WO2021159737A1 - Method for manufacturing flexible transparent thin film solar cell - Google Patents

Method for manufacturing flexible transparent thin film solar cell Download PDF

Info

Publication number
WO2021159737A1
WO2021159737A1 PCT/CN2020/124403 CN2020124403W WO2021159737A1 WO 2021159737 A1 WO2021159737 A1 WO 2021159737A1 CN 2020124403 W CN2020124403 W CN 2020124403W WO 2021159737 A1 WO2021159737 A1 WO 2021159737A1
Authority
WO
WIPO (PCT)
Prior art keywords
solar cell
flexible
film
transparent thin
film solar
Prior art date
Application number
PCT/CN2020/124403
Other languages
French (fr)
Chinese (zh)
Inventor
李源
张为苍
眭斌
张文进
杨亮
Original Assignee
信利半导体有限公司
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 信利半导体有限公司 filed Critical 信利半导体有限公司
Publication of WO2021159737A1 publication Critical patent/WO2021159737A1/en

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
    • H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • H01L31/1892—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof methods involving the use of temporary, removable substrates
    • H01L31/1896—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof methods involving the use of temporary, removable substrates for thin-film semiconductors
    • 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
    • H01L31/03926—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 comprising a flexible 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
    • H01L31/04—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 adapted as photovoltaic [PV] conversion devices
    • H01L31/06—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 adapted as photovoltaic [PV] conversion devices characterised by potential barriers
    • H01L31/068—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 adapted as photovoltaic [PV] conversion devices characterised by potential barriers the potential barriers being only of the PN homojunction type, e.g. bulk silicon PN homojunction solar cells or thin film polycrystalline silicon PN homojunction solar cells
    • H01L31/0682—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 adapted as photovoltaic [PV] conversion devices characterised by potential barriers the potential barriers being only of the PN homojunction type, e.g. bulk silicon PN homojunction solar cells or thin film polycrystalline silicon PN homojunction solar cells back-junction, i.e. rearside emitter, solar cells, e.g. interdigitated base-emitter regions back-junction cells
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/451—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising a metal-semiconductor-metal [m-s-m] structure
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/80—Manufacture or treatment specially adapted for the organic devices covered by this subclass using temporary substrates
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K77/00—Constructional details of devices covered by this subclass and not covered by groups H10K10/80, H10K30/80, H10K50/80 or H10K59/80
    • H10K77/10—Substrates, e.g. flexible substrates
    • H10K77/111—Flexible substrates
    • 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
    • Y02E10/547—Monocrystalline silicon PV cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • 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
    • Y02E10/549—Organic PV cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to the technical field of manufacturing transparent thin-film solar cells, and more specifically to a method for manufacturing a flexible transparent thin-film solar cell.
  • thin-film solar cells are applied to display modules (such as wearable electronic products), and the principle of light conversion electricity is used to power the display modules.
  • Technology is being used more and more widely.
  • a thin film solar cell includes a substrate, a front electrode, a photovoltaic layer, and a back electrode stacked in sequence.
  • the thin film solar cell covers the display module and the back electrode side of the thin film solar cell faces the display module.
  • the display module includes a middle display area and a non-display area surrounding the display area.
  • the thin-film solar cell is usually arranged in the non-display area and covers the non-display area to improve the photoelectric conversion efficiency.
  • the thin-film solar cell can also be arranged in the form of grid lines, so that the display area of the thin-film solar cell forms a semi-transparent photovoltaic power generation area.
  • the price of laser lift-off equipment is very expensive. Depending on the size of the substrate (G2.5 ⁇ G10.5), the price can range from tens of millions to a few. Ranging from 100 million yuan. Therefore, the current flexible devices that can only be made by laser methods limit the development of such products. In view of this, the development of a technology that can peel off the flexible device that forms the function of the solar cell from the rigid substrate (usually glass) without the use of laser technology has become an urgent problem to be solved.
  • the present invention provides a method for manufacturing flexible transparent thin-film solar cells without laser lift-off, that is, mechanical lift-off (MLO: Mechanism Lift-Off) method.
  • MLO Mechanism Lift-Off
  • the transparent thin film solar cell can be applied to 3D displays and flexible display modules, and the production of the flexible transparent thin film is simpler and more reliable.
  • a flexible transparent thin-film solar cell manufacturing method the transparent thin-film solar cell is applied on the side of the display surface of the flexible display module to provide the flexible display module Electricity, including the following steps:
  • S5 Attach the second protective layer on the outside of the flexible transparent film, and then perform single-grain cutting, binding, and functional and appearance inspections.
  • the method for making the flexible transparent film includes providing a rigid substrate, forming a release layer on the rigid substrate, and removing the outside of the release layer.
  • the surface energy of the ineffective area at the edge of the surface is adjusted to a water antenna less than 5° and the surface energy of the effective area in the middle of the outer surface of the release layer is adjusted to a water antenna in the range of 30°-50°, and then a liquid transparent material is applied.
  • the liquid transparent material is cured to form a flexible transparent film.
  • the transparent material is colorless and transparent polyimide with a thickness of 5 ⁇ m ⁇ 150 ⁇ m, the average transmittance in the visible band (360nm ⁇ 740nm) is greater than 80%.
  • the release layer is an inorganic layer or an organic layer with a thickness ⁇ 2 ⁇ m formed on the surface of the rigid substrate.
  • step S1 when the raw material of the flexible transparent film is an optical film type organic polymer material such as CPI, COP, TAC, PC, or PET, the method for manufacturing the flexible transparent film includes providing a rigid substrate, The surface of the rigid substrate is coated and cured with a coupling agent, then plasma treatment is performed, and then the optical film is attached to the rigid substrate to form a flexible transparent film.
  • an optical film type organic polymer material such as CPI, COP, TAC, PC, or PET
  • the method for manufacturing the flexible transparent film includes providing a rigid substrate, The surface of the rigid substrate is coated and cured with a coupling agent, then plasma treatment is performed, and then the optical film is attached to the rigid substrate to form a flexible transparent film.
  • step S1 the production of a first insulating layer is further included.
  • step S2 the production of a metal auxiliary electrode is further included, and the metal auxiliary electrode is connected to the front electrode and insulated and separated from the back electrode by a second insulating layer.
  • the flexible transparent thin-film solar cell of the embodiment of the present invention applied to the flexible display module can be formed in the visible area or the frame area of the flexible display module, or the frame area and the visible area are provided with the same Transparent thin-film solar cells, which are formed in the viewable area using grids or grids at intervals, so that the normal display of the flexible display module can be ignored;
  • the surface energy of the ineffective area of the outer surface of the release layer is adjusted to a water antenna less than 5° to make the edge of the flexible solar cell film and the release layer have good sealing performance and flexibility
  • the transparent film will not fall off the surface of the rigid substrate during the production process of the solar cell.
  • FIG. 1 is a schematic flow chart of a manufacturing method of a flexible transparent thin-film solar cell according to the present invention.
  • first”, “second”, and “third” are only used for descriptive purposes, and cannot be understood as indicating or implying relative importance or implicitly indicating the number of indicated technical features. Thus, the features defined with “first”, “second”, and “third” may explicitly or implicitly include one or more of these features.
  • “plurality” means two or more than two, unless otherwise specifically defined.
  • the terms “installed”, “connected”, “connected”, “fixed”, “set” and other terms should be understood in a broad sense.
  • it can be a fixed connection or a fixed connection. It can be detachably connected or integrated; it can be mechanically connected or electrically connected; it can be directly connected or indirectly connected through an intermediate medium, and it can also be the internal communication of two components or the interaction relationship between two components .
  • the specific meanings of the above-mentioned terms in the present invention can be understood according to specific situations.
  • the embodiment of the present invention provides a method for manufacturing a flexible transparent thin-film solar cell.
  • the transparent thin-film solar cell is applied on the side of the display surface of the flexible display module to provide power for the flexible display module.
  • the frame area of the display module can also be formed in the visible area of the flexible display module, or the frame area and the visible area can be provided with the transparent thin-film solar cell at the same time. Or the bars are arranged at intervals so that the normal display of the flexible display module can be ignored.
