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WO2014189003A1 - Substrat de verre et cellule solaire au cigs - Google Patents

Substrat de verre et cellule solaire au cigs Download PDF

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Publication number
WO2014189003A1
WO2014189003A1 PCT/JP2014/063219 JP2014063219W WO2014189003A1 WO 2014189003 A1 WO2014189003 A1 WO 2014189003A1 JP 2014063219 W JP2014063219 W JP 2014063219W WO 2014189003 A1 WO2014189003 A1 WO 2014189003A1
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WO
WIPO (PCT)
Prior art keywords
glass substrate
glass
amount
film
cigs
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2014/063219
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English (en)
Japanese (ja)
Inventor
健 岡東
剛 富澤
玲大 臼井
伸一 安間
裕 黒岩
朋美 安部
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
AGC Inc
Original Assignee
Asahi Glass Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Asahi Glass Co Ltd filed Critical Asahi Glass Co Ltd
Priority to JP2015518235A priority Critical patent/JPWO2014189003A1/ja
Publication of WO2014189003A1 publication Critical patent/WO2014189003A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • 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
    • H10F77/16—Material structures, e.g. crystalline structures, film structures or crystal plane orientations
    • H10F77/169—Thin semiconductor films on metallic or insulating substrates
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
    • C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
    • C03C3/087—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal containing calcium oxide, e.g. common sheet or container glass
    • 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
    • H10F77/12—Active materials
    • H10F77/126—Active materials comprising only Group I-III-VI chalcopyrite materials, e.g. CuInSe2, CuGaSe2 or CuInGaSe2 [CIGS]
    • 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
    • H10F77/12—Active materials
    • H10F77/126—Active materials comprising only Group I-III-VI chalcopyrite materials, e.g. CuInSe2, CuGaSe2 or CuInGaSe2 [CIGS]
    • H10F77/1265—Active materials comprising only Group I-III-VI chalcopyrite materials, e.g. CuInSe2, CuGaSe2 or CuInGaSe2 [CIGS] characterised by the dopants
    • 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
    • H10F77/16—Material structures, e.g. crystalline structures, film structures or crystal plane orientations
    • H10F77/169—Thin semiconductor films on metallic or insulating substrates
    • H10F77/1694—Thin semiconductor films on metallic or insulating substrates the films including Group I-III-VI materials, e.g. CIS or CIGS
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2204/00—Glasses, glazes or enamels with special properties
    • C03C2204/08—Glass having a rough surface
    • 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 glass substrate and a CIGS solar cell.
  • the glass substrate is formed into a plate shape by a float method and a fusion method, and is widely used as a substrate for solar cells, display devices, magnetic disks and the like.
  • a float method and a fusion method In the case of forming a thin film on such a glass substrate, there is a phenomenon in which alkali metal contained in the glass substrate diffuses from the surface of the glass substrate to the thin film by the heat treatment in the thin film forming process.
  • a semiconductor film is formed on a glass substrate as a photoelectric conversion layer.
  • semiconductors used for solar cells 11-13 and 11-16 compound semiconductors having a chalcopyrite crystal structure, and cubic or hexagonal 12-16 group compound semiconductors have a wavelength range from visible to near infrared. It has a large absorption coefficient for light. Therefore, it is expected as a material for high-efficiency thin film solar cells.
  • a typical example is Cu (In, Ga) Se 2 (hereinafter sometimes referred to as CIGS).
  • the photoelectric conversion efficiency of the CIGS solar cell can be increased by using a glass substrate containing an alkali metal, particularly Na, as such a glass substrate for CIGS solar cell.
  • a glass substrate containing an alkali metal, particularly Na as such a glass substrate for CIGS solar cell.
  • Na atoms contained in the glass substrate are diffused from the glass substrate surface into the CIGS film by heat-treating the glass substrate in the CIGS film forming step.
  • the carrier concentration of the CIGS film is increased and the photoelectric conversion rate can be increased.
  • Patent Document 1 discloses a glass substrate for a Cu—In—Ga—Se solar cell, in which the ratio of Ca, Sr and Ba between the glass substrate surface layer and the inside is a predetermined value, and the heat treatment of the Na amount of the glass substrate surface layer A glass substrate has been proposed in which the front-to-back ratio is a predetermined value, the glass substrate has a predetermined composition, and has a predetermined glass transition temperature and an average thermal expansion coefficient.
  • Na atoms easily move from the inside of the glass substrate to the surface layer because Ca, Sr, and Ba atoms are removed from the surface of the glass substrate. It diffuses into the CIGS film and improves the power generation efficiency of the solar cell.
  • an alkali control layer, a back electrode layer, a metal precursor film, a CIS light absorption layer, and an n-type transparent conductive film are sequentially formed on a high strain point glass substrate. ing.
  • Patent Document 2 it is introduced into the CIS light absorption layer by adding Na to the metal precursor film together with Na diffused from the glass substrate to the CIS light absorption layer by reducing the thickness of the alkali control layer.
  • the photoelectric conversion efficiency is increased by Na.
  • a CIGS film is usually formed on the surface of the glass substrate, and no CIGS film is formed on the back surface of the glass substrate.
  • Na atoms are released from the surface of the glass substrate where the CIGS film is not formed (that is, the back surface), and the Na atoms are re-applied to the CIGS film formed on the surface of the glass substrate while floating in the atmosphere. There is a phenomenon of adhering and doping.
  • Na atoms doped in such a route are difficult to control and may cause unevenness in battery characteristics, it is desirable that few Na atoms be detached from the back surface of the glass substrate.
  • Non-Patent Document 1 when a plurality of substrates are arranged and heated in order to reduce Na atoms that are separated from the non-formation surface of the CIGS film and are doped through the atmosphere, the CIGS film on one substrate is not formed.
  • Patent Document 3 discloses a glass having an average surface roughness (Ra) of 2 nm or less and an unpolished surface by forming a glass substrate by an overflow down draw method as a glass substrate for a solar cell having a good surface quality. A board is proposed. In the proposal of Patent Document 3, electrodes and the like are accurately patterned on the glass substrate by improving the surface quality of the glass substrate.
  • Ra average surface roughness
  • Patent Document 1 the diffusion of Na atoms is controlled by the ratio of Ca, Sr, and Ba between the surface of the glass substrate and the interior, but the ratio of Na between the surface of the glass substrate and the interior is not studied.
  • Patent Document 2 when a high strain point glass substrate having a Na 2 O content of 2 to 5% by weight is used, the diffusion of Na from the glass substrate to the CIS light absorption layer and the CIS light absorption layer from the outside are performed. Na has been introduced into the glass, but the ratio of Na between the glass substrate surface and the inside has not been studied.
  • Non-Patent Document 1 in order to reduce Na atoms released from the back surface of the glass substrate, the management of the substrate becomes complicated in the CIGS film forming process, and a simpler method is desired.
  • the glass substrate in which the ratio of Na between the glass substrate surface and the inside is controlled, it is desired to improve the surface characteristics of the glass substrate.
  • An object of the present invention is to provide a glass substrate capable of forming a thin film in which the doping amount of alkali atoms is accurately controlled.
  • the following glass substrate and CIGS embodiment battery are provided.
  • the ratio of the Na atom concentration in the surface layer of the first surface of the glass substrate to the Na atom concentration at a depth of 5000 nm from the first surface of the glass substrate is 0.5 or more,
  • the glass substrate whose ratio of Na atom concentration in the surface layer of the 2nd surface of a glass substrate with respect to Na atom concentration in the depth of 5000 nm from the 2nd surface of a glass substrate is less than 0.5.
  • a CIGS solar cell having the glass substrate according to any one of (1) to (8) and a photoelectric conversion layer formed on the first surface of the glass substrate and containing a CIGS compound.
  • the present invention it is possible to provide a glass substrate capable of forming a thin film in which the doping amount of alkali atoms is accurately controlled.
  • FIG. 1 is a cross-sectional view schematically showing an example of a solar cell according to an embodiment of the present invention.
  • FIG. 2A is a photograph of the glass substrate surface after polishing, in which the adhesion of the Mo film formed on the glass substrate in the example was evaluated.
  • FIG. 2B is an evaluation of the adhesion of the Mo film formed on the glass substrate in the example, and is a photograph of the surface of the glass substrate after polishing and cleaning.
  • the glass substrate according to an embodiment of the present invention Na 2 O content measured by X-ray fluorescence in (mass%), relative to Na 2 O weight at a depth 5000nm from the first surface of the glass substrate, the glass substrate 1
  • the ratio of the amount of Na 2 O on the surface of the surface is 0.8 or more, and the ratio of the amount of Na 2 O on the surface of the second surface of the glass substrate to the amount of Na 2 O at a depth of 5000 nm from the second surface of the glass substrate Is less than 0.8.
  • the amount of diffusion of Na atoms from the first surface to the thin film can be increased.
  • the conversion efficiency of the solar cell can be increased by increasing the amount of Na atoms diffused from the glass substrate surface to the CIGS film.
