WO2019180892A1 - Cellule solaire, cellule solaire à multiples jonctions, module de cellule solaire et système de production d'énergie solaire photovoltaïque - Google Patents

Cellule solaire, cellule solaire à multiples jonctions, module de cellule solaire et système de production d'énergie solaire photovoltaïque Download PDF

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WO2019180892A1
WO2019180892A1 PCT/JP2018/011508 JP2018011508W WO2019180892A1 WO 2019180892 A1 WO2019180892 A1 WO 2019180892A1 JP 2018011508 W JP2018011508 W JP 2018011508W WO 2019180892 A1 WO2019180892 A1 WO 2019180892A1
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solar cell
layer
intermediate layer
light absorption
electrode
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PCT/JP2018/011508
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English (en)
Japanese (ja)
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中川　直之
聡一郎 芝崎
紗良 吉尾
山崎　六月
祐弥 保西
山本　和重
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株式会社 東芝
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Priority to PCT/JP2018/011508 priority Critical patent/WO2019180892A1/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
    • H01L31/04—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

Definitions

  • the present invention relates to a solar cell, a multi-junction solar cell, a solar cell module, and a solar power generation system.
  • the problem to be solved by the present invention is to provide a solar cell, a multi-junction solar cell, a solar cell module, and a solar power generation system with excellent conversion efficiency.
  • the solar cell of the embodiment includes a transparent first electrode, a first intermediate layer including a metal oxide represented by M1O X , a second intermediate layer including a metal chalcogenide including a metal M2 and a chalcogen element M3, p A light absorption layer, an n-type layer, and a second electrode.
  • the first intermediate layer is disposed between the first electrode and the second intermediate layer.
  • the second intermediate layer is disposed between the first intermediate layer and the p-type light absorption layer.
  • M1 is one or more elements selected from the group consisting of Mo and W.
  • X satisfies 2 ⁇ X ⁇ 3.
  • M2 is one or more elements selected from the group consisting of Mo and W.
  • the chalcogen element M1 is one or more elements selected from the group consisting of S, Se, and Te.
  • FIG. 1 shows a cross-sectional view of the solar cell 100 of the first embodiment.
  • the solar cell 100 according to the first embodiment includes a first electrode 1, a first intermediate layer 2, a second intermediate layer 3, a p-type light absorption layer 4, and an n-type layer 5.
  • An intermediate layer (not shown) may be included between the n-type layer 5 and the second electrode 6. Sunlight enters from either the first electrode 1 side or the second electrode 6 side.
  • a substrate not shown in FIG. 1 may be provided on the first electrode 1 side or the second electrode 6 side.
  • the first electrode 1 is a transparent electrode.
  • the first electrode 1 is an electrode that is in direct contact with the first intermediate layer 2.
  • the first electrode 1 is either a single-layer film composed of one conductive layer or a laminated film including two or more conductive layers.
  • the first intermediate layer 2 is sandwiched between the first electrode 1 and the second intermediate layer 3.
  • the first electrode 1 includes at least an oxide transparent conductive film such as indium tin oxide (ITO).
  • the first electrode 1 may be a laminated film further including a metal film, an intermetallic compound film, or a metal film and an intermetallic compound film, in addition to one or more oxide transparent conductive films.
  • One layer of the oxide transparent conductive film included in the first electrode 1 is in direct contact with the first intermediate layer 2.
  • the thickness of the first electrode 1 is typically 5 nm or more and 1 ⁇ m or less. The film thickness in the present application is a distance in the stacking direction of the first electrode 1 and the first intermediate layer 2.
  • the oxide transparent conductive film included in the first electrode 1 includes tin oxide, titanium oxide, indium tin oxide, aluminum-doped zinc oxide (AZO), and boron-doped zinc oxide (BZO).
  • ITO Oxide
  • IGZO Indium Gallium Zinc Oxide
  • Hydrogen-doped Indium Oxide In 2 O 3
  • the tin oxide may further contain one or more metals selected from the group consisting of Zn, Al, Ga, In, Si, Ge, Ti, Cu, Sb, Nb, F, and Ta.
  • One or more metals selected from the group consisting of Zn, Al, Ga, In, Si, Ge, Ti, Cu, Sb, Nb, F, and Ta are, for example, 5 atom% or less with respect to tin in tin oxide. is there.
  • the total thickness of the oxide transparent conductive film contained in the first electrode 1 is determined by cross-sectional observation with an electron microscope, and is preferably 5 nm or more and 300 nm or less.
  • the oxide transparent conductive film in the first electrode 1 is, for example, SnO 2 / ITO, SnO 2 / AZO, SnO 2 / ITO / SiO 2 , SnO 2 / TiO 2 / ITO / SiO 2 from the first intermediate layer 2 side, Examples thereof include TiO 2 / SnO 2 / ITO / SiO 2 and TiO 2 / ITO / SiO 2 .
  • the laminated structure is not limited to these examples.
