CN112652675A - Color film photovoltaic module and preparation method thereof - Google Patents
Color film photovoltaic module and preparation method thereof Download PDFInfo
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 36
- 239000000758 substrate Substances 0.000 claims description 36
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 27
- 229910001887 tin oxide Inorganic materials 0.000 claims description 25
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 18
- 239000011787 zinc oxide Substances 0.000 claims description 18
- MARUHZGHZWCEQU-UHFFFAOYSA-N 5-phenyl-2h-tetrazole Chemical compound C1=CC=CC=C1C1=NNN=N1 MARUHZGHZWCEQU-UHFFFAOYSA-N 0.000 claims description 15
- 238000002207 thermal evaporation Methods 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 238000002230 thermal chemical vapour deposition Methods 0.000 claims description 8
- 238000005229 chemical vapour deposition Methods 0.000 claims description 7
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- 229910052710 silicon Inorganic materials 0.000 claims description 6
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- 239000000395 magnesium oxide Substances 0.000 claims description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 3
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- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 3
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 3
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 3
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- -1 cadmium telluride selenide Chemical class 0.000 claims description 2
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- 239000013077 target material Substances 0.000 description 2
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- COHYTHOBJLSHDF-UHFFFAOYSA-N indigo powder Natural products N1C2=CC=CC=C2C(=O)C1=C1C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-UHFFFAOYSA-N 0.000 description 1
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- 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
- H01L31/1828—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof the active layers comprising only AIIBVI compounds, e.g. CdS, ZnS, CdTe
- H01L31/1836—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof the active layers comprising only AIIBVI compounds, e.g. CdS, ZnS, CdTe comprising a growth substrate not being an AIIBVI compound
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- 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
- H01L31/02—Details
- H01L31/0216—Coatings
- H01L31/02161—Coatings for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/02167—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells
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- 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
- H01L31/042—PV modules or arrays of single PV cells
- H01L31/0445—PV modules or arrays of single PV cells including thin film solar cells, e.g. single thin film a-Si, CIS or CdTe solar cells
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- 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
- H01L31/054—Optical elements directly associated or integrated with the PV cell, e.g. light-reflecting means or light-concentrating means
- H01L31/0547—Optical elements directly associated or integrated with the PV cell, e.g. light-reflecting means or light-concentrating means comprising light concentrating means of the reflecting type, e.g. parabolic mirrors, concentrators using total internal reflection
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- H—ELECTRICITY
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- 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 at least one potential-jump barrier or surface barrier
- H01L31/072—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 at least one potential-jump barrier or surface barrier the potential barriers being only of the PN heterojunction type
- H01L31/073—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 at least one potential-jump barrier or surface barrier the potential barriers being only of the PN heterojunction type comprising only AIIBVI compound semiconductors, e.g. CdS/CdTe solar cells
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Abstract
The invention provides a preparation method of a color thin-film photovoltaic module, which is characterized in that an interference film layer, an optional barrier layer, a transparent front electrode layer and a battery layer are continuously formed into a whole, the color of the module is jointly determined by the types and the film thicknesses of the interference film layer, the optional barrier layer, the transparent front electrode layer and the battery layer, and the selective reflection of different sunlight wave bands is realized by utilizing the refractive index and the film thickness, so that the surface of the module presents different colors, the color adjusting range is larger, and the method is simpler. The new process is organically combined with the film assembly preparation process, the flow is simple, the manufacturing cost is low, and the continuous adjustment of the color can be carried out in real time. The invention also provides a color thin film photovoltaic module.
Description
Technical Field
The invention belongs to the technical field of photovoltaics, and particularly relates to a color film photovoltaic module and a preparation method thereof.
Background
With the development of society, on one hand, the consumption demand of human beings on energy sources is increasing, and on the other hand, the reserves of conventional energy sources are in short supply. In the energy consumption of the whole society, 1/3, which is the total energy consumption of buildings as the main activity places of human beings, is occupied. The development of green energy-saving buildings becomes a mainstream direction and an important national policy of countries in the world. The energy-saving building further has a new function of power generation on the basis of energy conservation, and is an energy revolution for green buildings. The photovoltaic power generation technology can be perfectly combined with a building due to unique advantages of the photovoltaic power generation technology, and the building power generation function is really realized. With the development of technology and the development of early market, the combination of photovoltaic power generation and buildings is mature day by day, the huge building photovoltaic demand and market are also thoroughly activated, and meanwhile, more and higher requirements are necessarily provided for building photovoltaic products.
Building photovoltaic products are different from traditional ground photovoltaic power station products, and as a part of building components, besides satisfying the power generation function, need satisfy the demand of building self simultaneously, including pleasing to the eye, life-span, economy, environmental impact is little (light pollution), and certain privacy etc. these demands have promoted the development and the application of colored photovoltaic module.
