WO2023120614A1 - 光電変換素子、太陽電池モジュール、パドル及び光電変換素子の製造方法 - Google Patents

光電変換素子、太陽電池モジュール、パドル及び光電変換素子の製造方法 Download PDF

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WO2023120614A1
WO2023120614A1 PCT/JP2022/047236 JP2022047236W WO2023120614A1 WO 2023120614 A1 WO2023120614 A1 WO 2023120614A1 JP 2022047236 W JP2022047236 W JP 2022047236W WO 2023120614 A1 WO2023120614 A1 WO 2023120614A1
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photoelectric conversion
region
layer
thickness
conversion element
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English (en)
French (fr)
Japanese (ja)
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元志 中村
幹雄 濱野
恭平 堀口
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Idemitsu Kosan Co Ltd
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Idemitsu Kosan Co Ltd
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    • H—ELECTRICITY
    • H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
    • H02S—GENERATION OF ELECTRIC POWER BY CONVERSION OF INFRARED RADIATION, VISIBLE LIGHT OR ULTRAVIOLET LIGHT, e.g. USING PHOTOVOLTAIC [PV] MODULES
    • H02S10/00—PV power plants; Combinations of PV energy systems with other systems for the generation of electric power
    • H02S10/40—Mobile PV generator systems
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F10/00—Individual photovoltaic cells, e.g. solar cells
    • H10F10/10—Individual photovoltaic cells, e.g. solar cells having potential barriers
    • H10F10/16—Photovoltaic cells having only PN heterojunction potential barriers
    • H10F10/167—Photovoltaic cells having only PN heterojunction potential barriers comprising Group I-III-VI materials, e.g. CdS/CuInSe2 [CIS] heterojunction photovoltaic cells
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F77/00—Constructional details of devices covered by this subclass
    • H10F77/10—Semiconductor bodies
    • H10F77/14—Shape of semiconductor bodies; Shapes, relative sizes or dispositions of semiconductor regions within semiconductor bodies
    • 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 element, a solar cell module, a paddle, and a method for manufacturing a photoelectric conversion element.
  • Patent Document 1 A photoelectric conversion element that converts light energy into electrical energy is known (Patent Document 1).
  • the photoelectric conversion element described in Patent Document 1 has a so-called CIS or CIGS light absorption layer.
  • a CIS-based or CIGS-based light absorption layer has a group I-III-VI group 2 compound semiconductor having a chalcopyrite structure.
  • Such a CIS-based or CIGS-based light absorption layer is formed by forming a precursor film made of group I (Cu, etc.) and group III (In, Ga, etc.) and then selenizing and/or sulfurizing the precursor film. formed by
  • the precursor film expands in the process of reacting with selenium and/or sulfur and growing into a light absorbing layer with a chalcopyrite structure.
  • This volume expansion causes strain inside the light absorption layer, and voids of 0.1 ⁇ m to several ⁇ m called voids are formed in the light absorption layer.
  • Patent Literature 1 describes that a high-quality light absorption layer can be produced by having voids in the light absorption layer within a certain range.
  • Patent Document 1 it is preferable that certain voids exist in the light absorption layer for the purpose of improving the photoelectric conversion efficiency.
  • the presence of voids may contribute to a decrease in the adhesion strength between the materials forming the photoelectric conversion element.
  • the inventors of the present application have found that, depending on the environment in which the photoelectric conversion element is used, further improvement in adhesion strength between materials constituting the photoelectric conversion element is desired. When a photoelectric conversion element is used in a severe environment such as in or outside the atmosphere, it is desirable that the adhesion strength between the materials constituting the photoelectric conversion element is higher.
  • a photoelectric conversion element has a chalcogen compound layer.
  • the chalcogen compound layer includes a first region that contributes to photoelectric conversion and a second region that does not contribute to photoelectric conversion.
  • the thickness of the second region of the chalcogen compound layer is smaller than the thickness of the first region of the chalcogen compound layer.
  • a method for manufacturing a photoelectric conversion element includes a first step of forming a precursor film over a first region that contributes to photoelectric conversion and a second region that does not contribute to photoelectric conversion; and a second step of forming a compound layer.
  • the precursor film is formed such that the thickness of the precursor film in the second region is smaller than the thickness of the precursor film in the first region.
  • FIG. 1 is a schematic plan view of a photoelectric conversion element according to one embodiment
  • FIG. 2A is a schematic cross-sectional view of the photoelectric conversion element along line 2A-2A in FIG. 1;
  • FIG. It is a schematic diagram for demonstrating one step in the manufacturing method of the photoelectric conversion element which concerns on one Embodiment.
  • FIG. 4 is a schematic enlarged view of a region A4 in FIG. 3; 5 is a schematic diagram showing a state after the precursor film shown in FIG. 4 is chalcogenized.
  • FIG. FIG. 4 is a schematic diagram for explaining one step in another method for manufacturing a photoelectric conversion element according to one embodiment;
  • FIG. 7 is a schematic diagram for explaining a step following FIG. 6;
  • 1 is a schematic plan view of a solar cell module including photoelectric conversion elements;
  • FIG. 1 is a schematic perspective view of an artificial satellite equipped with solar cell modules;
  • FIG. 1 is a schematic plan view of a photoelectric conversion element according to one embodiment.
