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WO2018104943A1 - Cellule photovoltaïque et son procédé de fabrication - Google Patents

Cellule photovoltaïque et son procédé de fabrication Download PDF

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Publication number
WO2018104943A1
WO2018104943A1 PCT/IL2017/051322 IL2017051322W WO2018104943A1 WO 2018104943 A1 WO2018104943 A1 WO 2018104943A1 IL 2017051322 W IL2017051322 W IL 2017051322W WO 2018104943 A1 WO2018104943 A1 WO 2018104943A1
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WO
WIPO (PCT)
Prior art keywords
layer
selenium
photovoltaic device
electrode
absorber layer
Prior art date
Application number
PCT/IL2017/051322
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English (en)
Inventor
Eran MAIMON
Original Assignee
Solarpaint Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Solarpaint Ltd. filed Critical Solarpaint Ltd.
Publication of WO2018104943A1 publication Critical patent/WO2018104943A1/fr

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Classifications

    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F77/00—Constructional details of devices covered by this subclass
    • H10F77/10—Semiconductor bodies
    • H10F77/12—Active materials
    • H10F77/121—Active materials comprising only selenium or only tellurium
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F77/00—Constructional details of devices covered by this subclass
    • H10F77/20—Electrodes
    • H10F77/206—Electrodes for devices having potential barriers
    • H10F77/211—Electrodes for devices having potential barriers for photovoltaic cells
    • H10F77/219—Arrangements for electrodes of back-contact photovoltaic cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy

Definitions

  • the present invention relates to photovoltaic devices and techniques for producing photovoltaic devices.
  • the invention is relevant to Selenium based photovoltaic devices. BACKGROUND
  • Photoelectric activity of various materials opened a door for various energy harvesting techniques and especially photovoltaic solar cells.
  • discoveries of photoelectric activity of Selenium (Se) may have opened the door for understanding of light-matter interactions and the photoelectric effect as described by Einstein in 1905.
  • the use of Selenium in photovoltaic devices was abandoned in favor of Silicon and various other compounds, which may partially include Selenium related compounds.
  • Si photovoltaic (PV) devices with thickness of hundreds of microns are the dominant technology with industry adoption of glass covered modules of this brittle material for protection.
  • 2nd and 3rd generation thin film technologies improve the design using less materials and adding the prospects of flexibility while lowering manufacturing temperatures.
  • the promise for PV device that are much cheaper than silicon has been left unfulfilled due to the inherent instability of most photoactive materials and the expensive encapsulation it entails.
  • Electrodes that is configured to interface an absorber layer from a back surface of the absorber layer, leaving front surface of the absorber to be exposed to impinging light.
  • US 2016/308,155 describes an electrode arrangement and plurality of micro- structures configured for use in conversion of a surface to photovoltaic cell.
  • the electrode arrangements comprising at least two sets of conducting wires comprising wires with coatings configured to allow selective transmission of charge carriers.
  • the wires are configured for charge collection from a medium in surroundings thereof.
  • the sets of conducting wires are arranged in the form of a grid such that the different wires overlay about one another defining a region of charge collection, and are insulated from one another in said region of charge collection.
  • WO 2016/199118 describes an optically active medium and an electrode arrangement for use in providing a photovoltaic device.
  • the optically active medium comprises a liquid carrier comprising: suspended colloidal structures comprising nucleation assisting particles and optically-active semiconducting structures; and at least one soluble material selected such that when said medium is applied on a surface and the liquid carrier is allowed to evaporate, said at least one soluble material interacts with said colloidal structures to form a continuous polycrystalline film of said optically- active semiconducting structures.
  • the electrode arrangement is configured for collection of charge carriers from a medium interacting with said electrodes.
  • the electrode arrangement comprising at least one pair of first and second electrode elements configured as spaced apart patterned electrode elements installable on and extendable along a surface and being configured for selectively collecting electrons and holes respectively.
  • WO 2017/056082 describes a method for use in producing an electrode arrangement.
  • the method comprises providing a first patterned structure, said first patterned structure having a first layer comprising a first electrically conducting material on one face thereof and a layer of an electrically insulating material on one other face thereof.
  • Said first patterned structure comprises a plurality of perforations forming said pattern.
  • Applying a second layer comprising a second electrically conducting material on said electrically insulating material of the first patterned structure thereby covering a face of said first patterned structure.
  • a pattern is formed of said first and second electrically conducting materials, being insulated between them and exposed to the environment on a second face of said electrode arrangement.
  • the present invention provides a photovoltaic device and production techniques utilizing active photo absorber layer that is mainly formed of Selenium (Se).
  • Selenium was one of the first materials discovered to produce photovoltaic activity in the 19th century and in fact, these discoveries were part of the inspirations of Einstein's Nobel Prize work on the photoelectric effect.
  • the industrial use of Selenium as photo absorber was abandoned in the 1950's due to the advent of Silicon technology.
  • charge selective Selenide-based compound may be formed at interface with one or more electrodes enabling to increased collection of energy converted from light.
  • the band gap of ⁇ 1.8eV of Selenium in its trigonal form makes it suitable as a standalone photo absorber with theoretical efficiency exceeding 20%.