  • the manufacturing method of the flexible transparent thin-film solar cell includes the following steps:
  • the method of making the flexible transparent film includes providing a rigid substrate, and forming a release layer on the rigid substrate to invalidate the outer surface edge of the release layer
  • the surface energy of the area is adjusted to a water antenna less than 5° and the surface energy of the effective area in the middle of the outer surface of the release layer is adjusted to a water antenna in the range of 30°-50°, and then a liquid transparent material is applied to the liquid
  • the transparent material is cured to form a flexible transparent film.
  • the coating and curing of the polyimide can use conventional techniques in the prior art, and the present invention is not specifically elucidated and limited.
  • the edge of the flexible solar cell film and the release layer are sealed well, and the flexible transparent film will not be damaged during the production process of the solar cell.
  • the case of peeling off the rigid substrate By adjusting the surface energy of the effective area in the middle of the outer surface of the release layer to a water antenna angle of 30°-50°, a simple mechanical peeling method can be used to peel off the flexible solar cell film from the rigid substrate.
  • the middle effective area refers to the area where the required products are laid out on the substrate in an orderly manner.
  • the edge invalid area refers to the area outside the orderly layout of the required products on the substrate.
  • Products refer to flexible thin-film solar cells.
  • the release layer is made by coating, plating, or attaching to form an inorganic or organic layer with a thickness of ⁇ 2 ⁇ m on the surface of the rigid substrate.
  • SiNx made by CVD at 200°C to 250°C is preferred, and the film formation rate is adjusted to maintain the surface energy of SiNx at 30°-50° (water contact angle);
  • organic materials Organic polymer materials such as siloxane, modified acrylic, COP, etc., whose thermogravimetric loss is less than 1% at the curing temperature of liquid PI are preferred.
  • the surface energy treatment method of the release layer adopts methods including, but not limited to, vacuum plasma (or atmospheric plasma), UV irradiation, etc., to respectively perform surface treatment on the middle effective area and the edge ineffective area of the release layer.
  • the edge invalid area of the release layer is processed first, and then the middle effective area is processed.
  • the middle effective area needs to be masked to ensure that the surface of the middle effective area can be maintained at a low level (water contact angle>50°), and then when the middle effective area is processed , It is no longer necessary to mask the edge invalid area.
  • the intermediate effective area When performing surface energy treatment, if the intermediate effective area is processed first, and then the edge invalid area is processed, only the intermediate effective area can be covered by a mask, which will cause the intermediate effective area to be contaminated and the surface energy will change Uneven.
  • the edge invalid area the middle effective area is masked
  • the middle effective area the contaminated area in the middle of the covering process can be cleaned by cleaning before the surface treatment such as plasma, so that it will not cause
  • the middle effective area is subject to secondary pollution to avoid affecting the final peeling effect.
  • the method for making the flexible transparent film can also be to provide a rigid substrate, The surface of the substrate is coated and cured with a coupling agent, then plasma treatment is performed, and then the optical film is attached to the rigid substrate to form a flexible transparent film.
  • the coupling agent is cured into a film, the surface has strong adhesion (adhesive force ⁇ 40gf/cm), but after UV irradiation or Plasma treatment, the surface adhesion drops to 5gf/cm ⁇ 10gf /cm.
  • the width of the shield is controlled to be 5mm ⁇ 20mm wide, and the preferred width is set to 10mm wide to make CPI etc.
  • the edge can be tightly bonded to the rigid substrate.
  • the optical film such as CPI will not be separated from the rigid substrate.
  • laser or mechanical The CPI of the treated area (middle) and the untreated area (edge) of the coupling agent is cut and separated into two parts, and then the middle part of the solar cell is mechanically peeled off without damaging the optical film such as CPI.
  • the transparent material of the optical film type when used to make the flexible transparent film, includes, but is not limited to, organic polymer materials such as PI, COP (cycloolefin polymer), TAC, PC, or PET.
  • organic polymer materials such as PI, COP (cycloolefin polymer), TAC, PC, or PET.
  • S2 The front electrode, the photovoltaic absorption layer, the back electrode and the first protective layer are sequentially fabricated on the flexible transparent film to form a transparent thin film solar cell.
  • the surface of the front electrode can also be textured with low-concentration HCl or alkaline substances to form an uneven surface to improve the absorption of ambient light and sunlight.
  • the photovoltaic absorption layer can be formed by chemical vapor deposition, which can be divided into a P layer, an I layer and an N layer, which are sequentially deposited and formed by different CVD processes.
  • the front electrode adopts TCO (transparent conductive oxide), which is generally one or a combination of AZO, ITO and other materials.
  • AZO transparent conductive oxide
  • ITO transparent conductive oxide
  • the film-forming temperature of AZO is 200°C-350°C, and the film thickness is between 300nm-1000nm; ITO can be formed at room temperature, and the film thickness is 50nm ⁇ 300nm, and preferably annealing at a temperature of 235°C and above to reduce the resistance of ITO and increase the transmittance of ITO.
  • the back electrode can be made of one or a combination of TCO or low-resistivity metal simple substance or alloy.
  • the film forming temperature of the back electrode is 40°C-180°C, and the film thickness is 200nm ⁇ 500nm.
  • a conductive blackened metal (metal oxide) such as molybdenum oxide can be used as the substrate layer of the back electrode.
  • the substrate layer is arranged on the side close to the photovoltaic layer, and the metal layer is deposited on the surface of the substrate layer.
  • the thickness of the blackened metal is 45 nm to 80 nm, which can effectively reduce the light reflection effect of the thin film solar cell device in use.
  • the film formation of the metal back electrode may be a coating method such as physical vapor deposition, but is not limited thereto. After the metal back electrode is formed into a film, it is exposed and imaged with glue and chemically etched.
  • the back electrode and the photovoltaic absorption layer are imaged first, and the back electrode can be etched and imaged first; then the dry etching machine is put into the dry etching machine to etch the photovoltaic absorption layer; then the front electrode is glued, exposed and imaged, and then chemically etched For etching, it is preferable to use chemical etching to perform imaging of the front electrode.
  • the first protective layer is used to protect the front electrode, the photovoltaic absorber layer and the back electrode, and can be formed by film formation or coating.
  • a SiNx and SiOx composite film made by CVD method and/or coated with organic high Made of molecular photoresist material.
  • the OCA adhesive layer has adhesiveness on both sides, one side is bonded and fixed with the transparent thin-film solar cell, and the other side is used for bonding and fixed with the flexible display module.
  • the OCA adhesive layer has its own release layer. When the transparent thin film solar cell and the flexible display module are not attached, the release layer of the OCA adhesive layer plays a role in protecting the OCA adhesive layer and can also strengthen the transparent thin film solar energy. For the strength of the battery, when it is necessary to attach the transparent thin-film solar cell to the flexible display module, tear off the release layer of the OCA adhesive layer and attach it to the display module.
  • the second protective layer can be OCA, heating type mucosity reducing film or UV mucosity reducing film [Before receiving sufficient heat and UV energy, one side of the film layer can maintain sufficient viscosity. When receiving sufficient heat and UV energy, it has The adhesive film becomes very weak (less than 5gf/cm) and can be easily peeled off].
  • the step S1 and step S2 also include the production of the first insulating layer, that is, the first insulating layer is first made on the flexible transparent film, and then the front electrode, the photovoltaic absorption layer, and the back In the production of the electrode, the first insulating layer is used to improve the mechanical and optical properties of the flexible transparent film, that is, the light trapping effect of the front electrode can be improved.
  • the step S2 and the step S3 further include the production of a metal auxiliary electrode, which is connected to the front electrode and insulated from the back electrode by a second insulating layer.
  • the film structure of the metal auxiliary electrode may be a sandwich structure of a first Mo layer, a metal layer, and a second Mo layer.
  • the metal layer may be made of materials with good conductivity such as Al, Ag, Au, Cu, etc.
  • the first Mo layer It can improve the adhesion between the middle metal layer and the front electrode, and the second Mo layer can play a protective role.
  • the second Mo layer can also use a metal with less activity.
  • the film forming temperature of the metal auxiliary electrode is 40
  • the thickness can be 50nm for the first Mo layer, 200nm-500nm for the metal layer, and 50nm for the second Mo layer at a temperature of -230°C.
  • the metal layer of the metal auxiliary electrode will reflect strongly when the sun is irradiated by the strong reflection of the metal layer of the metal auxiliary electrode.
  • blackened metal metal Oxide
  • the metal auxiliary electrode may be formed by a plating method such as physical vapor deposition, but is not limited thereto. After the metal auxiliary electrode is formed into a film, it is exposed and imaged with glue and chemically etched.

