CN100432290C - Preparation method of Sb2S3 thermal electric film - Google Patents

Preparation method of Sb2S3 thermal electric film Download PDF

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CN100432290C
CN100432290C CNB2006100431563A CN200610043156A CN100432290C CN 100432290 C CN100432290 C CN 100432290C CN B2006100431563 A CNB2006100431563 A CN B2006100431563A CN 200610043156 A CN200610043156 A CN 200610043156A CN 100432290 C CN100432290 C CN 100432290C
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solution
substrate
antimony chloride
distilled water
sbcl
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CN1904138A (en
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黄剑锋
曹丽云
吴建鹏
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Shaanxi University of Science and Technology
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Shaanxi University of Science and Technology
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Abstract

This invention relates to a process for producing Sb2S3 thermoelectric membrane. First dissolve antimony chloride SbCl3 and sulfocarbamide SC(NH2)2 respectively in distilled water to prepare antimony chloride solution; Then mix them to gain growth solution; the third step is washing heat resisting glass basal plate or silica-based support basal plate in distilled water and absolute alcohol clearly, and torrefing vacuum drying oven, irradiating in ultraviolet light, soaking in SC(NH2)2 solution, open-air drying, irradiating in ultraviolet light again; the fourth step is put the above-mentioned basal plate in growth solution for depositing 12-36 hours, then vacuum drying at 50-80DEG C; the last step is exposing basal plate in Ar atmosphere for heat treatment at 300-500DEG C for 0.5-2hours