  • An additional advantage to the use of Selenium as photo absorber, is its suitable band gap for use in tandem cell applications.
  • the Selenium photovoltaic device may be coupled with additional photovoltaic device having lower band gap materials and especially Silicon with its l. leV band gap.
  • the present technique provides a photovoltaic device comprising active absorber layer comprising Selenium active material.
  • the active absorber layer is in electrical contact with at least a pair of electrodes configured for collection of free charge carriers generated in response to absorption of light by the active material.
  • the electrodes generally comprise at least one hole collecting electrode and at least one electron collecting electrode, each arranged for collecting charge carriers from surface of the active absorber layer.
  • the device further comprises a charge selective layer at an interface of least one of the hole collecting and electron collecting electrodes with the active absorber layer, formed by Selenium-based compound providing charge selectivity of the layer.
  • the electrode arrangement may comprise at least one of the following: electron collecting electrode comprising Zinc interfacing the active absorber layer; hole collecting electrode comprising Copper interfacing the active absorber layer; and hole collecting electrode comprising Molybdenum interfacing the active absorber layer.
  • electron collecting electrode comprising Zinc interfacing the active absorber layer
  • hole collecting electrode comprising Copper interfacing the active absorber layer
  • hole collecting electrode comprising Molybdenum interfacing the active absorber layer.
  • the active absorber layer may be deposited from liquid solution in which Selenium material is dissolved at concentration in the range of 0.5 gr/ml to 0.05gr/ml in liquid mixture.
  • the liquid mixture may be a mixture of thiol and amine related molecules, capable of dissolving Selenium while also suitable for sufficient drying under suitable conditions for forming solid residue of Selenium on a surface.
  • the solution may include Tetramethylethylenediamine (TMEDA) and ⁇ - mercaptoethanol.
  • TMEDA may be replaced by Ethanolamine, providing a mixture of Ethanolamine and ⁇ -mercaptoethanol as solvent for Selenium. Additional solvents include Ethanethiol and Triethylamine.
  • the active absorber layer may be formed from a thin layer of trigonal (gray) Selenium, having thickness of 5-100 micrometer, and may include additional material, e.g. up to 50% by weight or preferably up to 20% by weight.
  • the liquid solution is applied on a surface, e.g. an electrode arrangement, and allowed to dry or evaporate, by heating and/or curing.
  • the remaining Selenium containing residue may be further annealed for generating a layer of trigonal (gray) Selenium capable of providing photoelectric activity. It should be noted that such annealing may be accompanied with transmission of current through the active absorber layer for forming the Selenide-based charge selective layer at corresponding electrodes' interfaces.
  • formation of Selenide-based charge selective layer interfacing the active absorber layer and corresponding electrodes provides for simplifying production process and costs of the resulting photovoltaic device.
  • the present invention provides a photovoltaic device comprising active absorber layer comprising Selenium active material in electrical contact with at least one electron collection electrode and at least one hole collection electrode; wherein said photoelectric device comprises charge selective layer comprising a selenium compound based charge selective layer.
  • the Selenium active material may preferably be in trigonal crystalline form, or be converted to such form by suitable annealing.
  • the electron collection electrode may comprise Zn metal, said charge selective layer comprising Zinc Selenide layer formed by interaction of the electron collection electrode material with said active absorber layer material.
  • the hole collection electrode may comprise Copper metal, said charge selective layer comprising Copper Selenide layer formed by interaction of the hole collection electrode material with said active absorber layer material.
  • the hole collecting electrode may be configured as Aluminum electrode coated with Copper layer.
  • the hole collection electrode may further comprise a metallic compound of at least one of: Aluminum, Stainless steel, nickel, and configured such that the Copper layer is located between said active absorber layer and the metallic compound.
  • the hole collection electrode may comprise molybdenum, said charge selective layer comprising molybdenum selenide layer formed by interaction of the hole collection electrode material with said active absorber layer material.
  • the hole collection electrode further comprises a metallic compound of at least one of: Aluminum, Stainless steel, nickel, and configured such that the molybdenum layer is located between said active absorber layer and the metallic compound.
  • the electron collection electrode may comprise at least one of the following materials: fullerenes, Aluminum, copper, Nickel, Titanium and Chrome. Further, the electron collection electrode may comprise at least one of the following materials: Al, Sn, Zn, Mo, Ti, Cu, Pb, Ag, Ni, C, conductive polymer, conductive oxide, conductive nitride, conductive chalcogenide, FTO, ITO, AZO, PEDOT and combinations thereof.
  • the hole collection electrode may comprise at least one of the following materials: Molybdenum, Molybdenum trioxide (Mo03), Lithium fluoride, Carbon nanotubes, graphite, SP2-SP3 mixes of carbon species, carbon black and Tungsten oxide. Further, the hole collection electrode may comprise at least one of the following conducting materials: Al, Sn, Zn, Mo, Ti, Cu, Pb, Ag, Ni, C, conductive polymer, conductive oxide, conductive nitride, conductive chalcogenide, FTO, ITO, AZO, PEDOT and combinations thereof.
  • the at least one electron 5 collection electrode and at least one hole collection electrode may be arranged to interface said active absorber layer through a common surface thereof, thereby providing back electrode configuration.