Landscapes

  • Engineering & Computer Science (AREA)
  • Electromagnetism (AREA)
  • Physics & Mathematics (AREA)
  • Computer Hardware Design (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Development (AREA)
  • Photovoltaic Devices (AREA)

Abstract

A method for manufacturing a flexible transparent thin film solar cell. The transparent thin film solar cell is applied to the side of a display surface of a flexible display module to provide electric power for the flexible display module. The method comprises the following steps: manufacturing a flexible transparent thin film on a rigid substrate; sequentially manufacturing a front electrode, a photovoltaic absorption layer, a back electrode, and a first protective layer on the flexible transparent thin film to form a transparent thin film solar cell; attaching an OCA adhesive layer to the transparent thin film solar cell; cutting an edge invalid region and stripping the flexible solar cell thin film from the rigid substrate to form a flexible transparent thin film solar cell large plate; attaching a second protective layer to the outer side of the flexible transparent thin film, and then performing single-grain cutting, binding, and function and appearance inspection. The transparent thin film solar cell can be applied to 3D display and flexible display modules, and the flexible transparent thin film of the transparent thin film solar cell is easy and reliable to manufacture.

Description

一种可挠曲的透明薄膜太阳能电池制作方法Method for manufacturing flexible transparent thin-film solar cell 技术领域Technical field
本发明涉及透明薄膜太阳能电池的制作技术领域，更具体地涉及一种可挠曲的透明薄膜太阳能电池制作方法。The present invention relates to the technical field of manufacturing transparent thin-film solar cells, and more specifically to a method for manufacturing a flexible transparent thin-film solar cell.
背景技术Background technique
随着人们对能源的需求越来越高及薄膜太阳能电池技术的不断发展，将薄膜太阳能电池应用在显示模组（例如可穿戴电子产品）上，利用光转换电的原理给显示模组供电的技术得到越来越广泛的应用。With the increasing demand for energy and the continuous development of thin-film solar cell technology, thin-film solar cells are applied to display modules (such as wearable electronic products), and the principle of light conversion electricity is used to power the display modules. Technology is being used more and more widely.
通常薄膜太阳能电池包括依次层叠设置的基板、前电极、光伏层和背电极，薄膜太阳能电池覆盖在显示模组上且薄膜太阳能电池的背电极一侧朝向显示模组设置。显示模组包括中间显示区和围绕显示区的非显示区，所述薄膜太阳能电池通常设置在非显示区并覆盖所述非显示区以提高光电转换效率，为了进一步提高光电转换效率，在对应所述显示模组的显示区范围，也可以将薄膜太阳能电池设置成栅格线的形式，使薄膜太阳能电池的显示区形成半透明状的光伏发电区。Generally, a thin film solar cell includes a substrate, a front electrode, a photovoltaic layer, and a back electrode stacked in sequence. The thin film solar cell covers the display module and the back electrode side of the thin film solar cell faces the display module. The display module includes a middle display area and a non-display area surrounding the display area. The thin-film solar cell is usually arranged in the non-display area and covers the non-display area to improve the photoelectric conversion efficiency. For the display area range of the display module, the thin-film solar cell can also be arranged in the form of grid lines, so that the display area of the thin-film solar cell forms a semi-transparent photovoltaic power generation area.
然而，目前应用在显示模组中的薄膜太阳能电池多为刚性电池，应用在可挠曲的显示设备上实现曲面显示的柔性薄膜太阳能电池，尤其是柔性透明薄膜太阳能电池的技术还不够成熟，截至目前，还没有以可挠曲的透明薄膜太阳能电池应用在曲面显示装置或可挠曲显示装置中。另外，能够满足制程要求的柔性透明型薄膜太阳能电池的基板制作技术，是影响和限制此类产品发展的主要因素。目前多数CPI材料供应商只能提供透明的液体材料或者是只涂布了PI的柔性基板。这类柔性基板在应用于太阳能电池的制作后，只能通过激光剥离的方式（LLO: Laser Lift-Off ），才能将柔性器件从刚性基板上面完好的剥离下来，而激光剥离设备的价格非常昂贵，依基板的尺寸大小（G2.5~G10.5），价格从几千万到几亿元人民币不等。所以，目前只能通过激光方式才能制作的柔性器件，限制了此类产品的发展。鉴于此因，开发一种不需要使用激光技术，就能够将形成太阳能电池功能的柔性器件从刚性基板（一般是玻璃）上面剥离下来的技术，成为一种亟待解决的问题。However, most of the thin-film solar cells currently used in display modules are rigid cells. Flexible thin-film solar cells used in flexible display devices to achieve curved display, especially the technology of flexible transparent thin-film solar cells are not mature enough. At present, no flexible transparent thin-film solar cells have been applied to curved display devices or flexible display devices. In addition, the substrate manufacturing technology of flexible and transparent thin-film solar cells that can meet the requirements of the manufacturing process is the main factor that affects and limits the development of such products. At present, most CPI material suppliers can only provide transparent liquid materials or flexible substrates coated with PI only. After this type of flexible substrate is applied to the production of solar cells, it can only be lifted by laser (LLO: Laser Lift-Off) can peel off the flexible device from the rigid substrate. The price of laser lift-off equipment is very expensive. Depending on the size of the substrate (G2.5~G10.5), the price can range from tens of millions to a few. Ranging from 100 million yuan. Therefore, the current flexible devices that can only be made by laser methods limit the development of such products. In view of this, the development of a technology that can peel off the flexible device that forms the function of the solar cell from the rigid substrate (usually glass) without the use of laser technology has become an urgent problem to be solved.
技术解决方案Technical solutions
为了解决所述现有技术的不足，本发明提供了一种无需激光剥离的方式就可进行可挠曲的透明薄膜太阳能电池的制作方法，即采用机械剥离（MLO: Mechanism Lift-Off）的方法。该透明薄膜太阳能电池可应用在3D显示及柔性显示模组上，其柔性透明薄膜的制作更简单可靠。In order to solve the deficiencies of the prior art, the present invention provides a method for manufacturing flexible transparent thin-film solar cells without laser lift-off, that is, mechanical lift-off (MLO: Mechanism Lift-Off) method. The transparent thin film solar cell can be applied to 3D displays and flexible display modules, and the production of the flexible transparent thin film is simpler and more reliable.
本发明所要达到的技术效果通过以下方案实现：一种可挠曲的透明薄膜太阳能电池制作方法，所述透明薄膜太阳能电池应用在柔性显示模组的显示面一侧用于为柔性显示模组提供电力，包括以下步骤：The technical effect to be achieved by the present invention is achieved by the following scheme: a flexible transparent thin-film solar cell manufacturing method, the transparent thin-film solar cell is applied on the side of the display surface of the flexible display module to provide the flexible display module Electricity, including the following steps:
S1：在刚性基板上制作柔性透明薄膜；S1: Making a flexible transparent film on a rigid substrate;
S2：在柔性透明薄膜上依次制作前电极、光伏吸收层、背电极和第一保护层，形成透明薄膜太阳能电池；S2: The front electrode, the photovoltaic absorption layer, the back electrode and the first protective layer are sequentially fabricated on the flexible transparent film to form a transparent thin film solar cell;
S3：在透明薄膜太阳能电池上贴附OCA胶层；S3: Attach an OCA glue layer on the transparent thin-film solar cell;
S4：将边缘无效区域切割并将柔性太阳能电池薄膜从刚性基板上面剥离下来形成可挠曲的透明薄膜太阳能电池大板；S4: Cut the edge invalid area and peel off the flexible solar cell film from the rigid substrate to form a flexible transparent thin-film solar cell panel;
S5：在柔性透明薄膜的外侧进行第二保护层的贴附，再进行单粒切割、绑定及功能与外观检查。S5: Attach the second protective layer on the outside of the flexible transparent film, and then perform single-grain cutting, binding, and functional and appearance inspections.
优选地，在步骤S1中，当柔性透明薄膜的原材料以液态型式的透明材料制作时，柔性透明薄膜的制作方法包括提供一刚性基板，在刚性基板上制作离型层，将离型层的外表面边缘无效区域的表面能调整至水触角小于5°和将离型层的外表面中间有效区域的表面能调整至水触角在30°-50°的范围内，然后涂布液态的透明材料，将液态的透明材料固化形成柔性透明薄膜。Preferably, in step S1, when the raw material of the flexible transparent film is made of a liquid-type transparent material, the method for making the flexible transparent film includes providing a rigid substrate, forming a release layer on the rigid substrate, and removing the outside of the release layer. The surface energy of the ineffective area at the edge of the surface is adjusted to a water antenna less than 5° and the surface energy of the effective area in the middle of the outer surface of the release layer is adjusted to a water antenna in the range of 30°-50°, and then a liquid transparent material is applied. The liquid transparent material is cured to form a flexible transparent film.