  • the amount of Na atoms released from the second surface of the glass substrate into the atmosphere can be reduced.
  • Na atoms detached from the second surface can be prevented from adhering to the thin film on the first surface through the atmosphere. Thereby, the uniformity of the film characteristics of the glass substrate can be maintained.
  • the glass substrate according to the present embodiment can be preferably used for a glass substrate for solar cells, and more preferably can be used for a glass substrate for CIGS solar cells.
  • the first surface of the glass substrate can be treated as a CIGS film deposition surface
  • the second surface of the glass substrate can be treated as a non-film formation surface of the CIGS film.
  • the CIGS solar cell can reduce the defect density and improve the carrier concentration by doping with an alkali metal such as Na atom.
  • the glass substrate on which the CIGS film is formed contains Na 2 O as a raw material, and the Na atoms can be diffused from the glass substrate surface to the CIGS film by heat treatment in the CIGS film forming step. From this, it is desirable that more Na atoms diffuse from the glass substrate surface into the CIGS film.
  • the diffusion of Na atoms from the glass substrate to the CIGS film is strongly influenced by the amount of Na atoms in the vicinity of the surface of the glass substrate on which the CIGS film is formed.
  • the amount of Na 2 O near the surface of the first surface of the glass substrate is large, the amount of Na atoms diffused from the glass substrate into the CIGS film can be increased.
  • the glass substrate according to the present embodiment can be used for a glass substrate for a display device, a magnetic disk, etc. in addition to the glass substrate for a solar cell described above.
  • the ratio of O amount is 0.8 or more. This ratio is more preferably 0.85 or more, and still more preferably 0.90 or more.
  • the amount of Na 2 O on the surface of the first surface of the glass substrate can be made close to the amount of Na 2 O inside the glass substrate. This means a state in which Na atoms are not loose from the surface of the first surface of the glass substrate.
  • this ratio is 0.8 or more, when a thin film is formed on the first surface of the glass substrate, a sufficient amount of Na atoms diffused from the first surface to the thin film can be obtained. For example, when a CIGS film is formed on the first surface of the glass substrate, the amount of Na atoms diffused into the CIGS film can be increased.
  • SO 2 treatment is performed, and Na atoms on the surface of the glass substrate are released into the outside of the glass substrate as sulfates such as Na 2 SO 4 . Therefore, in the normal glass substrate, the amount of Na atoms on the surface is lower than that inside.
  • the SO 2 treatment is performed to form a protective film on the back surface for transporting the glass substrate.
  • This ratio is preferably as high as possible, and the upper limit is usually 1.0. That this ratio is 1.0 means that the distribution of Na atoms between the surface of the first surface of the glass substrate and the inside of the glass substrate is the same, and the first surface of the glass substrate with respect to the composition of the entire glass substrate. In this state, Na atoms are sufficiently present on the surface.
  • this ratio is less than 0.8, the amount of Na 2 O on the surface of the first surface of the glass substrate becomes smaller than the amount of Na 2 O inside the glass substrate. This means a state in which Na atoms are missing from the vicinity of the surface of the first surface of the glass substrate (a detached state).
  • the ratio of 2 O content is less than 0.8. This ratio is more preferably 0.78 or less, and even more preferably 0.75 or less.
  • this ratio is less than 0.8, the amount of Na 2 O on the surface of the second surface of the glass substrate can be sufficiently reduced. Thereby, the amount of Na atoms floating in the atmosphere from the second surface of the glass substrate can be reduced, and the amount of Na atoms reattached to the first surface of the glass substrate can be reduced.
  • Na atoms may be detached from the non-formation surface of the CIGS film of the glass substrate, and Na atoms may be doped again into the CIGS film while floating in the atmosphere. .
  • the Na atoms doped in this way are difficult to control and may cause unevenness in battery characteristics.
  • the amount of Na atoms floating from the second surface of the glass substrate can be reduced.
  • the amount of Na atoms reattached to the CIGS film on the glass substrate can be reduced, and a CIGS solar cell having uniform film characteristics can be provided.
  • This ratio is preferably as low as possible, but the lower limit is usually 0.5 in consideration of the composition of the entire glass substrate and the amount of Na released.
  • the Na 2 O content (mass%) can be measured by fluorescent X-rays.
  • the amount of Na 2 O (mass%) can be quantified by a calibration curve method of the fluorescent X-ray method using a standard sample for quantification measured with fluorescent X-rays having a tube voltage of 50 kV and 50 mA. it can.
  • RIX3000 manufactured by Rigaku Corporation can be used as a fluorescent X-ray measuring apparatus.
  • the amount of Na 2 O on the surface of the first surface of the glass substrate can be determined from a value obtained by measuring the average content in the range from the surface of the first surface of the glass substrate to about 3000 nm by fluorescent X-rays.
  • the amount of Na 2 O on the surface of the second surface of the glass substrate can be similarly determined.
  • the amount of Na 2 O at a depth of 5000 nm from the first surface of the glass substrate is about 3000 nm from the surface after removing the glass up to a depth of 5000 nm from the surface of the first surface of the glass substrate by fluorescent X-rays. It can obtain
  • the amount of Na 2 O at a depth of 5000 nm from the second surface of the glass substrate can be similarly determined.
  • a method for removing the glass a method of grinding with a water slurry such as cerium oxide, colloidal silica, diamond particles, SiC particles, a method of grinding with fixed abrasive grains carrying these abrasive particles, or the like is used. be able to.
  • the Na 2 O content at the surface of the first surface of the glass substrate by obtaining the ratio of the Na 2 O content at a depth 5000nm from the first surface of the glass substrate, the surface of the first surface of the glass substrate can be defined as the amount of Na atoms withdrawn to a depth of about 3000 nm. The same applies to the second surface of the glass substrate.
  • glass with respect to Na atom concentration at a depth of 5000 nm from the first surface of the glass substrate in Na atom concentration (atomic%) measured by X-ray photoelectron spectroscopy (XPS) is used.
  • the ratio of the Na atom concentration in the surface layer of the first surface of the substrate is 0.5 or more, and the measured Na atoms in the surface layer of the second surface of the glass substrate with respect to the Na atom concentration at a depth of 5000 nm from the second surface of the glass substrate The density ratio is less than 0.5.
  • the amount of Na atoms in the vicinity of the very surface of the glass substrate for example, at a depth of about 100 nm from the surface of the glass substrate (hereinafter sometimes referred to as the Na atom amount of the glass surface layer). I found it.
  • the amount of Na atoms at a depth of about 100 nm from the surface of the glass substrate can be measured by X-ray photoelectron spectroscopy.
  • the Na atom concentration (atomic%) measured by X-ray photoelectron spectroscopy Na in the surface layer of the first surface of the glass substrate with respect to the Na atom concentration at a depth of 5000 nm from the first surface of the glass substrate.
  • the atomic concentration ratio is 0.5 or more. This ratio is more preferably 0.6 or more, and still more preferably 0.7 or more.
  • the surface layer of the first surface of the glass substrate is a layer having a depth of about 100 nm from the surface of the first surface of the glass substrate.
  • the amount of Na atoms in the surface layer of the first surface of the glass substrate can be sufficiently increased.
  • a sufficient amount of Na atoms diffused from the first surface to the thin film can be obtained.
  • the amount of Na atoms diffused into the CIGS film can be increased.
  • This ratio is preferably as high as possible, and the upper limit is usually 1.0.
  • this ratio is less than 0.5, the amount of Na atoms in the surface layer of the first surface of the glass substrate becomes smaller than the amount of Na atoms in the glass substrate. This means a state in which Na atoms have escaped from the surface layer of the first surface of the glass substrate (a detached state).
  • the Na atoms in the surface layer of the second surface of the glass substrate with respect to the Na atom concentration at a depth of 5000 nm from the second surface of the glass substrate in the Na atom concentration (atomic%) measured by X-ray photoelectron spectroscopy is less than 0.5. This ratio is more preferably 0.4 or less, and still more preferably 0.3 or less.
  • the surface layer of the second surface of the glass substrate is a layer having a depth of about 100 nm from the surface of the second surface of the glass substrate.
  • this ratio is less than 0.5, the amount of Na atoms can be sufficiently reduced in the surface layer of the second surface of the glass substrate. Thereby, the amount of Na atoms floating in the atmosphere from the second surface of the glass substrate can be reduced, and the amount of Na atoms reattached to the first surface of the glass substrate can be reduced.
  • the amount of Na atoms floating from the second surface of the glass substrate can be reduced.
  • the amount of Na atoms reattached to the CIGS film on the glass substrate can be reduced, and a CIGS solar cell having uniform film characteristics can be provided.
  • This ratio is preferably as low as possible, but the lower limit is usually 0.2 considering the composition of the entire glass substrate and the amount of Na atoms removed.
  • the Na atom concentration (atomic%) can be measured by X-ray photoelectron spectroscopy.