  • the at least one electron collection electrode and at least one hole collection electrode may be arranged to form a porous membrane on film structure being in electrical contact with a common surface of
  • the at least one electron collection electrode and at least one hole collection electrode may be arranged in an interdigital configuration being in electrical contact with a common surface of said active absorber layer.
  • the electrodes may be arranged as two partially overlapping grids or other configurations enabling electrical contacts of both the electron and hole
  • the active absorber layer at least 60% by weight of Selenium.
  • the active absorber layer may further comprise at least one binding material selected from the group: polyalkylacrylates, poly(meth)acrylates, polyalkyl(meth)acrylate and polysiloxanes.
  • 20 layer may further comprise at least one doping material.
  • the active absorber layer may be configured with thickness between lOnm and 100 micron.
  • the active absorber layer may be configured with thickness between lOnm and 500 nm, or between lOOnm and 2 micron.
  • the active absorber layer may have thickness between 2 micron and
  • the photovoltaic device may be configured for use in various applications, including one or more of the following: for use on water reservoir covers; embedded in roofing materials; embedded in architectural materials; and embedded in roads surfaces under a "transparent asphalt”.
  • the present invention provides a method for producing photovoltaic device, the method comprising:
  • an electrode arrangement including at least one electrode for charge collection; applying solution comprising Selenium solute onto said electrode arrangement; heating said solution to evaporating solvent and leaving residue of polycrystalline Selenium on the electrode arrangement;
  • the method may further comprise applying a second electrode arrangement on said polycrystalline selenium layer.
  • the electrode arrangement may comprise two sets of charge collecting electrodes, being electrically insulated between them.
  • the electrode arrangement may comprise electrodes formed by at least one of Zinc, Copper and Molybdenum, and used to interface with said selenium residue.
  • the method may further comprise transmitting electrical current through the device for generating layer of Selenide-based charge selective layer at interface with at least one of the electrodes.
  • the Selenide-based charge selective layer may comprise at least one of ZnSe, CuSe2 and MoSe2.
  • the solution used may comprise Thiol and Amine solvents mixture.
  • the solution may comprise a mixture of Tetramethylethylenediamine (TMEDA) and ⁇ -mercaptoethanol at range of 0.8: 1 to 1.2:1 ratio.
  • the solution may comprise a mixture of Ethanolamine and ⁇ - mercaptoethanol in range of 0.8: 12 to 1.2:1 ratio, or a mixture of Ethanethiol and Trimethylamines in range of 0.8: 1 to 1.2: 1 ratio.
  • Fig. 1 illustrates schematically a photovoltaic device according to some embodiments of the invention
  • Fig. 2 illustrates schematically an additional configuration of a photovoltaic device according to some embodiments of the invention
  • Figs. 3A to 3E illustrate process of production a photovoltaic device according to some embodiments of the invention
  • Fig. 3A illustrates an electrode arrangement suitable of producing the device
  • Fig. 3B exemplifies Selenium containing solution applied on the electrode arrangement
  • Fig. 3C exemplifies evaporation of the liquid solvent
  • Fig. 3D exemplifies annealing and transmission of electrical current
  • Fig. 3E illustrates the final photovoltaic device according to some embodiments of the invention
  • Fig. 4 shows SEM image exemplifying crystalline grains of trigonal Selenium deposited from solution according to some embodiments of the invention
  • Fig. 5 shows I-V curve for Selenium photovoltaic device according to some embodiments of the invention
  • Fig. 6 shows I-V curve for Selenium photovoltaic device according to the embodiments on the invention utilizing back electrodes configuration
  • Fig. 7 A shows short circuit current of Selenium active absorber layer as known in the art.
  • Fig. 7B shows absorption spectrum of trigonal Selenium as known in the art.
  • the present invention provides a novel photovoltaic (PV) device utilizing a photo absorber layer including Selenium active material and electrode arrangement forming at least one interface of Selenide-based compound providing charge selective transmission layer.
  • Figs. 1 and 2 illustrating schematically PV devices 100 according to some embodiments of the invention.
  • the PV device exemplified here includes an active absorber layer 200 generally formed of Selenium in its trigonal (gray) form with certain amount of additive materials.
  • the active absorber layer is electrically coupled to at least one hole collecting electrodes 300 and at least one electron collecting electrode 400 (two such electrode contacts are shown here).
  • the electrodes are coupled to the active absorber layer along both front and back surfaces thereof, while Fig.
  • Interface regions between at least one of the hole and electron collecting electrode include corresponding charge selective layers formed of Selenide-based compounds, in the figure charge selective layers 350 and 450 are illustrated providing electron transmitting layer, and hole transmitting layer respectively. It should however be understood that in accordance with material selection and configurations, Selenide- based charge selective layers may be used at interface with one or both electron and hole collecting electrodes. Additional charge selective layers may be used formed of materials other than Selenide-based compounds.
