CN103236466A - Method for manufacturing window layers of copper, zinc, tin and sulfur solar cells - Google Patents
Method for manufacturing window layers of copper, zinc, tin and sulfur solar cells Download PDFInfo
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Abstract
The invention discloses a method for manufacturing window layers of copper, zinc, tin and sulfur solar cells, and belongs to the technical field of processes for manufacturing thin-film devices of solar cells. The method is characterized by comprising steps of manufacturing a ZnO seed crystal by means of magnetron sputtering; growing a ZnO nano-array by a hydrothermal process; and vulcanizing and growing a ZnS shell structure by the hydrothermal process. The method has the advantages that the adhesive strength of a substrate and a ZnO@ZnS nano-array shell structure manufactured by the hydrothermal process is high, the ZnO@ZnS nano-array shell structure is high in transmittance and excellent in electrical property and can be used as a window layer of a CZTS (copper, zinc, tin and sulfur) solar cell, and the method can be excellently connected with a follow-up process for manufacturing the cell.
Description
Technical field
The present invention relates to a kind of preparation method of copper-zinc-tin-sulfur solar battery window layer, belong to solar battery thin film device preparation technology technical field.
Background technology
Zinc oxide (ZnO) is a kind of II-VI family broad stopband oxide semiconductor material, and its bandwidth is about 3.37eV, presents good n type semiconducting behavior, has good photoelectric property.ZnO has the advantages that preparation cost is low, growth temperature is low, is conducive to reduce equipment cost, suppresses the solid phase outdiffusion, improves film quality, also is easy to realize mixing.Simultaneously, the abundant raw material of ZnO film, nontoxic, environment is not polluted, be a kind of ep-type material, based on these premium properties, ZnO can be used as the window material of solar cell.
Zinc sulphide (ZnS) also is wide bandgap semiconductor materials, and energy gap is 3.66eV under the room temperature, is considered to the preferred material of clading ZnO nano material; Also be a kind ofly to study at most and one of metal sulfide the most widely, because it has unique optical physics characteristic such as the thermal infrared transparency, fluorescence and phosphorescence, caused people's very big interest.ZnO is two kinds of semiconductors with different energy levels with ZnS, can make the composite colloid system of binary, forms the clad structure of the core-shell type of ZnS clading ZnO, carries out finishing with organic material again, and causes change of optical property.At present, for ZnO@ZnS 1-dimention nano system, substantially all be to be core with the ZnO nanometer rods, by the sulfuration ZnO nanometer rods ZnO@ZnS core-shell nano structure of growing.
ZnO@ZnS nano-array nucleocapsid structure has broad stopband, high permeability and good electric property, is suitable as the Window layer of CZTS, can form the pn knot with CZTS, prepares solar cell.
At present, the preparation method of ZnO@ZnS nano-array nucleocapsid structure has chemical vapour deposition technique (CVD), but the CVD reaction temperature is higher, and deposition rate is lower, is difficult to local deposits.The source of the gas and the reacted residual air that participate in deposition reaction have certain toxicity.Also do not put down in writing up to now with the ZnO@ZnS nano-array nucleocapsid structure of Hydrothermal Preparation as the CZTS window layer of solar battery.
Summary of the invention
At the defective that prior art exists, the purpose of this invention is to provide a kind of preparation method of copper-zinc-tin-sulfur solar battery window layer, the ZnO(that a kind of ZnS coats abbreviates ZnO@ZnS as) preparation method of nano-array nucleocapsid structure.
For achieving the above object, the present invention adopts following technical scheme:
A kind of preparation method of copper-zinc-tin-sulfur solar battery window layer utilizes spin-coating method to prepare ZnO nano-array crystal seed, utilizes Hydrothermal Growth ZnO nano-array, utilizes hydro thermal method sulfuration growing ZnS shell structurre, has following technical process and step:
A) cleaning of glass substrate: adopt slide as substrate, draw water flowing solution, acetone, absolute ethyl alcohol, deionized water under ultrasound condition, to clean respectively with song substrate earlier;
B) preparation of ZnO nano-array crystal seed: monoethanolamine and zinc acetate are dissolved in ethanol, and concentration is 0.05mol/L, and be ultrasonic even; The slide substrate is put into sol evenning machine, with dropper seed-solution is dropped in respectively on the substrate, carry out spin coating by sol evenning machine, rotating speed is 1000 r/min;
C) growth of ZnO nano-array: adopt Hydrothermal Growth ZnO nano-array; Growth solution is the aqueous solution of 0.05mol/L zinc nitrate and the aqueous solution of 0.05mol/L hexa (HMT); Two kinds of solution are respectively got 8mL, join in the hydrothermal reaction kettle after fully mixing, the slide substrate that makes ZnO nano-array crystal seed is also put into wherein, and placed 92.5 ℃ baking oven; Take out after 1 ~ 3 hour, with the particle of deionized water flush away surface attachment, use the electron tubes type furnace annealing at last; Annealing is carried out in N2 atmosphere, and temperature is 400 ℃, and the time is 30min;
D) growth of ZnS shell structurre: adopt hydro thermal method sulfuration growing ZnS shell structurre; Growth solution is the aqueous solution of 0.05 ~ 0.50mol/L thioacetamide (TAA), gets the 17ml growth solution, joins in the hydrothermal reaction kettle, and the ZnO nano-array that makes is also put into wherein; And place 90 ℃ baking oven; Vulcanize after 1 ~ 9 hour and take out, with the particle of deionized water flush away surface attachment, put into baking oven at last, oven dry obtains the ZnO nano-array nucleocapsid structure that ZnS coats, and is the copper-zinc-tin-sulfur solar battery window layer.
