CN101101939A - A technology for making absorption layer of Cu2ZnSnS4 film solar battery - Google Patents
A technology for making absorption layer of Cu2ZnSnS4 film solar battery Download PDFInfo
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- CN101101939A CN101101939A CNA2007101195100A CN200710119510A CN101101939A CN 101101939 A CN101101939 A CN 101101939A CN A2007101195100 A CNA2007101195100 A CN A2007101195100A CN 200710119510 A CN200710119510 A CN 200710119510A CN 101101939 A CN101101939 A CN 101101939A
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Abstract
The invention is concerned with the technique about making the Cu2ZnSnS4 film solar battery absorptive layer. It belongs to the photovoltaic battery technique field. It mixes chemically pure grain as the Cu grain, the Zn grain and the Sn grain with the mol ratio Cu: Zn: Sn=1.6-1.7: 1: 1, presses into the embryo and seals up for keeping in the vacuum quartz tube, in order to react with the smelting alloy bullion. It also, includes the 6-15mum brittleness alloy thin strip made of the swing strip technique. Finally, it mixes the Cu-Zn-Sn alloy strips with the sulfur power with 1: 0.8-1: 1.2, puts into the planet ball mill for milling 48-96hours to generate the dark brown composite power van body, which can be coating onto the molybdenum foil basal or the natrium calcium glass basal, annealing in the sulfur steam with the hydrogen gas or the nitrogen gas after dried. The advantages of the invention are: it insures the stoichiometric ratio strictly by applying the smelting method that reduces loses of the elements; the thin alloy strip is good for generating the composite power van body even smaller and more easily forming even absorbing layer.
Description
Technical field
The invention belongs to the photovoltaic cell technical field, a kind of preparation Cu particularly is provided
2ZnSnS
4The technology of absorbing layer of 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 1.51eV, 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; someone adopts following method to prepare electricity conversion is 7.8% battery: the Cu of first hybrid nanoscale; the In powder is made the mixed-powder that contains CuIn alloy, Cu, In simple substance behind the wet-milling certain hour, then be coated in to carry out selenizing on certain matrix.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.
Summary of the invention
The object of the present invention is to provide a kind of preparation Cu
2ZnSnS
4The technology of absorbing layer of 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 mol ratio Cu: Zn: Sn=1.6～1.7: 1: 1 pure Cu grain, Zn grain, Sn grains of mixed chemical, be pressed into φ 10mm cylinder pressed compact, seal up for safekeeping in vacuum degree 10
-4～10
-2In the quartz ampoule of pa, make it to form alloy pig by induction melting.Adopt belt-rejecting technology can make the brittle alloy strip of thickness 6～15 μ m.Again Cu-Zn-Sn alloy band and S powder are formed the mixed-powder presoma of brownish black according to proportioning mixing and ball milling 48～96h of 1: 0.8～1: 1.2, the mixed-powder presoma is coated on molybdenum foil matrix or the soda-lime glass matrix, anneals in hydrogen and sulfur vapor or nitrogen and sulfur vapor atmosphere in dry back.
Belt-rejecting technology parameter of the present invention is: voltage 220V, melted Cu-Zn-Sn alloy pig is put into the quartz ampoule that gets rid of carrying device, and (the quartz ampoule lower end has Φ 2mm osculum, purpose is that the fused solution alloy is flowed out) in, induction heating makes its thawing flow out from osculum rapidly, drop on the copper roller surface with the 200-1000r/min rotational speed, because Quench and copper roller high speed rotating, alloy throws away with belt-like form.
Milling parameters of the present invention is: Cu-Zn-Sn alloy band places planetary ball mill ball milling 48～96h according to 1: 0.8～1: 1.2 proportioning mix sulphur powder, makes the mixed-powder presoma of brownish black.
Parameter and annealing of the present invention is: in hydrogen and sulfur vapor or nitrogen and sulfur vapor atmosphere, heating rate with 5～15 ℃/min is heated to 180～220 ℃, insulation 30～90min, heating rate with 1～10 ℃/min is heated to 350 ℃～400 ℃ insulation 30～180min again, cools to room temperature then with the furnace.
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 mixed-powder presoma 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, than other vulcanization process, is easier to form uniform absorbed layer.
Description of drawings
Fig. 1 is that mixed-powder presoma that the present invention makes is coated on the soda-lime glass matrix X-ray diffractogram that obtains behind 350 ℃ of annealing 120min under nitrogen and the sulfur vapor atmosphere.Abscissa is an angle of diffraction, and ordinate is a relative intensity.
