WO2012070481A1 - 光電変換装置 - Google Patents
光電変換装置 Download PDFInfo
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- WO2012070481A1 WO2012070481A1 PCT/JP2011/076634 JP2011076634W WO2012070481A1 WO 2012070481 A1 WO2012070481 A1 WO 2012070481A1 JP 2011076634 W JP2011076634 W JP 2011076634W WO 2012070481 A1 WO2012070481 A1 WO 2012070481A1
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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
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
- H01L31/0264—Inorganic materials
- H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
- H01L31/0322—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising only AIBIIICVI chalcopyrite compounds, e.g. Cu In Se2, Cu Ga Se2, Cu In Ga Se2
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/042—PV modules or arrays of single PV cells
- H01L31/0445—PV modules or arrays of single PV cells including thin film solar cells, e.g. single thin film a-Si, CIS or CdTe solar cells
- H01L31/046—PV modules composed of a plurality of thin film solar cells deposited on the same substrate
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/042—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
Definitions
- the present invention relates to a photoelectric conversion device including an I-III-VI group compound semiconductor.
- Some photoelectric conversion devices used for solar power generation and the like have a light absorption layer formed of a chalcopyrite-based I-III-VI group compound semiconductor such as CIS or CIGS. Such a photoelectric conversion device is described in, for example, JP-A-6-37342.
- I-III-VI group compound semiconductors have a high light absorption coefficient, and are suitable for making photoelectric conversion devices thinner and larger in area and reducing manufacturing costs.
- Next generation using group I-III-VI group compound semiconductors Research and development of solar cells is underway.
- a photoelectric conversion device including such an I-III-VI group compound semiconductor has a configuration in which a plurality of photoelectric conversion cells are arranged side by side in a plane.
- Each photoelectric conversion cell has a lower electrode such as a metal electrode on a substrate such as glass, a photoelectric conversion layer formed of a semiconductor layer including a light absorption layer and a buffer layer, and an upper electrode such as a transparent electrode and a metal electrode.
- the plurality of photoelectric conversion cells are electrically connected in series by electrically connecting the upper electrode of one adjacent photoelectric conversion cell and the lower electrode of the other photoelectric conversion cell by a connecting conductor. Yes.
- the light absorption layer a layer in which the molar ratio of the IB group element, the III-B group element, and the VI-B group element is 1: 1: 2 is used.
- This conversion efficiency indicates the rate at which sunlight energy is converted into electrical energy in the photoelectric conversion device.
- the value of the electrical energy output from the photoelectric conversion device is the energy of sunlight incident on the photoelectric conversion device. of being divided by the value is derived by 100 is multiplied.
- This invention is made
- a photoelectric conversion device includes an electrode, a first semiconductor layer including an I-III-VI group compound semiconductor provided on the electrode, and provided on the first semiconductor layer. And a second semiconductor layer having a conductivity type different from that of the first semiconductor layer.
- the first semiconductor layer has a ratio C VI / C I of the VI-B group element content C VI to the IB group element content C I in the surface portion on the second semiconductor layer side. greater than the ratio C VI / C I in the balance.
- a photoelectric conversion device with high photoelectric conversion efficiency can be provided.
- FIG. 2 is a schematic diagram showing a cross section of the photoelectric conversion device taken along a section line II-II in FIG. It is a schematic view showing the surface portion and the remainder of the first semiconductor layer. It is sectional drawing which shows typically the mode in the middle of manufacture of a photoelectric conversion apparatus. It is sectional drawing which shows typically the mode in the middle of manufacture of a photoelectric conversion apparatus. It is sectional drawing which shows typically the mode in the middle of manufacture of a photoelectric conversion apparatus. It is sectional drawing which shows typically the mode in the middle of manufacture of a photoelectric conversion apparatus. It is sectional drawing which shows typically the mode in the middle of manufacture of a photoelectric conversion apparatus.
- FIG. 1 is a top view illustrating a configuration of the photoelectric conversion device 21.
