CN102618917A - Method for preparing wide band gap ZnS thin film material by combining hydrothermal method and pulse electro-deposition - Google Patents
Method for preparing wide band gap ZnS thin film material by combining hydrothermal method and pulse electro-deposition Download PDFInfo
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- CN102618917A CN102618917A CN2012100810052A CN201210081005A CN102618917A CN 102618917 A CN102618917 A CN 102618917A CN 2012100810052 A CN2012100810052 A CN 2012100810052A CN 201210081005 A CN201210081005 A CN 201210081005A CN 102618917 A CN102618917 A CN 102618917A
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Abstract
The invention discloses a method for preparing a wide band gap ZnS nano thin film material by combining a hydrothermal method and pulse electro-deposition. The method sequentially comprises the following steps of: (1) preparing and pre-treating ITO (Indium Tin Oxide) conductive glass; (2) performing pulse electro-deposition on the conductive glass to prepare ZnS nano crystal seeds; and (3) preparing the ZnS nano thin film material on the conductive glass on which the ZnS nano crystal seeds are deposited by the hydrothermal method. The ZnS nano thin film prepared by the method has a flat and compact surface and strong adhesion with a matrix. The fluorescence emission spectrum of the ZnS nano thin film material shows that a sample has an obvious emission peak at 469 nm and emits blue light; and the band gap width of ZnS can be calculated to be about 5.5 ev from ultraviolet transmission.
Description
Technical field
The invention belongs to technical field of semiconductor, particularly a kind of hydrothermal method combines pulse electrodeposition to prepare the method for broad stopband ZnS thin-film material.
Background technology
ZnS is a kind of II-VI compounds of group direct band-gap semicondictor material; Energy gap is 3.6～3.8eV; Have excellent photoelectric performance, be widely used in optics and the photoelectric device, like thin-film electroluminescent displays part, photodiode, ultraviolet detector device, solar cell etc.; Wherein as the n type Window layer of CIS base thin film solar battery, substitute the CdS film with its good photoelectric transformation efficiency and nontoxic, the value of environmental protection.At present, there have been many technology to be used for preparing ZnS film and other various sulfide films, such as hydrothermal method, vacuum-evaporation, magnetron sputtering, chemical vapour deposition, aerosol jet deposition, pulse electrodeposition etc.In these methods, it is simple that hydrothermal method has technology, and production cost is low, and the nanoparticle regular shape of preparing, purity are high, crystal formation is good and advantage such as may command, are a kind of very promising ZnS method for manufacturing thin film.Present method is pulse electrodeposition ZnS nanometer crystal seed on the ITO conductive glass at first, utilizes hydrothermal method to grow the ZnS thin-film material of orderly good dispersivity above that again.The method of utilizing hydrothermal method to combine pulse electrodeposition to prepare broad stopband ZnS thin-film material is not appeared in the newspapers.
Summary of the invention
The purpose of this invention is to provide a kind of hydrothermal method combines pulse electrodeposition to prepare the method for broad stopband ZnS thin-film material.
Concrete steps are:
(1) electrolytic solution consists of: every 100mL solution contains 0.001mol zinc chloride, 0.002mol Sodium Thiosulfate Pentahydrate, 0.001～0.002mol, two hydration trisodium citrates and 20～40mL DMSO 99.8MIN., and the use mass percent concentration is 98% vitriol oil accent pH to 2.5～4; Adopt two electrode systems, platinum electrode is as anode, and the ITO conductive glass is a negative electrode, keeps constant voltage 2.0V, 52 ℃ of bath temperatures, and pulse electrodeposition 30 minutes～60 minutes obtains ZnS nanometer crystal seed.
(2) hydro-thermal liquid consists of: every 100mL solution contains 0.001～0.003mol zinc nitrate hexahydrate, 0.003～0.009mol thiocarbamide and 0.001～0.0025mol5-sulphosalicylic acid; Measure the above-mentioned hydro-thermal liquid of 15mL with transfer pipet and place autoclave, will deposit step (1) ZnS nanometer crystal seed Conducting Glass and vertically place still, begin slowly to be warming up to 200 ℃ from room temperature; Reacted 12 hours; Take out naturally cooling after question response is accomplished, clean oven dry, obtain broad stopband ZnS thin-film material.
The ZnS nano thin-film surfacing of present method preparation is fine and close, and is strong with the matrix bounding force.ZnS nano film material fluorescence emission spectrum shows that sample has tangible emission peak, blue light-emitting at the 469nm place; The energy gap that can extrapolate this ZnS from ultraviolet permeability is about 5.5ev.
Description of drawings
The ZnS thin-film material fluorescence emission spectrogram that Fig. 1 makes for the embodiment of the invention 1.
The ZnS nano film material sem photograph that Fig. 2 makes for the embodiment of the invention 1.
The ZnS nano film material sem photograph that Fig. 3 makes for the embodiment of the invention 2.
Embodiment
Embodiment 1:
(1) pre-treatment of ITO: cutting ITO conductive glass size is 1cm * 3cm, and carries out clean, with its in the mixed solution of ydrogen peroxide 50, ammoniacal liquor and deionized water and absolute ethyl alcohol ultrasonic each 10 minutes successively, is placed in the absolute ethyl alcohol for use.
