CN111584643A - Solar cell and method for manufacturing same - Google Patents
Solar cell and method for manufacturing same Download PDFInfo
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- CN111584643A CN111584643A CN201910116388.4A CN201910116388A CN111584643A CN 111584643 A CN111584643 A CN 111584643A CN 201910116388 A CN201910116388 A CN 201910116388A CN 111584643 A CN111584643 A CN 111584643A
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 title claims description 38
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 212
- 239000011787 zinc oxide Substances 0.000 claims abstract description 106
- 239000011701 zinc Substances 0.000 claims abstract description 76
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 55
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 45
- 239000000758 substrate Substances 0.000 claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- 230000031700 light absorption Effects 0.000 claims abstract description 22
- 239000007789 gas Substances 0.000 claims description 93
- 239000002243 precursor Substances 0.000 claims description 62
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 32
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 32
- 229910052725 zinc Inorganic materials 0.000 claims description 32
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims description 30
- 238000000151 deposition Methods 0.000 claims description 29
- 238000005137 deposition process Methods 0.000 claims description 25
- 238000004518 low pressure chemical vapour deposition Methods 0.000 claims description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 18
- 230000008569 process Effects 0.000 claims description 18
- 229910052786 argon Inorganic materials 0.000 claims description 16
- 229910000085 borane Inorganic materials 0.000 claims description 15
- 238000001704 evaporation Methods 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- 239000001301 oxygen Substances 0.000 claims description 11
- KTSFMFGEAAANTF-UHFFFAOYSA-N [Cu].[Se].[Se].[In] Chemical compound [Cu].[Se].[Se].[In] KTSFMFGEAAANTF-UHFFFAOYSA-N 0.000 claims description 10
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical compound CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 claims description 9
- AXAZMDOAUQTMOW-UHFFFAOYSA-N dimethylzinc Chemical compound C[Zn]C AXAZMDOAUQTMOW-UHFFFAOYSA-N 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 9
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 8
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 8
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 7
- VVTSZOCINPYFDP-UHFFFAOYSA-N [O].[Ar] Chemical compound [O].[Ar] VVTSZOCINPYFDP-UHFFFAOYSA-N 0.000 claims description 7
- 125000004429 atom Chemical group 0.000 claims description 7
- 230000008020 evaporation Effects 0.000 claims description 7
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 7
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910001218 Gallium arsenide Inorganic materials 0.000 claims description 6
- 238000005229 chemical vapour deposition Methods 0.000 claims description 6
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 229910052980 cadmium sulfide Inorganic materials 0.000 abstract description 12
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 abstract description 11
- 230000003287 optical effect Effects 0.000 abstract description 6
- 239000010410 layer Substances 0.000 description 326
- 239000010408 film Substances 0.000 description 119
- 230000008021 deposition Effects 0.000 description 25
- 239000000463 material Substances 0.000 description 17
- 230000007547 defect Effects 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 4
- 238000002834 transmittance Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000005273 aeration Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- JQOATXDBTYKMEX-UHFFFAOYSA-N CC[Zn] Chemical compound CC[Zn] JQOATXDBTYKMEX-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000000231 atomic layer deposition Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000002346 layers by function Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920000307 polymer substrate Polymers 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000009423 ventilation Methods 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
- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
-
- 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
- H01L31/02—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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/036—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes
- H01L31/0392—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate
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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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention relates to a solar cell and a manufacturing method thereof, relating to the technical field of solar cells. The main technical scheme adopted is as follows: a solar cell, comprising: a bottom electrode layer, a light absorption layer, a buffer layer and a front electrode layer which are sequentially laminated and arranged on one surface of the substrate; wherein the buffer layer comprises a Zn (S, O) film layer; the front electrode layer comprises a boron-doped zinc oxide film layer. According to the solar cell provided by the embodiment of the invention, the buffer layer is the Zn (S, O) film layer, and the optical band gap of the buffer layer is wider than that of the cadmium sulfide layer, so that more solar energy, especially sunlight with the wavelength of 380-500nm can be transmitted, the amount of the sunlight entering the light absorption layer is further increased, the photoelectric conversion efficiency of the solar cell is effectively improved, and the solar cell is more suitable for practical use.
Description
Technical Field
The invention relates to the technical field of solar cells, in particular to a solar cell and a manufacturing method thereof.
Background
A solar cell is a power generation element that can convert light energy of sunlight into electric energy. Among them, the thin film solar cell has characteristics of stable performance, strong radiation resistance, and high photoelectric conversion efficiency, and thus the thin film solar cell is increasingly applied.
In the prior art, a structure of a thin film solar cell includes a light absorption layer, a buffer layer and a window layer disposed on a substrate, wherein the buffer layer employs a cadmium sulfide layer (CdS).
