WO2013082246A1 - Contrôle d'alcali dans des films minces de cig à travers du verre et par application d'une tension - Google Patents

Contrôle d'alcali dans des films minces de cig à travers du verre et par application d'une tension Download PDF

Info

Publication number
WO2013082246A1
WO2013082246A1 PCT/US2012/066993 US2012066993W WO2013082246A1 WO 2013082246 A1 WO2013082246 A1 WO 2013082246A1 US 2012066993 W US2012066993 W US 2012066993W WO 2013082246 A1 WO2013082246 A1 WO 2013082246A1
Authority
WO
WIPO (PCT)
Prior art keywords
glass substrate
alkali
voltage
glass
metal ions
Prior art date
Application number
PCT/US2012/066993
Other languages
English (en)
Inventor
Richard Michael FIACCO
Kenneth Edward HRDINA
Melissann ASHTON-PATTON
Original Assignee
Corning Incorporated
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 Corning Incorporated filed Critical Corning Incorporated
Publication of WO2013082246A1 publication Critical patent/WO2013082246A1/fr

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
    • H01L31/036—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
    • 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
    • C03C17/06—Surface treatment of glass, not in the form of fibres or filaments, by coating with metals
    • 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
    • C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
    • 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
    • C03C23/00—Other surface treatment of glass not in the form of fibres or filaments
    • C03C23/008—Other surface treatment of glass not in the form of fibres or filaments comprising a lixiviation step
    • 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
    • C03C23/00—Other surface treatment of glass not in the form of fibres or filaments
    • C03C23/009—Poling 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
    • 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
    • H01L31/03925—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 AIIBVI compound materials, e.g. CdTe, CdS
    • 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
    • C03C2217/00—Coatings on glass
    • C03C2217/20—Materials for coating a single layer on glass
    • C03C2217/25—Metals
    • C03C2217/257—Refractory metals
    • C03C2217/26—Cr, Mo, W
    • 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
    • C03C2217/00—Coatings on glass
    • C03C2217/20—Materials for coating a single layer on glass
    • C03C2217/28—Other inorganic materials
    • C03C2217/287—Chalcogenides
    • C03C2217/289—Selenides, tellurides
    • 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