  • X-ray photoelectron spectrometer for example, “ESCA5500” manufactured by ULVAC-PHI CORPORATION can be used.
  • the Na profile in the depth direction was measured with an X-ray photoelectron spectrometer while sputter etching from the surface of the first surface of the glass substrate to 100 nm with a C60 ion beam. You can ask for it.
  • the Na atom concentration in the surface layer of the second surface of the glass substrate can be determined in the same manner.
  • the glass having a depth of 5000 nm is removed from the surface of the first surface of the glass substrate, and then the sputter etching is performed to 100 nm with a C60 ion beam from the removed surface.
  • the Na profile in the depth direction can be determined by measuring with an X-ray photoelectron spectrometer.
  • the Na atom concentration at a depth of 5000 nm from the second surface of the glass substrate can be determined in the same manner.
  • the glass removal method there is a method of grinding to a depth of 4000 nm from the surface of the glass substrate with a water slurry of cerium oxide, then performing sputter etching with a C60 ion beam, and grinding to a depth of 5000 nm in total.
  • the depth from the surface of the first surface of the glass substrate is increased.
  • the amount of Na atoms released up to about 100 nm can be defined. The same applies to the second surface of the glass substrate.
  • the first surface of the glass substrate is preferably a non-polished surface. Since the first surface of the glass substrate is a non-polished surface, the surface roughness of the first surface is low, there are no polishing marks, scratches, polishing-derived residues, etc., and the thin film formed on the first surface and the first surface Adhesion with the surface can be improved.
  • the thin film formed directly on the first surface includes a Mo film as a back electrode layer for solar cells, a silica film for adjusting the amount of Na diffusion and improving the adhesion of the Mo film, a SiN film, and Al 2. Examples thereof include an O 3 film.
  • the non-polished surface is a surface that is not polished in a subsequent step of the SO 2 treatment when performing the SO 2 treatment described later. In this case, before the SO 2 treatment step, a polishing treatment may be performed, for example, by molding glass.
  • the glass substrate is produced by a float method, a fusion method or the like and is usually not polished and has an average surface roughness (Ra) of 0.1 to 0.5 nm. Therefore, the non-polished surface can be confirmed when Ra is 0.1 to 0.5 nm.
  • average surface roughness (Ra) refers to a value measured by a method based on SEMID 7-94 “Measurement method of surface roughness of FPD glass substrate”, and average surface roughness of the evaluation surface of the glass substrate. (Ra) is pointed out, and the end face of the glass substrate is not considered (hereinafter the same).
  • the non-polished surface can be confirmed by the absence of polishing marks or scratches due to polishing.
  • the polishing marks and the scratches are usually concave shapes having a length of 1 ⁇ m or more, a width of 0.05 ⁇ m or more, and a depth of 1 nm or more.
  • Such a concave shape is preferably 1 piece / ⁇ m 2 or less per unit area on the non-polished surface of the glass substrate.
  • the non-polished surface can be confirmed by the absence of inorganic particles such as abrasive grains and water glass used in the polishing treatment and a solvent on the surface of the glass substrate.
  • inorganic particles used for the polishing treatment include cerium oxide, silica, diamond, SiC, and the like, and the particle diameter is usually 0.01 to 2 ⁇ m.
  • the solvent used for the polishing treatment include water, organic solvents, acid and alkali solutions. It is preferable that the inorganic particles and the solvent used in these polishing processes are not substantially confirmed on the non-polished surface of the glass substrate.
  • polishing is not substantially confirmed on the 1st surface of a glass substrate.
  • the residue derived from polishing per unit area of the glass substrate is preferably 2.0 ng / cm 2 or less in terms of solid content.
  • cerium oxide as the inorganic particles in the polishing treatment is preferably 2.0 ng / cm 2 or less with Ce terms, more preferably 1.0 ng / cm 2 or less, more preferably 0.5 ng / cm 2 or less, particularly preferably 0.1 ng / cm 2 or less. Since there is little residue derived from polishing on the first surface of the glass substrate, the adhesion between the thin film formed on the first surface and the first surface can be enhanced.
  • the effect of removing foreign substances on the surface is obtained by polishing, it is preferably 0.005 ng / cm 2 or more, more preferably 0.01 ng / cm 2 or more, further preferably 0.02 ng / cm 2 or more, particularly preferably. It may be 0.05 ng / cm 2 or more.
  • residues derived from polishing include the inorganic particles and solvents described above. Further, glass fragments scraped by polishing are also included in the residue derived from polishing. Glass fragments as a residue derived from polishing usually have a maximum diameter of 0.01 to 1 ⁇ m.
  • the glass substrate preferably has a first surface Ra of 0.1 to 0.5 nm, more preferably 0.1 to 0.4 nm.
  • this Ra there is a method in which the first surface of the glass substrate is used without being polished. In this case, it is preferable that the glass substrate is arbitrarily cleaned and used as it is after the SO 2 treatment. Further, the first surface of the glass substrate may be used after being cleaned.
  • composition of the glass substrate common to the above-described embodiments will be described.
  • the composition of the glass substrate according to the present embodiment is not limited, but a glass substrate containing SiO 2 as a main component and containing 1 to 15% by mass of Na 2 O based on an oxide can be used.
  • composition of the glass substrate at a depth of 5000 nm or more from the surface of the glass substrate, by mass percentage display based on the following oxide, 50 to 72% of SiO 2 Al 2 O 3 1-15%, MgO 0-10%, CaO 0.1 to 11%, 0-18% SrO, BaO 0-11%, 1 to 15% Na 2 O, 2 to 21% of K 2 O, Containing 0 to 10.5% of ZrO 2 , MgO + CaO + SrO + BaO is 4-30%, CaO + SrO + BaO 3-30%, Na 2 O + K 2 O is 7 to 22%.
  • the reason for limiting to the above composition is as follows.
  • SiO 2 A component that forms a glass skeleton, and if it is less than 50% by mass (hereinafter simply referred to as “%”), the heat resistance and chemical durability of the glass may decrease, and the average thermal expansion coefficient may increase. Preferably it is 52% or more, More preferably, it is 54% or more, More preferably, it is 56% or more, Most preferably, it is 58% or more.
  • the high-temperature viscosity of the glass may increase, which may cause a problem of deterioration of solubility.
  • it is 70% or less, More preferably, it is 68% or less, More preferably, it is 67% or less, Most preferably, it is 66% or less.
  • Al 2 O 3 A component that increases the glass transition temperature, improves weather resistance (solarization), heat resistance and chemical durability, and increases Young's modulus. If the content is less than 1%, the glass transition temperature may be lowered. Moreover, there exists a possibility that an average thermal expansion coefficient may increase. Preferably it is 2% or more, more preferably 3% or more, still more preferably 4% or more, particularly preferably 5% or more.
  • the high-temperature viscosity of the glass may increase and the solubility may deteriorate. Further, the devitrification temperature is increased, and the moldability may be deteriorated.
  • it is 14% or less, More preferably, it is 13% or less, More preferably, it is 12% or less, Most preferably, it is 11.5% or less.
  • MgO A component that has an effect of reducing the viscosity at the time of melting the glass and promoting the melting, and may be contained at 10% or less. Preferably it is 0.1% or more, More preferably, it is 0.5%, More preferably, it is 1% or more.
  • the average thermal expansion coefficient may increase.
  • the devitrification temperature may increase. Preferably it is 8% or less, More preferably, it is 6% or less, More preferably, it is 4% or less, Most preferably, it is 3% or less.
  • CaO A component that has the effect of reducing the viscosity at the time of melting the glass and promoting the melting, and further promoting the diffusion of Na into the CIGS film, and can be contained at 0.1% or more. Preferably it is 1% or more, More preferably, it is 2% or more, More preferably, it is 3% or more, Most preferably, it is 4% or more. However, if it exceeds 11%, the average thermal expansion coefficient of the glass may increase. In addition, the power generation efficiency may be reduced, that is, the amount of Na diffusion described later may be reduced. Preferably it is 10% or less, More preferably, it is 9% or less, More preferably, it is 8% or less, Most preferably, it is 7% or less.
  • SrO A component that has the effect of reducing the viscosity at the time of melting the glass and promoting the melting, and further promoting the diffusion of Na into the CIGS film, and can be contained at 18% or less. However, if the content exceeds 18%, the average thermal expansion coefficient of the glass substrate increases, the density increases, and the glass may become brittle. It is preferably 15% or less, more preferably 12% or less, further preferably 10% or less, and particularly preferably 9% or less. Further, it is preferably 0.5% or more, more preferably 2% or more, still more preferably 3.5% or more, and particularly preferably 5% or more.
  • BaO A component that has the effect of reducing the viscosity at the time of melting the glass and promoting the melting, and further promoting the diffusion of Na into the CIGS film, and can be contained at 11% or less. Preferably it is 0.5% or more, More preferably, it is 1% or more, More preferably, it is 1.5% or more, Most preferably, it is 2% or more. However, if it exceeds 11%, the average thermal expansion coefficient of the glass substrate may increase. In addition, the specific gravity increases, the density increases, and the glass may become brittle. It is preferably 8% or less, more preferably 5% or less, further preferably 4% or less, and particularly preferably 3% or less.