However, the optical band gap of the cadmium sulfide layer is 2.4ev (2.4 electron volts), i.e. the light with energy greater than 2.4 electron volts in the sunlight, i.e. the sunlight with wavelength of 380-; in addition, the interlayer combination effect of the cadmium sulfide layer used as the buffer layer and the window layer containing the boron-doped zinc oxide film layer is poor, so that the solar transmittance is reduced, and the efficiency of the solar cell is reduced.
Disclosure of Invention
In view of the above, the present invention provides a solar cell and a method for manufacturing the same, which has a buffer layer with a wider optical band gap, thereby ensuring transmittance of sunlight and improving efficiency of the solar cell.
According to the present invention, a solar cell includes:
the solar cell comprises a substrate, and a bottom electrode layer, a light absorption layer, a buffer layer and a front electrode layer which are sequentially stacked on one side surface of the substrate;
wherein the buffer layer comprises a Zn (S, O) film layer;
the front electrode layer comprises a boron-doped zinc oxide film layer.
Preferably, the solar cell further comprises a high-resistance layer, wherein the high-resistance layer is an intrinsic zinc oxide layer, and the intrinsic zinc oxide layer is arranged between the buffer layer and the boron-doped zinc oxide film layer;
the light absorption layer is one of a copper indium gallium selenide film layer, a copper indium selenide film layer and a gallium arsenide film layer.
Preferably, in the solar cell, the thickness of the buffer layer is 10nm to 70 nm; the thickness of the intrinsic zinc oxide layer is 10nm-70 nm; the thickness of the boron-doped zinc oxide film layer is 300nm-500 nm.
Preferably, in the solar cell, the molar ratio of oxygen atoms in the Zn (S, O) film layer is 5% to 20%;
the molar ratio of boron atoms in the boron-doped zinc oxide film layer is 1-2%;
wherein the molar ratio of oxygen atoms refers to the ratio of the number of moles of oxygen atoms in the Zn (S, O) film to the number of moles of the total number of atoms in the Zn (S, O) film, and the molar ratio of boron atoms refers to the ratio of the number of moles of boron atoms in the boron-doped zinc oxide film to the number of moles of the total number of atoms in the boron-doped zinc oxide film.
In addition, the present invention also provides a method for manufacturing a solar cell, including:
preparing a bottom electrode layer on a substrate;
preparing a light absorption layer on the surface of the bottom electrode layer;
preparing a buffer layer including a Zn (S, O) film layer on the light absorbing layer using a monoatomic layer deposition process;
and preparing a front electrode layer on the buffer layer.
Preferably, in the solar cell, the step of preparing the front electrode layer on the buffer layer includes:
preparing a front electrode layer comprising a boron-doped zinc oxide film layer on the buffer layer by adopting a low-pressure chemical vapor deposition process;
and preparing an intrinsic zinc oxide layer between the buffer layer and the boron-doped zinc oxide film layer by adopting a monoatomic layer deposition process.
Preferably, in the solar cell, the step of preparing the buffer layer including the Zn (S, O) film layer by using the monoatomic layer deposition process includes:
alternately introducing a first precursor source and a second precursor source into the buffer layer reaction chamber in a pulse mode under the conditions of a first preset temperature and a first preset pressure, and continuously reacting for a first preset time to prepare the buffer layer of the Zn (S, O) film layer by deposition;
the first precursor source includes: a first mixed gas of a zinc-containing precursor gas and hydrogen;
the second precursor source comprises: a mixed gas of an argon-oxygen mixed gas composed of argon and oxygen and hydrogen sulfide;
wherein the first zinc-containing precursor gas is obtained by evaporating at least one of diethyl zinc and dimethyl zinc.
Preferably, in the solar cell, the step of preparing the buffer layer including the Zn (S, O) film layer by using the monoatomic layer deposition process includes:
the gas inlet speed of the first zinc-containing precursor gas is 1500-2200sccm, and the gas inlet speed of the hydrogen gas is 450-650 sccm;
the gas inlet speed of the argon-oxygen mixed gas is 1500-2200sccm, and the gas inlet speed of the hydrogen sulfide gas is 1700-2400 sccm;
wherein the molar ratio of oxygen to argon in the argon-oxygen mixed gas is (3-6): (94-97). Preferably, in the solar cell, the first preset temperature is 150-;
the first precursor source aeration rate is: the gas inlet speed of the first zinc-containing precursor gas is 1500-2200sccm, and the gas inlet speed of the hydrogen gas is 450-650 sccm;
the second precursor source aeration rate is: the inlet flow rate of the mixed gas of argon and oxygen is 1500-2200sccm, and the inlet flow rate of hydrogen is 450-650 sccm.