  • This disclosure relates generally to glass substrates with diffusion barrier layers or enhanced alkali layers and more particularly to glass substrates with alkali diffusion barrier layers or enhanced alkali layers which may be useful in photovoltaic applications, for example, thin film
  • PV photovoltaic
  • CdTe Cadmium Telluride
  • CGS Cadmium Indium Gallium Selenide
  • TCO transparent conducting oxide
  • CdTe thin films can degrade the device's efficiency in converting sunlight into electricity.
  • sputter-deposited silica Si02
  • alumina AI 2 O3
  • barrier layers can suppress the egress of alkali ions from the glass superstrate, but not completely block it.
  • the most commonly employed substrate material for both the CdTe and CIGS technologies is soda-lime-silica (SLG) float glass. This glass material is primarily used because it is readily available, low cost and contains a high concentration of sodium. This last attribute is desirable in some CIGS processes (e.g., rapid thermal processing and co-evaporation) because a high concentration of sodium can result in the rapid delivery of sodium during thin film deposition and can yield high cell efficiencies. Dopant levels of about ⁇ lxlO 19 sodium atoms per cm 3 within the CIGS thin film typically results in higher cell efficiency. Typical CIGS films are ⁇ 2.5 microns ( ⁇ or urn) thick. Therefore, the required sodium
  • concentration for every square centimeter of PV cells can be estimated at 95 ng/cm 2 or less for thinner CIGS films.
  • 1 gram of table salt (NaCl) has about the same amount of sodium in about 1 in 2 of a 3 mm thick plate of soda-lime-silica float glass (SLG) . This sodium is enough to dope about 41,000 m 2 of CIGS cells to a level of lxlO 19 atoms/cm 3 .
  • the barrier layer must also prevent or minimize the diffusion of alkali ions from the external dopant layer back into itself such that all of the alkali ions are available for diffusion into the CIGS film.
  • the most common barrier layers currently employed in the CIGS thin film stack are sputter-deposited silica or alumina. These barrier layers can suppress the egress of alkali ions from the glass substrate, but not completely block it. Additionally, these barrier layers have been found ineffective in preventing the back diffusion of alkali from the external dopant layer into themselves.
  • the glass pieces prefferably be SLG float glass because of its low cost.
  • the CTE of both glass pieces should be similar in order to prevent mechanical distortion during the lamination process.
  • a further desirable attribute of the glass is stability at high temperatures.
  • the performance of CdTe and CIGS cells can be enhanced at higher processing temperatures. Attributes that best describe this temperature resistance in glass are strain and anneal points. It is difficult to design a single glass composition that can effectively meet the all of the thermal expansion, temperature resistance and variable alkali delivery requirements simultaneously.
  • Typical PV CIGS processing result in a sodium concentration that is limited in the CIGS and molybdenum (Mo) layers due to either inhibited diffusion of sodium or a concentration of sodium that is limited by the concentration present in the glass.
  • the present disclosure is an improvement over the past PV cells in that both the rate of sodium diffusion is accelerated as well as the quantity of sodium in the cells can be increased to levels exceeding that in the glass.
  • the applied voltage increases the rate of diffusing sodium species by application of the voltage.
  • the application of the voltage serves to create an enrichment of sodium where the voltage is applied and thus may increase the concentration of sodium in the Mo and CIGS layers .
  • the thickness of the enriched or depleted surface layers can range from a few nanometers to about 10 microns, for example, from 3 nanometers to 10 microns, for example, from 10 nanometers to 1 micron.
  • One embodiment is a method of moving alkali ions in a glass substrate to form a glass substrate having an intrinsic alkali barrier layer, the method comprises:
  • a glass substrate comprising alkali metal ions, alkaline earth metal ions, or a combination thereof and having at least two opposing surfaces and a thickness between the surfaces;
  • Another embodiment is a method of moving alkali ions in a glass substrate to form a glass substrate having an enhanced alkali layer, the method comprises:
  • a glass substrate comprising alkali metal ions, alkaline earth metal ions, or a combination thereof and having at least two opposing surfaces and a thickness between the surfaces;
  • Another embodiment is an article comprising a glass substrate having a first region depleted in alkali metal ions, alkaline earth metal ions, or a combination thereof; and a second region having alkali metal ions, alkaline earth metal ions, or a combination thereof in a substantially uniform concentration in physical contact with the first region, wherein the glass substrate does not have a third region having an enhanced concentration of alkali metal ions,
  • alkaline earth metal ions or a combination thereof.
  • Figure 1 is a graph showing the net result of diffusion of sodium out of glass substrates when placed in a potassium containing salt bath.
  • Figure 2 is a schematic of methods according to some embodiments .
  • Figure 3 is a graph showing predicted amounts of sodium in ng delivered from the glass as a function of time and temperature if an ion exchange process was operating.
  • Figure 4A, Figure 4B, and Figure 4C are schematics of exemplary steps of the method, according to some embodiments.
  • Figure 5 is a graph of current as function of time for a SLG type glass.
  • Figure 6 is a graph of a sodium profile taken on the non-tin side of SLG glass by secondary ion mass spectrometry (SIMS) .
  • Figure 7 is a graph of sodium profiles in CIGS and Mo films by SIMS for Example 1.
  • Figure 8 is a graph of current behavior with a 50 volt applied field for Examples 1 and 2.
  • Figure 9 is a graph of a sodium profile for Example 2 by SIMS .
  • Figure 10 is a graph of potassium profiles in CIGS and Mo films by SIMS for Example 2.
  • Figure 11 is a graph of a sodium profile for Example 3 by SIMS.
  • Figure 12 is a graph of a sodium profile for Example 4 by SIMS.
  • Figure 13 is a graph of a sodium profile for Example 5 by SIMS.
  • Figure 14 is an illustration of features of a
  • photovoltaic device according to one embodiment.
  • Figure 15 is an illustration of features of a glass substrate according to some embodiments. DETAILED DESCRIPTION
  • the term "substrate” can be used to describe either a substrate or a superstrate depending on the configuration of the photovoltaic cell.
  • the substrate is a superstrate, if when assembled into a
  • the photovoltaic cell it is on the light incident side of a photovoltaic cell.
  • the superstrate can provide protection for the photovoltaic materials from impact and environmental degradation while allowing transmission of the appropriate wavelengths of the solar spectrum. Further, multiple
  • photovoltaic cells can be arranged into a photovoltaic module.
  • Photovoltaic device can describe either a cell, a module, or both .
  • Adjacent can be defined as being in close proximity. Adjacent structures may or may not be in physical contact with each other. Adjacent structures can have other layers and/or structures disposed between them.
  • One embodiment is a method of moving alkali ions in a glass substrate to form a glass substrate having an intrinsic alkali barrier layer, the method comprises:
