a material of a p-type semiconductor that functions as a light absorption layer of a solar cell is two kinds of elements that are equidistant from the IV group across the IV group (Si, Ge, etc.) in the periodic table of elements.
  • a compound When a compound is produced, it utilizes the property that a similar chemical bond is formed and becomes a semiconductor. It is an I-III-VI group 2 element belonging to the adamantine series, and its crystal structure is a chalcopyrite structure.
  • the chalcopyrite type crystal structure has a tetragonal crystal structure in which I group Cu, III group Ga, In, and VI group S and Se atoms are 4-coordinated.
  • Chalcopyrite type semiconductors have a forbidden band width ranging from 0.26 to 3.5 eV, but the I-III-VI Group 2 element has strong ionicity but mobility of I-IV- weaker than the V 2 group, Thus, a typical CIS and CIGS which have been conventionally used, operating at lower than desired bandgap.
  • the forbidden band width of the chalcopyrite type compound crystal is 1.04 eV for CIS, 1.68 eV for CGS, and 1.53 eV for CuInS.
  • the mobility of a p-type semiconductor is high it is desirable, each of the mobility, CIS is 50cm 2 / V ⁇ s, CGS is 40cm 2 / V ⁇ s, CuInS Is 15 cm 2 / V ⁇ s.
  • CuInS 2 has an ideal forbidden band width, but has low mobility for use as a solar cell.
  • CIS and CIGS which are currently widely used as light absorbing layers, use Se that is harmful to the human body, so there is an expectation to reduce Se as much as possible. Proposed.
  • Na group Ia element
  • a group Ia element for example, Na
  • Na is diffused from soda-lime glass into a CIGS thin film through a molybdenum Mo thin film used as a back electrode.
  • a Na compound such as sodium fluoride (NaF) is vapor-deposited after providing an alkali barrier layer to form a Na source, or NaF or the like during CIGS film formation.
  • the Na compound is co-deposited.
  • CIGSS in the light absorption layer of the CIGS solar cell has a structure in which CIS, CGS and CuInS 2 which are three basic crystals are mixed. That is, CIS having a forbidden band width of 1.04 eV and CGS having a forbidden band width of 1.68 eV are mixed to form a polycrystal of CIGS having a forbidden band width of 1.2 eV. This is a structure in which CuInS 2 polycrystal having a band width of 1.54 eV is mixed. Although CuInS 2 has a low mobility of 15 cm 2 / V ⁇ s, the final CIGSS band gap can be 1.4 eV.
  • the forbidden band width can be set to 1.4 to 1.5 eV, which is a desirable value as a solar cell, but the increase in Ga decreases the energy conversion efficiency.
  • the Ia group element can be diffused in the CIGSS light absorption layer, the carrier concentration can be increased by the alkali metal effect, and the energy conversion efficiency can be improved.
  • Na which is a group Ia element
  • Na-added CIGS quaternary alloy a CIGS quinary alloy added with Na
  • Na-added CIGSS quaternary alloy a CIGS quinary alloy added with Na
  • Na is diffused into the CIGS film and CIGSS film simultaneously when the light absorption layer is formed by sputtering or vacuum deposition.
  • uniform diffusion can be obtained.
  • the present invention uses Na-added CIGS quaternary alloy and Na-added CIGSSS quaternary alloy, a manufacturing method thereof, and a sputtering target made of Na-added CIGS quaternary alloy and Na-added CIGSSS quinary alloy in one process. It is the manufacturing method of the CIGS solar cell which manufactures the light absorption layer spread
  • the Na-added CIGS quaternary alloy has Cu, In, Ga, Se and Na as constituent elements.
  • In this element configuration when In simple substance and Se simple substance are mixed, they react chemically to generate heat, and in a remarkable case, they explode. Furthermore, Na reacts violently with water and oxygen. For this reason, In and Se are separated and crystallized so as not to mix the simple substances.
