WO2012176425A1 - Procédé de fabrication d'une couche tampon d'un élément de conversion photoélectrique et procédé de fabrication d'un élément de conversion photoélectrique - Google Patents

Procédé de fabrication d'une couche tampon d'un élément de conversion photoélectrique et procédé de fabrication d'un élément de conversion photoélectrique Download PDF

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WO2012176425A1
WO2012176425A1 PCT/JP2012/003968 JP2012003968W WO2012176425A1 WO 2012176425 A1 WO2012176425 A1 WO 2012176425A1 JP 2012003968 W JP2012003968 W JP 2012003968W WO 2012176425 A1 WO2012176425 A1 WO 2012176425A1
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buffer layer
photoelectric conversion
solution
film formation
chemical bath
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PCT/JP2012/003968
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Japanese (ja)
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河野　哲夫
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富士フイルム株式会社
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    • 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
    • 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
    • H01L21/02436—Intermediate layers between substrates and deposited layers
    • H01L21/02439—Materials
    • H01L21/02485—Other 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
    • H01L21/02521—Materials
    • H01L21/02551—Group 12/16 materials
    • H01L21/02554—Oxides
    • 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
    • H01L21/02551—Group 12/16 materials
    • H01L21/02557—Sulfides
    • 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
    • H01L21/02617—Deposition types
    • H01L21/02623—Liquid deposition
    • H01L21/02628—Liquid deposition using solutions
    • 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
    • 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
    • H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • 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 method for manufacturing a buffer layer of a photoelectric conversion element and a method for manufacturing a photoelectric conversion element.
  • a photoelectric conversion element including a photoelectric conversion layer and an electrode connected to the photoelectric conversion layer is used for applications such as solar cells.
  • Si-based solar cells using bulk single crystal Si or polycrystalline Si, or thin-film amorphous Si have been mainstream, but research and development of Si-independent compound semiconductor solar cells has been made. ing.
  • Known compound semiconductor solar cells include bulk systems such as GaAs systems and thin film systems such as CIS or CIGS systems composed of group Ib elements, group IIIb elements, and group VIb elements.
  • a buffer layer (Cd system such as CdS) is generally provided between a photoelectric conversion layer and a translucent conductive layer (transparent electrode) formed thereon.
  • Cd system such as CdS
  • the buffer layer is usually formed by a chemical bath deposition (CBD) method.
  • Possible roles of the buffer layer include (1) prevention of recombination of photogenerated carriers, (2) band discontinuous matching, (3) lattice matching, and (4) coverage of surface irregularities of the photoelectric conversion layer. .
  • the surface unevenness of the photoelectric conversion layer is relatively large.
  • the CBD method which is a liquid phase method is preferable.
  • Patent Document 1 In the film formation by the CBD method, the composition of the reaction solution changes as the buffer layer is deposited on the photoelectric conversion layer. Therefore, in Patent Document 1, a plurality of reaction solution tanks are installed adjacent to each other. In parallel with performing the film formation process in one liquid tank, the reaction liquid is exchanged for the liquid tank after the film formation process is completed, and the reaction is performed by repeatedly repeating the reaction liquid tank. There has been proposed a CBD apparatus in which a film forming process can be performed under conditions where the composition of the liquid does not change greatly. Patent Document 1 describes that it is preferable to form a film while stirring the reaction solution in order to improve the in-plane uniformity of the buffer layer.
  • Patent Document 2 discloses a manufacturing method including a step of removing particles (colloid) adhering to a film formation surface by washing the film formation surface with a rinsing liquid. Patent Document 2 describes that the same reaction is repeatedly used. In Patent Document 3, since the reaction solution becomes suspended due to an increase in particles (colloid), the transparency of the reaction solution is monitored, and the use of the reaction solution is stopped when the transparency decreases to some extent. Thus, a manufacturing method for forming a film under a condition in which a certain amount or more of particles (colloid) does not exist has been proposed.
  • Patent Document 4 discloses a method of producing a zinc oxide film as a transparent conductive film of a photoelectric conversion element by an electrodeposition method.
  • an apparatus having a circulation system in which impurities mixed in the electrodeposition liquid are removed by a filtration filter and circulated and returned to the electrodeposition bath has been proposed.
