WO2011040461A1 - 光電変換装置及びその製造方法 - Google Patents
光電変換装置及びその製造方法 Download PDFInfo
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- WO2011040461A1 WO2011040461A1 PCT/JP2010/066941 JP2010066941W WO2011040461A1 WO 2011040461 A1 WO2011040461 A1 WO 2011040461A1 JP 2010066941 W JP2010066941 W JP 2010066941W WO 2011040461 A1 WO2011040461 A1 WO 2011040461A1
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- photoelectric conversion
- chalcogen compound
- metal
- lower electrode
- layer
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 119
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- 229910052751 metal Inorganic materials 0.000 claims abstract description 101
- 150000001786 chalcogen compounds Chemical class 0.000 claims abstract description 89
- 239000004020 conductor Substances 0.000 claims abstract description 44
- 239000004065 semiconductor Substances 0.000 claims abstract description 42
- 239000000758 substrate Substances 0.000 claims abstract description 20
- 229910052798 chalcogen Inorganic materials 0.000 claims abstract description 16
- 150000001787 chalcogens Chemical class 0.000 claims abstract description 15
- 239000002184 metal Substances 0.000 claims description 99
- 238000000034 method Methods 0.000 claims description 22
- 239000002243 precursor Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000010410 layer Substances 0.000 description 143
- 238000000926 separation method Methods 0.000 description 38
- 230000031700 light absorption Effects 0.000 description 37
- 150000001875 compounds Chemical class 0.000 description 15
- 229910052733 gallium Inorganic materials 0.000 description 10
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 7
- KTSFMFGEAAANTF-UHFFFAOYSA-N [Cu].[Se].[Se].[In] Chemical compound [Cu].[Se].[Se].[In] KTSFMFGEAAANTF-UHFFFAOYSA-N 0.000 description 7
- 229910052951 chalcopyrite Inorganic materials 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- -1 chalcopyrite compound Chemical class 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000011669 selenium Substances 0.000 description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000010408 film Substances 0.000 description 4
- 229910052738 indium Inorganic materials 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- 238000004544 sputter deposition Methods 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 3
- DVRDHUBQLOKMHZ-UHFFFAOYSA-N chalcopyrite Chemical compound [S-2].[S-2].[Fe+2].[Cu+2] DVRDHUBQLOKMHZ-UHFFFAOYSA-N 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- 239000005083 Zinc sulfide Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- HVMJUDPAXRRVQO-UHFFFAOYSA-N copper indium Chemical compound [Cu].[In] HVMJUDPAXRRVQO-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 238000000682 scanning probe acoustic microscopy Methods 0.000 description 2
- 229910052711 selenium Inorganic materials 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- 229910052984 zinc sulfide Inorganic materials 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229910016001 MoSe Inorganic materials 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052795 boron group element Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- LCUOIYYHNRBAFS-UHFFFAOYSA-N copper;sulfanylideneindium Chemical compound [Cu].[In]=S LCUOIYYHNRBAFS-UHFFFAOYSA-N 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910001849 group 12 element Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- MHWZQNGIEIYAQJ-UHFFFAOYSA-N molybdenum diselenide Chemical compound [Se]=[Mo]=[Se] MHWZQNGIEIYAQJ-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 229940082569 selenite Drugs 0.000 description 1
- MCAHWIHFGHIESP-UHFFFAOYSA-L selenite(2-) Chemical compound [O-][Se]([O-])=O MCAHWIHFGHIESP-UHFFFAOYSA-L 0.000 description 1
- 150000003346 selenoethers Chemical class 0.000 description 1
- 239000005361 soda-lime glass Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- GKCNVZWZCYIBPR-UHFFFAOYSA-N sulfanylideneindium Chemical compound [In]=S GKCNVZWZCYIBPR-UHFFFAOYSA-N 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- 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
- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/042—PV modules or arrays of single PV cells
- H01L31/0445—PV modules or arrays of single PV cells including thin film solar cells, e.g. single thin film a-Si, CIS or CdTe solar cells
- H01L31/046—PV modules composed of a plurality of thin film solar cells deposited on the same substrate
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/042—PV modules or arrays of single PV cells
- H01L31/0445—PV modules or arrays of single PV cells including thin film solar cells, e.g. single thin film a-Si, CIS or CdTe solar cells
- H01L31/046—PV modules composed of a plurality of thin film solar cells deposited on the same substrate
- H01L31/0465—PV modules composed of a plurality of thin film solar cells deposited on the same substrate comprising particular structures for the electrical interconnection of adjacent PV cells in the module
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/06—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers
- H01L31/072—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers the potential barriers being only of the PN heterojunction type
- H01L31/0749—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers the potential barriers being only of the PN heterojunction type including a AIBIIICVI compound, e.g. CdS/CulnSe2 [CIS] heterojunction solar cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/541—CuInSe2 material PV cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Definitions
- the present invention relates to a photoelectric conversion device having a chalcogen compound semiconductor layer and a manufacturing method thereof.