  • sodium selenide (Na 2 Se) which is a group VI element and a compound with Se which is one of the constituent elements of the CIGS quaternary alloy is used.
  • a safe manufacturing method is required. Na diffuses into the CIGS crystal and exhibits the Na effect, and by making Se, which is a component of the CIGS quaternary alloy, the Group VIa element, the effect of filling Se vacancies in the CIGS crystal is produced.
  • FIG. 1 is a flowchart 10 showing an outline of a method for producing a Na-added CIGS quaternary alloy.
  • Step S1 Cu, In, and Ga, in which Se is removed from the elemental component of the CIGS quaternary alloy, are mixed to produce a CIG ternary alloy polycrystal.
  • step S2 the CIG ternary alloy is pulverized to mix Se and Na 2 Se. Since In is crystallized as a CIG alloy, it does not react chemically even when Se is mixed. Moreover, since Na is also used as the Na 2 Se compound, it can be mixed without reacting violently with water or oxygen.
  • step 3 the Na-added CIGS quaternary alloy is polycrystallized. Thereby, Na addition CIGS quaternary system alloy is completed.
  • FIG. 2 is a flowchart 12 showing a method for producing a Na-added CIGS quaternary alloy.
  • an ampoule for producing a CIG ternary alloy and an ampoule for producing a CIGS quaternary alloy are prepared.
  • the ampule for example, a quartz glass ampule is used and will be described as a quartz ampule, but the ampule is not limited to quartz glass. Quartz ampules are washed with aqua regia and hydrofluoric acid, and the moisture is evaporated in a dryer. After soaking in acetone, heat with a burner to remove soot. As a result, the quartz ampoule is carbon-coated, and impurities from quartz can be prevented from being mixed.
  • step S22 Cu, In, and Ga are washed with hydrochloric acid or the like, weighed so that the atomic ratio is 1: 0.8: 0.2, and vacuum-sealed in a carbon-coated quartz ampule.
  • step S23 the quartz ampule in which the raw material is vacuum-sealed is placed in an electric furnace for heating.
  • the heater in the furnace is energized to generate heat, and the temperature is raised to 1050 ° C. Then, a high temperature state of 1050 ° C. is maintained for a certain time, and the raw material is polycrystallized by crystal growth from the melt, and then the furnace temperature is lowered to room temperature in step S25. Thereby, a CIG ternary alloy is obtained.
  • step S26 the CIG ternary alloy is taken out from the quartz ampoule lowered to room temperature, and the taken out CIG ternary alloy is pulverized. At this time, a uniform fine powder is obtained through the mesh. Such crystal powder does not chemically react with Se because In is crystallized together with Cu and Ga.
  • step S27 the pulverized CIG ternary alloy, the Se element, and the number of Se element atoms including the Se component of Na 2 Se are weighed so that the ratio of the element atom number ratio is 1: 2.
  • the amount of Na added is controlled by the amount of Na 2 Se at this time.
  • the weighed material is vacuum-sealed in a carbon-coated quartz ampoule. And it puts into an electric furnace by step S28.
  • step 29 the furnace temperature is raised to 1050 ° C. and maintained at a temperature of 1050 ° C. for a certain period of time to grow crystals from the melt to form a polycrystal.
  • step S30 the furnace temperature is lowered to room temperature.
  • a Na-added CIGS quaternary alloy is taken out from the quartz ampule.
  • FIG. 3 is a diagram showing a manufacturing state 20 by an electric furnace in the Na-added CIGS quaternary alloy manufacturing process described in FIG.
  • a heater 24 for heating in the electric furnace 22, and the heater 24 generates heat due to external energization and raises the furnace temperature.
  • a quartz ampoule 28 Inside the electric furnace 22, a quartz ampoule 28 in which a raw material 26 is vacuum-sealed is placed. The furnace temperature is controlled by an external control device (not shown).