Preferably, in the solar cell, the step of preparing an intrinsic zinc oxide layer between the buffer layer and the boron-doped zinc oxide film layer by using a monoatomic layer deposition process includes:
alternately introducing a third precursor source and a fourth precursor source into a reaction chamber for preparing the intrinsic zinc oxide layer in a pulse mode under the conditions of a second preset temperature and a second preset pressure, continuously reacting for a first preset time, and depositing to prepare the intrinsic zinc oxide layer;
the third precursor source comprises a mixed gas of a second zinc-containing precursor gas and hydrogen, the gas inlet speed of the second zinc-containing precursor gas is 1500-2200sccm, and the gas inlet speed of the hydrogen is 450-650 sccm;
the fourth precursor source comprises water vapor, and the air inlet speed of the water vapor is 1550-;
wherein the second zinc-containing precursor gas is obtained by evaporating at least one of diethyl zinc and dimethyl zinc.
Preferably, in the solar cell, the second preset temperature is 170-.
Preferably, in the solar cell, the step of preparing the boron-doped zinc oxide film layer on the buffer layer by using a low-pressure chemical vapor deposition process includes:
introducing a first chemical vapor deposition gas source at a third preset temperature and a third preset pressure for reacting for a third preset time to prepare the boron-doped zinc oxide film layer;
the first chemical vapor deposition gas source comprises a third zinc-containing precursor gas, a borane mixture, water vapor and hydrogen;
the third zinc-containing precursor gas comprises gas formed by evaporation of at least one of diethyl zinc and dimethyl zinc;
the borane mixture comprises borane and argon, and the molar ratio of the borane to the argon is (1-3): (97-99).
Preferably, in the solar cell, the third preset temperature is 170-.
Preferably, in the solar cell, the gas inlet rate of the third precursor gas containing zinc is 1500-; the borane mixture was fed at a rate of 450-.
Preferably, in the solar cell, the boron-doped zinc oxide film layer is prepared by a continuous 3-5 times low-pressure chemical vapor deposition process, and the reaction time of each low-pressure chemical vapor deposition is 40-60 seconds.
By the technical scheme, the solar cell and the manufacturing method thereof at least have the following advantages:
in the technical scheme of the invention, the buffer layer of the solar cell comprises a Zn (S, O) film layer, and the front electrode layer is formed by a boron-doped zinc oxide film layer. Compared with the prior art, the solar cell provided by the invention adopts the buffer layer of the Zn (S, O) film layer and the front electrode layer of the boron-doped zinc oxide film layer, and the optical band gap of the buffer layer is wider than that of the cadmium sulfide layer, so that more solar energy can be transmitted, especially sunlight with the wavelength of 380-500nm, the quantity of the sunlight entering the light absorption layer is increased, the photoelectric efficiency of the solar cell is increased, and the total photoelectric conversion efficiency of the solar cell is effectively improved. And the buffer layer of the Zn (S, O) film layer and the front electrode layer of the boron-doped zinc oxide film layer are well combined, so that the sunlight passing rate can be ensured, and the photoelectric conversion efficiency of the solar cell is improved.
Drawings
Fig. 1 is a schematic structural diagram of a solar cell provided in an embodiment of the present invention;
FIG. 2 is a graph comparing light absorption rate of a solar cell provided by an embodiment of the present invention with a prior art cell;
fig. 3 is a schematic flow chart of a method for manufacturing a solar cell according to an embodiment of the present invention.
Detailed Description
To further illustrate the technical means and effects of the present invention adopted to achieve the predetermined objects, the following detailed description of the solar cell and the manufacturing method thereof, the specific implementation manner, the method, the structure, the features and the effects thereof according to the present invention are provided with the accompanying drawings and the preferred embodiments. In the following description, different "one embodiment" or "an embodiment" refers to not necessarily the same embodiment. Furthermore, the particular features, structures, or characteristics may be combined in any suitable manner in one or more embodiments.
Unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
Example one
As shown in fig. 1, an embodiment of the present invention provides a solar cell, which includes: a substrate 1, a bottom electrode layer 2, a light absorbing layer 3, a buffer layer 4, and a front electrode layer 6; the bottom electrode layer 2 is arranged on the substrate 1; the light absorption layer 3 is arranged on the bottom electrode layer 2; the buffer layer 4 includes a Zn (S, O) film layer, and the buffer layer 4 is prepared on the light absorbing layer 3; the front electrode layer 6 comprises a boron-doped zinc oxide film layer 6, and the boron-doped zinc oxide film layer 6 is prepared on the buffer layer 4 in a laminated mode.
Specifically, the substrate 1 may be a substrate of various properties, for example, a transparent substrate, a translucent substrate, or an opaque substrate may be selected according to the light transmittance; according to material selection, a glass substrate, a metal substrate, a polymer substrate or a ceramic substrate can be selected; or the substrate 1 may be a flexible substrate or a rigid substrate, depending on the bending characteristics. Among them, the substrate 1 is preferably a flexible substrate.
The bottom electrode layer 2 is a back electrode of the solar cell, and may be a molybdenum bottom electrode layer, or may be formed of a conductive material of other metals, or may be a single layer or a plurality of layers of different materials. It should be noted that the bottom electrode layer 2 needs to have a low resistivity and good adhesion to the substrate, and will not expand or peel off due to heat.
