CN102201498A - Method for preparing Cu2ZnSnS4 nanocrystalline thin-film solar cell - Google Patents

Method for preparing Cu2ZnSnS4 nanocrystalline thin-film solar cell Download PDF

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CN102201498A
CN102201498A CN2011101281653A CN201110128165A CN102201498A CN 102201498 A CN102201498 A CN 102201498A CN 2011101281653 A CN2011101281653 A CN 2011101281653A CN 201110128165 A CN201110128165 A CN 201110128165A CN 102201498 A CN102201498 A CN 102201498A
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solar cell
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water
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CN102201498B (en
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胡俊青
田启威
陈志钢
唐明华
徐晓峰
邹儒佳
孙彦刚
吴江红
张震宇
胡向华
彭彦玲
蒋扉然
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Donghua University
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Abstract

The invention relates to a method for preparing a Cu2ZnSnS4 nanocrystalline thin-film solar cell, which comprises the following steps of: performing chemical bath deposition on a ZnS film to form a buffer layer by taking molybdenum-plated metal aluminum as a flexible substrate and a film prepared from hydrophilic Cu2ZnSnS4 nanocrystalline as an absorption layer; and assembling the solar cell by performing magnetron sputtering on intrinsic ZnO, ITO and Ni-Al electrodes. By the method, vacuum equipment is not required, production cost is reduced, and convenience is brought to mass production; raw materials for preparing the Cu2ZnSnS4 solar cell are environment-friendly materials and have low prices, so that the cost of the solar cell is reduced to the great extent; and the method has a good application prospect.

Description

A kind of Cu 2ZnSnS 4The preparation method of nano-crystalline thin film solar cell
Technical field
The invention belongs to the preparation field of compound semiconductor thin film solar cell, particularly a kind of Cu 2ZnSnS 4The preparation method of nano-crystalline thin film solar cell.
Background technology
The huge advance made of society to increasing substantially of energy demand, has caused coal, oil, natural gas equal energy source sharply exhausted, and environmental pollution also increasingly sharpens, and people press for and seek the reproducible new forms of energy of cleaning.As the unlimited reproducible non-polluting energy sources of the earth---the application of solar energy causes people's attention day by day.At present, efficient, cheap, stable solar cell becomes the focus that the scientific worker studies.
Current solar cell mainly is divided into: silicon system (monocrystalline silicon, polysilicon and amorphous silicon membrane) solar cell, compound semiconductor (Cu 2ZnSnS 4, CuInSe 2, Cu (In, Ga) Se 2, CdTe, GaAs and InP) thin-film solar cells, organic solar batteries and dye sensitized nano crystal salar battery etc.Wherein, Cu 2ZnSnS 4The nano-crystalline thin film solar cell gets more and more people's extensive concerning because photoelectric conversion efficiency is higher, cost of manufacture is lower, does not have good characteristics such as performance degradation.
But prepare Cu at present 2ZnSnS 4Nano-crystalline thin film solar cell method mainly is to use the hydrophobic nano crystalline substance, needs to use poisonous organic solvent in the preparation process, as toluene, chloroform etc.Although doctor Mitzi of IBM Corporation utilizes nanocrystalline precursor to prepare conversion efficiency up to 9.6% Cu 2ZnSnS 4Nano-crystalline thin film solar cell, but the not only high poison of the hydrazine of using in the preparation process, and very easily blast.In addition, the Cu for preparing at present 2ZnSnS 4The nano-crystalline thin film solar cell all be with CdS as resilient coating, and Cd is not only poisonous but also difficult recovery.The use of glass substrate has simultaneously limited the application of this class battery in a lot of occasions, such as curved building.Therefore need the new battery preparation technique of exploitation, replace poisonous organic solvent, hydrazine and CdS resilient coating, the flexible substrate of development of new increases the use occasion of hull cell simultaneously.
Summary of the invention
Technical problem to be solved by this invention provides a kind of Cu 2ZnSnS 4The preparation method of nano-crystalline thin film solar cell, this method needing no vacuum equipment has reduced production cost, is convenient to scale and generates, preparation Cu 2ZnSnS 4The employed raw material of solar cell is environment-friendly material, and low price, has reduced the cost of solar cell greatly, has a good application prospect.
