CN102496656A - Manufacturing method for copper-zinc-tin-sulfur photovoltaic film - Google Patents
Manufacturing method for copper-zinc-tin-sulfur photovoltaic film Download PDFInfo
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- CN102496656A CN102496656A CN2011104355095A CN201110435509A CN102496656A CN 102496656 A CN102496656 A CN 102496656A CN 2011104355095 A CN2011104355095 A CN 2011104355095A CN 201110435509 A CN201110435509 A CN 201110435509A CN 102496656 A CN102496656 A CN 102496656A
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- zinc
- tin
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- copper foil
- sulfur
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- 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 discloses a manufacturing method for a copper-zinc-tin-sulfur photovoltaic film. The manufacturing method comprises the following steps of: carrying out oil removing, water washing and acid washing treatment on the surface of a copper foil substrate; depositing metal zinc on the surface of the copper foil substrate by adopting one of chemical plating, electroplating, sputtering, evaporating, molecular-beam epitaxy and hot dipping methods; and carrying out sulfur tinning treatment on a zinc coating in a protective atmosphere. According to the manufacturing method disclosed by the invention, the metal zinc is directly deposited on the pretreated copper foil substrate and then is subjected to sulfur tinning treatment to obtain a copper-zinc-tin-sulfur film. The manufacturing method disclosed by the invention has the advantages of low cost, short process flow, favorable repeatability, easy large-scale winding type production, suitability for component control and large-area growth of the film and the like. The metal zinc is directly deposited on a copper substrate; a copper foil has three functions of being used as a flexible mechanical carrier of a solar battery device, also providing a copper source of the copper-zinc-tin-sulfur film and being used as a back electrode of the solar battery. The manufactured film has favorable component controllability and uniformity as well as excellent crystallization quality and property.
Description
Technical field
The invention discloses a kind of copper-zinc-tin-sulfur (Cu
2ZnSnS
4) preparation method of photovoltaic film, be used to prepare the compound semiconductor film of thin film solar cell light absorption layer, belong to the photoelectric material technical field of new energies.
Background technology
Solar energy is inexhaustible, nexhaustible regenerative resource.Utilize in the mode the various of solar energy, solar cell is field with fastest developing speed, most active and that attract most attention, is expected to become the effective way of serious day by day energy crisis of solution and problem of environmental pollution.
Present widely used solar module is main with monocrystalline silicon and polysilicon; And thin film solar cell has high transformation efficiency of silicon solar cell and advantages of being cheap concurrently; Be the direct band gap material simultaneously, the absorption coefficient of light is high, is a kind of more preferred solar cell material.In numerous thin film solar cells, (chemical formula is CuIn with chalcogen compound CIGS with yellow copper structure
1-xGa
xSe
2, x=0～1) as the thin film solar cell of light absorbing zone (being called for short the CIGS solar cell) because characteristics such as its transformation efficiency the highest (having reached 20.3%), good stability, preparation be simple are paid close attention to by people most, become the focus and emphasis of research.
Yet the indium in the copper-indium-gallium-selenium compound, gallium and selenium are dissipated metals, cost an arm and a leg and reserves limited, their abundance in the earth's crust are seen table 1.The new type light absorbing layer film material that has cheap and environmental protection characteristics from reducing cost, economize on resources and protect the environment equal angles, seeking substitutes CIGS has become the important topic of pendulum in face of ours.
The abundance of several kinds of elements of table 1 in the earth's crust
Research at present at most, to be considered to the most potential substitution material be the copper-zinc-tin-sulfur (Cu that substitutes 1 phosphide atom with 0.5 zinc atom and 0.5 tin atom
2ZnSnS
4, be abbreviated as CZTS), reached 10.7% with its highest transformation efficiency of solar cell of processing.