The light absorbing layer 3 is a functional layer capable of absorbing sunlight and converting light into electricity, may use a copper indium gallium selenide film layer (CIGS), a copper indium selenide film layer (CuInSe), or a gallium arsenide film layer (GaAs), and may be prepared on the bottom electrode layer 2 by evaporation.
The buffer layer 4 may use a Zn (O, S) film layer, i.e., a film layer containing zinc, oxygen, and sulfur elements, and the thickness of the buffer layer 4 may be 10nm to 70nm, preferably 35nm, since the Zn (S, O) film layer has a wide optical band gap, more sunlight can pass through, and thus the amount of sunlight incident into the light absorbing layer can be ensured, and the buffer layer 4 may be prepared on the light absorbing layer 3 by a monoatomic layer deposition (ALD). In addition, since the light absorption layer 3 can be a copper indium gallium selenide film layer or a copper indium selenide film layer, and the lattices between the two film layers and the Zn (S, O) film layer are relatively close, it can be ensured that the pn junction (p type is the light absorption layer, and n type is the buffer layer) composed of the light absorption layer and the buffer layer has little interface mismatch and few defects.
The front electrode layer may include a boron-doped zinc oxide film layer 6. The thickness of the boron-doped zinc oxide film layer 6 can be 300-500nm, preferably 400nm, and can be prepared on the buffer layer 4 by a low-pressure chemical vapor deposition process.
In the technical scheme of the invention, the buffer layer of the solar cell comprises a Zn (S, O) film layer, and the front electrode layer is formed by a boron-doped zinc oxide film layer. Compared with the prior art, the solar cell provided by the invention adopts the buffer layer of the Zn (S, O) film layer and the front electrode layer of the boron-doped zinc oxide film layer, and the optical band gap of the buffer layer is wider than that of the cadmium sulfide layer, so that more solar energy can be transmitted, especially sunlight with the wavelength of 380-500nm, the quantity of the sunlight entering the light absorption layer is increased, the photoelectric efficiency of the solar cell is increased, and the total photoelectric conversion efficiency of the solar cell is effectively improved. And the buffer layer of the Zn (S, O) film layer and the front electrode layer of the boron-doped zinc oxide film layer are well combined, so that the sunlight passing rate can be ensured, and the photoelectric conversion efficiency of the solar cell is improved. In addition, compared with the prior art in which a cadmium sulfide film layer is used as a buffer layer, the buffer layer of the solar cell provided by the embodiment of the invention uses a Zn (S, O) film layer, which avoids the use of cadmium, i.e. avoids the pollution problem caused by the use of cadmium element.
In specific implementation, the solar cell further comprises a high-resistance layer, wherein the high-resistance layer is an intrinsic zinc oxide layer 5, and the intrinsic zinc oxide layer 5 is disposed between the buffer layer 4 and the boron-doped zinc oxide film layer 6.
Specifically, the structure of the intrinsic zinc oxide layer 5 and the boron-doped zinc oxide film layer 6 can be used as a window layer of the solar cell, and the intrinsic zinc oxide layer 5 can be used as a high-resistance layer. Wherein, the thickness of the intrinsic zinc oxide layer 5 can be 10nm-70nm, preferably 20nm, and can be prepared between the buffer layer 4 and the boron-doped zinc oxide film layer 6 by a single atomic layer deposition process (ALD).
In an implementation, in order to ensure the performance of the buffer layer 4, so that the buffer layer can have good light transmittance and a crystal lattice close to the light absorption layer 3, it is preferable that the molar ratio of oxygen atoms in the Zn (S, O) film layer of the buffer layer 4 is between 5% and 20%, that is, the ratio of the molar number of oxygen atoms in the Zn (S, O) film layer to the molar number of the total number of atoms in the Zn (S, O) film layer is between 5% and 20%. Similarly, in order to ensure that the boron-doped zinc oxide film layer 6 serves as a front electrode layer and an important structure of a window layer and has good performance, it is preferable that the molar ratio of boron atoms in the boron-doped zinc oxide film layer 6 is between 1% and 2%, i.e., the ratio of the molar number of boron atoms in the boron-doped zinc oxide film layer 6 to the molar number of total atoms in the boron-doped zinc oxide film layer 6 is between 1% and 2%.