- 2 is a cross-sectional view of the photoelectric conversion device 21 taken along the section line II-II in FIG. 1, that is, an XZ cross-sectional view of the photoelectric conversion device 21 at the position indicated by the one-dot chain line in FIG. 1 to 9 are provided with a right-handed XYZ coordinate system in which the arrangement direction of photoelectric conversion cells 10 (the horizontal direction in the drawing in FIG. 1) is the X-axis direction.
- the photoelectric conversion device 21 has a configuration in which a plurality of photoelectric conversion cells 10 are arranged in parallel on the substrate 1. In FIG. 1, only two photoelectric conversion cells 10 are shown for convenience of illustration, but there are many actual photoelectric conversion devices 21 in the horizontal direction of the drawing or in the vertical direction of the drawing perpendicular to the drawing.
- the photoelectric conversion cells 10 are arranged in a plane (two-dimensionally).
- Each photoelectric conversion cell 10 mainly includes a lower electrode layer 2, a photoelectric conversion layer 3, an upper electrode layer 4, and a collecting electrode 5.
- the main surface on the side where the upper electrode layer 4 and the collecting electrode 5 are provided is a light receiving surface. Further, the photoelectric conversion device 21 is provided with three types of groove portions such as first to third groove portions P1, P2, and P3.
- the substrate 1 supports a plurality of photoelectric conversion cells 10, and for example, a material such as glass, ceramics, resin, or metal can be adopted.
- a blue plate glass silica glass having a thickness of about 1 to 3 mm is used for the substrate 1.
- the lower electrode layer 2 is a conductive layer provided on one main surface of the substrate 1.
- Mo molybdenum
- Al aluminum
- Ti titanium
- Ta tantalum
- Au gold
- metal etc. or multilayer structure of these metals may be employed.
- the lower electrode layer 2 has a thickness of about 0.2 to 1 ⁇ m and is formed by a known thin film forming method such as sputtering or vapor deposition.
- the photoelectric conversion layer 3 has a configuration in which a first semiconductor layer 31 as a light absorption layer and a second semiconductor layer 32 as a buffer layer are stacked.
- the first semiconductor layer 31 is a semiconductor layer having a first conductivity type (here, p-type conductivity type) provided on the + Z side main surface (also referred to as one main surface) of the lower electrode layer 2. And has a thickness of about 1 to 3 ⁇ m.
- the first semiconductor layer 31 mainly includes an I-III-VI group compound semiconductor which is a chalcopyrite-based (also referred to as CIS-based) compound semiconductor from the viewpoint of increasing conversion efficiency at low cost with a small amount of material by thinning. Yes.
- I-III-VI group compound semiconductor is mainly included” means that 70 mol% or more of I-III-VI group compound semiconductor is included.
- the first semiconductor layer 31 mainly contains a chalcopyrite-based I-III-VI group compound semiconductor having p-type conductivity.
- the group I-III-VI compound is a group IB element (in this specification, the name of the group is described in the old IUPAC system. Note that the group IB element is 11 in the new IUPAC system.
- Group III-B elements also referred to as group 13 elements
- VI-B group elements also referred to as group 16 elements.
- I-III-VI group compound include CuInSe 2 (also referred to as copper indium diselenide, CIS), Cu (In, Ga) Se 2 (also referred to as copper indium diselenide / gallium, CIGS), Cu (In, Ga) (Se, S) 2 (also referred to as diselene / copper indium gallium sulphide / CIGSS) or the like.
- the first semiconductor layer 31 may be formed of a thin film of a multicomponent compound semiconductor such as copper indium selenide / gallium having a thin film of selenite / copper indium sulfide / gallium as a surface layer.
- a multicomponent compound semiconductor such as copper indium selenide / gallium having a thin film of selenite / copper indium sulfide / gallium as a surface layer.
- the light absorption layer 31 mainly contains CIGS.
- FIG. 3 is a schematic diagram showing a configuration focusing on the lower electrode layer 2, the first semiconductor layer 31, and the second semiconductor layer 32.
