CN105304763A - Method for preparing CZTS thin film solar cell based on full vacuum method - Google Patents

Method for preparing CZTS thin film solar cell based on full vacuum method Download PDF

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Publication number
CN105304763A
CN105304763A CN201510761249.9A CN201510761249A CN105304763A CN 105304763 A CN105304763 A CN 105304763A CN 201510761249 A CN201510761249 A CN 201510761249A CN 105304763 A CN105304763 A CN 105304763A
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tin
zinc
copper
thin film
solar cell
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Inventor
王书荣
李志山
蒋志
杨敏
刘涛
郝瑞婷
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Yunnan Normal University
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Yunnan Normal University
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00Semiconductor 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
    • H01L31/18Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104Forming layers
    • H01L21/02365Forming inorganic semiconducting materials on a substrate
    • H01L21/02367Substrates
    • H01L21/0237Materials
    • H01L21/02422Non-crystalline insulating materials, e.g. glass, polymers
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104Forming layers
    • H01L21/02365Forming inorganic semiconducting materials on a substrate
    • H01L21/02518Deposited layers
    • H01L21/02521Materials
    • H01L21/02551Group 12/16 materials
    • H01L21/02557Sulfides
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104Forming layers
    • H01L21/02365Forming inorganic semiconducting materials on a substrate
    • H01L21/02612Formation types
    • H01L21/02617Deposition types
    • H01L21/02631Physical deposition at reduced pressure, e.g. MBE, sputtering, evaporation
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention discloses a method for preparing a CZTS thin film solar cell based on a full vacuum method. The method comprises the following steps: 1) after magnetron sputtering, vulcanizing to prepare a CZTS thin film absorbing layer; 2) preparing 50-100nm CdS thin film buffer layer on the absorbing layer through radio frequency magnetron sputtering and then preparing 50-100nm intrinsic ZnO and 400nm Al:ZnO through radio frequency magnetron sputtering; and 3) finally preparing 2mu m Ni/Al electrode through evaporating. The traditional water bath method for preparation of the CdS film has the main defect that since waste water containing Cd (a toxic element) is generated in the preparation process of the CdS thin film, cost is largely increased in the process of waste water treatment, and ammonium hydroxide used in the process of sedimentation has volatility and toxicity and is harmful to human health, and in addition the volatility of ammonium hydroxide can change the pH value of a solution and further influences the property of the buffer layer. The sputtering method does not cause the pollution of waste water containing the Cd element, which occurs after the implementation of the water bath method; therefore, the sputtering method is friendly to the environment and is suitable for online preparation of thin film cells; in addition, the whole preparation process is carried out in vacuum and therefore the possibility of external impurity contamination to the thin film is very small.