  • the PV device 100 may be formed utilizing back/bottom electrodes. This configuration enables reduction in costs as the PV devices may utilize opaque electrodes and there is no actual need for use of transparent electrodes. Further, the use of back surface electrode arrangement enables simple conversion of any selected surface to photovoltaic device, e.g. by providing electrode arrangement on the selected surface, applying active absorber material from paint-like solution and drying the solution to provide photo absorber residue 200. Accordingly, the PV device 100 as described herein may be produced on top of a suitable electrode arrangement, e.g. as described in US 2016/308,155, WO 2016/199118, and WO 2017/056082 incorporated herein by reference with respect to the configuration of the electrode arrangement described therein, to provide a functioning PV device.
  • a suitable electrode arrangement e.g. as described in US 2016/308,155, WO 2016/199118, and WO 2017/056082 incorporated herein by reference with respect to the configuration of the electrode arrangement described therein, to provide a functioning PV device.
  • the present technique utilizes a dedicated electrode arrangement and a suitable material, for applying to (e.g. depositing on) the electrode arrangement to provide active absorber layer in contact with the electrode arrangement.
  • the material is preferably provided in the form of a liquid suspension or solution and may be applied on a surface (e.g. by painting the surface, thermal evaporation, electrospray, etc.) for providing active absorber layer forming a PV device on the surface.
  • deposition of the active material of the absorber layer may also be done from additional material forms such as powder, using corresponding powder deposition techniques such as powder spray.
  • the active absorber layer material may be deposited using vapor deposition and/or electrodeposition techniques.
  • the active material includes Selenium (Se) and is prepared such that when applied on a surface and subsequent to drying, curing and/or annealing processes, the remaining residue includes solid trigonal Selenium operable as photoactive film by generating charge carriers in response to electromagnetic radiation (e.g. optical radiation) incident thereon.
  • the material is in the form of a solution within a solvent suitable for use as a paint-like medium. More specifically, when applying the liquid solution on a surface and allowing the liquid carrier to evaporate, with or without specific heating, drying or curing processes, a polycrystalline/amorphous residue including Selenium active material is formed on the surface.
  • the solution concentration and desired amounts of solution applied are selected to provide Selenium based residue layer having thickness of 5-100 micrometer.
  • the formed residue can act as the active photo absorber layer enabling energy harvesting from optical radiation impinging thereon.
  • the electrode arrangement includes at least one hole collecting electrode 300 and at least one electron collecting electrode 400.
  • At least one of the electron or hole collecting electrodes is configured with metallic contacts of selected materials enabling formation of charge selective layers (350 or 450) along corresponding interface with the active absorber layer.
  • one or more of the hole and electron collecting electrodes (300 or 400) may be coated with one or more additional charge selective materials.
  • the active material may be deposited such that both electrodes are below the active absorber layer 200 (with respect to direction of light impinging on the device) or such that one electrode is below and one electrode is above the active absorber layer 200.
  • the active absorber layer 200 of the PV device 100 may in some embodiments be deposited from a liquid material mixture, e.g. acting as paint (or paint-like) when applied on a surface, alternatively the active absorber layer may be deposited by a vapor or powder coating applied to a surface thereon.
  • the applied liquid mixture may subsequently be dried/cured/annealed as required, leaving a photoactive film of the active material on the surface.
  • the material composition of the mixture is selected such that the photoactive film formed on the surface can generate charge carriers in response to absorbed incident electromagnetic radiation of one or more wavelength ranges.
  • the "paint" (or paint-like, liquid, powder, vapor etc.) providing the active material generally includes Selenium as the primary, optically active, material with some additional additives that do not exceed 50% by weight of the photoactive material as will be described in more details below.
  • material composition of the active absorber layer is herein referred to as Selenium, although may include up to 50% by weight of additional additives selected to increase stability and/or electrical properties of the active absorber layer.
  • the Selenium active material, and additives when used, may be provided as suspended or dissolved material in liquid carrier to provide a suspension mixture or a solution (termed here "liquid mixture”).
  • the "paint" mixture may be provided as a powder, in others the material can be melted to form a liquid.
  • the materials can be evaporated by e.g. e-beam, pulsed laser deposition (PLD), Chemical vapor deposition (CVD), atomic layer deposition (ALD), sputtering, thermal evaporation etc., alternatively, in some embodiments the material can be deposited from Hydrogen Selenide (H2Se) material or elemental selenium.
  • PLD pulsed laser deposition
  • CVD Chemical vapor deposition
  • ALD atomic layer deposition
  • sputtering thermal evaporation etc.
  • H2Se Hydrogen Selenide
  • selenium is melted at temperatures above 217 degrees Celsius and may thus be coated on a heated substrate accordingly by either pouring the melt on the substrate and wiping it with a blade to get the desired thickness or by applying predetermined force on a piece of selenium against a heated substrate to get a uniform deposited layer.
  • preparation of the active absorber layer may utilize liquid solution of Selenium in a selected mixture.
  • Selenium may be dissolved in a mixture of selected thiols and amines.
  • the solution may include Tetramethylethylenediamine (TMEDA) and ⁇ - mercaptoethanol.
  • TMEDA Tetramethylethylenediamine
  • the TMEDA may be replaced by Ethanolamine, providing a mixture of Ethanolamine and ⁇ -mercaptoethanol as solvent for Selenium.
  • Additional solvents include Ethanethiol and Triethylamine.
  • the solvent may be approximately 1 : 1 ratio of the materials, in which Selenium may be dissolved with concentration of between 0.5 gr/ml to 0.05 gr/ml.