Compared with prior art, the present invention has following outstanding substantive distinguishing features and obvious improvement:
Hydrothermal Preparation ZnO nano-array, deposition rate is stable, and by accurately controlling the hydrothermal growth time, thickness is easy to control, and good reproducibility.Utilize hydro thermal method to keep original columnar shape at ZnO nano-array film, the ZnS of preparation one deck shell structurre, thus form ZnO@ZnS nano-array nuclear-shell structurre, changed simple ZnO nanostructure.The hydro thermal method that adopts has been saved vapor phase method and has been prepared needed complex device, is a kind of simple and convenient, economical and practical method.The ZnO@ZnS nano-array nucleocapsid structure of Hydrothermal Preparation and the adhesive strength of substrate are higher, have high permeability, good electrology characteristic, can have good being connected with the preparation technology of follow-up battery as the Window layer of CZTS solar cell.Present device is simple, easy operating, good reproducibility.
Description of drawings
Fig. 1 is the X-ray diffraction spectrum (XRD) of ZnO@ZnS nano-array nucleocapsid structure sulfuration 6h, and TAA concentration is 0.20mol/L.
Fig. 2 is the UV, visible light light transmission rate collection of illustrative plates of ZnO@ZnS nano-array nucleocapsid structure sulfuration 6h.
Fig. 3 is ESEM (SEM) image of ZnO@ZnS nano-array nucleocapsid structure sulfuration 6h, and TAA concentration is 0.20mol/L.
Fig. 4 is ESEM (SEM) image of ZnO@ZnS nano-array nucleocapsid structure sulfuration 6h, and TAA concentration is 0.15mol/L.
Fig. 5 is ESEM (SEM) image of ZnO@ZnS nano-array nucleocapsid structure sulfuration 6h, and TAA concentration is 0.25mol/L.
Embodiment
Now details are as follows by reference to the accompanying drawings with embodiments of the invention:
Embodiment 1
A kind of preparation method of copper-zinc-tin-sulfur solar battery window layer utilizes spin-coating method to prepare ZnO nano-array crystal seed, utilizes Hydrothermal Growth ZnO nano-array, utilizes hydro thermal method sulfuration growing ZnS shell structurre, has following technical process and step:
A) cleaning of glass substrate: slide is carried out surface cleaning processing work, put into song successively and drew water flowing solution, acetone soln, absolute alcohol solution and deionized water each ultrasonic 15 minutes, then slide is dried.
B) preparation of ZnO nano-array crystal seed: adopt the spin-coating method legal system to be equipped with the ZnO crystal seed.Monoethanolamine and zinc acetate are dissolved in ethanol, and concentration is 0.05mol/L, and be ultrasonic even.The slide substrate is put into sol evenning machine, with dropper seed-solution is dropped on the substrate, rotating speed is 1000 r/min, and the spin coating time is 30 seconds, takes off slide and oven dry.
C) growth of ZnO nano-array: adopt Hydrothermal Growth ZnO nano-array.Growth solution is the aqueous solution of 0.05mol/L zinc nitrate and the aqueous solution of 0.05mol/L hexa (HMT), two kinds of solution are respectively got 8mL, join in the hydrothermal reaction kettle after fully mixing, the FTO substrate that makes crystal seed is also put into wherein, place 92.5 ℃ baking oven.Take out after 2 hours, with the particle of deionized water flush away surface attachment, use tube annealing at last.Annealing is at N
2Carry out in the atmosphere, temperature is 400 ℃, and the time is 30min.
D) growth of ZnS shell structurre: adopt hydro thermal method sulfuration growing ZnS shell structurre.Growth solution is the aqueous solution of the thioacetamide (TAA) of 0.15mol/L, gets 17ml, joins in the hydrothermal reaction kettle, and the ZnO nano-array that makes is also put into wherein, places 90 ℃ baking oven.Vulcanize after 6 hours and take out, with the particle of deionized water flush away surface attachment, put into baking oven at last, oven dry can obtain ZnO@ZnS nano-array nucleocapsid structure.During the performance of exosyndrome material, in the XRD test, as Fig. 1, the peak type is sharp-pointed, good crystallinity, and the free from admixture peak occurs, and proves that product is hexagonal wurtzite structure.As shown in Figure 2, ZnO@ZnS is as the Window layer of solar cell, light transmittance show the ZnO@ZnS nano-array at the mean transmissivity of visible region (400-800nm) more than 70%.Fig. 3 is scanning electron microscope image, and in the SEM test, the nanometer rods arrangement is very tight as can be seen, and pattern is regular, favorable orientation.The nanometer rods top is six prismatics, and diameter range is at 100-120nm.