A kind of Cu of the present invention 2ZnSnS 4The preparation method of nano-crystalline thin film solar cell comprises:
(1) substrate is plated molybdenum with magnetron sputtering method after by ethanol, deionized water ultrasonic cleaning, flexible substrate;
(2) adopt two step synthetic methods, reverse microemulsion method or solvent-thermal method to make water-soluble Cu 2ZnSnS 4Nanocrystalline; With water-soluble Cu 2ZnSnS 4Nanocrystalline be scattered in water or the ethanol dispersion liquid, add with dispersion liquid volume ratio be that 1: 5～10 ammoniacal liquor or monoethanolamine get water-based Cu 2ZnSnS 4Printing ink is with water-based Cu 2ZnSnS 4Ink printing is on above-mentioned flexible substrate, and illumination or sintering get Cu again 2ZnSnS 4Nanocrystalline dense film;
(3) solution of zinc sulfate and ammoniacal liquor are mixed, add above-mentioned Cu after putting into 50～100 ℃ of water-bath constant temperature 2ZnSnS 4Nanocrystalline dense film, (is mixing ratio of zinc sulfate, ammoniacal liquor and thiocarbamide to drip thiourea solution then?), post precipitation occurs and continue the Cu that deposition 10～40min must be coated with the ZnS resilient coating 2ZnSnS 4Nanocrystalline dense film; On this dense film,, promptly get Cu with magnetron sputtering method difference sputtering zinc oxide layer, tin indium oxide (ITO) conductive layer and Ni-Al electrode 2ZnSnS 4The nano-crystalline thin film solar cell.
Substrate in the described step (1) is a metal foil paper.
Described metal foil paper is aluminium foil or Copper Foil.
Printing water-based Cu in the described step (2) 2ZnSnS 4The technology of printing ink is that spin coating, volume are coated with or utilize the inkjet printing film-forming system.
Solution of zinc sulfate concentration in the described step (3) is 0.1-0.5mol/L, and ammonia concn is 0.2-0.8mol/L, and thiourea solution concentration is 0.3-1mol/L, and the mol ratio of zinc sulfate, ammoniacal liquor and thiocarbamide is 1: 2: 2.5～3.
In the described step (2) two step, synthetic method was for to utilize the high-temperature liquid-phase synthetic method to make hydrophobic Cu earlier 2ZnSnS 4Nanocrystalline, utilize the ligand exchange method with hydrophobic Cu again 2ZnSnS 4Nanocrystallinely change into water-soluble Cu 2ZnSnS 4Nanocrystalline.
Reverse microemulsion method in the described step (2) must two kinds of reverse microemulsion systems for source metal and sulphur source being dissolved in respectively in the oil phase that contains surfactant, and two kinds of reverse microemulsion system hybrid reactions make water-soluble Cu 2ZnSnS 4Nanocrystalline.
Solvent-thermal method in the described step (2) is for to be dissolved in metal complex in the polar solvent, and solvent thermal reaction makes water-soluble Cu behind the adding sulphur source 2ZnSnS 4Nanocrystalline.
The concrete technology of in the step (2) two step synthetic method is: with metal complex (acetylacetone copper, zinc acetylacetonate or acetylacetone,2,4-pentanedione tin) or metal acetate salt is source metal, with sulphur powder, thioacetamide or thiocarbamide is the sulphur source, source metal and sulphur source are dissolved in respectively in the organic solvent (oleyl amine, trioctylamine or octacosane), in source metal organic solution, feed nitrogen subsequently, and under 100-140 ℃, remove and anhydrate, be increased to 200-320 ℃ again and add sulphur source organic solution, reacted 10-120 minute, the cooling centrifugation promptly gets hydrophobicity Cu 2ZnSnS 4Nanocrystalline; With Cu 2ZnSnS 4In the nanocrystalline blend solution that is dispersed in water, ethanol and cyclohexane, in solution, add mercaptopropionic acid, promptly get water-soluble Cu 2ZnSnS 4Nanocrystalline.
