CN105679884A - Preparation method of CZTS photovoltaic cell - Google Patents
Preparation method of CZTS photovoltaic cell Download PDFInfo
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- CN105679884A CN105679884A CN201610236651.XA CN201610236651A CN105679884A CN 105679884 A CN105679884 A CN 105679884A CN 201610236651 A CN201610236651 A CN 201610236651A CN 105679884 A CN105679884 A CN 105679884A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000001704 evaporation Methods 0.000 claims abstract description 110
- 230000008020 evaporation Effects 0.000 claims abstract description 101
- 239000000758 substrate Substances 0.000 claims abstract description 55
- 229910052718 tin Inorganic materials 0.000 claims abstract description 39
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 32
- 229910052751 metal Inorganic materials 0.000 claims abstract description 22
- 239000002184 metal Substances 0.000 claims abstract description 22
- 230000004888 barrier function Effects 0.000 claims abstract description 10
- 238000000151 deposition Methods 0.000 claims abstract description 10
- YOXKVLXOLWOQBK-UHFFFAOYSA-N sulfur monoxide zinc Chemical compound [Zn].S=O YOXKVLXOLWOQBK-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052802 copper Inorganic materials 0.000 claims abstract description 5
- 239000011701 zinc Substances 0.000 claims description 56
- 229910052725 zinc Inorganic materials 0.000 claims description 46
- 239000010949 copper Substances 0.000 claims description 39
- 239000011669 selenium Substances 0.000 claims description 34
- 238000010438 heat treatment Methods 0.000 claims description 32
- 239000010409 thin film Substances 0.000 claims description 29
- 239000010408 film Substances 0.000 claims description 26
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 18
- 239000011135 tin Substances 0.000 claims description 17
- PCRGAMCZHDYVOL-UHFFFAOYSA-N copper selanylidenetin zinc Chemical compound [Cu].[Zn].[Sn]=[Se] PCRGAMCZHDYVOL-UHFFFAOYSA-N 0.000 claims description 11
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- 230000008021 deposition Effects 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- 229910001220 stainless steel Inorganic materials 0.000 claims description 5
- 239000010935 stainless steel Substances 0.000 claims description 5
- 229910000831 Steel Inorganic materials 0.000 claims description 4
- 239000011888 foil Substances 0.000 claims description 4
- 238000012544 monitoring process Methods 0.000 claims description 4
- 239000005361 soda-lime glass Substances 0.000 claims description 4
- 239000010959 steel Substances 0.000 claims description 4
- 238000000034 method Methods 0.000 abstract description 19
- 238000005516 engineering process Methods 0.000 abstract description 4
- 238000007738 vacuum evaporation Methods 0.000 abstract description 3
- 239000012535 impurity Substances 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 abstract 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 abstract 2
- 229910052804 chromium Inorganic materials 0.000 abstract 2
- 239000011651 chromium Substances 0.000 abstract 2
- 239000011787 zinc oxide Substances 0.000 abstract 2
- 238000012805 post-processing Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 8
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 3
- 229910052738 indium Inorganic materials 0.000 description 3
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 3
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 2
- 239000005083 Zinc sulfide Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- 238000001755 magnetron sputter deposition Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 239000003440 toxic substance Substances 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 229910052984 zinc sulfide Inorganic materials 0.000 description 2
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- HVMJUDPAXRRVQO-UHFFFAOYSA-N copper indium Chemical compound [Cu].[In] HVMJUDPAXRRVQO-UHFFFAOYSA-N 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
- H01L31/0264—Inorganic materials
- H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
- H01L31/0326—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising AIBIICIVDVI kesterite compounds, e.g. Cu2ZnSnSe4, Cu2ZnSnS4
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/042—PV modules or arrays of single PV cells
- H01L31/0445—PV modules or arrays of single PV cells including thin film solar cells, e.g. single thin film a-Si, CIS or CdTe solar cells
-
- 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
-