  • the metal film included in the first electrode 1 is preferably a film of one or more metals selected from the group consisting of Cu, Al, Ag, Mo, W, and Ta.
  • the intermetallic compound contained in the first electrode 1 is preferably an intermetallic compound film containing one or more kinds of metals mentioned in the metal film. If the film thickness of the metal film and the intermetallic compound film is too thick, the light transmittance is significantly reduced. Therefore, when the first electrode 1 further includes a metal film, an intermetallic compound film, or a metal film and an intermetallic compound film, the total film thickness of the metal film, the intermetallic compound film, or the metal film and the intermetallic compound film is 1 nm or more and 10 nm. The following is preferable.
  • the oxide transparent conductive film includes the first intermediate layer 2 and the metal film, the intermetallic compound film or the metal film, and the metal. It is preferable to dispose between the intercalation compound films.
  • the first intermediate layer 2 is a metal oxide layer disposed between the first electrode 1 and the second intermediate layer 3.
  • the surface of the first intermediate layer 2 facing the first electrode 1 is in direct contact with the oxide transparent conductive film included in the first electrode 1.
  • the entire surface of the first intermediate layer 2 facing the first electrode 1 is in direct contact with the entire surface of the oxide transparent conductive film included in the first electrode 1 facing the first intermediate layer 2. Is preferred.
  • the surface of the first intermediate layer 2 facing the second intermediate layer 3 is in direct contact with the surface of the second intermediate layer 3 facing the first intermediate layer 2.
  • the entire surface of the first intermediate layer 2 facing the second intermediate layer 3 is preferably in direct contact with the entire surface of the second intermediate layer 3 facing the first intermediate layer 2.
  • the band alignment of the solar cell 100 is improved by the arrangement configuration of the layers.
  • MoO X matches the band alignment with CIGSe as compared with SnO 2 and ITO as transparent electrodes. For example, when CIGSe is deposited directly on the oxide layer, an insulating GaO layer is always formed on the interface. Will be formed. It is preferable to insert MoSe that is in ohmic contact with CIGSe as a contact layer for further improving band alignment while preventing the formation of an insulating GaO layer.
  • the metal oxide of the first intermediate layer 2 contains a compound represented by M1O X.
  • M1 is one or more elements selected from the group consisting of Mo and W.
  • X of M1O X is larger than 2 and smaller than 3.
  • the first intermediate layer 2 is preferably a layer made of a compound represented by M1O X. Specific examples of the metal oxide of the first intermediate layer 2 include MoO X , WO X , and Mo Y W 1-Y O X (0 ⁇ Y ⁇ 1).
  • the thickness of the first intermediate layer 2 is determined by cross-sectional observation with an electron microscope, and is preferably 1 nm to 100 nm. If the first intermediate layer 2 is too thick, the conversion efficiency of the solar cell 100 is reduced by the resistance of the first intermediate layer 2. Therefore, the thickness of the first intermediate layer 2 is more preferably 1 nm or more and 50 nm or less. The thickness of the first intermediate layer 2 is more preferably 1 nm or more and 20 nm or less. The thickness of each layer is the distance in the stacking direction from the first electrode 1 to the second electrode 6 of each layer.
  • Oxygen concentration in the first intermediate layer 2 M1O X is preferably inclined in the thickness direction. It is preferable that the oxygen concentration on the second intermediate layer 3 side of the first intermediate layer 2 is inclined so as to be lower than the oxygen concentration on the first electrode 1 side of the first intermediate layer 2. Since the oxygen concentration is inclined, the band alignment from the first intermediate layer 2 to the p-type light absorption layer 4 is further improved. More specifically, the work function increases as the oxygen ratio of the metal oxide increases. As the work function increases, the hole carrier can be taken out better.
  • FIG. 2 shows work functions and band gaps (arrows) of CGS, CIGS, MoSe 2 , MoO 2 , MoO 3 , SnO 2 and ITO. Focusing on MoSe 2 , MoO 2 and MoO 3 , it can be seen that MoO 3 has a work function larger than that of MoO 2 as described above.
  • X of M1O X of the first intermediate layer 2 on the first electrode 1 side is preferably a value close to 3 or 3.
  • X of M1O X of the first intermediate layer 2 on the second intermediate layer 3 side is preferably 2 or a value close to 2.
  • a depth of 0.3D from the surface (starting point) facing the first electrode 1 side of the first intermediate layer 2 toward the p-type light absorption layer 4 is a depth of 0.3D (starting point) from the surface facing the first electrode 1 side of the first intermediate layer 2 toward the p-type light absorption layer 4 )
  • C1 which is the average value of the oxygen concentration in the region up to the end point
  • C2 which is an average value of the oxygen concentration
  • C1, C2, and C3 satisfy C1> C2> C3, and 2.5 ⁇ C1 ⁇ 3.0, 2.0 ⁇ C2 ⁇ 3.0, 2.0 ⁇ C3 It is preferable to satisfy ⁇ 2.5, and it is more preferable to satisfy 2.7 ⁇ C1 ⁇ 3.0, 2.3 ⁇ C2 ⁇ 2.7, and 2.0 ⁇ C3 ⁇ 2.3.