  • FIG. 4 shows a temperature control state 30 in the electric furnace in the manufacturing process of the Na-added CIGS quaternary alloy.
  • a quartz ampule in which the raw materials of Cu, In, and Ga are vacuum-sealed is placed in the furnace, and the heater temperature is increased by energizing the heater.
  • the temperature rise is raised to 1050 ° C. in 12 hours, for example.
  • the temperature raising time may be 12 hours or less, and may be 6 hours to 12 hours.
  • the temperature is kept constant at about 1050 ° C. for about 24 hours.
  • the time for keeping the temperature constant has a high degree of freedom, and strict time management is not required.
  • the heater is turned off and the furnace temperature is lowered by natural temperature drop. The time is within 6 hours.
  • the CIG polycrystal thus obtained is returned to room temperature and then pulverized, further mixed with Se and Na 2 Se, vacuum-sealed in a quartz ampule, and placed in the furnace again.
  • the temperature is raised from room temperature to 1050 ° C., for example, in 10 hours. This temperature of 1050 ° C. is maintained for about 24 hours. Strict control is not required for this time, and the subsequent temperature decrease to room temperature may be rapid cooling.
  • the ratio of Cu, In, and Ga have been described as having a ratio of the element atomic ratio of 1: 2, but the ratio of In to Ga is 1: x: (1-x) where 0 ⁇ x ⁇ Adjust within the range of 1 according to the purpose and function.
  • the ratio of Se with CIG ternary alloy as 1 is in the range of 1.7 to 2.3, which is also adjusted according to the purpose and function.
  • FIG. 5 is a flowchart 40 showing an outline of the Na-added CIGSS ternary alloy manufacturing method.
  • Constituent elements of the Na-added CIGSS ternary alloy are Cu, In, Ga, Se, S and Na.
  • In this element configuration when In simple substance and Se simple substance are mixed, they react chemically to generate heat, and in a remarkable case, they explode. Furthermore, Na reacts violently with water and oxygen. For this reason, In and Se are separated and crystallized so as not to mix the simple substances.
  • sodium selenide which is a group VI element and a compound with Se which is one of the constituent elements of the CIGSS ternary alloy is used.
  • a safe manufacturing method is required.
  • S which is one of the constituent elements of the CIGSS ternary alloy, is also a Group VI element, and sodium sulfide (Na 2 S) may be used as the sodium compound.
  • step S41 Cu, In and Ga obtained by removing Se and S from the elemental components of the CIGSS ternary alloy are mixed to produce a CIG ternary alloy polycrystal.
  • step S42 the CIG ternary alloy is pulverized and mixed with Se, S and Na 2 Se. Since In is crystallized as a CIG alloy, it does not react chemically even when Se is mixed. Moreover, since Na is also used as the Na 2 Se compound, it can be mixed without reacting violently with water or oxygen.
  • step 43 the Na-added CIGSS ternary alloy is polycrystallized. Thereby, Na addition CIGS quaternary system alloy is completed.
  • FIG. 6 is a detailed flowchart 42 of a Na-added CIGSS ternary alloy manufacturing method.
  • an ampoule for producing a CIG ternary alloy and an ampoule for producing a CIGSS ternary alloy are prepared.
  • the ampule for example, a quartz glass ampule is used and will be described as a quartz ampule, but the ampule is not limited to quartz glass. Quartz ampules are washed with aqua regia and hydrofluoric acid, and the moisture is evaporated in a dryer. After soaking in acetone, heat with a burner to remove soot. As a result, the quartz ampoule is carbon-coated, and impurities from quartz can be prevented from being mixed.
  • step S52 Cu, In and Ga are washed with hydrochloric acid or the like, and the element atomic ratio of Cu, In and Ga is weighed so as to be 1: 0.8: 0.2. Vacuum-filled quartz ampules.
  • the ratio of In to Ga is adjusted to the purpose and function within the range of 0 ⁇ x ⁇ 1 as 1: x: (1-x).
