WO2014002796A1 - Appareil de conversion photoélectrique et procédé permettant de fabriquer un appareil de conversion photoélectrique - Google Patents

Appareil de conversion photoélectrique et procédé permettant de fabriquer un appareil de conversion photoélectrique Download PDF

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Publication number
WO2014002796A1
WO2014002796A1 PCT/JP2013/066473 JP2013066473W WO2014002796A1 WO 2014002796 A1 WO2014002796 A1 WO 2014002796A1 JP 2013066473 W JP2013066473 W JP 2013066473W WO 2014002796 A1 WO2014002796 A1 WO 2014002796A1
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photoelectric conversion
semiconductor layer
electrode layer
film
conversion device
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PCT/JP2013/066473
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English (en)
Japanese (ja)
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憲 西浦
塁 鎌田
英章 浅尾
計匡 梅里
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京セラ株式会社
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Priority to JP2014522543A priority Critical patent/JP5791802B2/ja
Publication of WO2014002796A1 publication Critical patent/WO2014002796A1/fr

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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
    • H01L31/036—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 their crystalline structure or particular orientation of the crystalline planes
    • H01L31/0392—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 their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate
    • H01L31/03923—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 their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate including AIBIIICVI compound materials, e.g. CIS, CIGS
    • 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
    • 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
    • H01L31/042—PV modules or arrays of single PV cells
    • H01L31/0445—PV modules or arrays of single PV cells including thin film solar cells, e.g. single thin film a-Si, CIS or CdTe solar cells
    • H01L31/046—PV modules composed of a plurality of thin film solar cells deposited on the same substrate
    • 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

  • the present invention relates to a photoelectric conversion device using a semiconductor layer containing a group I-III-VI compound and a method for manufacturing the photoelectric conversion device.
  • a photoelectric conversion device used for solar power generation or the like there is a device using a semiconductor layer containing an I-III-VI group compound such as CIS or CIGS as a light absorption layer.
  • a photoelectric conversion device is described in, for example, Japanese Patent Application Laid-Open No. 2000-299486.
  • Such a photoelectric conversion device using a semiconductor layer containing an I-III-VI group compound has a configuration in which a plurality of photoelectric conversion cells are arranged side by side in a plane.
  • Each photoelectric conversion cell has a substrate such as glass, a lower electrode such as a metal electrode, a photoelectric conversion layer including a light absorption layer and a buffer layer, and an upper electrode such as a transparent electrode and a metal electrode in this order. It is constructed by stacking.
  • the plurality of photoelectric conversion cells are electrically connected in series by electrically connecting the upper electrode of one adjacent photoelectric conversion cell and the lower electrode of the other photoelectric conversion cell by a connecting conductor. Yes.
  • Such a semiconductor layer containing the I-III-VI group compound is formed by forming a film containing the raw material of the I-III-VI group compound on the lower electrode and heat-treating the film.
  • a salt or a complex of an element constituting the I-III-VI group compound is used as a raw material for the I-III-VI group compound.
  • a single source precursor single source source precursor in which Cu, Se and In or Ga are present in one organic compound is a compound of the I-III-VI group. It is described that it is used as a raw material.
  • This photoelectric conversion efficiency indicates the rate at which sunlight energy is converted into electric energy in the photoelectric conversion device.
  • the value of the electric energy output from the photoelectric conversion device is the amount of sunlight incident on the photoelectric conversion device. Divided by the value of energy and derived by multiplying by 100.
  • This invention aims at the improvement of the photoelectric conversion efficiency in a photoelectric conversion apparatus.
  • a photoelectric conversion device includes a semiconductor layer including a group 11 element, an indium element, a gallium element, a sulfur element, and a selenium element on an electrode layer, and the semiconductor layer includes the electrode.
  • the relative atomic number ratio of gallium element and the relative atomic number ratio of sulfur element to the total number of atoms of indium element and gallium element increase as the distance from the electrode layer increases.