  • a glass substrate comprising alkali metal ions, alkaline earth metal ions, or a combination thereof and having at least two opposing surfaces and a thickness between the surfaces;
  • Another embodiment is a method of moving alkali ions in a glass substrate to form a glass substrate having an enhanced alkali layer, the method comprises:
  • a glass substrate comprising alkali metal ions, alkaline earth metal ions, or a combination thereof and having at least two opposing surfaces and a thickness between the surfaces;
  • alkaline earth metal ions or the combination thereof near at least one surface move away from a negative voltage and toward a positive voltage on an opposing surface to form the glass substrate having the enhanced alkali layer.
  • the glass substrate made according to the disclosed methods can have a first region depleted in alkali metal ions, alkaline earth metal ions, or a combination thereof; and a second region having alkali metal ions, alkaline earth metal ions, or a combination thereof in a substantially uniform concentration in physical contact with the first region, wherein the glass substrate does not have a third region having an enhanced concentration of alkali metal ions,
  • alkaline earth metal ions or a combination thereof.
  • Another embodiment is an article comprising a glass substrate having a first region depleted in alkali metal ions, alkaline earth metal ions, or a combination thereof; and a second region having alkali metal ions, alkaline earth metal ions, or a combination thereof in a substantially uniform concentration in physical contact with the first region, wherein the glass substrate does not have a third region having an enhanced concentration of alkali metal ions,
  • alkaline earth metal ions or a combination thereof.
  • Voltage, both positive and negative can be used to control the amount of alkali migration seen in the glass substrate and then the amount of alkali entering into, for example, CIGS PV cells from the glass substrate.
  • voltages at levels in the range of from + 10 kv and -100 kv for example, -0.5 volts to -100 kv, for example, -0.5 volts to -10 kv, for example, from -0.5 volts to -1 kv, or, for example, -5 volts to -100 kv, for example, from -5 volts to -10 kv, for example, -5 volts to -1 kv are applied to the glass substrate with or without additional layers.
  • voltages are applied at levels of 1 kv or less, for example, 750 volts or less, for example, 700 volts or less, for example, 650 volts or less, for example, 600 volts or less, for example, 550 volts or less, for
  • 500 volts or less for example, 450 volts or less, for example, 400 volts or less, for example, 350 volts or less, for example 300 volts or less, for example, 250 volts or less to the glass substrate with or without additional layers.
  • voltages are applied at levels of from -5 volts to 1 kv, for example, from -5 volts to 750 volts, for example, from -5 volts to 700 volts, for example, from -5 volts to 650 volts, for example, from -5 volts to 600 volts, for example, from -5 volts to 550 volts, for example, from -5 volts to 500 volts, for example, from -5 volts to 450 volts, for example, from -5 volts to 400 volts, for example, from -5 volts to 350 volts, for example from -5 volts to 300 volts, for example, from -5 volts to 250 volts to the glass substrate with or without additional layers.
  • voltages are applied at levels of from 1 volt to 1000 volts, for example, 1 volt to 950 volts, for example, 1 volt to 900 volts, for example, 1 volt to 900 volts, for example, 1 volt to 850 volts, for example, 1 volt to 800 volts, for example, 1 volt to 750 volts, for example, 1 volt to 700 volts, for example, 1 volt to 650 volts, for example, 1 volt to 600 volts, for example, 1 volt to 550 volts, for example, 1 volt to 500 volts, for example, 2 volts to 500 volts, for example, 3 volts to 500 volts, for example, 4 volts to 500 volts, for example, 5 volts to 500 volts.
  • the various voltages can be applied for different lengths of time. Negative voltages will help deliver alkali while positive voltages can shut off or slow down the rate or amount of alkali migration.
  • the time for which the voltages are applied can vary between 1 nanosecond and multiple days. The total current applied in a certain temperature range may be used to quantify the amount of ion migration from the glass .
  • Voltage can be applied in a number of different ways including: applying a voltage on the Mo film during CIGS deposition; applying a voltage on the CIGS or Mo film after CIGS deposition but during the high temperature heat
  • the method can comprise applying a voltage to bare glass that is heated prior to application of Mo film to create an alkali enriched surface.
  • a voltage to bare glass that is heated prior to application of Mo film to create an alkali enriched surface.
  • Alkali-silicate glasses like the glasses being used in this disclosure, are known to be ionic conductors. At room temperature glasses are insulators, however at elevated temperatures the monovalent cations become mobile in the glass. When a glass is at elevated temperatures (T > 75°C) , contains high concentrations of mobile ions, and/or is in the presence of an electric field, alkali ions will move through the glass network towards one surface of the glass and away from the other.
  • glasses with large amounts of sodium like commercial soda lime silicates, will naturally form a sodium rich layer on the surface of the glass under at temperatures > 50°C, but ⁇ 100°C.
  • the presence of the electric field will increase the driving force behind the alkali migration above that of temperature alone, and allows the direction of the migration to be determined, for example, the positive alkali ions will move towards the negatively biased surface and away from the positively biased surface.
  • the weak electrolyte theory expresses the ionic conductivity as a product of the concentration of mobile ions and mobility of the conducting ion [Eq 1] :
  • n* is the number of mobile ions per unit volume
  • z is the charge of the mobile ion
  • e is the electronic charge
  • ti is the mobility of the ion.
  • One point in this disclosure is to maintain the conductivity of the alkali ions, but decreasing ⁇ *, the number of mobile ions per unit volume in the bulk of the glass. Controversy exists over exactly why sodium increases cell efficiency, but it indeed does. Perhaps there are multiple effects.
  • This disclosure identifies processes that can utilize a wide variety of glasses. As an example, a glass with less alkali will likely allow CIGS manufacturing at higher temperatures. This may improve efficiency by creating a better performing crystal structure or a change in the grain size or amount of sodium in the grains or the grain boundaries.
  • Figure 1 is a graph showing the net result of diffusion of sodium out of glass substrates when placed in a potassium containing salt bath.
  • glass substrates containing sodium are placed in potassium salt baths and heated to 600°C for a fixed length of time, for example, forty minutes.
  • the net result is diffusion of sodium out of the glass substrates, Line 12.
  • the salt bath diffusion data shown in Figure 1 is a predicted sodium profile in the glass that was modeled using the same thermal profile used to apply the CIGS coatings onto the same glass substrate.
  • Figure 1 shows that the actual sodium profile, Line 10, of the glass surface below the CIGS film has virtually no detectable sodium loss compared to that which would be expected for a glass surface ion exchanged in a salt bath.
  • FIG 2 is a schematic of methods according to some embodiments.
