CN110970524A - Solar cell and preparation method thereof - Google Patents
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- CN110970524A CN110970524A CN201811160969.XA CN201811160969A CN110970524A CN 110970524 A CN110970524 A CN 110970524A CN 201811160969 A CN201811160969 A CN 201811160969A CN 110970524 A CN110970524 A CN 110970524A
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- 238000002360 preparation method Methods 0.000 title abstract description 13
- KYKLWYKWCAYAJY-UHFFFAOYSA-N oxotin;zinc Chemical group [Zn].[Sn]=O KYKLWYKWCAYAJY-UHFFFAOYSA-N 0.000 claims abstract description 85
- 238000002834 transmittance Methods 0.000 claims abstract description 55
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 46
- 238000010521 absorption reaction Methods 0.000 claims abstract description 45
- 239000011787 zinc oxide Substances 0.000 claims abstract description 23
- 239000010408 film Substances 0.000 claims description 88
- 238000000034 method Methods 0.000 claims description 60
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 53
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 50
- 238000004544 sputter deposition Methods 0.000 claims description 44
- 238000000151 deposition Methods 0.000 claims description 35
- 229910052760 oxygen Inorganic materials 0.000 claims description 29
- 239000001301 oxygen Substances 0.000 claims description 29
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- 229910052786 argon Inorganic materials 0.000 claims description 27
- 230000008569 process Effects 0.000 claims description 22
- 239000011521 glass Substances 0.000 claims description 18
- 239000010409 thin film Substances 0.000 claims description 16
- 230000004888 barrier function Effects 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 15
- 239000007789 gas Substances 0.000 claims description 14
- 239000006096 absorbing agent Substances 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 20
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- 238000002474 experimental method Methods 0.000 description 4
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 3
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 3
- 238000000224 chemical solution deposition Methods 0.000 description 3
- 238000010549 co-Evaporation Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000004907 flux Effects 0.000 description 3
- 229910052733 gallium Inorganic materials 0.000 description 3
- 229910052738 indium Inorganic materials 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000011224 oxide ceramic Substances 0.000 description 3
- 229910052711 selenium Inorganic materials 0.000 description 3
- 238000005477 sputtering target Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000013077 target material Substances 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- KTSFMFGEAAANTF-UHFFFAOYSA-N [Cu].[Se].[Se].[In] Chemical compound [Cu].[Se].[Se].[In] KTSFMFGEAAANTF-UHFFFAOYSA-N 0.000 description 2
- -1 argon ions Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000005240 physical vapour deposition Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- VEUACKUBDLVUAC-UHFFFAOYSA-N [Na].[Ca] Chemical compound [Na].[Ca] VEUACKUBDLVUAC-UHFFFAOYSA-N 0.000 description 1
- VVTSZOCINPYFDP-UHFFFAOYSA-N [O].[Ar] Chemical compound [O].[Ar] VVTSZOCINPYFDP-UHFFFAOYSA-N 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
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- 239000011261 inert gas Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
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- 150000004706 metal oxides Chemical class 0.000 description 1
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- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000005361 soda-lime glass Substances 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- BNEMLSQAJOPTGK-UHFFFAOYSA-N zinc;dioxido(oxo)tin Chemical compound [Zn+2].[O-][Sn]([O-])=O BNEMLSQAJOPTGK-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
- H01L31/04—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
- H01L31/072—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 potential barriers the potential barriers being only of the PN heterojunction type
- H01L31/0749—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 heterojunction type including a AIBIIICVI compound, e.g. CdS/CulnSe2 [CIS] heterojunction 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
- H01L31/0248—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
- H01L31/0256—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 the material
- H01L31/0264—Inorganic materials
- H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
- H01L31/0322—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising only AIBIIICVI chalcopyrite compounds, e.g. Cu In Se2, Cu Ga Se2, Cu In Ga Se2
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Abstract
The application relates to a solar cell and a preparation method thereof. The application provides a solar cell and a preparation method thereof. The solar cell comprises a back plate, an absorption layer, a buffer layer, a first window layer and a second window layer. The first window layer is arranged on the surface of the buffer layer far away from the absorption layer. The material of the first window layer is zinc tin oxide. The second window layer is aluminum-doped zinc oxide. The light transmittance through the first window layer and the second window layer having higher light transmittance is high. The first window layer and the second window layer with the relatively close forbidden band widths are used as electron transmission layers, so that the mobility of electrons in the solar cell can be improved, and the photoelectric conversion efficiency of the solar cell is improved.
Description
Technical Field
The application relates to the field of photoelectric technology, in particular to a solar cell and a preparation method thereof.
Background
The CIGS (CIGS) thin-film solar cell is a research hotspot in the photovoltaic industry in recent years, and the CIGS thin-film material has the characteristics of high absorption coefficient, good stability and the like. Mature preparation of CIGS thin film materials comprises two major types, namely a co-evaporation method and a magnetron sputtering selenization method. Currently, a CIGS solar cell uses a P-type semiconductor material as an absorber layer and an N-type semiconductor material as a window layer, wherein zinc oxide in a high resistance state is often used as the window layer. The P-type semiconductor material is a semiconductor material having excess holes. An N-type semiconductor refers to a semiconductor material in which excess electrons are present. There are crystal defects due to zinc oxide. The solar cell using zinc oxide as the first window layer has low transmittance to visible light, and the photoelectric conversion efficiency of the solar cell is low.
