CN101026198A - Process for preparing Cu2ZnSnS4 semiconductor thin film solar cell - Google Patents

Process for preparing Cu2ZnSnS4 semiconductor thin film solar cell Download PDF

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Publication number
CN101026198A
CN101026198A CNA2007100649958A CN200710064995A CN101026198A CN 101026198 A CN101026198 A CN 101026198A CN A2007100649958 A CNA2007100649958 A CN A2007100649958A CN 200710064995 A CN200710064995 A CN 200710064995A CN 101026198 A CN101026198 A CN 101026198A
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strip
film solar
solar cell
technology
alloy
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CN100511729C (en
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果世驹
王璐鹏
杨永刚
聂红波
王延来
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University of Science and Technology Beijing USTB
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University of Science and Technology Beijing USTB
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    • 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
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Abstract

This invention relates to a technology for preparing Cu2ZnSnS4 semiconductor film solar cells, which mixes grains of Cu, Zn and Sn in the chemical measured ratio Cu : Zn : Sn=1.6-1.7 : 1 : 1 to press it to a cylindrical pressed shape in the diameter of 10mm and height of 15mm to be packaged in a quartz tube in the vacuum degree of 10-4-10-3pa to form an alloy ingot by inducing melt, then manufactures a brittle alloy thin strip of 15-30mum thick and 5-8mm wide by a strip-throwing technology, then mixes the strip with sulfur powder to be milled for 48-96 h to form black slurry to be coated on a Mo matrix or a glass matrix then to be dried and heated in H2 or N2 atmosphere, which can avoid loss of elements and guarantee strict chemical measurement ratio.