- chalcopyrite photoelectric conversion devices represented by CIS (copper indium selenide) are relatively low cost solar cell modules. R & D is being promoted because it is easy to increase the area.
- This chalcopyrite photoelectric conversion device includes a chalcogen compound semiconductor layer (chalcopyrite compound semiconductor layer) such as copper indium gallium selenide (CIGS) as a light absorption layer and a mixed crystal compound semiconductor such as cadmium sulfide as a buffer layer. ing. Further, such a photoelectric conversion device has a transparent conductive film as an upper electrode on the buffer layer. Furthermore, such a photoelectric conversion device has a silver grid electrode on a transparent conductive film. In such a photoelectric conversion device, a transparent conductive film and a silver grid electrode are also formed in the groove portion to form a connection conductor. This connection conductor electrically connects the upper electrode of one photoelectric conversion cell and the lower electrode of the other photoelectric conversion cell (see, for example, Patent Document 1).
- a chalcogen compound semiconductor layer such as copper indium gallium selenide (CIGS) as a light absorption layer
- a mixed crystal compound semiconductor such as cadmium sulfide
- the chalcogen compound semiconductor layer constituting the light absorption layer is relatively fragile, and the light absorption layer is peeled off during the processing of the groove, which easily causes poor connection between the connection conductor and the lower electrode. Such a connection failure may cause a decrease in photoelectric conversion efficiency of the photoelectric conversion device. Therefore, it is required to reduce the occurrence of connection failure as described above and increase the photoelectric conversion efficiency of the photoelectric conversion device.
- the present invention has been made in view of such problems, and an object thereof is to provide a photoelectric conversion device having high photoelectric conversion efficiency.
- One embodiment of the photoelectric conversion device of the present invention includes a substrate, a plurality of lower electrodes including a metal element provided on the substrate, and a chalcogen compound semiconductor provided on each of the plurality of lower electrodes.
- a plurality of photoelectric conversion layers Further, in the present embodiment, a plurality of upper electrodes respectively provided on the plurality of photoelectric conversion layers and a connection for electrically connecting one upper electrode to the other lower electrode between the adjacent photoelectric conversion layers. And a conductor.
- connection conductor includes a first connection portion connected to the lower electrode via a first metal chalcogen compound layer containing a chalcogen element contained in the metal element and the chalcogen compound semiconductor, and A second connection portion connected to the lower electrode without a first metal chalcogen compound layer.
- the first metal chalcogen compound layer including the metal element and the chalcogen element included in the chalcogen compound semiconductor is formed on the lower electrode
- the chalcogen compound semiconductor is included on the first metal chalcogen compound layer.
- a step of forming an upper electrode on the photoelectric conversion layer and a step of removing a part of the upper electrode, the photoelectric conversion layer, and the first metal chalcogen compound layer on the lower electrode.
- a step of forming a connection conductor so as to connect the upper electrode to the lower electrode.
- the connection conductor in the step of forming the connection conductor, the first connection portion connected to the lower electrode via the first metal chalcogen compound layer and the lower portion without passing through the first metal chalcogen compound layer A second connection portion connected to the electrode is formed.
- the photoelectric conversion device and method for manufacturing the photoelectric conversion device it is possible to provide a photoelectric conversion device having a good connection between the connection conductor and the lower electrode and having a high photoelectric conversion efficiency.