- the first semiconductor layer 31 includes a surface portion 31a and a remaining portion 31b.
- the surface portion 31 a constitutes a surface portion of the first semiconductor layer 31 on the second semiconductor layer 32 side.
- the remaining portion 31 b constitutes a portion on the lower electrode layer 2 side of the surface portion 31 a of the first semiconductor layer 31.
- the ratio C VI / C I of content C VI of Group VI-B element to the content C I of the I-B group element in the surface portion 31a is larger than the ratio C VI / C I in the balance 31b Yes.
- the surface portion 31a refers to thin layer region up to the second semiconductor layer 32 side surface from 100nm depth of the first semiconductor layer 31 (corresponding to the thickness T 31a of the surface portion 31a in FIG. 3) .
- the content of the IB group element and the VI-B element in the first semiconductor layer 31 is determined by analyzing the cross section of the first semiconductor layer 31 using any of XPS, XRD, SEM-EDS, and TEM-EDS analysis methods. Can be measured. From the viewpoint of increasing the light absorption rate of the first semiconductor layer 31 and increasing the photoelectric conversion efficiency, the thickness T 31b of the remaining portion 31b is 5 to 50 times the thickness T 31a of the surface portion 31a. Also good.
- the ratio C VI / C I in the surface portion 31a may be less than or equal to 1.4 times 1.1 times or more than the ratio C VI / C I in the balance 31b. Within this range, the composition change between the surface portion 31a and the remaining portion 31b can be made moderate, and a large change in physical properties can be suppressed, and carrier movement can be carried out satisfactorily.
- the average value of the ratio C VI / C I in the surface portion 31a has a 2.0 to 2.3 can do.
- the I-VI group compound for example, Cu 2 Se and / or CuSe
- the average value of the ratio C VI / C I in the remaining portion 31b can be 1.6 or more and 1.9 or less.
- the III-B group is formed in the surface portion 31a and the remaining portion 31b.
- the ratio C I / C III of content C I of the I-B group element for content C III elements may be 0.8 or more.
- the ratio C I / C III is 1. 1 or less.
- the first semiconductor layer 31 as described above is formed by a process called a coating method or a printing method.
- a coating method a solution for forming a semiconductor containing an element constituting the first semiconductor layer 31 is applied on the lower electrode layer 2, and thereafter, drying and heat treatment are sequentially performed.
- the second semiconductor layer 32 is a semiconductor layer provided on one main surface of the first semiconductor layer 31.
- the second semiconductor layer 32 has a conductivity type (here, n-type conductivity type) different from that of the first semiconductor layer 31.
- the second semiconductor layer 32 is provided in a form of heterojunction with the first semiconductor layer 31.
- photoelectric conversion cell 10 photoelectric conversion occurs in the first semiconductor layer 31 and the second semiconductor layer 32 constituting the heterojunction, and thus the first semiconductor layer 31 and the second semiconductor layer 32 are stacked. It functions as the photoelectric conversion layer 3.
- semiconductors having different conductivity types are semiconductors having different conductive carriers.
- the conductivity type of the second semiconductor layer 32 may be i-type instead of n-type. Further, there may be a mode in which the conductivity type of the first semiconductor layer 31 is n-type or i-type and the conductivity type of the second semiconductor layer 32 is p-type.
- the second semiconductor layer 32 includes, for example, cadmium sulfide (CdS), indium sulfide (In 2 S 3 ), zinc sulfide (ZnS), zinc oxide (ZnO), indium selenide (In 2 Se 3 ), In (OH , S), (Zn, In) (Se, OH), and (Zn, Mg) O and other compound semiconductors are mainly included.
- the second semiconductor layer 32 can have a resistivity of 1 ⁇ ⁇ cm or more.
- the second semiconductor layer 32 is formed to a thickness of, for example, 10 to 200 nm by, for example, a chemical bath deposition (CBD) method.
- the upper electrode layer 4 is a transparent conductive film having an n-type conductivity provided on the second semiconductor layer 32, and is an electrode (also referred to as an extraction electrode) that extracts charges generated in the photoelectric conversion layer 3. is there.