  • FIG. 2 is a schematic cross-sectional view of the photoelectric conversion element taken along line 2A-2A in FIG.
  • the photoelectric conversion element 10 may be a thin film type photoelectric conversion element.
  • photoelectric conversion element 10 is a solar cell element that converts light energy into electrical energy.
  • the photoelectric conversion element 10 has a substrate 20 that serves as a base for forming each film.
  • the substrate 20 may be made of glass, ceramics, resin, metal, or the like, for example.
  • Substrate 20 may be a flexible substrate. The shape and dimensions of the substrate 20 are appropriately determined according to the size of the photoelectric conversion element 10 and the like.
  • the substrate 20 is made of, for example, titanium (Ti), stainless steel (SUS), copper, aluminum, or alloys thereof.
  • the substrate 20 may have a laminated structure in which a plurality of metal base materials are laminated, and for example, stainless steel foil, titanium foil, or molybdenum foil may be formed on the surface of the substrate.
  • the photoelectric conversion element 10 may include at least a first electrode layer 22 , a second electrode layer 24 , and a photoelectric conversion layer 26 provided between the first electrode layer 22 and the second electrode layer 24 .
  • the photoelectric conversion layer 26 is a layer that contributes to mutual conversion between light energy and electric energy. In a solar cell element that converts light energy into electrical energy, the photoelectric conversion layer 26 is sometimes called a light absorption layer.
  • the first electrode layer 22 and the second electrode layer 24 are adjacent to the photoelectric conversion layer 26 .
  • the term "adjacent” shall mean not only that both layers are in direct contact, but also that both layers are adjacent through another layer.
  • the first electrode layer 22 is provided between the photoelectric conversion layer 26 and the substrate 20 .
  • the second electrode layer 24 is located on the side opposite to the substrate 20 with respect to the photoelectric conversion layer 26 . Therefore, the first electrode layer 22 is located on the side opposite to the second electrode layer 24 with respect to the photoelectric conversion layer 26 .
  • the second electrode layer 24 may be composed of a transparent electrode layer.
  • the second electrode layer 24 is composed of a transparent electrode layer, light incident on the photoelectric conversion layer 26 or emitted from the photoelectric conversion layer 26 passes through the second electrode layer 24 .
  • the first electrode layer 22 may be composed of an opaque electrode layer or a transparent electrode layer.
  • the first electrode layer 22 may be made of metal such as molybdenum, titanium or chromium, for example.
  • the thickness of the first electrode layer 22 may be, for example, 50 nm to 1500 nm.
  • the second electrode layer 24 may be made of an n-type semiconductor, more specifically, a material having n-type conductivity and relatively low resistance.
  • the second electrode layer 24 can function as both an n-type semiconductor and a transparent electrode layer.
  • the second electrode layer 24 comprises, for example, a metal oxide doped with a Group III element (B, Al, Ga, or In) as a dopant.
  • a Group III element B, Al, Ga, or In
  • the second electrode layer 24 is, for example, indium tin oxide (In 2 O 3 :Sn), indium titanium oxide (In 2 O 3 :Ti), indium zinc oxide (In 2 O 3 :Zn), tin zinc doped indium oxide.
  • the thickness of the second electrode layer 24 is, for example, 0.5 ⁇ m to 2.5 ⁇ m.
  • the photoelectric conversion layer 26 may contain, for example, a p-type semiconductor.
  • the photoelectric conversion layer 26 may function as, for example, a polycrystalline or microcrystalline p-type compound semiconductor layer.
  • the photoelectric conversion layer 26 has a chalcogen compound layer.
  • a chalcogen compound is a compound containing at least one chalcogen element. Chalcogen compounds include, for example, sulfides, selenides, and/or tellurides.
  • the photoelectric conversion layer 26 may include an I-III-VI Group 2 compound semiconductor layer having a chalcopyrite structure.
  • the Group I element can be selected from copper (Cu), silver (Ag), gold (Au), and the like.
  • Group III elements can be selected from indium (In), gallium (Ga), aluminum (Al), and the like.
  • the photoelectric conversion layer 26 may contain tellurium (Te), etc., in addition to selenium (Se) and sulfur (S) as VI group elements. Also, the photoelectric conversion layer 26 may contain alkali metals such as Li, Na, K, Rb, and Cs.
  • the photoelectric conversion layer 26 may include an I 2 -(II-IV)-VI Group 4 compound semiconductor layer which is a CZTS-based chalcogen compound containing Cu, Zn, Sn, S or Se.
  • CZTS-based chalcogen semiconductors include those using compounds such as Cu 2 ZnSnSe 4 and Cu 2 ZnSn(S, Se) 4 .
  • the photoelectric conversion element 10 may have a first buffer layer 27 between the photoelectric conversion layer 26 and the first electrode layer 22, if necessary.
  • the first buffer layer 27 may be a semiconductor material having the same conductivity type as the first electrode layer 22, or may be a semiconductor material having a different conductivity type.