Disclosure of Invention
Therefore, it is necessary to provide a solar cell and a method for manufacturing the same, which solve the problems of low visible light transmittance and low photoelectric conversion efficiency of the solar cell.
A solar cell, comprising:
a back plate;
the absorption layer is arranged on the surface of the back plate;
the buffer layer is arranged on the surface of the absorption layer far away from the back plate;
the first window layer is arranged on the surface of the buffer layer, which is far away from the absorption layer, and is made of a zinc tin oxide film; and
and the second window layer is arranged on the surface of the first window layer far away from the buffer layer, and the second window layer is aluminum-doped zinc oxide.
In one embodiment, the first window layer made of a zinc tin oxide film has a light transmittance in the visible region of 90% to 97%, and preferably, the first window layer has a light transmittance in the visible region of 92%, 93%, 95%, 96%.
In one embodiment, the first window layer made of the zinc tin oxide film has a forbidden bandwidth of 3.1eV-3.4eV, and preferably, the first window layer has a forbidden bandwidth of 3.25eV, 3.23eV, 3.38 eV.
In one embodiment, the thickness of the first window layer is 80nm to 130nm, optionally the thickness of the first window layer is 100nm to 120nm, preferably the thickness of the first window layer is 85nm, 90nm, 95nm, 105nm, 115nm or 125 nm.
In one embodiment, the solar cell further comprises: a back electrode layer disposed between the back plate and the absorption layer;
the barrier layer is arranged between the back plate glass and the back electrode layer and comprises a silicon nitride layer.
A method for manufacturing a solar cell includes the steps of:
s100, depositing an absorption layer on the surface of the back plate;
s200, depositing a buffer layer on the surface of the absorption layer;
s300, depositing a first window layer on the surface, far away from the absorption layer, of the buffer layer by adopting a magnetron sputtering method, wherein the first window layer is a zinc tin oxide film;
s400, depositing a second window layer on the surface, far away from the buffer layer, of the first window layer.
In one embodiment, in step S300, during the magnetron sputtering, the heating temperature of the back plate is 200 ℃ to 300 ℃, optionally the heating temperature is 250 ℃, and the sputtering pressure in the magnetron sputtering environment is 0.3Pa to 0.8Pa, optionally the sputtering pressure is 0.5 Pa.
In one embodiment, the preparation atmosphere of the magnetron sputtering process is a mixed gas of argon and oxygen, wherein the volume ratio of the argon to the oxygen in a standard state is as follows: 5:1-25:1.
In one embodiment, in the step S300,
the magnetron sputtering power is 150W-250W, the volume ratio of argon to oxygen is 5:1 to 25:1, the thickness of the first window layer is 80nm-130nm, optionally the thickness of the first window layer is 100nm-120nm, and preferably the thickness of the first window layer is 85nm, 90nm, 95nm, 105nm, 115nm or 125 nm.
In one embodiment, further comprising:
s500, depositing front plate glass on the surface, far away from the first window layer, of the second window layer.
In one embodiment, the step S100 further includes:
s110, depositing a back electrode layer on the surface of the back plate, wherein the back electrode layer is arranged between the back plate and the absorption layer.
In one embodiment, before the step S110, the method further includes:
s101, depositing a barrier layer on the surface of the back plate, wherein the barrier layer is arranged between the back plate and the back electrode layer.
The application provides a solar cell and a preparation method thereof. The solar cell comprises a back plate, an absorption layer, a buffer layer, a first window layer and a second window layer. The first window layer is arranged on the surface of the buffer layer far away from the absorption layer. The first window layer is made of a zinc tin oxide film. The second window layer is aluminum-doped zinc oxide. In order to improve the photoelectric conversion efficiency of the solar cell, the light transmittance of the window layer is required to be high, the light energy obtained by the absorption layer is higher, the number of excited electrons is increased, and the effective current output by the solar cell is improved.
Drawings
Fig. 1 is a schematic structural diagram of a solar cell provided in one embodiment of the present application;
FIG. 2 is a graph of the transmittance of a first window layer prepared using different process conditions as provided in one embodiment of the present application;
FIG. 3 is a graph of the transmittance of a first window layer prepared using different process conditions as provided in one embodiment of the present application;
FIG. 4 shows the transmittance test results of a first window layer prepared under different process conditions according to one embodiment of the present disclosure;
FIG. 5 shows the transmittance test results of a first window layer prepared under different process conditions according to one embodiment of the present disclosure;
fig. 6 shows the transmittance test results of the first window layer prepared under different process conditions according to one embodiment of the present application.