- FIG. 1st metal chalcogen compound layer It is sectional drawing for every process which shows an example of embodiment of the manufacturing method of the photoelectric conversion apparatus of this invention. It is sectional drawing for every process which shows the other example of embodiment of the manufacturing method of the photoelectric conversion apparatus of this invention. It is sectional drawing which shows the other example of embodiment of the photoelectric conversion apparatus of this invention. It is a partial expanded sectional view which shows the other example of embodiment of the photoelectric conversion apparatus of this invention.
- FIG. 1 is a perspective view showing a structure of a photoelectric conversion device according to an embodiment of the present invention
- FIG. 2 is a sectional view thereof.
- the photoelectric conversion device 21 includes a substrate 1, a lower electrode 2, a photoelectric conversion layer 33, an upper electrode 5, a connection electrode 7, a first metal chalcogen compound layer 8a, and a second metal chalcogen compound layer 8b. It is out.
- the photoelectric converting layer 33 has shown the example which comprises the light absorption layer 3 and the buffer layer 4 heterojunctioned to this, it is not limited to this.
- the photoelectric conversion layer 33 should just contain the chalcogen compound semiconductor at least the site
- the photoelectric conversion layer 33 may be formed by laminating the buffer layer 4 including the chalcogen compound semiconductor and the light absorption layer 3 from the lower electrode 2 side, and is obtained by homojunction of semiconductor layers of different conductivity types. Also good.
- the upper electrode 5 may be a semiconductor layer or a so-called window layer.
- the photoelectric conversion device 21 has a plurality of photoelectric conversion cells 20 arranged side by side.
- the upper electrode of the photoelectric conversion cell 20 is electrically connected to the portion where the lower electrode 2 of the adjacent photoelectric conversion cell 20 is extended by the connecting conductor 7 provided so as to straddle the light absorption layer 3 and the buffer layer 4. It is connected to the.
- the connection conductor 7 electrically connects the upper electrode 5 of one photoelectric conversion cell 20 and the lower electrode 2 of the other photoelectric conversion cell 20 between adjacent photoelectric conversion layers 33.
- adjacent photoelectric conversion cells 20 are connected in series along the X direction in FIG.
- the connection conductor 7 is provided so as to straddle the light absorption layer 3 and the buffer layer 4, and the light absorption layer 3 and the buffer sandwiched between the upper electrode 5 and the lower electrode 2. Photoelectric conversion is performed by the layer 4.
- the substrate 1 is for supporting the light absorption layer 3 and the like.
- the material used for the substrate 1 include glass, ceramics, resin, and metal.
- blue plate glass silica glass having a thickness of about 1 to 3 mm can be used.
- the lower electrode 2 is made of a metal such as molybdenum (Mo), aluminum (Al), titanium (Ti), tantalum (Ta), or gold (Au), or a laminated structure of these metals.
- Mo molybdenum
- Al aluminum
- Ti titanium
- Ta tantalum
- Au gold
- the lower electrode 2 is formed on the substrate 1 to a thickness of about 0.2 to 1 ⁇ m by sputtering or vapor deposition.
- the light absorption layer 3 includes a chalcogen compound semiconductor.
- the chalcogen compound semiconductor is a compound semiconductor containing a chalcogen element, sulfur (S), selenium (Se), or tellurium (Te).
- examples of the chalcogen compound semiconductor include an I-III-VI compound semiconductor and an II-VI compound semiconductor.
- An I-III-VI compound semiconductor is composed of a group IB element (also referred to as a group 11 element), a group III-B element (also referred to as a group 13 element), and a group VI-B element (also referred to as a group 16 element). It is a compound semiconductor, has a chalcopyrite structure, and is called a chalcopyrite compound semiconductor (also called a CIS compound semiconductor).
- the II-VI compound semiconductor is a compound semiconductor of a group II-B (also referred to as a group 12 element) and a group VI-B element. From the viewpoint of increasing the photoelectric conversion efficiency, an I-III-VI compound semiconductor which is a chalcopyrite compound semiconductor may be used.