Yet the method for preparing copper-zinc-tin-sulfur film of bibliographical information mainly comprises coevaporation and these two kinds of technology paths of preformed layer after cure at present.Wherein the film quality of coevaporation preparation is higher, but should the maximum development bottleneck of technology is that the uniformity of film of large tracts of land coevaporation preparation is poor, is difficult to obtain practical application.The preformed layer after cure is to adopt methods such as sputter, electro-deposition to prepare copper, zinc, tin ternary alloy three-partalloy preformed layer earlier; And then preformed layer heat-treated (sulfuration); Obtain copper-zinc-tin-sulfur film; This method is easy to realize the large-area preparation of film, but has problems such as preformed layer Composition Control difficulty, complex process, long flow path and reappearance be bad.
Summary of the invention
The object of the present invention is to provide that a kind of cost is low, the copper-zinc-tin-sulfur (Cu of advantage such as technological process weak point, favorable reproducibility, the Composition Control that is easy to extensive takeup type production and suitable film and large area deposition
2ZnSnS
4) preparation method of photovoltaic film.
The preparation method of a kind of copper-zinc-tin-sulfur photovoltaic film of the present invention may further comprise the steps:
The first step: copper foil base material surface treatment
With copper foil base material surface degreasing, washing, pickling;
Second step: copper foil base material surface deposition metallic zinc
Handle the copper foil base material surface deposition metallic zinc obtain in the first step, said deposition adopts a kind of in chemical plating, plating, sputter, vapor deposition, molecular beam epitaxy, the hot dip coating method;
The 3rd step: the sulphur tin heat-transmission of zinc coat is handled
There is the copper foil base material of metallic zinc to place protective atmosphere the surface deposition of the second step gained, is heated to 200～800 ℃,, zinc coat is carried out the heat-transmission of sulphur tin handle through carrier gas input sulphur source and Xi Yuan.
Among the preparation method of a kind of copper-zinc-tin-sulfur photovoltaic film of the present invention; Oil removing comprises that alkali lye oil removing and degreaser clean two steps in the said copper foil base material surface treatment; At first said copper foil base material being placed temperature is that 10～200 ℃ alkali lye soaked 1～300 minute, and placing temperature then is 10～100 ℃ degreaser sonic oscillation 1～300 minute; Said alkali lye is selected from least a in NaOH, sodium carbonate, sodium acid carbonate or the tertiary sodium phosphate; Said degreaser is selected from least a in liquid detergent, degreasing agent, ethanol or the acetone.
Among the preparation method of a kind of copper-zinc-tin-sulfur photovoltaic film of the present invention, said washing is to be 10～100 ℃ deionized water for ultrasonic vibration 1～300 minute with place temperature through the copper foil base material after the oil removing.
Among the preparation method of a kind of copper-zinc-tin-sulfur photovoltaic film of the present invention, said pickling is that the copper foil base material through washing is placed temperature is that 10～100 ℃, concentration are the acid solution sonic oscillation 1～100 minute of 0.1～3mol/L; Said acid is selected from least a in hydrochloric acid, sulfuric acid, acetic acid or the nitric acid.
Among the preparation method of a kind of copper-zinc-tin-sulfur photovoltaic film of the present invention, said sonic oscillation frequency is 20k～100kHz; Power is 50～1200W.
Among the preparation method of a kind of copper-zinc-tin-sulfur photovoltaic film of the present invention, tinization, first tin after cure, sulfuration and tinization were simultaneously ongoing a kind of after the mode that the sulphur tin heat-transmission of said zinc coat is handled was selected from and vulcanizes earlier.
Among the preparation method of a kind of copper-zinc-tin-sulfur photovoltaic film of the present invention, in the process that the sulphur tin heat-transmission of said zinc coat is handled, the sulphur source that sulfuration is adopted is at least a in hydrogen sulfide, elemental sulfur steam, stannic disulfide or the artificial gold, and the time is 0.1～4h.
Among the preparation method of a kind of copper-zinc-tin-sulfur photovoltaic film of the present invention, in the process that the sulphur tin heat-transmission of said zinc coat is handled, the Xi Yuan of tin employing is selected from least a in simple substance tin steam, stannic disulfide steam or the artificial gold steam, and the time is 0.1～4h.
Among the preparation method of a kind of copper-zinc-tin-sulfur photovoltaic film of the present invention, when said sulfuration and tinization were carried out simultaneously, the time was 0.1～4h.
