WO2015076208A1 - Feuille de verre - Google Patents

Feuille de verre Download PDF

Info

Publication number
WO2015076208A1
WO2015076208A1 PCT/JP2014/080242 JP2014080242W WO2015076208A1 WO 2015076208 A1 WO2015076208 A1 WO 2015076208A1 JP 2014080242 W JP2014080242 W JP 2014080242W WO 2015076208 A1 WO2015076208 A1 WO 2015076208A1
Authority
WO
WIPO (PCT)
Prior art keywords
glass
less
glass plate
solar cell
glass substrate
Prior art date
Application number
PCT/JP2014/080242
Other languages
English (en)
Japanese (ja)
Inventor
伸一 安間
裕 黒岩
朋美 安部
川本　泰
Original Assignee
旭硝子株式会社
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 旭硝子株式会社 filed Critical 旭硝子株式会社
Priority to JP2015549132A priority Critical patent/JPWO2015076208A1/ja
Publication of WO2015076208A1 publication Critical patent/WO2015076208A1/fr

Links

Images

Classifications

    • 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

Definitions

  • the present invention relates to a glass plate, and more particularly to a glass plate suitably used for a compound solar cell substrate.
  • a semiconductor film is formed on a glass substrate as a photoelectric conversion layer.
  • semiconductors used in solar cells 11-13 and 11-16 compound semiconductors having a chalcopyrite crystal structure, and cubic or hexagonal 12-16 group compound semiconductors have wavelengths from visible to near infrared. It has a large absorption coefficient for a range of light. Therefore, it is expected as a material for high-efficiency thin film solar cells.
  • Typical examples include Cu (In, Ga) Se 2 (hereinafter sometimes referred to as CIGS) and CdTe.
  • soda lime glass is used as a substrate and solar cells are obtained because they are inexpensive and have an average thermal expansion coefficient close to that of CIGS compound semiconductors and CdTe semiconductors.
  • glass materials that can withstand high heat treatment temperatures have been proposed as glass substrates for CIGS solar cells (see Patent Documents 1 to 3).
  • the photoelectric conversion efficiency of a 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 CIGS photoelectric conversion layer hereinafter also referred to as “CIGS layer”
  • the glass substrate is heat-treated in the CIGS layer forming step, so that Na atoms contained in the glass substrate are converted into the glass substrate. It diffuses from the surface to the CIGS layer.
  • the carrier concentration of the CIGS layer is increased and the photoelectric conversion rate can be increased.
  • Patent Documents 4 and 5 propose that in a glass plate for a solar cell, Na 2 O is an effective component for the growth of chalcopyrite crystals in the composition of the glass substrate and increases the photoelectric conversion efficiency.
  • Patent Documents 1 to 3 propose glass compositions having a relatively high annealing point, but the inventions described in Patent Documents 1 to 3 do not necessarily have high power generation efficiency. For example, it is desired to increase the power generation efficiency by diffusion of Na from the glass substrate to the photoelectric conversion layer together with the heat resistance of the glass substrate.
  • Patent Document 1 an object is to prevent the deformation and distortion of the glass substrate by controlling the annealing point and the thermal expansion coefficient, but power generation efficiency has not been studied in terms of the amount of Na diffusion.
  • Patent Document 2 Na 2 O is blended for diffusion of Na, but the blending amount of Na 2 O is limited to prevent a decrease in strain point (see paragraph 0027). Further, there is a problem that in Patent Document 2, the strain point from the viewpoint amount of Al 2 O 3 is less lowered.
  • Patent Document 3 the blending amount of Na 2 O is limited in consideration of the strain point, the thermal expansion coefficient, and the warp of the glass substrate, but the power generation efficiency is not examined from the point of Na diffusion amount.
  • Patent Document 4 proposes that Na 2 O is added while BaO is less than 1% by mass, so that the mobility of sodium ions is advantageously acted on to increase the efficiency of the solar cell.
  • the mobility of the sodium ions by Na 2 O while increasing the mobility of the sodium ions by Na 2 O, heat resistance and devitrification resistance of the glass substrate is increased only Na 2 O may be reduced.
  • Patent Document 5 Na 2 O and K 2 O is mentioned as a component to increase the photoelectric conversion efficiency.
  • the blending amount of Na 2 O and K 2 O is limited in consideration of the strain point, the thermal expansion coefficient, and the devitrification characteristics, there is a problem that the photoelectric conversion efficiency cannot be sufficiently increased.
  • An object of the present invention is to provide a glass plate that obtains excellent heat resistance and devitrification characteristics, and increases power generation efficiency by increasing the amount of Na diffusion when used as a compound solar cell substrate.
  • SiO 2 is 45 to 65%
  • Al 2 O 3 is 9 to 17%
  • B 2 O 3 is 0 to 1%
  • MgO is 0 to 2%
  • ZrO 2 2-6% Na 2 O 5-10%
  • MgO + CaO + SrO + BaO is 15 to 30%
  • 2 (SrO—BaO) + (K 2 O—Na 2 O) is 11.5% or less.
  • the glass plate of the present invention excellent heat resistance and devitrification characteristics can be obtained, and the amount of Na diffusion can be increased to increase power generation efficiency. Moreover, the solar cell using this can be provided.
  • FIG. 1 is a cross-sectional view schematically showing an example of the CIGS solar cell of the present embodiment.
  • FIG. 2 is a cross-sectional view schematically showing an example of the CdTe solar cell of the present embodiment.
  • Glass plate according to the present embodiment by mass percentage based on the following oxides, the SiO 2 45 - 65%, the Al 2 O 3 9 ⁇ 17% , the B 2 O 3 0 ⁇ 1% , MgO 0 to 2%, CaO 1-12%, SrO 1-15%, BaO 1.4-12%, ZrO 2 2-6%, Na 2 O 5-10%, K 2 O 2-10 %, MgO + CaO + SrO + BaO is 15 to 30%, and 2 (SrO—BaO) + (K 2 O—Na 2 O) is 11.5% or less.
  • the content ratio of the glass composition component is expressed in terms of mass percentage (mass%), and these are also simply referred to as%.
  • the glass transition temperature and the devitrification characteristics can be set to the preferred ranges shown below by being in the above composition range.