- 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 preparation method of a CZTS photovoltaic cell. The method comprises the steps in a vacuum evaporation chamber of: 1, firstly, successively depositing a metal chromium barrier layer and a Mo back electrode on a substrate, and then distributing Cu, ZN, Sn and Se evaporation sources under the back electrode of the substrate; 2, co-evaporating ZN, Sn and Se on the Mo back electrode, and forming a preset layer film; 3, co-evaporating Cu and Se and forming a Cu-enriched absorbing layer film; 4, co-evaporating ZN, Sn and Se, and forming a Cu-poor absorbing layer film on the Mo back electrode; 5, carrying out temperature reduction on Sn and Se atmospheres of the substrate, then carrying out temperature reduction on again on the Se atmosphere, and forming a Cu, ZN, Sn and Se film absorbing layer; and 6, successively manufacturing a first zinc oxysulfide buffer layer, a second zinc oxide buffer layer, an intrinsic zinc oxide layer, a transparent conductive film window layer and a metal gate electrode on the Cu, ZN, Sn and Se film absorbing layer. According to the invention, multi-source coevaporation is utilized to prepare the Cu, ZN, Sn and Se photovoltaic cell absorbing layer film, the preparation process is completed by one time in the vacuum evaporation chamber, the selenizing post-processing process is not needed, the technology flow is simpler, and the metal chromium barrier layer can effectively preventing impurities from diffusing to the absorbing layer.
Description
Technical field
The invention belongs to film photovoltaic cell technical field, the preparation method particularly relating to a kind of CZTS photovoltaic cell.
Background technology
Along with the fast development of World Economics and industry, the mankind are also rising year by year for the demand of the energy. But the non-renewable fossil energy reserves as main energy sources source constantly consume minimizing, and bring serious environmental pollution and ecological disruption. In this context, as the extensive concern that solar energy is renewable with it, pollution-free, advantage that is that have wide range of applications receives people of new forms of energy important component part, and the research of solaode and utilization are wherein the most valued fields.
In the middle of many photovoltaic cell materials, CIGS (CIGS) thin-film material has conversion efficiency height, and long-time stability are good, the feature that Radiation hardness is strong, it is believed that gather around and have wide practical use. But, copper-indium-gallium-selenium photovoltaic used in battery to indium (In) be a kind of rare, in the earth's crust, content is few, cause, the production cost of copper indium gallium selenide cell higher; Additionally, indium, gallium (Ga) have certain toxicity, these all constrain the industrialized development of copper-indium-gallium-selenium film photovoltaic cell.
Quaternary compound copper-zinc-tin-selenium (CZTSe) is considered as most possible one of material replacing CIGS, copper-zinc-tin-selenium is a kind of direct band gap material in p-type conductivity, its absorption coefficient of light, up to 104cm-1, is suitable as absorbed layer material and prepares film photovoltaic cell. Compared with indium, zinc (Zn) and stannum (Sn) rich reserves in the earth's crust, cheap and nontoxic, the impact of ecological environment is less. In recent years, along with progressively going deep into of research work, the performance of copper-zinc-tin-selefilm film photovoltaic cell is also improving constantly, and the copper-zinc-tin-selefilm film photovoltaic cell photoelectric transformation efficiency of the doping sulfur (S) of report alreadys more than 11% at present.
Copper-zinc-tin-selefilm film absorbed layer material have multiple preparation method, it is possible to be divided into vacuum moulding machine and conventional non-vacuum deposition two kinds.In antivacuum method, it is capable of the spin coating co-reducing process of greater efficiency at present, using hydrazine hydrate as reducing agent, but there is due to hydrazine strong toxicity and severe corrosive, be difficult to process from the angle of safety and environmental protection. Another kind of conventional method is selenizing method after electrochemical deposition of metal predecessor. And in vacuum method, commonplace employing is selenization after splash-proofing sputtering metal initialization layer, electrochemical deposition and sputtering and selenization technique will through selenidation process, it is necessary to two steps just can complete, and technics comparing is complicated.