The concrete technology of reverse microemulsion method in the step (2) is: be oil phase with the normal heptane, with butanedioic acid two (2 ethylhexyl) ester sodium sulfonate (AOT) is surfactant, add the acetate blend aqueous solution of copper, zinc and tin and thioacetamide or thiourea solution therein respectively and get two kinds of reverse microemulsion systems, after stirring 1h respectively two kinds of reverse microemulsion systems are mixed, in 120-220 ℃ of reaction 1-24h, behind the natural cooling, adding acetone precipitates centrifuge washing with gained and vacuumize promptly gets water-soluble Cu 2ZnSnS 4Nanocrystalline.
The concrete technology of solvent-thermal method in the step (2) is: metal complex (acetylacetone copper, zinc acetylacetonate or acetylacetone,2,4-pentanedione tin) or metal acetate salt are dissolved in the polar solvent (DMSO, DMF or polyalcohol), add sulphur source (thioacetamide or thiocarbamide) again, stir behind the 10-30min in 120-220 ℃ of solvent heat treatment 1-24h, behind the natural cooling, adding acetone or ethanol precipitate centrifuge washing with gained and vacuumize promptly gets water-soluble Cu 2ZnSnS 4Nanocrystalline.
Cu of the present invention 2ZnSnS 4The nano-crystalline thin film solar cell is a flexible substrate with the metal aluminum foil of plating molybdenum, with hydrophilic Cu 2ZnSnS 4The film of nanocrystalline preparation is an absorbed layer, and the ZnS film of chemical bath deposition is a resilient coating, comes the assembling solar battery by magnetron sputtering intrinsic ZnO, ITO and Ni-Al electrode then.
Beneficial effect
(1) substrate that uses among the present invention has not only alleviated the weight of battery, and can make battery applications more extensive for the metal aluminum foil flexible substrate of plating molybdenum;
(2) Cu that uses among the present invention 2ZnSnS 4Nanocrystalline is the hydrophilic nano crystalline substance, and these nanocrystalline can being dispersed in well in the non-polar solven, as water and ethanol, has avoided preparation process with an organic solvent, causes environmental pollution;
(3) the preparation Cu of the present invention's use 2ZnSnS 4The method of nanocrystalline dense film is come modes such as spin coating, volume are coated with, printing for utilizing the brilliant China ink of water nano, and needing no vacuum equipment has reduced production cost, is convenient to scale generate;
(4) resilient coating of the present invention's use is nontoxic ZnS, has reduced the environmental pollution of solar cell;
(5) the present invention prepares Cu 2ZnSnS 4The employed raw material of solar cell is environment-friendly material, and low price, has reduced the cost of solar cell greatly, has a good application prospect.
Description of drawings
The Cu of Fig. 1 for being invented among the present invention 2ZnSnS 4Nano-crystal film preparation technology flow chart.
The Cu of Fig. 2 for being invented among the present invention 2ZnSnS 4The process flow for assembling figure of nano-crystalline thin film solar cell.
The Cu of Fig. 3 for being invented among the present invention 2ZnSnS 4The sem photograph of nano-crystalline thin film solar cell section.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Embodiment 1
1, the preparation of flexible substrate
At first selecting flexible aluminium-foil paper is substrate, by ethanol, deionized water ultrasonic cleaning, removes surperficial oil stain then, adopts the method plating layer of metal molybdenum of magnetron sputtering to prepare flexible substrate then.
2, hydrophily Cu 2ZnSnS 4Nanocrystalline preparation
First step hydrophobic synthetic Cu 2ZnSnS 4Nanocrystalline: 0.35mmol acetylacetone copper, 0.3mmol zinc acetylacetonate, 0.25mmol acetylacetone,2,4-pentanedione tin are dissolved in the 15mL oleyl amine solution, will feed nitrogen in the oleyl amine solution subsequently, and heating up 120 ℃ dewaters; Elevated temperature to 300 ℃ again injects and contains the oleyl amine solution that 5mL contains 1mmol sulphur, react 30 minutes, cools off centrifugation and can obtain Cu 2ZnSnS 4Nanocrystalline.With 1mmol Cu 2ZnSnS 4In the nanocrystalline blend solution that is dispersed in 25mL water/25mL ethanol/50mL cyclohexane, in solution, add the mercaptopropionic acid of 0.05mmol again, stirring at room 24h, centrifugation is washed three times, is distributed in the 50mL ethanol standby again.