  • the diffusion amount of Na to the photoelectric converting layer formed on a glass substrate from a glass substrate can be increased, and the efficiency of a solar cell can be improved. it can.
  • it can be set as the preferable range which shows a viscosity characteristic, an average thermal expansion coefficient, and a density by being the said composition range below.
  • the glass transition temperature (Tg) of the glass plate of this embodiment is preferably higher than the glass transition temperature of ordinary soda lime glass that is widely used in general, and is specifically preferably 640 ° C. or higher. .
  • the glass transition temperature (Tg) is more preferably 645 ° C. or higher, and more preferably 650 ° C. or higher in order to ensure the formation of the CIGS layer at a high temperature. 655 ° C. or higher is particularly preferable.
  • the temperature be 750 ° C. or lower. More preferably, it is 720 degrees C or less, Most preferably, it is 690 degrees C or less.
  • the relationship between the temperature (T4) at which the viscosity is 10 4 dPa ⁇ s and the devitrification temperature (TL) is preferably T4 ⁇ TL> 0.
  • T4-TL is 0 ° C. or lower, devitrification is likely to occur during the formation of the sheet glass, and it may be difficult to form the glass sheet.
  • T4-TL is more preferably 5 ° C. or higher, and further preferably 10 ° C. or higher.
  • the devitrification temperature is the maximum temperature at which crystals are not generated on the glass surface and inside when the glass is held at a specific temperature for 17 hours.
  • T4 is preferably 1230 ° C. or lower. T4 is more preferably 1220 ° C. or less, and further preferably 1210 ° C. or less.
  • the glass plate of the present embodiment has a temperature (T2) at which the viscosity becomes 10 2 dPa ⁇ s is 1650 ° C. or less in consideration of the solubility of the glass, that is, the improvement of homogeneity and the improvement of productivity. Is preferred. T2 is more preferably 1630 ° C. or lower, and further preferably 1620 ° C. or lower.
  • the average thermal expansion coefficient of the glass plate of this embodiment at 50 to 350 ° C. is preferably 70 ⁇ 10 ⁇ 7 to 90 ⁇ 10 ⁇ 7 / ° C.
  • the glass plate of the present embodiment is used as a glass substrate of a CIGS solar cell, if it is less than 70 ⁇ 10 ⁇ 7 / ° C. or more than 90 ⁇ 10 ⁇ 7 / ° C., the difference in thermal expansion from the CIGS layer becomes too large, and the CIGS layer
  • the CIGS layer may be peeled off during or after the film formation. More preferably, it is 85 ⁇ 10 ⁇ 7 / ° C. or less.
  • the glass plate of the present embodiment preferably has a density of 2.85 g / cm 3 or less.
  • the density is more preferably 2.83 g / cm 3 or less.
  • when manufacturing a glass plate by normal methods, such as a float process and a fusion method when it considers setting it as the glass composition range which can be manufactured easily, it is 2.4 g / cm ⁇ 3 > or more normally.
  • the glass plate according to the present embodiment has the above composition, so that the glass transition temperature is high and excellent heat resistance is obtained, and the T4-TL is large and excellent devitrification characteristics are obtained. Since the amount of diffusion is large, the power generation efficiency can be increased. Furthermore, since the viscosity characteristics, average thermal expansion coefficient, and density of T4 and T2 are in an appropriate range, solubility and moldability can be improved during production of the glass substrate. Accordingly, the glass plate according to the present embodiment has various characteristics in a well-balanced manner, and can be preferably used as a glass substrate for CIGS solar cells or CdTe solar cells.
  • the reason for limiting to the above composition is as follows.
  • SiO 2 is a component that forms a glass skeleton. If it is less than 45% by mass, the heat resistance and chemical durability of the glass plate are lowered, and the average thermal expansion coefficient may be increased. Preferably it is 47% or more, more preferably 49% or more, and particularly preferably 51% or more. However, if it exceeds 65%, the high-temperature viscosity of the glass increases, which may cause a problem that the solubility deteriorates. Preferably it is 63% or less, More preferably, it is 62% or less, More preferably, it is 61% or less, Especially preferably, it is 59% or less, More preferably, it is 57.5% or less.
  • Al 2 O 3 increases the glass transition temperature, improves weather resistance (solarization), heat resistance and chemical durability, and increases Young's modulus. There exists a possibility that glass transition temperature may fall that the content is less than 9%. Moreover, there exists a possibility that an average thermal expansion coefficient may increase. More preferably, it is 9.5% or more, more preferably 10% or more, particularly preferably 11% or more, and further preferably 12% or more.
  • the high-temperature viscosity of the glass is increased, and the solubility may be deteriorated. Further, the devitrification temperature is increased, and the moldability may be deteriorated.
  • it is 16% or less, More preferably, it is 15% or less.
  • B 2 O 3 may be contained up to 1% in order to improve the solubility. If the content exceeds 1%, the glass transition temperature may decrease, or the average thermal expansion coefficient may decrease, which is not preferable for the process of forming a photoelectric conversion layer. Moreover, devitrification temperature rises and it becomes easy to devitrify, and plate glass shaping
  • the content is preferably 0.5% or less. More preferably, it does not contain substantially.
  • “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.
  • MgO has the effect of lowering the viscosity at the time of melting the glass and promoting the melting, so it may be contained up to 2%. If it is 2% or less, a desired average thermal expansion coefficient can be obtained. Further, it is preferable that the devitrification temperature does not increase. Preferably it is 1.5% or less, More preferably, it is 1.0%, More preferably, it is 0.5% or less, Most preferably, it is 0.1% or less.