Fig. 2 is that mixed-powder presoma that the present invention makes is coated on the soda-lime glass matrix X-ray diffractogram that obtains behind 400 ℃ of annealing 120min under nitrogen and the sulfur vapor atmosphere.Abscissa is an angle of diffraction, and ordinate is a relative intensity.
Fig. 3 is that mixed-powder presoma that the present invention makes is coated on the soda-lime glass matrix X-ray diffractogram that obtains behind 350 ℃ of annealing 120min under hydrogen and the sulfur vapor atmosphere.Abscissa is an angle of diffraction, and ordinate is a relative intensity.
Fig. 4 is that mixed-powder presoma that the present invention makes is coated on the soda-lime glass matrix X-ray diffractogram that obtains behind 400 ℃ of annealing 120min under hydrogen and the sulfur vapor atmosphere.Abscissa is an angle of diffraction, and ordinate is a relative intensity.
Embodiment
The melting of Cu-Zn-Sn alloy
(1) at first gets the metallic particles that atomic ratio is Cu: Zn: Sn=1.6～1.7: 1: 1, be pressed into pressed compact after evenly mixing.
(2) pressed compact is sealed in the quartz ampoule, owing in seal process, need to bleed, and vacuum degree need be controlled at 10
-4～10
-2Below the pa, therefore can add suitable getter.
(3) utilize the method for induction melting, voltage control, stops to heat when melt boiling back continues 5min at 220V, naturally cools to room temperature, obtains argenteous alloy.
The Cu-Zn-Sn alloy get rid of the band and Cu-Zn-Sn alloy band add the sulphur ball milling
(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 rotation, 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) with the proportioning mix sulphur powder of Cu-Zn-Sn alloy band, place planetary ball mill ball milling 48～96h, make the mixed-powder presoma of brownish black according to 1: 0.8～1: 1.2.
(3) the mixed-powder presoma is coated on molybdenum foil matrix or the soda-lime glass matrix, dry back is to be heated.
Example 1:Cu
2ZnSnS
4The nitrogen of absorbed layer and sulfur vapor atmosphere (350 ℃) preparation
(1) will be coated with the soda-lime glass matrix of mixed-powder presoma, place the controlled atmosphere tube type resistance furnace, logical nitrogen deaeration 15min.
(2) speed according to 10 ℃/min is warming up to 200 ℃, insulation 60min.
(3) speed according to 2 ℃/min is warming up to 350 ℃ by 200 ℃, is chilled to room temperature with stove behind the insulation 120min and takes out, and obtains blue-black absorbed layer.
Example 2:Cu
2ZnSnS
4The nitrogen of absorbed layer and sulfur vapor atmosphere (400 ℃) preparation
(1) will be coated with the soda-lime glass matrix of mixed-powder presoma, place the controlled atmosphere tube type resistance furnace, logical nitrogen deaeration 15min.
(2) speed according to 10 ℃/min is warming up to 200 ℃, insulation 60min.
(3) speed according to 2 ℃/min is warming up to 400 ℃ by 200 ℃, is chilled to room temperature with stove behind the insulation 120min and takes out, and obtains blue-black absorbed layer.
Example 3:Cu
2ZnSnS
4The hydrogen of absorbed layer and sulfur vapor atmosphere (350 ℃) preparation
(1) will be coated with the soda-lime glass matrix of mixed-powder presoma, and place the controlled atmosphere tube type resistance furnace, logical hydrogen deaeration is tested pure three times.
(2) speed according to 10 ℃/min is warming up to 200 ℃, insulation 60min.
(3) speed according to 2 ℃/min is warming up to 350 ℃ by 200 ℃, is chilled to room temperature with stove behind the insulation 120min and takes out, and obtains blue-black absorbed layer.
Example 4:Cu
2ZnSnS
4The hydrogen of absorbed layer and sulfur vapor atmosphere (400 ℃) preparation
(1) will be coated with the soda-lime glass matrix of mixed-powder presoma, and place the controlled atmosphere tube type resistance furnace, logical hydrogen deaeration is tested pure three times.
(2) speed according to 10 ℃/min is warming up to 200 ℃, insulation 60min.
(3) speed according to 2 ℃/min is warming up to 400 ℃ by 200 ℃, is chilled to room temperature with stove behind the insulation 120min and takes out, and obtains blue-black absorbed layer.
Example 5: the XRD of sample after the heat treatment
With the soda-lime glass matrix that is coated with the mixed-powder presoma under nitrogen and sulfur vapor atmosphere and hydrogen and the sulfur vapor atmosphere after 350 ℃ and 400 ℃ of heat treatment, Cu
2ZnSnS
4(112), (200), (220), (312) crystal face diffraction maximum is fairly obvious.After hydrogen and 350 ℃ of heat treatments of sulfur vapor atmosphere, obtained very pure Cu
2ZnSnS
4Phase.