  • the ratio of Se with a CIG ternary alloy as 1 is in the range of 1.7 to 2.3, which can also be adjusted according to the purpose and function.
  • step S53 the quartz ampule in which the raw material is vacuum-sealed is placed in an electric furnace for heating.
  • the heater in the furnace is energized to generate heat, the temperature is raised to 1050 ° C., the high temperature state is maintained for a certain period of time, and crystals are grown from the melt to form a polycrystalline raw material.
  • the furnace temperature is rapidly cooled within 6 hours. This is to obtain a high-quality CIG crystal.
  • step S56 in order to sufficiently mix the obtained CIG crystal with S and Se, the CIG crystal is pulverized and powdered.
  • the powdered CIG crystal is weighed so that the element atomic ratio of S and Se is 0.2: 0.8.
  • the amount of Se is the number of element atoms of Se to which the Se component of Na 2 Se is added.
  • the amount of Na added is controlled by the amount of Na 2 Se.
  • the amount of S is the number of elemental atoms of S including the S component of Na 2 S.
  • step S57 the weighed material, that is, CIG polycrystal powder, Se, S and Na 2 Se, is vacuum-sealed in a carbon-coated quartz ampoule. And it puts into an electric furnace by step S58.
  • the furnace temperature is raised to 200 ° C. and maintained for a certain time in step S59, and then raised to 1050 ° C. in step S60.
  • the furnace temperature is lowered to room temperature in step S61, and the Na-added CIGSS ternary alloy is taken out from the quartz ampule.
  • FIG. 7 shows a temperature control state 44 in the electric furnace in the manufacturing process of the SIGSS ternary alloy.
  • a quartz ampule in which raw materials of Cu, In, and Ga are vacuum-sealed is placed in a furnace, and a heater is energized to raise the furnace temperature to 1050 ° C.
  • the temperature rise is raised to 1050 ° C. in 12 hours, for example.
  • the temperature raising time may be 12 hours or less, and may be 6 hours to 12 hours.
  • the temperature is kept constant at about 1050 ° C. for about 24 hours.
  • the temperature in this high temperature state is 1000 ° C. to 1100 ° C., and crystals grow from the melt in about 12 to 24 hours to form polycrystals.
  • the time for keeping the temperature constant has a high degree of freedom, and strict time management is not required.
  • energization of the heater is stopped and the furnace temperature is lowered by natural temperature drop. Decrease in time within 6 hours.
  • the CIG polycrystal thus obtained is returned to room temperature and then pulverized, further mixed with Se, S and Na 2 Se, vacuum-sealed in a quartz ampule, and placed in the furnace again.
  • the temperature is raised to about 200 ° C. as the first step. This is because Se and S have a low melting point, and after sufficiently melting at 200 ° C., other crystals of the mixture with other elements are grown from the melt. Thereby, a high-quality polycrystal can be obtained.
  • the temperature rise to 200 ° C. is raised to 200 ° C. in 2 hours. This state is maintained for about 12 hours and then raised to 1050 ° C. in 6 hours. Furthermore, this high temperature state is kept constant for about 24 hours. Note that this maintaining time has a high degree of freedom, and strict time management is not required. Then stop the electric furnace heater and return to room temperature. In this case, after stopping energization to the heater, it may be left until it becomes close to room temperature.
  • FIG. 8 shows a temperature control state 46 in the manufacturing method of the Na-added CIGSS ternary alloy manufactured in one process.
  • An ampoule in which Cu, In, Ga, Se, S and Na 2 Se are sealed in a vacuum is first heated to 200 ° C. to fully melt Se and S in consideration of the low melting point of Se and S. Then, after maintaining for a certain time, the temperature is raised to 1050 ° C. The time for maintaining the high temperature has a high degree of freedom, and strict time management is not required. Then stop the electric furnace heater and return to room temperature. After stopping energization of the heater, it may be left until it is close to room temperature.