  • a film containing a group 11 element and an indium element and containing a gallium element at least on the surface portion opposite to the electrode layer is formed on an electrode layer. And heating the film in an atmosphere containing sulfur element, and then heating the film in an atmosphere containing selenium element to form the film on the surface portion opposite to the electrode layer with indium element and gallium element. And a step of forming a semiconductor layer in which a relative atomic number ratio of gallium element and a relative atomic number ratio of sulfur element increase with increasing distance from the electrode layer.
  • Any embodiment of the present invention can provide a photoelectric conversion device with high photoelectric conversion efficiency.
  • FIG. 1 It is a perspective view which shows an example of embodiment of the photoelectric conversion apparatus produced using the manufacturing method of the photoelectric conversion apparatus which concerns on one Embodiment of this invention.
  • FIG. 1 It is sectional drawing of the photoelectric conversion apparatus of FIG. It is a graph which shows the composition distribution of the thickness direction of a 1st semiconductor layer.
  • FIG. 1 is a perspective view showing an example of a photoelectric conversion device 11 according to an embodiment of the present invention.
  • FIG. 2 is an XZ sectional view of the photoelectric conversion device 11 of FIG. 1 to 9 are provided with a right-handed XYZ coordinate system in which the arrangement direction of photoelectric conversion cells 10 (the horizontal direction in the drawing in FIG. 1) is the X-axis direction.
  • the photoelectric conversion device 11 has a configuration in which a plurality of photoelectric conversion cells 10 are arranged in parallel on a substrate 1.
  • a plurality of photoelectric conversion cells 10 are arranged in parallel on a substrate 1.
  • FIG. 1 only two photoelectric conversion cells 10 are shown for convenience of illustration, but an actual photoelectric conversion device 11 includes a large number of photoelectric conversion cells in the X-axis direction of the drawing or further in the Y-axis direction of the drawing.
  • the conversion cells 10 are arranged two-dimensionally (two-dimensionally).
  • Each photoelectric conversion cell 10 mainly includes a lower electrode layer 2, a first semiconductor layer 3, a second semiconductor layer 4, an upper electrode layer 5, and a collecting electrode 7.
  • the main surface on the side where the upper electrode layer 5 and the collecting electrode 7 are provided is a light receiving surface. Further, the photoelectric conversion device 11 is provided with three types of groove portions such as first to third groove portions P1, P2, and P3.
  • the substrate 1 supports the plurality of photoelectric conversion cells 10 and is made of, for example, a material such as glass, ceramics, resin, or metal.
  • a blue plate glass sina lime glass having a thickness of about 1 to 3 mm may be used as the substrate 1.
  • the lower electrode layer 2 is a conductive layer provided on one main surface of the substrate 1.
  • Mo molybdenum
  • Al aluminum
  • Ti titanium
  • Ta tantalum
  • Au gold
  • the lower electrode layer 2 has a thickness of about 0.2 to 1 ⁇ m and is formed by a known thin film forming method such as sputtering or vapor deposition.
  • the first semiconductor layer 3 as the light absorption layer is provided on a main surface (also referred to as one main surface) on the + Z side of the lower electrode layer 2 and has a first conductivity type (here, p-type conductivity type). And a thickness of about 1 to 3 ⁇ m.
  • the first semiconductor layer 3 is a semiconductor layer containing an I-III-VI group compound.
  • Group I-III-VI compounds are Group 11 elements (also referred to as Group IB elements in the former IUPAC system), Group 13 elements (also referred to as Group III-B elements), and Group 16 elements (Group VI-B). (Also referred to as an element).
  • the first semiconductor layer 3 has at least a surface portion 3a opposite to the lower electrode layer 2 (hereinafter referred to as a surface portion 3a opposite to the lower electrode layer 2 of the first semiconductor layer 3).