The reference numbers illustrate:
Barrier layer 110
Detailed Description
In order to make the objects, technical solutions and advantages of the present application more apparent, the present application is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the present application and are not intended to limit the present application.
Referring to fig. 1, in one embodiment, a solar cell 10 is provided, which includes a back sheet 100, an absorber layer 310, a buffer layer 320, a first window layer 330, and a second window layer 400.
The backplate 100 may be monocrystalline silicon, polycrystalline silicon, amorphous silicon, glass, or soda lime glass. The choice of the back plate 100 can be continuously updated according to the development of technology. In one embodiment, the back sheet 100 is provided with a back electrode layer 200 on the surface during the factory shipment. The back electrode layer 200 is disposed between the back plate 100 and the absorption layer 310.
The absorption layer 310 is disposed on the surface of the back plate 100. The absorber layer 310 may be a copper indium gallium selenide (abbreviated CIGS) thin film. In one embodiment, a CIGS thin film is prepared using a co-evaporation method. The absorption layer 310 may be formed by using four elements of Cu, In, Ga, and Se In different proportions. The specific element ratio and thickness of the absorption layer 310 are not specifically limited herein.
The buffer layer 320 is disposed on the surface of the absorption layer 310 away from the back plate 100. The buffer layer 320 may be cadmium sulfide (CdS). The buffer layer 320 is prepared using a CBD chemical water bath in one embodiment. The thickness of the buffer layer 320 and the specific preparation method are not limited in this regard.
The first window layer 330 is disposed on a surface of the buffer layer 320 away from the absorber layer 310. The first window layer 330 is made of a zinc tin oxide film. The forbidden bandwidth of the zinc tin oxide film material is wide, the sunlight absorption capacity is weak, and the light transmittance of the zinc tin oxide film material is high. The light transmittance can reach 96%, under the condition that the irradiance of the light is fixed, the light transmittance is high, the effective solar energy received by the absorption layer is higher, under the excitation of the solar energy, the absorption layer made of the p-type semiconductor material and the buffer layer made of the n-type semiconductor material form a p-n junction to form a potential difference, namely, the light energy is converted into electric energy, so that the photoelectric conversion efficiency of the solar cell 10 is higher. In addition, the zinc tin oxide material used as the first window layer 330 has the characteristics of high electron mobility, easily adjustable carrier concentration and good conductivity, so as to reduce the series resistance of the first window layer and improve the photoelectric conversion efficiency of the solar cell 10.
In one embodiment, the first window layer 330 is prepared using a magnetron sputtering method. In the magnetron sputtering process, the sputtering target material is a zinc tin oxide ceramic target material, the sputtering power is 150W-250W, the sputtering atmosphere is a mixed gas of argon and oxygen, and when the zinc tin oxide film is prepared by adopting the magnetron sputtering method, oxygen is added into the sputtering atmosphere to participate in sputtering, so that the chemical ratio in the film can be effectively adjusted, the oxygen vacancy defect is reduced, the carrier concentration is reduced, and the resistivity is improved. Controlling the volume ratio of argon to oxygen in sputtering atmosphere within the range of 5:1 to 25:1, wherein the obtained zinc tin oxide film has less oxygen vacancy defects, low carrier concentration and high resistance, and the thickness of the first window layer is 80nm-130 nm. The first window layer 330 used in one embodiment of the present application is zinc tin oxide, the forbidden bandwidth of the zinc tin oxide prepared by the preparation method of the present application is 3.23V, and the first window layer 330 prepared by the magnetron sputtering method of the present application has good adhesion and bonding force.
The second window layer 400 is disposed on a surface of the first window layer 330 away from the buffer layer 320. In one embodiment, the first window layer 330 may be a mixture of zinc oxide and metallic aluminum. The thickness of the first window layer 330 and the specific manufacturing method are not limited herein.
The first window layer 330 and the second window layer 400 are both for increasing the light transmittance of the solar cell 10. The first window layer 330 and the second window layer 400 are both made of zinc oxide doped with metal, so that the light transmittance of the transparent conductive layer is improved. The first window layer 330 and the second window layer 400 are doped with different metal materials, in different doping ratios, and in different doping process parameters. The first window layer 330 and the second window layer 400 may have different thicknesses, different resistivities, and different light transmittances.