Description

Vacuum legal system is for the method for copper-zinc-tin-sulfur film solar cell
Technical field
The present invention relates to the method for a kind of vacuum legal system for copper-zinc-tin-sulfur film solar cell, for the preparation of thin film solar cell material, belong to photoelectric material technical field of new energies.
Background technology
Although Copper Indium Gallium Selenide (CIGS) and cadmium telluride (CdTe) solar cell remain the mainstay material of compound semiconductor film battery obsorbing layer, but because of its component indium in CIGS and gallium few at occurring in nature content, belong to rare element, and it is expensive, and because its Cd is heavy metal element in CdTe, serious threat can be caused to environment.Therefore, based on I 2-II-IV-VI 4quaternary compound semiconductor: Cu 2znSnS 4(CZTS), Cu 2znSnSe 4, and Cu (CZTSe) 2znSn (S 1-xse x) 4, because its component is abundant and nontoxic at occurring in nature, TW level can be met and produce, and its price is relatively low.Moreover it belongs to direct band gap p-type semiconductor, there is high absorption coefficient (> 10 4cm -1), band gap is by control S/(S+Se) ratio 0 ~ 1 regulate and make it between 1.0eV ~ 1.5eV.And its theoretical efficiency of its solar cell can reach 32.2%, be that one has alternative CdTe and Cu(In, Ga) Se 2(CIGS) novel thin film solar cell material.Current bibliographical information prepare copper-zinc-tin-sulfur film solar cell resilient coating method be all chemical bath deposition preparation, immersion method is prepared in CdS film process can produce a large amount of waste water containing toxic element Cd, belong to the unfriendly type method of environment, in post-processed waste water process, considerably increase cost; In addition, the ammoniacal liquor used in deposition process has high volatility and toxicity is harmful to human health; Moreover the volatilization of ammoniacal liquor will change the pH value of solution and and then affect the performance of resilient coating.And immersion method prepares the thickness that can not control film in CdS course of reaction at any time.Based on this, immersion method is prepared resilient coating and is restricted in large-scale production from now on to some extent.
Summary of the invention
Because the above-mentioned defect of prior art, technical problem the present invention to be solved by this invention adopts magnetron sputtering to prepare resilient coating, not only can not to environment, but also saving material, make its thickness controlled, and whole device fabrication process is all carried out under vacuum, avoid extraneous pollution.
A kind of vacuum legal system involved in the present invention is implemented according to the following steps for the method for copper-zinc-tin-sulfur film solar cell:
(1) substrate cleaning: by soda-lime glass successively by acetone, alcohol, deionized water ultrasonic cleaning, and dry up for subsequent use with nitrogen;
(2) put into by cleaned soda-lime glass in magnetic control sputtering system and be warming up to 100 ~ 150 DEG C of baking 30 ~ 60min, then the molybdenum back electrode film depositing 1 μm subsequently on soda-lime glass is warming up to 220 baking 30min;
(3) preparation of copper-zinc-tin-sulfur preformed layer: utilize magnetic control sputtering system, with ZnS, Sn and CuS for target carries out radio frequency sputtering according to the order of SLG/Mo/ZnS/CuS/Sn, the copper-zinc-tin-sulfur film preformed layer of deposition 700 ~ 1000nm;
(4) preparation of copper-zinc-tin-sulfur film absorbed layer: vulcanizing treatment of being annealed under nitrogen or argon by the copper-zinc-tin-sulfur film preformed layer prepared by step 3), obtains copper-zinc-tin-selefilm film absorbed layer after cooling naturally;
(5) on the CZTS film prepared, the CdS resilient coating of 50-100nm is prepared with magnetron sputtering, subsequently the intrinsic ZnO of magnetron sputtering 50-100nm and the Al:ZnO of 400nm;
(6) then at the Ni/Al electrode of Evaporation preparation 2 μm, finally by whole device 220 DEG C of process 20min in quick anneal oven.
The present invention adopt in a kind of method of multi-element compounds list target Slag coating copper-zinc-tin-selefilm film absorbed layer as described in step (2) as described in substrate put into and in magnetic control sputtering system, to be warming up to 100 ~ 150 DEG C of baking 30 ~ 60min.
The present invention adopt a kind of vacuum legal system in the method for copper-zinc-tin-sulfur film solar cell as step (2) deposited the molybdenum back electrode film of 1 μm after be warming up to 220 baking 30min, so that the diffusion of sodium ion.
The present invention adopts a kind of vacuum legal system to be SLG/Mo/ZnS/CuS/Sn for the sputtering order of the copper-zinc-tin-selefilm film preformed layer in the method for copper-zinc-tin-sulfur film solar cell as described in step (3), and film thickness is designed to 700-1000nm.
The present invention adopts a kind of vacuum legal system for the CdS resilient coating of the 50-100nm prepared with magnetron sputtering in the method for copper-zinc-tin-sulfur film solar cell as described in step (5).
The present invention adopt a kind of vacuum legal system in the method for copper-zinc-tin-sulfur film solar cell as described in step (6), after prepared by whole battery device, by its in quick anneal oven 220 DEG C process 20min.
