EP2429962A1 - Cellule solaire en couches minces et procédé de fabrication d'une cellule solaire en couches minces - Google Patents

Cellule solaire en couches minces et procédé de fabrication d'une cellule solaire en couches minces

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Publication number
EP2429962A1
EP2429962A1 EP10720348A EP10720348A EP2429962A1 EP 2429962 A1 EP2429962 A1 EP 2429962A1 EP 10720348 A EP10720348 A EP 10720348A EP 10720348 A EP10720348 A EP 10720348A EP 2429962 A1 EP2429962 A1 EP 2429962A1
Authority
EP
European Patent Office
Prior art keywords
solar cell
substrate glass
thin
glass
substrate
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.)
Withdrawn
Application number
EP10720348A
Other languages
German (de)
English (en)
Inventor
Burkhard Speit
Eveline Rudigier-Voigt
Silke Wolff
Wolfgang Mannstadt
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.)
Schott AG
Original Assignee
Schott AG
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Filing date
Publication date
Application filed by Schott AG filed Critical Schott AG
Publication of EP2429962A1 publication Critical patent/EP2429962A1/fr
Withdrawn legal-status Critical Current

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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
    • C03C3/11—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen
    • C03C3/112—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine
    • 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
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
    • C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
    • C03C17/3605—Coatings of the type glass/metal/inorganic compound
    • 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
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
    • C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
    • C03C17/3649—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer made of metals other than silver
    • 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
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
    • C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
    • C03C17/3668—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the multilayer coating having electrical properties
    • C03C17/3678—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the multilayer coating having electrical properties specially adapted for use in solar cells
    • 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
    • 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
    • C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
    • C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
    • C03C3/093—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium containing zinc or zirconium
    • 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
    • C03C3/095—Glass compositions containing silica with 40% to 90% silica, by weight containing rare earths
    • 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
    • C03C3/11—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen
    • C03C3/112—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine
    • C03C3/115—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine containing boron
    • C03C3/118—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine containing boron containing aluminium
    • 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
    • C03C4/00—Compositions for glass with special properties
    • C03C4/0092—Compositions for glass with special properties for glass with improved high visible transmittance, e.g. extra-clear glass
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
    • H01L31/036—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes
    • H01L31/0392—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate
    • H01L31/03923—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate including AIBIIICVI compound materials, e.g. CIS, CIGS
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/541—CuInSe2 material PV cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the invention relates to a thin-film solar cell and a method for producing a thin-film solar cell.
  • thin-film technology is today a major competitor to the established c-Si wafer technology in photovoltaics.
  • Large-scale deposition processes at mostly lower efficiencies make these technologists attractive in terms of manufacturing costs and thus the so-called € / Wp.
  • An advantage of thin-film technology is a comparably short value-added chain, since semiconductor, cell and module manufacturing are in one hand. Nevertheless, cost-cutting measures are also playing an increasingly important role for thin-film technology in photovoltaics.
  • the cost reduction potentials are above all a reduction in material consumption, a reduction in process times and, associated with this, a higher throughput as well as an increase in the yield.
  • Solar cell concepts based on thin films mainly live on coating technologies on a large area.
  • a major challenge is the homogeneous coating of large areas (> 1 m 2 ), in particular edge effects or non-homogeneous ion exchange effects from, for example, the glass substrate locally affect the quality of the layers produced, which is macroscopically in a reduction of the yield but also the energy conversion efficiency of the module reflected.
  • Compound semiconductor-based thin film solar cells such as CdTe or CIGS (having the general formula Cu (In x -x , Ga ⁇ ) (Si- y , Sey) 2 ) show excellent stability as well as very high energy conversion efficiencies
  • BESTATIGUNGSKOPIE Solar cell structure is known for example from US 5,141,564. These materials are characterized in particular by the fact that they are direct semiconductors and absorb the sunlight effectively even in a relatively thin layer (about 2 ⁇ m).
  • the deposition technologies for such thin photoactive layers require high process temperatures to achieve high efficiencies. Typical temperature ranges lie between 450 and 600 ° C., the maximum temperature being limited in particular by the substrate. For large area applications, glass is generally used as the substrate.
