CN111341859B - Cadmium telluride thin film solar cell and preparation method thereof - Google Patents
Cadmium telluride thin film solar cell and preparation method thereof Download PDFInfo
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- 239000010409 thin film Substances 0.000 title claims abstract description 54
- MARUHZGHZWCEQU-UHFFFAOYSA-N 5-phenyl-2h-tetrazole Chemical compound C1=CC=CC=C1C1=NNN=N1 MARUHZGHZWCEQU-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims description 14
- 239000000758 substrate Substances 0.000 claims abstract description 26
- 125000004430 oxygen atom Chemical group O* 0.000 claims abstract description 24
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- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 16
- 125000004429 atom Chemical group 0.000 claims abstract description 9
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 claims abstract 10
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- 239000007789 gas Substances 0.000 claims description 13
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- QWUZMTJBRUASOW-UHFFFAOYSA-N cadmium tellanylidenezinc Chemical compound [Zn].[Cd].[Te] QWUZMTJBRUASOW-UHFFFAOYSA-N 0.000 claims description 5
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- 238000000859 sublimation Methods 0.000 claims description 4
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- SKJCKYVIQGBWTN-UHFFFAOYSA-N (4-hydroxyphenyl) methanesulfonate Chemical compound CS(=O)(=O)OC1=CC=C(O)C=C1 SKJCKYVIQGBWTN-UHFFFAOYSA-N 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
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- 229910052782 aluminium Inorganic materials 0.000 claims description 3
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- 229910052804 chromium Inorganic materials 0.000 claims description 3
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- 125000004434 sulfur atom Chemical group 0.000 claims description 3
- 229910052714 tellurium Inorganic materials 0.000 claims description 3
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims description 3
- WYUZTTNXJUJWQQ-UHFFFAOYSA-N tin telluride Chemical compound [Te]=[Sn] WYUZTTNXJUJWQQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052793 cadmium Inorganic materials 0.000 claims 3
- AQCDIIAORKRFCD-UHFFFAOYSA-N cadmium selenide Chemical compound [Cd]=[Se] AQCDIIAORKRFCD-UHFFFAOYSA-N 0.000 description 52
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 29
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 29
- 238000000034 method Methods 0.000 description 24
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Images
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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
- H01L31/0296—Inorganic materials including, apart from doping material or other impurities, only AIIBVI compounds, e.g. CdS, ZnS, HgCdTe
- H01L31/02963—Inorganic materials including, apart from doping material or other impurities, only AIIBVI compounds, e.g. CdS, ZnS, HgCdTe characterised by the doping material
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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
- H01L31/073—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers the potential barriers being only of the PN heterojunction type comprising only AIIBVI compound semiconductors, e.g. CdS/CdTe solar cells
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/1828—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof the active layers comprising only AIIBVI compounds, e.g. CdS, ZnS, CdTe
- H01L31/1836—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof the active layers comprising only AIIBVI compounds, e.g. CdS, ZnS, CdTe comprising a growth substrate not being an AIIBVI compound
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Abstract
The invention provides a cadmium telluride thin-film solar cell, which comprises a substrate layer, a transparent conductive oxide thin-film layer, a high-resistance buffer layer, a cell window layer, a cell layer, a back contact layer and a back electrode which are sequentially arranged; the cell window layer comprises an oxygen-doped CdSe layer; the content of oxygen atoms in the oxygen-doped CdSe layer is 0.1-75% of the total content of the oxygen atoms and the Se atoms. Compared with the prior art, the window layer of the cadmium telluride thin-film solar cell provided by the invention comprises the oxygen-doped CdSe layer, so that the uniformity of the window layer is improved, and the cell efficiency of the solar cell is improved by doping oxygen.
Description
Technical Field
The invention belongs to the technical field of solar cells, and particularly relates to a cadmium telluride thin-film solar cell and a preparation method thereof.