Accompanying drawing explanation
Fig. 1 is the XRD figure of copper-zinc-tin-selefilm film absorbed layer prepared in embodiment 1 and 2
Fig. 2 is the Raman figure of copper-zinc-tin-selefilm film absorbed layer prepared in embodiment 1 and 2
Fig. 3 is the SEM figure of copper-zinc-tin-selefilm film absorbed layer prepared in embodiment 1 and 2
Fig. 4 is embodiment 1(a) and embodiment 2(b) in the XRD figure of prepared CdS film
Fig. 5 is embodiment 1(a) and embodiment 2(b) in the transmission spectrum of prepared CdS film
Fig. 6 is embodiment 1(a) and embodiment 2(b) CdS film SEM figure
The battery efficiency I-V figure of Fig. 7 prepared by embodiment 1
The battery efficiency I-V figure of Fig. 8 prepared by embodiment 1.
Embodiment
Embodiment 1
(1) substrate cleaning: soda-lime glass is used successively acetone, alcohol, deionized water ultrasonic cleaning, and dry up with nitrogen for subsequent use;
(2) put into by cleaned soda-lime glass in magnetic control sputtering system and be warming up to 150 DEG C of baking 30min, carry out direct current sputtering using the molybdenum target being of a size of 76.2mm*3mm as target, base vacuum is 5.0*10 -4pa, underlayer temperature is 160 DEG C, and build-up of luminance air pressure is 1.6pa, power is 150W, sputters 15min when argon gas is 1.6pa, regulates argon gas to be that 0.3pa sputters 105min subsequently, operate in molybdenum back electrode film soda-lime glass obtaining 1 μm by above-mentioned requirements, be then warming up to 220 baking 30min; ;
(3) preparation of copper-zinc-tin-sulfur film initialization layer: with ZnS, Sn and CuS of being of a size of 76.2mm*3mm for target carries out radio frequency sputtering according to the order of SLG/Mo/ZnS/CuS/Sn, the copper-zinc-tin-sulfur film preformed layer of deposition 700 ~ 1000nm, base vacuum is 5.0*10-4pa, underlayer temperature is room temperature, build-up of luminance air pressure is 1.6pa, power is for being 50W, and operating pressure is 0.3pa, the basis operating in step (2) obtains the copper-zinc-tin-sulfur film initialization layer of 800nm by above-mentioned requirements.
(4) preparation of copper-zinc-tin-sulfur film absorbed layer: the copper-zinc-tin-sulfur film initialization layer prepared by step (3) and 0.5 gram of selenium powder and 0.02 gram of glass putty are put into graphite boat, subsequently graphite boat is put into annealing furnace and be warming up to the vulcanizing treatment that 580 DEG C are carried out 20min under nitrogen protection, naturally cool to room temperature and sample taking-up is obtained copper-zinc-tin-sulfur film absorbed layer;
(5) on the CZTS film prepared, prepare the CdS resilient coating of 50nm with rf magnetron sputtering, power is 25W, subsequently the intrinsic ZnO of rf magnetron sputtering 50nm and the Al:ZnO of 400nm, and power is respectively 25W and 50W.Base vacuum is 5.0*10 -4pa, underlayer temperature is room temperature, and operating air pressure is 0.5pa;
(6) then at the Ni/Al electrode of Evaporation preparation 2 μm, finally by whole device 220 DEG C of process 20min in quick anneal oven.
Embodiment 2
(1) substrate cleaning: soda-lime glass is used successively acetone, alcohol, deionized water ultrasonic cleaning, and dry up with nitrogen for subsequent use;
(2) put into by cleaned soda-lime glass in magnetic control sputtering system and be warming up to 150 DEG C of baking 30min, carry out direct current sputtering using the molybdenum target being of a size of 76.2mm*3mm as target, base vacuum is 5.0*10 -4pa, underlayer temperature is 160 DEG C, and build-up of luminance air pressure is 1.6pa, power is 150W, sputters 15min when argon gas is 1.6pa, regulates argon gas to be that 0.3pa sputters 105min subsequently, operate in molybdenum back electrode film soda-lime glass obtaining 1 μm by above-mentioned requirements, be then warming up to 220 baking 30min; ;
(3) preparation of copper-zinc-tin-sulfur film initialization layer: with ZnS, Sn and CuS of being of a size of 76.2mm*3mm for target carries out radio frequency sputtering according to the order of SLG/Mo/ZnS/CuS/Sn, the copper-zinc-tin-sulfur film preformed layer of deposition 700 ~ 1000nm, base vacuum is 5.0*10-4pa, underlayer temperature is room temperature, build-up of luminance air pressure is 1.6pa, power is for being 50W, and operating pressure is 0.3pa, the basis operating in step (2) obtains the copper-zinc-tin-sulfur film initialization layer of 800nm by above-mentioned requirements.
(4) preparation of copper-zinc-tin-sulfur film absorbed layer: the copper-zinc-tin-sulfur film initialization layer prepared by step (3) and 0.5 gram of selenium powder and 0.02 gram of glass putty are put into graphite boat, subsequently graphite boat is put into annealing furnace and be warming up to the vulcanizing treatment that 580 DEG C are carried out 20min under nitrogen protection, naturally cool to room temperature and sample taking-up is obtained copper-zinc-tin-sulfur film absorbed layer;
(5) on the CZTS film prepared, prepare the CdS resilient coating of 100nm with rf magnetron sputtering, power is 25W, subsequently the intrinsic ZnO of rf magnetron sputtering 50nm and the Al:ZnO of 400nm, and power is respectively 25W and 50W.Base vacuum is 5.0*10 -4pa, underlayer temperature is room temperature, and operating air pressure is 0.5pa;
(6) then at the Ni/Al electrode of Evaporation preparation 2 μm, finally by whole device 220 DEG C of process 20min in quick anneal oven.