优选地，所述透明材料为无色透明的聚酰亚胺，厚度为5μm ~150μm，可见波段（360nm~740nm）透过率平均值大于80%。Preferably, the transparent material is colorless and transparent polyimide with a thickness of 5 μm ~150μm, the average transmittance in the visible band (360nm~740nm) is greater than 80%.
优选地，所述离型层为在刚性基板的表面形成厚度≤2μm的无机层或有机层。Preferably, the release layer is an inorganic layer or an organic layer with a thickness ≤ 2 μm formed on the surface of the rigid substrate.
优选地，在步骤S1中，当柔性透明薄膜的原材料为光学膜型式的CPI、COP、TAC、PC或PET等有机高分子材料时，所述柔性透明薄膜的制作方法包括提供一刚性基板，在刚性基板的表面进行耦合剂涂布和固化，然后进行等离子体处理，再将光学膜贴附在刚性基板上形成柔性透明薄膜。Preferably, in step S1, when the raw material of the flexible transparent film is an optical film type organic polymer material such as CPI, COP, TAC, PC, or PET, the method for manufacturing the flexible transparent film includes providing a rigid substrate, The surface of the rigid substrate is coated and cured with a coupling agent, then plasma treatment is performed, and then the optical film is attached to the rigid substrate to form a flexible transparent film.
优选地，在步骤S1与步骤S2之间还包括第一绝缘层的制作。Preferably, between step S1 and step S2, the production of a first insulating layer is further included.
优选地，在步骤S2与步骤S3之间还包括金属辅助电极的制作，所述金属辅助电极与前电极连接并与背电极通过第二绝缘层绝缘隔开。Preferably, between step S2 and step S3, the production of a metal auxiliary electrode is further included, and the metal auxiliary electrode is connected to the front electrode and insulated and separated from the back electrode by a second insulating layer.
有益效果Beneficial effect
1、 本发明实施例的可挠曲的透明薄膜太阳能电池应用在柔性显示模组上可以形成在柔性显示模组的可视区或者边框区，还可以是边框区和可视区同时设有该透明薄膜太阳能电池，其形成在可视区时采用栅格状或者栅条状间隔设置，以对柔性显示模组的正常显示可以忽略不计；1. The flexible transparent thin-film solar cell of the embodiment of the present invention applied to the flexible display module can be formed in the visible area or the frame area of the flexible display module, or the frame area and the visible area are provided with the same Transparent thin-film solar cells, which are formed in the viewable area using grids or grids at intervals, so that the normal display of the flexible display module can be ignored;
2、在采用液态透明材料制作柔性透明薄膜时，通过将离型层的外表面边缘无效区域的表面能调整至水触角小于5°使得柔性太阳能电池薄膜与离型层的边缘密封性好，柔性透明薄膜在太阳能电池的制作过程中不会发生从刚性基板表面脱落的情况。通过将离型层的外表面中间有效区域的表面能调整至水触角在30°-50°，使得可以采用简单的机械剥离方式，将柔性太阳能电池薄膜从刚性基板上剥离下来，无需采用高昂的激光剥离设备。2. When the flexible transparent film is made of liquid transparent material, the surface energy of the ineffective area of the outer surface of the release layer is adjusted to a water antenna less than 5° to make the edge of the flexible solar cell film and the release layer have good sealing performance and flexibility The transparent film will not fall off the surface of the rigid substrate during the production process of the solar cell. By adjusting the surface energy of the effective area in the middle of the outer surface of the release layer to a water antenna angle of 30°-50°, a simple mechanical peeling method can be used to peel the flexible solar cell film from the rigid substrate without the need for expensive Laser peeling equipment.
附图说明Description of the drawings
图1为本发明一种可挠曲的透明薄膜太阳能电池制作方法的流程示意图。FIG. 1 is a schematic flow chart of a manufacturing method of a flexible transparent thin-film solar cell according to the present invention.
本发明的实施方式Embodiments of the present invention
下面结合附图和实施例对本发明进行详细的说明，所述实施例的示例在附图中示出，其中自始至终相同或类似的标号表示相同或类似的元件或具有相同或类似功能的元件。下面通过参考附图描述的实施例是示例性的，旨在用于解释本发明，而不能理解为对本发明的限制。The present invention will be described in detail below with reference to the accompanying drawings and embodiments. Examples of the embodiments are shown in the accompanying drawings, in which the same or similar reference numerals indicate the same or similar elements or elements with the same or similar functions. The embodiments described below with reference to the accompanying drawings are exemplary, and are intended to explain the present invention, but should not be construed as limiting the present invention.
在本发明的描述中，需要理解的是，术语“长度”、“宽度”、“上”、“下”、“前”、“后”、“左”、“右”、“竖直”、“水平”、“顶”、“底”、“内”、“外”等指示的方位或位置关系为基于附图所示的方位或位置关系，仅是为了便于描述本发明和简化描述，而不是指示或暗示所指的装置或元件必须具有特定的方位、以特定的方位构造和操作，因此不能理解为对本发明的限制。In the description of the present invention, it should be understood that the terms "length", "width", "upper", "lower", "front", "rear", "left", "right", "vertical", The orientation or positional relationship indicated by "horizontal", "top", "bottom", "inner", "outer", etc. is based on the orientation or positional relationship shown in the drawings, and is only for the convenience of describing the present invention and simplifying the description. It does not indicate or imply that the pointed device or element must have a specific orientation, be constructed and operated in a specific orientation, and therefore cannot be understood as a limitation of the present invention.
此外，术语“第一”、“第二”、“第三”仅用于描述目的，而不能理解为指示或暗示相对重要性或者隐含指明所指示的技术特征的数量。由此，限定有“第一”、“第二”、“第三”的特征可以明示或者隐含地包括一个或者多个该特征。在本发明的描述中，“多个”的含义是两个或两个以上，除非另有明确具体的限定。In addition, the terms "first", "second", and "third" are only used for descriptive purposes, and cannot be understood as indicating or implying relative importance or implicitly indicating the number of indicated technical features. Thus, the features defined with "first", "second", and "third" may explicitly or implicitly include one or more of these features. In the description of the present invention, "plurality" means two or more than two, unless otherwise specifically defined.
在本发明中，除非另有明确的规定和限定，术语“安装”、“相连”、“连接”、“固定”、“设置”等术语应做广义理解，例如，可以是固定连接，也可以是可拆卸连接，或成一体；可以是机械连接，也可以是电连接；可以是直接相连，也可以通过中间媒介间接相连，还可以是两个元件内部的连通或两个元件的相互作用关系。对于本领域的普通技术人员而言，可以根据具体情况理解上述术语在本发明中的具体含义。In the present invention, unless otherwise clearly defined and defined, the terms "installed", "connected", "connected", "fixed", "set" and other terms should be understood in a broad sense. For example, it can be a fixed connection or a fixed connection. It can be detachably connected or integrated; it can be mechanically connected or electrically connected; it can be directly connected or indirectly connected through an intermediate medium, and it can also be the internal communication of two components or the interaction relationship between two components . For those of ordinary skill in the art, the specific meanings of the above-mentioned terms in the present invention can be understood according to specific situations.
本发明实施例提供一种可挠曲的透明薄膜太阳能电池制作方法，所述透明薄膜太阳能电池应用在柔性显示模组的显示面一侧用于为柔性显示模组提供电力，其可以形成在柔性显示模组的边框区，也可以形成在柔性显示模组的可视区，还可以是边框区和可视区同时设有该透明薄膜太阳能电池，其形成在可视区时优选采用栅格状或者栅条状间隔设置，以对柔性显示模组的正常显示可以忽略不计。The embodiment of the present invention provides a method for manufacturing a flexible transparent thin-film solar cell. The transparent thin-film solar cell is applied on the side of the display surface of the flexible display module to provide power for the flexible display module. The frame area of the display module can also be formed in the visible area of the flexible display module, or the frame area and the visible area can be provided with the transparent thin-film solar cell at the same time. Or the bars are arranged at intervals so that the normal display of the flexible display module can be ignored.
如图1所示，所述可挠曲的透明薄膜太阳能电池制作方法包括以下步骤：As shown in Figure 1, the manufacturing method of the flexible transparent thin-film solar cell includes the following steps:
S1：在刚性基板上制作柔性透明薄膜。S1: Make a flexible transparent film on a rigid substrate.
在本步骤中，当柔性透明薄膜的原材料以液态型式的透明材料制作时，柔性透明薄膜的制作方法包括提供一刚性基板，在刚性基板上制作离型层，将离型层的外表面边缘无效区域的表面能调整至水触角小于5°和将离型层的外表面中间有效区域的表面能调整至水触角在30°-50°的范围内，然后涂布液态的透明材料，将液态的透明材料固化形成柔性透明薄膜。所述聚酰亚胺的涂布和固化可采用现有技术中的常规技术，本发明不作具体阐述和限定。In this step, when the raw material of the flexible transparent film is made of liquid-type transparent materials, the method of making the flexible transparent film includes providing a rigid substrate, and forming a release layer on the rigid substrate to invalidate the outer surface edge of the release layer The surface energy of the area is adjusted to a water antenna less than 5° and the surface energy of the effective area in the middle of the outer surface of the release layer is adjusted to a water antenna in the range of 30°-50°, and then a liquid transparent material is applied to the liquid The transparent material is cured to form a flexible transparent film. The coating and curing of the polyimide can use conventional techniques in the prior art, and the present invention is not specifically elucidated and limited.