Background
The cadmium telluride thin film (CdTe) solar cell has the advantages of high power generation efficiency, low manufacturing cost, wide application and small influence on the environment, and is one of solar cell technologies with good future development prospects. In a traditional cadmium telluride thin film solar cell process, cadmium sulfide (CdS) is adopted as a window layer material. However, the optical band gap of CdS is near 2.4eV, so that the CdS can obviously absorb short wave bands (300-600 nm) of sunlight, short wave absorption loss is caused, the improvement of short-circuit current (Jsc) of the solar cell is limited, and the power generation efficiency of the cell is further influenced.
The Yan Yanfa research team of the university of Toledo in the united states firstly adopts a cadmium selenide (CdSe) film to replace CdS as a window layer material of the battery, finds that the CdSe can interdiffuse with the CdTe to form a CdSeTe alloy, improves the short-wave response and the long-wave response of the battery, and greatly improves the short-circuit current (Jsc) of the battery. However, experiments show that the open-circuit voltage (Voc) and the Filling Factor (FF) of the battery adopting the CdSe window layer are obviously reduced, and the overall power generation efficiency (Eff) of the battery is not improved. Further research results on CdSe window layer cells indicate that there are inhomogeneities in the CdSe diffusion and distribution, and that the CdSe window layer has an effect on the quality of the CdTe thin film deposited thereon. The problem is not well solved at present, so that the CdSe window layer cannot be well applied to the industrial process of the cadmium telluride thin film battery.
Similar to CdSe window layer materials, CdS window layer materials also suffer from diffusion and distribution non-uniformity problems from the outset. The Wu-Chong team of Longyan energy technology (Hangzhou) GmbH adopts the oxygen-doped CdS (CdS: O) process to improve the non-uniform diffusion and consumption of CdS. The university of Sichuan consults the CdS: O process, and preliminarily tries the preparation and application of a CdSe: O window layer material by adopting a pulsed laser deposition method (PLD); the experimental result shows that the CdSe O can relatively improve the Voc, FF and Jsc of the batteries, but the overall battery efficiency is lower (less than 9 percent, and the performance is abnormal compared with the current normal battery efficiency of about 13 to 15 percent); the PLD deposition method is not suitable for preparing high-efficiency cadmium telluride thin-film solar cells, and the PLD equipment is expensive, the size of experimental samples is small, and the PLD deposition method is not suitable for large-scale industrial production.
Disclosure of Invention
In view of the above, the present invention provides a cadmium telluride thin film solar cell and a manufacturing method thereof, wherein the cadmium telluride thin film solar cell has high efficiency and a simple manufacturing method.
The invention provides a cadmium telluride thin-film solar cell, which comprises a substrate layer, a transparent conductive oxide thin-film layer, a high-resistance buffer layer, a cell window layer, a cell layer, a back contact layer and a back electrode which are sequentially arranged;
the cell window layer comprises an oxygen-doped CdSe layer;
the content of oxygen atoms in the oxygen-doped CdSe layer is 0.1-75% of the total content of the oxygen atoms and the Se atoms.
Preferably, the thickness of the oxygen-doped CdSe layer is 10-400 nm.
Preferably, the cell window layer further comprises a CdS layer and/or an oxygen-doped CdS layer; the content of oxygen atoms in the oxygen-doped CdS layer is 0.1-75% of the total content of the oxygen atoms and the S atoms.
Preferably, the oxygen-doped CdSe layer is in contact with the cell layer.
Preferably, the thickness of the CdS layer and/or the oxygen-doped CdS layer is 1-100 nm; the thickness of the oxygen-doped CdSe layer is 10-400 nm.
Preferably, the substrate layer is selected from a soda-lime glass layer or a borosilicate glass layer;
the transparent conductive oxide film layer is selected from one or more of an F-doped tin oxide layer, an In-doped zinc oxide layer, an Al-doped zinc oxide layer, a Ga-doped zinc oxide layer and a Cd-doped zinc oxide layer;
the high-resistance buffer layer is selected from one or more of a tin oxide layer, a zinc oxide layer, a Zn-doped tin oxide layer, an Mg-doped zinc oxide layer, an F-doped tin oxide layer and a Cd-doped tin oxide layer;
the cell layer is selected from one or more of a cadmium telluride layer, a cadmium selenium telluride layer, a cadmium zinc telluride layer and a cadmium magnesium telluride layer;
the back contact layer is selected from one or more of a copper-containing carbon paste layer, a copper-containing zinc telluride layer, a cadmium zinc telluride layer, a tin telluride layer and a tellurium layer;
the back electrode is selected from one or more of aluminum, silver, gold, copper, nickel, chromium, molybdenum, titanium, oxides of the above metals and nitrides of the above metals.