  • the first buffer layer 27 may be made of a material having higher electrical resistance than the first electrode layer 22 .
  • the first buffer layer 27 is not particularly limited, but may be, for example, a layer containing a chalcogenide compound of a transition metal element having a layered structure.
  • the first buffer layer 27 may be composed of a compound composed of a transition metal material such as M, W, Ti, V, Cr, Nb, Ta and a chalcogen element such as O, S, Se. .
  • the first buffer layer 27 may be, for example, a ⁇ 866(Se, S) 2 layer, a ⁇ réelleSe 2 layer, or a ⁇ BudapestS 2 layer.
  • the first buffer layer 27 can be formed on the surface of the first electrode layer 22 when forming the photoelectric conversion layer 26 by chalcogenizing a precursor layer used as a precursor of the photoelectric conversion layer 26 .
  • the photoelectric conversion element 10 may have a second buffer layer 28 between the photoelectric conversion layer 26 and the second electrode layer 24, if necessary.
  • the second buffer layer 28 may be a semiconductor material having the same conductivity type as the second electrode layer 24, or may be a semiconductor material having a different conductivity type.
  • the second buffer layer 28 may be made of a material with higher electrical resistance than the second electrode layer 24 .
  • a second buffer layer 28 is formed on the photoelectric conversion layer 26 .
  • the thickness of the second buffer layer 28 may be, for example, 10 nm to 100 nm.
  • the second buffer layer 28 can be selected from compounds including zinc (Zn), cadmium (Cd), and indium (In).
  • Compounds containing zinc include, for example, ZnO, ZnS, Zn(OH) 2 , or mixed crystals thereof such as Zn(O,S) and Zn(O,S,OH), as well as ZnMgO and ZnSnO.
  • compounds containing cadmium include CdS, CdO, and mixed crystals thereof such as Cd(O,S) and Cd(O,S,OH).
  • Examples of compounds containing indium include In 2 S 3 , In 2 O 3 , and mixed crystals thereof In 2 (O, S) 3 and In 2 (O, S, OH) 3 . 2 O 3 , In 2 S 3 , In(OH) x and the like can be used.
  • the second buffer layer may have a laminated structure of these compounds.
  • the second buffer layer 28 has the effect of improving characteristics such as photoelectric conversion efficiency, it can be omitted. If the second buffer layer 28 is omitted, the second electrode layer 24 is directly formed on the photoelectric conversion layer 26 .
  • the laminated structure of the photoelectric conversion element 10 is not limited to the above aspect, and can take various aspects.
  • the photoelectric conversion element 10 may have a structure in which both the n-type semiconductor and the p-type semiconductor are sandwiched between the first electrode layer and the second electrode layer.
  • the second electrode layer does not have to be made of an n-type semiconductor.
  • the photoelectric conversion element 10 is not limited to a pn junction type structure, and may have a pin junction type structure including an intrinsic semiconductor layer (i-type semiconductor) between an n-type semiconductor and a p-type semiconductor. may have.
  • the photoelectric conversion element 10 includes a collector electrode 30 adjacent to the second electrode layer 24 .
  • the current collecting electrode 30 collects charge carriers from the second electrode layer 24 and is formed of a conductive material.
  • the collector electrode 30 may be in direct contact with the second electrode layer 24 . From the viewpoint of improving power generation efficiency, the area of the current collecting electrode 30 is preferably as small as possible.
  • the collector electrode 30 may have a plurality of substantially linear first portions 31 and second portions 32 connected to the first portions 31 .
  • the first portion 31 is sometimes referred to as a "finger”.
  • the second portion 32 is sometimes referred to as a "busbar”.
  • the first portions 31 are arranged at intervals from each other.
  • a plurality of linear first portions 31 are connected to second portions 32 .
  • the first portion 31 has a function of guiding electricity generated in the photoelectric conversion layer 26 to the second portion 32 .
  • the substantially linear first portion 31 extends straight along one direction (the X direction in the drawing) in the illustrated embodiment.
  • the first portion 31 may extend in a wavy or zigzag polygonal line.
  • linear is defined by a concept including not only straight lines but also elongated curved lines such as wavy lines and polygonal lines.
  • a plurality of first portions 31 of the current collecting electrode 30 may be provided side by side in the first direction (the Y direction in the drawing).
  • a plurality of linear first portions 31 may be connected to the same second portion 32 .
  • the second portion 32 of the collector electrode 30 may extend in the first direction (the Y direction in the drawing).
  • the second portion 32 may be connected to the first portion 31 at the end of the first portion 31 .
  • the plurality of first portions 31 may extend from the second portion 32 along the second direction (the X direction in the drawing).
  • the second portion 32 of the collector electrode 30 may substantially extend from near one end of the photoelectric conversion element 10 to near the other end in the first direction (the Y direction in the drawing).
  • the width of the second portion 32 of the collector electrode 30 (the width in the X direction in the figure) may be greater than the width of each first portion 31 (the width in the Y direction in the figure).