  • Na 2 O is a component that contributes to improving the power generation efficiency of CIGS solar cells, and is an essential component. Further, it has the effect of lowering the viscosity at the glass melting temperature and facilitating melting, so 1 to 15% is contained. Na diffuses into the CIGS photoelectric conversion layer formed on the glass to increase the power generation efficiency, but if the content is less than 1%, the amount of Na diffusion into the CIGS photoelectric conversion layer on the glass substrate becomes insufficient, The power generation efficiency may also be insufficient.
  • the content is preferably 2% or more, more preferably 2.5% or more, further preferably 3% or more, and particularly preferably 3.5% or more.
  • the content is preferably 13% or less, more preferably 11% or less, even more preferably 9% or less, and particularly preferably less than 7%.
  • K 2 O Since it has the same effect as Na 2 O, 2 to 21% is contained. However, if it exceeds 21%, the power generation efficiency decreases, that is, the diffusion of Na is inhibited, the amount of Na diffusion described later decreases, the glass transition temperature decreases, and the average thermal expansion coefficient may increase. It is preferably 3% or more, more preferably 4% or more, still more preferably 5% or more, and particularly preferably 6% or more. It is preferably 16% or less, more preferably 12% or less, still more preferably 10% or less, and particularly preferably 8% or less.
  • ZrO 2 A component that has an effect of lowering the viscosity at the time of melting of glass, promoting melting, and increasing Tg, and may be contained at 10.5% or less. Preferably, it is contained at 0.5% or more. More preferably, it is 1% or more, further preferably 1.5% or more, and particularly preferably 2% or more. However, if the content exceeds 10.5%, the power generation efficiency decreases, that is, the amount of Na diffusion described later decreases, the devitrification temperature increases, and the average thermal expansion coefficient of the glass substrate may increase. It is preferably 9% or less, more preferably 7% or less, further preferably 5% or less, and particularly preferably 4% or less.
  • MgO, CaO, SrO and BaO The total amount of MgO, CaO, SrO and BaO can be 4 to 30% from the viewpoint of decreasing the viscosity at the time of melting the glass and promoting the melting. However, if the total amount exceeds 30%, the average thermal expansion coefficient increases, and the devitrification temperature may increase. It is preferably 6% or more, more preferably 9% or more, further preferably 12% or more, and particularly preferably 14% or more. Moreover, 25% or less is preferable, 21% or less is more preferable, 18% or less is further more preferable, and 17% or less is especially preferable.
  • the total amount of CaO, SrO and BaO can be 3 to 30% from the viewpoint of promoting the diffusion of Na into the CIGS film. More preferably 6% or more, still more preferably 8% or more, particularly preferably 10% or more. However, if it exceeds 30%, the average thermal expansion coefficient increases, and the devitrification temperature may increase. It is preferably 27% or less, more preferably 24% or less, further preferably 21% or less, and particularly preferably 18% or less.
  • SrO and BaO generate a sulfate film (SrSO 4 , BaSO 4 ) in the SO 2 treatment, and these are other sulfate films (MgSO 4 , CaSO 4 , Na 2 SO 4 , K). 2 SO 4 ) is less soluble in water than the SO 2 ), and thus the sulfate film is difficult to remove when washing the sulfate film. Therefore, the total amount of SrO and BaO is preferably 16% or less, more preferably 14% or less, further preferably 12% or less, and particularly preferably 10% or less.
  • Na 2 O and K 2 O In order to sufficiently reduce the viscosity at the glass melting temperature and to improve the power generation efficiency of the CIGS solar cell, the total amount of Na 2 O and K 2 O is 7 to 22%. To do. Preferably it is 8% or more, More preferably, it is 9% or more, More preferably, it is 10% or more, Most preferably, it is 11% or more.
  • Tg is too low and the average thermal expansion coefficient may be too high.
  • ZrO 2 is 0.5% in terms of mass percentage based on the following oxide.
  • Preferred is a combination containing 9 to 9%, CaO + SrO + BaO 6 to 21% and SrO + BaO 0 to 16%, and further containing ZrO 2 1.5 to 7%, CaO + SrO + BaO 8 to 18%, SrO + BaO 0 to 10% The combination which is is more preferable.
  • the glass substrate according to the present embodiment is preferably essentially composed of the above composition, but may contain other components typically in a total amount of 5% or less as long as the object of the present invention is not impaired.
  • B 2 O 3 , ZnO, Li 2 O, WO 3 , Nb 2 O 5 , V 2 O 5 , Bi 2 O 3 for the purpose of improving weather resistance, solubility, devitrification, ultraviolet shielding, etc.
  • MoO 3 may contain P 2 O 5 or the like.
  • B 2 O 3 may be contained up to 2% in order to improve the solubility.
  • the content exceeds 2%, the glass transition temperature decreases or the average thermal expansion coefficient decreases, which is not preferable for the process of forming a CIGS film. More preferably, the content is 1% or less. The content is particularly preferably 0.5% or less, more preferably substantially not contained.
  • substantially does not contain means that it is not contained other than inevitable impurities mixed from raw materials or the like, that is, it is not intentionally contained. The same applies hereinafter.
  • these raw materials may be added to the matrix composition raw material so that the glass contains SO 3 , F, Cl, SnO 2 in a total amount of 2% or less. Good.
  • Y 2 O 3 , La 2 O 3 , TiO 2 and SnO 2 may be contained in the glass in a total amount of 5% or less.
  • Y 2 O 3 , La 2 O 3 and TiO 2 contribute to the improvement of the Young's modulus of the glass.
  • the glass may contain a colorant such as Fe 2 O 3 in the glass.
  • a colorant such as Fe 2 O 3 in the glass.
  • the content of such a colorant is preferably 1% or less.
  • the glass substrate according to the present embodiment considering the environmental burden, it is preferred not to contain As 2 O 3, Sb 2 O 3 substantially. In consideration of stable float forming, it is preferable that ZnO is not substantially contained. Note that the glass substrate according to the present embodiment is not limited to being formed by the float process, but may be manufactured by forming by the fusion process.
  • the glass transition temperature (Tg) of the glass substrate according to the present embodiment is preferably 580 ° C. or higher.
  • the Tg is preferably 600 ° C. or higher, more preferably 610 ° C. or higher, further preferably 620 ° C. or higher, and particularly preferably 630 ° C. or higher.
  • This Tg is higher than the Tg of ordinary soda lime glass, thereby ensuring the formation of a photoelectric conversion layer at a high temperature.
  • the upper limit value of Tg of the present invention is preferably 750 ° C. or lower. This Tg is more preferably 720 ° C. or less, and still more preferably 700 ° C. or less.
  • Tg can be measured by using a differential thermal dilatometer (TMA) and can be determined by JIS R3103-3 (2001) as described in the examples described later.
  • the average thermal expansion coefficient at 50 to 350 ° C. of the glass substrate according to the present embodiment is preferably 70 ⁇ 10 ⁇ 7 to 110 ⁇ 10 ⁇ 7 / ° C. By being in this range, it is possible to prevent the difference in thermal expansion from the CIGS film or the like formed on the glass substrate from becoming too large, and to prevent peeling or the like.
  • the average coefficient of thermal expansion at 50 to 350 ° C. can be measured by using a differential thermal dilatometer (TMA) and determined from JIS R 3102 (1995) as described in the examples described later. Furthermore, when a solar cell is assembled (specifically, when a glass substrate having a CIGS photoelectric conversion layer and a cover glass are heated and bonded together), the glass substrate can be prevented from being deformed.
  • the average thermal expansion coefficient is preferably 100 ⁇ 10 ⁇ 7 / ° C. or less, more preferably 95 ⁇ 10 ⁇ 7 / ° C. or less, and further preferably 90 ⁇ 10 ⁇ 7 / ° C. or less.
  • the average thermal expansion coefficient is preferably 73 ⁇ 10 ⁇ 7 / ° C. or more, more preferably 75 ⁇ 10 ⁇ 7 / ° C. or more, and further preferably 80 ⁇ 10 ⁇ 7 / ° C. or more.
  • a predetermined SO 2 treatment is performed after melting and forming a glass raw material.
  • the glass substrate used for the SO 2 treatment can be obtained by adjusting the raw materials so that the glass substrate has an arbitrary composition and performing the melting step and the molding step in the same manner as the method for producing a conventional glass substrate. it can.
  • the raw material is adjusted according to the composition of the obtained glass substrate, this raw material is continuously charged into a melting furnace, heated to obtain molten glass, and then this molten glass is formed into a plate-like glass plate can do. It is preferable to adjust the raw materials so that the composition of the glass substrate becomes the above-described composition.
  • the melting temperature of the glass raw material can usually be 1450 to 1700 ° C., more preferably 1500 to 1650 ° C.