The invention also provides a preparation method of the cadmium telluride thin film solar cell, which comprises the following steps:
preparing a transparent conductive oxide thin film layer and a high-resistance buffer layer on a substrate in sequence;
then depositing a battery window layer on the high-resistance buffer layer through reactive magnetron sputtering; the cell window layer comprises an oxygen-doped CdSe layer; the content of oxygen atoms in the oxygen-doped CdSe layer is 0.1-75% of the total content of the oxygen atoms and the Se atoms;
and preparing a cell layer on the cell window layer, annealing the deposited cell layer to improve the performance and passivation defects of the cell layer, and then preparing a back contact layer and a deposited back electrode to obtain the cadmium telluride thin-film solar cell.
Preferably, the sputtering power of the reactive magnetron sputteringIs 40-600W; the sputtering power density is 0.1-5W/cm2(ii) a The air pressure is 1 to 40 mTorr.
Preferably, the sputtering gas is a mixed gas of oxygen and argon when the oxygen-doped CdSe layer is deposited by reactive magnetron sputtering; the flow ratio of the oxygen/oxygen and argon is 0.1-50%.
Preferably, the cell layer is obtained by close space sublimation deposition; the temperature of the substrate compounded with the transparent conductive oxide film layer, the high-resistance buffer layer and the cell window layer during the close-space sublimation deposition is 500-620 ℃, and the source temperature is 580-680 ℃; the air pressure is 0.1 to 20 Torr;
annealing treatment of the battery layer to CdCl2Heat treatment, wherein the heat treatment temperature is 360-500 ℃; the time of the annealing treatment is 1-60 min.
The invention provides a cadmium telluride thin-film solar cell, which comprises a substrate layer, a transparent conductive oxide thin-film layer, a high-resistance buffer layer, a cell window layer, a cell layer, a back contact layer and a back electrode which are sequentially arranged; the cell window layer comprises an oxygen-doped CdSe layer; the content of oxygen atoms in the oxygen-doped CdSe layer is 0.1-75% of the total content of the oxygen atoms and the Se atoms. Compared with the prior art, the window layer of the cadmium telluride thin-film solar cell provided by the invention comprises the oxygen-doped CdSe layer, so that the uniformity of the window layer is improved, and the cell efficiency of the solar cell is improved through the oxygen-doped content.
Experiments show that the cell efficiency of the cadmium telluride thin film solar cell prepared by the invention can exceed 16 percent maximally.
Drawings
FIG. 1 is a schematic structural view of a cadmium telluride thin film solar cell provided by the present invention;
FIG. 2 is a schematic view of a cadmium telluride thin film solar cell manufacturing process provided by the present invention;
FIG. 3 is a graph comparing the performance of solar cells prepared in examples 1 and 2 of the present invention and comparative example 1;
FIG. 4 is a graph of the I-V performance of a solar cell prepared in example 2 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings of the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a cadmium telluride thin-film solar cell, which comprises a substrate layer, a transparent conductive oxide thin-film layer, a high-resistance buffer layer, a cell window layer, a cell layer, a back contact layer and a back electrode which are sequentially arranged; the cell window layer comprises an oxygen-doped CdSe layer; the content of oxygen atoms in the oxygen-doped CdSe layer is 0.1-75% of the total content of the oxygen atoms and the Se atoms.
Referring to fig. 1, fig. 1 is a schematic structural diagram of a cadmium telluride thin film solar cell provided by the present invention, wherein 1 is a substrate layer, 2 is a transparent conductive oxide thin film layer, 3 is a high resistance buffer layer, 4 is a cell window layer, 5 is a cell layer, 6 is a back contact layer, and 7 is a back electrode.