通过将离型层的外表面边缘无效区域的表面能调整至水触角小于5°使得柔性太阳能电池薄膜与离型层的边缘密封性好，柔性透明薄膜在太阳能电池的制作过程中不会发生从刚性基板上脱落的情况。通过将离型层的外表面中间有效区域的表面能调整至水触角在30°-50°使得可以采用简单的机械剥离方式，将柔性太阳能电池薄膜从刚性基板上剥离下来。By adjusting the surface energy of the ineffective area of the outer surface of the release layer to a water antenna less than 5°, the edge of the flexible solar cell film and the release layer are sealed well, and the flexible transparent film will not be damaged during the production process of the solar cell. The case of peeling off the rigid substrate. By adjusting the surface energy of the effective area in the middle of the outer surface of the release layer to a water antenna angle of 30°-50°, a simple mechanical peeling method can be used to peel off the flexible solar cell film from the rigid substrate.
需要说明的是，所述中间有效区域是指所需产品在基板上面有序排版的区域，反之，所述边缘无效区域是指所需产品在基板上面有序排版之外的区域，其中所需产品是指柔性薄膜太阳能电池。It should be noted that the middle effective area refers to the area where the required products are laid out on the substrate in an orderly manner. On the contrary, the edge invalid area refers to the area outside the orderly layout of the required products on the substrate. Products refer to flexible thin-film solar cells.
其中，离型层的制作采用涂布或镀膜或贴附等方式在刚性基板的表面形成厚度≤2μm的无机层或有机层。当采用无机材料时，优选以CVD方式在200℃~250℃下制作的SiNx，通过调整成膜速率使SiNx的表面能维持在30°~50°（水接触角）；当采用有机材料时，优选在液态PI固化温度下的热重损失＜1%的硅氧烷、改性亚克力、COP等有机高分子材料。Among them, the release layer is made by coating, plating, or attaching to form an inorganic or organic layer with a thickness of ≤ 2 μm on the surface of the rigid substrate. When inorganic materials are used, SiNx made by CVD at 200°C to 250°C is preferred, and the film formation rate is adjusted to maintain the surface energy of SiNx at 30°-50° (water contact angle); when organic materials are used, Organic polymer materials such as siloxane, modified acrylic, COP, etc., whose thermogravimetric loss is less than 1% at the curing temperature of liquid PI are preferred.
所述离型层的表面能处理方法采用包括但不限于真空等离子（或大气等离子）、UV照射等方法，分别对离型层的中间有效区域及边缘无效区域进行表面处理。优选地，先对离型层的边缘无效区域进行处理，再对中间有效区域进行处理。在对边缘无效区域进行处理时，需对中间有效区域进行遮蔽，以保证该中间有效区域的表面能维持在较低的水平（水接触角＞50°），然后再对中间有效区域进行处理时，则不再需要对边缘无效区域进行遮蔽。The surface energy treatment method of the release layer adopts methods including, but not limited to, vacuum plasma (or atmospheric plasma), UV irradiation, etc., to respectively perform surface treatment on the middle effective area and the edge ineffective area of the release layer. Preferably, the edge invalid area of the release layer is processed first, and then the middle effective area is processed. When processing the edge invalid area, the middle effective area needs to be masked to ensure that the surface of the middle effective area can be maintained at a low level (water contact angle>50°), and then when the middle effective area is processed , It is no longer necessary to mask the edge invalid area.
在进行表面能处理的时候，如果先处理中间有效区域，再处理边缘无效区域时，只能使用遮蔽物对中间有效区域进行接触式覆盖，这样会导致中间有效区域受到污染，使表面能会变得不均。而先处理边缘无效区域（中间有效区域被遮蔽），再处理中间有效区域的时候，可以通过清洗的方式将覆盖过程中间受到污染的区域先清洁干净再进行等离子等表面处理，这样就不会使得中间有效区域受到二次污染，避免影响最终的剥离效果。When performing surface energy treatment, if the intermediate effective area is processed first, and then the edge invalid area is processed, only the intermediate effective area can be covered by a mask, which will cause the intermediate effective area to be contaminated and the surface energy will change Uneven. When processing the edge invalid area (the middle effective area is masked) first, and then when the middle effective area is processed, the contaminated area in the middle of the covering process can be cleaned by cleaning before the surface treatment such as plasma, so that it will not cause The middle effective area is subject to secondary pollution to avoid affecting the final peeling effect.
在本步骤中，当柔性透明薄膜的原材料为光学膜型式的CPI、COP、TAC、PC或PET等有机高分子材料时，所述柔性透明薄膜的制作方法还可以是提供一刚性基板，在刚性基板的表面进行耦合剂涂布和固化，然后进行等离子体处理，然后再将光学膜贴附在刚性基板上，形成柔性透明薄膜。优选的，所述耦合剂在固化成膜后，表面具有较强的粘性（粘附力≥40gf/cm），但是在经过UV照射或Plasma处理后，表面粘附力下降到5gf/cm~10gf/cm。使用UV和/或Plasma对耦合剂处理前，需要使用“回”字型治具对刚性基板的四周进行遮蔽，遮蔽的宽度控制在5mm~20mm宽，优选的宽度设置在10mm宽，使得CPI等光学膜貼附在耦合剂表面之后，边缘与刚性基板之间能够紧密粘结，在太阳能电池的制程中，CPI等光学膜不会与刚性基板分离，且在完成所有制程后，利用激光或机械的方式将耦合剂的被处理区（中间）和未处理区（边缘）的CPI切割分离成两个部分，然后再将形成太阳能电池的中间部分机械剥离下来，而不会损伤CPI等光学膜。In this step, when the raw material of the flexible transparent film is an optical film type organic polymer material such as CPI, COP, TAC, PC or PET, the method for making the flexible transparent film can also be to provide a rigid substrate, The surface of the substrate is coated and cured with a coupling agent, then plasma treatment is performed, and then the optical film is attached to the rigid substrate to form a flexible transparent film. Preferably, after the coupling agent is cured into a film, the surface has strong adhesion (adhesive force≥40gf/cm), but after UV irradiation or Plasma treatment, the surface adhesion drops to 5gf/cm~10gf /cm. Before using UV and/or Plasma to process the couplant, you need to use a "back" type jig to shield the periphery of the rigid substrate. The width of the shield is controlled to be 5mm~20mm wide, and the preferred width is set to 10mm wide to make CPI etc. After the optical film is attached to the surface of the coupling agent, the edge can be tightly bonded to the rigid substrate. In the solar cell manufacturing process, the optical film such as CPI will not be separated from the rigid substrate. After all the manufacturing processes are completed, laser or mechanical The CPI of the treated area (middle) and the untreated area (edge) of the coupling agent is cut and separated into two parts, and then the middle part of the solar cell is mechanically peeled off without damaging the optical film such as CPI.
具体地，所述的以光学膜型式的透明材料来制作柔性透明薄膜时，光学膜型式的透明材料包括但不限于PI、COP（环烯烃聚合物）、TAC、PC或PET等有机高分子材料，要求：可见光波段（360nm~740nm）透过率平均值≥85%，CTE＜150ppm/℃（20℃~250℃），光学位相延迟量（Rth）≤150nm，且能够长时间耐受200℃的高温而不改变其各种性能。Specifically, when the transparent material of the optical film type is used to make the flexible transparent film, the transparent material of the optical film type includes, but is not limited to, organic polymer materials such as PI, COP (cycloolefin polymer), TAC, PC, or PET. Requirement: visible light waveband (360nm~740nm) average transmittance ≥85%, CTE＜150ppm/℃ (20℃~250℃), optical phase retardation (Rth) ≤150nm, and can withstand 200℃ for a long time The high temperature does not change its various properties.
S2：在柔性透明薄膜上依次制作前电极、光伏吸收层、背电极和第一保护层，形成透明薄膜太阳能电池。S2: The front electrode, the photovoltaic absorption layer, the back electrode and the first protective layer are sequentially fabricated on the flexible transparent film to form a transparent thin film solar cell.
其中前电极的表面还可以采用低浓度HCl或碱性物质制绒，形成凹凸不平的表面，以提高外界环境光和太阳光的吸收。所述光伏吸收层可以采用化学气相沉积成膜，其可以分为P层、I层和N层，通过不同CVD工艺依次沉积形成。The surface of the front electrode can also be textured with low-concentration HCl or alkaline substances to form an uneven surface to improve the absorption of ambient light and sunlight. The photovoltaic absorption layer can be formed by chemical vapor deposition, which can be divided into a P layer, an I layer and an N layer, which are sequentially deposited and formed by different CVD processes.
所述前电极采用TCO（透明导电氧化物），一般为AZO、ITO等材质的一种或组合。组合使用时，AZO与光伏吸收层接触以减少接触电阻，其中AZO 的成膜温度为200℃-350℃，成膜厚度为300nm-1000nm之间；ITO可以采用常温成膜，膜厚为50nm~300nm，并优选采用235℃及以上的温度退火以降低ITO电阻，并提高ITO的透过率。The front electrode adopts TCO (transparent conductive oxide), which is generally one or a combination of AZO, ITO and other materials. When used in combination, AZO is in contact with the photovoltaic absorption layer to reduce contact resistance. The film-forming temperature of AZO is 200℃-350℃, and the film thickness is between 300nm-1000nm; ITO can be formed at room temperature, and the film thickness is 50nm~ 300nm, and preferably annealing at a temperature of 235°C and above to reduce the resistance of ITO and increase the transmittance of ITO.