  • CaO is contained in an amount of 1 to 12% because it has the effect of lowering the viscosity of the glass during melting and promoting the melting. Preferably it is 2% or more, More preferably, it is 3% or more, More preferably, it is 4% or more, Most preferably, it is 5% or more. However, if it exceeds 12%, the average thermal expansion coefficient of the glass plate may increase. Moreover, when using as a glass substrate for solar cells, sodium (Na) is difficult to move in the glass substrate, and power generation efficiency may be reduced. Preferably it is 11% or less, More preferably, it is 10% or less, More preferably, it is 9% or less, Most preferably, it is 8.5% or less.
  • SrO is contained in an amount of 1 to 15% because it has the effect of reducing the viscosity at the time of melting the glass and promoting the melting. Moreover, when it uses in the glass substrate, when using the glass plate of this embodiment as a glass substrate of a CIGS solar cell, there exists an effect which accelerates
  • BaO has an effect of lowering the viscosity at the time of melting the glass and promoting the melting, so it is contained in an amount of 1.4 to 12%. Moreover, when using the glass plate of this embodiment as a glass substrate of a CIGS solar cell by containing BaO in a glass plate, there exists an effect which accelerates
  • ZrO 2 has an effect of reducing the viscosity at the time of melting the glass and promoting the melting, so it is contained at 2% or more. If it is 6% or less, the power generation efficiency is good, the devitrification temperature is not increased and devitrification does not occur, and plate glass molding is easy. 5.5% or less is preferable, 5% or less is more preferable, and 4.6% or less is more preferable. Further, it is preferably 2.3% or more, more preferably 2.5% or more, further preferably 3% or more, and particularly preferably 3.5% or more.
  • Na 2 O is a component for contributing to the improvement of power generation efficiency of the CIGS solar cell when using the glass plate of the present embodiment as a glass substrate of the CIGS solar cell, and is an essential component. Further, it has the effect of lowering the viscosity at the glass melting temperature and facilitating melting, so it is contained in an amount of 5 to 10%.
  • Sodium (Na) diffuses into the CIGS layer formed on the glass substrate to increase the power generation efficiency. However, if the content is less than 5%, Na diffusion to the CIGS layer on the glass substrate becomes insufficient, resulting in power generation efficiency. May be insufficient.
  • the content is preferably 5.3% or more, more preferably 5.5% or more, and particularly preferably 5.6% or more.
  • the Young's modulus may be reduced.
  • the content is preferably 9% or less, more preferably 8% or less, and even more preferably 7.5% or less.
  • K 2 O is contained in an amount of 2 to 10% because it has an effect of promoting the diffusion of sodium (Na) into the CIGS layer on the glass substrate. However, if it exceeds 10%, the glass transition temperature is lowered, the average thermal expansion coefficient is increased, and the specific gravity may be increased.
  • the content is preferably 2.5% or more, and more preferably 3% or more. Further, it is preferably 9% or less, more preferably 8% or less, further preferably 7% or less, and particularly preferably 6% or less.
  • TiO 2 When TiO 2 is contained, the devitrification temperature rises, so it is preferable not to contain it.
  • the glass plate of this embodiment is easy to produce a foam layer on the surface of the molten glass when the glass substrate is manufactured, as compared with normal soda lime glass. When the foam layer is generated, the temperature of the molten glass does not rise, it becomes difficult to clarify, and the productivity tends to deteriorate.
  • a titanium compound may be supplied as an antifoaming agent to the foam layer generated on the surface of the molten glass. The titanium compound is taken into the molten glass and exists as TiO 2 .
  • This titanium compound may be an inorganic titanium compound (titanium tetrachloride, titanium oxide, etc.) or an organic titanium compound.
  • examples of the organic titanium compound include titanic acid esters or derivatives thereof, titanium chelates or derivatives thereof, titanium acylates or derivatives thereof, and oxalic acid titanates.
  • TiO 2 is allowed to be contained in the glass substrate at 0.2% or less as an impurity.
  • MgO + CaO + SrO + BaO total content of MgO, CaO, SrO and BaO
  • MgO, CaO, SrO and BaO are contained in an amount of 15% or more in terms of the total content of MgO, CaO, SrO and BaO from the viewpoint of reducing the viscosity at the time of melting the glass and promoting the melting.
  • the total amount of these alkaline earth oxides exceeds 30%, the devitrification temperature rises and the moldability may be deteriorated. 16% or more is preferable, and 17% or more is more preferable.
  • 26% or less is preferable, 25% or less is more preferable, 23% or less is further more preferable, and 21% or less is especially preferable.
  • SrO + BaO total content of SrO and BaO: Both SrO and BaO have the effect of increasing the diffusion of sodium that diffuses into the CIGS layer formed on the glass substrate and increases the power generation efficiency while maintaining the heat resistance of the glass plate. Therefore, it is preferable to contain in the range which SrO + BaO becomes 6% or more. More preferably, it is 6.5% or more, further preferably 7% or more, and particularly preferably 7.5% or more. However, if SrO + BaO is too large, the specific gravity of the glass is increased and the strength as a glass substrate is lowered. Therefore, it is preferable to contain SrO + BaO in a range of 18% or less. More preferably, it is 17% or less, More preferably, it is 16.5% or less, Most preferably, it is 16% or less.
  • SrO—BaO (a value obtained by subtracting the BaO content from the SrO content): BaO has a larger effect of increasing the diffusion of sodium while maintaining heat resistance than SrO, so it is preferable to contain BaO in a range where SrO—BaO is 7.5% or less. More preferably, it is 7% or less, more preferably 6.5% or less, and particularly preferably 6% or less.
  • Na 2 O + K 2 O total content of Na 2 O and K 2 O