- the upper electrode layer 4 mainly contains a substance having a lower resistivity than the second semiconductor layer 32.
- the upper electrode layer 4 includes what is called a window layer, and when a transparent conductive film is further provided in addition to the window layer, these may be regarded as an integrated upper electrode layer 4.
- the upper electrode layer 4 is made of a transparent, low-resistance material having a wide forbidden band, such as zinc oxide (ZnO), a compound of zinc oxide (Al, boron (B), gallium (Ga), indium (In), and A metal comprising at least one of fluorine (F), indium oxide (ITO) containing tin (Sn), and tin oxide (SnO 2 ). It mainly contains oxide semiconductors.
- the upper electrode layer 4 is formed to have a thickness of 0.05 to 3.0 ⁇ m by sputtering, vapor deposition, chemical vapor deposition (CVD), or the like.
- the upper electrode layer 4 can have a resistivity of less than 1 ⁇ ⁇ cm and a sheet resistance of 50 ⁇ / ⁇ or less. .
- the second semiconductor layer 32 and the upper electrode layer 4 mainly include a material having a property (also referred to as light transmissive property) that allows light to easily pass through the wavelength region of light absorbed by the first semiconductor layer 31. Thereby, a decrease in light absorption efficiency in the first semiconductor layer 31 caused by providing the second semiconductor layer 32 and the upper electrode layer 4 is suppressed.
- a property also referred to as light transmissive property
- the upper electrode layer 4 can be made to a thickness of 0.05 ⁇ 0.5 [mu] m. Further, from the viewpoint of preventing light reflection loss at the interface between the upper electrode layer 4 and the second semiconductor layer 32, the absolute refractive index is substantially between the upper electrode layer 4 and the second semiconductor layer 32. It can be made the same.
- the current collecting electrodes 5 are spaced apart from each other in the Y-axis direction, and each of the current collecting parts 5a is connected to a plurality of current collecting parts 5a extending in the X-axis direction and extends in the Y-axis direction. Connecting portion 5b.
- the current collecting electrode 5 is an electrode having conductivity, and mainly contains, for example, a metal such as silver (Ag).
- the current collector 5 a plays a role of collecting charges generated in the photoelectric conversion layer 3 and taken out in the upper electrode layer 4. If the current collector 5a is provided, the upper electrode layer 4 can be thinned.
- connection part 45 is comprised by the extension part 4a of the upper electrode layer 4, and the hanging part 5c from the connection part 5b formed on it.
- the current collecting electrode 5 has a width of 50 to 400 ⁇ m so that good conductivity is ensured and a decrease in the light receiving area that affects the amount of light incident on the light absorbing layer 31 is minimized. can do.
- FIGS. 4 to 9 are cross-sectional views schematically showing a state in the process of manufacturing the photoelectric conversion device 21.
- Each of the cross-sectional views shown in FIGS. 4 to 9 shows a state in the middle of manufacturing a portion corresponding to the cross-section shown in FIG.
- a lower electrode layer 2 made of Mo or the like is formed on substantially the entire surface of the cleaned substrate 1 using a sputtering method or the like. Then, the first groove portion P1 is formed from the linear formation target position along the Y direction on the upper surface of the lower electrode layer 2 to the upper surface of the substrate 1 immediately below the formation position.
- the first groove portion P1 can be formed by, for example, a scribe process in which a groove process is performed by irradiating a formation target position while scanning with a laser beam such as a YAG laser.
- FIG. 5 is a diagram illustrating a state after the first groove portion P1 is formed.
- FIG. 6 is a diagram illustrating a state after the first semiconductor layer 31 and the second semiconductor layer 32 are formed.
- a solution for forming a semiconductor for forming the first semiconductor layer 31 is prepared.
- a solution for forming a semiconductor comprises a group IB element, a group III-B element, and a group VI-B element (hereinafter referred to as elements for these raw materials), which are raw materials for forming a group I-III-VI compound semiconductor. (Also referred to as a raw material element) is dissolved or dispersed in a solvent.