Among the preparation method of a kind of copper-zinc-tin-sulfur photovoltaic film of the present invention, said sulphur source and Xi Yuan be through carrier gas transportation, and said carrier gas is selected from least a in argon gas, nitrogen, the neon, and flow is 1～1000sccm.
The preparation method of copper-zinc-tin-sulfur photovoltaic film disclosed by the invention compared with prior art has following key character:
1, the thin-film technique of the present invention's employing is with low cost, and flow process is simple, is easy to scale.Compare with the preformed layer after cure method (promptly adopting copper, zinc, the tin ternary alloy three-partalloy preformed layer of preparations such as electro-deposition or sputter to vulcanize) of document widespread reports, controllable component property is better, and has shortened technological process, can significantly reduce the technology cost.
2, direct plated metal zinc on Copper Foil, Copper Foil is as the flexible mechanical carrier of flexible thin-film solar cell device, and also having played simultaneously provides copper source in the copper-zinc-tin-sulfur film and as the triple role of solar cell back electrode.
The preparation method of a kind of copper-zinc-tin-sulfur photovoltaic film that 3, the present invention relates to; Adopt the mode of sulfuration and tinization to handle zinc-plated copper strips; Because copper had both been made base material, had participated in the reaction of formation of film again, this helps forming the good copper-zinc-tin-sulfur film of strong adhesion, optics and electrical properties.
In sum, the present invention is plated metal zinc on copper foil base material after the preliminary treatment directly, carries out the processing of sulphur tin again to obtain copper-zinc-tin-sulfur film.Advantages such as this method has that cost is low, technological process weak point, favorable reproducibility, the Composition Control that is easy to extensive takeup type production and suitable film and large area deposition.Direct plated metal zinc in the copper substrate, Copper Foil is as the flexible mechanical carrier of solar cell device, and also having played simultaneously provides copper source in the copper-zinc-tin-sulfur film and as the triple role of solar cell back electrode.Prepared film has good controllable component property, uniformity, and superior crystalline quality and character.
Embodiment
Embodiment 1
The first step: copper foil base material surface treatment
With copper foil base material surface degreasing, washing, pickling;
1. the high temperature alkaline solution oil removal treatment of copper foil base material
15g NaOH and 200ml deionized water are joined in the 500ml beaker, and the Copper Foil that will be of a size of 60 * 30 * 1mm places above-mentioned solution, and sonic oscillation cleaned 1 minute under 200 ℃ of high temperature.Copper Foil is placed the 500ml beaker that fills the 50ml ethanolic solution, cleaned 290 minutes at 12 ℃ of following sonic oscillations.
2. the sonic oscillation of copper foil base material washing
Above-mentioned Copper Foil is placed the 1000ml beaker that fills the 200ml deionized water, 55 ℃ of following cleaned by ultrasonic vibration 120 minutes.
3. copper foil base material the sonic oscillation pickling
In filling the 1000ml beaker of 150ml deionized water, add the 5ml mass fraction and be 38% concentrated hydrochloric acid and be mixed with acid solution, Copper Foil is placed in one, 11 ℃ of following cleaned by ultrasonic vibration 300 minutes.1.-3. said sonic oscillation frequency of step is 50kHz; Power is 700W.
Second step: copper foil base material surface deposition metallic zinc
Copper Foil oven dry with cleaned connects positive source with coated metal zinc as anode, to be connect power cathode by the copper facing paper tinsel as negative electrode, is that main salting liquid system is electroplated with zinc oxide, NaOH and an amount of additive.Said zincate galvanizing operation, its technology is conventionally known to one of skill in the art.The present invention does not have specific (special) requirements to the method for zinc-plated processing, generally speaking, can obtain the zinc coating of even compact.