  • Increasing the proportion of Na 2 O + K 2 O in the composition has the effect of increasing the diffusion of sodium to increase the power generation efficiency by diffusing into the CIGS layer configured on the glass substrate for CIGS solar cells.
  • It is preferable that Na 2 O + K 2 O is contained within a range of 7% or more. More preferably, it is 7.5% or more, More preferably, it is 8% or more, Most preferably, it is 9% or more.
  • Na 2 O + K 2 O becomes too large, the glass transition point of the glass is lowered and the heat resistance of the glass substrate is lowered, so that Na 2 O + K 2 O is preferably contained in an amount of 15% or less. More preferably, it is 14% or less, more preferably 13.5% or less, and particularly preferably 13% or less.
  • K 2 O—Na 2 O (value obtained by subtracting the content of Na 2 O from the content of K 2 O): Since Na 2 O has a larger ratio of the effect of increasing the diffusion of sodium to the effect of decreasing the heat resistance than K 2 O, from the viewpoint of increasing the diffusion of sodium while maintaining the heat resistance, K 2 O —Na 2 O is preferably contained within a range of 2% or less. More preferably, it is 1% or less, more preferably 0% or less, particularly preferably -1.3%.
  • Glass plate of the present embodiment consists essentially of the above matrix composition (SiO 2, Al 2 O 3 , B 2 O 3, MgO, CaO, SrO, BaO, ZrO 2, Na 2 O, and K 2 O)
  • each of the following other components may be contained in an amount of 1% or less, and a total of 5% or less of these added components and the above-described TiO 2 may be contained.
  • ZnO, Li 2 O, WO 3 , Nb 2 O 5 , V 2 O 5 , Bi 2 O 3 , MoO 3 for the purpose of improving weather resistance, solubility, devitrification, ultraviolet shielding, refractive index, and the like.
  • P 2 O 5 or the like may be contained.
  • these raw materials are matrix composition raw materials so that each glass contains 1% or less of SO 3 , F, Cl, SnO 2 and 2% or less in total. You may add to. Further, in order to improve the chemical durability of the glass plate, 2% or less of Y 2 O 3 and / or La 2 O 3 may be contained in the glass.
  • the matrix composition (SiO 2, Al 2 O 3 , B 2 O 3, MgO, CaO, SrO, BaO, ZrO 2 , Na 2 O, and K 2 O) are preferably contained in an amount of 0.06 parts by mass or less in terms of Fe 2 O 3 with respect to 100 parts by mass. More preferably, it is 0.055 mass part or less, More preferably, it is 0.05 mass part or less, Most preferably, it is 0.045 mass part or less.
  • the iron oxide is preferably 0.2 parts by mass or less, more preferably 0.15 parts by mass or less in terms of Fe 2 O 3 with respect to 100 parts by mass of the mother composition. 0.12 parts by mass or less is more preferable. Further, when the content of the iron oxide is 0.01 parts by mass or more, an industrial raw material in which the mixing of the iron oxide component is unavoidable can be used.
  • examples of the iron oxide input raw material include a valve stem and iron oxide powder.
  • the glass plate of 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.
  • the glass plate of the present embodiment is not limited to being formed by the float method, and may be manufactured by forming by the fusion method.
  • the manufacturing method of the glass plate of this embodiment is demonstrated.
  • molding process are implemented similarly to the time of manufacturing the conventional glass plate.
  • the glass plate of this embodiment is an alkali containing glass substrate containing an alkali metal oxide (Na 2 O and K 2 O), SO 3 can be effectively used as a fining agent, and molding
  • a float method and a fusion method (down draw method) are suitable.
  • a float method capable of easily and stably forming a large-area glass substrate with an increase in the size of the solar cell. Is preferably used.
  • molten glass obtained by melting raw materials is formed into a plate shape.
  • raw materials are prepared so that the obtained glass substrate has the above composition, the raw materials are continuously charged into a melting furnace, and heated to 1550 to 1700 ° C. to obtain molten glass.
  • this molten glass is formed into a ribbon-like glass plate by applying, for example, a float process.
  • a cooling means after drawing the ribbon-shaped glass plate from the float forming furnace, it is cooled to room temperature by a cooling means, and after cutting, the glass plate can be obtained.
  • the glass plate by this embodiment can be preferably used as a glass substrate for solar cells, a cover glass for solar cells, and a back plate glass for solar cells.
  • a 11-13 group or 11-16 group compound semiconductor having a chalcopyrite crystal structure, or a cubic or hexagonal group 12-16 compound semiconductor can be preferably used.
  • Representative examples include CIGS compounds, CdTe compounds, CIS compounds, CZTS compounds, and the like.
  • a silicon compound, an organic compound, or the like may be used as the photoelectric conversion layer of the solar cell.
  • the glass plate by this embodiment can be preferably used for a CIGS solar cell.
  • the thickness of a glass substrate shall be 3 mm or less, More preferably, it is 2 mm or less, More preferably, it is 1.5 mm or less.
  • the method for forming the CIGS layer on the glass substrate is not particularly limited. However, since the glass plate of the present embodiment has a high glass transition temperature, the heating temperature for forming the CIGS layer is 500 to 700 ° C., preferably 550. It can be set to ⁇ 700 ° C., more preferably 580 to 700 ° C., further preferably 600 to 700 ° C., particularly preferably 620 to 700 ° C.
  • a cover glass etc. are not restrict
  • Other examples of the composition of the cover glass include ordinary soda lime glass that is widely used.
  • the thickness of a cover glass shall be 3 mm or less, More preferably, it is 2 mm or less, More preferably, it is 1.5 mm or less.
  • the method of assembling the cover glass on the glass substrate having the CIGS layer is not particularly limited, but when assembled by heating, the heating temperature is 500 to 700 ° C., preferably 600 to 700 ° C. be able to.
  • the glass plate of the present embodiment together with the glass substrate and the cover glass of the CIGS solar cell because the average thermal expansion coefficient is equivalent and thermal deformation or the like during the assembly of the solar cell does not occur.