  • the solution may be mixed and applied onto a selected surface, e.g. electrode arrangement, and dried and annealed to provide a layer of polycrystalline gray Selenium.
  • the liquid solution may be applied onto a selected surface such as pre-prepared electrode arrangement including suitable array of electron and hole collecting electrodes, an arrangement of one of the electron or hole collecting electrode, or temporary substrate. After evaporating the liquid solvents, the remaining residue contains mostly (50% weight or more) solid polycrystalline Selenium.
  • an additional electrode configuration may be applied onto the Selenium layer, in the case that the layer was deposited on one of the electrodes, and the region of the photovoltaic device may be divided to selected segments.
  • the Selenium layer is preferably annealed at relatively high temperature of 150 to 350 degrees Celsius in selected pressure conditions.
  • the annealing process may be performed at any stage after deposition of the Selenium layer and typically provides for converting the Selenium layer to its trigonal form, in which the layer acts as active absorber layer.
  • the annealing process may be operated for short time period such as 10 milliseconds, e.g. using rapid thermal anneal (RTA) or light strobe, and up, e.g. up to 2 minutes per PV device region.
  • RTA rapid thermal anneal
  • the annealing process is performed at increased pressure conditions.
  • the annealing process may be done with pressure conditions above lbar and preferably not exceeding lOOObar.
  • the annealing process transforms the amorphous selenium layer to the grey allotrope, which has photovoltaic properties.
  • Annealing may typically be a key factor in the fabrication of a selenium solar cell.
  • the annealing process may also define the grain size and crystal orientation.
  • the Selenium layer may be annealed on a hot plate at temperatures in the range of 150-350 degrees Celsius, e.g. at 217 degrees Celsius, for different time durations.
  • the Selenium layer may be annealed under mechanical pressure (press) and/or increased pressure, using selected gas mixture such as air, inert gas etc.
  • the Selenium layer may be annealed under selected illumination conditions such as white light, ultra-violet (UV) or infrared (IR) illumination at high intensity.
  • flash annealing may be used, e.g. using a RTA (rapid thermal annealing) system such as VIS flash lamps, UV lamps and more, enabling quick annealing process of the Selenium absorber layer.
  • RTA rapid thermal annealing
  • Additional annealing techniques include microwave and RF annealing.
  • electric or magnetic fields may be used to induce a preferred orientation of the crystalline grains. Conductance in the selenium crystals along direction defined by chains of bonded Selenium atoms is preferred over conductance between chains.
  • the Selenium absorber layer may be grown under electric field conditions.
  • growth under electric field provides selected growth direction as radical formation at the chain ends typically induce further growth from these ends.
  • the hole and electron collecting electrodes are generally configured for one or more electrically conducting materials, and may include selected coating, or interface material between the electrically conducting electrode and the active absorber layer, that limits transmission of charge carriers in accordance with charge thereof.
  • a suitable charge selective layer may be formed at interface of the Selenium active absorber layer and the corresponding electrode.
  • Such charge selective layer is generally formed by interaction of the electrode material and the Selenium of the active absorber in selected conditions.
  • the at least one hole collecting and at least one electron collecting electrodes may generally include at least one of Zinc (Zn) electron collecting electrode, Copper (Cu) hole collecting electrode and Molybdenum (Mo) hole collecting electrode.
  • the selenide charge selective layer may be formed at the corresponding interface by transmitting electrical current between the hole and electron collecting electrode through the Selenium absorber layer and/or heating the material.
  • the resulting photovoltaic device may be further coated with protection coating and may be ready for use.
  • an aluminum electrode coated by lOnm copper and 1 micron of Se was heated to lOOC for less than 1 hour.
  • the copper layer was transformed is substantially uniform manner into copper selenide layer. This process is fast and requires not additional materials other than proper conditions.
  • the Copper Selenide layer the thermodynamic minimum associated with interaction of the material, and is formed at high temperature conditions. Transmission of current at voltage of 200V for 5 min, while maintaining current density lower than lOuA/cm , also provides suitable conditions for full or partial transformation of copper to copper selenide.
  • FIG. 3A an electrode arrangement 600 is provided as a substrate for the PV device.
  • the electrode arrangement 600 is configured as porous membrane on film structure including hole collecting electrode 300 arranged within electron collecting electrode
  • the electrode arrangement may be arranged in various configurations including double array electrodes and other configurations, e.g. as described in previous patent publications by the inventors including US 2016/308,155, WO 2016/199118, and WO 2017/056082 incorporated herein by reference with respect to the configuration of the
  • a Selenium carrying solution 250 is be applied onto the electrode arrangement.
  • the solution is in contact with the electrodes and may be held in place by surface tension, viscosity, or using proper tools such as a container.
  • the solution may be applied by electrospray to provide effective coverage of the surface, but may also be
  • the band gap of the Selenium active absorber layer may be tuned by various additives. For example, adding small amounts of Tellurium (Te) to the Selenium solution (or powder) such that the Tellurium is being evaporated ensuring that it is embedded in the selenium
  • 25 chain and does not segregated into tellurium zones may reduce the band gap of the Se- Te alloy to better fit the solar spectrum and allow the absorption of more photons by the active material.