Description

A kind of preparation Cu 2ZnSnS 4The technology of semiconductor thin-film solar cell
Technical field
The invention belongs to the photovoltaic cell technical field, a kind of preparation Cu particularly is provided 2ZnSnS 4The technology of semiconductor thin-film solar cell.
Background of invention
Cu 2ZnSnS 4It is a kind of semi-conducting material as absorbing layer of thin film solar cell.It has the energy gap of 1.5eV, 10 4Cm -1Absorption coefficient, very meet the desired condition of solar cell.The element that contains in the compound all in the earth's crust reserves abundant, do not contain the toxic metals Cd that contains among other solar cell materials such as the CdTe, do not contain CuInSe yet 2Used noble metal In is a kind of material very friendly to environment, and therefore suitable absorbed layer as solar cell has very wide application prospect.
The research institution of a lot of countries has all carried out the research to this compound, has obtained very big progress.Preparation technology commonly used at present comprises sulfuration vapor deposition precursor body method, magnetron sputtering method, mixing sputtering method etc.Its common point is it all is by preparing one deck Cu, Zn, Sn element someway in advance than certain alloy-layer, then vulcanize again, finally obtaining needed Cu 2ZnSnS 4Absorbed layer.Said method can be concise and to the point be divided into for two steps: the preparation of (1) alloy film; (2) sulfuration.
For with Cu 2ZnSnS 4Belong to the CuInSe of brass class solar energy materials 2, the someone adopts following method to prepare the battery that electricity conversion is: the Cu of first hybrid nanoscale, the In powder is made the mixed-powder that contains CuIn alloy, Cu, In simple substance powder behind the wet-milling certain hour, then be coated on certain matrix and vulcanize.Therefore for Cu 2ZnSnS 4, can adopt similar method to be prepared equally.And with respect to additive method, this method preparation cost is lower, is suitable for large-scale batch production.But this method does not break away from two steps of aforementioned preparation scheme, the i.e. preparation of alloy film and sulfuration equally.Flow process is comparatively complicated.
Summary of the invention
The object of the present invention is to provide a kind of preparation Cu 2ZnSnS 4The technology of semiconductor thin-film solar cell.At the pure Cu of preparing of success 2ZnSnS 4On the basis of absorbed layer, simplify processing step, made it more appropriate to actual production.
Formation of the present invention:
According to stoichiometric proportion Cu: Zn: Sn=1.6-1.7: the Cu grain of 1: 1 mixed chemical purity, Zn grain, Sn grain, be pressed into diameter 10mm, the cylinder pressed compact of high 15mm is sealed up for safekeeping in vacuum degree 10 -4~10 -3In the quartz ampoule of pa, make it to form alloy pig by induction melting.Adopt belt-rejecting technology to make thickness 15~30 μ m, the brittle alloy strip of width 5~8mm.Strip mix sulphur sphere of powder mill was formed the slurry of black in 48~96 hours, on molybdenum matrix or glass basis, annealed in hydrogen or nitrogen atmosphere 2~3 hours in dry back with slurry coating again.
The invention has the advantages that: adopt the method for molten alloy, form certain alloy phase earlier, and add method in the system one by one to, avoided the loss of element as much as possible, guaranteed strict stoichiometric proportion than other single elements.Get rid of the band back and form extremely thin fragile alloy band, be beneficial to the follow-up phase ball milling and go out the smaller slurry of component particle size.Alloy band mix sulphur powder fully mixes in mechanical milling process, forms uniform mixture, owing to contain the sulphur that meets stoichiometric proportion in the film after the coating,, be easier to form uniform absorbed layer than other vulcanization process, and need not sulphur atmosphere, the simple use in the operation.
Description of drawings
Fig. 1 is that the mixed slurry that the present invention makes is coated on the electro-conductive glass matrix at N 2The X-ray diffractogram that obtains after the following 350 ℃ of heat treatments of atmosphere.Abscissa is an angle of diffraction, and ordinate is a relative intensity.
Fig. 2 is that the mixed slurry that the present invention makes is coated on the electro-conductive glass matrix at N 2The X-ray diffractogram that obtains after the following 400 ℃ of heat treatments of atmosphere.Abscissa is an angle of diffraction, and ordinate is a relative intensity.
Fig. 3 is that the mixed slurry that the present invention makes is coated on the electro-conductive glass matrix at H 2The X-ray diffractogram that obtains after the following 350 ℃ of heat treatments of atmosphere.Abscissa is an angle of diffraction, and ordinate is a relative intensity.
Fig. 4 is that the mixed slurry that the present invention makes is coated on the electro-conductive glass matrix at H 2The X-ray diffractogram that obtains after the following 400 ℃ of heat treatments of atmosphere.Abscissa is an angle of diffraction, and ordinate is a relative intensity.
Embodiment
The melting of CuZnSn presoma alloy
(1) at first getting atomic ratio is Cu: Zn: Sn=1.6-1.7: 1: 1 metallic particles, be pressed into the cylinder pressed compact of Ψ 10mm after the mixing, and because tin is softer, therefore be easy to compacting, pressure does not need very big.
(2) pressed compact is sealed in the quartz ampoule, owing in seal process, need to bleed, and vacuum degree need be controlled at 1 * 10 -3Below the pa, therefore can add suitable getter.
(3) utilize the method for induction melting, voltage control is at 220V, when melt boiling back a moment, stops to heat, and naturally cools to room temperature, obtains argenteous alloy.
The dribbling of getting rid of of CuZnSn alloy is ground
(1) (the quartz ampoule lower end has osculum melted alloy pig to be placed the quartz ampoule that gets rid of carrying device, purpose is that the fused solution alloy is flowed out) in, induction heating makes its thawing flow out from osculum, be dropped on the copper roller of high speed rotating, because Quench and high speed rotating, alloy throws away with belt-like form, because the more crisp and thinner thickness of metal tape that throws away, can rupture, be easy to follow-up ball milling.
(2) will get rid of alloy band behind the band with alloy: the proportioning mix sulphur powder of sulphur powder=10: 3, and after the mixed with 10 gram material, 23 gram absolute ethyl alcohols, placed the planetary ball mill ball milling 48-96 hour, make mixed slurry.
(3) mixed slurry is coated on the molybdenum matrix (perhaps electro-conductive glass), dry back is to be heated.
Example 1:Cu 2ZnSnS 4The N of absorbed layer 2Atmosphere (350 ℃) preparation
(1) will scribble the molybdenum sheet (or electro-conductive glass) of slurry, place resistance furnace, logical N 2Deaeration 15 minutes, back 50 ℃ of preheatings ten minutes.
(2) speed according to 10 ℃/min is warming up to 200 ℃, is incubated one hour.
(3) speed according to 2 ℃/min is warming up to 350 ℃ by 200 ℃, is incubated after two hours and is chilled to the room temperature taking-up with stove, obtains blue-black absorbed layer.
Example 2:Cu 2ZnSnS 4The N of absorbed layer 2Atmosphere (400 ℃) preparation
(1) will scribble the molybdenum sheet (or electro-conductive glass) of slurry, place resistance furnace, logical N 2Deaeration 15 minutes, 50 ℃ of preheatings are ten minutes then.
(2) speed according to 10 ℃/min is warming up to 200 ℃, is incubated one hour.
(3) speed according to 2 ℃/min is warming up to 400 ℃ by 200 ℃, is incubated after two hours and is chilled to the room temperature taking-up with stove, obtains blue-black absorbed layer.
Example 3:Cu 2ZnSnS 4The H of absorbed layer 2Atmosphere (350 ℃) preparation
(1) will scribble the molybdenum sheet (or electro-conductive glass) of slurry, place resistance furnace, logical H 2Deaeration is tested pure three times, and 50 ℃ of preheatings are ten minutes then.
(2) speed according to 10 ℃/min is warming up to 200 ℃, is incubated one hour.
(3) speed according to 2 ℃/min is warming up to 350 ℃ by 200 ℃, is incubated after two hours and is chilled to the room temperature taking-up with stove, obtains blue-black absorbed layer.
Example 4:Cu 2ZnSnS 4The H of absorbed layer 2Atmosphere (400 ℃) preparation
(1) will scribble the molybdenum sheet (or electro-conductive glass) of slurry, place resistance furnace, logical H 2Deaeration is tested pure three times, and 50 ℃ of preheatings are ten minutes then.
(2) speed according to 10 ℃/min is warming up to 200 ℃, is incubated one hour.
(3) speed according to 2 ℃/min is warming up to 400 ℃ by 200 ℃, is incubated after two hours and is chilled to the room temperature taking-up with stove, obtains blue-black absorbed layer.
Example 5: the XRD of sample after the heat treatment
Be coated on slurry on the electro-conductive glass matrix at N 2Atmosphere and H 2Under the atmosphere after 350 ℃ and 400 ℃ of annealing, Cu 2ZnSnS 4(112), (200), (220), (312) crystal face diffraction maximum is fairly obvious.At H 2Obtained very pure Cu after 350 ℃ of heat treatments of atmosphere 2ZnSnS 4Phase.