  • the glass plate according to the present embodiment has the above characteristics, it can be preferably used for a CdTe solar cell.
  • the glass plate of the present embodiment having high glass strength is also suitably used as a glass substrate for CdTe solar cells.
  • it since it has a high glass transition temperature, it can be formed at a high temperature when forming the CdTe layer, which can contribute to the power generation efficiency of the CdTe 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.
  • the method for forming the CdTe layer on the glass substrate is not particularly limited. However, since the glass substrate of the present embodiment has a high glass transition temperature, the heating temperature for forming the CdTe layer is preferably 500 to 700 ° C. Can be set to 550 to 700 ° C, more preferably 580 to 700 ° C, still more preferably 600 to 700 ° C, and particularly preferably 620 to 700 ° C.
  • the thickness of the back plate glass is preferably 3 mm or less, more preferably 2 mm or less, and even more preferably 1.5 mm or less.
  • the method of assembling the back glass on the glass substrate having the CdTe layer is not particularly limited, but when assembled by heating, the heating temperature is 500 to 700 ° C., preferably 600 to 700 ° C. Can do.
  • the average thermal expansion coefficient is equivalent, so that thermal deformation or the like during solar cell assembly does not occur, which is preferable.
  • the CIGS solar cell of this embodiment includes a glass substrate, a cover glass, and a Cu—In—Ga—Se photoelectric conversion layer disposed between the glass substrate and the cover glass. At least one of the substrate and the cover glass is the glass plate of this embodiment.
  • FIG. 1 is a cross-sectional view schematically illustrating an example of the CIGS solar cell of the present embodiment.
  • the CIGS solar cell 1 of the present embodiment includes a glass substrate 5, a cover glass 19, and a CIGS layer 9 between the glass substrate 5 and the cover glass 19. At least one of the glass substrate 5 and the cover glass 19 is the glass plate of the present embodiment described above.
  • the glass substrate 5 is the glass plate according to the present embodiment, the effect of Na diffusion can be enhanced.
  • both the glass substrate 5 and the cover glass 19 are the glass plates according to the present embodiment, it is possible to prevent peeling and the like by matching the thermal expansion coefficients.
  • the solar cell 1 has the back electrode layer of Mo film which is the plus electrode 7 on the glass substrate 5, and has the CIGS layer 9 on it.
  • the composition of the CIGS layer, Cu (In 1-X Gax ) Se 2 can be exemplified.
  • x represents the composition ratio of In and Ga, and 0 ⁇ x ⁇ 1.
  • a transparent conductive film 13 such as ZnO, ITO, or Al doped ZnO (AZO) is provided through the buffer layer 9, and an extraction electrode such as an Al electrode (aluminum electrode) that is a negative electrode 15 is provided thereon.
  • 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 negative electrode 15.
  • a cover glass 19 may be provided on the negative electrode 15, and if necessary, the resin between the negative electrode and the cover glass may be sealed with resin or may be bonded with a transparent resin for bonding.
  • the edge part of a CIGS layer or the edge part of a solar cell may be sealed.
  • a material for sealing the same material as the glass plate of this embodiment, other glass, resin etc. are mentioned, for example. Note that the thickness of each layer of the solar cell shown in the accompanying drawings is not limited to the drawings.
  • the CIGS solar cell of the present embodiment uses the glass plate of the present embodiment as a glass substrate, and in the second stage of the CIGS layer deposition process, the CIGS layer is deposited under heating conditions of 500 ° C. or higher. High power generation efficiency can be obtained.
  • the heating temperature in the second stage is preferably 550 ° C. or higher, more preferably 580 ° C. or higher, further preferably 600 ° C. or higher, and particularly preferably 620 ° C. or higher.
  • Other processes other than the CIGS layer forming process in the CIGS solar cell manufacturing method, for example, the buffer layer and transparent conductive film layer forming process, etc., may be performed in the same manner as the normal CIGS solar cell manufacturing process. it can.
  • the CdTe solar cell of this embodiment includes a glass substrate, a back plate glass, and a CdTe photoelectric conversion layer (CdTe layer) disposed between the glass substrate and the back plate glass. At least one of the back plate glasses is the glass plate of the present embodiment.
  • a solar cell using a back film having water resistance and oxygen resistance permeability may be used instead of the back glass.
  • FIG. 2 is a cross-sectional view schematically showing an example of the embodiment of the CdTe solar cell of the present embodiment.
  • a solar cell (CdTe solar cell) 21 according to this embodiment includes a glass substrate 22 having a thickness of 1 to 3 mm, a back plate glass 27 having a thickness of 1 to 3 mm, and a gap between the glass substrate 22 and the back plate glass 27.
  • a CdTe layer 25 having a thickness of 3 to 15 ⁇ m is provided.
  • At least one of the glass substrate 22 and the back plate glass 27 is the glass plate of the present embodiment described above. Further, since both the glass substrate 22 and the back plate glass 27 are the glass plates according to the present embodiment, it is possible to prevent peeling and the like by matching the thermal expansion coefficients.
  • the CdTe solar cell 21 has a transparent conductive film 23 having a thickness of 100 to 1000 nm on a glass substrate 22.
  • the heating temperature when forming the CdTe layer or the transparent conductive film is 500 ° C. or higher, preferably 550 ° C. or higher, more preferably 580 ° C. or higher, further preferably 600 ° C. or higher, and particularly preferably 620 ° C. or higher.
  • the transparent conductive film 23 for example, In 2 O 3 or the like doped with doped In 2 O 3 and F of Sn and the like.
  • a buffer layer 24 eg, CdS layer
  • CdTe layer 25 is provided on the buffer layer 24.