  • the obtained Na-added CIGSS ternary alloy is a CIGSS polycrystal and is used as a material for forming a light absorption layer of a solar cell by a sputtering device, and is a safe solar cell that does not use sulfur gas or selenium gas harmful to the human body. Can be manufactured.
  • this Na-added CIGSS ternary alloy In order to install this Na-added CIGSS ternary alloy in a sputtering apparatus for forming a light absorption layer of a solar cell, it is formed into a sputtering target and used.
  • the Na-added CIGS quaternary alloy and Na-added CIGSS quinary alloy are used as materials for forming a light absorption layer of a solar cell. For this reason, a sputtering target is manufactured in order to obtain a shape suitable for a sputtering apparatus.
  • the manufacturing method of the sputtering target is the same for the Na-added CIGS quaternary alloy and the Na-added CIGS quaternary alloy, and the Na-added CIGS quaternary alloy will be described below.
  • FIG. 9 is a flowchart 48 of the sputtering target manufacturing method.
  • the method of manufacturing the sputtering target from the Na-added CIGS quaternary alloy first, in Step S71, the polycrystal of the Na-added CIGS quaternary alloy is pulverized and pulverized, and then in Step S72, the powder is formed into a desired shape.
  • the mold is filled and then bulked by pressure processing, and in step S73, the bulked CIGS quaternary alloy is sliced to form a sputtering target.
  • FIG. 10 is a diagram showing a structure 50 of a CIGS solar cell in which Na is diffused in the CIGS film.
  • a Mo (molybdenum) layer is laminated as a back electrode 54 on the substrate 52.
  • the light absorption layer 56 is composed of a CIGS thin film in which Na is diffused.
  • An n-type buffer layer 58 is formed on the p-type CIGS thin film that is the light absorption layer 56 to function as a solar cell.
  • CdS cadmium sulfide
  • a high resistance buffer layer 60 is laminated by ZnO (zinc oxide) or the like, and a transparent electrode 62 made of ITO or the like is formed on the top.
  • polyimide film not containing Na component, titanium foil, stainless steel or the like can be used.
  • buffer layer 58 an n-type zinc compound, an indium compound, or the like is also used.
  • the high-resistance buffer layer 60 is provided to compensate for the influence of non-uniformity of the light absorption layer 56, and ZnMgO (magnesium zinc oxide) is used in addition to ZnO.
  • FIG. 11 is a diagram showing a structure 64 of a CIGSS solar cell in which Na is diffused in the CIGSS film.
  • the CIGSS solar cell shown in FIG. 11 is also similar to the structure 50 of the CIGSS solar cell shown in FIG. 10, except that S is added to the light absorption layer 52 in the CIGSS solar cell. For this reason, the solar cell using the sputtering target of Na addition CIGS quaternary system alloy is explained.
  • FIG. 12 shows a conceptual diagram of one-process formation 66 of a light absorption layer by sputtering using a Na-added CIGS quaternary alloy sputtering target manufactured according to the present invention.
  • a CIGS thin film that becomes the light absorption layer 56 is formed on the back electrode 54 by sputtering and adhering sputtered atoms of Na-added CIGS. Thereby, a CIGS layer in which Na is diffused uniformly is obtained.
  • the light absorption layer 56 in which Na is uniformly diffused can be formed in one process.
  • FIG. 13 is a diagram for explaining a manufacturing state 70 of the light absorption layer by the sputtering apparatus.
  • the sputtering apparatus 72 is provided with an opening for performing vacuum suction 74, an opening for introducing Ar (argon) gas 76, and an opening for injecting cooling water 82.
  • a Mo substrate 86 having a Mo back electrode formed on a glass substrate is placed on the sample stage 84.
  • a sputtering target 80 attached to the electrode 78 is installed on the upper part of the sputtering apparatus 72.