  • the collector electrode 30 (the first portion 31 and the second portion 32 ) may be made of a material having higher conductivity than the material of the second electrode layer 24 .
  • a material for forming the collector electrode 30 (the first portion 31 and the second portion 32) a material that has good conductivity and can obtain high adhesion to the second electrode layer 24 is used. be.
  • materials constituting the collector electrode 30 include indium tin oxide (In 2 O 3 :Sn), indium titanium oxide (In 2 O 3 :Ti), indium zinc oxide (In 2 O 3 :Zn), and tin zinc.
  • the collecting electrode 30 may be made of an alloy or a laminate made of a combination of the materials described above.
  • the photoelectric conversion element 10 includes wiring 50 joined to the collector electrode 30 .
  • the wiring 50 may be joined to the second portion 32 of the collector electrode 30 .
  • the wiring 50 includes, for example, an interconnector 52 for electrically connecting to the outside of the photoelectric conversion element 10 and/or a connector 54 for connecting with a bypass diode that electrically bypasses cells that cannot be photoelectrically converted. good.
  • a plurality of interconnectors 52 may be arranged on the second portion 32 of the collector electrode 30 at intervals.
  • the interconnect 52 may be, for example, a ribbon wire of conductive metal containing Ag.
  • the interconnector 52 may have a strip shape with a thickness of about 30 ⁇ m and a width of about 2.5 mm.
  • the junction between the current collecting electrode 30 and the wiring 50, particularly the junction between the current collecting electrode 30 and the interconnector 52, is provided at a position overlapping the photoelectric conversion layer 26 when viewed from the direction orthogonal to the interface of the photoelectric conversion layer 26. (see Figure 2).
  • the photoelectric conversion layer 26 including a chalcogen compound layer includes a first region R1 that contributes to photoelectric conversion and a second region R2 that does not contribute to photoelectric conversion.
  • the first region R1 is a region that contributes to light reception or light emission.
  • the first region R1 may be a region having no opaque layer on the surface side of the photoelectric conversion layer 26 in the thickness direction of the photoelectric conversion element 10 .
  • the second region R2 is a region that does not contribute to light reception or light emission.
  • the second region R2 may be a region having an opaque layer on the surface side of the photoelectric conversion layer 26 in the thickness direction of the photoelectric conversion element 10 .
  • the second region R2 of the photoelectric conversion layer 26 may be defined by, for example, a region that overlaps the second portion 32 of the current collecting electrode 30 in the thickness direction of the photoelectric conversion element 10 .
  • the thickness T2 of the second region R2 of the chalcogen compound layer that constitutes the photoelectric conversion layer 26 is smaller than the thickness T1 of the first region R1 of the chalcogen compound layer.
  • the thickness of the first region R1 of the chalcogen compound layer and the thickness of the second region R2 of the chalcogen compound layer may be calculated by, for example, an average value of thicknesses measured at a plurality of points.
  • the chalcogen compound layer can be formed by chalcogenizing the precursor film, as described later.
  • the precursor film is formed such that the thickness of the precursor film in the second region R2 is smaller than the thickness of the precursor film in the first region R1.
  • voids 60 are generated in the chalcogen compound layer during the chalcogenization of the precursor film (see Patent Document 1 mentioned above).
  • the thermal energy given to the precursor film during chalcogenization is effectively given to the second region R2 having a relatively small thickness. Therefore, the material (element) located in the portion corresponding to the second region R2 of the precursor film is easily diffused by the thermal energy, and the distribution of the element in the second region R2 is easily made more uniform.
  • the number of voids 60 generated in the second region R2 of the chalcogen compound layer is smaller than the number of voids 60 generated in the first region R1. Since the generation of voids 60 is suppressed in the second region R2, the adhesion strength of the chalcogen compound layer 26 increases. Thereby, the photoelectric conversion element 10 having high adhesion strength can be provided. Moreover, since the second region R2 in which the generation of the void 60 is suppressed is a region that does not contribute to photoelectric conversion, the photoelectric conversion efficiency of the photoelectric conversion element 10 does not substantially decrease.
  • the chalcogen compound layer 26 that constitutes the photoelectric conversion layer 26 has a plurality of voids 60 .
  • the gap 60 satisfies the condition "0.1T ⁇ D ⁇ 0.7T”.
  • the number density of the voids 60 in the second region R2 of the chalcogen compound layer that constitutes the photoelectric conversion layer 26 is preferably smaller than the number density of the voids 60 in the first region R1 of the chalcogen compound layer.
  • the “number density” may be defined by the number of voids 60 per unit area on a plane parallel to each layer of the photoelectric conversion element 10 . This can further increase the adhesion strength of the chalcogen compound layer.
  • the thickness T1 of the first region R1 of the chalcogen compound layer forming the photoelectric conversion layer 26 is preferably in the range of 1.0 ⁇ m to 4.0 ⁇ m, for example.
  • the thickness T2 of the second region R2 of the chalcogen compound layer is preferably smaller than the thickness T1 of the first region R1, for example within the range of 0.1 ⁇ m to 3.9 ⁇ m.
  • the thickness T2 of the second region R2 is preferably within the above range.