The 3rd step: the sulphur tin heat-transmission of zinc coat is handled
Above-mentioned ormolu coating is cleaned oven dry place the self-control consersion unit, add an amount of SnS
2Powder in evaporating dish, SnS
2Powder will decompose under heating condition, and sulphur source and Xi Yuan can be provided simultaneously.Open mechanical pump reactor is vacuumized, feed inert gas N again
2Fully drain the O in the device
2
Start reaction unit, heat temperature raising to 750 ℃ is kept this heat-treated 2h, continues to feed N in the heat treatment process
2, Ventilation Rate is 80sccm, and absorbs the poisonous tail gas of processing.Reaction finishes, and the film of said method preparation has good component uniformity and high crystalline quality, and superior optics, electrical properties, and it is 0.96% thin film solar cell device that the copper-zinc-tin-sulfur material of preparation has made transformation efficiency as light absorbing zone.
Embodiment 2
This embodiment explains the preparation method of a kind of copper-zinc-tin-sulfur photovoltaic film provided by the invention.
The first step: copper foil base material surface treatment
With copper foil base material surface degreasing, washing, pickling;
1. the high temperature alkaline solution oil removal treatment of copper foil base material
35g sodium carbonate and 200ml deionized water are joined in the 500ml beaker, and the Copper Foil that will be of a size of 70 * 35 * 1mm places above-mentioned solution, and sonic oscillation cleaned 120 minutes under 105 ℃ of high temperature.Copper Foil is placed the 500ml beaker that fills an amount of degreaser, cleaned 90 seconds at 100 ℃ of following sonic oscillations.
2. sonic oscillation washing
Above-mentioned Copper Foil is placed the 1000ml beaker that fills the 240ml deionized water, 95 ℃ of following cleaned by ultrasonic vibration 1 minute.
3. the sonic oscillation pickling of copper foil base material
In filling the 1000ml beaker of 200ml deionized water, add the 3ml mass fraction and be 98% the concentrated sulfuric acid and be mixed with acid solution, Copper Foil is placed in one, 67 ℃ of following cleaned by ultrasonic vibration 150 minutes.1.-3. said sonic oscillation frequency of step is 22kHz; Power is 60W.
Second step: copper foil base material surface deposition metallic zinc
With cleaned Copper Foil oven dry, adopt magnetron sputtering apparatus plated metal zinc, the technology of magnetron sputtering deposition metal is conventionally known to one of skill in the art.The present invention does not have specific (special) requirements to the processing method of magnetron sputtering metallic zinc, generally speaking, can obtain the zinc coating of even compact.
The 3rd step: the sulphur tin heat-transmission of zinc coat is handled
1. heat of vulcanization is handled
Above-mentioned ormolu is cleaned oven dry place the self-control consersion unit, open mechanical pump reactor is vacuumized, feed inert gas Ar again and fully drain the O in the device
2Start reaction unit, heat temperature raising to 250 ℃ is kept this heat-treated 0.5h, continues to feed H in the heat treatment process
2S+N
2, Ventilation Rate is 950sccm, and absorbs the poisonous tail gas of processing.
2. the tin heat-transmission is handled
Ormolu after the above-mentioned vulcanizing treatment is placed the self-control consersion unit, add an amount of artificial gold powder, open mechanical pump reactor is vacuumized, feed N again at evaporating dish
2Fully drain sulphur atmosphere remaining in the device.Start reaction unit, heat temperature raising to 650 ℃ is kept this heat-treated 2.5h, and absorbs and handle poisonous tail gas.
Reaction finishes, and the film of said method preparation has good component uniformity and high crystalline quality, and superior optics, electrical properties.It is 1.27% thin film solar cell device that the copper-zinc-tin-sulfur material of preparation has made transformation efficiency as light absorbing zone.
Embodiment 3
This embodiment explains the preparation method of a kind of copper-zinc-tin-sulfur photovoltaic film provided by the invention.
The first step: copper foil base material surface treatment
With copper foil base material surface degreasing, washing, pickling;
1. the high temperature alkaline solution oil removal treatment of copper foil base material
24g tertiary sodium phosphate and 220ml deionized water are joined in the 500ml beaker, and the Copper Foil that will be of a size of 84 * 27 * 1mm places above-mentioned solution, and sonic oscillation cleaned 288 minutes under 15 ℃ of high temperature.Copper Foil is placed the 500ml beaker that fills 20ml acetone, 25ml ethanol, cleaned 150 minutes at 50 ℃ of following sonic oscillations.