  • the melting time is not particularly limited, and is usually 1 to 48 hours.
  • a clarifier can be used in the dissolution step.
  • SO 3 can be effectively used as a clarifier from the above clarifiers.
  • a float method As a molding method, a float method, a fusion method (download method), or the like can be used.
  • a float method capable of stably forming a glass substrate having a large area as the size of the solar cell increases.
  • SO 2 treatment can be performed simultaneously in the slow cooling step.
  • the SO 2 treatment is a treatment in which SO 2 gas is sprayed from one side to a glass substrate formed into a plate shape.
  • This SO 2 treatment is usually performed by spraying SO 2 gas on the surface of one side of the glass substrate, specifically, the surface of the glass substrate on the side in contact with the transfer roller, and forming a protective film of Na or K sulfate. It is carried out to prevent surface scratches from being formed and conveyed.
  • the amount of Na 2 O on the first surface, the inside, and the second surface of the glass substrate is adjusted by adjusting the SO 2 processing conditions. That is, if the surface on which the SO 2 gas is sprayed is the second surface, Na atoms are desorbed and the amount of Na 2 O decreases on the second surface due to the blowing of SO 2 gas. Since the operation of suppressing the reaction with the SO 2 gas is performed on the first surface, desorption of Na atoms is suppressed, and the amount of Na 2 O is prevented from being reduced. The 2O amount ratio can be reduced.
  • the SO 2 treatment is preferably carried out in the molding process by the float method when the glass is slowly cooled to room temperature in the slow cooling furnace after being taken out from the molding furnace.
  • SO 2 gas can be sprayed before the glass substrate enters the annealing furnace. It is also possible by blowing SO 2 gas continuously even after the glass substrate has entered the annealing furnace. Alternatively, the SO 2 gas spray may be started after the glass substrate enters the slow cooling furnace.
  • the SO 2 treatment can be performed usually at a glass substrate surface temperature of 300 to 750 ° C., more preferably 500 to 700 ° C.
  • the SO 2 treatment time can usually be 1 to 15 minutes, and more preferably 3 to 10 minutes.
  • the cooling rate at the time of slow cooling is preferably 1 to 100 ° C./min.
  • the SO 2 treatment may be performed while reheating after the glass substrate is formed and slowly cooled.
  • the temperature and time for reheating can be the same as described above, and it is preferable to reproduce the slow cooling of the molding process.
  • the SO 2 gas concentration in the SO 2 treatment can be 0.01 to 10% by volume, and more preferably 0.05 to 5% by volume.
  • the total amount of SO 2 gas sprayed can be 0.01 to 5 l / m 2 , more preferably 0.05 to 2 l / m 2 .
  • SO 2 treatment the surface temperature of the glass substrate described above, the processing time, by the spraying amount of concentration and SO 2 gas in SO 2 gas, the first surface of the glass substrate, internal, Na 2 O ratio of the second surface Can be within the scope of the present invention.
  • High surface temperature of the glass substrate, a long processing time, high concentration of SO 2 gas, by spraying amount of SO 2 gas is large, each independently, Na 2 O between the first surface and the interior of the glass substrate
  • the quantity ratio can be reduced. This effect can also be obtained by increasing the sealing performance of the slow cooling furnace.
  • the surface temperature of the glass substrate is too low, the first surface of the glass substrate, internal, hardly a difference in Na 2 O weight ratio of the second surface is attached, it may not be a desired surface state.
  • Na 2 O weight ratio of the first and second surfaces of the glass substrate As a method of adjusting the Na 2 O weight ratio of the first and second surfaces of the glass substrate, with the above SO 2 treatment conditions, Na 2 O weight ratio of the first surface and the interior of the glass 0.
  • the Na 2 O content ratio between the second surface of the glass and the inside can be adjusted to be less than 0.8.
  • the concentration of SO 2 gas in contact with the first surface and the second surface of the glass substrate can be changed. That is, when the SO 2 gas is sprayed onto the second surface of the glass substrate, the SO 2 gas is not sprayed onto the first surface of the glass substrate, or the SO 2 gas sprayed onto the second surface wraps around the first surface. By avoiding this, the SO 2 gas concentration can be changed. Thereby, the amount of SO 2 gas blown into the first surface can be reduced, and the amount of Na atoms desorbed from the first surface can be reduced.
  • the surface and the interior of the second surface of the glass substrate The Na 2 O amount ratio is set to be less than 0.8.
  • the Na 2 O amount ratio between the surface and the inside of the first surface of the glass substrate may be less than 0.8.
  • a Na 2 O weight ratio between the inside and the first surface may be 0.8 or more.
  • the polishing amount at this time can be 0.3 to 5 ⁇ m on the surface layer.
  • the polishing method is not particularly limited, and examples include grinding with an aqueous slurry of cerium oxide.
  • the surface may be rougher than when the first surface of the glass substrate is used as it is.
  • a rough surface is not suitable for thin film formation.
  • the surface roughness can be reduced by washing after polishing.
  • the SO 2 treatment surface of the glass substrate that is, the second surface is preferably washed to remove a film such as sulfate. Moreover, you may wash
  • the glass substrate cleaning method is not particularly limited, and for example, cleaning with water, cleaning with a cleaning agent, cleaning with a brush or the like while spraying a slurry containing cerium oxide, and the like can be used.
  • an acidic detergent such as hydrochloric acid or sulfuric acid.
  • the glass substrate surface after washing is free of dirt and irregularities on the glass substrate surface due to the deposits such as cerium oxide. If there are irregularities, irregularities on the surface of the film, film thickness deviations, pinholes in the film, and the like may occur during film formation of the electrode film and its underlying layer, and power generation efficiency may be reduced.
  • the glass substrate After cleaning, the glass substrate can be obtained by cutting into a predetermined size.
  • a glass substrate As a glass substrate for CIGS solar cells, it is preferable to wash
  • the first surface of the glass substrate is polished, it is preferable to clean the first surface in order to remove the polishing residue.
  • an electrode film such as Mo or a base layer (for example, SiO 2 ) or the like is formed on the glass substrate surface, there is a possibility that the film cannot be formed normally if the glass substrate surface is dirty.
  • the glass substrate is substantially free from polishing residue on the first surface.
  • the residue derived from polishing per unit area of the glass substrate is preferably 2.0 ng / cm 2 or less in terms of solid content.
  • cerium oxide when used as the inorganic particles, it is preferably 2.0 ng / cm 2 or less in terms of Ce. Therefore, it is more preferable not to perform the polishing process in the glass substrate manufacturing method.
  • the residue derived from the polishing is sufficiently washed thereafter.
  • the first surface is preferably a non-polished surface. Therefore, in the manufacturing method of a glass substrate, it is more preferable not to perform a polishing process after arbitrarily cleaning after the SO 2 process.
  • the glass substrate preferably has a first surface Ra of 0.1 to 0.5 nm. Therefore, it is more preferable not to perform the polishing process in the glass substrate manufacturing method. For example, without first polishing the first surface of the glass substrate, the glass substrate can be arbitrarily cleaned and used as it is after the SO 2 treatment.
  • the glass substrate by this embodiment can be preferably used as a glass substrate for solar cells, and specifically can be used as a glass substrate for solar cells and a cover glass for solar cells.
  • a 11-13 group, 11-16 group compound semiconductor having a chalcopyrite crystal structure, or a cubic or hexagonal 12-16 group compound semiconductor can be preferably used.
  • Representative examples include CIGS compounds, CdTe compounds, CIS compounds, CZTS compounds, and the like. Particularly preferred are CIGS compounds.
  • a silicon compound, an organic compound, or the like may be used as the photoelectric conversion layer of the solar cell.
  • the thickness of the glass substrate is preferably 3 mm or less, more preferably 2 mm or less, and even more preferably 1.5 mm or less.
  • a method for forming a photoelectric conversion layer of a CIGS film on a glass substrate a method in which at least a part of the CIGS film is formed by a selenization method or a vapor deposition method is preferable.
  • the heating temperature when forming the photoelectric conversion layer can be set to 500 to 650 ° C.
  • the thickness of the glass substrate is preferably 0.2 mm or more, more preferably 0.5 mm or more, still more preferably 0.7 mm or more, and particularly preferably 1.0 mm or more.
  • cover glass composition include soda lime glass.
  • the thickness of the cover glass is preferably 4 mm or less, more preferably 2.5 mm or less, and even more preferably 1.5 mm or less.
  • the method for assembling the cover glass on the glass substrate having the photoelectric conversion layer is not particularly limited.
  • the heating temperature can be set to 500 to 650 ° C.
  • the thickness of the glass substrate is preferably 0.2 mm or more, more preferably 0.5 mm or more, further preferably 0.7 mm or more, and particularly preferably 1.0 mm or more.
  • the CIGS solar cell glass substrate of this embodiment is used in combination with a CIGS solar cell glass substrate and a cover glass, since the average thermal expansion coefficient is the same, so that thermal deformation or the like during solar cell assembly does not occur.