  • the thickness T1 of the first region R1 of the chalcogen compound layer is 2.3 ⁇ m or more, and the thickness T2 of the second region R2 of the chalcogen compound layer is less than 2.3 ⁇ m.
  • the adhesion of the chalcogen compound layer can change abruptly at a thickness around 2.3 ⁇ m. Therefore, by setting the thicknesses of the first region R1 and the second region R2 within the above range, the chalcogen compound layer can have higher adhesiveness in the second region R2.
  • the ratio of the thickness T2 of the second region R2 to the thickness T1 of the first region R1 of the chalcogen compound layer may be 0.9 or less.
  • the thermal energy generated during chalcogenization is more effectively given to the second region R2. Therefore, there is a possibility that the adhesion strength of the second region R2 of the chalcogen compound layer can be more effectively improved with respect to the first region R1. From this point of view, it is preferable that the ratio of the thickness T2 of the second region R2 to the thickness T1 of the first region R1 of the chalcogen compound layer is small.
  • FIG. 3 is a schematic diagram for explaining one step in the method for manufacturing a photoelectric conversion element according to one embodiment.
  • FIG. 4 is a schematic enlarged view of area A4 in FIG.
  • FIG. 5 is a schematic diagram showing a state after the precursor film shown in FIG. 4 is chalcogenized.
  • the first electrode layer 22 , the first buffer layer 27 , the photoelectric conversion layer 26 , the second buffer layer 28 and the second electrode layer 24 are formed on the substrate 20 .
  • the first buffer layer 27 and the second buffer layer 28 may be formed as required.
  • the first electrode layer 22 is formed by depositing a material forming the first electrode layer 22 on the surface of the substrate 20 by, for example, sputtering.
  • the material forming the first electrode layer 22 is as described above.
  • the sputtering method may be a direct current (DC) sputtering method or a radio frequency (RF) sputtering method.
  • the first electrode layer 22 may be formed using a CVD (chemical vapor deposition) method, an ALD (atomic layer deposition) method, or the like instead of the sputtering method.
  • the photoelectric conversion layer 26 is formed by forming a film on the first electrode layer 22 .
  • the photoelectric conversion layer 26 is formed by, for example, forming thin-film precursor films 26a and 26b on the first electrode layer 22 and chalcogenizing the precursor films 26a and 26b.
  • the precursor films 26a and 26b can be formed by physical vapor deposition (PVD), for example.
  • PVD physical vapor deposition
  • Examples of physical vapor deposition (PVD) include sputtering and vapor deposition.
  • the vapor deposition method is a method of forming a film using atoms or the like that are in a vapor phase by heating a vapor deposition source.
  • the precursor films 26a and 26b are formed over a first region R1 that contributes to photoelectric conversion of the manufactured photoelectric conversion element 10 and a second region R2 that does not contribute to photoelectric conversion. (first step).
  • the precursor films 26a and 26b are formed such that the thickness of the precursor films 26a and 26b in the second region R2 is smaller than the thickness of the precursor films 26a and 26b in the first region R1. .
  • the precursor film may include a film 26b containing a Group I element and a film 26a containing a Group III element. More specifically, the precursor film may be formed as a laminate of a film 26a containing a group III element and a film 26b containing a group I element.
  • the material forming the film 26b containing the Group I element can be selected from, for example, Ag, Cu, Au, and the like.
  • the material forming the film 26a containing the group III element can be selected from indium, gallium, aluminum, and the like.
  • the precursor films 26a and 26b may additionally contain alkali metals such as Li, Na, K, Rb, and Cs. Further, the precursor films 26a and 26b may additionally contain tellurium in addition to selenium and sulfur as a Group VI element.
  • the precursor films 26a and 26b are formed by physical vapor deposition (PVD) such as sputtering (see FIG. 3).
  • PVD physical vapor deposition
  • a photoelectric conversion element 10 a in the process of being formed is provided on a stage 102 within a sputtering apparatus 100 .
  • a target material 200 on which a film is to be formed is placed facing the element 10a on the stage 102 .
  • Desired precursor films 26a and 26b are formed on the device 10a by vapor deposition such as sputtering.
  • the first regions R1 and the second regions R2 of the precursor films 26a and 26b are formed together by physical vapor deposition.
  • the photoelectric conversion layer 26 having a plurality of regions with different thicknesses can be formed at the same time (see FIG. 4).
  • the first step is performed in the second region R2 at a position away from the substrate 20 on which the precursor films 26a and 26b are to be formed and in a direction orthogonal to the film surfaces of the precursor films 26a and 26b. It includes forming the precursor films 26a and 26b with the shielding plate 106 placed at the overlapping position (see FIG. 4). Since the shielding plate 106 is arranged at a position overlapping the second region R2, the thickness of the precursor films 26a and 26b formed in the second region R2 is the same as that of the precursor films 26a and 26b formed in the first region R1. It becomes smaller than the thickness (see FIG. 5). Thereby, the precursor films 26a and 26b having different thicknesses can be easily formed.
  • a chalcogen compound layer is formed by chalcogenizing the precursor films 26a and 26b (second step).