  • floated soda lime glass (window glass) is used as the substrate, as can be seen from the publications DE 43 33 407, WO 94/07269 , 555 ° C and limits all subsequent processes to about 525 ° C, since otherwise it leads to so-called "sagging", ie warping, and begins to bend
  • Tg transformation temperature
  • warping or bending leads to problems, in particular in so-called inline processes / plants, for example at the locks and as a result the throughput and / or the yield become worse
  • Higher temperatures say> 550 ° C., can be achieved, for example, on metal foils, Ti foils, which withstand these temperatures, as described in WO 2005/006393
  • such systems have the disadvantage that they do not react because of their inherent conductivity are suitable for a monolithically integrated series connection of
  • Solar cells on metal foil are generally connected in series. Due to their low weight, such modules are particularly suitable for extraterrestrial applications. In principle, glass substrates are preferable for terrestrial applications, besides the static properties and the lighter ones Processing, above all because of the significantly higher achievable efficiencies.
  • DE 100 05 088 and JP 11-135819 A describe glass substrates for thin-film photovoltaic modules based on compound semiconductors.
  • the CTE has been adapted, which corresponds to the CTE of the first layer, the back contact (for example made of molybdenum).
  • the back contact for example made of molybdenum.
  • CTE mismatch of the glass substrate and the CIGS semiconductor layer does not ensure the layer adhesion of the CIGS layer on the Mo-coated substrate glass.
  • these substrates contain boron, which especially at high temperatures, ie> 550 0 C, can outgas from the substrate and acts as a semiconductor poison in the CIGS.
  • JP 11-135819 A describes substrates which have no CTE mismatch.
  • these glasses contain a high proportion of alkaline earth ions. wasjdazu results in that the mobility of the alkali ions in the substrate is drastically reduced or prevented. It is generally known that alkali ions play an important role during the layer deposition of the compound semiconductor thin films, and therefore it is desirable to have a substrate for the deposition process that allows for spatially and temporally homogeneous alkali ion delivery.
  • this alkali Lonenbewegige further limited by the unfavorable molar ratio of S1O2 / AI2O3> 8.
  • Such glass structures are dominated by the structural element of the Si 4+ oxygen tetrahedron without sufficient diffusion paths which builds up the structural element Al 3+ / Na + in the oxygen anions sublattice.
  • DE 196 16 679 C1 and DE 196 16 633 C1 describe a material with a similar glass composition.
  • this material may contain arsenic, which is a semiconductor poison for these layer systems and in particular can outgas at high temperatures and thus contaminate the semiconductor layer. Therefore, this material is not suitable as a glass substrate for CIGS-based solar cells. At this point it is either to use arsenic-free substrates by alternative refining agents to prevent the outgassing of arsenic over applied barrier layers or to make it difficult to degas via a targeted modification of the glass substrate.
  • Thin polycrystalline layers / layer packages based on Cu (In I-X1 Ga x ) (Si y , Se y ) 2 can be prepared in principle by a number of processes, including co-evaporation and the so-called sequential process.
  • methods such as liquid coatings or electrodeposition associated with a temperature step in chalcogen atmosphere are also suitable.
  • a deposition method that is particularly suitable for large areas and has a relatively stable process window compared to others is the sequential process. This process allows relatively short process times, in the range of a few minutes, in which case the limiting factor is the cooling of the substrate, and thus promises a high degree of economy.
  • the process is based on furnace processes, which are known in particular from the thick-film doping of silicon for photovoltaics, and enables a comparatively simple process control (US 2004115938).
  • a molybdenum layer is first applied to the substrate, which has the function of the back contact.
  • a so-called metallic precursor layer consisting of Cu, In and / or Ga, for example, deposited by sputtering and then thermally reacted in chalcogen atmosphere at temperatures of at least 500 0 C.
  • the back of the glass substrates can be attacked .
  • the SO 2 or SeO 2 fraction contained in the sulfur or selenium vapor can react with the sodium ions in the soda lime glass surface to form water-soluble Na 2 SO 4 or Na 2 SeO 4 , as a result of which the glass surface can be damaged sigmfikant-ge2020digtwer_d.en_kann.
  • cracking of the IITL layer may occur, for example due to heat inhomogeneities of the layer package during the coating process, spatially non-homogeneous diffusion of the alkali ions from the glass into the layer or generation of mechanical stresses of the glass in the event of rapid cooling.
  • Corrosion resistance is a key issue for thin film solar cells in general and for CIGS semiconductor based solar cells in particular. Corrosion-inducing processes can be: the handling of the glass samples, the external weathering, in particular with regard to long-term stability requirements (up to 20 years) and the CIGS deposition process itself, since such corrosion effects occur particularly when the substrate is exposed to high temperatures in an S / Reinforce se atmosphere.