  • the solvent is evaporated in Fig. 3C, e.g. under heating 235 at high pressure conditions, leaving a solid residue 230 including amorphous and/or polycrystalline 30 Selenium in one or more crystal structures.
  • a scanning electron microscope image of the Selenium active absorber layer is shown in Fig. 4.
  • an additional electrode may be applied, in case the material is deposited on electrode arrangement including only one of the hole or electron collecting electrodes.
  • annealing of the Selenium layer under high pressure conditions might be important for providing continuous and effective Selenium active absorber layer. This is due to the tendency of Selenium to contract during phase transition to trigonal form.
  • suitably high-pressure conditions may avoid creation of voids in the film and accordingly improve results of the so-formed PV device.
  • Fig. 3D illustrates generating charge selective layer 350 and 450 at interface of the Selenium active absorber 200 and at least one of the hole and electron collecting electrodes.
  • the device is heated and annealed for inducing the formation of trigonal Selenium as well as formation of Selenide containing compounds such as Zinc Selenide, Copper Selenide or Molybdenum Selenide, at interfaces with the respective materials of the electrodes.
  • This provides a functioning Selenium based PV device illustrated in Fig. 3E.
  • Fig. 5 shows measured I-V curve for Selenium PV device using Aluminum/Copper electric contacts and Copper Selenide hole transmitting layer interfacing Selenium active absorber layer in dark conditions and under normal illumination conditions.
  • Fig. 6 shows additional graph of measured I-V curve for a device using back electrode configuration as described above in dark conditions and under normal illumination conditions.
  • At least an exemplary device, constructed as described herein provides performance including: short circuit current from this cell in the range of 90-120 A/m and open circuit voltage in the range of 600mV-880mV. It should be noted that these are exemplary measurements and optimized performance is expected.
  • the PV device may be configured for operating in tandem cell configuration.
  • the materials for the electrodes and supporting structures are preferably selected to be substantially transparent, as to allow most incoming radiation not absorbed by the photoactive layer to be transmitted therethrough and impinge on an additional photovoltaic device located downstream with respect to direction of light propagation.
  • glass cover of a Silicon PV (or other PV with different band gap) module may be converted into a Selenium solar cell, in accordance with the above described production techniques, before being attached to the Silicon PV module.
  • This provides tandem configuration to the Silicon module, where the electricity collecting wires may be collected by a junction box enabling collection of electric charges from devices of different open circuit operation voltage levels.
  • tandem cell may be provided by using glass cover and providing a thin wallpaper-like Selenium solar system to be attached to the glass, e.g. by using a transparent adhesive on the back of the wall paper.
  • the glass cover may then be attached to an existing PV module while connecting charge collecting wires of the Selenium cell through a suitable junction box providing current or voltage conversion either at the module level or at a larger level to optimize the combined power output.
  • Another example for production process of Selenium PV device is associated with the following: providing a glass cover, and coating the glass with first substantially transparent electrode, e.g. by sputtering, CBD or spray pyrolysis of ITO, FTO, AZO, coating with PEDOT:PSS, metal nano mesh, etc. Further, coating the transparent electrode with a transparent carrier selective layer suitable for electron transmission layer (ETL) or hole transmission layer (HTL) as described above. Coating the carrier selective layer with Selenium layer (with or without adhesion and conversion intermediate layers), e.g. by applying Selenium containing solution and evaporating the liquid carrier. At this stage coating the other carrier selective layer (HTL or ETL) and coating another transparent electrode.
  • ETL electron transmission layer
  • HTL hole transmission layer
  • an insulating or protective layer may be used for separating between the Selenium based PV cell and the Silicon based cell attached in tandem configuration. And additional set of electrodes and charge selective layer are further applied to be associated with the following active absorber (Silicon cell).
  • the Selenium PV cell may also be formed with back electrode arrangement.
  • a set of electrode arrangement is applied onto a transparent substrate.
  • the electrode arrangement may preferably be configured to be substantially transparent, and the different electrodes are insulated from each other, and may be coated by suitable charge selective layers.
  • a Selenium layer in applied onto the electrode arrangement and annealed to form trigonal crystalline structure.
  • generation of charge selective layer based on Selenide -related materials such as Zinc Selenide, Copper Selenide or Molybdenum Selenide, may simplify the structure and process as the selenide-based material may be formed at suitable material interface after the Selenium layer of fully formed.
  • Such configurations provide that both charge carrier collecting electrodes are on one side of the Selenium layer, thus creating a back junction solar cell.
  • An additional advantage identified by the inventors of the present invention to the use of Selenium in PV device is associated with stability of Selenium in its trigonal form.
  • air stable active material based solar cell allows for eliminating the need to use barriers layers configured to reduce environmental effects on the absorber layer. Such environmental effects may typically be associated with oxygen, humidity, etc., which may degrade the active absorber material. This enables longer lifetime and reduces costs for protection layers that might need to be used.
  • manufacturing processes may be much simplified as the system does not have to be in inert atmosphere during production and before encapsulation by a protective layer, thus reducing manufacturing costs significantly.
  • bottom/back electrode arrangement as described above, in addition with deposition of the selenium active material from solution dramatically enhances the robustness of both the manufacturing process and the final PV device.