  • a DC power source 92 is connected to the electrode 78 and the sample stage 84 with the sample stage 84 as an anode.
  • the sputtering target 80 made of Na-added CIGS quaternary alloy
  • the sputtering target 80 made of Na-added CIGS quaternary alloy.
  • the sputtered atoms 90 on the surface are blown off, the sputtered atoms 90 reach and deposit on the Mo substrate 86 to form a film, and a CIGS thin film in which Na is uniformly diffused is formed in one process.
  • FIG. 14 is a flowchart showing an example of a solar cell manufacturing method 96 using a NaGS-added CIGS quaternary alloy sputtering target by the CIGS film forming method in one process.
  • step S81 Mo is deposited on the substrate by sputtering.
  • step S82 the back electrode is shaved and patterned for series connection of the cells.
  • step S83 as described above, a CIGS light absorption layer in which Na is diffused is formed by a sputtering process in one process.
  • step S84 the formed CIGS light absorption layer is immersed in a strong alkaline aqueous solution, and a buffer layer is formed by a solution growth method. Subsequently, in step S85, the CIGS light absorption layer and the buffer layer are shaved to form a pattern.
  • step S86 a transparent conductive film layer is formed on the buffer layer by using, for example, ZnO or the like by a MOCVD (Metal Organic Chemical Vapor Deposition) apparatus.
  • step S87 the conductive film layer is again scraped and patterned.
  • step S88 a buster electrode made of aluminum or the like is soldered to the back electrode, and the layer laminated on the substrate is sealed with a cover glass. Stop to complete the solar cell.
  • FIG. 15 is a plan view of the vacuum deposition apparatus 100, which includes a vacuum chamber 102, a diffusion pump 104, a mechanical booster pump 106, and an oil rotary pump 108.
  • the light absorption layer is formed by the CIGS quaternary alloy 118 according to the present invention.
  • the air inside the vacuum chamber 102 is exhausted by the diffusion pump 104 and the oil rotary pump 108.
  • the mechanical booster pump 106 is configured such that two mayu rotors in a casing enter a drive gear at the shaft end and rotate synchronously in opposite directions.
  • the gas entering from the intake port is confined in the space between the casing and the rotor, and is released into the atmosphere from the exhaust port side by the rotation of the rotor. For this reason, the exhaust speed can be significantly increased by combining the mechanical booster pump 106 with the diffusion pump 104 and the oil rotary pump 108.
  • FIG. 16 shows a state where a light absorption layer is formed on the Mo substrate 86 by vapor deposition from the Na-added CIGS quaternary alloy 118 in the vacuum chamber 102 of the vacuum vapor deposition apparatus 100.
  • a tungsten board 110 on which a Mo substrate 86 and a sputtering target 80 are mounted, and a heater 112 are disposed.
  • a shutter 116 is provided for stopping the film formation when the thickness of the light absorption layer reaches a predetermined thickness.
  • Na-added CIGS quaternary alloy 118 as a vapor deposition sample is put into a tungsten boat 110, and then the evacuation is performed by rotating the diffusion pump 104, the oil rotary pump 108, and the mechanical booster pump 106.
  • the heater power supply 114 is turned on and a current is supplied to the heater 112 to heat it.
  • the shutter 116 is opened. Thereby, the vapor deposition material from the CIGS quaternary alloy 118 is deposited on the Mo substrate 86 to form a film.
  • the shutter 116 is closed and the vapor deposition is finished.
  • the Na-added CIGS quaternary alloy according to the present invention can be used as a material for forming a light absorption layer by a vacuum vapor deposition method using a vacuum vapor deposition apparatus.