  • a plurality of reaction liquid tanks are provided, and the reaction liquid tanks are sequentially changed to form a film by sequentially replacing the reaction liquid tanks, temperature control for each reaction liquid tank, disposal of the solution, Control of the entire apparatus such as replacement is complicated.
  • particulate solids and particles can be removed to some extent by washing the film formation surface as in Patent Document 2, it is desired to suppress the deposits adhering to the film formation surface in the first place. Even in the case of using a method of monitoring the transparency of a reaction solution and confirming whether or not the reaction solution is used as in Patent Document 3, it is not always possible to sufficiently prevent the adhesion of particulate solids. Can not.
  • the present invention has been made in view of the above circumstances, and in the CBD method, when film formation is performed a plurality of times using the same reaction solution, it is effective to attach particulate solids to the buffer layer surface.
  • An object of the present invention is to provide a method for manufacturing a buffer layer that can be suppressed to a low level.
  • Another object of the present invention is to provide a method for producing a photoelectric conversion element of good quality.
  • the buffer layer manufacturing method of the present invention is a photoelectric conversion element having a stacked structure in which a lower electrode, a photoelectric conversion semiconductor layer, a buffer layer made of a Zn compound, and a light-transmitting conductive layer are stacked in this order on a substrate.
  • a method for manufacturing the buffer layer comprising: Repeated n times (n is an integer of 2 or more) using the same chemical bath deposition solution, and the same film formation time on the photoelectric conversion semiconductor layer of a new substrate having the photoelectric conversion semiconductor layer on the outermost surface each time When forming the buffer layer with During the m-th film formation (m is an integer satisfying 2 ⁇ m ⁇ n) or at the stage where the film formation between the m ⁇ 1th film formation and the mth film formation is not performed.
  • the chemical bath deposition solution is filtered using
  • the formation of a single buffer layer is not limited to a process for a single substrate, but may be a process for a plurality of substrates. However, the processing is performed on the same substrate processing area (usually the area of a certain substrate ⁇ the number of substrates) for each of 1 to n times.
  • the chemical bath deposition solution is filtered not only during the m-th film formation (m is an integer satisfying 2 ⁇ m ⁇ n), but also during each film formation, or during the m-1th film formation and the m-th film formation. It is preferable to carry out not only at a stage where film formation is not performed but also at a stage where film formation is not performed every time.
  • the filtration is performed only when the film is not formed, and the chemical bath deposition solution is not stirred during the buffer layer formation each time.
  • the temperature of the chemical bath deposition solution during the filtration is preferably 60 ° C. or lower.
  • the zinc ion concentration in the chemical bath deposition solution at room temperature before the first film formation is x 0 [M]
  • the k ⁇ 1th film formation (k is an integer satisfying 2 ⁇ k ⁇ n) and the above-described film formation.
  • the zinc ion concentration dissolved in the chemical bath deposition solution during the k-th film formation is x k-1 [M]
  • the zinc ion concentration x k-1 is x k-1 ⁇ x 0 -0.005
  • the zinc ion concentration x [M] in the chemical bath deposition solution is x 0 before the k-th film formation. ⁇ 0.005 ⁇ x ⁇ x 0 +0.005
  • the zinc ion concentration corresponds to the total ion concentration of the Zn source when a plurality of zinc ion species are present.
  • the method for producing a photoelectric conversion element of the present invention includes a photoelectric conversion element having a laminated structure in which a lower electrode, a photoelectric conversion semiconductor layer, a buffer layer made of a Zn compound, and a light-transmitting conductive layer are laminated in this order on a substrate.
  • the buffer layer is manufactured by the method for manufacturing a buffer layer of the present invention.
  • the same chemical bath deposition solution is used repeatedly n times (n is an integer of 2 or more), and the photoelectric conversion of the substrate provided with the photoelectric conversion semiconductor layer on the outermost surface each time.