  • the chalcogen compound layer constitutes the photoelectric conversion layer 26 .
  • the chalcogenization treatment of the precursor film includes heat-treating the precursor film including the film 26b containing the group I element and the film 26a containing the group III element in an atmosphere containing the group VI element. do. Thereby, the precursor film is chalcogenized to form the photoelectric conversion layer 26 .
  • selenization is first performed by a vapor-phase selenization method.
  • Selenization is performed by heating the precursor layer in an atmosphere of a selenium source gas containing selenium as a group VI element source (eg, hydrogen selenide or selenium vapor).
  • a selenium source gas containing selenium as a group VI element source eg, hydrogen selenide or selenium vapor.
  • selenization is preferably carried out at a temperature within the range of 300° C. or higher and 600° C. or lower, for example, in a heating furnace.
  • the precursor film is converted into a compound (photoelectric conversion layer 26) containing a group I element, a group III element, and selenium.
  • the compound (photoelectric conversion layer 26) containing a group I element, a group III element, and selenium may be formed by a method other than the vapor phase selenization method.
  • such compounds can also be formed by solid-phase selenization, vapor deposition, ink coating, electrodeposition, and the like.
  • sulfuration of the photoelectric conversion layer 26 containing a group I element, a group III element, and selenium is performed.
  • Sulfurization is performed by heating the photoelectric conversion layer 26 in an atmosphere of a sulfur source gas containing sulfur (for example, hydrogen sulfide or sulfur vapor).
  • a sulfur source gas containing sulfur for example, hydrogen sulfide or sulfur vapor.
  • the photoelectric conversion layer 26 is converted into a semiconductor compound containing a group I element, a group III element, and selenium and sulfur as group VI elements.
  • the sulfur source gas plays a role of substituting sulfur for selenium in a crystal composed of a group I element, a group III element, and selenium, such as a chalcopyrite crystal, on the surface of the photoelectric conversion layer 26 .
  • sulfurization is preferably carried out at a temperature within the range of 450°C or higher and 650°C or lower, for example, in a heating furnace.
  • the precursor film is converted into the photoelectric conversion layer 26 by the above selenization and fluidization.
  • the first buffer layer 27 containing a compound composed of a transition metal material such as M, W, Ti, V, Cr, Nb, and Ta and a chalcogen element such as O, S, and Se is formed in the first buffer layer 27. It is formed between the electrode layer 22 and the photoelectric conversion layer 26 .
  • the precursor layer is formed as a thin film of Cu--Zn--Sn or Cu--Zn--Sn--Se--S.
  • the precursor layer containing Cu, Zn, and Sn is sulfurized and selenized in a hydrogen sulfide atmosphere and a hydrogen selenide atmosphere at 500° C. to 650° C.
  • a CZTS-based photoelectric conversion layer 26 having Cu 2 ZnSn(S, Se) 4 can be formed.
  • the first buffer layer 27 is formed between the first electrode layer 22 and the photoelectric conversion layer 26 by the sulfurization and selenization described above.
  • both selenization and sulfurization are performed when converting the precursor film into the photoelectric conversion layer 26 .
  • the precursor film may be converted into the photoelectric conversion layer 26 by any chalcogenization treatment.
  • the thickness of the precursor film corresponding to the second region R2 is smaller than the thickness of the precursor film corresponding to the first region R1. Therefore, the thickness of the second region R2 of the photoelectric conversion layer 26 after chalcogenization is also smaller than the thickness of the first region R1 of the photoelectric conversion layer 26 after chalcogenization.
  • the second buffer layer 28 is formed by forming a film on the photoelectric conversion layer 26 by a method such as a CBD (chemical bath deposition) method, a sputtering method, a CVD method, an ALD method, or the like.
  • a method such as a CBD (chemical bath deposition) method, a sputtering method, a CVD method, an ALD method, or the like.
  • the material forming the second buffer layer is as described above.
  • the second electrode layer 24 is formed on the second buffer layer 28 by a method such as sputtering, CVD, or ALD. Alternatively, the second electrode layer 24 is formed directly on the photoelectric conversion layer 26 if the second buffer layer 28 is not present.
  • the material forming the second electrode layer 24 is as described above.
  • the collector electrode 30 (the first portion 31 and the second portion 32) is formed on the second electrode layer 24.
  • the collecting electrode 30 can be formed by applying a sputtering method, a CVD method, an ALD method, an AD method, a vapor deposition method, as well as a printing process such as an inkjet method or a screen printing method, for example.
  • the collector electrode 30 may include a plurality of linear first portions 31 and second portions 32 connected to the plurality of first portions 31 .
  • the collector electrode 30 is preferably formed such that the second region R2 of the chalcogen compound layer overlaps the second portion 32 of the collector electrode 30 in the thickness direction of the photoelectric conversion element 10 .
  • a wiring 50 is joined to the collector electrode 30 as necessary.
  • the chalcogen compound layer is formed by chalcogenizing the precursor film.
  • voids 60 may occur in the chalcogen compound layer due to the difference in reactivity of a plurality of metal elements contained in the precursor film to selenium and/or sulfur.