3, Cu 2ZnSnS 4The preparation of nanocrystalline dense film
Get 5mL Cu in the above-mentioned steps 2 2ZnSnS 4Nanocrystalline alcohol dispersion liquid adds the 0.5mL monoethanolamine and obtains water-based Cu 2ZnSnS 4Printing ink.Method by spin coating is with water-based Cu then 2ZnSnS 4Ink printing is on flexible substrate, and the method by illumination obtains Cu 2ZnSnS 4Nano-crystal film
4, the preparation of ZnS resilient coating
The ammoniacal liquor of the solution of zinc sulfate of 0.2mol/L, 0.4mol/L stirred make it to mix, the gained mixed liquor is put into water-bath, behind 70 ℃ of the constant temperature, in mixed liquor, add prepared Cu 2ZnSnS 4Nanocrystalline dense film drips the thiourea solution of 0.5mol/L then, and the mol ratio of zinc sulfate, ammoniacal liquor and thiocarbamide is 1: 2: 2.5, and solution moment occurs milky white muddy, continues deposition 20min subsequently and gets final product.
5, the assembling of battery
With the film of the above-mentioned preparation method by magnetron sputtering, at first sputter one deck intrinsic zinc oxide and then sputter one deck ITO conductive layer are used sputter Ni-Al electrode at last, finish the assembling of solar cell.
Embodiment 2
1, the preparation of flexible substrate
At first selecting flexible Copper Foil is substrate, by ethanol, deionized water ultrasonic cleaning, removes surperficial oil stain then, adopts the mode of magnetron sputtering to plate the layer of metal molybdenum then and prepares flexible substrate.
2, hydrophily Cu 2ZnSnS 4Nanocrystalline preparation
With the 20mL normal heptane is oil phase, is surfactant with butanedioic acid two (2 ethylhexyl) ester sodium sulfonate, adds the 2mL aqueous solution and prepares the reverse microemulsion system, is divided into two parts.First kind of aqueous solution contains the 0.35mmol Schweinfurt green, 0.3mmol zinc acetate and 0.25mmol tin acetate, and second kind of aqueous solution contains the 1mmol thioacetamide.Two kinds of reverse microemulsion systems are stirred about 1h respectively, obtain very limpid colourless solution, subsequently they are mixed, stir 20min.Mixture is transferred to water heating kettle, and encapsulation is at 180 ℃ of hydrothermal treatment consists 12h.Behind the natural cooling, add 5mL acetone breakdown of emulsion, again with 12, the centrifugal 20min of 000rpm.With normal heptane and ethanol washing and precipitating successively, high speed centrifugation is removed AOT and other impurity of absorption several times again, with obtain nanocrystalline be scattered in again in the 50mL ethanol standby.
3, Cu 2ZnSnS 4The preparation of nanocrystalline dense film
Get 5mL Cu in the above-mentioned steps 2 2ZnSnS 4Nanocrystalline alcohol dispersion liquid adds 1mL ammoniacal liquor and obtains water-based Cu 2ZnSnS 4Printing ink.The method that is coated with by volume is with water-based Cu then 2ZnSnS 4Ink printing on flexible substrate, and then under the sulphur atmospheric condition, 450 ℃ of annealing 20min.
4, the preparation of ZnS resilient coating
The ammoniacal liquor of the solution of zinc sulfate of 0.3mol/L, 0.4mol/L stirred make it to mix, the gained mixed liquor is put into water-bath, in mixed liquor, add prepared Cu behind 60 ℃ of the constant temperature 2ZnSnS 4Nanocrystalline dense film drips the thiourea solution of 0.5mol/L then, and the mol ratio of zinc sulfate, ammoniacal liquor and thiocarbamide is 1: 2: 3, and solution moment occurs milky white muddy, continues deposition 30min subsequently and gets final product.
5, the assembling of battery
With the film of the above-mentioned preparation method by magnetron sputtering, at first sputter one deck intrinsic zinc oxide and then sputter one deck ITO conductive layer are used sputter Ni-Al electrode at last, finish the assembling of solar cell.