  • n is an integer of 2 or more
  • the buffer layer is formed on the conversion semiconductor layer with the same film formation time, during the m-th film formation (m is an integer satisfying 2 ⁇ m ⁇ n) or the m ⁇ 1th film formation. Since the chemical bath deposition solution is filtered using a filtration filter when no film formation is performed between the first and mth film formation, the surface of the buffer layer formed a plurality of times is also particulate solid. The adhesion of objects can be suppressed.
  • the amount of particulate solids generated increases as the time used is longer. Therefore, if the solution is used as it is without filtration, it is compared with the first film formation surface. The later the later, the more solid solid matter adheres to the film formation surface. On the other hand, according to the production method of the present invention, since the solution is used while being appropriately filtered, the amount of the particulate solid in the solution is suppressed, and the adhesion of the particulate solid is also suppressed on the surface of the plurality of film formations. be able to.
  • Patent Document 4 proposes a method of circulating and reusing an electrodeposition solution while filtering impurities in the electrodeposition method, but in the CBD method, precipitation of particles (colloid) is proposed.
  • the CBD method it was conspicuous in comparison with the electrodeposition method, and it was thought that there was no room for studying the reuse of the reaction liquid in which a certain amount of particles (colloid) were deposited.
  • the present inventor has clarified that in the CBD method according to the present invention, it is possible to reuse the reaction liquid while maintaining good film forming performance, and the effect of reducing the manufacturing cost by the reuse of the reaction liquid. Can also be obtained.
  • the buffer layer manufacturing method of the present invention is a photoelectric conversion element having a stacked structure in which a lower electrode, a photoelectric conversion semiconductor layer, a buffer layer made of a Zn compound, and a light-transmitting conductive layer are stacked in this order on a substrate.
  • the method for producing the buffer layer when the buffer layer is formed repeatedly n times (n is an integer of 2 or more) using the same chemical bath deposition solution, the mth (2 ⁇ m ⁇ n is an integer satisfying n), or the chemical bath deposition solution is filtered by a filtration filter at the stage where film formation is not performed between the m ⁇ 1th film formation and the mth film formation. It is characterized by doing.
  • the buffer layer at least one selected from ZnS, Zn (S, O), and Zn (S, O, OH), which are Zn compounds, is formed.
  • the buffer layer is formed by a chemical bath deposition (CBD) method.
  • CBD method is a general formula [M (L) i ] m + M M n + + iL (wherein, M: metal element, L: ligand, m, n, i: each represents a positive number).
  • CBD solution As a chemical bath deposition solution (hereinafter referred to as CBD solution), if a buffer layer made of a Zn-based compound of ZnS, Zn (S, O) and / or Zn (S, O, OH) can be deposited, the reaction
  • concentration of each component in the liquid is not particularly limited.
  • component (Z) which is at least one zinc source component (S) which is at least one sulfur source, component (C) which is at least one citric acid compound, ammonia and ammonium salt It contains at least one component (N) selected from the group consisting of water, and the concentration of component (C) is 0.001 to 0.25 M, and the concentration of component (N) is It is preferable to use a reaction solution having a pH of 0.001 to 0.40 M and a pH of 9.0 to 12.0 before the start of the reaction.
  • the component (Z) is not particularly limited, and preferably contains at least one selected from the group consisting of zinc sulfate, zinc acetate, zinc nitrate, zinc chloride, zinc carbonate, and hydrates thereof.
  • the concentration of component (Z) is not particularly limited and is preferably 0.001 to 0.5M.
  • Component (S) is not particularly limited, and compounds containing sulfur such as thiourea (CS (NH 2 ) 2 ), thioacetamide (C 2 H 5 NS), thiosemicarbazide, thiourethane, diethylamine, Ethanolamine or the like can be used. In particular, it is preferable to contain thiourea.
  • the concentration of component (S) is not particularly limited and is preferably 0.01 to 1.0M.
  • Component (C) is a component that functions as a complex-forming agent and the like, and a complex is easily formed by optimizing the type and concentration of component (C).
  • component (C) which is at least one kind of citric acid compound
  • a complex is more easily formed than in a reaction solution that does not use a citric acid compound, crystal growth by the CBD reaction is well controlled, and the base is covered well. Thus, a stable film can be formed.
  • Component (C) is not particularly limited, and preferably contains sodium citrate and / or a hydrate thereof.