  • a depiction of voltage is being applied to the Mo film during a heat treatment in order to control the amount of sodium getting into the CIGS film.
  • Voltage V can be applied to molybdenum (Mo) film 16 and at least one surface of the glass substrate 14 during a heat treatment.
  • the amount of sodium getting into the CIGS film may be controlled by
  • Figure 3 is a graph showing predicted amounts of sodium in ng delivered from the glass to the multilayers, for
  • CIGS layers as a function of time and temperature.
  • Lines 24, 22, 20, and 18 show temperature curves for 225°C, 250°C, 350°C, and 500°C, respectively. This prediction is extrapolating the sodium diffusion data at 500°C and 600°C down to lower temperatures. It is assumed that the application of the voltage can result in diffusion rates similar to that in the salt bath. In reality, the application of more voltage may actually enhance diffusion further and also real diffusion values as opposed to the extrapolated values maybe greater than those shown in the figure. Much sodium can be extracted from the CIGS layers, even at temperatures less than 400°C. The graph shows that doping the multilayer at low temperatures is indeed possible in reasonable lengths of time. The
  • extrapolated data shown here indicates that doping at levels of lxlO 19 sodium atoms/cm 3 (-95 ng sodium/cm 2 cell for 2.5 urn thick CIGS layer) can be accomplished in less than a day at temperatures of 250°C or more. Most of the sodium would be expected to populate the grain boundaries.
  • Alkali profiles in the glass can be customized by applying positive and then no or even negative voltages for different lengths of time and temperatures such as
  • Figures 4A, 4B, and 4C are schematics of exemplary steps of the method, according to some embodiments.
  • the method steps can be used to create an enhanced alkali layer at or near the surface of the glass substrate.
  • Figure 4A shows that the as-made glass, prior to any treatment, has more or less a uniform sodium level, Line 21, throughout the surface and the bulk.
  • Figure 4B shows that during exemplary step 1, the surface 23 of the glass substrate is enriched with alkali and the bulk starts to deplete of alkali as the sample is heated under the presence of a voltage.
  • Figure 4C shows that during exemplary step 2, reversing the bias or removing the bias, with heat drives the alkali into the surface, Line 25.
  • features 101 of a photovoltaic device comprise the glass substrate 86
  • the photovoltaic device can comprise more than one of the glass substrates, for example, as a substrate and/or as a
  • the photovoltaic device 101 comprises the glass sheet as a substrate and/or superstrate 86, a conductive material 88 adjacent to the substrate, and an active photovoltaic medium 92 adjacent to the conductive material.
  • the active photovoltaic medium comprises a CIGS layer. In one embodiment, the active
  • photovoltaic medium comprises a cadmium telluride (CdTe) layer.
  • the photovoltaic device comprises a functional layer comprising copper indium gallium diselenide or cadmium telluride.
  • the photovoltaic device the functional layer is copper indium gallium diselenide.
  • the functional layer is cadmium telluride.
  • a molybdenum back contact conducting layer may be deposited directly onto the glass surface (adjacent to the barrier layer) and in between the CIGS functional layer. This moly film would be layer 88 in Figure 14.
  • the barrier layer is adjacent to a transparent conductive oxide (TCO) layer, wherein the TCO layer is disposed between or adjacent to the functional layer and the barrier layer.
  • TCO transparent conductive oxide
  • a TCO may be present in a photovoltaic device comprising a CdTe functional layer.
  • a glass substrate 86 features 201 of a glass substrate 86 are shown.
  • the glass substrate can have a first region 94 depleted in alkali metal ions, alkaline earth metal ions, or a combination thereof; and a second region 96 having alkali metal ions, alkaline earth metal ions, or a combination thereof in a substantially uniform concentration in physical contact with the first region, wherein the glass substrate does not have a third region having an enhanced concentration of alkali metal ions, alkaline earth metal ions, or a
  • the concentration in the second region can be equal to that found in the bulk glass or as made glass prior to application of voltage.
  • the glass substrate can further comprise another region 98, having an enhanced concentration of alkali metal ions, alkaline earth metal ions, or a
  • the enhanced layer is in physical contact with the second region and can have a concentration equal to that found in the bulk glass or as made glass prior to application of voltage.
  • the first region may be absent.
  • the glass sheet is optically transparent. In one embodiment, the glass sheet as the substrate and/or superstrate is optically transparent.
  • the glass sheet has a thickness of 4.0mm or less, for example, 3.5mm or less, for example, 3.2mm or less, for example, 3.0mm or less, for example, 2.5mm or less, for example, 2.0mm or less, for example, 1.9mm or less, for example, 1.8mm or less, for example, 1.5mm or less, for example, 1.1mm or less, for example, 0.5mm to 2.0mm, for example, 0.5mm to 1.1mm, for example, 0.7mm to 1.1mm.
  • the glass sheet can have a thickness of any numerical value including decimal places in the range of from 0.1mm up to and including 4.0mm.
  • Embodiments described herein may provide one or more of the following advantages: can improve efficiency of CIGS cells by controlling alkali levels in the cells, or controlling where and when alkali is present in multilayered cells. For example, the process enables the presence of sodium during growth or after growth of the CIGS film. To date, it is not explicitly known if efficiency is dependent on when the sodium is present during forming of the CIGS cell; the improved efficiency can be obtained for glasses of various advantages: can improve efficiency of CIGS cells by controlling alkali levels in the cells, or controlling where and when alkali is present in multilayered cells. For example, the process enables the presence of sodium during growth or after growth of the CIGS film. To date, it is not explicitly known if efficiency is dependent on when the sodium is present during forming of the CIGS cell; the improved efficiency can be obtained for glasses of various
  • compositions are inexpensive glasses to be used or glasses with higher strain points which may allow processing at higher temperatures. This may facilitate processing speed or a preferred temperature dependent
  • microstructure in the CIGS and or Mo films to be obtained may facilitate processing speed by increasing diffusion rates of alkali such as sodium and potassium; the use of voltage will make for a more robust, repeatable process, less dependent on prior sample history such as aging effects of the glass or impact of cleaning, washing, grinding or polishing procedures on the glass; lower alkali content and or less mobile alkali content glasses will improve the shelf life of the glass prior to processing, thus alleviating inventory and allowing a better supply chain; and/or the alkali content can be tailored to different device manufacturing processes in order to better maximize cell efficiency for specific processing histories.
  • One example would be a 2 minute process vs a 1 hour process vs. a process which desires very low level alkali.
  • An advantage of the current disclosure over sputter- deposited barrier layers is that the depleted layer is intrinsic to the glass as an extension of the bulk glass structure. This eliminates any issues of adhesion or