The current preparation method of the color component mainly comprises the following steps: 1) the method has the advantages that the process is simple, the weather resistance of the dye or the colored glaze is poor in long-term environment, the sunlight transmission influence is large, and the photovoltaic module power generation efficiency is influenced. 2) The colored packaging adhesive film comprising EVA, PVB and the like is adopted to package the colored material inside the component so as to avoid the influence of atmospheric environment, however, the method is only suitable for the light-transmitting component, and the colored material has the problems of instability and non-uniform color, influences the light transmittance of the whole component and the like. 3) The colored glass is obtained by adding a certain metal element into the glass, and except for the complex preparation process of the glass, the metal impurities in the glass have the possibility of diffusion in the preparation and use processes of the photovoltaic module and further influence the stability of the module; and the colored glass can greatly reduce the transmission of sunlight and the efficiency of the assembly. 4) The interference film glass technology is to deposit metal oxide film on glass to make it favorable to the light interference principle to present specific color. The advantages are that the influence on sunlight transmission is small, and the glass can be directly used as the front plate glass of the crystalline silicon cell component.
In the existing color film photovoltaic module technology, the color dye, the adhesive film and the glass technology have the problems of long-term instability and large light transmission loss; the interference film technology is a crystal silicon assembly technology, wherein an interference film is deposited on glass in advance to form colored glass, and the colored glass is used as an independent part and is packaged into a colored assembly through an adhesive film and a prepared thin film assembly. The method has complex process and high manufacturing cost, and is not suitable for large-scale popularization and use. Meanwhile, the process is not beneficial to the adjustment of the color of the assembly by an assembly manufacturer, and the variety of the colored photovoltaic assembly is relatively few.
Disclosure of Invention
The invention aims to provide a color film photovoltaic module and a preparation method thereof, the preparation method of the color film photovoltaic module greatly simplifies the production flow and complexity of the color module, obviously reduces the manufacturing cost of the color module, and is more suitable for large-scale popularization and application. Meanwhile, the novel production process of the color film assembly can realize continuous adjustment of online colors, and is suitable for manufacturing various color film photovoltaic assemblies.
The invention provides a preparation method of a color film photovoltaic module, which comprises the following steps:
sequentially compounding an interference film layer, an optional barrier layer, a transparent front electrode layer, a battery layer and a back electrode layer on a glass substrate;
the interference film layer is compounded on the glass substrate by adopting a sputtering, thermal evaporation or chemical vapor deposition method;
the optional barrier layer is compounded on the surface of the interference film layer by a sputtering, thermal evaporation or chemical vapor deposition method;
the transparent front electrode layer is compounded on the surface of the interference film by a chemical vapor deposition or sputtering method.
Preferably, the interference film layer comprises one or more of silicon oxide, titanium oxide, magnesium oxide, zinc oxide, zirconium oxide, tin oxide, calcium oxide, tantalum oxide, indium oxide and silicon nitride;
the interference film layer is a single film layer or a composite film layer with 1-7 layers;
the thickness of the interference film layer is 60-300 nm.
Preferably, the optional barrier layer comprises one or more of silicon oxide, silicon carbide and tin oxide;
the thickness of the optional barrier layer is 60-200 nm.
Preferably, the transparent front electrode layer comprises one or more of F-doped tin oxide, In-doped zinc oxide, Sb-doped tin oxide, Al-doped zinc oxide, Ga-doped zinc oxide and Cd-doped tin oxide;
the thickness of the transparent front electrode layer is 300-900 nm.
Preferably, the transparent front electrode layer further includes a high resistance layer;
the high-resistance layer is selected from one or more of tin oxide, zinc oxide, Zn-doped tin oxide, Mg-doped zinc oxide and F-Cd-doped tin oxide.
Preferably, the battery layer is selected from one or more of cadmium telluride, cadmium selenide telluride, copper indium gallium selenide, gallium arsenide, amorphous silicon, perovskite, thin film crystalline silicon and organic dye-sensitive batteries; the thickness of the battery layer is 2-6 mu m.
Preferably, the interference film takes Ti and Si as targets and is O2In a mixed atmosphere of Ar andpreparing by a magnetron sputtering method;
the power density of the magnetron sputtering is 0.1-20W/cm2The pressure of the magnetron sputtering is 1-20 mTorr.
Preferably, the transparent front electrode layer is at O2And Ar in a mixed atmosphere, and preparing by adopting a magnetron sputtering method;
the power density of the magnetron sputtering is 0.1-20W/cm2The pressure of the magnetron sputtering is 1-20 mTorr.
Preferably, the outer surface of the glass substrate has a textured structure.
The invention provides a color thin film photovoltaic module prepared according to the preparation method.