  • the second intermediate layer 3 is a metal chalcogenide layer disposed between the first intermediate layer 2 and the p-type light absorption layer 4.
  • the surface of the second intermediate layer 3 facing the first intermediate layer 2 is in direct contact with the first intermediate layer 2.
  • the entire surface of the second intermediate layer 3 facing the first intermediate layer 2 is preferably in direct contact with the entire surface of the first intermediate layer 2 facing the second intermediate layer.
  • the surface of the second intermediate layer 3 facing the p-type light absorption layer 4 is in direct contact with the p-type light absorption layer 4.
  • the entire surface of the second intermediate layer 3 facing the p-type light absorption layer 4 is preferably in direct contact with the entire surface of the p-type light absorption layer 4 facing the second intermediate layer 3.
  • the arrangement configuration of the layers prevents oxidation of the p-type light absorption layer 4 on the first electrode 1 side, and improves the band alignment of the solar cell 100.
  • the metal chalcogenide of the second intermediate layer 3 includes a metal M2 and a chalcogen element M3.
  • M2 is one or more elements selected from the group consisting of Mo and W.
  • M3 is one or more elements selected from the group consisting of S, Se, and Te.
  • the second intermediate layer 3 is preferably a layer made of metal chalcogenide.
  • the metal chalcogenide of the second intermediate layer 3 is at least one selected from the group consisting of MoS Z , MoSe Z , MoTe Z , WS Z , WSe Z and WTe Z.
  • Z in the above chemical formula preferably satisfies 1.0 ⁇ Z ⁇ 2.0.
  • M1 and M2 are the same metal element.
  • two layers of the first intermediate layer 2 and the second intermediate layer 3 can be formed by selenizing part of the Mo oxide after forming the film.
  • This manufacturing method is not limited to the above combination. However, it is more preferable to match the band alignment than to make the metals of M1 and M2 the same.
  • the thickness of the second intermediate layer 3 is determined by cross-sectional observation with an electron microscope, and is preferably 1 nm or more and 100 nm or less. If the second intermediate layer 3 is too thick, the light transmittance of the solar cell 100 is lowered. Therefore, the thickness of the second intermediate layer 3 is more preferably 1 nm or more and 50 nm or less. The thickness of the second intermediate layer 3 is more preferably 1 nm or more and 10 nm or less.
  • the element concentration in each layer is determined by measurement using a 3D atom probe.
  • a sharp needle-like sample having a tip diameter of 10 nm is prepared.
  • the length of the needle-shaped sample may be longer than the region to be analyzed and suitable for analysis.
  • the needle-shaped sample is prepared so that the first electrode 1 is included on the tip side, and the second intermediate layer 3 is present at least on the root side of the needle-shaped sample. Five acicular samples are prepared for one solar cell 100 to be analyzed.
  • the surface of the first electrode 1 of the solar cell 100 is divided into four equal parts in a lattice shape, and four points at the center of the divided region and one point at the center of the surface of the first electrode 1 of the solar cell 100 are divided. To include.
  • the 3D atom probe LEAP4000X Si manufactured by AMETEK was used, the measurement mode was set to Laser pulse, the laser power was set to 35 pJ, and the temperature of the needle-like sample was set to 70K.
  • the interface between the first electrode 1 and the first intermediate layer 2 is determined from the signal intensity of Mo or W.
  • the interface between the first intermediate layer 2 and the second intermediate layer 3 is determined from the signal intensity of the chalcogen element.
  • the interface between the second intermediate layer 3 and the p-type light absorption layer 4 is determined from the signal intensity of the group Ib element.
  • the signal intensity is a state in which the detected element is corrected to atom%.
  • the average value of the results of the five needle samples is used as the analysis value.
  • XPS X-ray photoelectron spectroscopy
  • the p-type light absorption layer 4 of the embodiment is a photoelectric conversion layer of the solar cell 100.
  • the p-type light absorption layer 4 is a p-type compound semiconductor layer disposed between the second intermediate layer 3 and the n-type layer 5.
  • the surface of the p-type light absorption layer 4 facing the second intermediate layer 3 is in direct contact with the surface of the second intermediate layer 3 facing the p-type light absorption layer 4.
  • the entire surface of the p-type light absorption layer 4 facing the second intermediate layer 3 is in direct contact with the entire surface of the second intermediate layer 3 facing the p-type light absorption layer 4.
  • the surface of the p-type light absorption layer 4 facing the n-type layer 5 is in direct contact with the surface of the n-type layer 5 facing the p-type light absorption layer 4.
  • the entire surface of the p-type light absorption layer 4 facing the n-type layer 5 is in direct contact with the entire surface of the n-type layer 5 facing the p-type light absorption layer 4. Since the first intermediate layer 2 and the second intermediate layer 3 are included in the solar cell 100, the band alignment from the first intermediate layer 2 to the p-type light absorption layer 4 is improved, so that the extraction of hole carriers is improved. The conversion efficiency of the solar cell 100 is improved.