  • delamination due to the absence of a sharp interface between the surface layer and bulk glass due to the absence of a sharp interface between the surface layer and bulk glass.
  • An additional advantage of the depleted surface layer is that it significantly improves chemical durability of that glass surface and prevents or minimizes alkali and/or alkaline-earth egress over long exposure times to the environment (particularly water vapor) .
  • This protection scheme will improve electrical reliability of PV modules and enable better retention of photoconversion efficiency over the module's lifetime.
  • Modification of the glass surface via applied voltage also provides a methodology for engineering the glass surface to control alkali delivery and removes this constraint on the bulk glass composition. This tremendously increases the glass compositional space that can be employed to optimize other bulk glass attributes such as CTE, strain point, melting, forming, cost, etc.
  • Example 1 A soda lime silica glass (SLG) whose two surfaces were sputtered with gold was heated to 400°C in air for 20 minutes and held at temperature for 10 minutes. Then a DC voltage of 50 V was applied across the two faces with the positive lead on the non-tin side of the glass. After 10 minutes with voltage at 400°C, the samples was cooled to 100°C in 30 minutes with the voltage maintained at 50 volts. Then the voltage was removed and the sample was allowed to cool to room temperature. The current behavior from the point at which the voltage was applied for this sample is shown in
  • Figure 5 is a graph of current as function of time for a SLG type glass. From this data, the total coulomb flow through the sample was calculated to be 0.042C/cm ' which then allows an estimate of the depletion depth to be made. Based on the glass composition, a depletion depth of 388 nm was estimated assuming a square sodium profile, shown by area 28 under Line 26. Point 30 on Line 26 shows the point at which the glass was beginning to cool.
  • FIG. 6 is a graph of a sodium profile taken on the non-tin side of SLG glass by secondary ion mass spectrometry (SIMS) .
  • Line 32 shows the Na profile on the fracture surface of the glass
  • Line 34 shows the Na profile after voltage treatment on the positively biased glass surface
  • Line 35 shows the hydrogen profile after voltage treatment on the positively biased glass
  • a depletion depth of 125 nm was achieved with a then gradual increase of sodium back to bulk levels.
  • FIG. 7 is a graph of sodium profiles in CIGS and Mo films by SIMS for Example 1. A comparison is made with a standard piece of non-voltage treated SLG glass, Line 42. The data shows that the voltage depleted sodium in the surface of the SLG glass, Line 44, has resulted in reduced levels of sodium in both the Mo, Line 36, and the CIGS films. Line 38 represents In in the CIGS film and Line 40 represents 0 from the glass surface.
  • Example 2 A sodium free, potassium rich silicate glass whose two surfaces were sputtered with gold was heated to 400°C in air for 20 minutes and held at temperature for 10 minutes. Then a DC voltage of 50 V was applied across the two faces. After 10 minutes with voltage at 400°C, the samples was cooled to 100°C in 30 minutes with the voltage maintained at 50 volts. Then the voltage was removed and the sample was allowed to cool to room temperature. The current behavior from the point at which the voltage was applied for this sample is shown in Figure 8.
  • Figure 8 is a graph of current behavior with a 50 volt applied field for examples 1 and 2, Lines 46 and 48, respectively.
  • FIG. 10 is a graph of potassium profiles in CIGS and Mo films by SIMS for Example 2. A comparison is made with a standard piece of untreated glass, Line 64. The data shows that the voltage depleted potassium in the surface of the glass, Line 60 has resulted in significantly reduced levels of potassium in both the Mo, Line 58, and the CIGS films, In, Line 66, 0, Line 62.
  • Example 3 A soda lime silica glass (SLG) whose two surfaces were sputtered with gold was heated to 425°C in air in 1.5 hours and held at temperature for 10 minutes. Then a DC voltage of 25 V was applied across the two faces. After 10 minutes with voltage at 425°C, the voltage was turned off and the sample was cooled to 100°C in 8 hours with no applied voltage. The application of the voltage is believed to have pulled sodium to the surface of the (-) electrode region between the gold and the glass. The slow cooling was expected to allow diffusion of the sodium back into the glass in order to enrich the surface of the glass.
  • SSG soda lime silica glass
  • SIMS was then performed on the glass sample, both the (+) and the (-) lead sides of the glass, Lines 72 and 68, respectively, and the results are shown in Figure 11 along with that of an untreated piece of glass, Line 70.
  • the positive lead side of the glass is still depleted in sodium and the (-) lead side of the glass has become enriched in sodium .
  • Example 4 A sodium rich silica glass whose two surfaces were sputtered with gold was heated to 425°C in air in 1.5 hours and held at temperature for 10 minutes. Then a DC voltage of 25 V was applied across the two faces. After 10 minutes with voltage at 425°C, the voltage was turned off and the sample was cooled quickly to 100°C in 10 minutes with no applied voltage. The application of the voltage was found to have pulled sodium to the surface of the (-) electrode region between the gold and the glass. The sodium in the glass itself at the (-) electrode side appeared to have sodium levels approximately equal to that of the bulk glass at the near surface region. The positive electrode side of the glass has a sodium depleted region to a depth of about 200 nm.
  • Figure 12 is a graph of a sodium profile for Example 4 by SIMS. SIMS was then performed on the glass sample, both the (+) and the (-) lead sides of the glass, Lines 78 and 74, respectively, and the results are shown in Figure 12 along with that of an untreated piece of glass, Line 76. The positive lead side of the glass is depleted in sodium.
  • Example 5 A sodium rich silica glass whose two surfaces were sputtered with gold was heated to 425°C in air in 1.5 hours and held at temperature for 10 minutes. Then a DC voltage of 5 V was applied across the two faces. After 10 minutes with voltage at 425°C, the voltage was turned off and the sample was cooled quickly to 100°C in 10 minutes with no applied voltage. The application of the voltage was found to have pulled sodium to the surface of the (-) electrode region between the gold and the glass. The sodium in the glass itself at the (-) electrode side appeared to have sodium levels approximately equal to that of the bulk glass at the near surface region. The positive electrode side of the glass has a sodium depleted region to a depth of about 100 nm.
  • Figure 13 is a graph of a sodium profile for Example 5 by SIMS. SIMS was then performed on the glass sample, both the (+) and the (-) lead sides of the glass, Lines 84 and 80, respectively, and the results are shown in Figure 12 along with that of an untreated piece of glass, Line 82. The positive lead side of the glass is depleted in sodium.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Geochemistry & Mineralogy (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electromagnetism (AREA)
  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Computer Hardware Design (AREA)
  • General Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Photovoltaic Devices (AREA)
  • Surface Treatment Of Glass (AREA)