- the raw material elements are contained in the semiconductor forming solution in the form of a simple substance, in the form of a compound such as a complex or salt, or in the form of simple fine particles or compound fine particles.
- one of the IB group elements, III-B group elements and VI-B group elements constituting the I-III-VI group compound semiconductor is one.
- a single source precursor contained in one molecule (see US Pat. No. 6,992,202) dissolved in a solvent can be used as a semiconductor forming solution. Further, various organic solvents and water is used as the solvent used in the semiconductor forming solution.
- the semiconductor forming solution may be may not include Group VI-B element.
- a VI-B group element may be included in the atmosphere when heat-treating the film formed using the semiconductor forming solution.
- the first semiconductor layer 31 is formed by applying the semiconductor-forming solution prepared as described above onto one main surface of the lower electrode layer 2, and drying to form a film as a precursor (hereinafter also referred to as a precursor layer). After the is formed, the precursor layer is formed by heat treatment. Application of the semiconductor forming solution is performed using, for example, a spin coater, screen printing, dipping, spraying, or a die coater.
- the drying for forming the precursor layer is performed in an inert atmosphere or a reducing atmosphere, and the temperature at the time of drying may be, for example, 50 to 300 ° C.
- the inert atmosphere include a nitrogen atmosphere.
- the reducing atmosphere for example, a forming gas atmosphere or a hydrogen atmosphere and the like. You may carry out to pyrolysis of an organic component in the case of this drying.
- first method As a formation method (first method) of the surface portion 31a and the remaining portion 31b having different content ratios of the IB group element and the VI-B group element, first, the VI-B group element with respect to the IB group element is used. By sequentially laminating the semiconductor forming solutions with different content ratios, precursor layers as laminates having different content ratios of the group IB element and the group VI-B element are formed. The precursor layer thus formed is heat-treated at a temperature rising rate of 5 to 30 ° C./min to a maximum temperature of 500 to 600 ° C., for example, so that the first semiconductor having the surface portion 31a and the remaining portion 31b is obtained. Layer 31 is formed. The heat treatment of the precursor layer is performed in an inert atmosphere or a reducing atmosphere. The atmosphere for this heat treatment may contain a chalcogen element (referred to as S, Se, Te among VI-B group elements) as a VI-B group element constituting the I-III-VI group compound semiconductor. .
- first, III-B with respect to the group IB element is used as another formation method (second method) of the surface portion 31a and the remaining portion 31b having different content ratios of the group IB element and the group VI-B element.
- content ratio of group elements precursor layer as a different laminate is formed.
- the precursor layer thus formed has a surface portion 31a and a remaining portion 31b by heat treatment in an atmosphere containing a chalcogen element as a VI-B group element constituting the I-III-VI group compound semiconductor.
- a first semiconductor layer 31 is formed.
- the I-- generated during the heat treatment of the precursor layer is used.
- the movement of the group B element toward the lower electrode layer 2 is used to form the surface portion 31a and the remaining portion 31b.
- the precursor layer is held at a relatively low temperature range of 100 ° C. or higher and 400 ° C. or lower for a predetermined time. As a result, the raw material elements constituting the precursor layer are liquefied by melting.
- the solubility of the IB group element is relatively smaller than that of other elements (III-B group element or IV-B group element). Shows a tendency to move to the lower electrode layer 2 side. As a result, surface portions 31a and the balance 31b are formed.
- an atmosphere for the heat treatment an inert atmosphere, a reducing atmosphere, or a chalcogen element-containing atmosphere is used.
- the second semiconductor layer 32 is formed by a solution growth method (also referred to as a CBD method). For example, cadmium acetate and thiourea are dissolved in ammonia water, and the substrate 1 on which the formation of the first semiconductor layer 31 has been performed is immersed therein, whereby the first semiconductor layer 31 is made of CdS. Two semiconductor layers 32 are formed.