The cadmium telluride thin film solar cell provided by the invention comprises a substrate layer; the substrate layer is preferably a glass substrate layer, and more preferably a soda-lime glass layer or a borosilicate glass layer; the thickness of the substrate layer is preferably 1-4 mm, more preferably 2-4 mm, still more preferably 3-3.5 mm, and most preferably 3.2 mm.
A transparent conductive oxide film layer is arranged on the substrate layer; the transparent oxide thin film layer is preferably one or more of an F-doped tin oxide layer, an In-doped zinc oxide layer, an Al-doped zinc oxide layer, a Ga-doped zinc oxide layer and a Cd-doped zinc oxide layer; the thickness of the transparent conductive oxide thin film layer is preferably 300-900 nm, more preferably 300-600 nm, and further preferably 400-500 nm; the light transmittance of the transparent conductive oxide thin film layer is more than 78%, and more preferably, the light transmittance is more than or equal to 80%; the square resistance of the transparent conductive oxide thin film layer is preferably 3-20 omega/□; the carrier concentration of the transparent conductive oxide thin film layer is preferably 1021cm-3An order of magnitude.
A high-resistance buffer layer is arranged on the transparent conductive oxide thin film layer; the thickness of the high-resistance buffer layer is preferably 5-100 nm, more preferably 20-80 nm, and further preferably 40-60 nm; the high-resistance buffer layer is preferably one or more of a tin oxide layer, a zinc oxide layer, a Zn-doped tin oxide layer, an Mg-doped zinc oxide layer, an F-doped tin oxide layer and a Cd-doped tin oxide layer; the resistivity of the high-resistance buffer layer is preferably 10-2～105Omega cm. A buffer layer between the transparent conductive oxide thin Film (FTO) and the window layer has certain resistivity, so that the direct contact between the cell layer and the FTO can be prevented, and the interface recombination is reduced.
A battery window layer is arranged on the high-resistance buffer layer; the thickness of the battery window layer is preferably 10-400 nm; the cell window layer comprises an oxygen-doped CdSe layer; the content of oxygen atoms in the oxygen-doped CdSe layer is 0.1-75% of the total content of oxygen atoms and Se atoms, preferably 1-30%, more preferably 1-25%, still more preferably 5-25%, still more preferably 10-25%, and most preferably 15-20%; the cell window layer can be only an oxygen-doped CdSe layer or can be a composite layer comprising an oxygen-doped CdSe layer and other layers; when the cell window layer only comprises the oxygen-doped CdSe layer, the thickness of the cell window layer is preferably 20-400 nm, more preferably 50-300 nm, still more preferably 50-200 nm, and most preferably 100-200 nm; when the cell window layer is a composite layer, the cell window layer preferably further comprises a CdS layer and/or an oxygen-doped CdS layer; the number of the layers of the composite layer is preferably 2-4, and more preferably 2-3; the content of oxygen atoms in the oxygen-doped CdS layer is preferably 0.1-75% of the total content of oxygen atoms and S atoms, more preferably 1-30%, still more preferably 5-25%, still more preferably 10-25%, still more preferably 15-25%, and most preferably 20-25%; when the cell window layer is a composite layer, the oxygen-doped CdSe layer is preferably in contact with the cell layer; the thickness of the oxygen-doped CdSe layer is preferably 10-300 nm, more preferably 20-200 nm, still more preferably 40-200 nm, still more preferably 60-200 nm, still more preferably 80-200 nm, and most preferably 100-190 nm; the thickness of the CdS layer and/or the oxygen-doped CdS layer is preferably 1-100 nm, more preferably 5-60 nm, and even more preferably 10-30 nm.
A battery layer is arranged on the battery window layer; the thickness of the battery layer is preferably 3-6 μm; the cell layer is preferably one or more of a cadmium telluride layer, a cadmium selenium telluride layer, a cadmium zinc telluride layer and a cadmium magnesium telluride layer.
A back contact layer is arranged on the battery layer; the thickness of the back contact layer is preferably 5-6 μm or 20-100 nm; the back contact layer is preferably one or more of a copper-containing carbon paste layer, a copper-containing zinc telluride layer, a cadmium zinc telluride layer, a tin telluride layer and a tellurium layer.