The invention provides a preparation method of a color film photovoltaic module, which comprises the following steps: sequentially compounding an interference film layer, an optional barrier layer, a transparent front electrode layer, a battery layer and a back electrode layer on a glass substrate; the interference film layer is compounded on the glass substrate by adopting a sputtering, thermal evaporation or chemical vapor deposition method; the optional barrier layer is compounded on the surface of the interference film layer by a sputtering, thermal evaporation or chemical vapor deposition method; the transparent front electrode layer is compounded on the surface of the interference film by a chemical vapor deposition or sputtering method. The interference film layer, the optional barrier layer, the transparent front electrode layer and the battery layer are continuously formed into a whole, the color of the component is determined by the types and the film thicknesses of the four layers of the interference film layer, the optional barrier layer, the transparent front electrode layer and the battery layer, and the selective reflection of different sunlight wave bands is realized by utilizing the refractive index and the film thickness, so that the surface of the component presents different colors, the color adjusting range is larger, and the method is simpler. In addition, the preparation method provided by the invention also has the following advantages: 1) the interference film, the optional barrier layer and the cell layer are all wide band gap materials, except for the reflected wave band, sunlight of other wave bands can penetrate through and enter the cell layer, and therefore high cell current and efficiency are achieved. And even in the reflected band, the reflectivity can be adjusted and optimized to meet both color and efficiency requirements. 2) The interference film, the optional barrier layer and the battery layer are made of inorganic materials with stable performance, and have good high-temperature resistance and other performances; decomposition does not occur in the preparation of the cell, impurities are not introduced in the preparation process of the cell, and the process and the performance of the photovoltaic module are not influenced; the service life is long, and the service life is the same as or longer than that of the battery layer. 3) The new process is organically combined with the film assembly preparation process, the flow is simple, the manufacturing cost is low, and the continuous adjustment of the color can be carried out in real time.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 is a schematic structural diagram of a color thin film photovoltaic module with a top light-admitting structure according to the present invention,
from bottom to top in sequence: the solar cell comprises a glass substrate 1, an interference film layer 2, an optional barrier layer 3, a transparent front electrode layer (TCO)4, a battery layer 5 (a power generation layer 5), a back electrode layer 6 and back packaging glass 7, 8, wherein the back packaging glass is a suede structure on the outer surface of the glass substrate 1;
FIG. 2 is a process flow diagram of method 1 of the present invention;
FIG. 3 is a process flow diagram of method 2 of the present invention;
FIG. 4 is a process flow diagram of method 3 of the present invention;
FIG. 5 is a process flow diagram of method 4 of the present invention;
FIG. 6 is a process flow diagram of method 5 of the present invention;
FIG. 7 is a graph showing color changes of samples of the respective processes in example 1 of the present invention;
FIG. 8 is the light transmission data for both interference film processes of example 1 and example 2;
FIG. 9 is a color change of an assembly sputtered with different thickness ITO films on a light blue interference film;
FIG. 10 is a graph of color change for an assembly sputtered with different thickness ITO films on a light red interference film;
FIG. 11 is a normalized parameter of the power generation parameters for the color film assembly of the present invention and a normal conventional assembly.
Detailed Description
The invention provides a preparation method of a color film photovoltaic module, which comprises the following steps:
sequentially compounding an interference film layer, an optional barrier layer, a transparent front electrode layer, a battery layer and a back electrode layer on a glass substrate;
the interference film layer is compounded on the glass substrate by adopting a sputtering, thermal evaporation or chemical vapor deposition method;
the optional barrier layer is compounded on the surface of the interference film layer by a sputtering, thermal evaporation or chemical vapor deposition method;
the transparent front electrode layer is compounded on the surface of the interference film by a chemical vapor deposition or sputtering method.
The preparation process of the color thin film photovoltaic module is different according to the structure of the thin film module, for example, the thin film module (such as CdTe battery and amorphous silicon battery) with a downward light inlet structure can be prepared by the following methods 1-4; a thin film module (e.g., a CIGS or the like cell) with a top-in light structure can be prepared by the method of method 5 below.
In the invention, the color thin film photovoltaic module with the upper light-entering structure has a structure as shown in fig. 1, and sequentially comprises the following components from bottom to top: the solar cell comprises a glass substrate 1, an interference film layer 2, an optional barrier layer 3, a transparent front electrode layer (TCO)4, a cell layer 5, a back electrode layer 6 and back packaging glass 7, 8, wherein the back packaging glass is a textured structure on the outer surface of the glass substrate 1.
The glass substrate 1 is tempered or non-tempered float plain or ultra-white glass, comprising soda-lime glass and borosilicate glass, and the thickness of the glass is 1-10 mm.
The interference film layer 2 is a single-layer or multi-layer oxide or nitride film, and the interference film layer mainly comprises one or more of silicon oxide, titanium oxide, magnesium oxide, zinc oxide, zirconium oxide, tin oxide, calcium oxide, tantalum oxide, indium oxide and silicon nitride. The preparation method can adopt the processes of sputtering, thermal evaporation, chemical vapor phase and the like. The interference film is a single film or a composite film layer with 1-7 layers, and the total thickness is 60-300 nm, preferably 100-250 nm, and more preferably 150-200 nm.