  • the p-type light absorption layer 4 is preferably a compound semiconductor having a chalcopyrite structure, a compound semiconductor having a stannite structure, or a compound semiconductor having a kesterite structure.
  • a layer made of a compound semiconductor having a chalcopyrite structure is preferably used as the p-type light absorption layer 4.
  • the compound semiconductor having a chalcopyrite structure includes a compound semiconductor having a chalcopyrite structure such as CIGSe, CIGSSe, CGSSe, or CGSe, which includes an Ib (IB) group element, an IIIb (IIIA) group element, and a VIb (VIA) group element. Layers can be used.
  • the n-type layer 5 is comprised with the same compound as the p-type light absorption layer 4 which contains n dopant further.
  • Examples of the group Ib element include one selected from the group consisting of Cu and Ag. As the Ib group element, Cu is preferable.
  • Examples of the group IIIb element include at least one element selected from the group consisting of Al, In, and Ga. More preferably, the group IIIb element contains at least In or Ga. The IIIb group element is more preferably both In and Ga, or Ga.
  • Examples of the group VIb element include one or more elements selected from the group consisting of Se, S, and Te. As a VIb group element, it is more preferable that Se or S is included, or that Se and S are included. Of the group IIIb elements, it is more preferable to use In because the band gap can be easily set to a target value by combination with Ga.
  • the p-type light absorption layer 4 Cu (In, Ga) (S, Se) 2 , Cu (Al, Ga, In) Se 2 or the like, more specifically, Cu (In, Ga) is used. Se 2, CuInSe 2, it is possible to use a compound semiconductor such as CuGaSe 2.
  • the thickness of the p-type light absorption layer 4 is determined by cross-sectional observation with an electron microscope, and is preferably 1000 nm or more and 3000 nm or less.
  • the thickness of the p-type light absorption layer 4 is more preferably 1500 nm or more and 2500 nm or less.
  • the n-type layer 5 is an n-type semiconductor layer disposed between the p-type light absorption layer 4 and the second electrode 6.
  • the p-type light absorption layer 4 and the n-type layer 5 are homojunction type, the p-type light absorption layer 4 and the n-type layer 5 are integrated.
  • the second electrode 6 on the n-type layer 5 side of the light absorption layer in which the p-type light absorption layer 4 and the n-type layer 5 are integrated is provided.
  • the facing surface is in direct contact with the surface facing the n-type layer side of the light absorption layer in which the p-type light absorption layer 4 and the n-type layer 5 of the second electrode 6 are integrated.
  • the second electrode 6 on the n-type layer 5 side of the light absorption layer in which the p-type light absorption layer 4 and the n-type layer 5 are integrated is provided.
  • the entire surface facing is preferably in direct contact with the entire surface facing the n-type layer side of the light absorption layer in which the p-type light absorption layer 4 and the n-type layer 5 of the second electrode 6 are integrated.
  • the surface of the n-type layer 5 facing the p-type light absorption layer is directly with the surface of the p-type light absorption layer 4 facing the n-type layer 5. Are touching.
  • the p-type light absorption layer 4 and the n-type layer 5 are heterojunction type, the entire surface of the n-type layer 5 facing the p-type light absorption layer is formed of the n-type layer 5 of the p-type light absorption layer 4. It is preferably in direct contact with the entire surface facing.
  • the surface of the n-type layer 5 facing the second electrode 6 is directly with the surface of the second electrode 6 facing the n-type layer 5. Is in contact with When the p-type light absorption layer 4 and the n-type layer 5 are heterojunction type, the entire surface of the n-type layer 5 facing the second electrode 6 is the surface of the second electrode 6 facing the n-type layer 5. It is preferably in direct contact with the entire surface.
  • an intermediate layer (not shown) that is a high resistance layer or a semi-insulating layer may be disposed between the n-type layer 5 and the second electrode 6.
  • the n-type layer 5 and the second electrode 6 are not in direct contact with each other, and the surface (or the entire surface) facing the n-type layer 5 of the intermediate layer, which is a high-resistance layer or a semi-insulating layer, It is in direct contact with the surface (or the entire surface) facing the intermediate layer which is a resistance layer or a semi-insulating layer.
  • the region containing a large amount of n-dope such as Cd or Zn is the n-type layer 5.
  • the thickness of the n-type layer 5 is preferably 2 nm to 100 nm, and more preferably 5 nm to 20 nm.
  • the thickness of the n-type layer 5 can be measured from a change in the concentration of Cd and Zn using a 3D atom probe.
  • an n-type compound semiconductor layer is used for the n-type layer 5.
  • the compound semiconductor used for the n-type layer 5 is not particularly limited.
  • the n-type layer 5 is preferably an n-type semiconductor whose Fermi level is controlled so that a high open-circuit solar cell can be obtained.