- FIG. 7 is a diagram illustrating a state after the second groove portion P2 is formed.
- the second groove portion P2 is formed at a position slightly shifted in the X direction (in the drawing, + X direction) from the first groove portion P1.
- the transparent upper electrode layer 4 mainly composed of indium oxide (ITO) containing Sn, for example, is formed on the second semiconductor layer 32.
- the upper electrode layer 4 is formed by sputtering, vapor deposition, CVD, or the like.
- Figure 8 is a diagram showing a state after the upper electrode layer 4 is formed.
- the collector electrode 5 is formed.
- a conductive paste also referred to as a conductive paste
- a metal powder such as Ag is dispersed in a resin binder or the like is printed so as to draw a desired pattern, and this is dried. It is formed by solidifying.
- the solidified state is the solidified state after melting when the binder used in the conductive paste is a thermoplastic resin, and the curing when the binder is a curable resin such as a thermosetting resin or a photocurable resin. Includes both later states.
- Figure 9 is a diagram showing the state after the collector electrode 5 is formed.
- the third groove portion P3 is formed from the linear formation target position on the upper surface of the upper electrode layer 4 to the upper surface of the lower electrode layer 2 immediately below it.
- the width of the third groove portion P3 is preferably about 40 to 1000 ⁇ m, for example.
- the third groove portion P3 is preferably formed by mechanical scribing similarly to the second groove portion P2. In this way, the photoelectric conversion device 21 shown in FIGS. 1 and 2 is manufactured by forming the third groove portion P3.
- the first semiconductor layer 31 has a void, and the porosity of the remaining portion 31 b is larger than the void ratio of the surface portion 31 a (including those having no void in the surface portion 31 a). May be.
- the porosity of the remaining portion 31 b is larger than the void ratio of the surface portion 31 a (including those having no void in the surface portion 31 a).
- the porosity can be measured by the ratio of the area occupied by the voids in the first semiconductor layer 31 from the SEM image obtained by SEM observation of the cross section of the first semiconductor layer 31. From the viewpoint of improving the electrical connection between the surface portion 31a and the second semiconductor layer 32, the porosity of the surface portion 31a may be 0 to 5%. On the other hand, from the viewpoint of enhancing stress relaxation, the porosity of the remaining portion 31b may be 6 to 50%.
- the first semiconductor layer 31 having a different porosity in the thickness direction can be manufactured as follows.
- the first semiconductor layer 31 is formed as a multilayer structure, and when the layer on the lower electrode layer 2 side of this multilayer structure is manufactured, a heat treatment is performed at a relatively high temperature increase rate to generate voids. It becomes easy.
- heat treatment is performed at a relatively slow temperature increase rate, which tends to become dense.
- the first semiconductor layer 31 may be formed by combining a plurality of crystal particles, and the average particle size of the crystal particles in the remaining portion 31b may be smaller than the average particle size of the crystal particles in the surface portion 31a.
- the recombination of carriers generated by photoelectric conversion can be reduced by relatively increasing the average particle size of the crystal particles in the surface portion 31a, and the crystal particles in the remaining portion 31b can be reduced.
- the thermal stress can be relaxed and the occurrence of cracks and the like in the first semiconductor layer 31 can be effectively reduced.
- the balance 31b since the conductivity is increased by the content ratio as above C VI / C I is smaller than the surface portion, electrically be many grain boundaries between crystal grains Connection can be maintained well.
- the average grain size of the crystal particles in the first semiconductor layer 31 is determined by regarding the maximum diameter of each crystal grain as the grain size in an SEM image obtained by SEM observation of the cross section of the first semiconductor layer 31. It is obtained by calculating the average value. From the viewpoint of improving the electrical connection between the surface portion 31a and the second semiconductor layer 32, the average grain size of crystal grains in the surface portion 31a may be 600 to 1000 nm. On the other hand, from the viewpoint of enhancing stress relaxation, the average grain size of the crystal grains in the remaining portion 31b may be 30 to 500 nm.