Embodiment 2
The operating procedure of present embodiment is substantially the same manner as Example 1, and difference is d) growth solution TAA concentration in the step is 0.15mol/L.Fig. 4 is scanning electron microscope image.The nanometer rods top is six prismatics, and diameter is about 90nm.
Embodiment 3
The operating procedure of present embodiment is substantially the same manner as Example 1, and difference is d) growth solution TAA concentration in the step is 0.25mol/L.Fig. 5 is scanning electron microscope image.The nanometer rods top is six prismatics, and diameter range is at 120-140nm.
Claims (1)
1. the preparation method of a copper-zinc-tin-sulfur solar battery window layer, it is characterized in that, utilize spin-coating method to prepare ZnO nano-array crystal seed, utilize Hydrothermal Growth ZnO nano-array, utilize hydro thermal method sulfuration growing ZnS shell structurre, have following technical process and step:
A) cleaning of glass substrate: adopt slide as substrate, draw water flowing solution, acetone, absolute ethyl alcohol, deionized water under ultrasound condition, to clean respectively with song substrate earlier;
B) preparation of ZnO nano-array crystal seed: monoethanolamine and zinc acetate are dissolved in ethanol, and concentration is 0.05 mol/L, and be ultrasonic even; The slide substrate is put into sol evenning machine, with dropper seed-solution is dropped on the substrate, carry out spin coating by sol evenning machine, rotating speed is 1000 r/min; After the spin coating crystal seed is heat-treated;
C) growth of ZnO nano-array: adopt Hydrothermal Growth ZnO nano-array; Growth solution is the aqueous solution of 0.05mol/L zinc nitrate and the aqueous solution of 0.05mol/L hexa; Two kinds of solution are respectively got 8mL, join in the hydrothermal reaction kettle after fully mixing, the slide substrate that makes ZnO nano-array crystal seed is also put into wherein, and placed 92.5 ℃ baking oven; Take out after 1 ~ 3 hour, with the particle of deionized water flush away surface attachment, use the electron tubes type furnace annealing at last; Annealing is at N
2Carry out in the atmosphere, temperature is 400 ℃, and the time is 30min;
D) growth of ZnS shell structurre: adopt hydro thermal method sulfuration growing ZnS shell structurre; Growth solution is the aqueous solution of 0.05 ~ 0.50mol/L thioacetamide, gets the 17ml growth solution, joins in the hydrothermal reaction kettle, and the ZnO nano-array that makes is also put into wherein; And place 90 ℃ baking oven; Vulcanize after 1 ~ 9 hour and take out, with the particle of deionized water flush away surface attachment, put into baking oven at last, oven dry obtains the ZnO nano-array nucleocapsid structure that ZnS coats, and is the copper-zinc-tin-sulfur solar battery window layer.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108630770A (en) * | 2017-03-15 | 2018-10-09 | 神华集团有限责任公司 | A kind of thin-film solar cells and preparation method thereof |
| CN112225244A (en) * | 2020-10-13 | 2021-01-15 | 江曙 | Preparation method of monodisperse nano copper-zinc-tin-sulfur for solar cell |
| CN115872439A (en) * | 2022-12-09 | 2023-03-31 | 湖北工业大学 | Method for preparing film for promoting growth of copper-zinc-tin-sulfur particles by nano-crystal |
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| CN101974781A (en) * | 2010-11-08 | 2011-02-16 | 上海大学 | Method for preparing ZnO nano-rod array at normal temperature and normal pressure |
| CN102800747A (en) * | 2012-07-11 | 2012-11-28 | 上海大学 | Preparation method of ZnS-cladded ZnO nanoarray core-shell structure |
| US20130000713A1 (en) * | 2011-06-29 | 2013-01-03 | Korea Advanced Institute Of Science And Technology | Nanostructure and manufacturing method thereof, and solar cell including the same |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101974781A (en) * | 2010-11-08 | 2011-02-16 | 上海大学 | Method for preparing ZnO nano-rod array at normal temperature and normal pressure |
| US20130000713A1 (en) * | 2011-06-29 | 2013-01-03 | Korea Advanced Institute Of Science And Technology | Nanostructure and manufacturing method thereof, and solar cell including the same |
| CN102800747A (en) * | 2012-07-11 | 2012-11-28 | 上海大学 | Preparation method of ZnS-cladded ZnO nanoarray core-shell structure |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108630770A (en) * | 2017-03-15 | 2018-10-09 | 神华集团有限责任公司 | A kind of thin-film solar cells and preparation method thereof |
| CN112225244A (en) * | 2020-10-13 | 2021-01-15 | 江曙 | Preparation method of monodisperse nano copper-zinc-tin-sulfur for solar cell |
| CN115872439A (en) * | 2022-12-09 | 2023-03-31 | 湖北工业大学 | Method for preparing film for promoting growth of copper-zinc-tin-sulfur particles by nano-crystal |
| CN115872439B (en) * | 2022-12-09 | 2023-11-17 | 湖北工业大学 | Method for preparing film for promoting growth of copper zinc tin sulfide particles by nanocrystalline |
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Application publication date: 20130807 |