  • a back electrode 26 for example, a carbon electrode doped with Cu or a Mo electrode
  • a back plate glass 27 is provided on the back electrode 26.
  • the back electrode 26 and the back plate glass 27 are preferably sealed with a resin or bonded with an adhesive resin.
  • the end of the CdTe layer or the end of the solar cell may be sealed.
  • a material for sealing the same material as the glass substrate for CdTe solar cells of this embodiment, other glass materials, resin, etc. are mentioned, for example.
  • the thickness of each layer of the solar cell shown in the attached drawings is not limited to the drawings.
  • Table 1 shows examples (Examples 1 to 5) and comparative examples (Examples 6 to 11) of the glass plate of the present embodiment.
  • the composition ratio of Table 1 is shown in mass% on the basis of oxide.
  • the raw materials of each component of the glass were prepared so as to have the glass composition shown in Table 1, and 0.1 part by mass of SO 3 in terms of SO 3 was added to the raw material with respect to 100 parts by mass of the raw material for the glass plate component.
  • the mixture was heated at 1650 ° C. for 3 hours for dissolution.
  • the blending amount of Fe 2 O 3 is based on the mother composition (SiO 2 , Al 2 O 3 , B 2 O 3 , MgO, CaO, SrO, BaO, ZrO 2 , Na 2 O, and K 2 O).
  • the mass part with respect to 100 mass parts is shown.
  • a platinum stirrer was inserted and stirred for 1 hour to homogenize the glass. Subsequently, the molten glass was poured out, formed into a plate shape, and then cooled to obtain a glass plate.
  • the average thermal expansion coefficient (unit: ⁇ 10 ⁇ 7 / ° C.), glass transition temperature Tg (unit: ° C.), density (unit: g / cm 3 ), and viscosity of 10 2 dPa ⁇ s of the glass plate thus obtained.
  • Temperature (T2) (unit: ° C.)
  • temperature (T4) (unit: ° C.) at which the viscosity becomes 10 4 dPa ⁇ s
  • TL devitrification temperature
  • Na diffusion amount were measured. .
  • the results are also shown in Table 1. The measuring method of each physical property is shown below.
  • each physical property is the same value with a glass plate and a glass substrate.
  • a glass substrate can be obtained by processing and polishing the obtained glass plate.
  • TMA differential thermal dilatometer
  • Density About 20 g of glass lump containing no foam, cut out from a glass plate, was measured by Archimedes method.
  • Viscosity Measured using a rotational viscometer, temperature T2 (dissolvable reference temperature) when viscosity ⁇ is 10 2 dPa ⁇ s, and temperature when viscosity ⁇ is 10 4 dPa ⁇ s T4 (reference temperature for moldability) was measured.
  • T2 dissolvable reference temperature
  • T4 reference temperature for moldability
  • the obtained glass plate was used for a solar cell substrate, an evaluation solar cell was prepared as shown below, and the Na diffusion amount was evaluated using the solar cell. The production of the solar cell for evaluation will be described below with reference to FIG. In FIG. 1, a sample in which the glass substrate 5, the positive electrode 7, and the CIGS layer 9 were formed was prepared and used for evaluating the Na diffusion amount.
  • the obtained glass plate was processed into a size of 3 cm ⁇ 3 cm and a thickness of 1.1 mm to obtain a glass substrate.
  • a Mo (molybdenum) film was formed as a positive electrode 7 on the glass substrate 5 by a sputtering apparatus. Film formation was performed at room temperature to obtain a Mo film having a thickness of 500 nm.
  • a CuGa alloy layer is formed with a CuGa alloy target using a sputtering apparatus, and then an In layer is formed using an In target to form an In—CuGa precursor film.
  • a film was formed. Film formation was performed at room temperature. The thickness of each layer was adjusted so that the composition of the precursor film measured by fluorescent X-rays was Cu / (Ga + In) ratio of 0.8 and Ga / (Ga + In) ratio of 0.25. Obtained.
  • the precursor film was heat-treated in an argon and hydrogen selenide mixed atmosphere (hydrogen selenide is 5% by volume with respect to argon) using an RTA (Rapid Thermal Annealing) apparatus.
  • argon and hydrogen selenide mixed atmosphere hydrogen selenide is 5% by volume with respect to argon
  • RTA Rapid Thermal Annealing
  • the value of Na diffusion amount shown in Table 1 is a relative amount when the glass plate used in Example 8 is 118.
  • the glass plates of the examples have a glass transition temperature (Tg) of 640 ° C. or higher, and have high heat resistance from the result of the glass transition temperature. -TL). Moreover, it is predicted that the amount of Na diffusion is large and the power generation efficiency is high. Moreover, T2 and T4 were low and it was the range suitable for manufacture of a glass plate. Moreover, the average coefficient of thermal expansion and the density were also in a range suitable for the glass plate. In Examples 1 and 2, 2 (SrO—BaO) + (K 2 O—Na 2 O) is limited to 11.5% or less, and by increasing the amount of BaO, a sufficient amount of Na diffusion can be obtained. Heat resistance could be improved. In Examples 3 and 5, 2 (SrO—BaO) + (K 2 O—Na 2 O) is limited to 11.5% or less, and by increasing the amount of Na 2 O, heat resistance can be sufficiently obtained. , Na diffusion amount could be increased.
  • Example 6 the amount of BaO and Na 2 O were mainly small, and the target Na diffusion amount and devitrification characteristics were not obtained.
  • Example 7 the amount of BaO was mainly small and the amount of Na diffusion decreased.
  • the glass transition temperature decreased.
  • 2 (SrO—BaO) + (K 2 O—Na 2 O) exceeded 11.5%, and the devitrification characteristics were deteriorated.
  • Example 10 there was a problem that the amount of SrO was large, Tg was increased, and the meltability of the glass raw material was lowered.
  • the glass plate of the present invention can obtain excellent heat resistance and devitrification characteristics and increase the amount of Na diffusion to increase power generation efficiency, it can be preferably used for a glass substrate for solar cells. Furthermore, a predetermined average coefficient of thermal expansion, glass density, solubility at the time of production of a glass plate and formability are good, and it can be preferably used for a glass substrate for a solar cell.