- the first semiconductor layer 31 having a different average particle diameter in the thickness direction can be manufactured as follows. For example, when the first semiconductor layer 31 is manufactured, crystallization is promoted on the surface portion and the particle size is easily increased by positively heating the surface of the second semiconductor layer 32 with an IR lamp or the like. .
- the precursor layer to be the first semiconductor layer 31 is formed by the semiconductor layer forming solution, but is not limited thereto.
- the precursor layer is formed by a thin film forming method such as sputtering or vapor deposition is also conceivable.
- the configuration in which CIGS is adopted as the I-III-VI group compound constituting the light absorption layer 31 has been mainly described, but the configuration is not limited thereto.
- the I-III-VI group compound has other compositions such as CIS and CIGSS, the conversion efficiency in the photoelectric conversion device is improved.
- the photoelectric conversion device 21 will be described with a specific example.
- [A] 10 mmol (mmol) of Cu (CH 3 CN) 4 .PF 6 as an organometallic complex of a group IB element and 20 mmol of P (C 6 H 5 ) 3 as a Lewis basic organic compound was dissolved in 100 ml of acetonitrile, and then the first complex solution was prepared by stirring at room temperature (for example, about 25 ° C.) for 5 hours.
- step [C] To the first complex solution prepared in step [a], the second complex solution prepared in step [b] is dropped at a rate of 10 ml per minute, and a white precipitate (precipitate) is formed. occured. After completion of the dropping treatment, stirring for 1 hour at room temperature and precipitation extraction with a centrifugal separator were sequentially performed. When extracting the precipitate, the process of dispersing the precipitate once taken out by the centrifuge in 500 ml of methanol and then taking out the precipitate again by the centrifuge is repeated twice. by being dried, the precipitate comprising a single source precursor was obtained. In this single source precursor, one complex molecule contains Cu, In, and Se, or contains Cu, Ga, and Se.
- a substrate in which a lower electrode layer made of Mo or the like is formed on the surface of a substrate made of glass is prepared.
- a semiconductor forming solution is applied on the lower electrode layer by a blade method
- 300 ° C. film was formed by drying held 10 minutes.
- the precursor layer was formed by sequentially performing treatment including application by blade method and subsequent drying 10 times.
- various solutions having different content ratios of the raw material elements described above are used. The content ratio was different.
- each substrate on which the layers up to the first semiconductor layer are formed is immersed in a solution of zinc acetate and thiourea in ammonia water, so that ZnS having a thickness of 50 nm is formed on the first semiconductor layer.
- a second semiconductor layer made of was formed.
- a transparent conductive film made of ZnO doped with Al is formed on the second semiconductor layer by sputtering, and finally an extraction electrode made of Al is formed by vapor deposition to produce a photoelectric conversion device. It was done.
- FIG. 10 shows that when the ratio C VI / C I of the VI-B group element content C VI to the IB group element content C I in the surface portion is larger than the remaining ratio C VI / C I It turns out that the conversion efficiency is high.
- the average value of the ratio C VI / C I in the surface portion is not less 2.0 to 2.3, when the average value of the ratio C VI / C I in balance 1.6 to 1.9, It was found that the conversion efficiency was higher.