Abstract

La présente invention concerne un procédé de déplacement d'ions métalliques alcalins dans un substrat en verre pour former un substrat en verre comportant une couche de barrière intrinsèque aux métaux alcalins ou une couche enrichie aux métaux alcalins par application d'une tension à au moins l'une des surfaces du substrat de sorte qu'au moins une partie des ions métalliques alcalins, des ions métalliques alcalino-terreux, ou des combinaisons de ceux-ci, qui se trouvent dans l'au moins une surface, se déplacent dans l'épaisseur du substrat en verre.
PCT/US2012/066993 2011-11-30 2012-11-29 Contrôle d'alcali dans des films minces de cig à travers du verre et par application d'une tension WO2013082246A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201161565109P 2011-11-30 2011-11-30
US61/565,109 2011-11-30

Publications (1)

Publication Number Publication Date
WO2013082246A1 true WO2013082246A1 (fr) 2013-06-06

Family

ID=48536039

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2012/066993 WO2013082246A1 (fr) 2011-11-30 2012-11-29 Contrôle d'alcali dans des films minces de cig à travers du verre et par application d'une tension

Country Status (2)

Country Link
TW (1) TW201329009A (fr)
WO (1) WO2013082246A1 (fr)

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2876694A1 (fr) * 2013-11-20 2015-05-27 Samsung SDI Co., Ltd. Cellule solaire
WO2016187266A1 (fr) * 2015-05-19 2016-11-24 Corning Incorporated Verre présentant une couche de surface modifiée
US9593042B2 (en) 2014-10-08 2017-03-14 Corning Incorporated Glasses and glass ceramics including a metal oxide concentration gradient
US9908811B2 (en) 2015-12-11 2018-03-06 Corning Incorporated Fusion formable glass-based articles including a metal oxide concentration gradient
US10017417B2 (en) 2016-04-08 2018-07-10 Corning Incorporated Glass-based articles including a metal oxide concentration gradient
US10579106B2 (en) 2015-07-21 2020-03-03 Corning Incorporated Glass articles exhibiting improved fracture performance
US11021393B2 (en) 2014-11-04 2021-06-01 Corning Incorporated Deep non-frangible stress profiles and methods of making
CN112955412A (zh) * 2018-10-31 2021-06-11 康宁股份有限公司 韧性玻璃复合物和方法
US11079309B2 (en) 2013-07-26 2021-08-03 Corning Incorporated Strengthened glass articles having improved survivability
US11084756B2 (en) 2014-10-31 2021-08-10 Corning Incorporated Strengthened glass with ultra deep depth of compression
US11492291B2 (en) 2012-02-29 2022-11-08 Corning Incorporated Ion exchanged glasses via non-error function compressive stress profiles
US11613103B2 (en) 2015-07-21 2023-03-28 Corning Incorporated Glass articles exhibiting improved fracture performance
US11634359B2 (en) 2014-02-24 2023-04-25 Corning Incorporated Strengthened glass with deep depth of compression
US11878941B2 (en) 2014-06-19 2024-01-23 Corning Incorporated Glasses having non-frangible stress profiles
US11963320B2 (en) 2016-04-08 2024-04-16 Corning Incorporated Glass-based articles including a stress profile comprising two regions