  • the object of the invention is therefore to find a comparison with the prior art improved thin-film solar cell. Furthermore, it is an object of the invention to find a comparison with the prior art improved method for producing a thin-film solar cell.
  • the solar cell according to the invention should also be economical to produce by means of known methods or by means of the method according to the invention and have a higher efficiency.
  • Requirements that are placed on the invention are, moreover, the overcoming:
  • thermally induced substrate glass warping in particular in the case of flat modules, as occurs at high temperatures in the case of soda lime substrate glass,
  • the object is achieved according to claim 1 by means of a thin-film solar cell comprising at least one Na 2 O-containing multi-component substrate glass, wherein the substrate glass is not phase-separated and has a content of ß-OH of 25 to 80 mmol / l. Furthermore, it has been shown that it is advantageous if the substrate glass of the solar cell according to the invention
  • Tg a transformation temperature Tg of greater than 550 ° C., in particular of greater than 600 ° C., and / or
  • the solar cell can be a planar, curved, spherical or cylindrical thin-film solar cell.
  • the solar cell according to the invention is a substantially planar (flat) solar cell or a substantially tubular solar cell, wherein preferably flat substrate glasses or tubular substrate glasses are used.
  • the solar cell according to the invention is subject to no restriction with regard to its shape or to the shape of the substrate glass.
  • the outer diameter of a tubular substrate glass of the solar cell is preferably 5 to 5 mm, and the wall thickness of the tubular substrate glass is preferably 0.5 to 10 mm.
  • Cell in particular a solar cell according to claim 1 or 2, comprises at least the following steps: a) providing a Na 2 O-containing multicomponent substrate glass, wherein the substrate glass has a content of ⁇ -OH of 25 to 80 mmol / l and wherein the substrate glass is not phase-demixed b) applying a metal layer to the substrate glass, wherein the metal layer forms an electrical back contact of the thin-film solar cells, c) applying an intrinsically p-type polycrystalline layer of a compound semiconductor material, in particular a CIGS
  • Composite semiconductor material comprising at least one high-temperature step at a temperature> 550 0 C, d) applying a p / n transition, in particular via a combination of buffer layer and subsequent window layer.
  • a metallic front side contact is applied.
  • metal layer here includes all suitable, electrically conductive layers.
  • the solar cells according to the invention and the solar cells produced by the process according to the invention have an over 2% absolute higher efficiency compared to the prior art.
  • Step b) preferably comprises applying a metal layer to the substrate, wherein the metal layer forms an electrical back contact of the thin-film solar cells, and is a single-layer or multi-layer system of suitable materials, more preferably a monolayer system of molybdenum ,
  • Step c) preferably comprises the application of an intrinsically p-type polycrystalline layer of a compound semiconductor material, particularly preferably based on CIGS, with at least one high-temperature step in the temperature range 550 0 C ⁇ T ⁇ 700 0 C, particularly preferably 600 ° C ⁇ T ⁇ 700 ° C.
  • Step d) preferably comprises the application of an intrinsically n-type buffer layer of a semiconducting material, more preferably of CdS, In (OH), InS o.a. and a window layer of a transparent conductive material, more preferably ZnO: Al, ZnO: Ga or SnO: F, said window layer consisting of an intrinsic layer and a heavily doped layer.
  • a semiconducting material more preferably of CdS, In (OH), InS o.a.
  • a window layer of a transparent conductive material more preferably ZnO: Al, ZnO: Ga or SnO: F, said window layer consisting of an intrinsic layer and a heavily doped layer.
  • a substrate glass is not phase-separated in the sense of this invention if it has less than 10, preferably less than 5, surface defects in a surface area of 100 ⁇ 100 nm 2 after a conditioning experiment.
  • the conditioning experiment was carried out as follows: At 500 to 600 0 C, a flow of compressed air in the range between 15 to 50 ml / min and a flow of sulfur dioxide gas (SO 2 ) in the range 5 to 25 ml / min, for a period of 5 to 20 minutes, the substrate glass surface to be examined is gassed. Irrespective of the glass type, a crystalline coating forms on the substrate glass.
  • the surface defects per substrate glass surface area are determined microscopically, as shown for example in FIG. If less than 10, in particular less than 5, surface defects are present in a surface area of 100 ⁇ 100 nm 2 , the substrate glass is considered not to be phase-separated. All surface defects which have a diameter of> 5 nm are counted.
  • the ⁇ -OH content of the substrate glass was determined as follows.