Landscapes

  • 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)
  • Photovoltaic Devices (AREA)
  • Glass Compositions (AREA)

Abstract

　Par le biais de la présente invention, d'excellentes caractéristiques de résistance à la chaleur et de dévitrification sont obtenues, et la capacité de diffusion du Na est augmentée ainsi que l'efficacité de production d'énergie lorsque la présente invention est utilisée en tant que substrat de verre destiné à une cellule solaire à semi-conducteurs composés. L'invention concerne une feuille de verre comprenant, en pourcentage en masse sur la base des oxydes ci-dessous, de 45 à 65 % de SiO2, de 9 à 17 % d'Al2O3, de 0 à 1 % de B2O3, de 0 à 2 % de MgO, de 1 à 12 % de CaO, de 1 à 15 % de SrO, de 1,4 à 12 % de BaO, de 2 à 6 % de ZrO2, de 5 à 10 % de Na2O, et de 2 à 10 % de K2O, la teneur en MgO + CaO + SrO + BaO étant située dans la plage allant de 15 à 30 %, et 2(SrO-BaO) + (K2O-Na2O) représentant une valeur inférieure ou égale à 11,5 %.
PCT/JP2014/080242 2013-11-19 2014-11-14 Feuille de verre WO2015076208A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2015549132A JPWO2015076208A1 (ja) 2013-11-19 2014-11-14 ガラス板