The invention provides an example of the light absorption rate comparison of the solar cell provided by the invention and the cell in the prior art, which comprises the following steps:
as shown in fig. 2, the ordinate EQE represents the external quantum efficiency, which reflects the absorption capacity of the solar cell for sunlight of different wavelength bands, the abscissa wavelength represents the wavelength of sunlight, and the three curves in the graph represent the absorption capacity or efficiency of the solar cell with three structures for sunlight of different wavelength bands. The solar cell with the three structures is a structure formed by sequentially stacking a substrate, a bottom electrode layer, a light absorption layer, a buffer layer and a window layer, and the substrate, the bottom electrode layer and the light absorption layer are made of the same material and have the same structure. One of the solar cells with three structures is the solar cell structure provided by the embodiment of the invention, the buffer layer is a Zn (S, O) film layer, and the window layer is a combined structure of an intrinsic zinc oxide layer and a boron-doped zinc oxide film layer, namely the structure of the boron-doped zinc oxide film layer plus the Zn (S, O) film layer; the other two are the solar cell structure provided by the prior art, one buffer layer is a cadmium sulfide film layer, the window layer is a combined structure of an intrinsic zinc oxide layer and a boron-doped zinc oxide film layer, namely the boron-doped zinc oxide film layer is added with the cadmium sulfide film layer structure, the other buffer layer is a combined structure of the cadmium sulfide film layer, the window layer is the intrinsic zinc oxide layer and an aluminum-doped zinc oxide film layer, namely the aluminum-doped zinc oxide film layer is added with the cadmium sulfide film layer structure. As can be seen from the three curves in the figure, it can be seen that the solar cell structure provided by the embodiment of the present invention, i.e., the structure in which the boron-doped zinc oxide film layer and the Zn (S, O) film layer have the strongest sunlight absorption capability, i.e., the highest conversion efficiency. In conclusion, the solar cell provided by the embodiment of the invention has higher power generation capacity.
Example two
As shown in fig. 3, a method for manufacturing a solar cell according to a second embodiment of the present invention includes:
201. a bottom electrode layer is prepared on the substrate.
Specifically, the substrate of the solar cell provided by the embodiment of the present invention may be various substrates provided in the above embodiments, that is, may be selected according to specific use requirements. The bottom electrode layer can be prepared on the substrate by various means such as evaporation, deposition or sputtering, and can also be selected according to specific process, quality and use requirements, wherein the bottom electrode layer can be a molybdenum bottom electrode layer.
202. And preparing a light absorption layer on the surface of the bottom electrode layer.
Specifically, the light absorption layer can use a copper indium gallium selenide film layer (CIGS), a copper indium selenide film layer (CuInSe) or a gallium arsenide film layer (GaAs), and then is prepared on the bottom electrode layer in an evaporation mode, the thickness of the required evaporation is set according to specific use requirements, various technical parameters required by the evaporation can be set by referring to the prior art, and the details are not repeated here.
203. A buffer layer including a Zn (S, O) film layer is prepared on the light absorbing layer using a monoatomic layer deposition process.
Specifically, the monoatomic layer deposition process is a method which can plate substances on the surface of a substrate layer by layer in the form of monoatomic films, the monoatomic layer deposition is similar to the common low-pressure chemical vapor deposition, both of which are to obtain substances to be deposited through the reaction of reaction materials and form a deposition film on the substrate, but the low-pressure chemical vapor deposition is to reduce metal ions in the reaction materials by using a suitable reducing agent and deposit the metal ions on the surface of the substrate, wherein the metal ions are deposited according to the reduction amount; in a monoatomic layer deposition process, the chemical reaction of a new atomic film is directly related to the previous one, in such a way that only one layer of atoms is deposited per reaction. Compared with the method of preparing the buffer layer by low-pressure chemical vapor deposition, the method has the advantages that the film layer prepared by preparing the buffer layer by adopting the monoatomic layer deposition process is more compact, and the defects of the film layer can be effectively reduced. The buffer layer is prepared by adopting a monoatomic layer deposition process, so that the problems of looseness and more defects of a generated film layer due to the fact that the buffer layer is prepared by adopting a chemical water bath deposition method in the prior art are solved, and a smooth, compact and few-defect base layer can be provided for the preparation of a high-resistance layer and a front electrode layer in a window layer; the problems that due to the fact that the buffer layer is loose and has a large number of defects, photo-generated carriers are compounded in the buffer layer and the window layer and between the buffer layer and the window layer, the current of the solar cell is reduced, and the conversion efficiency is reduced are solved.
204. And preparing a front electrode layer on the buffer layer.
Further, the step of preparing a front electrode layer on the buffer layer includes:
preparing a front electrode layer comprising a boron-doped zinc oxide film layer on the buffer layer by adopting a low-pressure chemical vapor deposition process; and preparing an intrinsic zinc oxide layer between the buffer layer and the boron-doped zinc oxide film layer by adopting a monoatomic layer deposition process.
Specifically, in order to realize continuous production and avoid the problem that the film layer is oxidized due to the switching between vacuum and non-vacuum environments when different functional film layers are produced, the Zn (S, O) film layer serving as the buffer layer is prepared by a monoatomic layer deposition process which is a vacuum environment preparation process. It is preferable to prepare the buffer layer and the front electrode layer in a continuous vacuum environment, i.e., different layers can be produced by one continuous vacuum environment, only switching the deposition process. In addition, in order to ensure that the boron-doped zinc oxide film layer is also produced in a vacuum environment, a low-pressure chemical vapor deposition process can be adopted to prepare the boron-doped zinc oxide film layer. And then, through the steps 203 and 204, the buffer layer and the front electrode layer are both prepared in a vacuum environment, so that the problem of oxidation caused by switching different film-making processes between a vacuum environment and a non-vacuum environment is solved. Thereby ensuring the interface performance between two adjacent film layers.