  • the surface portion 3a of the first semiconductor layer 3 includes at least an indium element (hereinafter also referred to as an In element) and a gallium element (hereinafter also referred to as a Ga element) as group 13 elements, and at least as a group 16 element. It contains selenium element (hereinafter also referred to as Se element) and sulfur element (hereinafter also referred to as S element).
  • Examples of the I-III-VI group compound contained in the surface portion 3a include Cu (In, Ga) (Se, S) 2 (also referred to as diselen / copper indium / gallium / CIGSS).
  • the first semiconductor layer 3 has a portion 3b other than the surface portion 3a (hereinafter, the portion 3b other than the surface portion 3a of the first semiconductor layer 3 is also referred to as a remaining portion 3b of the first semiconductor layer 3).
  • the S element may or may not be contained.
  • the remaining portion 3b of the first semiconductor layer 3 contains at least an In element and a Ga element as group 13 elements and at least an Se element as group 16 elements.
  • Examples of the I-III-VI group compound contained in the remaining part 3b include Cu (In, Ga) Se 2 (also referred to as copper indium selenide / gallium, CIGS), CIGSS, and the like. That is, the first semiconductor layer 3 may be a layer containing CIGSS as a whole, or the surface portion 3a may contain CIGSS and the remaining portion 3b may contain CIGS.
  • the first semiconductor layer 3 has, on the surface portion 3a, the relative atomic number ratio Ga / (In + Ga) of the Ga element to the total atomic number of the In element and the Ga element and the relative atomic number ratio S / (In + Ga) of the S element. ) Increases as the distance from the lower electrode layer 2 increases.
  • the conduction band is shifted to the high energy side and the valence band is shifted to the low energy side in the surface portion 3a of the first semiconductor layer 3 that forms a pn junction with the second semiconductor layer 4. Since the band gap can be increased, the pn junction can be improved to suppress interface recombination, and the open circuit voltage can be increased.
  • the composition distribution in the thickness direction of the first semiconductor layer 3 is expressed, for example, as shown in FIG.
  • the composition distribution in the thickness direction of the first semiconductor layer 3 can be measured by various elemental analysis methods. For example, for the Ga element and the S element, elemental analysis is performed by X-ray electron spectroscopy (XPS) while the first semiconductor layer 3 is shaved in the thickness direction by sputtering or the like, or a cross section of the first semiconductor layer 3 is obtained. Can be measured by elemental analysis by energy dispersive X-ray analysis (EDS) using a transmission electron microscope (TEM). Further, the oxygen element can be measured by elemental analysis by secondary ion mass spectrometry (SIMS) while cutting the first semiconductor layer 3 in the thickness direction by sputtering or the like.
  • XPS X-ray electron spectroscopy
  • EDS energy dispersive X-ray analysis
  • TEM transmission electron microscope
  • SIMS secondary ion mass spectrometry
  • the thickness of the surface portion 3a of the first semiconductor layer 3 in which the relative atomic number ratio of Ga element and the relative atomic number ratio of S element increases as the distance from the lower electrode layer 2 increases. It is sufficient that the thickness is about 0.15 to 0.5 times the total thickness.
  • the relative atomic number ratio of Ga element to the total number of In elements and Ga element in the surface portion 3a of the first semiconductor layer 3 is a portion on the second semiconductor layer 4 side in the surface portion 3a (first semiconductor layer 3a). In the vicinity of the interface between the semiconductor layer 3 and the second semiconductor layer 4, it is 0.1 to 0.5, and the portion on the lower electrode layer 2 side in the surface portion 3 a (in the case of FIG. In a portion where the number ratio is minimal, it may be 0.05 to 0.4.
  • the relative atomic number ratio of the S element to the total number of In elements and Ga elements in the surface portion 3a of the first semiconductor layer 3 is a portion on the second semiconductor layer 4 side in the surface portion 3a (first semiconductor layer 3a). It is 0.05 to 1 in the vicinity of the interface between the semiconductor layer 3 and the second semiconductor layer 4, and the portion on the lower electrode layer 2 side in the surface portion 3 a (in the case of FIG. 3, the relative atomic number ratio of Ga element) In the region where the minimum is 0), it may be 0 to 0.05.