In particular, in an embodiment of the invention, the interference film is made of TiO2And SiO2The multilayer film is prepared by adopting a reactive sputtering process: using Ti and Si as target material in O2Sputtering in an Ar atmosphere, O2/(O2+ Ar) in a volume proportion of 1-50%, preferably 3-20%, optimally 5-15%; the sputtering power density is 0.1-20W/cm2Preferably 1 to 10W/cm2More preferably 4 to 7W/cm2(ii) a The pressure of the magnetron sputtering is preferably 1 to 20mTorr, preferably 3 to 15mTorr, and more preferably 5to 10 mTorr.
In the present invention, the optional barrier layer 3 is mainly to prevent impurity elements such as Na ions in the glass substrate and the interference film from entering the TCO and the cell layer, thereby affecting the cell performance and long-term stability. The material of the barrier layer 3 comprises one or more of silicon oxide, silicon carbide and tin oxide, or a composite film of the silicon oxide, the silicon carbide and the tin oxide, and the total thickness is preferably 60-200 nm, more preferably 100-150 nm. The preparation method of the barrier layer 3 comprises the processes of chemical vapor deposition, sputtering, thermal evaporation and the like.
In the present invention, the TCO layer 4 comprises one or more of F-doped tin oxide (FTO), In-doped zinc oxide (ITO), Sb-doped tin oxide (SnO2: Sb), Al-doped zinc oxide (AZO), Ga-doped zinc oxide (GZO) and Cd-doped tin oxide (CTO). The thickness of the TCO layer 4 is preferably 300-900nm, more preferably 400-800 nm, and most preferably 500-700 nm; the light transmittance (300-900nm) of the TCO is generally more than 78%, the sheet resistance is 3-20 omega/□, and the carrier concentration is 1020-1021 cm-3A quantity level. The TCO film can be prepared by adopting a chemical vapor deposition method or a sputtering process.
Specifically, in the embodiment of the present invention, the TCO layer is preferably an ITO layer, and is prepared by a sputtering process: o is2/(O2+ Ar) in a volume proportion of 0-3%, preferably 0-1%, optimally 0-0.2%; the sputtering power density is 0.1-20W-cm2Preferably 1 to 10W/cm2More preferably 4 to 7W/cm2(ii) a The pressure of the magnetron sputtering is 1-20 mTorr, preferably 3-15 mTorr, and more preferably 5-10 mTorr.
In the present invention, the TCO layer 4 may also comprise a layer of a high barrier material, such as tin oxide (SnO)2) Zinc oxide (ZnO), Zn-doped tin oxide (SnO)2Zn), Mg-doped zinc oxide (MgZnO), one or more of F-doped or Cd-doped tin oxide, or a composite layer thereof. The main function of the high-resistance layer is to prevent the TCO layer from directly contacting with the cell layer to generate micro short circuit so as to reduce the performance of the cell. The resistivity of the high-resistance layer is usually 10-2Ω·cm～105Omega cm, can be prepared by chemical vapor deposition method or sputtering process.
Specifically, in an embodiment of the present invention, the high-resistance layer may be doped with Mg — zinc oxide (MgZnO). The thickness of the MgZnO high-resistance layer is preferably 10-100 nm, more preferably 20-80 nm, most preferably 30-70 nm, most preferably 40-60 nm, and specifically 20-40nm and O2/(O2+ Ar) in a volume ratio of 10-30%, preferably 15-25%, and a sputtering power density of 3-10W/cm2Preferably 4 to 9W/cm2More preferably 5to 8W/cm2The pressure of the magnetron sputtering is 5-10mTorr, preferably 6-9 mTorr, and more preferably 7-8 mTorr.
The invention relates to a design of a composite colorful transparent conductive electrode consisting of an interference film and TCO (comprising ITO, FTO, AZO and CTO, the thickness of 200-.
In the present invention, the battery layer 5 is a pn junction, or a pin junction, composed of a window layer and a battery layer. The cell layer material comprises cadmium telluride, cadmium selenide telluride, copper indium gallium selenide, gallium arsenide, amorphous silicon, perovskite, thin film crystalline silicon, organic dye-sensitive cells and the like, or a two-junction or three-junction laminated cell structure of the materials.
Specifically, in the embodiment of the invention, the battery layer is cadmium telluride (CdTe), and is prepared by a vapor deposition method, wherein in the vapor deposition, the substrate temperature is preferably 500-62 DEG0 ℃, more preferably 530 to 600 ℃, and most preferably 550 to 580 ℃; the temperature of the crucible in which the raw material is placed is preferably 580-680 ℃, more preferably 600-650 ℃, and the vapor deposition pressure is preferably 0.1-20 Torr, more preferably 1-15 Torr, and most preferably 5-10 Torr; said O is2/(N2+O2) The volume ratio of (A) is preferably 0to 100%, more preferably 10to 90%, most preferably 20to 80%; the thickness of the battery layer is 2-6 μm.