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102156986B1 (ko) * 2018-12-20 2020-09-16 에스케이씨 주식회사 유리접합용 필름 및 이를 포함하는 접합유리

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3505049A (en) * 1965-05-06 1970-04-07 Glaverbel Process and apparatus for electrochemical modification of glass
US20030233847A1 (en) * 2002-06-19 2003-12-25 Fridrich Elmer G. Manufacture of elongated fused quartz member
US20040229444A1 (en) * 2003-02-18 2004-11-18 Couillard James G. Glass-based SOI structures
US20060049390A1 (en) * 2004-08-23 2006-03-09 Klaus Ufert Resistively switching nonvolatile memory cell based on alkali metal ion drift
US7285510B2 (en) * 2002-12-25 2007-10-23 Nippon Sheet Glass Company, Limited Glass composition for poling and glass functional product containing the same
US20080308147A1 (en) * 2007-06-12 2008-12-18 Yiwei Lu Rear electrode structure for use in photovoltaic device such as CIGS/CIS photovoltaic device and method of making same
US20100133093A1 (en) * 2009-04-13 2010-06-03 Mackie Neil M Method for alkali doping of thin film photovoltaic materials

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3505049A (en) * 1965-05-06 1970-04-07 Glaverbel Process and apparatus for electrochemical modification of glass
US20030233847A1 (en) * 2002-06-19 2003-12-25 Fridrich Elmer G. Manufacture of elongated fused quartz member
US7285510B2 (en) * 2002-12-25 2007-10-23 Nippon Sheet Glass Company, Limited Glass composition for poling and glass functional product containing the same
US20040229444A1 (en) * 2003-02-18 2004-11-18 Couillard James G. Glass-based SOI structures
US20060049390A1 (en) * 2004-08-23 2006-03-09 Klaus Ufert Resistively switching nonvolatile memory cell based on alkali metal ion drift
US20080308147A1 (en) * 2007-06-12 2008-12-18 Yiwei Lu Rear electrode structure for use in photovoltaic device such as CIGS/CIS photovoltaic device and method of making same
US20100133093A1 (en) * 2009-04-13 2010-06-03 Mackie Neil M Method for alkali doping of thin film photovoltaic materials