Claims (5)

1. in a kind of vacuum legal system for the method for copper-zinc-tin-sulfur film solar cell, it is characterized in that, comprise the following steps:
Substrate cleans: by soda-lime glass successively by acetone, alcohol, deionized water ultrasonic cleaning, and dry up for subsequent use with nitrogen;
Put into by cleaned soda-lime glass in magnetic control sputtering system and be warming up to 100 ~ 150 DEG C of baking 30 ~ 60min, then the molybdenum back electrode film depositing 1 μm subsequently on soda-lime glass is warming up to 220 baking 30min;
The preparation of copper-zinc-tin-sulfur preformed layer: utilize magnetic control sputtering system, with ZnS, Sn and CuS for target carries out radio frequency sputtering according to the order of SLG/Mo/ZnS/CuS/Sn, the copper-zinc-tin-sulfur film preformed layer of deposition 700 ~ 1000nm;
The preparation of copper-zinc-tin-sulfur film absorbed layer: vulcanizing treatment of being annealed under nitrogen or argon by the copper-zinc-tin-sulfur film preformed layer prepared by step 3), obtains copper-zinc-tin-selefilm film absorbed layer after cooling naturally;
On the CZTS film prepared, the CdS resilient coating of 50-100nm is prepared, subsequently the intrinsic ZnO of magnetron sputtering 50-100nm and the Al:ZnO of 400nm with magnetron sputtering;
Then at the Ni/Al electrode of Evaporation preparation 2 μm, finally by whole device 220 DEG C of process 20min in quick anneal oven.
2. a kind of vacuum legal system as claimed in claim 1 is for the method for copper-zinc-tin-sulfur film solar cell, it is characterized in that initialization layer deposits according to the order of SLG/Mo/ZnS/CuS/Sn.
3. a kind of vacuum legal system as claimed in claim 1 is for the method for copper-zinc-tin-sulfur film solar cell, it is characterized in that Mo prepare complete be warming up to 220 DEG C baking 30min so that the diffusion of sodium ion.
4. a kind of vacuum legal system as claimed in claim 1 is for the method for copper-zinc-tin-sulfur film solar cell, it is characterized in that the described resilient coating CdS preparing 50-100nm with magnetron sputtering.
5. a kind of vacuum legal system as claimed in claim 1 is for the method for copper-zinc-tin-sulfur film solar cell, it is characterized in that described whole device after completing by its 200 DEG C of process 20min in quick anneal oven.
CN201510761249.9A 2015-11-10 2015-11-10 Method for preparing CZTS thin film solar cell based on full vacuum method Pending CN105304763A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106374012A (en) * 2016-11-11 2017-02-01 云南师范大学 Simple structure-based method for manufacturing Cu2ZnSnS4 thin film solar cell
CN106449812A (en) * 2016-11-15 2017-02-22 云南师范大学 Method sputtering tin target and copper sulfide target to prepare copper-tin-sulfur film and battery
CN106653898A (en) * 2016-11-04 2017-05-10 中利腾晖光伏科技有限公司 CZTS solar cell
CN112802924A (en) * 2021-01-13 2021-05-14 清华大学 Preparation method of copper-potassium-zinc-tin-sulfur absorption layer

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Publication number Priority date Publication date Assignee Title
CN101452969A (en) * 2008-12-29 2009-06-10 上海太阳能电池研究与发展中心 Copper zincium tin sulfur compound semiconductor thin-film solar cell and manufacturing method
CN101840942A (en) * 2010-05-19 2010-09-22 深圳丹邦投资集团有限公司 Thin-film solar cell and manufacturing method thereof
CN102569443A (en) * 2012-01-04 2012-07-11 范东华 Band gap tunable copper zinc tin sulfur semiconductor film and preparation method thereof
CN102610673A (en) * 2012-03-23 2012-07-25 华东师范大学 Copper zinc tin sulfur compound thin-film solar cell and preparation method thereof
CN103688368A (en) * 2011-07-19 2014-03-26 日本电气硝子株式会社 Glass base
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

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101452969A (en) * 2008-12-29 2009-06-10 上海太阳能电池研究与发展中心 Copper zincium tin sulfur compound semiconductor thin-film solar cell and manufacturing method
CN101840942A (en) * 2010-05-19 2010-09-22 深圳丹邦投资集团有限公司 Thin-film solar cell and manufacturing method thereof
CN103688368A (en) * 2011-07-19 2014-03-26 日本电气硝子株式会社 Glass base
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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

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106653898A (en) * 2016-11-04 2017-05-10 中利腾晖光伏科技有限公司 CZTS solar cell
CN106374012A (en) * 2016-11-11 2017-02-01 云南师范大学 Simple structure-based method for manufacturing Cu2ZnSnS4 thin film solar cell
CN106374012B (en) * 2016-11-11 2020-07-07 云南师范大学 Method for preparing copper-zinc-tin-sulfur thin film solar cell with simple structure
CN106449812A (en) * 2016-11-15 2017-02-22 云南师范大学 Method sputtering tin target and copper sulfide target to prepare copper-tin-sulfur film and battery
CN112802924A (en) * 2021-01-13 2021-05-14 清华大学 Preparation method of copper-potassium-zinc-tin-sulfur absorption layer
CN112802924B (en) * 2021-01-13 2023-01-13 清华大学 Preparation method of copper-potassium-zinc-tin-sulfur absorption layer

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Application publication date: 20160203