After the compact buffer layer with few defects is obtained in step 203, the intrinsic zinc oxide layer can be prepared on the buffer layer by adopting a monoatomic layer deposition process in a continuous vacuum environment, so that the compact intrinsic zinc oxide layer with few defects can be obtained, a defect region formed between the intrinsic zinc oxide layer and the buffer layer can be reduced, photogenerated carriers are effectively prevented from being compounded between the intrinsic zinc oxide layer and the buffer layer, and the light conversion efficiency is ensured.
In a specific implementation, the step of preparing the buffer layer including the Zn (S, O) film layer using the monoatomic layer deposition process includes:
the first precursor source and the second precursor source are alternately deposited in a pulse mode to prepare the buffer layer, for example, the pulse time of the first precursor source is set to be 300-600ms and the cleaning time is set to be 5-20s, the pulse time of the second precursor source is set to be 200-400ms and the cleaning time is set to be 15-30 s; the first precursor source includes: a first mixed gas of a zinc-containing precursor gas and hydrogen; the second precursor source comprises: a mixture of argon, oxygen and hydrogen sulfide; wherein the first zinc-containing precursor gas is obtained by evaporating at least one of diethyl zinc and dimethyl zinc.
Specifically, when the deposition material is used for preparing the Zn (S, O) film layer, the preparation is carried out at a first preset temperature, a first preset pressure and a first preset reaction time: for example, the first predetermined temperature may be 150-; when a Zn (S, O) film layer deposition reaction is carried out and deposition materials of the Zn (S, O) film layer are mixed into a reaction chamber of the monoatomic layer deposition process, the ventilation speed of the first precursor source is as follows: the first zinc-containing precursor gas has an inlet flow rate of 1500-2200sccm (standard milliliter/minute), and the hydrogen gas has an inlet flow rate of 450-650 sccm; the aeration rate of the second precursor source was: the gas inlet speed of the mixed gas of argon and oxygen is 1500-2200 sccm; the gas inlet speed of the hydrogen sulfide gas is 1700-2400 sccm; wherein the molar ratio of oxygen to argon in the mixed gas of argon and oxygen is (3-6): (94-97), preferably with a molar ratio of oxygen to argon of 5: 95, and a mixture thereof. In addition, in order to obtain a high-quality film, it is necessary to ensure a high purity of each raw material in the above-mentioned mixed material.
Further, when the deposition material is used for preparing the Zn (S, O) film layer, the preferable deposition reaction technical conditions are as follows: the first preset temperature is 155 ℃, the first preset pressure is 0.3-0.7mBar, and the first preset reaction time is 40-60 seconds; when a Zn (S, O) film layer deposition reaction is carried out and deposition materials of the Zn (S, O) film layer are mixed into a reaction chamber of the monoatomic layer deposition process, the gas inlet speed of the first zinc-containing precursor gas is 1800sccm, the gas inlet speed of the argon-oxygen mixed gas is 1800sccm, the gas inlet speed of the hydrogen sulfide gas is 1700sccm and the gas inlet speed of the hydrogen gas is 500 sccm.
In a specific implementation, the step of preparing the intrinsic zinc oxide layer between the buffer layer and the boron-doped zinc oxide film layer by using a monoatomic layer deposition process comprises: the third precursor source and the fourth precursor source are alternately deposited in a pulse mode to prepare the intrinsic zinc oxide layer, for example, the pulse time of the third precursor source is set to 600-900ms and the cleaning time is set to 10-20s, and the pulse time of the fourth precursor source is set to 400-700ms and the cleaning time is set to 30-40 s; the third precursor source comprises a mixed gas of a second zinc-containing precursor gas and hydrogen, wherein the gas inlet speed of the second zinc-containing precursor gas is 1500-2200sccm, and the gas inlet speed of the hydrogen is 450-650 sccm; the fourth precursor source comprises water vapor, and the air inlet speed of the water vapor is 1550-; wherein the second zinc-containing precursor gas is obtained by evaporating at least one of diethyl zinc and dimethyl zinc.
Specifically, when the intrinsic zinc oxide layer is prepared by using the deposition material, the intrinsic zinc oxide layer is prepared at a second preset temperature, a second preset pressure and a second preset reaction time: for example, the second predetermined temperature may be 170-.
Further, when the above deposition materials are used for preparing the zinc oxide layer, the preferable deposition reaction technical conditions are as follows: the second preset temperature is 180 ℃; the second preset pressure is 0.3-0.7mBar and the second preset reaction time is 40-60 seconds. When the deposition material for characterizing the zinc oxide layer is mixed into the reaction chamber of the monoatomic layer deposition process, the gas inlet speed of the second zinc-containing gas is 1800sccm, the gas inlet speed of the water vapor is 1850sccm, and the gas inlet speed of the hydrogen gas is 550 sccm.