The forbidden bandwidth of the first window layer 330 is closer to the forbidden bandwidth of the second window layer 400, so that the first window layer 330 and the second window layer 400 can realize a larger light passing window. The first window layer 330 and the second window layer 400 are made of different materials and have different forbidden bandwidths. In one embodiment, the first window layer 330 is made of the zinc-tin oxide material with a forbidden band width of 3.1eV-3.4 eV. The second window layer 400 is made of aluminum-doped zinc oxide with a forbidden band width of about 3.2eV, so that the first window layer 330 and the second window layer 400 have larger light passing windows. It is understood that in the solar cell 10, the forbidden bandwidth of each layer of material can define a light channel with a certain width, and the larger the forbidden bandwidth is, the wider the light channel is, the stronger the energy of the light that can pass through. It is further understood that, in the case that the forbidden band width of the material is constant, the higher the transmittance of the material is, the higher the photoelectric conversion efficiency of the solar cell 10 is. The close band gaps of the first window layer 330 and the absorption layer 310 can make the light channel of the solar cell 10 wider. For example, in one embodiment, in the structure of the solar cell 10, the second window layer 400 has a forbidden bandwidth of 3.4eV, the first window layer 330 has a forbidden bandwidth of 3.23eV, the buffer layer 320 has a forbidden bandwidth of 2.42eV, and the absorber layer 310 has a forbidden bandwidth of 1.7 eV. The forbidden band widths of the layers stacked from the side of the solar cell 10 contacting light are sequentially decreased, so that the light path of the solar cell 10 is wider. In the case where the optical path is fixed, if it is desired to further improve the photoelectric conversion efficiency of the solar cell 10, the light transmittance of each layer can be improved.
In one embodiment, a front glass 600 may also be provided. The front plate glass 600 is disposed on a surface of the second window layer 400 away from the first window layer 330. In one embodiment, the front glass 600 may employ a collector Ni/Al electrode. The thickness of the film layer of the front glass 600 and the specific manufacturing method are not limited herein.
In this embodiment, the solar cell 10 includes the back sheet 100, the absorber layer 310, the buffer layer 320, the first window layer 330, and the second window layer 400. Specifically, a Zinc Tin Oxide (ZTO) thin film is used as the first window layer 330. The zinc tin oxide film has the advantages of abundant and easily-obtained raw materials, high light transmittance and 3.1-3.4 eV band gap. Electrons in the zinc tin oxide film are directly transmitted through a conduction band, so that the zinc tin oxide film has stronger electron transmission capability. A Zinc Tin Oxide (ZTO) thin film is used as the first window layer 330, and aluminum-doped zinc oxide (AZO) is used as the second window layer 400. The first window layer 330 and the second window layer 400 both serve as electron transport layers, and the band gap widths of the two layers are close to each other, so that the electron transport motion is facilitated. The first window layer 330 and the second window layer 400 with the close forbidden band widths are used as electron transport layers, so that the light throughput of the solar cell 10 can be increased, and the photoelectric conversion efficiency of the solar cell 10 can be improved.
In one embodiment, the solar cell 10 further includes a back electrode layer 200. The back electrode layer 200 is disposed between the back plate 100 and the absorption layer 310.
In this embodiment, the back electrode layer 200 may be made of molybdenum (Mo). The thickness of the back electrode layer 200 is not particularly limited, and for example, the thickness of the back electrode layer 200 may be 0.3 μm to 0.7 μm. In one embodiment, the back electrode 200 is deposited with a thickness of 0.5 μm using this magnetron sputtering method.
In one embodiment, the solar cell 10 further includes a barrier layer 110. The barrier layer 110 serves to increase adhesion between the back sheet 100 and the back electrode layer 200. The barrier layer 110 has a thickness of 0.3 μm to 0.5 μm. In one embodiment, the barrier layer 110 is 0.4 μm thick.
In the embodiment of the present application, the first window layer and the second window layer with the close forbidden band widths are used as the electron transport layers, so that the throughput of the light of the solar cell 10 can be increased, and the photoelectric conversion efficiency of the solar cell 10 can be further improved.
In one embodiment, the thickness of the first window layer 330 is 80nm to 130nm, and preferably, the thickness of the first window layer 330 is 80 nm. In this embodiment, the first window layer 330 with a reasonable thickness is disposed, which is beneficial to the absorption layer 310, the buffer layer 320 and the first window layer 330 to realize high efficiency conversion of solar energy.
In one embodiment, a method for fabricating a solar cell is provided, including the steps of:
s100, depositing an absorption layer 310 on the surface of the back plate 100, wherein the absorption layer 310 forms a p region.
S200, depositing a buffer layer 320 on the surface of the absorption layer 310 to perform p-n bonding with the absorption layer 310.
S300, depositing a first window layer 330 on the surface of the buffer layer 320 far away from the absorption layer 310 by adopting a magnetron sputtering method. The buffer layer 320 and the first window layer 330 together form an n-region. The first window layer 330 is zinc tin oxide. The first window layer 330 is prepared by a magnetron sputtering method. The sputtering target used in the preparation of the first window layer 330 is a zinc tin oxide ceramic target, the sputtering power is 150W-250W, the sputtering atmosphere is that the volume ratio of argon to oxygen is in the range of 5:1 to 25:1, and the thickness of the first window layer 330 is 80nm-130 nm. Optionally, the thickness of the first window layer 330 is 100nm to 120nm, and preferably, the thickness of the first window layer 330 is 85nm, 90nm, 95nm, 105nm, 115nm or 125 nm.
S400, depositing a second window layer 400 on the surface of the first window layer 330 away from the buffer layer 320.
S500, depositing front plate glass 600 on the surface of the second window layer 400 far away from the first window layer 330.