  • the precursor film contains multiple elements such as In and Ga as group III elements, the voids 60 may be generated from the difference in reactivity of the multiple elements to selenium and/or sulfur.
  • the thermal energy applied to the precursor film is effectively applied to the second region R2 having a relatively small thickness. Therefore, the material (element) located in the portion corresponding to the second region R2 of the precursor film is easily diffused by the thermal energy, and the distribution of the element in the second region R2 is easily made more uniform. Thereby, the generation of voids 60 is suppressed more in the second region R2 of the chalcogen compound layer than in the first region R1. Since the generation of voids 60 in the second region R2 of the chalcogen compound layer is suppressed, the adhesion strength of the chalcogen compound layer increases.
  • the voids 60 generated in the photoelectric conversion layer 26 expand due to the heat applied during the formation of the collector electrode 30 , particularly the second portion 32 of the collector electrode 30 , and may reduce the adhesion of the photoelectric conversion layer 26 .
  • the second region R2 of the photoelectric conversion layer 26 with the low number density of the voids 60 is positioned directly below the second portion 32 of the collector electrode 30 . Therefore, it is possible to reduce the possibility that the adhesion of the photoelectric conversion layer 26 is lowered due to the heat applied during the formation of the second portion 32 of the current collecting electrode 30 .
  • FIG. 6 is a schematic diagram for explaining one step in another method for manufacturing a photoelectric conversion element according to one embodiment.
  • FIG. 7 is a schematic diagram for explaining steps following FIG. Note that FIGS. 6 and 7 show regions corresponding to the photoelectric conversion elements 10 shown in FIG.
  • the first electrode layer 22 , the first buffer layer 27 , the photoelectric conversion layer 26 , the second buffer layer 28 and the second electrode layer 24 are formed on the substrate 20 .
  • the first buffer layer 27 and the second buffer layer 28 may be formed as required.
  • the first electrode layer 22 can be formed in the same manner as described above.
  • the photoelectric conversion layer 26 is formed by forming a film on the first electrode layer 22 .
  • the photoelectric conversion layer 26 is formed by, for example, forming thin-film precursor films 26a and 26b on the first electrode layer 22 and chalcogenizing the precursor films 26a and 26b.
  • the precursor films 26a and 26b can be formed, for example, by physical vapor deposition (PVD).
  • the precursor films 26a and 26b are formed over a first region R1 that contributes to photoelectric conversion of the manufactured photoelectric conversion element 10 and a second region R2 that does not contribute to photoelectric conversion. (first step).
  • the precursor films 26a and 26b may be formed to have the same thickness in the first region R1 and the second region R2 (see FIG. 6).
  • the first step includes forming the precursor films 26a and 26b over the first region R1 and the second region R2, and then reducing the thickness of the precursor films 26a and 26b formed in the second region R2. (See FIG. 7). Specifically, the precursor films 26a and 26b formed in the second region R2 are preferably partially removed in the thickness direction. After that, chalcogenization treatment is performed in the same manner as in the manufacturing method 1 described above.
  • the materials forming the precursor films 26a and 26b are the same as in the manufacturing method described above. Furthermore, the second buffer layer 28, the second electrode layer 24, the collector electrode 30, and the wiring 50 may be formed by a method similar to the manufacturing method 1 described above.
  • the photoelectric conversion element is composed of molybdenum.
  • the first buffer layer includes a group VI compound layer made of Mo(Se,S) 2 .
  • the photoelectric conversion layer is a CIS-type layer containing a chalcogen semiconductor containing a chalcogen element. Specifically, the photoelectric conversion layer was formed by selenizing and sulfurizing a metal precursor film containing Cu, In and Ga by the selenization method described above.
  • the second electrode layer is a transparent conductive film.
  • the photoelectric conversion element according to Experimental Example 1 has current collecting electrodes and wiring. Bonding of the wiring (silver foil) to the collector electrode was performed by fusion bonding. Note that in Experimental Example 1, the photoelectric conversion layer was formed with a uniform thickness over the first region R1 and the second region R2. In Experimental Example 1, the thickness of the photoelectric conversion layer was approximately 2.5 ⁇ m.
  • Example 2 In Experimental Example 2, the thickness of the photoelectric conversion layer is different from that of the photoelectric conversion element in Experimental Example 1. FIG. In Experimental Example 2, the thickness of the photoelectric conversion layer was approximately 2.2 ⁇ m.
  • Table 1 The measured tensile strength is shown in Table 1 below.
  • Table 1 shows the ratio of tensile strength expressed by normalizing the test result (tensile strength) in Experimental Example 1 to "1".
  • the second region of the photoelectric conversion layer 26 is , is considered to contribute highly to adhesion.
  • the thickness ratio of the photoelectric conversion layer is approximately 0.88.
  • the tensile strength ratio (adhesion strength ratio) is 2.1.
  • the tensile strength ratio (adhesion strength ratio) is about twice or more. Therefore, it can be seen that the ratio of the thickness T2 of the second region R2 to the thickness T1 of the first region R1 of the chalcogen compound layer is more preferably 0.9 or less.