  • the process may be suitable using standard roll to roll equipment, and enables elimination of expensive materials required for transparent electrodes, although in some configurations transparent electrodes are desired.
  • the photovoltaic device according to the present technique may be applied onto almost any surface and be used in the various applications, including for example: "wallpaper" PV device configured to be attached to selected surfaces (practically any surface); PV device for indoor applications; PV device as electrical source for use in various smart devices (e.g. internet of things or IoT devices) and sensors; Tandem cell with additional PV module; PV device for use on a semitransparent surface where the radiation not absorbed by the photoactive material is desired for additional use (e.g. red illumination); device for use on reservoir covers, such as PVC covers where there is a need for a lightweight and flexible solar system in order not to complicate floatation.
  • wallpaper PV device configured to be attached to selected surfaces (practically any surface)
  • PV device for indoor applications PV device as electrical source for use in various smart devices (e.g. internet of things or IoT devices) and sensors
  • Tandem cell with additional PV module PV device for use on a semitransparent surface where the radiation not absorbed by the photoactive material is desired for additional use (e.
  • the PV device of the present technique may be configured to be embedded in roofing materials such as plastic shingles etc. this may be used where lightweight PV solutions are desired.
  • the PV device may also be embedded in architectural materials such as wall stones or streets.
  • the device may further be embedded in roads surfaces, e.g. under a "transparent asphalt” where a stable, robust and unbreakable system is much preferable than the attempt to protect a brittle silicon cell.
  • the PV device is produced on a transparent electrode provided on a transparent substrate (e.g. fluorine doped tin oxide (FTO), Indium tin oxide (ITO), aluminum zinc oxide (AZO) and metal (usually silver) nano-wires, Poly(3,4-ethylenedioxythiophene) (PEDOT) or other transparent electrodes on substrate of glass, Polyethylene terephthalate (PET), Polyimide (PI), polytetrafluoroethylene (PTFE), Polyvinylidene fluoride (PVDF), Polydimethylsiloxane (PDMS), or other substrates).
  • the electrode is typically coated with an electron transmitting layer (ETL) having conduction band or LUMO states of between 3.4eV and 4.4eV (e.g.
  • the electron transmitting layer may be further coated with a thin adhesion layer of e.g. Te, In, Th etc. with thickness of between 0.1 nm and lOOnm for improved electrical contact with the active absorber layer.
  • a thin adhesion layer e.g. Te, In, Th etc. with thickness of between 0.1 nm and lOOnm for improved electrical contact with the active absorber layer.
  • a Selenium active absorber layer is applied on the adhesive surface having thickness between 25nm and 20 microns.
  • the Selenium layer may be applied from solution as described above, using vapor deposition and/or deposited from Melt and/or solution of Selenium.
  • the Selenium layer may be further coated with Hole transmitting layer having HOMO states (valance band states) between 4.8eV and 6eV such as MoSe2, CuSe2 or other charge selective layers (e.g.
  • the hole transmitting layer may be provided by high work function material such as carbon, gold, platinum, or Molybdenum.
  • An additional electrode is further provided on the hole transmitting layer.
  • the additional electrode may be transparent for use in tandem cells of not.
  • the device may be coated with a protective overcoat to reduce wear while operating.
  • the active region and the electrodes may be divided to sub units for optimizing performance and simplifying maintenance. The division may be done using any known technique such as e.g. "PI, P2, P3" technique, and may be done either as a last step or intermediate steps between layers in order to provide desired parallel and series connections between the sub units.
  • the photovoltaic device and specifically the Selenium active absorber layer, is annealed at 200C for 20s under pressure of 1-1000 bar to encourage forming of trigonal Selenium layer. This step may be done at any stage after the deposition of the selenium layer as following process and application steps necessitate.
  • the initial transparent electrode may be operable as electron or hole collecting in accordance with material selection of the electrode and the corresponding charge selective layer.
  • a commercial FTO coated glass substrate (TEC 8) is coated by a spray pyrolysis in a process known in the art with 60nm thick Ti02.
  • the Ti02 is further coated FTO and the sample is provided into a thermal evaporator and pumped to a vacuum of ⁇ 1 micro-torr. Additional layers were deposited on the FTO layer including layer of lnm tellurium acting as an adhesion layer; layer of 2 microns of selenium deposited on the tellurium as active photo absorber layer. Further a layer of 15nm /Mo03 is deposited on the selenium to provide Hole transmitting charge selective layer. The corresponding electrode including layer of graphitic carbon is further deposited on the Mo03. The cell is hot pressed at 200C for 20 seconds at pressure of 50 psi to achieve conversion of the amorphous selenium to the grey crystalline form.
  • Another non-limiting example includes sandwiching assembly technique.
  • an electron collecting electrode in provided on a substrate suitable charge selective layer is applied onto the electrode, and photo absorbing Selenium layer is deposited on the charge selective layer. Similar configuration is provided for the hole collecting electrode and the two photovoltaic device pieces are attached together interfacing at the active absorber layer thereof.
  • a metal foil is coated with carbon paste, annealed, put into the thermal evaporator and pumped to a vacuum of ⁇ 1 micro-torr.