  • the concentration of component (C) is preferably 0.001 to 0.25M, more preferably 0.001 to 0.1M.
  • Component (N) is a component that functions as a pH adjuster or the like, but is also a component that functions as a complexing agent or the like.
  • the ammonium salt suitable for use as the component (N) is not particularly limited, and examples thereof include NH 4 OH.
  • the concentration of component (N) is preferably 0.001 to 0.40M.
  • the solubility and supersaturation degree of metal ions can be adjusted by adjusting the pH with the component (N). If the concentration of component (N) is within the range of 0.001 to 0.40M, the reaction rate is fast, and film formation is carried out at a practical production rate without providing a fine particle layer formation step before the film formation step. can do. When the concentration of the component (N) exceeds 0.40 M, the reaction rate becomes slow, and it is necessary to devise such as adding a fine particle layer before the film forming step.
  • the concentration of component (N) is more preferably 0.01 to 0.30M.
  • the reaction temperature during the formation of the buffer layer is 70 to 95 ° C. If the reaction temperature is less than 70 ° C., the reaction rate becomes slow, and the thin film does not grow, or even if the thin film is grown, it is difficult to obtain a desired thickness (for example, 50 nm or more) at a practical reaction rate. When the reaction temperature exceeds 95 ° C., generation of bubbles and the like increases in the reaction solution, which adheres to the film surface and makes it difficult to grow a flat and uniform film. Furthermore, when the reaction is carried out in an open system, a concentration change due to evaporation of the solvent or the like occurs, making it difficult to maintain stable thin film deposition conditions.
  • the reaction temperature is preferably 80 to 90 ° C.
  • the film formation time is not particularly limited. Although the film formation time depends on the reaction temperature, for example, the base can be satisfactorily covered in 10 to 60 minutes, and a layer having a sufficient thickness as a buffer layer can be formed. In the present invention, the film forming process is simplified by setting the film forming time for each time in the film forming process repeated n times to be the same.
  • the stirring includes not only stirring by a stirrer or the like but also liquid circulation and application of ultrasonic waves to the reaction solution. Agitation of the reaction solution promotes the generation of particles (colloid) in the reaction solution and increases the amount of particles (colloid) floating in the reaction solution, so that the particulate solid adheres to the surface of the deposited film. The possibility of becomes high.
  • the particulate solid is a solid in which particles having a primary particle size of the order of several tens to several hundreds of nanometers are aggregated. If a photoelectric conversion element is produced with particulate solids (secondary aggregates) having an equivalent circle diameter of 1 ⁇ m or more adhering to the buffer layer surface, the particulate solids become a leak path, which deteriorates the performance of the photoelectric conversion element. There is a possibility of connection.
  • the buffer layer without stirring the reaction solution, the generation of particulate solids can be suppressed as compared with the case of stirring.
  • the same CBD solution is used for forming the buffer layer a plurality of times (n times). Since the particulate solids in the CBD solution increase as the reaction time increases, in order to remove the particulate solids, the m-th film formation stage or the m-1 and m-th formations are performed. The reaction solution is filtered at a stage between the membranes.
  • the filtration when filtration is performed during film formation, the filtration may be performed only for a specific plurality of times, or may be performed during each film formation. Also, when filtration is performed at a stage between the film formations, the filtration may be performed only between specific film formation times. Adherence of particulate solids to the surface can be further suppressed, which is more preferable.
  • the filtration method is not particularly limited, and may be filtered by liquid circulation through a filtration filter using a CBD device comprising a CBD tank and a circulation flow path equipped with a filtration filter, or a separate container is used. Alternatively, the solution may be filtered. When using another container, the filtered solution is returned to the CBD tank and reused.
  • the pore size of the filtration filter is preferably about 1 ⁇ m to 1000 ⁇ m. If it is less than 1 ⁇ m, it takes too much time for filtration, and if it exceeds 1000 ⁇ m, a relatively large particulate solid will remain in the solution after filtration.
  • the pore size is more preferably about 1 ⁇ m to 20 ⁇ m.
  • the temperature of the solution during filtration is preferably lower than the temperature during film formation, specifically 60 ° C. or less.