In this embodiment, the first window layer 330 (the zinc tin oxide film) is prepared by magnetron sputtering. The method for manufacturing a solar cell manufactures the zinc tin oxide thin film as the first window layer 330. When the first window layer 330 is prepared by a magnetron sputtering method, the thickness or the film forming state of the zinc tin oxide film can be further controlled by changing the magnetron sputtering conditions. The zinc tin oxide film prepared by the preparation method of the zinc tin oxide film in the embodiment has high electron mobility (can reach about 3.2cm2VS), and the zinc tin oxide film has active carriers and high light transmittance.
In one embodiment, in step S300, the heating temperature is 200 ℃ to 300 ℃, optionally the heating temperature is 250 ℃, and the sputtering pressure is 0.3Pa to 0.8Pa, optionally the sputtering pressure is 0.5 Pa.
In one embodiment, in the step S300, the magnetron sputtering power is 150W, the heating temperature is 250 ℃, and the sputtering pressure is 0.5 Pa.
In one embodiment, in step S300, the magnetron sputtering power is 150W, the magnetron sputtering atmosphere is a volume ratio of argon to oxygen of 15:1, the sputtering pressure is 0.5Pa, and the thickness of the first window layer 330 is 110 nm.
In one embodiment, in step S300, the magnetron sputtering power is 250W, the magnetron sputtering atmosphere is argon gas to oxygen gas volume ratio of 15:1, the sputtering pressure is 0.5Pa, and the thickness of the first window layer 330 is 130 nm.
The magnetron sputtering conditions of the zinc tin oxide film are defined in the above 3 examples respectively. In the above embodiments, the suitable magnetron sputtering environment is set so that the first window layer 330 can have a relatively flat surface, which is more beneficial to better match the zinc tin oxide film with other films in the solar cell 10 to improve the conversion efficiency of the solar cell 10.
In one embodiment, the step S100 further includes: s110, depositing a back electrode layer 200 on the surface of the back plate 100, wherein the back electrode layer 200 is disposed between the back plate 100 and the absorption layer 310.
In one embodiment, before the step S110, the method further includes:
s101, depositing a barrier layer 110 on the surface of the back plate 100, wherein the barrier layer 110 is arranged between the back plate 100 and the back electrode layer 200. The barrier layer 110 may increase adhesion between the back sheet 100 and the back electrode layer 200.
In one embodiment, the solar cell 10 may be fabricated by a process including Physical Vapor Deposition (PVD), Chemical Bath Deposition (CBD), or other processes that one skilled in the art would recognize as being useful. In a specific embodiment, the backing plate 100 is selected from a degreased calcium sodium glass. The dimensions of the back plate can be chosen to be 0.55mm thick, with a length x width equal to 800mm x 800 mm.
S10, placing the back plate 100 in a magnetron sputtering apparatus. The discharge gas is set to argon (Ar). Selecting a silicon-aluminum target material, wherein the ratio of Si to Al is 98 to 2. Setting the gas for magnetic control work to be N2The pressure of magnetron sputtering is 0.5Pa, and a magnetron radio frequency power supply deposits Si on the glass back plate3N4As a transition layer. The thickness of the transition layer is 0.05 μm. Alternatively, the thickness of the transition layer may be 0.02 μm to 0.1 μm.
And S20, depositing the back electrode layer 200 on the transition layer by adopting a magnetron sputtering method. The conditions for depositing the back electrode layer 200 are as follows: the discharge gas was argon, the sputtering pressure was 0.5Pa, and a Direct Current (DC) power supply. The back electrode layer 200 is deposited on the surface of the transition layer. The back electrode layer 200 may be a Mo electrode. The thickness of the back electrode layer 200 deposited may be 0.3 μm to 0.7 μm. The deposition thickness in this example was 0.5 μm.
S30, depositing the absorption layer 310 on the back electrode layer 200. In a chamber of a vacuum deposition apparatus, Cu, In, Se, and Ga are disposed as deposition sources. When the vacuum degree in the chamber reaches 2X 10-4Pa, heating the evaporation source to make Cu reach 1100 deg.C, In reach 780 deg.C, Ga reach 950 deg.C and Se reach 280 deg.C. And forming the absorption layer 310 on the back electrode layer 200 by adopting three-step co-evaporation, wherein the absorption layer 310 is a copper indium gallium selenide thin film. The thickness of the absorption layer 310 may be 1.5 μm to 2.5 μm. In one embodiment, the thickness of the absorption layer 310 is 2 μm. The atomic ratio of each element in the absorption layer 310 is Cu: in: ga: se is 23.5%: 19.5%: 7%: 50 percent.
S40, depositing the buffer layer 320 on the surface of the absorption layer 310 away from the back electrode 200. The buffer layer 320 may be CdS, Zn-based compound.
S50, depositing the first window layer 330 on the surface of the buffer layer 320 away from the absorber layer 310. A magnetron sputtering device is adopted, argon is selected as discharge gas, sputtering pressure is 0.5Pa, and a Radio Frequency (RF) power supply deposits the first window layer 330 on the surface of the buffer layer 320. Specifically, the first window layer 330 may be zinc tin oxide. The sputtering target is a zinc tin oxide ceramic target, the sputtering power is 150W-250W, the volume ratio of argon to oxygen is in the range of 5:1 to 25:1 in the sputtering atmosphere, and the thickness of the first window layer 330 is 80nm-130 nm.