  • the thickness of the n-type layer 5 is determined by cross-sectional observation with an electron microscope, and is preferably 2 nm to 800 nm, preferably 5 nm to 50 nm. More preferred.
  • a p-type semiconductor layer that is a precursor of the p-type light absorption layer 4 and the n-type layer 5 is formed on the second intermediate layer 3, and the p-type on the side where the second electrode 6 is formed.
  • the region of the semiconductor layer is made n-type.
  • a compound semiconductor layer in which the p-type light absorption layer 4 and the n-type layer 5 are homojunction is obtained.
  • the p-type semiconductor layer is the p-type light absorption layer 4.
  • a thin film forming method such as a vapor deposition method (three-step method) or a sputtering method having a rapid cooling process between the second and third steps can be given.
  • a vapor deposition method three-step method
  • a sputtering method having a rapid cooling process between the second and third steps can be given.
  • Ga or In and Se or S are deposited on the second intermediate layer 3
  • Cu and Se are deposited at a high temperature, and then rapidly cooled and again Ga or In at a low temperature.
  • a p-type semiconductor layer can be formed by depositing Se or S.
  • the following manufacturing method is a vapor deposition method
  • the temperature of the member on which the first electrode 1 is formed on the substrate is heated to 200 ° C. or more and 400 ° C. or less, and a group IIIb element such as In or Ga and a group VIb element such as Se. Is deposited (first stage).
  • the substrate temperature is heated to 450 ° C. or higher and 550 ° C. or lower to deposit Cu, which is an Ib group element, and VIb group elements such as Se.
  • the deposition of Cu, which is an Ib group element is stopped once the Cu, which is an Ib group element, is in an excessive composition (second stage).
  • the substrate is rapidly cooled by natural quenching or by locally injecting an inert gas such as nitrogen or argon to cool the substrate temperature to 400 ° C. or lower.
  • an inert gas such as nitrogen or argon
  • a IIIb group element such as In or Ga and a VIb group element such as Se are deposited again (third stage) to slightly increase the IIIb group element excessive composition such as In or Ga.
  • the crystal Since the second intermediate layer 3 side of the p-type semiconductor layer is formed at a high temperature, the crystal has a large particle size.
  • the rapid cooling after the completion of the second stage deposition causes the p-type semiconductor layer to The second electrode 6 side has a small particle size or is amorphous.
  • the diffusion of Cu which is a group Ib element, is suppressed, and the second electrode 6 side of the p-type semiconductor layer is compared with the case where rapid cooling is not performed. Thus, many Cu vacancies exist.
  • n-type doping on a member having many Cu vacancies because many n-type dopants penetrate into the Cu vacancy site and function as an n-type semiconductor having many n-type dopants.
  • a part of the p-type semiconductor layer is removed from the p-type by doping in a liquid phase using a solution containing an n-type dopant such as Cd or Zn (for example, an ammonia solution containing cadmium sulfate). It can be made n-type.
  • the p-type light absorption layer 4 and the n-type layer 5 become a homojunction type.
  • the treatment is performed so that the n dopant concentration on the side where the second electrode 6 is formed becomes high.
  • the heterojunction p-type light absorption layer 4 of the embodiment was deposited by the same vapor deposition method (three-stage method) except that cooling was not performed at the third stage.
  • a CdS layer is employed as the n-type layer 5
  • a CdS layer can be formed on the p-type light absorption layer 4 by chemical solution deposition (CBD). It is obtained by dissolving cadmium sulfate in an aqueous ammonia solution, adding thiourea, taking it out after a certain period of time and washing it with water.
  • the second electrode 6 is a transparent electrode.
  • the second electrode 6 is an electrode present on the n-type layer 5. In FIG. 1, the second electrode 6 is in direct contact with the n-type layer 5.
  • a transparent conductive film is preferable. It is preferable to use the same material as the first electrode 2 for the transparent conductive film.
  • the second electrode 6 may be provided with an extraction electrode.
  • a high resistance layer such as ZnMgO or ZnOS, or a semi-insulating layer such as i-ZnO may be provided between the n-type layer 5 and the second electrode 6.
  • a substrate not shown in FIG. 1 As a substrate not shown in FIG. 1, it is desirable to use glass containing Na such as blue plate glass.
  • a substrate not shown in FIG. 1 is stacked with the first electrode 1 and the second electrode 6 so as to sandwich the first electrode 1, the second electrode 6, or the solar cell 100.
  • the first intermediate layer 2 may be disposed between a substrate (not shown) and the first electrode 1.
  • the second electrode 6 may be disposed between a substrate (not shown) and the n-type layer 5.
  • An antireflection film may be further provided so as to be disposed closer to the light incident side than the electrode on the light incident side.
  • the antireflection film is a film for easily introducing light into the p-type light absorption layer 4.
  • MgF 2 is desirably used as the antireflection film.
  • the film thickness of the antireflection film is, for example, 90 nm or more and 120 nm or less.