Claims (1)

1, a kind of preparation Cu 2ZnSnS 4The technology of semiconductor thin-film solar cell is characterized in that: according to stoichiometric proportion Cu: Zn: Sn=1.6-1.7: the Cu grain of 1: 1 mixed chemical purity, Zn grain, Sn grain, be pressed into diameter 10mm, and the cylinder pressed compact of high 15mm is sealed up for safekeeping in vacuum degree 10 -4~10 -3In the quartz ampoule of pa, make it to form alloy pig by induction melting; Adopt belt-rejecting technology to make thickness 15~30 μ m, the brittle alloy strip of width 5~8mm; Strip mix sulphur sphere of powder mill was formed the slurry of black in 48~96 hours, on molybdenum matrix or glass basis, annealed in hydrogen or nitrogen atmosphere 2~3 hours in dry back with slurry coating again.
CNB2007100649958A 2007-03-30 2007-03-30 Process for preparing Cu*ZnSnS* semiconductor thin film solar cell Expired - Fee Related CN100511729C (en)

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Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100466305C (en) * 2007-11-22 2009-03-04 北京科技大学 Method for producing copper-indium-selenium thin-film solar cell wealthy-indium optical absorption layer
CN101771106A (en) * 2010-03-05 2010-07-07 中国科学院上海硅酸盐研究所 Method for preparing copper-zinc-cadmium-tin-sulfur-selenium thin film solar cell light absorption layer
WO2010094779A1 (en) 2009-02-19 2010-08-26 Carl Von Ossietzky Universität Oldenburg Method for wet chemical synthesizing of dicopper-zinc-tin-tetrasulfide and/or -tetraselenide (czts), a method for producing a semiconductor layer made of czts and a colloidal suspension
CN101645473B (en) * 2009-09-09 2011-01-05 北京有色金属研究总院 Preparation method of selenide material for absorbing layer of thin film solar cell
CN102315333A (en) * 2011-10-13 2012-01-11 南京大学 Preparation of ZnSnS film and ZnSnS/SnS heterojunction, and application of solar cells
CN102344166A (en) * 2011-07-04 2012-02-08 东华大学 Preparation method for Cu2ZnSnS4 solar energy absorption layer material
CN101659394B (en) * 2009-09-17 2012-05-30 上海交通大学 Preparation method of copper-zinc-tin-sulfur nano particles
CN102492972A (en) * 2011-12-12 2012-06-13 云南师范大学 Electrochemical preparation process of Cu2ZnSnS4 film
US8470287B2 (en) 2009-11-25 2013-06-25 E I Du Pont De Nemours And Company Preparation of copper zinc tin sulfide
US8480944B2 (en) 2010-12-09 2013-07-09 E I Du Pont De Nemours And Company Quaternary chalcogenide wafers
US8709657B2 (en) 2010-12-09 2014-04-29 E I Du Pont De Nemours And Company Quaternary chalcogenide wafers
US8828767B2 (en) 2011-12-30 2014-09-09 Industrial Technology Research Institute Fabriation method for light absorption layer of solar cell
CN104245573A (en) * 2012-02-27 2014-12-24 日本麦可罗尼克斯股份有限公司 Method for fabricating alloy for czts solar cell
CN104556207A (en) * 2015-01-12 2015-04-29 东华大学 Preparation method of p-type Cu2ZnSnS4 nano rod
CN109956504A (en) * 2019-03-29 2019-07-02 昆明理工大学 A kind of preparation method that cuprum-nickel-stannum sulphur is nanocrystalline