  • the relative atomic number ratio of Ga element to the total atomic number of In element and Ga element may increase as it approaches the lower electrode layer 2. With such a configuration, charge transfer can be made better, and the photoelectric conversion efficiency of the photoelectric conversion device 11 becomes higher.
  • Such a composition distribution of the remaining portion 3b is expressed as shown in FIG. 3, for example.
  • the relative atomic number ratio of the Ga element to the total number of In elements and Ga elements in the remaining part 3b of the first semiconductor layer 3 is a part on the second semiconductor layer 4 side in the remaining part 3b (in the case of FIG. 3). Is 0.05 to 0.4 at the portion where the relative atomic number ratio of Ga element is minimized, and the portion on the lower electrode layer 2 side (the first semiconductor layer 3 and the lower electrode layer 2) in the remaining portion 3b. In the vicinity of the interface, it may be 0.1 to 0.7.
  • the first semiconductor layer 3 may further contain an oxygen element at least in the surface portion 3a.
  • the oxygen element enters lattice defects in the first semiconductor layer 3, and charge recombination can be reduced.
  • the number of oxygen atoms contained per unit volume in the surface portion 3a may be about 10 18 to 10 22 atms / cm 3 .
  • the content of the oxygen element may increase as the distance from the lower electrode layer 2 increases as in the case of the Ga element and the S element. That is, as the Ga element and S element increase, the oxygen element also increases.
  • the content (number of atoms) at each site in the thickness direction of the oxygen element may be, for example, about 5 to 30% of the S element at each site.
  • the second semiconductor layer 4 is a semiconductor layer provided on one main surface of the first semiconductor layer 3.
  • the second semiconductor layer 4 has a conductivity type (here, n-type conductivity type) different from that of the first semiconductor layer 3.
  • a conductivity type here, n-type conductivity type
  • positive and negative carriers generated by photoelectric conversion in the first semiconductor layer 3 are well separated.
  • semiconductors having different conductivity types are semiconductors having different main conductive carriers.
  • the conductivity type of the second semiconductor layer 4 may be i-type instead of n-type.
  • the second semiconductor layer 4 includes, for example, cadmium sulfide (CdS), indium sulfide (In 2 S 3 ), zinc sulfide (ZnS), zinc oxide (ZnO), indium selenide (In 2 Se 3 ), In (OH , S), (Zn, In) (Se, OH), and (Zn, Mg) O. From the viewpoint of reducing current loss, the second semiconductor layer 4 can have a resistivity of 1 ⁇ ⁇ cm or more.
  • the second semiconductor layer 4 is formed by, for example, a chemical bath deposition (CBD) method or the like.
  • the second semiconductor layer 4 has a thickness in the normal direction of one main surface of the first semiconductor layer 3. This thickness is set to, for example, 10 to 200 nm.
  • the upper electrode layer 5 is a transparent conductive film provided on the second semiconductor layer 4 and is an electrode for extracting charges generated in the first semiconductor layer 3.
  • the upper electrode layer 5 is made of a material having a lower resistivity than the second semiconductor layer 4.
  • the upper electrode layer 5 includes what is called a window layer, and when a transparent conductive film is further provided in addition to the window layer, these may be regarded as an integrated upper electrode layer 5.
  • the upper electrode layer 5 mainly includes a material having a wide forbidden band, transparent, and low resistance.
  • a metal oxide semiconductor such as ZnO, In 2 O 3 and SnO 2 can be adopted.
  • These metal oxide semiconductors may contain any element of Al, B, Ga, In, F, and the like.
  • Specific examples of the metal oxide semiconductor containing such an element include, for example, AZO (Aluminum Zinc Oxide), GZO (Gallium Zinc Oxide), IZO (Indium Zinc Oxide), ITO (Indium Tin Oxide), FTO ( Fluorine tin Oxide).