  • the antireflection film can be formed by, for example, an electron beam evaporation method.
  • FIG. 3 is a conceptual cross-sectional view of the multi-junction solar cell 200 of the second embodiment.
  • the multi-junction solar cell 200 of FIG. 3 includes the solar cell (first solar cell) 100 and the second solar cell 201 of the first embodiment on the light incident side.
  • the band gap of the light absorption layer of the second solar cell 201 has a smaller band gap than the light absorption layer 3 of the solar cell 100 of the first embodiment.
  • the multi-junction solar cell 200 of the embodiment includes a solar cell in which three or more solar cells are joined.
  • one or more compound semiconductor layers selected from the group consisting of CIGS, CIT, and CdTe that have a high In content ratio, and a group consisting of crystalline silicon and a perovskite compound are used. It is preferable that it is 1 type chosen.
  • FIG. 4 is a conceptual perspective view of the solar cell module 300 of the third embodiment.
  • the solar cell module 300 in FIG. 4 is a solar cell module in which a first solar cell module 301 (top cell) and a second solar cell module 302 (bottom cell) are stacked.
  • the first solar cell module 301 is on the light incident side, and uses the solar cell 100 of the first embodiment.
  • the second solar cell module 302 uses the second solar cell 201 of the second embodiment.
  • FIG. 5 shows a conceptual cross-sectional view of the solar cell module 300.
  • FIG. 5 shows the structure of the first solar cell module 301 in detail.
  • the structure of the second solar cell module 302 is not shown.
  • the structure of a solar cell module is selected suitably according to the light absorption layer etc. of the solar cell to be used.
  • the solar cell module of FIG. 5 includes a plurality of submodules 303 surrounded by a broken line in which a plurality of solar cells 100 (solar cells) are arranged in the horizontal direction and electrically connected in series. Electrically connected in parallel or in series. Adjacent submodules 303 are electrically connected by a bus bar 304.
  • the solar cell 100 is scribed P1, P2, and P3, and the adjacent first solar cell 100 is connected to the first electrode 1 on the upper side and the second electrode 6 on the lower side.
  • the substrate 7 is shown in the solar cell 100 of the first solar cell module 301.
  • the solar cell 100 of the third embodiment also includes the first electrode 1, the first intermediate layer 2, the second intermediate layer 3, the p-type light absorption layer 4, and the n-type layer 5.
  • a second electrode 6 is provided. Both ends of the solar cell 100 in the submodule 303 are connected to the bus bar 304, and the bus bar 304 electrically connects the plurality of submodules 303 in parallel or in series to adjust the output voltage with the second solar cell module 302. It is preferable that it is comprised.
  • the fourth embodiment relates to a photovoltaic power generation system.
  • the solar cell module 300 of the third embodiment can be used as a generator that generates power in the solar power generation system of the fourth embodiment.
  • the solar power generation system according to the embodiment generates power using a solar cell module.
  • the solar cell module that generates power means for converting the generated electricity, and the generated electricity
  • FIG. 6 shows a conceptual diagram of the configuration of the photovoltaic power generation system 400 of the embodiment.
  • the solar power generation system of FIG. 6 includes a solar cell module 401 (300), a converter 402, a storage battery 403, and a load 404.
  • the storage battery 403 or the load 404 may be omitted.
  • the load 404 may be configured to be able to use electrical energy stored in the storage battery 403.
  • the converter 402 is a device including a circuit or element that performs power conversion such as transformation or DC / AC conversion, such as a DC-DC converter, a DC-AC converter, or an AC-AC converter.
  • a suitable configuration may be adopted according to the configuration of the generated voltage, the storage battery 403, and the load 404.
  • the solar cell module 401 is provided with a solar light tracking drive device for always directing the solar cell module 401 toward the sun, a condensing body for concentrating sunlight, a device for improving power generation efficiency, and the like. It is preferable to add.
  • the solar power generation system 400 is preferably used for real estate such as a residence, a commercial facility, a factory, or used for movable property such as a vehicle, an aircraft, or an electronic device.
  • a residence such as a residence, a commercial facility, a factory, or used for movable property such as a vehicle, an aircraft, or an electronic device.
  • Example 1 A blue plate glass is used as a substrate, and a SnO 2 / ITO laminated film to be a first electrode is deposited by about 100 nm / 150 nm by sputtering. On the first electrode, a metal oxide layer made of Mo and oxygen was deposited by reactive sputtering while oxygen was flowed as a first intermediate layer with Mo as a target. A metal chalcogenide layer was deposited as a second intermediate layer on the first intermediate layer using a MoSe 2 target. The metal oxide layer and the metal chalcogenide layer were each 10 nm.
  • a CuGaSe 2 thin film to be a p-type light absorption layer was deposited by an evaporation method (three-step method).
  • the substrate temperature is heated to 300 ° C. to deposit Ga and Se (first stage).
  • the substrate temperature is heated to 500 ° C., and Cu and Se are deposited.