Embodiment 3
1, the preparation of flexible substrate
At first selecting flexible aluminium foil is substrate, by ethanol, deionized water ultrasonic cleaning, removes surperficial oil stain then, adopts the mode of magnetron sputtering to plate the layer of metal molybdenum then and prepares flexible substrate.
2, hydrophily Cu 2ZnSnS 4Nanocrystalline preparation
(A) take by weighing 0.35mmol CuCl 22H 2O, 0.3mmol ZnSO 47H 2O, 0.25mmol SnCl 22H 2O places round-bottomed flask, adds 10mL ethylene glycol, stirs, with each substance dissolves.(B) take by weighing the Na of 5mmol 2S is dissolved in the 10mL ethylene glycol ultrasonic dissolution.Under stirring condition, B is poured among the A, continue to stir half an hour, be transferred in the autoclave, 220 ℃, 24 hours.After reaction finishes, centrifugation.Can obtain Cu 2ZnSnS 4, be scattered in the 50mL ethanolic solution standby again.
3, Cu 2ZnSnS 4The preparation of nanocrystalline dense film
Get 5mL Cu in the above-mentioned steps 2 2ZnSnS 4Nanocrystalline alcohol dispersion liquid adds the 0.5mL monoethanolamine and obtains water-based Cu 2ZnSnS 4Printing ink.The method that is coated with by volume is with water-based Cu then 2ZnSnS 4Ink printing on flexible substrate, and then under the selenium atmospheric condition, 450 ℃ of annealing 20min.
4, the preparation of ZnS resilient coating
The ammoniacal liquor of the solution of zinc sulfate of 0.3mol/L, 0.6mol/L stirred make it to mix, the gained mixed liquor is put into water-bath, in mixed liquor, add prepared Cu behind 80 ℃ of the constant temperature 2ZnSnS 4Nanocrystalline dense film drips the thiourea solution of 0.5mol/L then, and the mol ratio of zinc sulfate, ammoniacal liquor and thiocarbamide is 1: 2: 2.6, and solution moment occurs milky white muddy, continues deposition 10min subsequently and gets final product.
5, the assembling of battery
With the film of the above-mentioned preparation method by magnetron sputtering, at first sputter one deck intrinsic zinc oxide and then sputter one deck ITO conductive layer are used sputter Ni-Al electrode at last, finish the assembling of solar cell.

Claims (8)

1. Cu 2ZnSnS 4The preparation method of nano-crystalline thin film solar cell comprises:
(1) substrate is plated molybdenum with magnetron sputtering method after by ethanol, deionized water ultrasonic cleaning, flexible substrate;
(2) adopt two step synthetic methods, reverse microemulsion method or solvent-thermal method to make water-soluble Cu 2ZnSnS 4Nanocrystalline; With water-soluble Cu 2ZnSnS 4Nanocrystalline be scattered in water or the ethanol dispersion liquid, add with dispersion liquid volume ratio be that 1: 5～10 ammoniacal liquor or monoethanolamine get water-based Cu 2ZnSnS 4Printing ink is with water-based Cu 2ZnSnS 4Ink printing is on above-mentioned flexible substrate, and illumination or sintering get Cu again 2ZnSnS 4Nanocrystalline dense film;
(3) solution of zinc sulfate and ammoniacal liquor are mixed, add above-mentioned Cu after putting into 50～100 ℃ of water-bath constant temperature 2ZnSnS 4Nanocrystalline dense film drips thiourea solution then, post precipitation occurs and continues the Cu that deposition 10～40min must be coated with the ZnS resilient coating 2ZnSnS 4Nanocrystalline dense film; On this dense film,, promptly get Cu with magnetron sputtering method difference sputtering zinc oxide layer, conductive indium-tin oxide layer and Ni-Al electrode 2ZnSnS 4The nano-crystalline thin film solar cell.
2. a kind of Cu according to claim 1 2ZnSnS 4The preparation method of nano-crystalline thin film solar cell is characterized in that: the substrate in the described step (1) is a metal foil paper.
3. a kind of Cu according to claim 2 2ZnSnS 4The preparation method of nano-crystalline thin film solar cell is characterized in that: described metal foil paper is aluminium foil or Copper Foil.