  • the zinc ion concentration in the chemical bath deposition solution at room temperature before the first film formation is x 0 [M], in the chemical bath deposition solution between the k ⁇ 1th film formation and the kth film formation.
  • the zinc ion concentration x [M] in the chemical bath deposition solution is x 0 -0.005 ⁇ x ⁇ x 0 +0.005.
  • a zinc source is added to the chemical bath deposition solution so that
  • the thickness of the buffer layer deposited each time is relatively uniform (average value of about ⁇ 5%) ).
  • zinc sulfate zinc acetate, zinc nitrate, zinc chloride, zinc carbonate, or a hydrate thereof can be used.
  • the zinc ion concentration in the chemical bath deposition solution may be measured sequentially or may be measured in advance by the same process.
  • the zinc ion concentration x 0 [M] dissolved in the solution in the unused stage does not require measurement because the preparation concentration is known. From the second time on, the zinc ion concentration is measured before each film formation. For the concentration measurement, ICP emission spectroscopy is used.
  • the reaction solution for sampling for concentration measurement may or may not be filtered, but ICP emission spectroscopic analysis uses a sample in a filtered state. The reason for using the sample in the filtered state is to measure the concentration of zinc ions dissolved in the solution.
  • the reaction solution is sampled during the interval between film formation and the zinc ion concentration is measured, and the zinc ion concentration becomes x 0 -0.005 [M] or less.
  • the zinc source may be added to the solution as described above and dissolved in the solution, and then the film may be formed.
  • the zinc ion concentration x 1 [M] before the second film formation (after the first film formation) was larger than x 0 -0.005, but before the third film formation (after the second film formation).
  • the third film formation may be performed.
  • the concentration measurement is performed during the interval, there is a problem that the interval time becomes long and the yield decreases. Therefore, the number of film formation times when the zinc ion concentration becomes x 0 -0.005 or less is measured in advance. It is desirable to keep it.
  • the number of times of film formation the zinc ion concentration x 0 -0.005 or less and the amount of the zinc source to be added are obtained.
  • a predetermined amount of zinc source may be added at the zinc addition timing.
  • FIG. 1 shows a schematic configuration of a CBD apparatus for realizing the buffer film manufacturing method of the present invention.
  • the CBD device 100 includes a reaction tank 103 that stores a reaction liquid 102 that forms a buffer layer, and a circulation channel 105 that discharges the reaction liquid 102 from the reaction tank 103 and supplies it to the reaction tank 103 again.
  • the passage 105 is provided with a filtration filter 106, a heating means (quick heater) 107 for raising the temperature of the reaction liquid 102, and a circulation pump P for circulating the liquid.
  • the circulation channel 105 includes a first circulation path 105a extending from the reaction tank 103 to the filtration filter 106 and a second circulation path 105b extending from the filtration filter 106 to the reaction tank 103.
  • the circulation pump P and the heating means 107 are the second circulation path 105b. Is provided in the circulation path 105b.
  • the reaction vessel 103 is provided with a temperature control means (not shown) including a heating means and a thermometer for maintaining the reaction solution 102 at a predetermined temperature.
  • a substrate holding member (substrate holder) 120 that holds the substrate 10 so as to bring the reaction solution 102 into contact with the surface of the photoelectric conversion semiconductor layer without bringing the substrate 10 into contact with the reaction solution 102 is provided above the reaction vessel 103. Is provided.
  • the substrate holder 120 is formed so that the lower electrode 20 and the photoelectric conversion semiconductor layer 30 formed in this order on the substrate 10 can contact the reaction liquid 102 only on the surface on which the photoelectric conversion semiconductor layer 30 is formed. 10 is held by the liquid leakage prevention jig 121 toward the substrate holder main body 123.
  • the liquid leakage prevention jig 121 prevents the reaction liquid 102 from entering through a gap between the liquid leakage prevention jig 121 and the substrate 10 on which the held photoelectric conversion semiconductor layer 30 is formed by the fixing frame 122 that can be fastened and fixed. And the substrate 10 on which the photoelectric conversion semiconductor layer 30 is formed is fastened and fixed. Note that the position of the liquid leakage prevention jig 121 and the fixed frame 122 can be shifted so as to appropriately correspond to the size of the substrate 10.