  • the upper electrode layer 5 is formed to have a thickness of 0.05 to 3 ⁇ m by sputtering, vapor deposition, chemical vapor deposition (CVD), or the like.
  • the upper electrode layer 5 has a resistivity of less than 1 ⁇ ⁇ cm and a sheet resistance of 50 ⁇ / ⁇ or less. Can do.
  • the second semiconductor layer 4 and the upper electrode layer 5 may be made of a material having a property (also referred to as light transmission property) that allows light to easily pass through the wavelength region of light absorbed by the first semiconductor layer 3. Thereby, a decrease in light absorption efficiency in the first semiconductor layer 3 caused by providing the second semiconductor layer 4 and the upper electrode layer 5 is reduced.
  • a property also referred to as light transmission property
  • the upper electrode layer 5 can have a thickness of 0.05 to 0.5 ⁇ m. Further, from the viewpoint of reducing light reflection loss at the interface between the upper electrode layer 5 and the second semiconductor layer 4, the absolute refractive index between the upper electrode layer 5 and the second semiconductor layer 4 is substantially equal. It can be made the same.
  • the current collecting electrodes 7 are spaced apart in the Y-axis direction, and each extend in the X-axis direction.
  • the collector electrode 7 is an electrode having conductivity, and is made of a metal such as silver (Ag), for example.
  • the collecting electrode 7 plays a role of collecting charges generated in the first semiconductor layer 3 and taken out in the upper electrode layer 5. If the current collecting electrode 7 is provided, the upper electrode layer 5 can be thinned.
  • connection conductor 6 is constituted by a portion extending in the Y-axis direction of the current collecting electrode 7 as shown in FIG.
  • connection conductor 6 is not limited to this, You may be comprised by the extension part of the upper electrode layer 5.
  • the current collecting electrode 5 has a width of 50 to 400 ⁇ m so that good conductivity is ensured and a decrease in the light receiving area that affects the amount of light incident on the first semiconductor layer 3 is minimized. Can be.
  • FIGS. 4 to 9 are cross-sectional views each schematically showing a state during the manufacture of the photoelectric conversion device 11.
  • Each of the cross-sectional views shown in FIGS. 4 to 9 shows a state in the middle of manufacturing a portion corresponding to the cross-section shown in FIG.
  • a lower electrode layer 2 made of Mo or the like is formed on substantially the entire surface of the cleaned substrate 1 using a sputtering method or the like. Then, the first groove portion P1 is formed from the linear formation target position along the Y direction on the upper surface of the lower electrode layer 2 to the upper surface of the substrate 1 immediately below the formation position.
  • the first groove portion P1 can be formed, for example, by laser scribing, in which groove processing is performed by irradiating the formation target position while scanning with laser light from a YAG laser or the like.
  • FIG. 5 is a diagram illustrating a state after the first groove portion P1 is formed.
  • the surface region containing the group 11 element and the In element on the lower electrode layer 2 and at least opposite to the lower electrode layer 2 (hereinafter, opposite to the lower electrode layer 2 of the film)
  • the surface region on the side is also simply referred to as the surface region of the film) to prepare a film containing Ga element.
  • the film is heated and sulfurized in an atmosphere containing S element, and then heated in an atmosphere containing Se element to selenize the film.
  • This makes it possible to easily control the content ratios of Ga element and S element in the surface portion 3a of the first semiconductor layer 3, and in the surface portion 3a on the side opposite to the lower electrode layer 2, the In element and Ga element.
  • the first semiconductor layer 3 in which the relative atomic number ratio of Ga element and the relative atomic number ratio of S element with respect to the total number of atoms with the element increases as the distance from the lower electrode layer 2 increases easily and stably. can do.