  • a layer of lnm of tellurium is deposited on the carbon paste followed by deposition of selenium to provide a portion of the active absorber layer.
  • the two parts of the cell are attached (sandwiched) together at the Selenium surface, and are hot pressed at 200C for 20s at 50psi to achieve conversion of the amorphous selenium to the grey crystalline form and connection between the two parts where the amorphous selenium connects both sides during crystallization.
  • the tellurium adhesive layer may be substituted with additional alternative layers such as indium.
  • a layer of hole conductor selective layer such as MoSe 2 (or MoO 3 ) may preferably deposited on the conducting electrode material.
  • MoSe 2 or MoO 3
  • the use of Molybdenum metal, deposited on the foil may be preferred, enabling formation of a thin layer of MoSe 2 by interacting the conducting metal with the Selenium active absorber layer.
  • a back-contact device is produced using Se photo-active absorber layer.
  • An electron transmitting layer (ETL) having LUMO of between 3.4eV and 4.4eV e.g. formed of Ti0 2 , ZnO, Sn0 2 , ln 2 0 3 , combinations thereof, combination with magnesia, alumina, zirconia, silica, in order to better tune the conduction band minimum
  • ETL electron transmitting layer
  • a thin (0.5-5 um thick) membrane with through pores of diameters 5-20um is adhered on to a carrier using a sacrificial release.
  • the membrane is then metalized using Copper or Molybdenum layer, in some other examples that membrane was metalized and coated with hole transmitting layer as mentioned above.
  • the hole transport membrane is released from the sacrificial release layer and placed on the Electron transport electrode.
  • a lnm tellurium layer was applied for use as an adhesion layer (and dopant) and 2 microns of selenium were deposited on the back-contact substrate.
  • the active layer is annealed to provide trigonal crystal phase of the Selenium and was held in high temperature to allow formation of Selenide based interface of the copper or Molybdenum with the Selenium active absorber.
  • the device may be coated with a protective overcoat to reduce wear while operating.

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  • Photovoltaic Devices (AREA)

Abstract

La présente invention concerne un dispositif photovoltaïque. Le dispositif comprend une couche d'absorbeur active comprenant un matériau actif de sélénium et étant en contact électrique avec au moins une électrode de collecte d'électrons et au moins une électrode de collecte de trous. Le dispositif photoélectrique comprend une couche sélective de charge comprenant une couche sélective de charge à base de composé de sélénium, telle qu'un matériau à base de séléniure, au niveau de l'interface de l'electrode de collecte d'electr et/ou de l'electrode de collecte d'électrons avec la couche d'absorbeur active.
PCT/IL2017/051322 2016-12-06 2017-12-06 Cellule photovoltaïque et son procédé de fabrication WO2018104943A1 (fr)

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US11411191B2 (en) * 2017-02-14 2022-08-09 International Business Machines Corporation Selenium-fullerene heterojunction solar cell
WO2022192750A1 (fr) * 2021-03-11 2022-09-15 Worcester Polytechnic Institute Fabrication assistée par pression de cellules solaires et de dispositifs électroluminescents
US11557690B2 (en) * 2017-02-14 2023-01-17 International Business Machines Corporation Semitransparent chalcogen solar cell
US11978815B2 (en) 2018-12-27 2024-05-07 Solarpaint Ltd. Flexible photovoltaic cell, and methods and systems of producing it

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US20050172996A1 (en) * 2004-02-05 2005-08-11 Advent Solar, Inc. Contact fabrication of emitter wrap-through back contact silicon solar cells
US20080092945A1 (en) * 2006-10-24 2008-04-24 Applied Quantum Technology Llc Semiconductor Grain and Oxide Layer for Photovoltaic Cells
US20100229931A1 (en) * 2008-03-18 2010-09-16 Solexant Corp. Back contact for thin film solar cells
US20120061247A1 (en) * 2010-09-09 2012-03-15 International Business Machines Corporation Method and Chemistry for Selenium Electrodeposition

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US20050172996A1 (en) * 2004-02-05 2005-08-11 Advent Solar, Inc. Contact fabrication of emitter wrap-through back contact silicon solar cells
US20080092945A1 (en) * 2006-10-24 2008-04-24 Applied Quantum Technology Llc Semiconductor Grain and Oxide Layer for Photovoltaic Cells
US20100229931A1 (en) * 2008-03-18 2010-09-16 Solexant Corp. Back contact for thin film solar cells
US20120061247A1 (en) * 2010-09-09 2012-03-15 International Business Machines Corporation Method and Chemistry for Selenium Electrodeposition

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11411191B2 (en) * 2017-02-14 2022-08-09 International Business Machines Corporation Selenium-fullerene heterojunction solar cell
US11557690B2 (en) * 2017-02-14 2023-01-17 International Business Machines Corporation Semitransparent chalcogen solar cell
US11978815B2 (en) 2018-12-27 2024-05-07 Solarpaint Ltd. Flexible photovoltaic cell, and methods and systems of producing it
WO2022192750A1 (fr) * 2021-03-11 2022-09-15 Worcester Polytechnic Institute Fabrication assistée par pression de cellules solaires et de dispositifs électroluminescents

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