In the present invention, the window layer is preferably cadmium sulfide or cadmium selenide, such as oxygen-doped cadmium sulfide or oxygen-doped cadmium selenide.
The thickness of the oxygen-doped cadmium sulfide layer (CdS: O) is 1-40 nm, more preferably 5-35 nm, and most preferably 10-30 nm; o in sputtering gas2/(Ar+O2) The volume ratio of (A) is 1-7%, preferably 2-6%, more preferably 3-5%, and the sputtering power density is 3-10W/cm2Preferably 4 to 9W/cm2More preferably 5to 8W/cm2The pressure of the magnetron sputtering is 5to 10mTorr, more preferably 6 to 9mTorr, and most preferably 7 to 8 mTorr.
The thickness of the oxygen-doped cadmium selenide layer (CdSe: O) is 1-40 nm, more preferably 5-35 nm, and most preferably 10-30 nm; o in sputtering gas2/(Ar+O2) The volume ratio of (A) is 1-7%, preferably 2-6%, more preferably 3-5%, and the sputtering power density is 3-10W/cm2Preferably 4 to 9W/cm2More preferably 5to 8W/cm2The pressure of the magnetron sputtering is 5to 10mTorr, more preferably 6 to 9mTorr, and most preferably 7 to 8 mTorr.
In the present invention, the back electrode layer 6 is aluminum, silver, gold, copper, nickel, chromium, molybdenum, titanium, or their metal oxides, metal nitrides, or their composite layers. The preparation method adopts sputtering or thermal evaporation process.
Specifically, in the embodiment of the invention, the metal back electrode can be a Mo/Al/Cr metal back electrode, wherein the thickness of the Mo layer is 5-80 nm, preferably 10-70 nm, more preferably 20-60 nm, and most preferably 30-50 nm; the thickness of the Al layer is 40-400nm, preferably 50-350 nm, more preferably 100-300, and most preferably 150-250 nm; the thickness of the Cr layer is preferably 5to 60nm, more preferably 10to 50nm, and most preferably 20to 40 nm.
In the present invention, the back electrode 6 may also include a back contact layer made of carbon paste, zinc telluride, tellurium, and their doped compounds. The back contact layer mainly improves interface adhesion and interface carrier recombination.
Specifically, in the embodiment of the invention, the back contact layer can be made by annealing carbon paste or ZnTe back contact layer with the Cu content of 0.001% -1% at 160-360 ℃ for 1-60 min in a nitrogen atmosphere.
In the invention, the outer surface of the battery layer is also compounded with back packaging glass 7, and the back packaging glass 7 is tempered or non-tempered common float glass and has the thickness of 3-10 mm.
In the invention, the outer surface of the glass substrate 1 is provided with the suede 8, so that the light reflection of the glass surface can be reduced, and the light pollution phenomenon of the building surface is reduced. The suede 8 can be prepared by adopting the processes of sanding, stamping, frosting and the like; in the working procedure, the solar cell module can be prepared before the film is deposited on the glass substrate 1, and can also be prepared after the cell module is finished, namely, the suede is firstly made or then is made; the rear suede has the advantage of being beneficial to the scribing process performed by the laser from the glass surface; the suede is made firstly, and the assembly process integration can be realized by adopting the process of etching from the membrane surface.
Method 1：
The process flow of method 1 is shown in figure 2,
the ultra-white or common glass substrate 1 produced by the float process can be toughened or non-toughened; depositing a single-layer or multi-layer interference film 2 on a glass substrate 1 by adopting a magnetron sputtering or vapor phase chemical method; sputtering or vapor depositing one or more optional barrier layers 3 on the interference film 2; depositing a TCO layer 4 (transparent electrode layer 4) (which may also include a high resistance layer) on the barrier layer 3 or on the interference film 2 by sputtering or vapor phase chemical method; scribing the TCO layer 4 from the glass surface or the film surface by adopting a laser process or a mechanical process (a first scribing process); preparing a power generation layer 5 on the TCO layer 4, wherein the power generation layer comprises a pn junction or a pin junction or a plurality of pn junctions or pin junctions; scribing the power generation layer 5 from the glass surface or the film surface by a laser process or a mechanical process (a second scribing process); sputtering and depositing a back electrode layer 6 comprising a back contact layer; scribing the cell layer 5 from the glass surface by using a laser process or scribing the back electrode layer 6 from the film surface by using a mechanical process (a third scribing process); packaging the components by adopting back plate glass 7; and finally, performing texturing on the outer surface of the substrate 1 by adopting a frosting process.