  • Ga element when a film containing Ga element is formed at least on the surface as described above, and this film is sulfurized and then selenized, first, in sulfide, Ga element produces sulfide crystals rather than In element. It tends to be easy. For this reason, the Ga element and the S element react and crystallize at the surface portion of the film where the reaction with the S element in the atmosphere is likely to occur, and the less reactive In element moves to the lower electrode layer 2 side. Then, by selenizing the film, the first semiconductor layer 3 having a configuration in which the relative atomic number ratio of the Ga element and the S element becomes higher as the distance from the lower electrode layer 2 in the surface portion 3a is easily manufactured. Is possible.
  • each element of group 11 element, In element, and Ga element in the film may be uniformly mixed in the film, but a state in which a plurality of elements exist in separate layers (specific elements are It may be present only in a part of the thickness direction of the film. This is because, in the case of a film having a thickness of several ⁇ m to several tens of ⁇ m, even when a plurality of elements are present in separate layers, each element diffuses when the film is heat-treated, This is because each element can react with each other.
  • the coating can be produced using a raw material containing any one or more of group 11 elements, In elements and Ga elements.
  • the film can be formed by applying a raw material solution containing the above raw materials, or by sputtering, vapor deposition, or the like.
  • the film may be a laminate composed of a plurality of layers.
  • Each element of group 11 element, In element, and Ga element may be present in the film in any state of a compound, an alloy, and a simple substance. From the viewpoint that the reactivity with the S element in the atmosphere is increased and the relative atomic number ratio of the Ga element in the surface portion of the first semiconductor layer 3 to be generated can be more easily increased, each of the above elements has an organic coordination. It may be present in the film in the state of an organic complex coordinated by a child. In particular, from the viewpoint of increasing the reactivity and improving the crystallinity, as the organic complex, an organic chalcogen compound is coordinated as an organic ligand to at least one of group 11 element, In element and Ga element. A thing may be used.
  • An organic chalcogen compound is an organic compound containing a chalcogen element, and is an organic compound having a covalent bond between a carbon element and a chalcogen element.
  • chalcogen element Se element or S element can be used.
  • organic chalcogen compound for example, thiol, sulfide, disulfide, selenol, selenide, diselenide and the like can be used.
  • an organic complex in which an organic chalcogen compound is coordinated include an organic complex in which an organic chalcogen compound is coordinated with a group 11 element such as a Cu element or an Ag element, an organic complex in which an organic chalcogen compound is coordinated with an In element, Ga
  • An organic complex in which an organic chalcogen compound is coordinated to an element, or an organic chalcogen compound is coordinated to both a group 11 element and a group 13 element and has a group 11 element, a group 13 element, and a chalcogen element in one molecule A single source organic complex (see Patent Document 2) or the like can be used.
  • the organic complex containing any of the group 11 element, In element and Ga element as described above is dissolved in an organic solvent such as pyridine or aniline to obtain a raw material solution. Then, this raw material solution is deposited in the form of a film on the first electrode layer 2 by, for example, a spin coater, screen printing, dipping, spraying, a die coater, etc., and the solvent is removed by drying to form a film. Can do.
  • membrane is good also as a laminated body of two or more layers by repeating the said film formation process.
  • the produced film is then sulfided by heating at 300 to 650 ° C. for 10 to 120 minutes in an atmosphere containing S element as sulfur vapor or hydrogen sulfide. Thereafter, this film is selenized by heating at 400 to 650 ° C. for 10 to 120 minutes in an atmosphere containing Se element as selenium vapor or hydrogen selenide.
  • sulfidation stage in such a heating process sulfidation of Ga element in the film is particularly facilitated by S element in the atmosphere, and the ratio of Ga element and S element in the surface portion increases.
  • the subsequent selenization step selenization proceeds inside and below the film where the sulfidation of the film is not completed, and the Ga element easily moves to the lower electrode layer 2 side.
  • the Ga element reacted at the time of sulfidation of the surface portion hardly moves during selenization.
  • the first semiconductor layer in which the relative atomic number ratio of the Ga element and the relative atomic number ratio of the S element with respect to the total number of atoms of the In element and the Ga element increase as the distance from the lower electrode layer 2 increases. 3 can be obtained.