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Abstract
Description
図1は、光電変換装置21の構成を示す上面図である。図2は、図1の切断面線II-IIにおける光電変換装置21の断面図、つまり図1で一点鎖線にて示された位置における光電変換装置21のXZ断面図である。なお、図1から図9には、光電変換セル10の配列方向(図1の図面視左右方向)をX軸方向とする右手系のXYZ座標系が付されている。
図4から図9は、光電変換装置21の製造途中の様子をそれぞれ模式的に示す断面図である。なお、図4から図9で示される各断面図は、図2で示された断面に対応する部分の製造途中の様子を示す。
なお、本発明は上述の実施の形態に限定されるものではなく、本発明の要旨を逸脱しない範囲において種々の変更、改良等が可能である。
上記光電変換装置21において、第1の半導体層31は複数の結晶粒子が結合して成り、残部31bにおける結晶粒子の平均粒径が表面部31aにおける結晶粒子の平均粒径よりも小さくてもよい。このような構成であると、表面部31aでの結晶粒子の平均粒径を比較的大きくすることによって光電変換で生じたキャリアの再結合を低減することができるとともに、残部31bでの結晶粒子の平均粒径を比較的小さくすることによって熱応力を緩和してクラック等が第1の半導体層31に生じるのを有効に低減できる。ここで、残部31bは、上記のように含有率比CVI/CIが表面部よりも小さくなっていることによって導電率が高まっているため、結晶粒子同士の粒界が多くても電気的な接続を良好に維持することができる。
上記一実施形態では、第1の半導体層31となる前駆体層が半導体層形成用溶液により形成されたが、これに限られない。例えば、スパッタリングや蒸着等の薄膜形成方法によって前駆体層が形成される態様も考えられる。
2 下部電極層
3 光電変換層
4 上部電極層
5 集電電極
10 光電変換セル
21 光電変換装置
31 第1の半導体層
31a 表面部
31b 残部
32 第2の半導体層
45 接続部
Claims (6)
- 電極と、
該電極上に設けられた、I-III-VI族化合物半導体を含む第1の半導体層と、
該第1の半導体層上に設けられた、該第1の半導体層とは異なる導電型の第2の半導体層とを具備しており、
前記第1の半導体層は、前記第2の半導体層側の表面部におけるI-B族元素の含有率CIに対するVI-B族元素の含有率CVIの比CVI/CIが残部における比CVI/CIよりも大きいことを特徴とする光電変換装置。 - 前記表面部および前記残部におけるIII-B族元素の含有率CIIIに対するI-B族元素の含有率CIの比CI/CIIIがそれぞれ0.8以上1.1以下である請求項1に記載の光電変換装置。
- 前記表面部における比CVI/CIの平均値が2.0以上2.3以下であり、前記残部における比CVI/CIの平均値が1.6以上1.9以下である請求項1または2に記載の光電変換装置。
- 前記I-B族元素がCuであり、前記VI-B族元素がSeである請求項1乃至3のいずれかに記載の光電変換装置。
- 前記第1の半導体層は空隙を有しており、前記残部の空隙率が前記表面部の空隙率よりも大きいことを特徴とする請求項1乃至4のいずれかに記載の光電変換装置。
- 前記第1の半導体層は複数の結晶粒子が結合して成り、前記残部における前記結晶粒子の平均粒径が前記表面部における前記結晶粒子の平均粒径よりも小さいことを特徴とする請求項1乃至5のいずれかに記載の光電変換装置。
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EP11843239.2A EP2645422A4 (en) | 2010-11-22 | 2011-11-18 | PHOTOELECTRIC CONVERSION DEVICE |
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- 2011-11-18 US US13/988,391 patent/US20130240948A1/en not_active Abandoned
- 2011-11-18 EP EP11843239.2A patent/EP2645422A4/en not_active Withdrawn
- 2011-11-18 CN CN201180054698XA patent/CN103222063A/zh active Pending
- 2011-11-18 JP JP2012545715A patent/JP5451899B2/ja not_active Expired - Fee Related
- 2011-11-18 WO PCT/JP2011/076634 patent/WO2012070481A1/ja active Application Filing
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2015016128A1 (ja) * | 2013-07-30 | 2015-02-05 | 京セラ株式会社 | 光電変換装置 |
JP6023336B2 (ja) * | 2013-07-30 | 2016-11-09 | 京セラ株式会社 | 光電変換装置 |
Also Published As
Publication number | Publication date |
---|---|
JPWO2012070481A1 (ja) | 2014-05-19 |
US20130240948A1 (en) | 2013-09-19 |
JP5451899B2 (ja) | 2014-03-26 |
EP2645422A4 (en) | 2016-02-17 |
EP2645422A1 (en) | 2013-10-02 |
CN103222063A (zh) | 2013-07-24 |
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