Method 2
The process flow of method 2 is shown in figure 3,
the ultra-white or common glass substrate 1 is produced by a float process and can be toughened or non-toughened; depositing a single-layer or multi-layer interference film 2 on a glass substrate 1 by adopting a sputtering or vapor phase chemical method; optionally, sputtering or vapor depositing one or more barrier layers 3 on the interference film 2; depositing a TCO layer 4 (which may also include a high-resistance layer) on the barrier layer 3 or the interference film 2 by sputtering or vapor-phase chemical method; preparing a power generation layer 5 on the TCO layer 4, wherein the power generation layer comprises a pn junction or a pin junction or a plurality of pn junctions or pin junctions; scribing the TCO layer 4 from the glass surface by adopting a laser process or scribing the TCO layer 4 and the power generation layer 5 from the film surface by adopting a mechanical process (a first scribing process); filling insulating materials at the scribing positions; scribing the power generation layer 5 from the glass surface or the film surface by a laser process or a mechanical process (a second scribing process); sputtering and depositing a back electrode layer 6 comprising a back contact layer; scribing the power generation layer 5 from the glass surface by adopting a laser process or scribing the back electrode layer 6 from the film surface by adopting a mechanical process (a third scribing process); packaging the components by adopting back plate glass 7; and finally, performing texturing on the outer surface of the substrate 1 by adopting a frosting process.
The process flow of method 3 is shown in figure 4,
the ultra-white or common glass substrate 1 is produced by a float process and can be toughened or non-toughened; texturing the outer surface of the substrate 1 by adopting a frosting process; depositing a single-layer or multi-layer interference film 2 on the inner surface of a glass substrate 1 by adopting a sputtering or vapor phase chemical method; optionally, sputtering or vapor depositing one or more barrier layers 3 on the interference film 2; depositing a TCO layer 4 (which may also include a high-resistance layer) on the barrier layer 3 or the interference film 2 by sputtering or vapor-phase chemical method; scribing the TCO layer 4 from the glass surface or the film surface by adopting a laser process or a mechanical process (a first scribing process); preparing a power generation layer 5 on the TCO layer 4, wherein the power generation layer comprises a pn junction or a pin junction or a plurality of pn junctions or pin junctions; scribing the power generation layer 5 from the glass surface or the film surface by a laser process or a mechanical process (a second scribing process); sputtering and depositing a back electrode layer 6 comprising a back contact layer; scribing the cell layer 5 from the glass surface by using a laser process or scribing the back electrode layer 6 from the film surface by using a mechanical process (a third scribing process); and (4) packaging the components by using a back plate glass 7.
Method 4
The process flow of method 4 is shown in figure 5,
the ultra-white or common glass substrate 1 is produced by a float process and can be toughened or non-toughened; texturing the outer surface of the substrate 1 by adopting a frosting process; depositing a single-layer or multi-layer interference film 2 on the inner surface of a glass substrate 1 by adopting a sputtering or vapor phase chemical method; optionally, sputtering or vapor depositing one or more barrier layers 3 on the interference film 2; depositing a TCO layer 4 (which may also include a high-resistance layer) on the barrier layer 3 or the interference film 2 by sputtering or vapor-phase chemical method; preparing a power generation layer 5 on the TCO layer 4, wherein the power generation layer comprises a pn junction or a pin junction or a plurality of pn junctions or pin junctions; scribing the TCO layer 4 and the power generation layer 5 from the film surface by adopting a laser or a mechanical process (a first scribing process); filling insulating materials at the scribing positions; scribing the power generation layer 5 from the film surface by using laser or mechanical process (second scribing process); sputtering and depositing a back electrode layer 6 comprising a back contact layer; scribing the back electrode layer 6 from the film surface by laser or mechanical process (third scribing process); and (4) packaging the components by using a back plate glass 7.
For a film assembly (e.g., a CIGS or like cell) with a bottom-in-light and top-out light structure, the following method 5 can be used.
Method 5
The process flow of method 5 is shown in figure 6,
the ultra-white or common glass substrate is produced by a float process and can be toughened or non-toughened; a barrier layer is prepared on a glass substrate to prevent impurities in the substrate from entering the cell. And depositing a back electrode layer on the barrier layer, and scribing the back electrode layer from the film surface by adopting a laser or a mechanical process (a first scribing procedure). The cell layer deposition is then performed on the back electrode, and the cell layer is scribed from the film side using a laser or mechanical process (second scribing step). And then depositing a TCO layer on the cell layer, and scribing the TCO layer from the film surface by using a laser or a mechanical process (a third scribing process). Optionally performing one or more barrier layer depositions on the TCO; the single or multilayer interference film is then deposited using sputtering or vapor phase chemical methods. And finally, packaging the components by using suede glass.