  • FIG. 8 is a schematic plan view of a solar cell module including photoelectric conversion elements.
  • a solar cell module 300 may comprise one or more photoelectric conversion elements 10 .
  • FIG. 8 shows a photoelectric conversion module 300 including a plurality of photoelectric conversion elements 10 .
  • One or more photoelectric conversion elements 10 may be sealed, for example, with a sealing material.
  • the plurality of photoelectric conversion elements 10 may be arranged in at least one direction, preferably in a grid pattern. In this case, the plurality of photoelectric conversion elements 10 may be electrically connected in series and/or in parallel with each other.
  • the photoelectric conversion elements 10 are arranged so as to partially overlap each other. Of the photoelectric conversion elements 10 arranged in one direction, adjacent photoelectric conversion elements 10 partially overlap each other. Specifically, as shown in FIG. 8, one photoelectric conversion element 10 may be arranged so as to cover the second portion 32 of the collector electrode 30 of the adjacent photoelectric conversion element 10 . Instead of the embodiment shown in FIG. 8, adjacent photoelectric conversion elements 10 may be spaced apart from each other. The interconnector 52 described above electrically connects the photoelectric conversion elements 10 adjacent to each other.
  • FIG. 9 is a schematic perspective view of an artificial satellite equipped with solar cell modules.
  • Satellite 900 may have a base 910 and a paddle 920 .
  • the base 910 may include devices (not shown) necessary for controlling the satellite 900 and the like.
  • Antenna 940 may be attached to base 910 .
  • the paddle 920 may include the solar cell module 300 described above.
  • the paddle 920 with the solar cell module 300 can be used as a power source for operating various devices provided on the base 910 .
  • the solar cell module 300 can be applied to paddles for artificial satellites.
  • the paddle 920 for a satellite is exposed to a high-temperature environment and a severe temperature change environment during the launch and operation of the satellite, so the solar cell module 300 including the above-described photoelectric conversion element 10 having high heat resistance is used. It is desirable that
  • the paddle 920 may have a connecting portion 922 and a hinge portion 924 .
  • the connecting portion 922 corresponds to a portion connecting the paddle 920 to the base portion 910 .
  • the hinge portion 924 extends along one direction, and the paddle 920 can be bent around the hinge portion 924 as a rotation axis.
  • Each paddle 920 may have at least one, and preferably multiple hinges 924 .
  • paddle 920 having solar cell module 300 is configured to be foldable into a small size.
  • the paddle 920 may be in a folded state when the satellite 900 is launched.
  • the paddle 920 may be deployed when receiving sunlight to generate power.
  • the paddle 920 may have a cylindrical shape formed by winding. This allows the paddle 920 to assume a substantially flat unfolded state by rotation of the wound portion. During launch of satellite 900, paddle 920 may maintain a generally cylindrical shape. The paddle 920 may be deployed so as to be in a substantially flat state when receiving sunlight to generate power.
  • the photoelectric conversion layer (light absorption layer) 26 has a chalcogen compound layer.
  • the chalcogen compound layer may constitute another layer among the layers constituting the photoelectric conversion element 10 . Even in this case, the adhesion strength of the layers constituting the photoelectric conversion element 10 can be increased by adjusting the thickness of the chalcogen compound layer.

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05116692A (ja) * 1991-10-30 1993-05-14 Nec Eng Ltd 人工衛星用太陽電池パドル
JP2012004427A (ja) * 2010-06-18 2012-01-05 Showa Shell Sekiyu Kk Ｃｉｓ系薄膜太陽電池
JP2016072367A (ja) * 2014-09-29 2016-05-09 日東電工株式会社 半導体層およびその製造方法ならびにその半導体層を有する化合物太陽電池
JP2016157808A (ja) * 2015-02-24 2016-09-01 京セラ株式会社 光電変換装置
KR20190032331A (ko) * 2019-03-19 2019-03-27 한국항공대학교산학협력단 개구형 투광타입 cigs박막 태양 전지의 버스 바의 접합 방법
WO2020129803A1 (ja) * 2018-12-19 2020-06-25 出光興産株式会社 光電変換素子および光電変換素子の製造方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05116692A (ja) * 1991-10-30 1993-05-14 Nec Eng Ltd 人工衛星用太陽電池パドル
JP2012004427A (ja) * 2010-06-18 2012-01-05 Showa Shell Sekiyu Kk Ｃｉｓ系薄膜太陽電池
JP2016072367A (ja) * 2014-09-29 2016-05-09 日東電工株式会社 半導体層およびその製造方法ならびにその半導体層を有する化合物太陽電池
JP2016157808A (ja) * 2015-02-24 2016-09-01 京セラ株式会社 光電変換装置
WO2020129803A1 (ja) * 2018-12-19 2020-06-25 出光興産株式会社 光電変換素子および光電変換素子の製造方法
KR20190032331A (ko) * 2019-03-19 2019-03-27 한국항공대학교산학협력단 개구형 투광타입 cigs박막 태양 전지의 버스 바의 접합 방법

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