A back electrode is arranged on the back contact layer; the thickness of the back electrode is preferably 200-500 nm; the back electrode is preferably one or more of aluminum, silver, gold, copper, nickel, chromium, molybdenum, titanium, oxides of the above metals, and nitrides of the above metals.
The window layer of the cadmium telluride thin-film solar cell provided by the invention comprises the oxygen-doped CdSe layer, so that the uniformity of the window layer is improved, and the cell efficiency of the solar cell is improved through the oxygen-doped content.
The invention also provides a preparation method of the cadmium telluride thin film solar cell, which comprises the following steps: preparing a transparent conductive oxide thin film layer and a buffer layer or a high-resistance layer on a substrate in sequence; then depositing a battery window layer on the buffer layer or the high-resistance layer through reactive magnetron sputtering; the cell window layer comprises an oxygen-doped CdSe layer; the content of oxygen atoms in the oxygen-doped CdSe layer is 0.1-75% of the total content of the oxygen atoms and the Se atoms; and preparing a cell layer on the cell window layer, annealing the deposited cell layer to improve the performance and passivation defects of the cell layer, and then preparing a back contact layer and a deposited back electrode to obtain the cadmium telluride thin-film solar cell.
The present invention is not particularly limited in terms of the source of all raw materials, and may be commercially available.
Referring to fig. 2, fig. 2 is a schematic view of a manufacturing process of a cadmium telluride thin film solar cell provided by the invention.
The substrate, the transparent conductive oxide thin film layer, the high-resistance buffer layer, the cell window layer, the cell layer, the back contact layer and the back electrode are the same as those described above, and are not described again.
Preparing a transparent conductive oxide thin film layer and a high-resistance buffer layer on a substrate in sequence; the transparent conductive oxide film and the high-resistance buffer layer can be prepared by adopting a chemical vapor deposition method and can also be prepared by adopting a sputtering process.
Then depositing a battery window layer on the high-resistance buffer layer through reactive magnetron sputtering, preferably cleaning the substrate compounded with the transparent conductive oxide thin film layer and the high-resistance buffer layer, and then depositing the battery window layer on the high-resistance buffer layer through reactive magnetron sputtering; the power supply during the reactive magnetron sputtering is preferably a radio frequency or pulse power supply; the sputtering power of the reactive magnetron sputtering is preferably 40-600W, more preferably 50-500W, and further preferably 100-300W; the sputtering power density is preferably 0.1-5W/cm2More preferably 0.5 to 2W/cm2(ii) a The air pressure during reactive magnetron sputtering is preferably 1-40 mTorr, more preferably 5-35 mTorr, still more preferably 10-30 mTorr, still more preferably 10-25 mTorr, and most preferably 15-25 mTorr; the sputtering gas is preferably a mixed gas of oxygen and argon when the oxygen-doped CdSe layer is deposited by reactive magnetron sputtering; the flow ratio of oxygen/oxygen + argon is preferably 0.1% to 100%, more preferably 0.1% to 50%, still more preferably 0.5% to 20%, still more preferably 1% to 10%, most preferably 1.5% to 10%; the cell window layer in the present invention preferably further comprises a CdS layer and/or an oxygen-doped CdS layer; the CdS layer and/or the oxygen-doped CdS layer are/is deposited by preferably adopting reactive magnetron sputtering; the parameters of the reactive magnetron sputtering are the same as above; but when it deposits a CdS layer, the sputtering gas preferably contains only argon.