4. a kind of Cu according to claim 1 2ZnSnS 4The preparation method of nano-crystalline thin film solar cell is characterized in that: the step of two in the described step (2), synthetic method was for to utilize the high-temperature liquid-phase synthetic method to make hydrophobic Cu earlier 2ZnSnS 4Nanocrystalline, utilize the ligand exchange method with hydrophobic Cu again 2ZnSnS 4Nanocrystallinely change into water-soluble Cu 2ZnSnS 4Nanocrystalline.
5. a kind of Cu according to claim 1 2ZnSnS 4The preparation method of nano-crystalline thin film solar cell, it is characterized in that: the reverse microemulsion method in the described step (2) must two kinds of reverse microemulsion systems for source metal and sulphur source being dissolved in respectively in the oil phase that contains surfactant, and two kinds of reverse microemulsion system hybrid reactions make water-soluble Cu 2ZnSnS 4Nanocrystalline.
6. a kind of Cu according to claim 1 2ZnSnS 4The preparation method of nano-crystalline thin film solar cell is characterized in that: the solvent-thermal method in the described step (2) is for to be dissolved in metal complex in the polar solvent, and solvent thermal reaction makes water-soluble Cu behind the adding sulphur source 2ZnSnS 4Nanocrystalline.
7. a kind of Cu according to claim 1 2ZnSnS 4The preparation method of nano-crystalline thin film solar cell is characterized in that: the printing water-based Cu in the described step (2) 2ZnSnS 4The technology of printing ink is that spin coating, volume are coated with or utilize the inkjet printing film-forming system.
8. a kind of Cu according to claim 1 2ZnSnS 4The preparation method of nano-crystalline thin film solar cell, it is characterized in that: the solution of zinc sulfate concentration in the described step (3) is 0.1-0.5mol/L, ammonia concn is 0.2-0.8mol/L, and thiourea solution concentration is 0.3-1mol/L, and the mol ratio of zinc sulfate, ammoniacal liquor and thiocarbamide is 1: 2: 2.5～3.
CN201110128165.3A 2011-05-18 2011-05-18 Method for preparing Cu2ZnSnS4 nanocrystalline thin-film solar cell Expired - Fee Related CN102201498B (en)

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CN102496656A (en) * 2011-12-22 2012-06-13 中南大学 Manufacturing method for copper-zinc-tin-sulfur photovoltaic film
CN102593246A (en) * 2012-02-13 2012-07-18 南京航空航天大学 Low cost solution method for preparing solar cell absorption layer material Cu2ZnSnS4
CN102593246B (en) * 2012-02-13 2015-05-20 南京航空航天大学 Low cost solution method for preparing solar cell absorption layer material Cu2ZnSnS4
CN103956406A (en) * 2014-04-16 2014-07-30 渤海大学 Non-vacuum manufacturing method of copper-zinc-tin-sulfur solar battery of superstrate structure
WO2015192739A1 (en) * 2014-06-19 2015-12-23 常州天合光能有限公司 Solar cell local-area doping method
CN104370302A (en) * 2014-10-23 2015-02-25 上海交通大学 Nano-pouring synthetic method of copper-zinc-tin-sulfur nano-crystal
CN105226131A (en) * 2015-08-24 2016-01-06 中国工程物理研究院材料研究所 A kind of chemical synthesis process of copper zinc tin sulfur absorption layer film
CN105226131B (en) * 2015-08-24 2017-09-29 中国工程物理研究院材料研究所 A kind of chemical synthesis process of copper zinc tin sulfur absorption layer film
CN108864517A (en) * 2018-06-20 2018-11-23 湖南辰砾新材料有限公司 A kind of wear resistant packing and preparation method thereof
CN108864517B (en) * 2018-06-20 2021-07-13 湖南辰砾新材料有限公司 Wear-resistant packing and preparation method thereof
CN112397598A (en) * 2020-11-17 2021-02-23 南京邮电大学 Precursor solution and method for preparing silver-copper-zinc-tin-sulfur thin-film solar cell by using same
CN112397598B (en) * 2020-11-17 2022-07-08 南京邮电大学 Precursor solution and method for preparing silver-copper-zinc-tin-sulfur thin-film solar cell by using same

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