S60, depositing the second window layer 400 on the surface of the first window layer 330. The second window layer 400 may be aluminum-doped zinc oxide. The thickness of the second window layer 400 may be set to 0.3 μm to 1 μm. In one embodiment, the thickness of the second window layer 400 is 0.6 μm.
S70, depositing the front plate glass 600 on the surface of the second window layer 400. And adopting a magnetron sputtering device, selecting argon as discharge gas, sputtering pressure of 0.5Pa, and depositing the front glass 600 on the surface of the second window layer 400 by using a Direct Current (DC) power supply. The thickness of the front plate glass 600 can be selected within the range of 0.03 mu m to 0.1 mu m. In one embodiment, the front glass 600 is made of Al, and the thickness of the front glass 600 is 0.05 μm.
In a specific embodiment, when the first window layer 330 is prepared by magnetron sputtering in step S50, a proper ratio of argon and oxygen needs to be selected. For metal oxide films, argon is the most common inert gas used for sputtering, and the addition of oxygen to participate in sputtering can effectively adjust the chemical ratio in the film, reduce oxygen vacancy defects, reduce carrier concentration and improve resistivity. The effective mass of oxygen is much smaller than that of argon, the bombardment effect on the surface of the film is smaller during sputtering, so the damage to the crystal quality of the film is smaller, but argon ions have higher sputtering probability than oxygen ions, and the film deposition rate is higher.
After the first window layer 330 film is prepared by a magnetron sputtering method, certain characteristics need to be performed on the performance of the zinc tin oxide film. The light transmittance of the zinc tin oxide film is an important test parameter. Transmittance is the ratio of radiant energy projected through and through an object to the total radiant energy projected onto the object during the incident flux as it passes from the illuminated surface or medium entrance surface to the other surface, and is referred to as the transmittance of the object. The light transmittance can be represented by TT%. Specific light transmittance refers to the percentage of the luminous flux of a material that is capable of passing through a transparent or translucent body as compared to the luminous flux of light incident upon it. For example, the intensity is I at a wavelength λ. When the monochromatic light of (a) is irradiated on a certain solution, a part of the light is absorbed, a part of the light is transmitted, and the transmission light intensity is I, the light transmittance T satisfies the following formula: t ═ I ÷ I0)×100％。
The zinc tin oxide film is prepared by adopting a magnetron sputtering method. The backing sheet can be heated appropriately during the preparation of the zinc tin oxide film. The temperature of the backing plate affects the properties of the zinc tin oxide film. If the temperature of the backing plate is too low, atomic kinetic energy deposited on the surface of the backing plate is small, and the atoms are not easy to migrate to the place where the free energy is minimum, and a low-density, rough-surface and porous film may be formed. When the temperature of the back plate is moderate, the surface atoms can be promoted to rapidly migrate to the position with lower free energy, and the appearance of the zinc tin oxide film is improved. When the temperature of the backing plate is high, some atoms with weak bonding can be re-evaporated.
In addition, the growth rate and properties of the zinc tin oxide film during magnetron sputtering are affected by a variety of parameters. In order to obtain a desired film, these growth parameters need to be adjusted comprehensively during the process, and the adjustment results of the properties of the zinc tin oxide film by different growth parameters during different processes are given in the following examples.
The first embodiment is as follows: and preparing the zinc tin oxide film on a glass substrate by adopting a magnetron sputtering method. Experiments are carried out under different process conditions as shown in table 1, and the test results of the light transmittance of the zinc tin oxide film in different wavelength ranges are obtained. The specific steps for preparing the zinc tin oxide film in table 1 are: sputtering deposition is carried out on the glass substrate at normal temperature, and the sputtering pressure is 0.5 Pa. The proportion of the argon gas to the oxygen gas mixture is 5:1, 15:1 or 25:1 respectively in the sputtering environment. The magnetron sputtering power is 150W, and the thickness of the zinc tin oxide film deposited is expected to be 100 nm.
Table 1: light transmittance test of zinc tin oxide film prepared under different process conditions
Referring to fig. 2, fig. 2 is a graph comparing the transmittance of the zinc tin oxide thin film prepared under different process conditions in table 1 with that of a control (intrinsic zinc oxide thin film, and argon-oxygen ratio 15:1, actual thickness 80nm) sample. Fig. 2 shows that the zinc tin oxide film prepared by the magnetron sputtering method has good binding force as an electron transport layer. The forbidden bandwidth of the tin-zinc oxide film is about 3.23eV, which is larger than the forbidden bandwidth of the second semiconductor 320 and approaches the forbidden bandwidth of the second window layer 400. Experiments prove that when the zinc tin oxide film is prepared by a magnetron sputtering method, the ratio of argon to oxygen is proper at 15:1, and the light transmittance of the zinc tin oxide film is superior to that of an intrinsic zinc oxide film in the visible wavelength range (390 nm-780 nm).