Summary of the invention
The present invention solves the technical problem existed in known technology and provide a kind of technological process simple and easy to do, without rear selenization, do not adopt strong toxicant, safety and environmental protection, and the preparation method of the CZTS photovoltaic cell that thin film is uniform, electric property is good.
The present invention includes following technical scheme:
The preparation method of CZTS photovoltaic cell, is characterized in: comprise the following steps:
Being sequentially depositing crome metal barrier layer and Mo back electrode on step 1. first substrate, then face down with the one of Mo back electrode on substrate and insert in evaporation chamber in rotatable specimen holder, substrate heater is put in the top of substrate; Cu, Zn, Sn, Se as evaporation source are evenly distributed on periphery below the Mo back electrode at the bottom of evaporation cavity chamber liner, are equipped with an evaporation source baffle plate above each evaporation source;
Evaporation cavity indoor are evacuated to 10-4Pa by step 2. vacuum pump, by silicon to 380 DEG C, by in each evaporation source Cu heating to 1100 DEG C～1200 DEG C, Zn heating to 280 DEG C～380 DEG C, Sn heating to 1000 DEG C～1100 DEG C, Se heat to 200 DEG C～250 DEG C, Rotary Specimen Rack, open the evaporation source baffle plate above Zn, Sn, Se, coevaporation Zn, Sn, Se on the Mo back electrode of substrate, evaporation time is one layer of initialization layer thin film of deposition on 10min, Mo back electrode;
Step 3., when substrate continues heating to 500 DEG C, is closed the evaporation source baffle plate above Zn, Sn, is opened the evaporation source baffle plate above Cu, coevaporation Cu, Se, and evaporation time is 23min, and the initialization layer thin film in step 2 becomes rich Cu absorbed layer thin film;
Step 4. closes the evaporation source baffle plate above Cu, stops the heating of Cu evaporation source, opens the evaporation source baffle plate of Zn, Sn, coevaporation Zn, Sn, Se, and evaporation time is 12min, and the rich Cu absorbed layer thin film in step 3 becomes lean Cu absorbed layer thin film;
Step 5. closes Zn evaporation source baffle plate, stops the heating of Zn evaporation source, and substrate lower the temperature with the speed of 20-30 DEG C/min under Sn, Se atmosphere, until underlayer temperature lower than 450 DEG C after close the evaporation source baffle plate of Sn, stop Sn evaporation source and heat; Substrate continues to be cooled to the evaporation source baffle plate closing Se after lower than 350 DEG C, stops the heating of Se evaporation source, stops substrate and rotates, and is cooled to after room temperature until substrate and takes out, and the lean Cu absorbed layer thin film on Mo back electrode forms copper-zinc-tin-selefilm film absorbed layer;
Step 6. makes the first zinc oxysulfide cushion, the second zinc bloom buffer layer, native oxide zinc layers, transparent conductive film Window layer and metal gate electrode successively on copper-zinc-tin-selefilm film absorbed layer.
The present invention can also adopt following technical measures:
Described substrate is soda-lime glass, titanium foil or stainless steel foil; The thickness on described crome metal barrier layer is 2 μm, and described Mo back electrode thickness is 1 μm.
Described substrate heater is made up of the electric furnace heating wire being coiled on rustless steel pallet.
The thermocouple for monitoring evaporating temperature all it is equipped with inside each evaporation source described.
Described copper-zinc-tin-selefilm film absorbed layer is the p-type copper-zinc-tin-selenium absorbed layer of 1.5 μ m-thick; Described first zinc oxysulfide cushion is the n-type zinc sulfide cushion that 25nm is thick, and described second zinc bloom buffer layer is the n-type zinc bloom buffer layer that 50nm is thick; The thickness of described native oxide zinc layers is 50nm; The thickness of described transparent conductive film Window layer is 300～500nm; Described metal gate electrode is Ni/Al metal gate electrode.