  • the film is sulfidized, if the film is heated to a temperature of 400 ° C. or higher, which is the crystallization temperature of the first semiconductor layer 3, the film is sulfidized satisfactorily. The concentration distribution of elements can be maintained better.
  • the concentration distribution of S element and the concentration distribution of Ga element in the first semiconductor layer 3 can be easily changed. For example, as the heating temperature at the time of sulfiding is increased or the heating time is increased, the thickness of the surface portion 3a in the first semiconductor layer 3 increases or the surface portion 3a of the first semiconductor layer 3 increases. There is a tendency that the change rate of the relative atomic number ratio of the Ga element or the S element increases (that is, the slope of the distribution of the Ga element or the slope of the distribution of the S element increases in the surface portion of the graph of FIG. 3).
  • the rate of change of the relative atomic number ratio of Ga element in the remaining portion 3b of the first semiconductor layer increases (that is, in FIG. There is a tendency for the slope of the Ga element distribution in the remainder of the graph to increase.
  • multiple heating steps may be performed.
  • sulfiding may be performed at 500 to 600 ° C. after sulfiding at 300 to 450 ° C.
  • selenization may be performed at 500 to 600 ° C. after performing selenization at 350 to 450 ° C.
  • selenization may be performed at 450 to 550 ° C. after performing selenization at 500 to 600 ° C.
  • oxygen may be included in the atmosphere, for example, 1 to 100 ppmv at a partial pressure ratio.
  • the oxygen element can be included in the surface portion so as to increase as the distance from the lower electrode layer 2 is increased, similarly to the Ga element and the S element.
  • efficiency reduction due to carrier recombination can be reduced. Can be suppressed.
  • the film is heated in an atmosphere containing no chalcogen element, for example, at 50 to 350 ° C. to thermally decompose organic components in the film. It may be left. Thereby, it can reduce that an organic component remains in the 1st semiconductor layer 3, and can improve the photoelectric conversion efficiency of the 1st semiconductor layer 3 more.
  • an oxidizing gas such as water vapor or oxygen may be contained in the atmosphere at a partial pressure ratio of about 50 to 300 ppmv. Thereby, an oxygen element can be contained in the first semiconductor layer 3. As a result, the recombination of charges can be reduced by the oxygen element entering the lattice defects of the first semiconductor layer 3.
  • Se element may be included in the above film.
  • Se element may be included in the above film.
  • the degree of sulfidation can be easily controlled, and the concentration distribution of S element on the surface portion can be easily made desired.
  • an organic selenium compound may be used as the organic chalcogen compound as described above.
  • the film may be selenized to such an extent that the film is not completely selenized by heating in the Se atmosphere before heating the film in the S element atmosphere.
  • the second semiconductor layer 4 can be formed by a solution growth method (also referred to as a CBD method). For example, cadmium acetate and thiourea are dissolved in ammonia water, and the substrate 1 that has been formed up to the formation of the first semiconductor layer 3 is immersed in the second semiconductor layer 3 so as to contain the second CdS on the first semiconductor layer 3.
  • the semiconductor layer 4 can be formed.
  • the upper electrode layer 5 is a transparent conductive film containing, for example, indium oxide (ITO) containing Sn as a main component, and can be formed by a sputtering method, a vapor deposition method, a CVD method, or the like.
  • FIG. 7 is a view showing a state after the second semiconductor layer 4 and the upper electrode layer 5 are formed.
  • ITO indium oxide
  • the second groove portion P ⁇ b> 2 is formed from the linear formation target position along the Y direction on the upper surface of the upper electrode layer 5 to the upper surface of the lower electrode layer 2 immediately below it.
  • the second groove portion P2 can be formed by, for example, mechanical scribing using a scribe needle.
  • FIG. 8 is a diagram illustrating a state after the second groove portion P2 is formed.