Example two: and preparing the zinc tin oxide film on a glass substrate by adopting a magnetron sputtering method. Experiments are carried out under different process conditions as shown in table 2, and the test results of the light transmittance of the zinc tin oxide film in different wavelength ranges are obtained. The specific steps for preparing the zinc tin oxide film in table 2 are: in the normal temperature environment, in the environment of preparing the zinc tin oxide film by adopting a magnetron sputtering method, fixing argon: the oxygen ratio was 15:1, and the fixed sputtering power was 150W. The thicknesses of the zinc tin oxide films are expected to be 60nm, 80nm and 100nm, respectively. In addition, a zinc oxide film was prepared on the glass substrate by a magnetron sputtering method as the first window layer 330 as a comparative example, and argon gas was fixed in the environment of magnetron sputtering: the ratio of oxygen is 15:1, the thickness of the zinc oxide film is 1nm-80nm, and the test data is shown in figure 2.
Table 2: light transmittance test of zinc tin oxide film prepared under different process conditions
Referring to fig. 3, fig. 3 shows the transmittance of the zinc-tin oxide thin film at different film thicknesses. It can be seen in fig. 3 that the peak of the spectral transmittance curve gradually red-shifts with increasing film thickness, deviating more from the curve of the present characteristic zinc oxide. The peak value of the spectral transmittance curve gradually moves blue along with the continuous reduction of the thickness of the zinc tin oxide film, and the curve tends to an intrinsic zinc oxide curve.
Example three: and preparing the zinc tin oxide film on a glass substrate by adopting a magnetron sputtering method. Experiments were performed under different process conditions as shown in table 3, and the results of the transmittance of the zinc-tin oxide film in different wavelength ranges were obtained. The specific steps for preparing the zinc tin oxide film in table 3 are: and depositing the zinc tin oxide film on a glass backboard by adopting a magnetron sputtering method at normal temperature. Three sets of data in table 3 were with fixed argon: the oxygen ratio is 15:1, the thickness of the zinc tin oxide film is 80nm, and the sputtering power is 100W, 150W and 250W respectively. In addition, a zinc oxide thin film was prepared on the glass substrate by magnetron sputtering as the first window layer 330 as a comparative example, the sputtering power was 150W, the thickness was 80nm, and the test data is shown in fig. 4.
Table 3: light transmittance test of zinc tin oxide film prepared under different process conditions
Referring to fig. 4, fig. 4 is a graph comparing the transmittance of the zno-sn thin film and intrinsic zno prepared at different sputtering powers. It can be seen in fig. 4 that the curve for the zinc tin oxide film produced with a sputtering power of 250W substantially coincides with the curve for the zinc tin oxide film produced with a sputtering power of 100W. From the spectral transmittance curve, the peak value of the spectral transmittance decreases and then increases with the increase of the sputtering power. The combination of table 3 can find that the peak value of the spectral transmittance curve of the zinc tin oxide film gradually red shifts and deviates from the curve of intrinsic zinc oxide as the thickness of the zinc tin oxide film increases. With the continuous reduction of the thickness of the zinc tin oxide film, the peak value of the spectral transmittance curve of the zinc tin oxide film gradually shifts blue, and the peak value tends to the spectral transmittance curve of intrinsic zinc oxide.
Example four: fixing argon by adopting a magnetron sputtering method: the oxygen ratio was 15:1 (except for the oxygen-free control group), the expected film thickness of the zinc tin oxide film was 80nm, and the sputtering power was 150W, 250W. In this example, the influence of the aerobic and anaerobic environments on the spectral transmittance during heating at 250 ℃ was verified, and the influence of the sputtering power on the spectral transmittance during heating was also verified. Experimental tests show that the results shown in fig. 5 and fig. 6 are obtained. Fig. 5 shows the effect of sputtering power and oxygen content on spectral transmission at a heating temperature of 250 c. Fig. 6 shows the effect of sputtering power and oxygen content on spectral transmission (intrinsic zinc oxide added spectral transmission) at a heating temperature of 250 c.
Table 4: light transmittance test of zinc tin oxide film prepared under different process conditions
As is clear from Table 4, FIG. 5 and FIG. 6, when the heating temperature was 250 ℃, the sputtering power was 150W, the sputtering pressure was 0.5Pa, the thickness of the sputtered film was estimated to be 80nm, and the argon gas was introduced: under the sputtering condition that the oxygen is 15:1, the spectral transmittance of the zinc tin oxide film when oxygen is introduced is better than that of the zinc tin oxide film when oxygen is not introduced. As can be seen from the spectral transmittance graphs of fig. 5 and 6, argon gas was introduced during heating: the light transmittance of the zinc tin oxide film with the oxygen of 15:1 in a short wave band is slightly improved, and the light transmittance in a long wave band is not obviously improved. It can also be seen in fig. 5 and 6 that the spectral transmittance curves for a sputtering power of 150W and a sputtering power of 250W substantially coincide at a heating temperature of 250 ℃.