In a specific implementation, the step of preparing the boron-doped zinc oxide film layer on the buffer layer by using a low-pressure chemical vapor deposition process comprises:
introducing a first chemical vapor deposition gas source into the low-pressure chemical vapor deposition process chamber at a third preset temperature and a third preset pressure for a third preset time to prepare the boron-doped zinc oxide film layer; the first chemical vapor deposition gas source comprises a third zinc-containing precursor gas, a borane mixture, water vapor and hydrogen; the third zinc-containing precursor gas comprises gas formed by evaporating at least one of diethyl zinc, dimethyl zinc and ethyl zinc.
Specifically, when the boron-doped zinc oxide film is prepared by using the deposition material, the third preset temperature may be 170-. When the boron-doped zinc oxide film layer deposition reaction is carried out and the deposition material of the boron-doped zinc oxide film layer is mixed into the low-pressure chemical vapor deposition process reaction chamber, the air inlet speed of the third zinc-containing precursor gas is 1500-650 sccm, the air inlet speed of the water vapor is 1550-2250sccm, and the air inlet speed of the hydrogen is 450-650 sccm; the borane mixture is prepared by mixing borane and argon in a molar ratio of (1-3): (97-99) and the inlet gas rate is 450-650 sccm.
Further, when the deposition material is used for preparing the boron-doped zinc oxide film layer, the preferable deposition reaction technical conditions are as follows: the third preset temperature is 180 ℃; the third preset temperature is 0.3-0.7mBar, and the third preset temperature is 120-300 seconds. When the boron-doped zinc oxide film layer deposition reaction is carried out and the deposition material of the boron-doped zinc oxide film layer is mixed into the low-pressure chemical vapor deposition process reaction chamber, the gas inlet speed of the third zinc-containing precursor gas is 1800sccm, the gas inlet speed of the water vapor is 1850sccm, and the gas inlet speed of the hydrogen gas is 500 sccm; the borane mixture had a borane to argon molar ratio of 2:98 and a feed rate of 550 sccm.
In the specific implementation, because the boron-doped zinc oxide film layer has a large thickness, the time consumed in the deposition reaction in the continuous vacuum environment is several times that of the buffer layer and the intrinsic zinc oxide layer, and the boron-doped zinc oxide film layer can be prepared by multiple times in order to realize the production continuity, and in addition, the buffer layer is similar to the thickness of the intrinsic zinc oxide layer, so the preparation times of the boron-doped zinc oxide film layer can be set according to the multiple relation of the thicknesses between the boron-doped zinc oxide film layer and the buffer layer, for example, the boron-doped zinc oxide film layer can be prepared by a continuous 3-5 times low-pressure chemical vapor deposition process, and the deposition reaction time is 40-60 seconds each time. And the preparation time of the boron-doped zinc oxide film layer can be the same as that of the intrinsic zinc oxide layer and the buffer layer each time through the preparation in different times, and the buffer layer, the intrinsic zinc oxide layer and the boron-doped zinc oxide film layer can be prepared continuously through a monoatomic layer deposition process and a low-pressure chemical vapor deposition process in a continuous vacuum environment.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and any simple modification, equivalent change and modification made to the above embodiment according to the technical spirit of the present invention are still within the scope of the technical solution of the present invention.
Claims (15)
1. The solar cell is characterized by comprising a substrate, and a bottom electrode layer, a light absorption layer, a buffer layer and a front electrode layer which are sequentially stacked on one surface of the substrate;
wherein the buffer layer comprises a Zn (S, O) film layer;
the front electrode layer comprises a boron-doped zinc oxide film layer.
2. The solar cell of claim 1, further comprising a high resistance layer, wherein the high resistance layer is an intrinsic zinc oxide layer disposed between the buffer layer and the boron-doped zinc oxide film layer;
the light absorption layer is one of a copper indium gallium selenide film layer, a copper indium selenide film layer and a gallium arsenide film layer.
3. The solar cell according to claim 2,
the thickness of the buffer layer is 10nm-70 nm; the thickness of the intrinsic zinc oxide layer is 10nm-70 nm; the thickness of the boron-doped zinc oxide film layer is 300nm-500 nm.
4. The solar cell according to claim 1,
the molar ratio of oxygen atoms in the Zn (S, O) film layer is 5-20%;
the molar ratio of boron atoms in the boron-doped zinc oxide film layer is 1-2%;
wherein the molar ratio of the oxygen atoms refers to the ratio of the number of moles of oxygen atoms in the Zn (S, O) film to the number of moles of the total amount of all atoms in the Zn (S, O) film, and the molar ratio of the boron atoms refers to the ratio of the number of moles of boron atoms in the boron-doped zinc oxide film to the number of moles of the total amount of all atoms in the boron-doped zinc oxide film.