The specific process parameters in the methods 1 to 5 may refer to the process parameters for preparing each layer, which are not described herein again.
Based on the preparation process, the invention also provides the color thin film photovoltaic module prepared by the preparation method.
Compared with the prior art, the invention has the following advantages:
1. the color film component is mainly made of materials with different refractive indexes and thicknesses, comprises an interference film, an optional barrier layer, a high-resistance layer, a window layer and a battery layer, selectively reflects sunlight, and has the advantages of good high-temperature stability and high sunlight transmittance.
2. The film layers playing a color role in the invention are all made of inorganic materials, and can ensure the 25-year service life which is as long as the service life of the component product.
3. The color film photovoltaic module has the advantages of color, high power generation efficiency and low light pollution.
4. The invention simplifies the production flow of the color film photovoltaic module, organically integrates the preparation of the color glass with the preparation process of the solar cell, slightly adds the preparation functional blocks of a plurality of materials on the original TCO, high-resistance layer and other film devices, can realize the preparation of the color film photovoltaic module, does not need additional devices to carry out the work of glass color coating and the like, is suitable for realizing the industrialization of the color film photovoltaic module, and can greatly reduce the manufacturing cost of the color film photovoltaic module.
In order to further illustrate the present invention, the following detailed description of a color thin film photovoltaic module and a method for manufacturing the same is provided in connection with the examples, which should not be construed as limiting the scope of the present invention.
EXAMPLE 1 preparation of cadmium telluride colored thin film assemblies
Using 5mm ultra-white float glass as substrate, sputtering and depositing SiO on the glass2/TiO2Two interference films with a thickness of 80/100nm (denoted as reflective film 1). All prepared by adopting a reactive sputtering process: using Ti and Si as target material in O2Sputtering in an Ar atmosphere, wherein the ratio of O2/(O2+ Ar) is 5 percent; the sputtering power density is 1.2W/cm2(ii) a Air pressure: 10 mTorr.
Sputter deposition of an ITO electrode layer, O, on the interference film2/(O2+ Ar) ratio 0.1%; sputtering power density 2W/cm2(ii) a Air pressure: 10 mTorr.
Then sputtering and depositing an MZO high-resistance layer and a CdS O window layer;
MgZnO high resistance layer: 20nm, O2/(O2+ Ar) ratio of 24%, sputtering power density of 4W/cm2Air pressure: 10 mTorr;
CdS O with thickness of 30nm and O in sputtering gas2/(Ar+O2) The proportion of (A) is 1.5%, and the sputtering power density is 3W/cm2Air pressure: 10 mTorr.
Then depositing a CdTe battery layer by adopting a close space sublimation process, wherein the substrate temperature is 560 ℃, the source temperature is 660 ℃, the deposition pressure is 8Torr, and O is2/(N2+O2) The ratio was 1.5%, and the thickness of the battery layer was 3 μm.
Subsequently CdCl is carried out on the CdTe battery layer2Heat treatment and CdTe surface treatment, the concentration of the cadmium chloride solution is 5%, the spraying amount is 10mL, the heat treatment temperature is 400 ℃, and the heat treatment time is 30 minutes.
And carrying out first laser scribing, filling an insulating material at the scribing position, preparing a back contact layer, wherein the back contact layer is a carbon paste with the Cu content of 0.001% or a ZnTe back contact layer, and annealing for 30min at 200 ℃ in a nitrogen atmosphere.
And performing second laser scribing, sputtering and depositing a Mo/Al/Cr metal back electrode: the thickness of Mo is 20nm, the thickness of Al is 100nm, and the thickness of Cr is 20 nm.
And carrying out the third laser scribing, packaging the assembly and finally carrying out surface frosting treatment.
FIG. 7 shows the color change of the samples of the processes of this example 1, wherein the color of the color module during the preparation process is mainly changed at the processes of ITO, CdS, CdTe and module, and the final color of the module is close to the color of the deposited CdTe battery layer. The color of the CdTe color element is thus mainly determined by the reflective layer, the front electrode, the window layer and the cell layer together.
Table 1 power generation performance parameters of the color thin film photovoltaic module in example 1 of the present invention
As can be seen from Table 1, the small module efficiency is between 11.95% and 14.67% depending on the thickness of each layer and the fabrication process, with the highest efficiency module using the interference film 2 and 200nm ITO process. The best colour module power generation performance is compared to the conventional module data as shown in figure 11. FIG. 11 is a normalized parameter of power generation parameters for a color film module and a normal conventional module. The efficiency of the color module reaches 93% of that of the conventional module, wherein the open circuit voltage (Voc) and the Fill Factor (FF) of the color module are similar to those of the conventional module, and the short circuit current (Jsc) is lower, and the relative proportion is 93.4%. The main reason for the low Jsc is the selective reflection of sunlight.