  • the amount of Na 2 O (mass%) and / or the Na atom concentration (atomic%) of the surface of the first surface and / or the surface layer of the glass substrate is uniform throughout the glass substrate for CIGS solar cells.
  • the range of variation within the glass substrate is within 30% of the target value, more preferably within 20%, even more preferably within 10%, and particularly preferably within 5%. Accordingly, it is possible to prevent the occurrence of a portion with low power generation efficiency, and to prevent the power generation efficiency of the solar cell from being affected by the portion.
  • the solar cell according to the present embodiment includes the glass substrate according to the present embodiment described above and a photoelectric conversion layer formed on the first surface of the glass substrate and including a CIGS compound.
  • Preferred embodiments include a glass substrate, a cover glass, a photoelectric conversion layer containing a CIGS compound disposed between the glass substrate and the cover glass, and at least one of the glass substrate and the cover glass is the above-described embodiment. It is a glass substrate by.
  • each layer of the solar cell shown in drawing is shown typically, and is not limited to this.
  • FIG. 1 is a schematic cross-sectional view showing an example of the solar cell according to the present embodiment.
  • a solar cell (CIGS solar cell) 1 includes a glass substrate 5, a cover glass 19, and a CIGS film 9 as a photoelectric conversion layer between the glass substrate 5 and the cover glass 19.
  • the glass substrate according to the present embodiment described above can be used for at least one of the glass substrate 5 and the cover glass 19.
  • the surface on which the CIGS film 9 is formed be the first surface of the glass substrate.
  • the solar cell 1 has a Mo film 7 that is a positive electrode on the glass substrate 5 as a back electrode layer, and has a CIGS film 9 thereon.
  • a CIGS film 9 of alkali metal or impurity element from the glass substrate. It is also possible to control the amount of diffusion.
  • the CIGS film 9 is a photoelectric conversion layer containing a CIGS compound.
  • the composition of the CIGS compound is, for example, Cu (In 1-X Ga x ) Se 2 .
  • x represents the composition ratio of In and Ga, and 0 ⁇ x ⁇ 1.
  • CIGS film 9 may contain a CIGS compound alone, but may contain a CdTe compound, a CIS compound, a silicon compound, a CZTS compound, and the like.
  • a transparent conductive film 13 of ZnO or ITO is provided via a CdS (cadmium sulfide) or ZnS (zinc sulfide) layer as the buffer layer 11.
  • An extraction electrode 15 such as an electrode (aluminum electrode) is provided.
  • An antireflection film may be provided at a necessary place between these layers.
  • an antireflection film 17 is provided between the transparent conductive film 13 and the extraction electrode 15.
  • a cover glass 19 is provided on the extraction electrode 15, and if necessary, the extraction electrode 15 and the cover glass 19 are sealed with resin or bonded with a transparent resin for bonding.
  • the cover glass 19 may not be provided.
  • the end of the photoelectric conversion layer or the end of the solar cell may be sealed.
  • the material for sealing include the same material as the glass substrate according to the present embodiment, other glass, and resin.
  • a CuGa alloy layer is formed using a CuGa alloy target, and then an In layer is formed using an In target.
  • An In—CuGa precursor film is formed.
  • the film formation temperature is not particularly limited, but can usually be room temperature.
  • the composition of the precursor film has a Cu / (Ga + In) ratio (atomic ratio) of 0.7 to 0.95 and a Ga / (Ga + In) ratio (atomic ratio) of 0.1 to 0.5, as measured by fluorescent X-ray. It is preferable that This composition can be obtained by adjusting the film thicknesses of the CuGa alloy layer and the In layer.
  • the precursor film is heat-treated using an RTA (Rapid Thermal Annealing) apparatus.
  • RTA Rapid Thermal Annealing
  • the hydrogen selenide mixed atmosphere preferably contains 1 to 20% by volume of hydrogen selenide in an inert gas such as argon or nitrogen.
  • the hydrogen selenide mixed atmosphere is replaced with a hydrogen sulfide mixed atmosphere, and further held at 200 to 700 ° C. for 1 to 120 minutes to grow CIGS crystals, thereby forming a CIGS film.
  • the hydrogen sulfide mixed atmosphere preferably contains 1 to 30% by volume of hydrogen sulfide in an inert gas such as argon or nitrogen.
  • the thickness of the CIGS film is preferably 1 to 5 ⁇ m.
  • the glass substrate according to the present embodiment can be used for glass substrates for display devices such as glass substrates for LCD panels, glass substrates for plasma display panels, and glass substrates for inorganic and organic electroluminescence display panels. Can be used.
  • the display device preferably includes the glass substrate according to the above-described embodiment and the display device member formed on the first surface of the glass substrate.
  • Examples of the display device member include an array and a color filter included in the LCD panel.
  • a transparent electrode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and the like included in the OLED can be given.
  • ⁇ Test of Na 2 O content ratio of SO 2 treated surface relative to glass substrate a glass substrate suitable for a glass substrate for a CIGS solar cell is prepared, and SO 2 gas is sprayed on the surface of the glass substrate (hereinafter sometimes referred to as an SO 2 treatment surface), and then the inside of the glass substrate is applied.
  • SO 2 treatment surface SO 2 gas is sprayed on the surface of the glass substrate (hereinafter sometimes referred to as an SO 2 treatment surface), and then the inside of the glass substrate is applied.
  • the Na 2 O content ratio on the SO 2 treated surface was evaluated.
  • Table 1 shows the glass compositions of Examples 1 to 6. Each component is represented by an oxide-based mass percentage display at a depth of 5000 nm or more from the surface of the glass substrate.
  • the raw material of each component was prepared so that it might become a glass composition shown in Table 1.
  • Na 2 SO 4 as a clarifier was added to the raw material so as to be 0.4 parts by mass in terms of SO 3 .
  • the raw material after the sulfate addition was placed in a platinum crucible and heated at a temperature of 1600 ° C. for 3 hours to dissolve.
  • a platinum stirrer was inserted into a platinum crucible and stirred for 1 hour to homogenize the glass.
  • the molten glass was poured out and cooled after being formed into a plate shape.
  • grinding was performed to a size of 30 ⁇ 30 mm and a thickness of 1.1 mm, and both sides of 30 ⁇ 30 mm were mirror-finished and washed.
  • the glass substrates of Examples 1 to 5 were subjected to SO 2 treatment in the electric furnace, simulating the drawing from the float forming furnace and the slow cooling in the slow cooling furnace, and then taken out from the electric furnace and cooled to room temperature.
  • the SO 2 treatment was performed by blowing SO 2 gas from the surface of the glass substrate (SO 2 treatment surface).
  • the SO 2 treatment conditions A to E of Examples 1 to 5 are as shown in Table 1, and details are shown below.
  • the glass substrate was removed by grinding with a water slurry of cerium oxide. After removal, cleaning was performed by ultrasonic cleaning in ethanol.
  • the average thermal expansion coefficient, glass transition temperature (Tg) of the glass substrate thus obtained, and the Na 2 O content ratio of the SO 2 treated surface with respect to the inside of the glass substrate were evaluated. The results are also shown in Table 1.
  • Tg Glass transition temperature
  • Ratio of Na 2 O content of the SO 2 treated surface with respect to the glass substrate inside The amount of Na 2 O (% by mass) of the glass substrate was measured using a fluorescent X-ray measuring apparatus (“RIX3000” manufactured by Rigaku Corporation) at a tube voltage of 50 kV and a current of 50 mA, and then glass. The substrate was measured, and the amount of Na 2 O (mass%) was quantified by a calibration curve method. Na 2 O amount of SO 2 treated surface of the glass substrate (wt%), the surface of the glass substrate (SO 2 treated surface) was measured by fluorescence X-ray measuring apparatus, Na 2 O weight in the range from the surface to about 3000nm (Mass%) was measured and determined as the average content.
  • RIX3000 fluorescent X-ray measuring apparatus
  • the amount of Na 2 O (% by mass) inside the glass substrate is determined by grinding the glass from the surface of the glass substrate (SO 2 treated surface) to a depth of 5000 nm by grinding with an aqueous slurry of cerium oxide, and the surface of the glass substrate after grinding. To about 3000 nm, the amount of Na 2 O (mass%) was measured and determined as the average content. Na 2 O amount ratio of SO 2 treated surface to the glass substrate inside, from the measurement result, (Na 2 O content of SO 2 treated surface of a glass substrate (wt%)) / (Na 2 O content of the glass substrate ( Mass%)).
  • the glass substrate surface was subjected to SO 2 treatment, and the amount of Na 2 O on the glass substrate surface (SO 2 treated surface) decreased compared to the inside of the glass substrate.