  • the second groove portion P2 is formed at a position slightly deviated in the X direction (+ X direction in the drawing) from the first groove portion P1.
  • the collecting electrode 7 and the connecting conductor 6 are formed.
  • a conductive paste also referred to as a conductive paste
  • a metal powder such as Ag is dispersed in a resin binder is printed in a desired pattern and heated.
  • FIG. 9 is a view showing a state after the current collecting electrode 7 and the connection conductor 6 are formed.
  • the third groove portion P ⁇ b> 3 is formed from the linear formation target position on the upper surface of the upper electrode layer 5 to the upper surface of the lower electrode layer 2 immediately below it.
  • the width of the third groove portion P3 can be set to about 40 to 1000 ⁇ m, for example.
  • the 3rd groove part P3 can be formed by a mechanical scribing process similarly to the 2nd groove part P2. In this way, the photoelectric conversion device 11 shown in FIGS. 1 and 2 is manufactured by forming the third groove portion P3.
  • Substrate 2 Lower electrode layer 3: First semiconductor layer 3a: Surface portion 3b: Remaining portion 4: Second semiconductor layer 5: Upper electrode layer 6: Connection conductor 7: Current collecting electrode 10: Photoelectric conversion cell 11: Photoelectric conversion device

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Abstract

La présente invention a pour objet d'améliorer l'efficacité de conversion photoélectrique d'un appareil de conversion photoélectrique. Un appareil de conversion photoélectrique (11) comprend : une couche semi-conductrice (3) agencée sur une couche d'électrode (2), ladite couche semi-conductrice contenant un élément du groupe 11, un élément indium, un élément gallium, un élément soufre et un élément sélénium. Dans la partie superficielle (3a) de la couche semi-conductrice (3), ladite partie superficielle se trouvant sur le côté opposé de la couche d'électrode (2), le nombre relatif d'atomes de l'élément gallium et le nombre relatif d'atomes de l'élément soufre par rapport au nombre total d'atomes de l'élément indium et de l'élément gallium augmentent vers le côté qui se trouve loin de la couche d'électrode (2).
PCT/JP2013/066473 2012-06-25 2013-06-14 Appareil de conversion photoélectrique et procédé permettant de fabriquer un appareil de conversion photoélectrique WO2014002796A1 (fr)

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JPH10341029A (ja) * 1997-06-05 1998-12-22 Matsushita Electric Ind Co Ltd 半導体薄膜の製造方法および薄膜太陽電池の製造方法
JP2000174306A (ja) * 1998-12-01 2000-06-23 Asahi Chem Ind Co Ltd 化合物半導体薄膜の製造方法
JP2009135299A (ja) * 2007-11-30 2009-06-18 Showa Shell Sekiyu Kk Ｃｉｓ系薄膜太陽電池の光吸収層の製造方法
WO2011152334A1 (fr) * 2010-05-31 2011-12-08 京セラ株式会社 Dispositif de conversion photoélectrique
JP2012074671A (ja) * 2010-08-31 2012-04-12 Kyocera Corp 光電変換装置とその製造方法および光電変換モジュ−ル
JP2013098191A (ja) * 2011-10-28 2013-05-20 Kyocera Corp 光電変換装置

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JP2000174306A (ja) * 1998-12-01 2000-06-23 Asahi Chem Ind Co Ltd 化合物半導体薄膜の製造方法
JP2009135299A (ja) * 2007-11-30 2009-06-18 Showa Shell Sekiyu Kk Ｃｉｓ系薄膜太陽電池の光吸収層の製造方法
WO2011152334A1 (fr) * 2010-05-31 2011-12-08 京セラ株式会社 Dispositif de conversion photoélectrique
JP2012074671A (ja) * 2010-08-31 2012-04-12 Kyocera Corp 光電変換装置とその製造方法および光電変換モジュ−ル
JP2013098191A (ja) * 2011-10-28 2013-05-20 Kyocera Corp 光電変換装置

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