2. the sonic oscillation of copper foil base material washing
Above-mentioned Copper Foil is placed the 1000ml beaker that fills the 350ml deionized water, 13 ℃ of following cleaned by ultrasonic vibration 295 minutes.
3. sonic oscillation pickling
In filling the 1000ml beaker of 320ml deionized water, add the 5ml mass fraction and be 98% the concentrated sulfuric acid, 20ml acetic acid and be mixed with acid solution, Copper Foil is placed in one, 97 ℃ of following cleaned by ultrasonic vibration 2 minutes.1.-3. said sonic oscillation frequency of step is 90kHz; Power is 1150W.
Second step: copper foil base material surface deposition metallic zinc
With cleaned Copper Foil oven dry, adopt resistance-type evaporation coating machine plated metal zinc on Copper Foil, the technology of vacuum thermal evaporation method plated metal is conventionally known to one of skill in the art.The present invention does not have specific (special) requirements to the processing method of plated metal zinc, generally speaking, can obtain the zinc coating of even compact.
The 3rd step: the sulphur tin heat-transmission of zinc coat is handled
1. tin ormolu
Above-mentioned ormolu is cleaned oven dry place the self-control consersion unit, add an amount of tin ash powder in evaporating dish, powder decomposes under heating condition and Xi Yuan and sulphur source is provided.Open mechanical pump reactor is vacuumized, feed inert gas Ar again and fully drain the O in the device
2
Start reaction unit, heat temperature raising to 210 ℃ is kept this heat-treated 3.9h, continues to feed N in the heat treatment process
2, Ventilation Rate is 395sccm, and absorbs the poisonous tail gas of processing.
2. heat of vulcanization is handled
Ormolu after the above-mentioned tin processing is placed the self-control consersion unit, remove stannic disulfide powder remaining in the evaporating dish, and add an amount of sulphur powder.Open mechanical pump reactor is vacuumized, feed N again
2Fully drain tail gas remaining in the device.Start reaction unit, heat temperature raising to 780 ℃ is kept this heat-treated 0.2h, continues to feed N in the heat treatment process
2And absorbing the poisonous tail gas of processing, Ventilation Rate is 12sccm.
Reaction finishes, and the film of said method preparation has good component uniformity and high crystalline quality, and superior optics, electrical properties.It is 0.74% thin film solar cell device that prepared copper-zinc-tin-sulfur material has made transformation efficiency as light absorbing zone.
Claims (10)
1. the preparation method of a copper-zinc-tin-sulfur photovoltaic film may further comprise the steps:
The first step: copper foil base material surface treatment
With copper foil base material surface degreasing, washing, pickling;
Second step: copper foil base material surface deposition metallic zinc
Handle the copper foil base material surface deposition metallic zinc obtain in the first step, said deposition adopts a kind of in chemical plating, plating, sputter, vapor deposition, molecular beam epitaxy, the hot dip coating method;
The 3rd step: the sulphur tin heat-transmission of zinc coat is handled
There is the copper foil base material of metallic zinc to place protective atmosphere the surface deposition of the second step gained, is heated to 200～800 ℃,, zinc coat is carried out the heat-transmission of sulphur tin handle through carrier gas input sulphur source and Xi Yuan.
2. the preparation method of a kind of copper-zinc-tin-sulfur photovoltaic film according to claim 1; It is characterized in that: oil removing comprises that alkali lye oil removing and degreaser clean two steps in the said copper foil base material surface treatment; At first said copper foil base material being placed temperature is that 10～200 ℃ alkali lye soaked 1～300 minute, and placing temperature then is 10～100 ℃ degreaser sonic oscillation 1～300 minute; Said alkali lye is selected from least a in NaOH, sodium carbonate, sodium acid carbonate or the tertiary sodium phosphate; Said degreaser is selected from least a in liquid detergent, degreasing agent, ethanol or the acetone.
3. the preparation method of a kind of copper-zinc-tin-sulfur photovoltaic film according to claim 2 is characterized in that: said washing is to be 10～100 ℃ deionized water for ultrasonic vibration 1～300 minute with place temperature through the copper foil base material after the oil removing.