  • the amount of Na 2 O on the surface of the glass substrate is small, when a thin film is formed on the surface of the glass substrate, the amount of Na atoms diffused from the glass substrate surface to the thin film is determined from the amount of Na 2 O originally contained in the glass substrate. This is less than the expected amount of diffusion of Na atoms. In order to reduce this difference, it is very effective to bring the composition of the glass surface close to the composition inside the glass substrate.
  • Example 5 the reactivity between the SO 2 gas and the glass substrate surface was weakened by the SO 2 treatment condition E, and a decrease in the amount of Na 2 O on the glass substrate surface after the SO 2 treatment could be prevented.
  • the Na 2 O content ratio of the SO 2 treated surface to the inside of the glass substrate is 0.85.
  • the SO 2 treatment condition E of Example 5 the low temperature, the low SO 2 concentration, and the short time are comprehensively compared with the SO 2 treatment conditions A to D of Examples 1 to 4.
  • Example 6 by removing the depth 5000nm from the SO 2 treated surface of the glass substrate after SO 2 treatment, and removing a layer Na atoms are eliminated, Na 2 O of the glass substrate surface after removal of glass It becomes the same as the inside of the substrate, and the Na 2 O content ratio of the SO 2 treated surface (ie, the surface after removal) to the inside of the glass substrate is 1.
  • the amount of Na atoms diffused from the glass substrate after removal into the thin film is the amount of Na atoms expected from the amount of Na 2 O contained as the original composition of the glass substrate. And the same level.
  • Example 5 and Example 6 are suitable for using as a 1st surface of a glass substrate.
  • the SO 2 treated surface of the glass substrate of Example 5 and the surface after removal of the glass substrate of Example 6 can be preferably used as the CIGS film forming surface of the glass substrate for CIGS solar cells.
  • the amount of Na 2 O on the surface of the glass substrate is small, the amount of Na atoms floating in the atmosphere from the surface of the glass substrate can be reduced.
  • the film characteristics may be non-uniform.
  • Examples 1 to 4 are suitable for use as the second surface of the glass substrate.
  • the SO 2 treated surface of the glass substrate of Examples 1 to 4 can be preferably used as the non-formation surface of the CIGS film of the glass substrate for CIGS solar cell.
  • ⁇ Test of diffusion ratio of Na atoms from glass substrate to CIGS film> a glass substrate suitable for a glass substrate for CIGS solar cells is produced, SO 2 gas is blown onto the second surface (back surface) of the glass substrate, and then Na 2 on the first surface (front surface) with respect to the inside of the glass substrate.
  • the O amount ratio was measured, and further, a CIGS film was formed on the first surface (front surface) of the glass substrate, and the diffusion amount ratio of Na atoms from the glass substrate to the CIGS film was evaluated.
  • the Na atom concentration ratio of the first surface (surface layer) relative to the inside of the glass substrate was measured.
  • Table 2 shows the glass compositions of Examples 7-12. Each component is represented by an oxide-based mass percentage display at a depth of 5000 nm or more from the surface of the glass substrate.
  • the raw material of each component was prepared so that it might become a glass composition shown in Table 2.
  • Na 2 SO 4 as a clarifier was added to the raw material so as to be 0.4 parts by mass in terms of SO 3 .
  • the raw material after the sulfate addition was placed in a platinum crucible and heated at a temperature of 1600 ° C. for 3 hours to dissolve.
  • a platinum stirrer was inserted into a platinum crucible and stirred for 1 hour to homogenize the glass.
  • the molten glass was poured out and cooled after being formed into a plate shape.
  • grinding was performed to a size of 30 ⁇ 30 and a thickness of 1.1 mm, and both surfaces of 30 ⁇ 30 mm were mirror-finished and washed.
  • the glass substrate obtained was subjected to SO 2 treatment in an electric furnace, simulating the drawing from the float forming furnace and the slow cooling in the slow cooling furnace, and then taken out from the electric furnace and cooled to room temperature.
  • the SO 2 treatment was performed by blowing SO 2 gas from the back surface of the glass substrate.
  • the SO 2 treatment conditions were a glass surface temperature of 300 to 750 ° C., an SO 2 concentration of 0.01 to 10 (volume)%, and a treatment time of 1 to 15 minutes. Within the range of the SO 2 treatment conditions, the glass substrate surface was adjusted to have the physical property values shown in Table 2.
  • Example 11 after the glass substrate was treated with SO 2 , a layer having a depth of 5000 nm was removed from the surface of the glass substrate.
  • the glass substrate was removed by grinding with a water slurry of cerium oxide. After removal, washing was performed by ultrasonic washing in water and ethanol.
  • CIGS films for solar cells were formed on the glass substrates of Examples 7 to 12 described above. At this time, the surface on which the SO 2 gas was sprayed was the second surface (back surface), the other surface was the first surface (front surface), and a CIGS film was formed on the first surface (front surface).
  • the formation of the CIGS film will be described below with reference to FIG.
  • the obtained glass substrate was processed into a size of 3 cm ⁇ 3 cm and a thickness of 1.1 mm to obtain a glass substrate.
  • a molybdenum film (Mo) 7 was formed as a back electrode layer on the glass substrate 5 using a sputtering apparatus. Film formation was performed at room temperature to obtain a Mo film 7 having a thickness of 500 nm.
  • CIGS film 9 was formed on Mo film 7.
  • a CuGa alloy layer is formed using a CuGa alloy target, and then an In layer is formed using an In target.
  • An In—CuGa precursor film was formed. Film formation was performed at room temperature. The thickness of each layer is set so that the composition of the precursor film measured by fluorescent X-ray is Cu / (Ga + In) ratio (atomic ratio) is 0.8 and Ga / (Ga + In) ratio (atomic ratio) is 0.25. Thus, a precursor film having a thickness of 650 nm was obtained.
  • the precursor film was mixed with argon and hydrogen selenide mixed atmosphere (hydrogen selenide is 5% by volume with respect to argon) and hydrogen sulfide mixed atmosphere (hydrogen sulfide is 5 volumes with respect to argon) using an RTA (Rapid Thermal Annealing) apparatus. %).
  • holding was performed at 500 ° C. for 10 minutes in a hydrogen selenide mixed atmosphere, and Cu, In, and Ga were reacted with Se.
  • the CIGS film 9 was formed by growing the CIGS crystal by holding at 580 ° C. for 30 minutes as the second stage. The thickness of the obtained CIGS film 9 was 2 ⁇ m.
  • Na atom concentration ratio of surface layer to the inside of glass substrate The Na atom concentration (atomic%) of the glass substrate is determined by using an X-ray photoelectron spectrometer (“ESCA5500” manufactured by ULVAC-PHI) while the sputter etching is performed to 100 nm with a C60 ion beam from the glass substrate surface. The Na profile in the direction was measured and obtained.
  • ESA5500 X-ray photoelectron spectrometer
  • the Na atom concentration (atomic%) on the surface of the glass substrate was determined by measuring the surface of the glass substrate with an X-ray photoelectron spectrometer and measuring the Na atomic concentration (atomic%) in the range from the surface to 100 nm (ie, the surface layer). .
  • the Na atom concentration (atomic%) inside the glass substrate was measured by measuring the glass substrate surface after grinding from the glass substrate surface to a depth of 5000 nm using an X-ray photoelectron spectrometer, and from the ground surface to 100 nm. The Na atom concentration (atomic%) in the range was measured and determined. In grinding the glass substrate, it was ground to 4000 nm with a cerium oxide water slurry, and then sputter-etched with a C60 ion beam to total a depth of 5000 nm.
  • the Na atom concentration ratio of the surface layer relative to the inside of the glass substrate was determined as (Na atom concentration of the glass substrate surface layer (atomic%)) / (Na atom concentration inside the glass substrate (atomic%)).
  • “Diffusion ratio of Na atoms from glass substrate to CIGS film” The ratio of the amount of Na atoms diffused from the glass substrate to the CIGS film was determined as the ratio of the amount of Na atoms diffused from the glass substrate surface to the amount of Na atoms diffused from the inside of the glass substrate.
  • a glass substrate in which a CIGS film was formed on the surface of the glass substrate as described above after the SO 2 treatment on the back surface of the glass substrate as described above was used.
  • the amount of Na atoms diffused into the CIGS film was measured by secondary ion mass spectrometry.
  • ADEPT 1010 manufactured by ULVAC-PHI was used as the measuring device.
  • the amount of Na diffusion into the CIGS film was measured by secondary ion mass spectrometry in the same manner as described above.
  • the glass substrate was ground by grinding with a water slurry of cerium oxide.
  • the ratio of the amount of Na atoms diffused from the glass substrate to the CIGS film was determined from the above results as (the amount of Na atoms diffused from the glass substrate surface) / (the amount of Na atoms diffused from the inside of the glass substrate).
  • Example 7 Example 8, Example 11 and Example 12
  • the Na 2 O amount ratio of the surface relative to the inside of the glass substrate was 0.80 or more, and the diffusion amount ratio of Na atoms from the glass substrate to the CIGS film was high.