The efficiency loss of the colored cadmium telluride thin film component is 23% or less, preferably 7%, which is far lower than the efficiency loss of more than 40% of the traditional colored component process, and the colored cadmium telluride thin film component has higher power generation efficiency.
Example 2
A colored thin film photovoltaic module was prepared according to the method of example 1, except that SiO was sputter deposited on the glass2/TiO2Two interference films with a thickness of 160/130nm (denoted as reflective film 2).
The light transmittance test was performed on the reflective film 1 in example 1 and the reflective film 2 in example 2, and the results are shown in fig. 8, where fig. 8 is the light transmittance data of two interference film processes, and the light transmittance of the reflective film 1 in the wavelength band of 300-500nm is reduced, so that the short wave can be selectively reflected to make the sample appear light blue. The light transmission of the reflecting film 2 at the 800-1100nm wave band is reduced, and long waves can be selectively reflected to enable the sample to be light red. The figure also shows the light transmission data of the reflecting film 2 after high-temperature treatment (580 ℃, 25min), and the result shows that the light transmission change of the interference film after the high-temperature treatment is extremely small, and the interference film has good high-temperature resistance. Therefore, in the preparation process of the battery, the interference film has stable performance, no impurity is introduced, and the high-temperature preparation process of the thin-film battery can be well met.
Example 3
100, 200, 300 and 400nm ITO were sputtered on the light blue interference film, respectively, and component samples were prepared as in example 1, with the results shown in FIG. 9. As can be seen from fig. 9, as the thickness of ITO increases, the sample of the device sequentially shows regular changes of indigo, violet, blue, and light blue, wherein the black device is a conventional sample. Experiments show that the color of the component can be adjusted through the thickness of the ITO.
Example 4
100, 200, 300 and 400nm ITO were sputtered on the light red interference film and prepared into component samples, respectively, according to the method in example 1, and the results are shown in FIG. 10. As can be seen from FIG. 10, with the variation of the thickness of the ITO, the color of the component can be adjusted from red to green.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A preparation method of a color thin film photovoltaic module comprises the following steps:
sequentially compounding an interference film layer, an optional barrier layer, a transparent front electrode layer, a battery layer and a back electrode layer on a glass substrate;
the interference film layer is compounded on the glass substrate by adopting a sputtering, thermal evaporation or chemical vapor deposition method;
the optional barrier layer is compounded on the surface of the interference film layer by a sputtering, thermal evaporation or chemical vapor deposition method;
the transparent front electrode layer is compounded on the surface of the interference film by a chemical vapor deposition or sputtering method.
2. The method according to claim 1, wherein the interference film layer comprises one or more of silicon oxide, titanium oxide, magnesium oxide, zinc oxide, zirconium oxide, tin oxide, calcium oxide, tantalum oxide, indium oxide and silicon nitride;
the interference film layer is a single film layer or a composite film layer with 1-7 layers;
the thickness of the interference film layer is 60-300 nm.
3. The method of claim 1, wherein the optional barrier layer comprises one or more of silicon oxide, silicon carbide and tin oxide;
the thickness of the optional barrier layer is 60-200 nm.
4. The method according to claim 1, wherein the transparent front electrode layer comprises one or more of F-doped tin oxide, In-doped zinc oxide, Sb-doped tin oxide, Al-doped zinc oxide, Ga-doped zinc oxide, and Cd-doped tin oxide;
the thickness of the transparent front electrode layer is 300-900 nm.
5. The production method according to claim 4, wherein the transparent front electrode layer further comprises a high-resistance layer;
the high-resistance layer is selected from one or more of tin oxide, zinc oxide, Zn-doped tin oxide, Mg-doped zinc oxide and F-Cd-doped tin oxide.
6. The preparation method of claim 1, wherein the battery layer is selected from one or more of cadmium telluride, cadmium telluride selenide, copper indium gallium selenide, gallium arsenide, amorphous silicon, perovskite, thin film crystalline silicon and organic dye-sensitive battery; the thickness of the battery layer is 2-6 mu m.
7. The method according to any one of claims 1 to 6, wherein the interference film is prepared by using Ti and Si as targets and using Ti and Si as precursors in O2And Ar in a mixed atmosphere, and preparing by adopting a magnetron sputtering method;
the power density of the magnetron sputtering is 0.1-20W/cm2The pressure of the magnetron sputtering is 1-20 mTorr.
8. The method according to any one of claims 1 to 6, wherein the transparent front electrode layer is O2And Ar in a mixed atmosphere, and preparing by adopting a magnetron sputtering method;
the power density of the magnetron sputtering is 0.1-20W/cm2The pressure of the magnetron sputtering is 1-20 mTorr.
9. The manufacturing method according to any one of claims 1 to 6, wherein the outer surface of the glass substrate has a textured structure.
10. A color thin film photovoltaic module prepared by the method of any one of claims 1 to 9.
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