In summary, the zinc tin oxide film prepared in the application has optical parameters superior to those of the traditional intrinsic zinc oxide film. Therefore, the zinc tin oxide film can be used as an electron transport layer in a solar cell structure.
The present application provides a solar cell 10 that employs the zinc tin oxide film as the first window layer 330. And preparing the zinc tin oxide film by adopting a magnetron sputtering method under different conditions of certain power, gas flow, vacuum pressure, deposition temperature and the like. And the optical performance, cost, utilization rate and the like of the zinc tin oxide film prove that the zinc tin oxide material can be used as the first window layer 330, so that the photoelectric conversion efficiency of the solar cell 10 is improved.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present application, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the concept of the present application, which falls within the scope of protection of the present application. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (12)
1. A solar cell, comprising:
a back plate (100);
an absorption layer (310) disposed on a surface of the backsheet (100);
a buffer layer (320) arranged on the surface of the absorption layer (310) far away from the backboard (100);
the first window layer (330) is arranged on the surface of the buffer layer (320) far away from the absorption layer (310), and the first window layer (330) is made of a zinc tin oxide film; and
the second window layer (400) is arranged on the surface, far away from the buffer layer (320), of the first window layer (330), and the second window layer (400) is made of aluminum-doped zinc oxide.
2. The solar cell according to claim 1, wherein the first window layer (330) made of a zinc tin oxide thin film has a light transmittance in the visible region of 90% to 97%, preferably the first window layer (330) has a light transmittance in the visible region of 92%, 93%, 95%, 96%.
3. The solar cell according to claim 1, wherein the first window layer (330) made of a zinc tin oxide thin film has a forbidden bandwidth of 3.1eV-3.4eV, preferably the first window layer (330) has a forbidden bandwidth of 3.25eV, 3.23eV, 3.38 eV.
4. The solar cell according to claim 1, wherein the thickness of the first window layer (330) is 80nm to 130nm, optionally the thickness of the first window layer (330) is 100nm to 120nm, preferably the thickness of the first window layer (330) is 85nm, 90nm, 95nm, 105nm, 115nm or 125 nm.
5. The solar cell of claim 1, further comprising:
a back electrode layer (200) disposed between the back sheet (100) and the absorber layer (310);
a barrier layer (110) disposed between the backplane glass (100) and the back electrode layer (200), the barrier layer comprising a silicon nitride layer (110).
6. A method for manufacturing a solar cell, comprising:
s100, depositing an absorption layer (310) on the surface of the backboard (100);
s200, depositing a buffer layer (320) on the surface of the absorption layer (310);
s300, depositing a first window layer (330) on the surface, far away from the absorption layer (310), of the buffer layer (320) by adopting a magnetron sputtering method, wherein the first window layer (330) is a zinc tin oxide film;
s400, depositing a second window layer (400) on the surface of the first window layer (330) far away from the buffer layer (320).
7. The method of claim 6, wherein in the step S300, the heating temperature of the back plate (100) is 200 ℃ to 300 ℃ during the magnetron sputtering process, optionally the heating temperature is 250 ℃, and the sputtering pressure in the magnetron sputtering environment is 0.3Pa to 0.8Pa, optionally the sputtering pressure is 0.5 Pa.
8. The method according to claim 6, wherein the magnetron sputtering process is performed in a mixed gas of argon and oxygen, wherein the volume ratio of argon to oxygen in the standard state is: 5:1-25:1.
9. The method of claim 6, wherein in step S300, the magnetron sputtering power is 150W-250W, the thickness of the first window layer (330) is 80nm-130nm, optionally the thickness of the first window layer (330) is 100nm-120nm, preferably the thickness of the first window layer (330) is 85nm, 90nm, 95nm, 105nm, 115nm or 125 nm.
10. The method of claim 6, further comprising:
s500, depositing front glass (600) on the surface, away from the first window layer (330), of the second window layer (400).
11. The method for manufacturing a solar cell according to claim 6, further comprising, in step S100:
s110, depositing a back electrode layer (200) on the surface of the back plate (100), wherein the back electrode layer (200) is arranged between the back plate (100) and the absorption layer (310).
12. The method for manufacturing a solar cell according to claim 10, further comprising, before the step S110:
s101, depositing a barrier layer (110) on the surface of the back plate (100), wherein the barrier layer (110) is arranged between the back plate (100) and the back electrode layer (200).
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Effective date of registration: 20210915 Address after: 201203 3rd floor, no.665 Zhangjiang Road, China (Shanghai) pilot Free Trade Zone, Pudong New Area, Shanghai Applicant after: Shanghai zuqiang Energy Co.,Ltd. Address before: 518054 Room 201, building A, 1 front Bay Road, Shenzhen Qianhai cooperation zone, Shenzhen, Guangdong Applicant before: Shenzhen Zhengyue development and Construction Co.,Ltd. |
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| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200407 |