The present invention has the advantage that and good effect:
The present invention adopts the method for multi-source coevaporation to prepare copper-zinc-tin-selenium photovoltaic cell absorbed layer thin film, and preparation process is disposable in vacuum evaporation room to be completed, it is not necessary to through the last handling process of selenizing, technological process is easier. Due to the fact that and carry out in vacuum-tight evaporation chamber, it is not necessary to using the extremely toxic substances such as hydrazine, safe preparation process is higher, and environmental effect is less. The absorbed layer preparation technology flow process that the present invention adopts is first at one layer of initialization layer of deposited on substrates, then deposit Cu, Se thereon and form rich Cu structure, then deposit Zn, Se, Sn make thin film entirety composition reach close to the metering of copper-zinc-tin-selenium materials chemistry than and the requirement of slightly lean Cu; The advantage of this method is in that in membrane-film preparation process to experienced by the process of a rich Cu, the liquid CuxSey Binary-phase formed in this course contributes to growing up of copper-zinc-tin-selenium material grains, improve the crystalline quality of thin film, reduce the carrier compound at grain boundaries, and then improve the electric property of thin film. The present invention adopts Rotary Specimen Rack, improves the uniformity of copper-zinc-tin-selenium photovoltaic cell absorbed layer thin film, and crome metal barrier layer can effectively prevent impurity to be diffused into described absorbed layer simultaneously.
Accompanying drawing explanation
Fig. 1 is present invention evaporation chamber schematic side view;
In figure, 1-evaporates chamber, 2-substrate heater, 3-substrate, 4-specimen holder, 5-vacuum pump, 6-Cu evaporation source, 7-Zn evaporation source, 8-Sn evaporation source, 9-Se evaporation source, 10-evaporation source baffle plate.
Detailed description of the invention
For the summary of the invention of the present invention, feature and effect can be disclosed further, especially exemplified by following instance and be described in detail as follows in conjunction with accompanying drawing:
The preparation method of CZTS photovoltaic cell, is characterized in: comprise the following steps:
Being sequentially depositing crome metal barrier layer and Mo back electrode on step 1. first substrate, then face down with the one of Mo back electrode on substrate and insert in evaporation chamber in rotatable specimen holder, substrate heater is put in the top of substrate; Cu, Zn, Sn, Se as evaporation source are evenly distributed on periphery below the Mo back electrode at the bottom of evaporation cavity chamber liner, are equipped with an evaporation source baffle plate above each evaporation source;
Evaporation cavity indoor are evacuated to 10-4Pa by step 2. vacuum pump, by silicon to 380 DEG C, by in each evaporation source Cu heating to 1100 DEG C～1200 DEG C, Zn heating to 280 DEG C～380 DEG C, Sn heating to 1000 DEG C～1100 DEG C, Se heat to 200 DEG C～250 DEG C, Rotary Specimen Rack, open the evaporation source baffle plate above Zn, Sn, Se, coevaporation Zn, Sn, Se on the Mo back electrode of substrate, evaporation time is one layer of initialization layer thin film of deposition on 10min, Mo back electrode;
Step 3., when substrate continues heating to 500 DEG C, is closed the evaporation source baffle plate above Zn, Sn, is opened the evaporation source baffle plate above Cu, coevaporation Cu, Se, and evaporation time is 23min, and the initialization layer thin film in step 2 becomes rich Cu absorbed layer thin film;
Step 4. closes the evaporation source baffle plate above Cu, stops the heating of Cu evaporation source, opens the evaporation source baffle plate of Zn, Sn, coevaporation Zn, Sn, Se, and evaporation time is 12min, and the rich Cu absorbed layer thin film in step 3 becomes lean Cu absorbed layer thin film;
Step 5. closes Zn evaporation source baffle plate, stops the heating of Zn evaporation source, and substrate lower the temperature with the speed of 20-30 DEG C/min under Sn, Se atmosphere, until underlayer temperature lower than 450 DEG C after close the evaporation source baffle plate of Sn, stop Sn evaporation source and heat; Substrate continues to be cooled to the evaporation source baffle plate closing Se after lower than 350 DEG C, stops the heating of Se evaporation source, stops substrate and rotates, and is cooled to after room temperature until substrate and takes out, and the lean Cu absorbed layer thin film on Mo back electrode forms copper-zinc-tin-selefilm film absorbed layer;
Step 6. makes the first zinc oxysulfide cushion, the second zinc bloom buffer layer, native oxide zinc layers, transparent conductive film Window layer and metal gate electrode successively on copper-zinc-tin-selefilm film absorbed layer.