所述背电极可以采用TCO或低电阻率的金属单质或合金等材质的一种或组合。背电极的成膜温度为40℃-180℃，膜厚采用200nm~500nm 。当所述背电极采用金属材料时，由于金属层的强反射作用，导致太阳光入射到金属层时反射强烈，影响视觉效果。为减小该现象，可以使用导电的氧化钼等黑化金属(金属氧化物)作为该背电极的衬底层，该衬底层设置在靠近光伏层一侧，金属层沉积在此衬底层表面。优选的，黑化金属厚度为45nm~80nm，可以有效减小该薄膜太阳能电池器件使用时的反光作用。所述金属背电极的成膜可以是物理气相沉积等镀膜方式，但不限于此。金属背电极成膜后再经过涂胶曝光成像并化学刻蚀。The back electrode can be made of one or a combination of TCO or low-resistivity metal simple substance or alloy. The film forming temperature of the back electrode is 40℃-180℃, and the film thickness is 200nm~500nm. When the back electrode is made of a metal material, due to the strong reflection of the metal layer, sunlight is strongly reflected when it is incident on the metal layer, which affects the visual effect. In order to reduce this phenomenon, a conductive blackened metal (metal oxide) such as molybdenum oxide can be used as the substrate layer of the back electrode. The substrate layer is arranged on the side close to the photovoltaic layer, and the metal layer is deposited on the surface of the substrate layer. Preferably, the thickness of the blackened metal is 45 nm to 80 nm, which can effectively reduce the light reflection effect of the thin film solar cell device in use. The film formation of the metal back electrode may be a coating method such as physical vapor deposition, but is not limited thereto. After the metal back electrode is formed into a film, it is exposed and imaged with glue and chemically etched.
成膜清洗后先对背电极和光伏吸收层进行成像，可以先选用刻蚀成像背电极；接着投入干刻机台，刻蚀光伏吸收层；再对前电极进行涂胶曝光成像后进行化学刻蚀，优选可以采用化学刻蚀的方式进行前电极的成像。After the film is formed and cleaned, the back electrode and the photovoltaic absorption layer are imaged first, and the back electrode can be etched and imaged first; then the dry etching machine is put into the dry etching machine to etch the photovoltaic absorption layer; then the front electrode is glued, exposed and imaged, and then chemically etched For etching, it is preferable to use chemical etching to perform imaging of the front electrode.
所述第一保护层用于保护前电极、光伏吸收层和背电极，可通过成膜或者涂布的方式形成，优选的可以采用CVD方式制作的SiNx和SiOx复合膜和/或涂布有机高分子光阻材料制作而成。The first protective layer is used to protect the front electrode, the photovoltaic absorber layer and the back electrode, and can be formed by film formation or coating. Preferably, a SiNx and SiOx composite film made by CVD method and/or coated with organic high Made of molecular photoresist material.
S3：在透明薄膜太阳能电池上贴附OCA胶层。S3: Attach an OCA glue layer on the transparent thin-film solar cell.
所述OCA胶层双面具有粘性，一面与透明薄膜太阳能电池粘接固定，另一面用于与柔性显示模组粘接固定。所述OCA胶层自带离型层，当透明薄膜太阳能电池与柔性显示模组不贴合时，所述OCA胶层的离型层起到保护OCA胶层的作用，还可以加强透明薄膜太阳能电池的强度，当需要将透明薄膜太阳能电池与柔性显示模组贴合时，撕下OCA胶层的离型层与显示模组贴合即可。The OCA adhesive layer has adhesiveness on both sides, one side is bonded and fixed with the transparent thin-film solar cell, and the other side is used for bonding and fixed with the flexible display module. The OCA adhesive layer has its own release layer. When the transparent thin film solar cell and the flexible display module are not attached, the release layer of the OCA adhesive layer plays a role in protecting the OCA adhesive layer and can also strengthen the transparent thin film solar energy. For the strength of the battery, when it is necessary to attach the transparent thin-film solar cell to the flexible display module, tear off the release layer of the OCA adhesive layer and attach it to the display module.
S4：将边缘无效区域切割，并将柔性太阳能电池薄膜从刚性基板上面剥离下来形成可挠曲的透明薄膜太阳能电池大板。S4: Cut the edge invalid area, and peel off the flexible solar cell film from the rigid substrate to form a flexible transparent thin-film solar cell panel.
S5：在柔性透明薄膜的外侧进行第二保护层的贴附，再进行单粒切割、绑定及功能与外观检查。优选的，第二保护层可以是OCA、加热型减粘膜或UV减粘膜【受到足够的热量和UV能量之前，膜层的一面可以保持足够的粘性，当受到足够的热量和UV能量之后，具有粘附性的膜层变得粘附力非常微弱（小于5gf/cm），可以将其轻易剥离起来】。S5: Attach the second protective layer on the outside of the flexible transparent film, and then perform single-grain cutting, binding, and functional and appearance inspections. Preferably, the second protective layer can be OCA, heating type mucosity reducing film or UV mucosity reducing film [Before receiving sufficient heat and UV energy, one side of the film layer can maintain sufficient viscosity. When receiving sufficient heat and UV energy, it has The adhesive film becomes very weak (less than 5gf/cm) and can be easily peeled off].
作为本发明实施例的进一步改进，所述步骤S1与步骤S2之间还包括第一绝缘层的制作，即先在柔性透明薄膜上制作第一绝缘层，再进行前电极、光伏吸收层、背电极的制作，所述第一绝缘层用于提高柔性透明薄膜的机械特性和光学特性，即可以提高前电极的陷光效应。As a further improvement of the embodiment of the present invention, the step S1 and step S2 also include the production of the first insulating layer, that is, the first insulating layer is first made on the flexible transparent film, and then the front electrode, the photovoltaic absorption layer, and the back In the production of the electrode, the first insulating layer is used to improve the mechanical and optical properties of the flexible transparent film, that is, the light trapping effect of the front electrode can be improved.
作为本发明实施例的进一步改进，所述步骤S2与步骤S3之间还包括金属辅助电极的制作，所述金属辅助电极与前电极连接并与背电极通过第二绝缘层绝缘隔开。As a further improvement of the embodiment of the present invention, the step S2 and the step S3 further include the production of a metal auxiliary electrode, which is connected to the front electrode and insulated from the back electrode by a second insulating layer.
所述金属辅助电极的膜层结构可以是第一Mo层、金属层和第二Mo层的三明治结构，其中金属层可以采用Al，Ag，Au，Cu等导电性好的材质，第一Mo层可以提高中间金属层与前电极的粘附力，第二Mo层可以起到保护作用，所述第二Mo层同样可以使用活性不强的金属，其中所述金属辅助电极的成膜温度为40℃-230℃，厚度可以是第一Mo层为50nm，金属层为200nm-500nm，第二Mo层为50nm。当所述背电极采用TCO材料时，金属辅助电极的金属层由于强反射作用，导致太阳入射光面在光照射时反射光强烈，为减小该现象，可以使用氧化钼等黑化金属（金属氧化物）作为该金属辅助电极的衬底层，减小该薄膜太阳能电池器件使用时的反光作用。所述金属辅助电极的成膜可以是物理气相沉积等镀膜方式，但不限于此。金属辅助电极成膜后再经过涂胶曝光成像并化学刻蚀。The film structure of the metal auxiliary electrode may be a sandwich structure of a first Mo layer, a metal layer, and a second Mo layer. The metal layer may be made of materials with good conductivity such as Al, Ag, Au, Cu, etc. The first Mo layer It can improve the adhesion between the middle metal layer and the front electrode, and the second Mo layer can play a protective role. The second Mo layer can also use a metal with less activity. The film forming temperature of the metal auxiliary electrode is 40 The thickness can be 50nm for the first Mo layer, 200nm-500nm for the metal layer, and 50nm for the second Mo layer at a temperature of -230°C. When the back electrode is made of TCO material, the metal layer of the metal auxiliary electrode will reflect strongly when the sun is irradiated by the strong reflection of the metal layer of the metal auxiliary electrode. In order to reduce this phenomenon, blackened metal (metal Oxide) is used as the substrate layer of the metal auxiliary electrode to reduce the light reflection effect of the thin-film solar cell device in use. The metal auxiliary electrode may be formed by a plating method such as physical vapor deposition, but is not limited thereto. After the metal auxiliary electrode is formed into a film, it is exposed and imaged with glue and chemically etched.
最后需要说明的是，以上实施例仅用以说明本发明实施例的技术方案而非对其进行限制，尽管参照较佳实施例对本发明实施例进行了详细的说明，本领域的普通技术人员应当理解依然可以对本发明实施例的技术方案进行修改或者等同替换，而这些修改或者等同替换亦不能使修改后的技术方案脱离本发明实施例技术方案的范围。Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the embodiments of the present invention and not to limit them. Although the embodiments of the present invention are described in detail with reference to the preferred embodiments, those of ordinary skill in the art should It is understood that modifications or equivalent replacements can still be made to the technical solutions of the embodiments of the present invention, and these modifications or equivalent replacements cannot cause the modified technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims (7)