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100466305C (en) * 2007-11-22 2009-03-04 北京科技大学 Method for producing copper-indium-selenium thin-film solar cell wealthy-indium optical absorption layer
WO2010094779A1 (en) 2009-02-19 2010-08-26 Carl Von Ossietzky Universität Oldenburg Method for wet chemical synthesizing of dicopper-zinc-tin-tetrasulfide and/or -tetraselenide (czts), a method for producing a semiconductor layer made of czts and a colloidal suspension
DE102009009550A1 (en) 2009-02-19 2010-09-02 Carl Von Ossietzky Universität Oldenburg A process for wet chemically synthesizing dicopper-zinc-tin-tetrasulfide and / or tetraselenide (CZTS), a process for producing a semiconductor layer from CZTS and a colloidal suspension
CN101645473B (en) * 2009-09-09 2011-01-05 北京有色金属研究总院 Preparation method of selenide material for absorbing layer of thin film solar cell
CN101659394B (en) * 2009-09-17 2012-05-30 上海交通大学 Preparation method of copper-zinc-tin-sulfur nano particles
US8470287B2 (en) 2009-11-25 2013-06-25 E I Du Pont De Nemours And Company Preparation of copper zinc tin sulfide
CN101771106A (en) * 2010-03-05 2010-07-07 中国科学院上海硅酸盐研究所 Method for preparing copper-zinc-cadmium-tin-sulfur-selenium thin film solar cell light absorption layer
US8709657B2 (en) 2010-12-09 2014-04-29 E I Du Pont De Nemours And Company Quaternary chalcogenide wafers
US8480944B2 (en) 2010-12-09 2013-07-09 E I Du Pont De Nemours And Company Quaternary chalcogenide wafers
CN102344166B (en) * 2011-07-04 2013-06-05 东华大学 Preparation method for Cu2ZnSnS4 solar energy absorption layer material
CN102344166A (en) * 2011-07-04 2012-02-08 东华大学 Preparation method for Cu2ZnSnS4 solar energy absorption layer material
CN102315333A (en) * 2011-10-13 2012-01-11 南京大学 Preparation of ZnSnS film and ZnSnS/SnS heterojunction, and application of solar cells
CN102492972A (en) * 2011-12-12 2012-06-13 云南师范大学 Electrochemical preparation process of Cu2ZnSnS4 film
US8828767B2 (en) 2011-12-30 2014-09-09 Industrial Technology Research Institute Fabriation method for light absorption layer of solar cell
CN104245573A (en) * 2012-02-27 2014-12-24 日本麦可罗尼克斯股份有限公司 Method for fabricating alloy for czts solar cell
CN104245573B (en) * 2012-02-27 2016-06-08 日本麦可罗尼克斯股份有限公司 The manufacture method of CZTS system alloy used for solar batteries
CN104556207A (en) * 2015-01-12 2015-04-29 东华大学 Preparation method of p-type Cu2ZnSnS4 nano rod
CN104556207B (en) * 2015-01-12 2016-08-24 东华大学 A kind of p-type Cu2znSnS4the preparation method of nanometer rods
CN109956504A (en) * 2019-03-29 2019-07-02 昆明理工大学 A kind of preparation method that cuprum-nickel-stannum sulphur is nanocrystalline

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