The present invention can also adopt following technical measures:
Described substrate is soda-lime glass, titanium foil or stainless steel foil; The thickness on described crome metal barrier layer is 2 μm, and described Mo back electrode thickness is 1 μm.
Described substrate heater is made up of the electric furnace heating wire being coiled on rustless steel pallet.
The thermocouple for monitoring evaporating temperature all it is equipped with inside each evaporation source described.
Described copper-zinc-tin-selefilm film absorbed layer is the p-type copper-zinc-tin-selenium absorbed layer of 1.5 μ m-thick; Described first zinc oxysulfide cushion is the n-type zinc sulfide cushion that 25nm is thick, and described second zinc bloom buffer layer is the n-type zinc bloom buffer layer that 50nm is thick; The thickness of described native oxide zinc layers is 50nm; The thickness of described transparent conductive film Window layer is 300～500nm; Described metal gate electrode is Ni/Al metal gate electrode.
Embodiment 1
Adopt soda-lime glass as substrate 3, on substrate, be sequentially depositing the crome metal barrier layer of 2 μ m-thick and the Mo back electrode of 1 μ m-thick by the method for magnetron sputtering; Mo back electrode is prepared copper-zinc-tin-selenium absorbed layer; The preparation process of described copper-zinc-tin-selenium absorbed layer is: (1) is inserted in the rotatable sample frame 4 evaporating chamber 1 as shown in Figure 1 by facing down with the one of Mo back electrode on substrate; The top of substrate is equipped with the substrate heater 2 being made up of the electric furnace heating wire being coiled on rustless steel pallet; Cu, Zn, Sn, Se as evaporation source are evenly distributed on the periphery below the Mo back electrode of evaporation cavity indoor, be provided with the thermocouple for monitoring evaporating temperature, be equipped with evaporation source baffle plate 10 above each evaporation source inside each evaporation source; (2) by vacuum pump 5, evaporation cavity indoor are evacuated to 10-4Pa, by silicon to 380 DEG C; By thermocouple control, heating Cu evaporation source 6 to 1100 DEG C～1200 DEG C, heating Zn evaporation source 7 to 280 DEG C～380 DEG C, heating Sn evaporation source 8 to 1000 DEG C～1100 DEG C, heating Se evaporation source 9 to 200 DEG C～250 DEG C; Opening specimen holder, make specimen holder rotate in the horizontal direction, substrate rotates with specimen holder, to ensure the uniformity of film forming on substrate; Open the evaporation source baffle plate of Zn, Sn, Se, coevaporation Zn, Sn, Se on Mo back electrode, evaporation time is one layer of initialization layer thin film of deposition on 10min, Mo back electrode; (3) by silicon to 500 DEG C, closing Zn, Sn evaporation source baffle plate, open the evaporation source baffle plate of Cu, coevaporation Cu, Se, evaporation time is 23min, obtains rich Cu absorbed layer thin film; (4) closing Cu evaporation source baffle plate, stop the heating of Cu evaporation source, open the evaporation source baffle plate of Zn, Sn, coevaporation Zn, Sn, Se, evaporation time is 12min, and rich Cu absorbed layer thin film becomes lean Cu absorbed layer thin film; (5) closing Zn evaporation source baffle plate, stop the heating of Zn evaporation source, substrate lower the temperature with the speed of 20-30 DEG C/min under Sn, Se atmosphere, until underlayer temperature lower than 450 DEG C after close the evaporation source baffle plate of Sn, stop Sn evaporation source and heat;Continue to be cooled to underlayer temperature lower than 350 DEG C after close the evaporation source baffle plate of Se, stop the heating of Se evaporation source, stop substrate and rotate; Naturally cool to until substrate and take out after 25 DEG C of room temperatures, the Mo back electrode of substrate is formed the copper-zinc-tin-selefilm film absorbed layer of one layer of 1.5 μ m-thick; Then with the n-type zinc bloom buffer layer that n-type zinc oxysulfide cushion thick for ALD method deposition 25nm and 50nm are thick, on n-type zinc bloom buffer layer, native oxide zinc layers thick for 50nm and the Al-ZnO transparent conductive film Window layer of 500nm thickness is deposited with magnetron sputtering method, Al-ZnO transparent conductive film Window layer is evaporated Ni/Al gate electrode, prepares into CZTS photovoltaic cell.