  • the temperature of the reaction solution 102 is adjusted to a predetermined temperature of 70 ° C. to 95 ° C.
  • the substrate 10 with the photoelectric conversion semiconductor layer 30 supported by the substrate holder 120 is placed in the reaction liquid 102 adjusted to a predetermined temperature so that the surface of the photoelectric conversion semiconductor layer 30 is in contact with the reaction liquid 102.
  • a buffer layer is deposited on the photoelectric conversion semiconductor layer 30 by maintaining the reaction liquid 102 at a predetermined temperature and maintaining it for a predetermined time (for example, 30 minutes).
  • the substrate is taken out from the reaction solution 102.
  • the circulation pump P By operating the circulation pump P in a state where the substrate is not immersed in the reaction solution 102, the reaction solution in the reaction tank 103 is discharged to the first circulation path 105a. Since the first circulation path 105a is not heated, the temperature of the reaction liquid 102 decreases and is approximately 60 ° C. or less when passing through the filter 106. The reaction liquid that has passed through the filtration filter 106 passes through the second circulation path 105 b and is heated by the quick heater 107 and then returned to the reaction tank 103.
  • reaction solution is heated to a temperature substantially equal to the reaction temperature by the quick heater 107 and then supplied to the reaction vessel 103, the subsequent film formation process is continued for a time without lowering the temperature of the reaction solution in the reaction vessel. It can be done without leaving.
  • FIG. 2 shows a schematic cross-sectional view of a photoelectric conversion element of one embodiment manufactured by the method for manufacturing a photoelectric conversion element of the present invention.
  • the scale of each component in the figure is appropriately different from the actual one.
  • a photoelectric conversion element 1 shown in FIG. 2 includes a lower electrode (back electrode) 20, a photoelectric conversion semiconductor layer 30, a buffer layer 40, a window layer 50, a translucent conductive layer (transparent electrode) 60, and an upper electrode on a substrate 10.
  • (Grid electrode) 70 is an element that is sequentially laminated.
  • the method for producing a photoelectric conversion element of the present invention is a method for producing a photoelectric conversion element having a laminated structure of at least the lower electrode 20, the photoelectric conversion semiconductor layer 30, the buffer layer 40, and the light-transmitting conductive layer 60 on the substrate 10.
  • the buffer layer is manufactured by the buffer layer manufacturing method of the present invention.
  • each layer there are no particular restrictions on the method of forming each layer other than the buffer layer.
  • An example of the method for forming the substrate and each layer will be briefly described below.
  • the substrate is not particularly limited, and specifically, Glass substrate, A metal substrate such as stainless steel with an insulating film formed on the surface; An anodized substrate in which an anodized film mainly composed of Al 2 O 3 is formed on at least one surface side of an Al base material mainly composed of Al; An anodic oxide film mainly composed of Al 2 O 3 is formed on at least one surface side of a composite base material in which an Al material mainly composed of Al is combined on at least one surface side of the Fe material mainly composed of Fe.
  • An anodic oxide film mainly composed of Al 2 O 3 is formed on at least one surface side of a substrate on which an Al film composed mainly of Al is formed on at least one surface side of an Fe material mainly composed of Fe.
  • a resin substrate such as polyimide.
  • a soda lime glass (SLG) layer may be provided on the substrate.
  • SSG soda lime glass
  • Na can be diffused in the photoelectric conversion layer.
  • the photoelectric conversion layer contains Na, the photoelectric conversion efficiency can be further improved.
  • the main component of the lower electrode 20 is not particularly limited, and Mo, Cr, W, and combinations thereof are preferable, and Mo or the like is particularly preferable.
  • the thickness of the lower electrode 20 is not limited and is preferably about 200 to 1000 nm.
  • a film can be formed on the substrate by a sputtering method.
  • the main component of the photoelectric conversion semiconductor layer 30 is not particularly limited, and is preferably a compound semiconductor having at least one chalcopyrite structure because high photoelectric conversion efficiency can be obtained.
  • the Ib group element, the IIIb group element, and the VIb More preferably, it is at least one compound semiconductor composed of a group element.