  • the equipment used for the quantitative determination of the water over the OH stretching vibration around 2700 nm is the commercially available Nicolet FTIR spectrometer with attached computer evaluation. It was first measured the absorption in the wavelength range of 2500-6500 nm and determined the absorption maximum around 2700 nm.
  • the e value is taken from the work of H. Frank and H. Scholze from the "Glastechnische Berichte", Volume 36, Volume 9, page 350.
  • Thin-film solar cell is briefly referred to in the text for simplicity as solar cell, also in the dependent claims.
  • Substrate glass in the sense of this application may also comprise a superstrate glass.
  • Na 2 ⁇ -containing multicomponent substrate glass in the sense of this invention is meant that the substrate is glass in addition to Na 2 ⁇ further composition components such as B 2 O 3, BaO, CaO, SrO, ZnO, K 2 O, MgO, SiO 2 and Al 2 O 3 , but also non-oxide components such as F, P, N may contain.
  • B 2 O 3, BaO, CaO, SrO, ZnO, K 2 O, MgO, SiO 2 and Al 2 O 3 but also non-oxide components such as F, P, N may contain.
  • This invention enables the development of a low-cost, high-efficiency monolithic integrated photovoltaic module based on compound semiconductors, such as CdTe or CIGS. Cost-effective refers in the context of the invention to a possible small € / watt costs due mainly by higher efficiencies, faster process times and thus higher throughput, and higher yields.
  • the invention includes a substrate glass, in addition to its carrier function plays an active role in the semiconductor manufacturing process and in particular by an optimal CTE adaptation at high temperatures to the photoactive compound semiconductor thin film, and a high thermal (ie a high stiffness ness) and chemical (ie high corrosion resistance) stability.
  • the invention also includes tandem, multijunction or hybrid thin film solar modules from a high temperature process deposited on a substrate glass, and a process for making such modules. Furthermore, it is included in the invention that the solar module can have both flat, spherical, cylindrical or other geometric shapes. In particular embodiments, the glass may be colored.
  • Preferred technical features of the substrate glass included in the invention are: (i) highly corrosion resistant, (ii) material without spatial phase separation, (iii) As, B free, (iv) high temperature stable, (v) coefficient of thermal expansion (CTE) adjusted, (vi ) Na content, (vii) Mobility Na in glass, (viii) Stiffness (Ew-Tg)> 200 0 C.
  • the method according to the invention for producing a thin-film solar cell comprises at least one or all of the following steps:
  • high-alkali aluminosilicate glass systems met the requirements for a substrate glass for the thin-film solar cell produced in a high-temperature process.
  • the high-temperature CIGS manufacturing technology could be brought to the application with SubstratgJastempera- temperatures of up to 700 0 C, at the same time was adjusted to the CIGS semiconductor layer of the CTE of the substrate. Accordingly, 2% higher efficiencies of CIGS cells could be achieved compared to the standard process at temperatures - 525 ° C.
  • MgO + CaO + SrO + BaO 0, in particular> 0.5, preferably> 5
  • the glasses were melted in 4-liter platinum crucibles from conventional raw materials.
  • the AI raw material AI (OH) 3 was used and also an oxygen burner in the furnace chamber of the gas-heated melting furnace (Oxyfueltechnik) was used to achieve the high melting temperatures at oxidizing melt guide.
  • the raw materials were placed over a period of 8 hours at melting temperatures of 1580 0 C and then held for 14 hours at this temperature.
  • the molten glass was then poured within 8h to i4GQ G the mixture is cooled! Tund-anministerdJn a 500 0 C preheated graphite mold stirring.
  • Table 1 Exemplary embodiments of substrate glasses, as used according to the invention, composition components in mol%, molar ratios.
  • the molar ratios of the two glass formers SiO 2 to Al 2 O 3 are responsible for the achievement of high operating temperatures of the substrate glasses, since they determine the slope of the viscosity in the transformation point (Tg) to the softening point.
  • Such so-called long glasses can be thermally stressed not only up to the transformation point without deformation but also up to about 100 0 C below the softening point (Ew) of the glasses.
  • Ew softening point
  • the glasses of the above glass compositions meet exactly the requirements, as they are iron-free, but a water content of> 25 mmol / liter, preferably> 40 mmol / liter and more preferably> 50 mmol / liter ,
  • the semiconductors are chemically bound and can not get into the process even at temperatures> 550 0 C.