- I-III-VI compound semiconductor examples include copper indium diselenide (CuInSe 2 ), copper indium diselenide / gallium (Cu (In, Ga) Se 2 ), diselen selenide / copper indium / gallium (gallium ( Cu (In, Ga) (Se, S) 2 ), copper indium disulfide / gallium (Cu (In, Ga) S 2 ), and the like.
- the chalcopyrite compound semiconductor may be a multi-component compound semiconductor thin film of copper indium selenide, gallium, etc. having a thin film of selenite, copper indium sulfide, and gallium as a surface layer.
- the light absorption layer 3 is a thin film having a p-type conductivity and a thickness of about 1 to 3 ⁇ m, for example. Moreover, when the light absorption layer 3 consists of an I-III-VI compound semiconductor, you may have the buffer layer 4 for forming a heterojunction on the surface. Examples of the buffer layer 4 include mixed crystal compound semiconductors such as cadmium sulfide (CdS), indium sulfide (InS), and zinc sulfide (ZnS).
- CdS cadmium sulfide
- InS indium sulfide
- ZnS zinc sulfide
- a second metal chalcogen compound layer 8b including a metal element contained in the lower electrode 2 and a chalcogen element contained in the light absorption layer 3 is provided.
- the thickness of the second metal chalcogen compound layer 8b is about 1 nm to 1 ⁇ m. From the viewpoint of improving the adhesion between the light absorption layer 3 and the lower electrode 2 and improving the electrical connection between the light absorption layer 3 and the lower electrode 2, the thickness of the second metal chalcogen compound layer 8b is: It may be 5 nm to 200 nm.
- the second metal chalcogen compound layer 8b is, for example, molybdenum selenide (MoSe 2 ) when the lower electrode 2 is molybdenum and the light absorption layer is a compound semiconductor containing Se.
- MoSe 2 molybdenum selenide
- the adhesion strength between the light absorption layer 3 and the lower electrode 2 can be increased by the second metal chalcogen compound layer 8b.
- the second metal chalcogen compound layer 8 can be formed by bringing a raw material containing a gaseous or solid chalcogen element into contact with the lower electrode 2 and heating. From the viewpoint of simplifying the process, the second metal chalcogen compound layer 8b is formed simultaneously with the formation of the light absorption layer 3 by using a chalcogen element as a raw material of the light absorption layer 3 when the light absorption layer 3 is formed. It is preferable to form.
- the upper electrode 5 includes what is called a window layer.
- the upper electrode 5 may be made of a material having an n-type conductivity type with a wide forbidden band width, transparent, and low resistance. As such a material. Examples include zinc oxide (ZnO), compounds with zinc oxide containing aluminum, boron, gallium, indium, fluorine, and metal oxide semiconductor thin films such as indium oxide (ITO) and tin oxide (SnO 2 ) containing tin. It is done.
- the thickness of the upper electrode 5 may be about 1 to 2 ⁇ m. Since the window layer can be regarded as one electrode in the photoelectric conversion device 21, it is regarded as the upper electrode 5 in the present embodiment.
- the upper electrode 5 may further form a transparent conductive film in addition to such a window layer.
- connection conductor 7 penetrates the light absorption layer 3 and the buffer layer 4, and electrically connects the upper electrode 5 of one photoelectric conversion cell 20 and the lower electrode 2 of the other photoelectric conversion cell 20 between adjacent photoelectric conversion cells. Is a conductor connected to
- the connection conductor 7 includes a first connection portion A connected to the lower electrode 2 via the first metal chalcogen compound layer 8a, and a first metal chalcogen compound layer 8a. And a second connection portion B that is directly connected to the lower electrode 2. That is, in the present embodiment, the first metal chalcogen compound layer 8a partially provided on the lower electrode 2 is in the height direction of the connecting conductor 7 (Z direction in FIG. 1) from the surface of the lower electrode 2. It is provided so as to enter into the connection conductor 7. Therefore, in the present embodiment, the adhesion between the lower electrode 2 and the connection conductor 7 can be improved by the anchor effect by the first metal chalcogen compound layer 8a, so that the photoelectric conversion efficiency can be increased.