Preparing a battery layer on the battery window layer; the preparation method of the battery layer can adopt a sputtering process, near space sublimation, a chemical water bath method, a gas phase transmission process or a thermal evaporation process, and the battery layer is preferably obtained by near space sublimation deposition; the temperature of the substrate compounded with the transparent conductive oxide film layer, the high-resistance buffer layer and the cell window layer during the close space sublimation deposition is preferably 500-620 ℃, more preferably 520-600 ℃, further preferably 540-580 ℃, and most preferably 560 ℃; the source temperature is preferably 580 to 680 ℃, more preferably 600 to 680 ℃, still more preferably 620 to 680 ℃, still more preferably 640 to 680 ℃, most preferably 660 ℃; the pressure during the close-space sublimation deposition is preferably 0.1 to 20Torr, more preferably 1 to 20Torr, still more preferably 5to 15Torr, and most preferably 8to 10 Torr; the gas in the near-space sublimation deposition is preferably oxygen and/or nitrogen, and more preferably a mixed gas of oxygen and nitrogen; the flow ratio of oxygen/(oxygen + nitrogen) is preferably 0.1% to 99%, more preferably 1% to 50%, still more preferably 1% to 20%, still more preferably 1% to 10%, still more preferably 1% to 5%, most preferably 1% to 2%.
After the battery layer is deposited, cadmium chloride heat treatment is preferably carried out; the cadmium chloride heat treatment mainly has the effects of promoting the recrystallization and growth of crystal grains of the cell layer (cadmium telluride), increasing the size of the crystal grains and reducing crystal defects, and meanwhile, chlorine doping can improve the hole carrier concentration of the cell layer. The cadmium chloride heat treatment preferably adopts a wet process, namely spraying a cadmium chloride solution on the surface of the battery layer, and then carrying out heat treatment; the concentration of the cadmium chloride solution is preferably 0.1-20%, more preferably 1-20%, still more preferably 2-15%, still more preferably 3-12%, and most preferably 5-10%; the spraying amount is preferably 1-25 ml, more preferably 3-20 ml, further preferably 5-15 ml, further preferably 5-10 ml, and most preferably 5 ml; the temperature of the heat treatment is preferably 360-450 ℃, more preferably 380-440 ℃, further preferably 400-440 ℃, and most preferably 410-430 ℃; the time of the heat treatment is preferably 1-60 min, more preferably 5-50 min, still more preferably 5-40 min, still more preferably 10-30 min, and most preferably 10-20 min.
After the cadmium chloride is subjected to heat treatment, preferably, a dilute hydrochloric acid solution is adopted to corrode an oxide layer, and then, deionized water is used for cleaning and nitrogen is used for blow-drying; the concentration of the dilute hydrochloric acid solution is preferably 0.5-1%.
Then preparing a back contact layer; the back contact layer can be prepared by sputtering, close space sublimation, a gas phase transmission process, a thermal evaporation process or printing, different preparation methods can be selected according to different materials of the back contact layer, and the back contact layer is preferably a copper-containing carbon paste layer which is prepared by printing; the molar concentration of copper in the copper-containing carbon slurry layer is preferably 0.1% to 1%, more preferably 0.1% to 0.8%, and still more preferably 0.1% to 0.5%.
After the back contact layer is deposited, annealing treatment is preferably carried out; the temperature of the annealing treatment is preferably 160-360 ℃, more preferably 180-340 ℃, further preferably 180-300 ℃, further preferably 180-260 ℃, further preferably 200-240 ℃ and most preferably 210 ℃; the time of the annealing treatment is preferably 1-60 min, more preferably 10-50 min, still more preferably 20-40 min, and most preferably 30 min; the annealing treatment is preferably carried out in a protective atmosphere; the protective atmosphere is preferably nitrogen.
After annealing treatment, depositing a back electrode on the back contact layer to obtain a cadmium telluride thin film solar cell; the back electrode can be prepared by adopting a sputtering process, an evaporation process or a screen printing process, and the sputtering process is preferably adopted in the invention.
The method for preparing the cell window layer by adopting the large-area reactive magnetron sputtering process is simple and suitable for large-scale industrialization, and simultaneously can improve the cell efficiency of the solar cell by adjusting the oxygen content of the window layer.
In order to further illustrate the present invention, the cadmium telluride thin film solar cell and the preparation method thereof provided by the present invention are described in detail below with reference to the examples.
The reagents used in the following examples are all commercially available.
Example 1
In glass (3.2mm soda-lime glass)/FTO (thickness 500nm)/SnO2Depositing CdSe O window layer with thickness of 100nm on the substrate with thickness of 40nm by magnetron sputtering2/(Ar+O2) The flow rate is 1.5%, the sputtering power is 100W, and the gas pressure is 15 mTorr.