Embodiment 2
Adopt thickness be the stainless steel foil of 40 μm as substrate, other condition and embodiment 1 are identical, prepare into stainless steel lining bottom structure CZTS photovoltaic cell.
Embodiment 3
Adopt thickness be the titanium foil of 40 μm as substrate, other condition and embodiment 1 are identical, prepare into titanium substrat structure CZTS photovoltaic cell.
Although the preferred embodiments of the present invention being described above in conjunction with accompanying drawing; but the invention is not limited in above-mentioned detailed description of the invention; above-mentioned detailed description of the invention is merely schematic; it is not restrictive; those of ordinary skill in the art is under the enlightenment of the present invention; without departing under present inventive concept and scope of the claimed protection situation, it is also possible to make a lot of form. These belong within protection scope of the present invention.
Claims (5)
- The preparation method of 1.CZTS photovoltaic cell, it is characterised in that: comprise the following steps:Being sequentially depositing crome metal barrier layer and Mo back electrode on step 1. first substrate, then face down with the one of Mo back electrode on substrate and insert in evaporation chamber in rotatable specimen holder, substrate heater is put in the top of substrate; Cu, Zn, Sn, Se as evaporation source are evenly distributed on periphery below the Mo back electrode at the bottom of evaporation cavity chamber liner, are equipped with an evaporation source baffle plate above each evaporation source;Evaporation cavity indoor are evacuated to 10-4Pa by step 2. vacuum pump, by silicon to 380 DEG C, by in each evaporation source Cu heating to 1100 DEG C～1200 DEG C, Zn heating to 280 DEG C～380 DEG C, Sn heating to 1000 DEG C～1100 DEG C, Se heat to 200 DEG C～250 DEG C, Rotary Specimen Rack, open the evaporation source baffle plate above Zn, Sn, Se, coevaporation Zn, Sn, Se on the Mo back electrode of substrate, evaporation time is one layer of initialization layer thin film of deposition on 10min, Mo back electrode;Step 3., when substrate continues heating to 500 DEG C, is closed the evaporation source baffle plate above Zn, Sn, is opened the evaporation source baffle plate above Cu, coevaporation Cu, Se, and evaporation time is 23min, and the initialization layer thin film in step 2 becomes rich Cu absorbed layer thin film;Step 4. closes the evaporation source baffle plate above Cu, stops the heating of Cu evaporation source, opens the evaporation source baffle plate of Zn, Sn, coevaporation Zn, Sn, Se, and evaporation time is 12min, and the rich Cu absorbed layer thin film in step 3 becomes lean Cu absorbed layer thin film;Step 5. closes Zn evaporation source baffle plate, stops the heating of Zn evaporation source, and substrate lower the temperature with the speed of 20-30 DEG C/min under Sn, Se atmosphere, until underlayer temperature lower than 450 DEG C after close the evaporation source baffle plate of Sn, stop Sn evaporation source and heat; Substrate continues to be cooled to the evaporation source baffle plate closing Se after lower than 350 DEG C, stops the heating of Se evaporation source, stops substrate and rotates, and is cooled to after room temperature until substrate and takes out, and the lean Cu absorbed layer thin film on Mo back electrode forms copper-zinc-tin-selefilm film absorbed layer;Step 6. makes the first zinc oxysulfide cushion, the second zinc bloom buffer layer, native oxide zinc layers, transparent conductive film Window layer and metal gate electrode successively on copper-zinc-tin-selefilm film absorbed layer.