- the first metal chalcogen compound layer 8a may have the same thickness and material as the second metal chalcogen compound layer 8b described above.
- FIG. 3 is a schematic diagram for explaining the shape of the first metal chalcogen element 8a.
- the first metal chalcogen compound layer 8a is provided on the lower electrode 2 facing the gap C corresponding to a separation groove P2 described later.
- the buffer layer 4, the upper electrode 5, the current collecting electrode 6, and the connection conductor 7 are not drawn in order to explain the shape of the first metal chalcogen element 8 a.
- the shape of the first metal chalcogen element 8a may be, for example, a rectangle, an ellipse, or a circle as shown in FIG. 3 in plan view of the gap C from the lower electrode 2 side.
- the gap C is formed by separating the photoelectric conversion layer 33 into two, and has, for example, an elongated shape along the Y direction as shown in FIG.
- the first metal chalcogen compound layer 8a may be provided along the longitudinal direction of the gap C.
- the 1st metal chalcogen compound layer 8a can be formed larger than the width
- an anchor effect can be heightened more.
- the first metal chalcogen compound layer 8a may be provided at an end portion along the longitudinal direction of the gap C as shown in FIG. Thereby, the photoelectric conversion layer 33 in the vicinity of the end portion is hardly peeled off from the lower electrode 2.
- the area of the first connection portion A is preferably smaller than the area of the second connection portion B when the substrate 1 is viewed in plan.
- the area of the first metal chalcogen compound layer 8a is smaller than the entire area of the lower electrode 2 in the gap C when the substrate 1 is viewed in plan.
- the area ratio of the first metal chalcogen compound 8a to the entire area of the lower electrode 2 in the gap C is preferably 25% to 45%.
- low resistance can be implement
- Such an area ratio can be measured by using, for example, Auger electron spectroscopy after forming the gap C. Further, the area ratio may be measured by the above-described Auger electron spectroscopy when the connecting conductor 7 is removed along the Z direction in FIG. 1 and the first metal chalcogen compound layer 8a is exposed, for example.
- the connection conductor 7 may be the same material as the upper electrode 5 or may be a solidified metal paste. Solidification includes the solidified state after melting when the binder used for the metal paste is a thermoplastic resin, and after curing when the binder is a curable resin such as a thermosetting resin or a photocurable resin. The state of is also included. From the viewpoint of improving the connection reliability, a metal paste in which a metal powder such as Ag is dispersed in a resin binder or the like can be used.
- a current collecting electrode 6 may be provided on the upper electrode 5.
- the collector electrode 6 is formed in a linear shape from one end of the photoelectric conversion cell 20 to the connection conductor 7. Thereby, the electric charge generated by the photoelectric conversion of the light absorption layer 3 is collected by the current collecting electrode 6 through the upper electrode 5, and can be conducted well to the adjacent photoelectric conversion cell 20 through the connection conductor 7. it can. Therefore, by providing the current collecting electrode 6, even if the upper electrode 5 is thinned, the charge generated in the light absorption layer 3 can be taken out efficiently. As a result, power generation efficiency can be increased.
- the collecting electrode 6 may have a width of 50 to 400 ⁇ m from the viewpoint of reducing light blocking the light absorption layer 3 and having good conductivity.
- the current collecting electrode 6 may have a plurality of branched portions.
- the current collecting electrode 6 can be formed, for example, by printing a metal paste in which a metal powder such as Ag is dispersed in a resin binder or the like in a pattern, drying it and solidifying it.
- a lower electrode 2 is formed on substantially the entire surface of the cleaned substrate 1 using a sputtering method or the like.
- the lower electrode 2 is patterned by forming a dividing groove P1 using a YAG laser or the like.
- the light absorption layer 3 is formed on the patterned lower electrode 2 by using a sputtering method, a vapor deposition method, a printing method, or the like.
- the chalcogen element as the raw material of the light absorption layer 3 is reacted with the lower electrode 2, and the metal chalcogen compound layer 8 (first to third metal chalcogen compound layers) is formed at the interface between the lower electrode 2 and the light absorption layer 3.
- the buffer layer 4 is formed on the light absorption layer 3 by using a solution growth method (CBD method) or the like.