  • the water content can be determined with commercially available spectral measuring devices in the wavelength range from 2500 to 6000 nm using appropriate calibration standards.
  • FIG. 1 shows by way of example the water content ( ⁇ -OH) of a glass substrate according to the invention in comparison to the prior art. Infrared measurement in the wavelength range 2500 - 6000 nm with the maximum of the ⁇ -OH absorption of the water at 2800 nm from a soda-lime glass, a glass according to JP 11-135819A and example glass 4.
  • the mobility of the alkali ions in water-containing glasses such as those of the above composition, despite the increased proportion of alkaline earth ions, which meet the requirement of high Tg with high thermal expansion, however, the diffusion of smaller sodium Ions in the glass structure by the alkaline earth ions hinder, continues to exist.
  • the ion mobility of the sodium ions and their easier exchangeability in the glasses according to the invention is positively influenced especially by the residual water content in the glass structure, which with the selection of water-rich raw materials in the crystal lattice such as by Al (OH) 3 instead of Al 2 O 3 and by Oxygen-rich gas atmosphere in the melting process, also known as oxyfuel, can be realized.
  • the found ratio of SiO 2 / Al 2 O 3 is also necessary for a high alkali ion mobility.
  • the alkali ions can be spatially homogeneously distributed over the entire substrate surface to the overlying layers or diffused therethrough.
  • the release of the alkali ions does not break even at higher temperatures,> 600 0 C, not from.
  • such a substrate exhibits improved adhesion properties for the functional layers of molybdenum and compound semiconductors deposited thereon.
  • compound semiconductor layers can grow up ideally, ie homogeneous crystal growth over the surface and thus a higher yield can be realized, as well as ensuring a sufficiently large alkali ion reservoir during the deposition process.
  • alkali ions can be exchanged L K example, specifically in the upper region-of the glass substrate ⁇ , Li by Na or vice versa.
  • glasses of different compositions, s. Table 1 are conditioned so that they allow a spatially and temporally homogeneous alkali ion delivery of exactly one species.
  • Composite semiconductor thin film solar cells especially those produced in a high temperature step under a corrosive atmosphere, must have a high corrosion resistance.
  • a hydrolytic resistance of the above-described glasses of ⁇ 0.5 ⁇ g / g Na 2 O significantly reduces the risk of corrosion.
  • the hydrolytic resistance is determined according to DIN ISO 719.
  • the substrate glass is ground into Glasgries with 300 to 500 microns grain size and then placed for one hour in 98 0 C hot, demineralized water. The aqueous solution is then analyzed for the alkali content.
  • soda-lime glasses show a reaction with SO2 / SeO2, but in contrast to the soda-lime glasses, without any visible corrosion of the surface, as when cleaning with water.
  • a corroded glass surface pictured on the left, soda lime substrate glass
  • the uncorroded surface shown on the right
  • This is due not only to the high mobility of the sodium ions in the glass lattice, which are replenished in the reaction with the chalcogenide oxides from deeper layers below the surface, the phase stability of the glass. This allows a homogeneous diffusion of the sodium ions to the surface and thus prevents a visibly corroded surface.
  • the so-called stiffness (dimensional stability at high temperatures> 600 ° C.) can be estimated, inter alia, by the difference between Ew-Tg (in 0 ° C.) Requirement of at least 200 ° C. is necessary in order to obtain thinner substrates than the currently used 3 bis-3 7 5-mm r d ⁇ h.
  • the substrate glass of the above composition was prepared and formulated so that it has a high dimensional stability at temperatures> 600 0 C.
  • This dimensional stability can be expressed by the so-called stiffness, which is indicated, inter alia, by the modulus of elasticity of the glasses of> 70 kN / mm 2 and by the large difference between softening point (EW) and transformation point (Tg).
  • EW softening point
  • Tg transformation point
  • the substrate glass thickness reduction By this substrate glass thickness reduction, a faster heat transfer through the substrate glass can be realized, which allows accelerated process control in the semiconductor deposition process and thus savings in process time. In particular, this allows, for example, the cooling section to be significantly reduced, which, in addition to the process times, also significantly reduces the investment costs.
  • Thinner substrate glasses also mean lower material and manufacturing costs for the substrate glass itself, and can lead to a more positive cost balance in the production of solar cells through lossless transport of the substrate glasses including layers in in-line systems. Bent substrate glass is problematic, for example, in process chamber locks and can lead to a significant yield loss. In addition, it is of enormous advantage for the lamination process, if the solar cells are not bent, again, not quite planar substrate glass can lead to a yield loss.