  1. 一种可挠曲的透明薄膜太阳能电池制作方法，所述透明薄膜太阳能电池应用在柔性显示模组的显示面一侧用于为柔性显示模组提供电力，其特征在于，包括以下步骤：A method for manufacturing a flexible transparent thin-film solar cell, the transparent thin-film solar cell is applied on the side of the display surface of the flexible display module to provide power for the flexible display module, and is characterized in that it comprises the following steps:
    S1：在刚性基板上制作柔性透明薄膜；S1: Making a flexible transparent film on a rigid substrate;
    S2：在柔性透明薄膜上依次制作前电极、光伏吸收层、背电极和第一保护层，形成透明薄膜太阳能电池；S2: The front electrode, the photovoltaic absorption layer, the back electrode and the first protective layer are sequentially fabricated on the flexible transparent film to form a transparent thin film solar cell;
    S3：在透明薄膜太阳能电池上贴附OCA胶层；S3: Attach an OCA glue layer on the transparent thin-film solar cell;
    S4：将边缘无效区域切割并将柔性太阳能电池薄膜从刚性基板上面剥离下来形成可挠曲的透明薄膜太阳能电池大板；S4: Cut the edge invalid area and peel off the flexible solar cell film from the rigid substrate to form a flexible transparent thin-film solar cell panel;
    S5：在柔性透明薄膜的外侧进行第二保护层的贴附，再进行单粒切割、绑定及功能与外观检查。S5: Attach the second protective layer on the outside of the flexible transparent film, and then perform single-grain cutting, binding, and functional and appearance inspections.
  2. 如权利要求1所述的可挠曲的透明薄膜太阳能电池制作方法，其特征在于，在步骤S1中，当柔性透明薄膜的原材料以液态型式的透明材料制作时，柔性透明薄膜的制作方法包括提供一刚性基板，在刚性基板上制作离型层，将离型层的外表面边缘无效区域的表面能调整至水触角小于5°和将离型层的外表面中间有效区域的表面能调整至水触角在30°-50°的范围内，然后涂布液态的透明材料，将液态的透明材料固化形成柔性透明薄膜。The method for manufacturing a flexible transparent thin-film solar cell according to claim 1, wherein in step S1, when the raw material of the flexible transparent film is made of a liquid-type transparent material, the method for manufacturing the flexible transparent film includes providing A rigid substrate, the release layer is made on the rigid substrate, the surface energy of the ineffective area on the outer surface of the release layer is adjusted to a water antenna less than 5° and the surface energy of the effective area in the middle of the outer surface of the release layer is adjusted to water The tentacles are in the range of 30°-50°, and then the liquid transparent material is coated, and the liquid transparent material is cured to form a flexible transparent film.
  3. 如权利要求2所述的可挠曲的透明薄膜太阳能电池制作方法，其特征在于，所述透明材料为无色透明的聚酰亚胺，厚度为5μm ~150μm，可见波段（360nm~740nm）透过率平均值大于80%。The method for manufacturing a flexible transparent thin-film solar cell according to claim 2, wherein the transparent material is colorless and transparent polyimide, with a thickness of 5 μm to 150 μm, and a visible wavelength (360 nm to 740 nm) transparent material. The average over rate is greater than 80%.
  4. 如权利要求2所述的可挠曲的透明薄膜太阳能电池制作方法，其特征在于，所述离型层为在刚性基板的表面形成厚度≤2μm的无机层或有机层。The method for manufacturing a flexible transparent thin-film solar cell according to claim 2, wherein the release layer is an inorganic layer or an organic layer with a thickness ≤ 2 μm formed on the surface of the rigid substrate.
  5. 如权利要求1所述的可挠曲的透明薄膜太阳能电池制作方法，其特征在于，在步骤S1中，当柔性透明薄膜的原材料为光学膜型式的CPI、COP、TAC、PC或PET等有机高分子材料时，所述柔性透明薄膜的制作方法包括提供一刚性基板，在刚性基板的表面进行耦合剂涂布和固化，然后进行等离子体处理，再将光学膜贴附在刚性基板上形成柔性透明薄膜。The method for manufacturing a flexible transparent thin-film solar cell according to claim 1, characterized in that, in step S1, when the raw material of the flexible transparent film is optical film type CPI, COP, TAC, PC or PET and other organic high In the case of molecular materials, the manufacturing method of the flexible transparent film includes providing a rigid substrate, coating and curing the coupling agent on the surface of the rigid substrate, and then performing plasma treatment, and then attaching the optical film to the rigid substrate to form a flexible and transparent film.
  6. 如权利要求1所述的可挠曲的透明薄膜太阳能电池制作方法，其特征在于，在步骤S1与步骤S2之间还包括第一绝缘层的制作。5. The method for manufacturing a flexible transparent thin-film solar cell according to claim 1, characterized in that, between step S1 and step S2, it further comprises the preparation of a first insulating layer.
  7. 如权利要求1所述的可挠曲的透明薄膜太阳能电池制作方法，其特征在于，在步骤S2与步骤S3之间还包括金属辅助电极的制作，所述金属辅助电极与前电极连接并与背电极通过第二绝缘层绝缘隔开。The method for manufacturing a flexible transparent thin-film solar cell according to claim 1, characterized in that, between step S2 and step S3, it further comprises the manufacture of a metal auxiliary electrode, and the metal auxiliary electrode is connected to the front electrode and to the back The electrodes are insulated and separated by a second insulating layer.
PCT/CN2020/124403 2020-02-11 2020-10-28 Method for manufacturing flexible transparent thin film solar cell WO2021159737A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202010086576.X 2020-02-11
CN202010086576.XA CN111244229B (en) 2020-02-11 2020-02-11 Manufacturing method of flexible transparent thin-film solar cell