  • the deposition of Cu is stopped once with a Cu-excess composition (second stage).
  • Ga and Se again (third stage)
  • a slight Ga excess composition is obtained.
  • the film thickness of the CuGaSe 2 thin film was about 1600 nm.
  • Example 2 In deposition by reactive sputtering of the metal oxide layer is a first intermediate layer, the oxygen partial pressure, except that the deposition is varied from 1x10 -6 Torr or more 1x10 -4 Torr, the same method as in Example 1
  • the solar cell of Example 2 is manufactured, and the open-circuit voltage, the short-circuit current density, and the conversion efficiency are measured.
  • Comparative Example 1 Except not depositing a 1st intermediate
  • Comparative Example 2 Except not depositing a 2nd intermediate
  • Comparative Example 3 Except for not depositing the first intermediate layer and the second intermediate layer, a solar cell of Comparative Example 3 is prepared in the same manner as in Example 1, and the open-circuit voltage, the short-circuit current density, and the conversion efficiency are measured.
  • Example 3 A solar cell of Example 3 is fabricated in the same manner as in Example 1 except that W is used as the target of the first intermediate layer, and the open-circuit voltage, short-circuit current density, and conversion efficiency are measured.
  • Example 4 Except that MoS was used as a target for the second intermediate layer, the solar cell of Example 4 was prepared in the same manner as in Example 1, and the open-circuit voltage, short-circuit current density, and conversion efficiency were measured.
  • Example 5 The solar cell of Example 5 is produced by the same method as Example 1 except that MoTe is used as the target of the second intermediate layer, and the open-circuit voltage, the short-circuit current density, and the conversion efficiency are measured.
  • Example 6 Except that WSe was used as the target of the second intermediate layer, the solar cell of Example 6 was produced in the same manner as in Example 1, and the open-circuit voltage, short-circuit current density, and conversion efficiency were measured.
  • Example 7 Except that CuGa (S, Se) 2 was formed as a p-type light absorption layer, the solar cell of Example 7 was fabricated in the same manner as in Example 1, and the open-circuit voltage, short-circuit current density, and conversion efficiency were Measure.
  • Comparative Example 4 Except not depositing a 1st intermediate
  • Comparative Example 5 Except not depositing a 2nd intermediate
  • Comparative Example 6 Except not depositing a 1st intermediate
  • Example 8 A solar cell of Example 8 was produced in the same manner as in Example 1 except that Cu (In, Ga) (S, Se) 2 was formed as the p-type light absorption layer, and the open-circuit voltage and the short circuit were produced. Measure current density and conversion efficiency.
  • Comparative Example 7 Except not depositing a 1st intermediate
  • Comparative Example 8 Except not depositing a 2nd intermediate
  • Comparative Example 9 Except for not depositing the first intermediate layer and the second intermediate layer, the solar cell of Comparative Example 9 is produced in the same manner as in Example 8, and the open-circuit voltage, the short-circuit current density, and the conversion efficiency are measured.
  • Example 9 A solar cell of Example 9 is produced by the same method as in Example 1 except that the CdS layer is not formed and a homojunction type is used, and the open-circuit voltage, short-circuit current density, and conversion efficiency are measured. In addition, the rapid cooling after the 2nd deposition is performed, and the CGSe side of the member on which the CGSe thin film is formed is immersed in an ammonia solution containing cadmium sulfate.
  • Comparative Example 10 Except not depositing a 1st intermediate
  • Comparative Example 11 Except not depositing a 2nd intermediate
  • Comparative Example 12 Except not depositing a 1st intermediate
  • Example 10 A solar cell of Example 10 was fabricated in the same manner as in Example 1 except that the thickness of the metal oxide layer as the first intermediate layer was 50 nm, and the open-circuit voltage, short-circuit current density, and conversion efficiency were adjusted. taking measurement.
  • Example 11 A solar cell of Example 11 was prepared in the same manner as in Example 1 except that the thickness of the metal oxide layer as the first intermediate layer was 100 nm, and the open-circuit voltage, short-circuit current density, and conversion efficiency were adjusted. taking measurement.
  • Example 12 Except that the thickness of the metal chalcogenide layer, which is the second intermediate layer, is 50 nm, the solar cell of Example 12 is fabricated in the same manner as in Example 1, and the open-circuit voltage, short-circuit current density, and conversion efficiency are measured. To do.
  • Example 13 Except that the thickness of the metal chalcogenide layer as the second intermediate layer is 100 nm, the solar cell of Example 13 is manufactured in the same manner as in Example 1, and the open-circuit voltage, short-circuit current density, and conversion efficiency are measured. To do.
  • Example 14 Except for not forming an intermediate layer between the n-type layer and the second electrode, the solar cell of Example 14 is prepared in the same manner as in Example 1, and the open-circuit voltage, short-circuit current density, and conversion efficiency are measured. .