  • the metal film has a thickness of 0.2 to 5 microns, more preferably 0.5 to 1 micron and a conductivity of 0.6 x 10 5 to 2 x 10 5 Ohm.cm, more preferably 0.9 x 10 5 bis 1, 4 x 10 5 ohm.cm.
  • a substrate glass with a higher Tg than standard soda-lime glass allows for higher process temperatures during semiconductor deposition. It is known that higher deposition temperatures during chalcopyrite formation can lead to a significant minimization of crystal imperfections, to below the detection limit, such as the so-called CuAu order. This is especially true for the sequential process described above.
  • the semiconductor layers of the solar cells according to the invention with a substrate glass of the above composition and wherein a semiconductor layer was deposited at temperatures> 600 0 C meet the demand for a higher crystallinity and thus fewer defects. This can be seen in FIG. 4 on the basis of the Rama ⁇ spektre ⁇ . In FIG.
  • the A1 mode of a CIGS absorber layer is deposited according to the invention at high temperatures, and the A1 mode of a CIGS layer deposited on soda-lime glass is shown.
  • the lower half-width of the solar cell according to the invention is a direct measure of better crystal quality and thus fewer defects.
  • the mode shows in the CIGS layer according to the invention in the high-temperature step (T> 550 0 C) deposited on the basis of a substrate glass of the composition described lower half-width than a CIGS layer in the conventional process prepared on a Kalknatronsubstratglas (larger half-width).
  • FIG. 5 shows a solar cell produced according to the prior art, in particular an SEM micrograph of a cross section through the zonal structure of a multilayer molybdenum layer (three-layer process sequence) on a substrate glass (left in the image). Visible here are three steps in the molybdenum layer (center).
  • FIG. 6 shows a solar cell according to the invention, in particular a SEM micrograph of a cross section through the columnar, stepless structure of a molybdenum layer of a solar cell according to the invention, the molybdenum layer being applied by means of a single-layering process.

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Abstract

L'invention concerne une cellule solaire en couches minces comportant au moins un verre substrat multicomposant contenant Na2O, le verre substrat n'ayant pas fait l'objet d'une séparation des phases et présentant une teneur en ß-OH de 25 à 80 mMol/l. Le procédé de fabrication d'une cellule solaire en couches minces comporte les étapes suivantes : a) préparation d'un verre substrat multicomposant contenant Na2O, le verre substrat présentant une teneur en ß-OH de 25 à 80 mMol/l et n'ayant pas fait l'objet d'une séparation des phases, b) application d'une couche métallique sur le verre substrat, la couche métallique formant un contact électrique arrière des cellules solaires en couches minces, c) application d'une couche polycristalline intrinsèquement conductrice p, composée d'un matériau semi-conducteur composite, notamment d'un matériau semi-conducteur composite CIGS, comprenant au moins une étape haute température à une température > 550 °C, et d) application d'une jonction p/n. Le verre est composé de préférence, en moles %, de: SiO2 61 - 70,5; AI2O3 8,0 - 15,0; B2O3 0 - 4,0; Na2O 0,5 - 18,0; K2O 0,05 - 10,0; Li2O + Na2O + K2O 10,0 - 22,0; MgO 0 - 7,0; CaO 0 - 5,0; SrO 0 - 9,0; BaO 0 - 5.0; CaO + SrO + BaO + ZnO 0,5 - 11,0; TiO2 + ZrO2 0 - 4,0; SnO2 + CeO2 0 - 0,5; As2O3 + Sb2O3 + P2O5 + La2O3 0 - 2,0; F2 + Cl2 0 - 2.
EP10720348A 2009-05-12 2010-05-05 Cellule solaire en couches minces et procédé de fabrication d'une cellule solaire en couches minces Withdrawn EP2429962A1 (fr)

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DE102009020954 2009-05-12
DE102009050987A DE102009050987B3 (de) 2009-05-12 2009-10-28 Dünnschichtsolarzelle und Verfahren zur Herstellung einer Dünnschichtsolarzelle
PCT/EP2010/002742 WO2010130359A1 (fr) 2009-05-12 2010-05-05 Cellule solaire en couches minces et procédé de fabrication d'une cellule solaire en couches minces

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TW201103879A (en) 2011-02-01
CN101887922B (zh) 2012-09-05
KR20100122467A (ko) 2010-11-22
CN101887922A (zh) 2010-11-17
WO2010130359A1 (fr) 2010-11-18

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