Depositing 5-6 μm CdTe on CdSe/O by CSS process at 660 deg.C/560 deg.C under 8Torr in O2/(N2+O2) The flow rate ratio was 2%. The deposited CdTe is sprayed with CdCl with 10% concentration2Treating 5mL of the solution at 410 ℃ for 20min in an air atmosphere; the surface was then removed with 0.5% dilute HClThe oxide layer was printed with 0.2% Cu in molar concentration carbon paste (5.6 μm thick) and annealed at 210 ℃ under nitrogen for 30 min. Finally, sputtering and depositing a 30nm Mo/200nm Al/50nm Cr metal back electrode to finish the preparation of the battery.
Example 2
In glass (3.2mm soda-lime glass)/FTO (500nm)/SnO2Depositing CdS, O/CdSe and O window layer on (40nm) substrate by magnetron reactive sputtering process to obtain a layer with a thickness of 10nm/60nm and O2/(Ar+O2) The flow rate is 1.5%, the sputtering power is 100W, and the gas pressure is 15 mTorr.
Depositing 5-6 μm CdTe on CdSe/O by CSS process at 660 deg.C/560 deg.C under 8Torr in O2/(N2+O2) The flow rate ratio was 2%. The deposited CdTe is sprayed with CdCl with 10% concentration2Treating 5mL of the solution at 410 ℃ for 20min in an air atmosphere; the surface oxide layer was then removed with 0.5% dilute HCl, and a carbon paste (5.5 μm thick) with 0.2% Cu in molar concentration was printed and annealed at 210 ℃ under nitrogen for 30 min. Finally, sputtering and depositing a 30nm Mo/200nm Al/50nm Cr metal back electrode to finish the preparation of the battery.
Comparative example 1
In glass (3.2mm soda-lime glass)/FTO (500nm)/SnO2And (40nm) depositing a CdSe window layer on the substrate by adopting a reactive magnetron sputtering process, wherein the thickness of the CdSe window layer is 100nm, pure Ar sputtering is carried out, the sputtering power is 100W, and the air pressure is 15 mTorr.
Depositing 5-6 μm CdTe on CdSe by CSS process at 660 deg.C/560 deg.C under 8Torr in O2/(N2+O2) The flow rate ratio was 2%. The deposited CdTe is sprayed with CdCl with 10% concentration2Treating 5mL of the solution at 410 ℃ for 20min in an air atmosphere; the surface oxide layer was then removed with 0.5% dilute HCl, and a carbon paste (5.6 μm thick) with 0.2% Cu in molar concentration was printed and annealed at 210 ℃ under nitrogen for 30 min. Finally, sputtering and depositing a 30nm Mo/200nm Al/50nm Cr metal back electrode to finish the preparation of the battery.
The performance of the solar cells obtained in example 1, example 2 and comparative example 1 was tested according to the industrial standard (IEC 61646), and the specific equipment includes AM1.5 light source, standard crystal silicon wafer and original IV table(ii) a The obtained performance comparison graph is shown in FIG. 3, and FIG. 3 is a graph comparing the performance of the oxygen-free CdSe-O and oxygen-doped CdSe-O and CdS-O/CdSe-O composite window layer cell. Open circuit voltage (Voc) in fig. 3: voltage of the battery when open circuit; short-circuit current (Jsc): current measured when the battery is shorted; power generation efficiency (Eff): standard simulated sunlight (AM1.5,1000W/m)2) Under illumination and 25 ℃, the output power W/1000 x 100% of the solar panel; fill Factor (FF):
from FIG. 3, it can be seen that the cadmium telluride thin film cell employing the O window layer doped with oxygen CdSe has improved open circuit voltage, fill factor and short circuit current relative to the oxygen-free CdSe window layer. The efficiency of the oxygen-doped CdSe/O window layer battery is 1.05 times that of the CdSe window layer battery. By adopting the CdS/CdSe/O window layer, the Voc and Jsc of the battery are further improved, and the efficiency is improved by 1.09 times of that of the CdSe window layer battery.