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2013-238666 2013-11-19
JP2013238666 2013-11-19

Publications (1)

Publication Number Publication Date
WO2015076208A1 true WO2015076208A1 (fr) 2015-05-28

Family

ID=53179473

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2014/080242 WO2015076208A1 (fr) 2013-11-19 2014-11-14 Feuille de verre

Country Status (3)

Country Link
JP (1) JPWO2015076208A1 (fr)
TW (1) TW201524931A (fr)
WO (1) WO2015076208A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019021911A1 (fr) * 2017-07-26 2019-01-31 Ａｇｃ株式会社 Verre de support pour boîtiers de semi-conducteurs
CN113233758A (zh) * 2021-06-25 2021-08-10 北京北旭电子材料有限公司 玻璃组合物、玻璃原粉及其制备方法、以及玻璃粉及其制备方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10255669A (ja) * 1997-03-14 1998-09-25 Nippon Electric Glass Co Ltd フラットパネルディスプレイ用ガラス基板及びそれを用いたプラズマディスプレイ装置
JP2000072472A (ja) * 1998-08-24 2000-03-07 Nippon Sheet Glass Co Ltd 耐熱性ガラス組成物およびそれを用いたプラズマディスプレイパネル
WO2012153634A1 (fr) * 2011-05-10 2012-11-15 日本電気硝子株式会社 Plaque de verre pour une cellule solaire en couches minces
JP2013063880A (ja) * 2011-09-20 2013-04-11 Nippon Electric Glass Co Ltd ガラス板

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10255669A (ja) * 1997-03-14 1998-09-25 Nippon Electric Glass Co Ltd フラットパネルディスプレイ用ガラス基板及びそれを用いたプラズマディスプレイ装置
JP2000072472A (ja) * 1998-08-24 2000-03-07 Nippon Sheet Glass Co Ltd 耐熱性ガラス組成物およびそれを用いたプラズマディスプレイパネル
WO2012153634A1 (fr) * 2011-05-10 2012-11-15 日本電気硝子株式会社 Plaque de verre pour une cellule solaire en couches minces
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
WO2019021911A1 (fr) * 2017-07-26 2019-01-31 Ａｇｃ株式会社 Verre de support pour boîtiers de semi-conducteurs
JPWO2019021911A1 (ja) * 2017-07-26 2020-07-30 Ａｇｃ株式会社 半導体パッケージ用支持ガラス
CN113233758A (zh) * 2021-06-25 2021-08-10 北京北旭电子材料有限公司 玻璃组合物、玻璃原粉及其制备方法、以及玻璃粉及其制备方法

Also Published As

Publication number Publication date
TW201524931A (zh) 2015-07-01
JPWO2015076208A1 (ja) 2017-03-16

Similar Documents

Publication Publication Date Title
US8497220B2 (en) Glass substrate for solar cell
WO2011049146A1 (fr) Feuille de verre pour cellules solaires à base de cu-in-ga-se, et cellules solaires utilisant cette feuille de verre
WO2013105625A1 (fr) Verre
WO2012053549A1 (fr) Substrat en verre pour photopiles au cu-in-ga-se et photopile l'utilisant
WO2012102346A1 (fr) SUBSTRAT EN VERRE POUR DES PILES SOLAIRES EN Cu-In-Ga-Se ET PILE SOLAIRE COMPRENANT CE SUBSTRAT
WO2011152414A1 (fr) Substrat de verre et sa méthode de production
JP6048490B2 (ja) Ｃｕ−Ｉｎ−Ｇａ−Ｓｅ太陽電池用ガラス基板およびそれを用いた太陽電池
WO2012108345A1 (fr) Composition de verre, substrat de verre pour cellules solaires utilisant une composition de verre, et substrat de verre pour panneau d'affichage
TWI543952B (zh) 薄膜太陽電池用玻璃板
JP2010118505A (ja) 太陽電池用ガラス基板
JP6210136B2 (ja) ガラス基板
WO2013047246A1 (fr) SUBSTRAT DE VERRE POUR DES CELLULES SOLAIRES CdTe ET CELLULE SOLAIRE L'UTILISANT
US20150325725A1 (en) Glass substrate for solar cell
WO2015076208A1 (fr) Feuille de verre
JP6128128B2 (ja) 太陽電池用ガラス基板およびそれを用いた太陽電池
JP2016102058A (ja) 太陽電池用ガラス基板及びそれを用いた太陽電池
WO2014024850A1 (fr) SUBSTRAT DE VERRE POUR CELLULE SOLAIRE Cu-In-Ga-Se, ET CELLULE SOLAIRE METTANT EN ŒUVRE CELUI-CI
JP2016084247A (ja) ガラス板
JP2017014039A (ja) 太陽電池用ガラス基板及びｃｉｇｓ太陽電池
JP2018177592A (ja) Ｃｉｇｓ太陽電池
JP2016171158A (ja) Ｃｕ−Ｉｎ−Ｇａ−Ｓｅ太陽電池

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 14863218

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2015549132

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 14863218

Country of ref document: EP

Kind code of ref document: A1