  • Cu 2 ZnSnS 4, Cu 2 ZnSnSe 4, Cu 2 ZnSn (S, Se) may be 4 or the like.
  • the film thickness of the photoelectric conversion semiconductor layer 30 is not particularly limited, and is preferably 1.0 to 4.0 ⁇ m, particularly preferably 1.5 to 3.5 ⁇ m.
  • the film forming method of the photoelectric conversion semiconductor layer 30 is not particularly limited, and can be formed by a vacuum deposition method, a sputtering method, an MOCVD method, or the like.
  • the buffer layer 40 is manufactured by the above-described method for manufacturing a buffer layer of the present invention.
  • the conductivity type of the buffer layer 40 is not particularly limited, and n-type or the like is preferable.
  • the film thickness of the buffer layer 40 is not particularly limited, and is preferably 10 nm to 2 ⁇ m, and more preferably 15 to 200 nm.
  • the window layer 50 is an intermediate layer that captures light.
  • the composition of the window layer 50 is not particularly limited, and i-ZnO or the like is preferable.
  • the thickness of the window layer 50 is not particularly limited, and is preferably 10 nm to 2 ⁇ m, and more preferably 15 to 200 nm.
  • the method for forming the window layer 50 is not particularly limited, but a sputtering method or an MOCVD method is suitable.
  • the buffer layer 40 is manufactured by the liquid phase method, it is also preferable to use the liquid phase method in order to simplify the manufacturing process.
  • the window layer 50 is not essential and may be a photoelectric conversion element without the window layer 50.
  • the translucent conductive layer 60 is a layer that captures light and functions as an electrode that is paired with the lower electrode 20 and through which a current generated in the photoelectric conversion semiconductor layer 30 flows.
  • the composition of the translucent conductive layer 60 is not particularly limited, and n-ZnO such as ZnO: Al, ZnO: Ga, and ZnO: B is preferable.
  • the film thickness of the translucent conductive layer 60 is not particularly limited and is preferably 50 nm to 2 ⁇ m.
  • the film forming method of the translucent conductive layer 60 is not particularly limited, but the sputtering method and the MOCVD method are suitable as with the window layer. On the other hand, in order to simplify the manufacturing process, it is also preferable to use a liquid phase method.
  • the main component of the upper electrode 70 is not particularly limited, and examples thereof include Al.
  • the film thickness of the upper electrode 70 is not particularly limited and is preferably 0.1 to 3 ⁇ m.
  • the upper electrode is provided in a cell serving as a power extraction end among cells connected in series.
  • the photoelectric conversion element 1 manufactured by the manufacturing method of this embodiment is configured as described above.
  • the photoelectric conversion element 1 can be preferably used for a solar cell or the like. If necessary, a cover glass, a protective film, or the like can be attached to the photoelectric conversion element 1 to form a solar cell.
  • the photoelectric conversion element manufactured by the manufacturing method of the present invention can be applied not only to solar cells but also to other uses such as a CCD.
  • a substrate in which a CIGS layer was formed on a soda lime glass (SLG) substrate with a Mo electrode layer was prepared.
  • a Mo lower electrode is formed on a 30 mm ⁇ 30 mm square soda lime glass (SLG) substrate by sputtering to a thickness of 0.8 ⁇ m, and is further a kind of multi-source evaporation method on the Mo lower electrode 3 Using a step method, a Cu (In 0.7 Ga 0.3 ) Se 2 layer having a thickness of 1.8 ⁇ m was formed.
  • ⁇ Surface treatment> A reaction vessel containing a 10% aqueous solution of KCN was prepared, and the surface of the CIGS layer formed on the substrate was immersed for 3 minutes at room temperature to remove impurities from the CIGS layer surface. After taking out, it fully washed with water.
  • CBD solution Zinc sulfate aqueous solution (0.18 [M]) as aqueous solution (I) of component (Z), thiourea aqueous solution (thiourea 0.30 [M]) as aqueous solution (II) of component (S), component (C)
  • Aqueous solution of trisodium citrate (0.18 [M]) was prepared as an aqueous solution (III)
  • aqueous ammonia (0.30 [M] was prepared as an aqueous solution (IV) of component (N).