5. A method of manufacturing a solar cell, comprising:
preparing a bottom electrode layer on a substrate;
preparing a light absorption layer on the surface of the bottom electrode layer;
preparing a buffer layer including a Zn (S, O) film layer on the light absorbing layer using a monoatomic layer deposition process;
and preparing a front electrode layer on the buffer layer.
6. The method for manufacturing a solar cell according to claim 5,
a step of preparing a front electrode layer on the buffer layer, including:
preparing a front electrode layer comprising a boron-doped zinc oxide film layer on the buffer layer by adopting a low-pressure chemical vapor deposition process;
and preparing an intrinsic zinc oxide layer between the buffer layer and the boron-doped zinc oxide film layer by adopting a monoatomic layer deposition process.
7. The method for manufacturing a solar cell according to claim 5,
the step of preparing the buffer layer including the Zn (S, O) film layer using the monoatomic layer deposition process includes:
alternately introducing a first precursor source and a second precursor source into the buffer layer reaction chamber in a pulse mode under the conditions of a first preset temperature and a first preset pressure, continuously reacting for a first preset time, and depositing and preparing the buffer layer of the Zn (S, O) film layer;
the first precursor source includes: a first mixed gas of a zinc-containing precursor gas and hydrogen;
the second precursor source comprises: a mixed gas of an argon-oxygen mixed gas composed of argon and oxygen and hydrogen sulfide;
wherein the first zinc-containing precursor gas is obtained by evaporating at least one of diethyl zinc and dimethyl zinc.
8. The method for manufacturing a solar cell according to claim 7,
the step of preparing the buffer layer including the Zn (S, O) film layer using the monoatomic layer deposition process includes:
the gas inlet speed of the first zinc-containing precursor gas is 1500-2200sccm, and the gas inlet speed of the hydrogen gas is 450-650 sccm;
the gas inlet speed of the argon-oxygen mixed gas is 1500-2200sccm, and the gas inlet speed of the hydrogen sulfide gas is 1700-2400 sccm;
wherein the molar ratio of oxygen to argon in the argon-oxygen mixed gas is (3-6): (94-97).
9. The method for manufacturing a solar cell according to claim 8,
the first preset temperature is 150-170 ℃, the first preset pressure is 0.3-0.7mBar, and the first preset reaction time is 40-60 seconds.
10. The method for manufacturing a solar cell according to claim 6,
the step of preparing the intrinsic zinc oxide layer between the buffer layer and the boron-doped zinc oxide film layer by adopting a monoatomic layer deposition process comprises the following steps:
alternately introducing a third precursor source and a fourth precursor source into a reaction chamber for preparing the intrinsic zinc oxide layer in a pulse mode under the conditions of a second preset temperature and a second preset pressure, continuously reacting for a first preset time, and depositing to prepare the intrinsic zinc oxide layer;
the third precursor source comprises a mixed gas of a second zinc-containing precursor gas and hydrogen, the gas inlet speed of the second zinc-containing precursor gas is 1500-2200sccm, and the gas inlet speed of the hydrogen is 450-650 sccm;
the fourth precursor source comprises water vapor, and the air inlet speed of the water vapor is 1550-;
wherein the second zinc-containing precursor gas is obtained by evaporating at least one of diethyl zinc and dimethyl zinc.
11. The method for manufacturing a solar cell according to claim 10,
the second preset temperature is 170-195 ℃, the second preset pressure is 0.3-0.7mBar, and the second reaction time is 40-60 seconds.
12. The method for manufacturing a solar cell according to claim 6,
the step of preparing the boron-doped zinc oxide film layer on the buffer layer by adopting a low-pressure chemical vapor deposition process comprises the following steps of:
introducing a first chemical vapor deposition gas source at a third preset temperature and a third preset pressure for reacting for a third preset time to prepare the boron-doped zinc oxide film layer;
the first chemical vapor deposition gas source comprises a third zinc-containing precursor gas, a borane mixture, water vapor and hydrogen;
the third zinc-containing precursor gas comprises gas formed by evaporation of at least one of diethyl zinc and dimethyl zinc;
the borane mixture comprises borane and argon, and the molar ratio of the borane to the argon is (1-3): (97-99).
13. The method for manufacturing a solar cell according to claim 11,
the third preset temperature is 170-.
14. The method for manufacturing a solar cell according to claim 11,
the third zinc-containing precursor gas has an inlet flow rate of 1500-2200sccm,
the gas inlet speed of the water vapor is 1550-;
the borane mixture was fed at a rate of 450-.
15. The method for manufacturing a solar cell according to claim 13,
the boron-doped zinc oxide film layer is prepared by a continuous 3-5 times low-pressure chemical vapor deposition process, and the reaction time of each low-pressure chemical vapor deposition is 40-60 seconds.
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