- CBD method solution growth method
- the upper electrode 5 is formed on the buffer layer 4 by sputtering, metal organic chemical vapor deposition (MOCVD), or the like.
- separation grooves P2 are formed in the light absorption layer 3, the buffer layer 4, and the upper electrode 5 by mechanical scribing.
- the separation groove P2 is provided, for example, at a distance of about 0.1 to 1.0 mm from the division groove P1 provided in the lower electrode 2.
- the width of the separation groove P2 is, for example, about 100 to 1000 ⁇ m.
- the separation groove P2 having such a width can be formed, for example, by scribing continuously several times while shifting the pitch using a scribe needle having a scribe width of about 40 to 50 ⁇ m.
- the separation groove P2 may be formed by expanding and scribing the tip shape of the scribe needle to a predetermined width.
- the separation groove P2 may be formed by fixing two or more scribe needles in contact or in proximity to each other and performing scribe once to several times.
- the mechanical scribing strength is adjusted, and a part of the metal chalcogen compound layer 8 in the separation groove P2 is removed.
- the metal chalcogen compound layer 8 remaining on the lower electrode 2 is the first metal chalcogen compound layer 8a.
- the 1st metal chalcogen compound layer 8a obtained by leaving the metal chalcogen compound layer 8 partially can be formed with the following method.
- the pressing force of the scribing needle may be 0.1 to 0.5 MPa, and the speed may be 200 to 2000 mm / second.
- the power to remove the metal chalcogen compound layer 8 becomes weak, so that the metal chalcogen compound layer 8 can remain on the lower electrode 2.
- the metal chalcogen compound layer 8 located between the lower electrode 2 and the photoelectric conversion layer 33 is the second metal chalcogen compound layer 8b.
- the surface portion of the lower electrode 2 may be removed.
- the metal chalcogen compound layer 8 can be stably removed, and the connection reliability of the second connection portion described above can be improved.
- the method for removing the metal chalcogen compound layer 8 is not limited to mechanical scribing, and may be removed by etching or the like.
- the collector electrode 6 and the connecting conductor 7 are formed on the upper electrode 5 and in the separation groove P2 by printing silver paste or the like for reducing the resistance.
- the connection conductor 7 is electrically connected to the lower electrode 2 via the first metal chalcogen compound layer 8a, and not via the first metal chalcogen compound layer 8a.
- a second connection portion B that is directly connected to the lower electrode 2 can be formed.
- the light absorption layer 3, the buffer layer 4 and the upper electrode 5 are patterned by mechanical scribing to form separation grooves P3, and a plurality of photoelectric conversion cells 20 connected in series are formed.
- the photoelectric conversion device 21 is formed.
- the metal chalcogen compound layer 8 may be removed or left.
- the third metal chalcogen compound layer 8c is provided by leaving the metal chalcogen compound layer 8 in the formation of the separation groove P3, the lower electrode 2 in the separation groove P3 is formed by the third metal chalcogen compound layer 8c. Can be protected.
- the third metal chalcogen compound layer 8c is provided so as to cover the entire lower electrode 2 exposed in the separation groove P3, the moisture resistance can be further improved.
- the third metal chalcogen compound layer 8c is provided by, for example, setting the pressing force of the scribe needle to 0.02 to 0.05 MPa and the speed to 100 to 1500 mm / second. That's fine. Under such conditions, the light absorption layer 3, the buffer layer 4, and the upper electrode 5 can be removed while leaving the third metal chalcogen compound layer 8c on the lower electrode 2.
- the speed of the scribe needle may be 100 to 500 mm / second from the viewpoint of more surely removing the light absorption layer 3, the buffer layer 4 and the upper electrode 5 from the separation groove P3.
- the upper electrode 5 may be formed after only the separation groove P2 is formed by mechanical scribing before the upper electrode 5 is formed. At this time, the upper electrode 5 may be formed in the separation groove P ⁇ b> 2 and used as the connection conductor 7. Further, as shown in FIG. 4C, the buffer layer 4 and the upper electrode 5 may be formed before the separation groove P2 is formed. Thus, the upper electrode 5 is formed with the buffer layer 4 in a good state, and the electrical connection between the buffer layer 4 and the upper electrode 5 can be improved. Thereby, photoelectric conversion efficiency can be improved. Further, in the method shown in FIG. 4C, it is possible to reduce the deterioration of the surface of the buffer layer 4 due to shavings or the like generated when forming the separation groove P2.