  • aqueous solutions I, II, and III are mixed in the same volume, zinc sulfate 0.06 [M], thiourea 0.10 [M], trisodium citrate 0.06 [M].
  • the mixed solution was completed, and this mixed solution and 0.30 [M] aqueous ammonia were mixed in equal volumes to obtain a CBD solution (reaction solution) 1.
  • the aqueous solution (IV) was added last. In order to obtain a transparent reaction solution, it is important to add the aqueous solution (IV) last.
  • the CBD solution obtained by mixing was filtered using a filter having a pore size of 0.22 ⁇ m.
  • the pH of the finally obtained CBD solution 1 was 10.3.
  • a buffer layer was formed on the CIGS layer after the surface treatment by the CBD method.
  • the buffer layer was formed by immersing the substrate on which the CIGS layer was formed in 200 ml of the CBD solution adjusted to 90 ° C. for 30 minutes.
  • the substrate was placed so that the substrate surface was perpendicular to the bottom surface of the CBD solution container.
  • this CBD process was implemented, stirring the CBD solution (reaction liquid) without stirring.
  • stirring is accompanied by circulation filtration during film formation.
  • the stirring about the comparative example 1 shall be accompanied with the circulation of the solution by the circulation path which is not equipped with a filtration filter.
  • n buffer layers are formed as shown in Table 1, respectively.
  • a buffer layer was formed on the photoelectric conversion semiconductor layer using a new substrate having a photoelectric conversion semiconductor layer on the surface each time.
  • filtration method either a circulation method or another processing method was used.
  • a CBD apparatus having a circulation path including a reaction tank and a filtration filter as shown in FIG. 1 was used.
  • the size of the filter filter hole was as shown in Table 1.
  • a separate container and a filtration filter are prepared, suction filtration is performed, the filtrate is collected in a separate container, and returned to the reaction tank for reuse.
  • ⁇ Film surface evaluation> In the 100 ⁇ m ⁇ 100 ⁇ m field of view, the following criteria were used to evaluate the presence of deposits (aggregates found when the film surface was observed from directly above) where the particles with primary particle sizes of the order of several tens to several hundreds of nm were aggregated did. Good when the equivalent circle diameter is 3 ⁇ m or more is 1 or less (Good), 2 or more when the equivalent circle diameter is 3 ⁇ m or more is acceptable (OK), the equivalent circle diameter is 3 ⁇ m or more The case where the number was 11 or more was regarded as defective (NG).

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Abstract

La présente invention se rapporte à un procédé de fabrication d'une couche tampon d'un élément de conversion photoélectrique qui, lorsque la même solution de dépôt par bain chimique est utilisée de multiples fois pour déposer des couches tampons, supprime l'adhésion de solides sous forme de particules à la surface de la couche tampon. La même solution de dépôt par bain chimique (102) est utilisée à plusieurs reprises n fois (n étant un nombre entier égal ou supérieur à 2) afin de former, chaque fois au cours d'une période de formation de couche tampon prédéterminée, une couche tampon qui comprend un composé de zinc (Zn) sur une couche semi-conductrice de conversion photoélectrique (30) agencée sur la surface la plus extérieure d'un nouveau substrat (10). La solution de dépôt par bain chimique (102) est filtrée à l'aide d'un filtre (106) pendant la mième formation de couche tampon (m étant un nombre entier qui satisfait la relation 2 ≤ m ≤ n) ou pendant l'étape entre la (m - 1)ième formation de couche tampon et la mième formation de couche tampon lorsqu'une couche tampon n'est pas formée.
PCT/JP2012/003968 2011-06-24 2012-06-19 Procédé de fabrication d'une couche tampon d'un élément de conversion photoélectrique et procédé de fabrication d'un élément de conversion photoélectrique WO2012176425A1 (fr)

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JP2003124487A (ja) * 2001-10-18 2003-04-25 Matsushita Electric Ind Co Ltd 太陽電池の製造装置
WO2008120306A1 (fr) * 2007-03-28 2008-10-09 Showa Shell Sekiyu K.K. Procédé de fabrication d'un dispositif de cellule solaire en couches minces à base de cis
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