Cited By (36)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11492291B2 (en) 2012-02-29 2022-11-08 Corning Incorporated Ion exchanged glasses via non-error function compressive stress profiles
US11079309B2 (en) 2013-07-26 2021-08-03 Corning Incorporated Strengthened glass articles having improved survivability
EP2876694A1 (fr) * 2013-11-20 2015-05-27 Samsung SDI Co., Ltd. Cellule solaire
US11634359B2 (en) 2014-02-24 2023-04-25 Corning Incorporated Strengthened glass with deep depth of compression
US11878941B2 (en) 2014-06-19 2024-01-23 Corning Incorporated Glasses having non-frangible stress profiles
US10266447B2 (en) 2014-10-08 2019-04-23 Corning Incorporated Glasses and glass ceramics including a metal oxide concentration gradient
US10259746B2 (en) 2014-10-08 2019-04-16 Corning Incorporated Glasses and glass ceramics including a metal oxide concentration gradient
US10294151B2 (en) 2014-10-08 2019-05-21 Corning Incorporated Glasses and glass ceramics including a metal oxide concentration gradient
US10364182B2 (en) 2014-10-08 2019-07-30 Corning Incorporated Glasses and glass ceramics including a metal oxide concentration gradient
US11465937B2 (en) 2014-10-08 2022-10-11 Corning Incorporated Glasses and glass ceramics including a metal oxide concentration gradient
US10532947B2 (en) 2014-10-08 2020-01-14 Corning Incorporated Glasses and glass ceramics including a metal oxide concentration gradient
US11459270B2 (en) 2014-10-08 2022-10-04 Corning Incorporated Glasses and glass ceramics including a metal oxide concentration gradient
US11220456B2 (en) 2014-10-08 2022-01-11 Corning Incorporated Glasses and glass ceramics including a metal oxide concentration gradient
US10730791B2 (en) 2014-10-08 2020-08-04 Corning Incorporated Glasses and glass ceramics including a metal oxide concentration gradient
US9593042B2 (en) 2014-10-08 2017-03-14 Corning Incorporated Glasses and glass ceramics including a metal oxide concentration gradient
US11084756B2 (en) 2014-10-31 2021-08-10 Corning Incorporated Strengthened glass with ultra deep depth of compression
US11746046B2 (en) 2014-10-31 2023-09-05 Corning Incorporated Strengthened glass with ultra deep depth of compression
US11377388B2 (en) 2014-11-04 2022-07-05 Corning Incorporated Deep non-frangible stress profiles and methods of making
US11021393B2 (en) 2014-11-04 2021-06-01 Corning Incorporated Deep non-frangible stress profiles and methods of making
WO2016187266A1 (fr) * 2015-05-19 2016-11-24 Corning Incorporated Verre présentant une couche de surface modifiée
US10472271B2 (en) 2015-05-19 2019-11-12 Corning Incorporated Glass with modified surface layer
US11267228B2 (en) 2015-07-21 2022-03-08 Corning Incorporated Glass articles exhibiting improved fracture performance
US11613103B2 (en) 2015-07-21 2023-03-28 Corning Incorporated Glass articles exhibiting improved fracture performance
US10579106B2 (en) 2015-07-21 2020-03-03 Corning Incorporated Glass articles exhibiting improved fracture performance
US11472734B2 (en) 2015-12-11 2022-10-18 Corning Incorporated Fusion-formable glass-based articles including a metal oxide concentration gradient
US9908811B2 (en) 2015-12-11 2018-03-06 Corning Incorporated Fusion formable glass-based articles including a metal oxide concentration gradient
US10787387B2 (en) 2015-12-11 2020-09-29 Corning Incorporated Fusion-formable glass-based articles including a metal oxide concentration gradient
US11878936B2 (en) 2015-12-11 2024-01-23 Corning Incorporated Fusion-formable glass-based articles including a metal oxide concentration gradient
US10570059B2 (en) 2016-04-08 2020-02-25 Corning Incorporated Glass-based articles including a metal oxide concentration gradient
US10017417B2 (en) 2016-04-08 2018-07-10 Corning Incorporated Glass-based articles including a metal oxide concentration gradient
US11279652B2 (en) 2016-04-08 2022-03-22 Corning Incorporated Glass-based articles including a metal oxide concentration gradient
US11691913B2 (en) 2016-04-08 2023-07-04 Corning Incorporated Glass-based articles including a metal oxide concentration gradient
US11174197B2 (en) 2016-04-08 2021-11-16 Corning Incorporated Glass-based articles including a metal oxide concentration gradient
US11963320B2 (en) 2016-04-08 2024-04-16 Corning Incorporated Glass-based articles including a stress profile comprising two regions
US12116311B2 (en) 2016-04-08 2024-10-15 Corning Incorporated Glass-based articles including a metal oxide concentration gradient
CN112955412A (zh) * 2018-10-31 2021-06-11 康宁股份有限公司 韧性玻璃复合物和方法

Also Published As

Publication number Publication date
TW201329009A (zh) 2013-07-16

Similar Documents

Publication Publication Date Title
WO2013082246A1 (fr) Contrôle d'alcali dans des films minces de cig à travers du verre et par application d'une tension
US10196297B2 (en) Intermediate thermal expansion coefficient glass
EP2100335B1 (fr) Electrode frontale à base d'oxyde de zinc dopée à l'yttrium pour une utilisation dans un dispositif photovoltaïque ou autre dispositif similaire
JP2020073435A (ja) 太陽電池モジュールパッケージ
Jansen et al. A laboratory technique for the evaluation of electrochemical transparent conductive oxide delamination from glass substrates
DE102006046312B4 (de) Solarzellen mit stabilem, transparentem und leitfähigem Schichtsystem
JP2017216465A (ja) 光電池モジュールパッケージ
US20100288351A1 (en) Thin-film solar cell
CN102237447A (zh) 薄膜层光伏模块制品的处理
US20130133745A1 (en) Incorporation of alkaline earth ions into alkali-containing glass surfaces to inhibit alkali egress
US9461187B2 (en) Solar cell apparatus and method for manufacturing the same
TW201316528A (zh) 光伏模組封裝
US8921151B2 (en) Back-contact for thin film solar cells optimized for light trapping for ultrathin absorbers
CN101582461B (zh) 一种新型多层透明导电膜结构及其制备方法
JP2013522147A (ja) 構造化ｔｃｏ保護コーティングの製造方法
JP5983100B2 (ja) ガラス基材
Crupi et al. Laser irradiation of ZnO: Al/Ag/ZnO: Al multilayers for electrical isolation in thin film photovoltaics
EP3001881B1 (fr) Dispositifs photovoltaïques et leurs procédés de fabrication
US9437760B2 (en) Method of reducing semiconductor window layer loss during thin film photovoltaic device fabrication, and resulting device structure
KR20140027069A (ko) 확산-방지층을 갖는 박층 태양 전지
KR101014106B1 (ko) 태양전지 및 이의 제조방법
WO2013082343A1 (fr) Barrières de diffusion pour des dispositifs photovoltaïques par lixiviation
Snyder et al. Doping Control of Mg x Zn 1-x O Emitter through Fluorine Incorporation
JP6410108B2 (ja) ガラス基材
KR20190084454A (ko) 플렉시블 박막태양전지용 스테인레스 박판의 절연막 형성방법 및 그에 따라 제조된 태양전지

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: 12853369

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 12853369

Country of ref document: EP

Kind code of ref document: A1