- the photoelectric conversion cell 20 having a structure in which the substrate 1, the lower electrode 2, the light absorption layer 3, the buffer layer 4, and the upper electrode 5 are laminated in this order from the back side is formed.
- the photoelectric conversion device 21 has a structure in which a plurality of the photoelectric conversion cells 20 are electrically connected and integrated.
- FIG. 5 shows another embodiment of the method for manufacturing the photoelectric conversion device 21.
- FIGS. 5A to 5C are the same as FIGS. 4A to 4C. 5 differs from the manufacturing method of FIG. 4 in that the separation groove P3 is also formed when the separation groove P2 is formed in FIG. 5D. In this case, the separation grooves P2 and P3 can be formed in a single process, and the process can be simplified.
- the current collecting electrode 6 and the connecting conductor 7 are formed by printing a metal paste such as a silver paste on the upper electrode 5 and in the separation groove P2 in order to reduce the resistance. .
- the light absorption layer 3 and the buffer layer 4 between the separation groove P2 and the separation groove P3 act as a protective wall for preventing the metal paste from spreading and coming into contact with the adjacent photoelectric conversion cell 20. be able to.
- the separation groove P ⁇ b> 2 for forming the connection conductor 7 and the separation groove P ⁇ b> 3 for separating the photoelectric conversion cells 20 from each other are formed in a single step, and then separated.
- a connection conductor 7 is formed in the groove P2 with a metal paste. Therefore, in such a manufacturing method, a process can be simplified.
- the photoelectric conversion device 31 shown in FIG. 6 differs from the photoelectric conversion device 21 shown in FIGS. 1 and 2 in that the separation groove that separates the light absorption layer 3 and the buffer layer 4 is a single separation groove P2 '.
- symbol is attached
- connection conductor 7 is formed in the separation groove P2 'so as to cover substantially half of the separation groove P2' with a metal paste.
- a metal paste having an appropriate viscosity may be used so as not to flow and come into contact with the adjacent photoelectric conversion cell 30 after being applied in the separation groove P2 '.
- a recess is formed on the surface of the lower electrode 2 exposed in the separation groove P2 ′ corresponding to the gap portion C, compared to the photoelectric conversion device 21 in FIGS. Is different.
- symbol is attached
- FIG. In the photoelectric conversion device 41, the first connection portion A 'and the second connection portion B' are located in the recess. In this way, in the photoelectric conversion device 41 in which the first connection portion A ′ and the second connection portion B ′ are located in the recess, the anchor effect of the connection conductor 7 can be further enhanced, so that the connection with the lower electrode 2 is possible.
- Adhesion with the conductor 7 can be enhanced. Furthermore, in the photoelectric conversion device 41, since the connection conductor 7 is also connected to the inner side surface of the recess, the contact resistance can be reduced. As a result, in the present embodiment, since the current to be extracted can be increased, the conversion efficiency can be improved.