4. the preparation method of a kind of copper-zinc-tin-sulfur photovoltaic film according to claim 3 is characterized in that: said pickling is that the copper foil base material through washing is placed temperature is that 10～100 ℃, concentration are the acid solution sonic oscillation 1～100 minute of 0.1～3mol/L; Said acid is selected from least a in hydrochloric acid, sulfuric acid, acetic acid or the nitric acid.
5. according to the preparation method of any described a kind of copper-zinc-tin-sulfur photovoltaic film of claim 2～4, it is characterized in that: said sonic oscillation frequency is 20k～100kHz; Power is 50～1200W.
6. the preparation method of a kind of copper-zinc-tin-sulfur photovoltaic film according to claim 4 is characterized in that: tinization, first tin after cure, sulfuration and tinization were simultaneously ongoing a kind of after the mode that the sulphur tin heat-transmission of said zinc coat is handled was selected from and vulcanizes earlier.
7. the preparation method of a kind of copper-zinc-tin-sulfur photovoltaic film according to claim 6; It is characterized in that: in the process that the sulphur tin heat-transmission of said zinc coat is handled; The sulfuration sulphur source of being adopted is at least a in hydrogen sulfide, elemental sulfur steam, stannic disulfide or the artificial gold, and the time is 0.1～4h.
8. the preparation method of a kind of copper-zinc-tin-sulfur photovoltaic film according to claim 6; It is characterized in that: in the process that the sulphur tin heat-transmission of said zinc coat is handled; The Xi Yuan that tinization adopted is selected from least a in simple substance tin steam, stannic disulfide steam or the artificial gold steam, and the time is 0.1～4h.
9. the preparation method of a kind of copper-zinc-tin-sulfur photovoltaic film according to claim 6 is characterized in that: when said sulfuration and tinization were carried out simultaneously, the time was 0.1～4h.
10. according to the preparation method of any described a kind of copper-zinc-tin-sulfur photovoltaic film of claim 7-9; It is characterized in that: said sulphur source and Xi Yuan transport through carrier gas; Said carrier gas is selected from least a in argon gas, nitrogen, the neon, and flow is 1～1000sccm.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108336177A (en) * | 2017-12-20 | 2018-07-27 | 深圳先进技术研究院 | A kind of copper-zinc-tin-sulfur film solar cell and preparation method thereof |
| CN113013340A (en) * | 2021-03-03 | 2021-06-22 | 北京交通大学 | Heterojunction solar cell and manufacturing method thereof |
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| US6117703A (en) * | 1996-08-27 | 2000-09-12 | Ist - Institut Fuer Solartechnologien Gmbh | Process and device for producing a CIS-strip solar cell |
| WO2011066256A1 (en) * | 2009-11-25 | 2011-06-03 | E. I. Du Pont De Nemours And Company | Screen-printable quaternary chalcogenide compositions |
| CN102201498A (en) * | 2011-05-18 | 2011-09-28 | 东华大学 | Method for preparing Cu2ZnSnS4 nanocrystalline thin-film solar cell |
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2011
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|---|---|---|---|---|
| US6117703A (en) * | 1996-08-27 | 2000-09-12 | Ist - Institut Fuer Solartechnologien Gmbh | Process and device for producing a CIS-strip solar cell |
| WO2011066256A1 (en) * | 2009-11-25 | 2011-06-03 | E. I. Du Pont De Nemours And Company | Screen-printable quaternary chalcogenide compositions |
| CN102201498A (en) * | 2011-05-18 | 2011-09-28 | 东华大学 | Method for preparing Cu2ZnSnS4 nanocrystalline thin-film solar cell |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108336177A (en) * | 2017-12-20 | 2018-07-27 | 深圳先进技术研究院 | A kind of copper-zinc-tin-sulfur film solar cell and preparation method thereof |
| CN113013340A (en) * | 2021-03-03 | 2021-06-22 | 北京交通大学 | Heterojunction solar cell and manufacturing method thereof |
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Application publication date: 20120613 |