FIG. 4 is a graph of the I-V performance of the cell with high efficiency after optimization of the CdS: O/CdSe: O window layer process in example 2. The CdS/O/CdSe/O composite layer is used as a window layer of the cadmium telluride thin film battery, and the process is further optimized in FTO/SnO2Cell efficiencies of 16% or more based on CdSe O window layers were first achieved on the substrate.
Claims (6)
1. A cadmium telluride thin film solar cell is characterized by comprising a substrate layer, a transparent conductive oxide thin film layer, a high-resistance buffer layer, a cell window layer, a cell layer, a back contact layer and a back electrode which are sequentially arranged;
the high-resistance buffer layer is one or more of a tin oxide layer, a zinc oxide layer, a Zn-doped tin oxide layer, an Mg-doped zinc oxide layer, an F-doped tin oxide layer and a Cd-doped tin oxide layer;
the cell window layer comprises an oxygen-doped CdSe layer;
the content of oxygen atoms in the oxygen-doped CdSe layer is 0.1-75% of the total content of the oxygen atoms and the Se atoms;
the cell layer is one or more of a cadmium telluride layer, a tellurium-selenium-cadmium layer, a tellurium-zinc-cadmium layer and a tellurium-magnesium-cadmium layer;
the thickness of the oxygen-doped CdSe layer is 10-400 nm;
the cell window layer also comprises a CdS layer and/or an oxygen-doped CdS layer; the content of oxygen atoms in the oxygen-doped CdS layer is 0.1-75% of the total content of the oxygen atoms and S atoms;
the oxygen-doped CdSe layer is in contact with the cell layer;
the thickness of the CdS layer and/or the oxygen-doped CdS layer is 1-100 nm.
2. A cadmium telluride thin film solar cell as set forth in claim 1 wherein the substrate layer is selected from a soda lime glass layer or a borosilicate glass layer;
the transparent conductive oxide film layer is selected from one or more of an F-doped tin oxide layer, an In-doped zinc oxide layer, an Al-doped zinc oxide layer, a Ga-doped zinc oxide layer and a Cd-doped zinc oxide layer;
the back contact layer is selected from one or more of a copper-containing carbon paste layer, a copper-containing zinc telluride layer, a cadmium zinc telluride layer, a tin telluride layer and a tellurium layer;
the back electrode is selected from one or more of aluminum, silver, gold, copper, nickel, chromium, molybdenum, titanium, oxides of the above metals and nitrides of the above metals.
3. A method of manufacturing a cadmium telluride thin film solar cell as set forth in claim 1 including:
preparing a transparent conductive oxide thin film layer and a high-resistance buffer layer on a substrate in sequence;
then depositing a battery window layer on the high-resistance buffer layer through reactive magnetron sputtering; the cell window layer comprises an oxygen-doped CdSe layer; the content of oxygen atoms in the oxygen-doped CdSe layer is 0.1-75% of the total content of the oxygen atoms and the Se atoms;
and preparing a cell layer on the cell window layer, annealing the deposited cell layer to improve the performance and passivation defects of the cell layer, and then preparing a back contact layer and a deposited back electrode to obtain the cadmium telluride thin-film solar cell.
4. The preparation method according to claim 3, wherein the sputtering power of the reactive magnetron sputtering is 40-600W; the sputtering power density is 0.1-5W/cm2(ii) a The air pressure is 1 to 40 mTorr.
5. The preparation method according to claim 3, wherein the sputtering gas is a mixed gas of oxygen and argon when depositing the oxygen-doped CdSe layer by reactive magnetron sputtering; the flow ratio of the oxygen/oxygen and argon is 0.1-50%.
6. A production method according to claim 3, wherein the cell layer is obtained by near-space sublimation deposition; the temperature of the substrate compounded with the transparent conductive oxide film layer, the high-resistance buffer layer and the cell window layer during the close-space sublimation deposition is 500-620 ℃, and the source temperature is 580-680 ℃; the air pressure is 0.1 to 20 Torr;
annealing treatment of the battery layer to CdCl2Heat treatment, wherein the heat treatment temperature is 360-500 ℃; the time of the annealing treatment is 1-60 min.
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