- Substrate 2 Lower electrode 3: Light absorption layer 33: Photoelectric conversion layer 4: Buffer layer 5: Upper electrode 6: Current collecting electrode 7: Connection conductor 8: Metal chalcogen compound layer 8a: First metal chalcogen compound layer 8b: Second metal chalcogen compound layer 8c: Third metal chalcogen compound layer 20, 30, 40: Photoelectric conversion cells 21, 31, 41: Photoelectric conversion device
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Abstract
Description
窓層は光電変換装置21における一方の電極として見なすことができるため、本実施形態では上部電極5とみなしている。上部電極5は、このような窓層に加えてさらに透明導電膜を形成してもよい。
2:下部電極
3:光吸収層
33:光電変換層
4:バッファ層
5:上部電極
6:集電電極
7:接続導体
8:金属カルコゲン化合物層
8a:第1金属カルコゲン化合物層
8b:第2金属カルコゲン化合物層
8c:第3金属カルコゲン化合物層
20、30、40:光電変換セル
21、31、41:光電変換装置
Claims (11)
- 基板と、
前記基板上に設けられた、金属元素を含む複数の下部電極と、
前記複数の下部電極上にそれぞれ設けられた、カルコゲン化合物半導体を含む複数の光電変換層と、
前記複数の光電変換層上にそれぞれ設けられた複数の上部電極と、
隣り合う前記光電変換層間で一方の前記上部電極を他方の前記下部電極に電気的に接続する接続導体とを備え、
前記接続導体は、前記金属元素および前記カルコゲン化合物半導体に含まれるカルコゲン元素を含む第1金属カルコゲン化合物層を介して前記下部電極に接続された第1接続部と、前記第1金属カルコゲン化合物層を介さずに前記下部電極に接続された第2接続部とを有することを特徴とする光電変換装置。 - 前記接続導体は金属ペーストの固化物であることを特徴とする請求項1記載の光電変換装置。
- 前記上部電極上に、前記接続導体に接続された集電電極が設けられていることを特徴とする請求項1または請求項2記載の光電変換装置。
- 前記基板を平面視して、前記第1接続部の面積は、前記第2接続部の面積よりも小さいことを特徴とする請求項1乃至請求項3のいずれかに記載の光電変換装置。
- 前記下部電極と前記光電変換層との間に、前記金属元素および前記カルコゲン元素を含む第2金属カルコゲン化合物層をさらに備えたことを特徴とする請求項1乃至請求項4のいずれかに記載の光電変換装置。
- 前記下部電極は、前記接続導体側の表面に凹部を有しており、前記第1接続部および前記第2接続部のうち少なくとも一方が前記凹部内に位置していることを特徴とする請求項1乃至請求項5のいずれかに記載の光電変換装置。
- 隣り合う前記光電変換層の間に位置する前記下部電極の前記基板と反対側の表面に、前記金属元素および前記カルコゲン元素を含む第3金属カルコゲン化合物層をさらに設けたことを特徴とする請求項1乃至請求項6のいずれかに記載の光電変換装置。
- 前記接続導体は、前記光電変換層内に設けられた細長い形状の間隙部に配置されており、
前記第1金属カルコゲン化合物層は、前記間隙部の長手方向に沿うように設けられていることを特徴とする請求項1乃至請求項7のいずれかに記載の光電変換装置。 - 前記第1金属カルコゲン化合物層は、前記間隙部の長手方向に沿う端部に設けられていることを特徴とする請求項8に記載の光電変換装置。
- 金属元素を含む複数の下部電極が設けられた基板上に、カルコゲン化合物半導体の前駆体を形成する工程と、
前記前駆体を加熱することにより、前記下部電極上に前記金属元素と前記カルコゲン化合物半導体に含まれるカルコゲン元素とを含む第1金属カルコゲン化合物層を形成するとともに、前記第1金属カルコゲン化合物層上に前記カルコゲン化合物半導体を含む光電変換層を形成する工程と、
前記光電変換層上に上部電極を形成する工程と、
前記下部電極上で、前記上部電極、前記光電変換層および前記第1金属カルコゲン化合物層の一部を除去する工程と、
前記上部電極を前記下部電極に接続するように接続導体を形成する工程とを備え、
前記接続導体を形成する工程において、前記第1金属カルコゲン化合物層を介して前記下部電極に接続する第1接続部および前記第1金属カルコゲン化合物層を介さずに前記下部電極に接続する第2接続部を形成することを特徴とする光電変換装置の製造方法。 - 前記下部電極上で、前記第1金属カルコゲン化合物層の一部、前記光電変換層および前記上部電極を除去する工程は、メカニカルスクライブ加工で行なうことを特徴とする請求項10記載の光電変換装置の製造方法。
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CN201080003522.7A CN102246316B (zh) | 2009-09-29 | 2010-09-29 | 光电转换装置及其制造方法 |
JP2011534272A JP5355703B2 (ja) | 2009-09-29 | 2010-09-29 | 光電変換装置及びその製造方法 |
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