Claims (3)
1, a kind of preparation Cu
2ZnSnS
4The technology of absorbing layer of thin film solar cell is characterized in that: according to stoichiometric proportion Cu: Zn: Sn=1.6～1.7: 1: 1 pure Cu grain, Zn grain, Sn grains of mixed chemical, be pressed into pressed compact, seal up for safekeeping in vacuum degree 10
-4～10
-2In the quartz ampoule of pa, make it to form alloy pig by induction melting; Adopt belt-rejecting technology to make the brittle alloy strip of thickness 6～15 μ m; Again Cu-Zn-Sn alloy band and sulphur powder were formed the mixed-powder presoma of brownish black in 48～96 hours according to 1: 0.8～1: 1.2 proportioning mixing and ball milling, the mixed-powder presoma is coated on molybdenum foil matrix or the soda-lime glass matrix, anneals in hydrogen and sulfur vapor or nitrogen and sulfur vapor atmosphere in dry back.
2, according to the described technology of claim 1, it is characterized in that: described belt-rejecting technology parameter is: voltage 220V, melted Cu-Zn-Sn alloy pig is put into the quartz ampoule that gets rid of carrying device, induction heating makes its thawing flow out from the quartz ampoule osculum, drop on the copper roller surface with the 200-1000r/min rotational speed, alloy throws away with belt-like form.
3, according to the described technology of claim 1, it is characterized in that: described parameter and annealing is: in hydrogen and sulfur vapor or nitrogen and sulfur vapor atmosphere, heating rate with 5～15 ℃/min is heated to 180～220 ℃, insulation 30～90min, heating rate with 1～10 ℃/min is heated to 350 ℃～400 ℃ insulation 30～180min again, cools to room temperature then with the furnace.
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|---|---|---|---|
| CNA2007101195100A CN101101939A (en) | 2007-07-25 | 2007-07-25 | A technology for making absorption layer of Cu2ZnSnS4 film solar battery |
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|---|---|---|---|
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101452969B (en) * | 2008-12-29 | 2010-06-02 | 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 |
| 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 |
| CN102150276A (en) * | 2008-09-30 | 2011-08-10 | 思阳公司 | Thin film sodium species barrier method and structure for CIGS based thin film photovoltaic cell |
| 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 |
| CN102593252A (en) * | 2012-02-23 | 2012-07-18 | 中国科学院合肥物质科学研究院 | Method for preparing copper-zinc-tin-sulfur light absorbing layer of film solar batter |
| CN101740722B (en) * | 2009-12-25 | 2013-01-02 | 中国科学院光电技术研究所 | Almost perfect absorbing structure for wide wave band |
| CN109022854A (en) * | 2018-07-25 | 2018-12-18 | 中国兵器科学研究院宁波分院 | A kind of foundry alloy melting method of amorphous soft magnetic material |
| CN111040763A (en) * | 2020-01-06 | 2020-04-21 | 兰州理工大学 | Synthesis method of yellow rare earth nitride fluorescent powder precursor |
-
2007
- 2007-07-25 CN CNA2007101195100A patent/CN101101939A/en active Pending
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102150276A (en) * | 2008-09-30 | 2011-08-10 | 思阳公司 | Thin film sodium species barrier method and structure for CIGS based thin film photovoltaic cell |
| CN102150276B (en) * | 2008-09-30 | 2013-07-31 | 思阳公司 | Thin film sodium species barrier method and structure for CIGS based thin film photovoltaic cell |
| CN101452969B (en) * | 2008-12-29 | 2010-06-02 | 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 |
| 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 |
| CN101659394B (en) * | 2009-09-17 | 2012-05-30 | 上海交通大学 | Preparation method of copper-zinc-tin-sulfur nano particles |
| CN101740722B (en) * | 2009-12-25 | 2013-01-02 | 中国科学院光电技术研究所 | Almost perfect absorbing structure for wide wave band |
| 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 |
| CN102492972A (en) * | 2011-12-12 | 2012-06-13 | 云南师范大学 | Electrochemical preparation process of Cu2ZnSnS4 film |
| CN102593252A (en) * | 2012-02-23 | 2012-07-18 | 中国科学院合肥物质科学研究院 | Method for preparing copper-zinc-tin-sulfur light absorbing layer of film solar batter |
| CN109022854A (en) * | 2018-07-25 | 2018-12-18 | 中国兵器科学研究院宁波分院 | A kind of foundry alloy melting method of amorphous soft magnetic material |
| CN111040763A (en) * | 2020-01-06 | 2020-04-21 | 兰州理工大学 | Synthesis method of yellow rare earth nitride fluorescent powder precursor |
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