  • this invention includes the appropriate deformation

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Abstract

La présente invention se rapporte à un alliage à base de CIGS4 ou à un alliage à base de CIGSS5 qui sont préparés de telle sorte qu'il soit possible de réguler la diffusion du sodium (Na) dans un film de CIGS ou un film de CIGSS, qui est une couche absorbant la lumière d'une cellule solaire, avec une précision élevée et qui sont préparés de telle sorte que la production d'une cellule solaire soit également facile; et à un procédé permettant de produire l'alliage à base de CIGS4 et un alliage à base de CIGSS5. Le procédé permettant de produire un alliage à base de CIGS4 auquel du sodium (Na) a été ajouté, comprend : une première étape consistant à produire un alliage à base de CIG3 par scellement sous vide dans une ampoule d'un mélange qui contient du cuivre, de l'indium et du gallium, et à provoquer la cristallisation à une température élevée; une deuxième étape consistant à produire une poudre d'alliage à base de CIG3 par pulvérisation de l'alliage à base de CIG3; et une troisième étape consistant à produire un alliage à base de CIGS4 par mélange du sélénium et du séléniure de sodium avec l'alliage à base de CIG3 pulvérisé, par scellement sous vide dans une ampoule et à provoquer la cristallisation à une température élevée. L'alliage à base de CIGSS5 comprend en outre du soufre et le soufre est ajouté au cours de la troisième étape.
PCT/JP2013/063085 2012-05-15 2013-05-09 ALLIAGE POUR UNE COUCHE ABSORBANT LA LUMIÈRE AJOUTÉE AU SODIUM (Na), PROCÉDÉ PERMETTANT DE PRODUIRE CE DERNIER ET CELLULE SOLAIRE WO2013172252A1 (fr)

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Citations (4)

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JP2011111641A (ja) * 2009-11-25 2011-06-09 Mitsubishi Materials Corp Ｃｕ−Ｉｎ−Ｇａ−Ｓｅ四元系合金スパッタリングターゲットおよびその製造方法
WO2011083646A1 (fr) * 2010-01-07 2011-07-14 Jx日鉱日石金属株式会社 Cible de pulvérisation cathodique, couche mince de composé semi-conducteur, cellule solaire possédant une couche mince de composé semi-conducteur ainsi que procédé de fabrication d'une couche mince de composé semi-conducteur
WO2011148600A1 (fr) * 2010-05-24 2011-12-01 株式会社アルバック Procédé pour la production d'une poudre d'alliage de cu-in-ga, procédé pour la production d'une poudre d'alliage de cu-in-ga-se, procédé pour la production d'un alliage de cu-in-ga-se fritté, poudre d'alliage de cu-in-ga, et poudre d'alliage de cu-in-ga-se
JP2013100589A (ja) * 2011-11-10 2013-05-23 Mitsubishi Materials Corp スパッタリングターゲットおよびその製造方法

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CN101613091B (zh) * 2009-07-27 2011-04-06 中南大学 一种cigs粉末、靶材、薄膜及其制备方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011111641A (ja) * 2009-11-25 2011-06-09 Mitsubishi Materials Corp Ｃｕ−Ｉｎ−Ｇａ−Ｓｅ四元系合金スパッタリングターゲットおよびその製造方法
WO2011083646A1 (fr) * 2010-01-07 2011-07-14 Jx日鉱日石金属株式会社 Cible de pulvérisation cathodique, couche mince de composé semi-conducteur, cellule solaire possédant une couche mince de composé semi-conducteur ainsi que procédé de fabrication d'une couche mince de composé semi-conducteur
WO2011148600A1 (fr) * 2010-05-24 2011-12-01 株式会社アルバック Procédé pour la production d'une poudre d'alliage de cu-in-ga, procédé pour la production d'une poudre d'alliage de cu-in-ga-se, procédé pour la production d'un alliage de cu-in-ga-se fritté, poudre d'alliage de cu-in-ga, et poudre d'alliage de cu-in-ga-se
JP2013100589A (ja) * 2011-11-10 2013-05-23 Mitsubishi Materials Corp スパッタリングターゲットおよびその製造方法

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