  • Comparative Example 13 Except not depositing a 1st intermediate
  • Technical proposal 1 A transparent first electrode; A first intermediate layer including a metal oxide represented by M1O X ; A second intermediate layer comprising a metal chalcogenide comprising a metal M2 and a chalcogen element M3; a p-type absorber layer; an n-type layer; A second electrode, The first intermediate layer is disposed between the first electrode and the second intermediate layer; The second intermediate layer is disposed between the first intermediate layer and the p-type light absorption layer, M1 is one or more elements selected from the group consisting of Mo and W; X satisfies 2 ⁇ X ⁇ 3, M2 is one or more elements selected from the group consisting of Mo and W.
  • the chalcogen element M3 is a solar cell that is one or more elements selected from the group consisting of S, Se, and Te.
  • Technical plan 2 The solar cell according to the technical solution 1, wherein the first intermediate layer is inclined so that the oxygen concentration on the second intermediate layer side is lower than the oxygen concentration on the first electrode side of the first intermediate layer.
  • Technical plan 4 The thickness of the first intermediate layer is 1 nm or more and 100 nm or less, 4.
  • Technical plan 5 The thickness of the first intermediate layer is 1 nm or more and 50 nm or less,
  • middle layer is a solar cell of any one of the technical proposals 1 thru
  • the thickness of the first intermediate layer is 1 nm or more and 20 nm or less
  • Technical plan 7 The solar cell according to any one of the technical solutions 1 to 6, wherein the p-type light absorption layer is a compound semiconductor layer having a chalcopyrite structure including a group Ib element, a group IIIb element, and a group VIb element.
  • Technical plan 8 The solar cell according to Technical Solution 3, wherein C1, C2, and C3 satisfy a relationship of 2.5 ⁇ C1 ⁇ 3.0, 2.0 ⁇ C2 ⁇ 3.0, and 2.0 ⁇ C3 ⁇ 2.5.
  • Technical plan 9 The solar cell according to Technical Solution 3 or 8, wherein C1, C2, and C3 satisfy 2.7 ⁇ C1 ⁇ 3.0, 2.3 ⁇ C2 ⁇ 2.7, and 2.0 ⁇ C3 ⁇ 2.3.
  • Technical plan 10 The solar cell according to any one of the technical solutions 1 to 9, wherein the M1 and the M2 are the same element.
  • Technical plan 11 A solar cell according to any one of the technical solutions 1 to 10, and A multi-junction solar cell having a light absorption layer having a smaller band gap than the p-type light absorption layer of the solar cell according to any one of the technical solutions 1 to 10.
  • Technical plan 12 The technical solution in which the light absorption layer of the solar cell having a light absorption layer having a smaller band gap than the p-type light absorption layer of the solar cell according to any one of the technical solutions 1 to 10 is a compound semiconductor or crystalline silicon. 11 is a multijunction solar cell.
  • Technical plan 13 A solar cell module using the solar cell according to any one of the technical solutions 1 to 10.
  • Technical proposal 14 A solar cell having a light absorption layer having a smaller band gap than the light absorption layer of the solar cell according to any one of the technical solutions 1 to 10 and the solar cell according to any one of the technical solutions 1 to 10 The solar cell module used.
  • Technical plan 15 A solar power generation system that performs solar power generation using the solar cell module according to Technical Solution 13 or 14. In the specification, some elements are represented only by element symbols.
  • SYMBOLS 100 Solar cell (1st solar cell), 1 ... 1st electrode, 2 ... 1st intermediate

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Abstract

La présente invention aborde le problème de fournir : une cellule solaire qui a un rendement de conversion excellent ; une cellule solaire à multiples jonctions ; un module de cellule solaire ; et un système de production d'énergie solaire photovoltaïque. Une cellule solaire selon un mode de réalisation de la présente invention comprend : une première électrode transparente (1) ; une première couche intermédiaire (2) qui contient un oxyde métallique qui est représenté par M1OX ; une deuxième couche intermédiaire (3) qui contient un chalcogénure métallique qui contient un métal M2 et un atome de chalcogène M3 ; une couche d'absorption de lumière de type p (4) ; une couche de type n (5) ; et une deuxième électrode (6). La première couche intermédiaire (2) est disposée entre la première électrode (1) et la deuxième couche intermédiaire (3). La deuxième couche intermédiaire (3) est disposée entre la première couche intermédiaire (2) et la couche d'absorption de lumière de type p (4). M1 est composé d'un ou de plusieurs éléments choisis dans le groupe constitué de Mo et W. X respecte 2 < X < 3. M2 est composé d'un ou de plusieurs éléments choisis dans le groupe constitué de Mo et W. L'atome de chalcogène M3 est composé d'un ou de plusieurs éléments sélectionnés dans le groupe constitué de S, Se et Te.
PCT/JP2018/011508 2018-03-22 2018-03-22 Cellule solaire, cellule solaire à multiples jonctions, module de cellule solaire et système de production d'énergie solaire photovoltaïque WO2019180892A1 (fr)

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