  • “surface Na 2 O amount ratio relative to the inside of the glass substrate” represents the ratio of Na 2 O amount of the SO 2 treated surface to the inside of the glass substrate.
  • the diffusion amount of Na atoms from the glass substrate to the CIGS film could be close to the expected diffusion amount of Na atoms from the amount of Na 2 O contained in the composition of the glass substrate.
  • Example 11 since the CIGS film was prepared after grinding the glass substrate, the diffusion ratio of Na atoms from the glass substrate was 1.00. This is because the Na atom diffusion amount ratio is the ratio of the surface Na atom diffusion amount to the inside of the glass substrate.
  • the diffusion amount ratio of Na atoms from the glass substrate surface to the CIGS film is 0.50 or more.
  • the diffusion amount of Na atoms from the glass substrate surface to the CIGS film is more than half of the diffusion amount of Na atoms expected from the composition of the glass substrate (that is, the diffusion amount of Na atoms in the glass). It can be seen that the amount is secured.
  • Example 9 and Example 10 the Na 2 O amount ratio of the surface (SO 2 treated surface) with respect to the inside of the glass substrate is less than 0.80, and the diffusion amount ratio of Na atoms from the glass substrate to the CIGS film is significantly reduced. did.
  • the Na atom concentration ratio of the surface layer relative to the inside of the glass substrate is measured by an X-ray photoelectron spectrometer, and the influence of the Na atom concentration on the surface layer (up to about 100 nm) of the glass substrate can be evaluated.
  • the Na atom concentration ratio of the surface layer relative to the inside of the glass substrate was 0.5 or more, and the diffusion amount ratio of Na atoms from the glass substrate to the CIGS film was high.
  • Example 9 and Example 10 the Na atom concentration ratio of the surface layer with respect to the inside of the glass substrate was as low as 0.28, and the diffusion amount ratio of Na atoms from the glass substrate to the CIGS film was significantly reduced.
  • the diffusion of Na atoms from the glass substrate surface to the CIGS film is a physical phenomenon near the surface layer of the glass substrate. It can be seen that this is particularly caused by the Na atom concentration in the surface layer of the substrate.
  • the surface of the glass substrate was cleaned after polishing, a Mo film was formed on the cleaning surface, and the adhesion test was performed.
  • the glass substrate after polishing and cleaning is obtained by cleaning the surface of the glass substrate after polishing. Since abrasive grains or water glass may remain on the surface of the polished glass substrate, it is removed by surface cleaning.
  • acid cleaning was performed using a semi-clean DS-S (organic acid cleaning agent, manufactured by Yokohama Oil & Fats Co., Ltd.) diluted to a concentration of 2% by mass.
  • a Mo film was formed as a back electrode layer on the polished or cleaned surface of the glass substrate.
  • the Mo film was 0.5 ⁇ m thick.
  • a cross cut with an interval of 1 mm was made on the Mo film formed on the glass substrate using a dedicated jig, and an adhesive tape (CT-24, manufactured by Nichiban Co., Ltd.) was attached thereon.
  • CT-24 manufactured by Nichiban Co., Ltd.
  • 2A to 2B show photographs of the glass substrate surface after the adhesive tape is peeled off.
  • FIG. 2A is a photograph of the glass substrate surface after polishing
  • FIG. 2B is a photograph of the glass substrate surface after polishing and cleaning.
  • the adhesion between the glass substrate and the Mo film was lowered. This is because, when the polished surface is used as it is, polishing-derived residues such as abrasive grains and water glass are adhered to the surface of the glass substrate. Thus, in the state where the residue derived from polishing adheres to the glass substrate surface, the adhesion between the Mo film formed directly on the glass substrate and the glass substrate may be reduced.
  • the adhesion between the glass substrate and the Mo film could be improved by washing even after polishing. By removing the residue derived from polishing by washing, the adhesion between the glass substrate and the Mo film could be improved.
  • Average surface roughness of glass substrate (Ra)
  • the average surface roughness (Ra) of the next glass substrate was measured.
  • “average surface roughness (Ra)” refers to a value measured by a method based on SEMID 7-94 “Measurement method of surface roughness of FPD glass substrate”, and average surface roughness of the evaluation surface of the glass substrate. (Ra) is pointed out and the end face of the glass substrate is not considered.
  • the Ra of the glass substrate was low in the non-polished state because there was no residue of polishing marks and scratches, abrasive grains derived from polishing, water glass, etc. on the surface. On the other hand, when the glass substrate was polished, Ra was increased, and Ra was decreased by cleaning the polished surface thereafter.
  • the amount of residual abrasive grains of the next glass substrate was measured.
  • the amount of residual abrasive grains was measured by the ICP-MS method (“ELAN DRCII” manufactured by Perkin Elmer).
  • the adhesion between the glass substrate and the Mo film can be improved by washing the glass substrate after polishing as compared with after polishing. Further, the lower the Ra of the glass substrate, the higher the adhesion between the glass substrate and the Mo film. Further, the smaller the amount of residual abrasive on the glass substrate, the higher the adhesion between the glass substrate and the Mo film.
  • the glass substrate of the present invention can be preferably used for a glass substrate for a solar cell, particularly a glass substrate for a CIGS solar cell.
  • a glass substrate for a solar cell particularly a glass substrate for a CIGS solar cell.
  • it can be used for a glass substrate for solar cells and / or a cover glass for solar cells. Thereby, a solar cell with good power generation efficiency can be provided.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Glass Compositions (AREA)
  • Surface Treatment Of Glass (AREA)
  • Photovoltaic Devices (AREA)

Abstract

　L'invention porte sur un substrat de verre sur lequel un film mince peut être formé avec une quantité à effet dopant d'atomes de métaux alcalins, contrôlée avec une grande précision. Elle concerne un substrat de verre dans lequel le rapport entre la quantité de Na2O dans la surface d'une première face du substrat de verre, et la quantité de Na2O à une profondeur de 5000 nm à partir de la première face du substrat de verre, est de 0,8 ou plus, et le rapport entre la quantité de Na2O dans la surface d'une deuxième face du substrat de verre et la quantité de Na2O à une profondeur de 5000 nm à partir de la deuxième face du substrat de verre est inférieur à 0,8, en termes de quantité de Na2O (% en masse) telle que mesurée par les rayons X fluorescents.
PCT/JP2014/063219 2013-05-20 2014-05-19 Substrat de verre et cellule solaire au cigs Ceased WO2014189003A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017047366A1 (fr) * 2015-09-18 2017-03-23 旭硝子株式会社 Substrat de verre pour cellules solaires, et cellule solaire
JP2021088468A (ja) * 2019-12-02 2021-06-10 日本電気硝子株式会社 積層基板およびその製造方法

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Publication number Priority date Publication date Assignee Title
JPS63159238A (ja) * 1986-12-04 1988-07-02 グラヴルベル 脱アルカリシートガラスおよびその製造方法
JPH11278875A (ja) * 1998-03-26 1999-10-12 Asahi Glass Co Ltd ガラスの表面処理方法
WO2011068225A1 (fr) * 2009-12-04 2011-06-09 旭硝子株式会社 Plaque de verre et son procédé de fabrication
WO2012014854A1 (fr) * 2010-07-26 2012-02-02 旭硝子株式会社 SUBSTRAT EN VERRE POUR UNE BATTERIE SOLAIRE Cu-In-Ga-Se ET UTILISATION DE CETTE BATTERIE SOLAIRE
WO2013011860A1 (fr) * 2011-07-19 2013-01-24 日本電気硝子株式会社 Base de verre
JP2013063880A (ja) * 2011-09-20 2013-04-11 Nippon Electric Glass Co Ltd ガラス板

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63159238A (ja) * 1986-12-04 1988-07-02 グラヴルベル 脱アルカリシートガラスおよびその製造方法
JPH11278875A (ja) * 1998-03-26 1999-10-12 Asahi Glass Co Ltd ガラスの表面処理方法
WO2011068225A1 (fr) * 2009-12-04 2011-06-09 旭硝子株式会社 Plaque de verre et son procédé de fabrication
WO2012014854A1 (fr) * 2010-07-26 2012-02-02 旭硝子株式会社 SUBSTRAT EN VERRE POUR UNE BATTERIE SOLAIRE Cu-In-Ga-Se ET UTILISATION DE CETTE BATTERIE SOLAIRE
WO2013011860A1 (fr) * 2011-07-19 2013-01-24 日本電気硝子株式会社 Base de verre
JP2013063880A (ja) * 2011-09-20 2013-04-11 Nippon Electric Glass Co Ltd ガラス板

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017047366A1 (fr) * 2015-09-18 2017-03-23 旭硝子株式会社 Substrat de verre pour cellules solaires, et cellule solaire
JPWO2017047366A1 (ja) * 2015-09-18 2018-07-05 旭硝子株式会社 太陽電池用ガラス基板及び太陽電池
JP2021088468A (ja) * 2019-12-02 2021-06-10 日本電気硝子株式会社 積層基板およびその製造方法

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