(2) electrolytic solution consists of: every 100mL solution contains 0.001mol zinc chloride, 0.002mol Sodium Thiosulfate Pentahydrate, 0.001mol two hydration trisodium citrates and 30mL DMSO 99.8MIN., and the use mass percent concentration is 98% vitriol oil accent pH to 3; Adopt two electrode systems, platinum electrode is as anode, and the ITO conductive glass of step (1) gained is a negative electrode, keeps constant voltage 2.0V, 52 ℃ of bath temperatures, and pulse electrodeposition 60 minutes obtains ZnS nanometer crystal seed.
(3) hydro-thermal liquid consists of: every 100mL solution contains 0.003mol zinc nitrate hexahydrate, 0.009mol thiocarbamide and 0.002mol 5-sulphosalicylic acid; Measure the above-mentioned hydro-thermal liquid of 15mL with transfer pipet and place autoclave, will deposit step (2) ZnS nanometer crystal seed Conducting Glass and vertically place still, begin slowly to be warming up to 200 ℃ from room temperature; Reacted 12 hours; Take out naturally cooling after question response is accomplished, clean oven dry, obtain broad stopband ZnS thin-film material.
Can find out tangible emission peak, blue light-emitting are arranged from ZnS thin-film material fluorescence emission spectrum (like Fig. 1) at the 469nm place; The energy gap that can extrapolate this ZnS from ultraviolet permeability is about 4.5ev.
Be illustrated in figure 2 as the ESEM picture of gained sample, can obviously find out to be strip.
Embodiment 2:
Except that the 5-sulphosalicylic acid was 0.002mol, other conditions were with embodiment 1.Be illustrated in figure 3 as the ESEM picture of gained ZnS thin-film material, can obviously find out to be thick strip.
Claims (1)
1. a hydrothermal method combines pulse electrodeposition to prepare the method for broad stopband ZnS thin-film material, comprises the pre-treatment of ITO, it is characterized in that concrete steps are:
(1) electrolytic solution consists of: every 100mL solution contains 0.001mol zinc chloride, 0.002mol Sodium Thiosulfate Pentahydrate, 0.001～0.002mol, two hydration trisodium citrates and 20～40mL DMSO 99.8MIN., and the use mass percent concentration is 98% vitriol oil accent pH to 2.5～4; Adopt two electrode systems, platinum electrode is as anode, and the ITO conductive glass is a negative electrode, keeps constant voltage 2.0V, 52 ℃ of bath temperatures, and pulse electrodeposition 30 minutes～60 minutes obtains ZnS nanometer crystal seed;
(2) hydro-thermal liquid consists of: every 100mL solution contains 0.001～0.003mol zinc nitrate hexahydrate, 0.003～0.009mol thiocarbamide and 0.001～0.0025mol 5-sulphosalicylic acid; Measure the above-mentioned hydro-thermal liquid of 15mL with transfer pipet and place autoclave, will deposit step (1) ZnS nanometer crystal seed Conducting Glass and vertically place still, begin slowly to be warming up to 200 ℃ from room temperature; Reacted 12 hours; Take out naturally cooling after question response is accomplished, clean oven dry, obtain broad stopband ZnS thin-film material.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107123693A (en) * | 2017-04-14 | 2017-09-01 | 华南理工大学 | A kind of efficient CdTe nanometer crystalline solar cell with high transparency window layer material processed based on solwution method and preparation method thereof |
| CN109904255A (en) * | 2019-03-19 | 2019-06-18 | 湘潭大学 | A kind of preparation method of Cr-Se codope zinc sulphide solar battery buffer layer thin film material |
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| WO2002090262A1 (en) * | 2001-05-08 | 2002-11-14 | Lg Chem, Ltd. | Method for preparing single crystalline zns powder for phosphor |
| CN1996623A (en) * | 2005-12-28 | 2007-07-11 | 中国科学院大连化学物理研究所 | II-VI family semiconductor thin film used for the photovoltaic cell |
| CN101514470A (en) * | 2009-02-20 | 2009-08-26 | 陕西科技大学 | Method for preparing ZnS:Cu optical thin film |
| EP2319896A1 (en) * | 2008-08-06 | 2011-05-11 | Kuraray Co., Ltd. | Method for manufacturing zinc sulfide based phosphor |
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2012
- 2012-03-22 CN CN2012100810052A patent/CN102618917A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2002090262A1 (en) * | 2001-05-08 | 2002-11-14 | Lg Chem, Ltd. | Method for preparing single crystalline zns powder for phosphor |
| CN1996623A (en) * | 2005-12-28 | 2007-07-11 | 中国科学院大连化学物理研究所 | II-VI family semiconductor thin film used for the photovoltaic cell |
| EP2319896A1 (en) * | 2008-08-06 | 2011-05-11 | Kuraray Co., Ltd. | Method for manufacturing zinc sulfide based phosphor |
| CN101514470A (en) * | 2009-02-20 | 2009-08-26 | 陕西科技大学 | Method for preparing ZnS:Cu optical thin film |
Non-Patent Citations (2)
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| 周英智，等: "在脉冲纳米锌晶种上水热合成ZnS薄膜及其光学性能研究", 《人工晶体学报》 * |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107123693A (en) * | 2017-04-14 | 2017-09-01 | 华南理工大学 | A kind of efficient CdTe nanometer crystalline solar cell with high transparency window layer material processed based on solwution method and preparation method thereof |
| CN109904255A (en) * | 2019-03-19 | 2019-06-18 | 湘潭大学 | A kind of preparation method of Cr-Se codope zinc sulphide solar battery buffer layer thin film material |
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Application publication date: 20120801 |