Publications (1)

Publication Number Publication Date
WO2021159737A1 true WO2021159737A1 (en) 2021-08-19

Family

ID=70880977

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2020/124403 WO2021159737A1 (en) 2020-02-11 2020-10-28 Method for manufacturing flexible transparent thin film solar cell

Country Status (2)

Country Link
CN (1) CN111244229B (en)
WO (1) WO2021159737A1 (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111244229B (en) * 2020-02-11 2021-07-06 信利半导体有限公司 Manufacturing method of flexible transparent thin-film solar cell
CN114823975A (en) * 2022-04-20 2022-07-29 深圳市新旗滨科技有限公司 Flexible thin-film solar cell and preparation method thereof
CN115295666B (en) * 2022-07-15 2023-03-24 国家电投集团科学技术研究院有限公司 Substrate-free perovskite battery and preparation method thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110174377A1 (en) * 2010-01-20 2011-07-21 Keon Jae Lee Manufacturing method for flexible device, flexible device, solar cell, and light emitting device
CN102176435A (en) * 2010-12-27 2011-09-07 友达光电股份有限公司 Flexible substrate structure and manufacturing method thereof
CN102231359A (en) * 2011-03-18 2011-11-02 长兴化学工业股份有限公司 Method for manufacturing flexible element
CN104867964A (en) * 2015-05-18 2015-08-26 京东方科技集团股份有限公司 Array substrate, manufacturing method thereof and organic light-emitting diode display apparatus
CN110176506A (en) * 2019-05-31 2019-08-27 信利半导体有限公司 Film photovoltaic cell cascaded structure and the concatenated preparation process of film photovoltaic cell
CN111244229A (en) * 2020-02-11 2020-06-05 信利半导体有限公司 Manufacturing method of flexible transparent thin-film solar cell

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8455753B2 (en) * 2005-01-14 2013-06-04 Semiconductor Energy Laboratory Co., Ltd. Solar cell and semiconductor device, and manufacturing method thereof
JP5292622B2 (en) * 2010-08-06 2013-09-18 綜研化学株式会社 Resin mold, method for producing the same, and method for using the same
CN101980393A (en) * 2010-09-21 2011-02-23 福建钧石能源有限公司 Manufacturing method of large-area flexible photoelectric device
JP6050170B2 (en) * 2013-03-27 2016-12-21 富士フイルム株式会社 Laminate for temporary bonding for manufacturing semiconductor device and method for manufacturing semiconductor device
JP5975918B2 (en) * 2013-03-27 2016-08-23 富士フイルム株式会社 Laminate for temporary bonding for manufacturing semiconductor device and method for manufacturing semiconductor device
FR3010831B1 (en) * 2013-07-29 2019-06-28 Sunpartner Technologies RETROTECTIVE DISPLAY DEVICE WITH INTEGRATED PHOTOVOLTAIC CELLS
KR20160085620A (en) * 2015-01-08 2016-07-18 동우 화인켐 주식회사 Preparing method for flexible substrate
CN106158988B (en) * 2015-04-07 2017-12-12 昱晶能源科技股份有限公司 Solar cell and its manufacture method
CN110534615A (en) * 2019-08-27 2019-12-03 北京年管家信息科技有限公司 A kind of preparation method and solar battery of solar battery

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110174377A1 (en) * 2010-01-20 2011-07-21 Keon Jae Lee Manufacturing method for flexible device, flexible device, solar cell, and light emitting device
CN102176435A (en) * 2010-12-27 2011-09-07 友达光电股份有限公司 Flexible substrate structure and manufacturing method thereof
CN102231359A (en) * 2011-03-18 2011-11-02 长兴化学工业股份有限公司 Method for manufacturing flexible element
CN104867964A (en) * 2015-05-18 2015-08-26 京东方科技集团股份有限公司 Array substrate, manufacturing method thereof and organic light-emitting diode display apparatus
CN110176506A (en) * 2019-05-31 2019-08-27 信利半导体有限公司 Film photovoltaic cell cascaded structure and the concatenated preparation process of film photovoltaic cell
CN111244229A (en) * 2020-02-11 2020-06-05 信利半导体有限公司 Manufacturing method of flexible transparent thin-film solar cell

Also Published As

Publication number Publication date
CN111244229B (en) 2021-07-06
CN111244229A (en) 2020-06-05

Similar Documents

Publication Publication Date Title
WO2021159737A1 (en) Method for manufacturing flexible transparent thin film solar cell
WO2021056962A1 (en) Thin-film photovoltaic cell having high photoelectric conversion rate and preparation process therefor
EP2267794A1 (en) Solar cell module and solar cell
CN103474485B (en) A kind of flexible thin-film solar cell and preparation method thereof
US20020139411A1 (en) Thin-film solar cell module of see-through type
US20040191422A1 (en) Method for manufacturing solar cell module having a sealing resin layer formed on a metal oxide layer
TWI727728B (en) Thin film photovoltaic cell series structure and preparation process of thin film photovoltaic cell series
CN103746013B (en) A kind of Graphene solar cell and preparation method thereof
JP6568518B2 (en) Crystalline silicon solar cell manufacturing method and crystalline silicon solar cell module manufacturing method
US20130340826A1 (en) Flexible solar cell assembly and use of the same
JP2004228333A (en) Photovoltaic cell and its manufacturing method
JP2013225712A (en) Manufacturing method of thin film solar cell
CN107342333A (en) A kind of HIBC batteries and preparation method thereof
WO2019095662A1 (en) Solar battery with combined mwt and hit, and preparation method therefor
WO2017078164A1 (en) Method for manufacturing crystalline silicon-based solar cell and method for manufacturing crystalline silicon-based solar cell module
CN105355675A (en) Preparation method for high-haze composite transparent conductive electrode
CN103746014B (en) ITO grid line solar cell and preparation method thereof
JP5001722B2 (en) Method for manufacturing thin film solar cell
JP2008305945A (en) Substrate for thin film solar cell and manufacturing method of the same, and manufacturing method of thin film solar cell
WO2021189841A1 (en) Method for manufacturing solar cell with touch function
WO2020237696A1 (en) Manufacturing method for thin-film photovoltaic cell and thin-film photovoltaic cell
WO2023124614A1 (en) Metal electrode of solar cell, preparation method therefor, and solar cell
WO2023130803A1 (en) Back-contact silicon heterojunction solar cell and preparation method therefor
CN203733813U (en) Graphene solar cell
CN110113887A (en) One kind covering copper glass substrate and preparation method thereof

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: 20918494

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: 20918494

Country of ref document: EP

Kind code of ref document: A1