- 2. the preparation method of CZTS photovoltaic cell according to claim 1, it is characterised in that: described substrate is soda-lime glass, titanium foil or stainless steel foil; The thickness on described crome metal barrier layer is 2 μm, and described Mo back electrode thickness is 1 μm.
- 3. the preparation method of CZTS photovoltaic cell according to claim 1, it is characterised in that: described substrate heater is made up of the electric furnace heating wire being coiled on rustless steel pallet.
- 4. the preparation method of CZTS photovoltaic cell according to claim 1, it is characterised in that: all it is equipped with the thermocouple for monitoring evaporating temperature inside each evaporation source described.
- 5. the preparation method of CZTS photovoltaic cell according to claim 1, it is characterised in that: described copper-zinc-tin-selefilm film absorbed layer is the p-type copper-zinc-tin-selenium absorbed layer of 1.5 μ m-thick; Described first zinc oxysulfide cushion is the n-type zinc oxysulfide cushion that 25nm is thick, and described second zinc bloom buffer layer is the n-type zinc bloom buffer layer that 50nm is thick; The thickness of described native oxide zinc layers is 50nm; The thickness of described transparent conductive film Window layer is 300～500nm; Described metal gate electrode is Ni/Al metal gate electrode.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106298995A (en) * | 2016-11-03 | 2017-01-04 | 中国科学院兰州化学物理研究所 | A kind of Ag doping copper zinc tin sulfur selenium light absorbing zone thin-film material and application in solar cells thereof |
| CN106684210A (en) * | 2016-12-28 | 2017-05-17 | 中国电子科技集团公司第十八研究所 | CZTSSe thin film preparation method used for solar cell, thin film prepared by using said method and solar cell containing said thin film |
| CN114171636A (en) * | 2021-11-24 | 2022-03-11 | 湖北工业大学 | Preparation method of Cd-free tunneling buffer layer for CZTS thin-film solar cell |
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| CN104716227A (en) * | 2013-12-16 | 2015-06-17 | 中国电子科技集团公司第十八研究所 | Method for manufacturing CZTS thin film solar cell absorbing layer |
| CN104716229A (en) * | 2013-12-16 | 2015-06-17 | 中国电子科技集团公司第十八研究所 | Cu-Zn-Sn-Se thin film solar cell preparation method |
| CN105226118A (en) * | 2014-06-05 | 2016-01-06 | 中物院成都科学技术发展中心 | Flexible solar battery and preparation method thereof |
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| CN104716227A (en) * | 2013-12-16 | 2015-06-17 | 中国电子科技集团公司第十八研究所 | Method for manufacturing CZTS thin film solar cell absorbing layer |
| CN104716229A (en) * | 2013-12-16 | 2015-06-17 | 中国电子科技集团公司第十八研究所 | Cu-Zn-Sn-Se thin film solar cell preparation method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106298995A (en) * | 2016-11-03 | 2017-01-04 | 中国科学院兰州化学物理研究所 | A kind of Ag doping copper zinc tin sulfur selenium light absorbing zone thin-film material and application in solar cells thereof |
| CN106298995B (en) * | 2016-11-03 | 2017-12-22 | 中国科学院兰州化学物理研究所 | A kind of Ag doping copper zinc tin sulfur selenium light absorbing layer thin-film material and its application in solar cells |
| CN106684210A (en) * | 2016-12-28 | 2017-05-17 | 中国电子科技集团公司第十八研究所 | CZTSSe thin film preparation method used for solar cell, thin film prepared by using said method and solar cell containing said thin film |
| CN114171636A (en) * | 2021-11-24 | 2022-03-11 | 湖北工业大学 | Preparation method of Cd-free tunneling buffer layer for CZTS thin-film solar cell |
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