Description

A kind of Sb 2S 3The preparation method of thermal electric film
Technical field
The present invention relates to a kind of preparation method of thermal electric film, particularly a kind of preparation method of Sb2S3 thermal electric film.
Background technology
Thermal electric film and superlattice because have complicated density-of-states distribution, the energy that caused by quantum limitation effect is discontinuously arranged, unique carrier scattering mechanism and low-down phonon thermal conductivity, and have excellent thermoelectricity capability.Theoretical and experiment shows that thermoelectric nanostructured comprises thermoelectric superlattices, quantum wire and quantum dot, has the thermoelectricity capability more much bigger than body block of material.Thermoelectric superlattices generally are to carry out lamination and be etched on the basis of thermal electric film preparation, and therefore, thermal electric film is the basis that preparation has the thermoelectric preparation of high-performance of quantum structure.Metal chalcogenide class photoelectric material is because its unique photoelectric characteristic has been widely used in photoelectric devices such as making solar absorbing layer, solar cell and photodetector.In recent years, the preparation cadmium sulfide, bismuth sulfide, the method of the chalcogenide materials such as zinc sulphide and cadmium selenide is day by day ripe, wherein chemical liquid deposition has low cost of manufacture, be easy to incomparable advantage [the Nair P K of other method such as large tracts of land preparation, Nair M T S, Gomezdaza O, et al.Metal sulfide thin film photography usingphotoaccelerated chemical deposition of bismuch sulfide thin films[J] .J.Electrochem.Soc., 1993,140:1085-1089.] [Nair P K, Nair M T S.Chemicallydeposit ed ZnS thin films:application a s substrate for chemically depositedBi 2S 3, Cu xS and PbS thin films[J] .Semicond.Sci.Technol., 1992,7:239-244.].At present, about the research of antimony trisulfide film also seldom.The present mainly method of stocking has Savadogo[Savadogo O.Chemically and electrochemically deposited thin filmsfor solar energy materials[J] .Sol Energy Mater Sol Cells, 1998,52:361-388.] and Nair[Nair P K, Nair M T S, Garcia V M, et al.Semiconductor thin films bychemical bath deposition for solar energy related applications[J] .Sol EnergyMater Sol Cells, 1998,52:313-344.] etc. the chemistry of aqueous solution sedimentation that adopts of people, [Du Jinhui, Yu Zhenrui, Li Zhengqun etc. anhydrous chemical deposition prepares Sb 2S 3Film [J]. photoelectron laser, [Kalyashova ZN, the Sabinin VE such as the anhydrous chemical deposition that 2005,16 (5): 530-533] adopts and Kalyashova, Korolev VI, et al.Manufacture of diffractivestructure in Sb 2S 3Film by pulse laser irradiation.Proceedings of SPIE-TheInternational Society for Optical Engineering, 1993,2108:115-121.] the laser pulse radiation method that adopts etc.These procedure complexity of chemistry of aqueous solution sedimentation that the people such as Savadogo adopt need to be carried out under low-down temperature, often carry out in refrigerator, are not easy to realize big production.The method of the employings such as Du Jinhui need to be carried out in the organic solutions such as ethanol, has improved preparation cost.And laser pulse radiation method devices needed is more expensive.Based on this, the present invention proposes a kind of Sb that simply prepares in the aqueous solution 2S 3The method of film.
Summary of the invention
The objective of the invention is to overcome the shortcoming of above-mentioned prior art, a kind of Sb that can simply obtain single phase is provided 2S 3Microcrystalline film, preparation cost is low, and the surfacing densification of film, the simple Sb of technological operation 2S 3The preparation method of thermal electric film.
For achieving the above object, the technical solution used in the present invention is: at first with antimony chloride SbCl 3Be dissolved in the antimony chloride solution that is mixed with 0.1mol/L in the distilled water, regulate antimony chloride solution until the precipitation dissolving with the HCl solution of 1mol/L again; With thiocarbamide SC (NH 2) 2It is for subsequent use to be dissolved in two kinds of thiourea solutions that are mixed with 0.1mol/L and 0.02mol/L in the distilled water; Press SbCl 3: SC (NH 2) 2=2: 3 mol ratio preparation SbCl 3And SC (NH 2) 2Mixed solution, during preparation, the thiourea solution with 0.1mol/L slowly is added drop-wise in the antimony chloride solution of the 0.1mol/L after HCl solution is regulated earlier, and adds thermal agitation, HCl solution with 1mol/L is adjusted to sediment completely dissolve simultaneously, namely has been made into required growth solution; Heat resistant glass substrate or silicon substrate are dried in vacuum drying chamber with Ultrasonic Cleaning is totally rear in distilled water and absolute ethyl alcohol, and under ultraviolet light, shine 5-10min; Again substrate be impregnated in the SC (NH of 60 ℃ 0.02mol/L 2) 25-10min in the solution takes out then substrate and naturally dries, under ultraviolet light, shine 5-10min again after, substrate is positioned in the growth solution deposition takes out after 12-36 hour, in 50-80 ℃ of lower vacuum drying; With after drying substrate under the Ar atmosphere protection in 300-500 ℃ of heat treatment 0.5-2 hour, namely can obtain Sb 2S 3Film.
The present invention adopts bionic method, processes by substrate surface, and take thiocarbamide and trichloride antimony as primary raw material, bionical deposition Sb in the aqueous solution 2S 3Film, the Sb that obtains 2S 3Property of thin film is stable, surfacing, pure, can prepare Sb at multiple matrix materials such as pottery, glass, silicon chip and resins 2S 3Film, and substrate surface can have any shape.
Description of drawings
The Sb of Fig. 1 embodiment of the invention 1 preparation 2S 3The atomic force microscopy structure photo of film;
The Sb of Fig. 2 embodiment of the invention 2 preparations 2S 3The atomic force microscopy structure photo of film;
The Sb of Fig. 3 embodiment of the invention 3 preparations 2S 3The atomic force microscopy structure photo of film.
Embodiment
Embodiment 1: at first with antimony chloride SbCl 3Be dissolved in the antimony chloride solution that is mixed with 0.1mol/L in the distilled water, regulate antimony chloride solution until the precipitation dissolving with the HCl solution of 1mol/L again; With thiocarbamide SC (NH 2) 2It is for subsequent use to be dissolved in two kinds of thiourea solutions that are mixed with 0.1mol/L and 0.02mol/L in the distilled water; Press SbCl 3: SC (NH 2) 2=2: 3 mol ratio preparation SbCl 3And SC (NH 2) 2Mixed solution, during preparation, the thiourea solution with 0.1mol/L slowly is added drop-wise in the antimony chloride solution of 0.1mol/L earlier, and adds thermal agitation, the HCl solution with 1mol/L is adjusted to sediment completely dissolve simultaneously, namely has been made into required growth solution; Heat resistant glass substrate or silicon substrate are dried in vacuum drying chamber with Ultrasonic Cleaning is totally rear in distilled water and absolute ethyl alcohol, and under ultraviolet light, shine 5min; Again substrate be impregnated in the SC (NH of 60 ℃ 0.02mol/L 2) 25min in the solution takes out then substrate and naturally dries, under ultraviolet light, shine 5min again after, substrate is positioned in the growth solution deposition takes out after 12 hours, in 50 ℃ of lower vacuum drying; With after drying substrate under the Ar atmosphere protection in 300 ℃ of heat treatments 1 hour, namely can obtain Sb as shown in Figure 1 2S 3Film.
Embodiment 2: at first with antimony chloride SbCl 3Be dissolved in the antimony chloride solution that is mixed with 0.1mol/L in the distilled water, regulate antimony chloride solution until the precipitation dissolving with the HCl solution of 1mol/L again; With thiocarbamide SC (NH 2) 2It is for subsequent use to be dissolved in two kinds of thiourea solutions that are mixed with 0.1mol/L and 0.02mol/L in the distilled water; Press SbCl 3: SC (NH 2) 2=2: 3 mol ratio preparation SbCl 3And SC (NH 2) 2Mixed solution, during preparation, the thiourea solution with 0.1mol/L slowly is added drop-wise in the antimony chloride solution of 0.1mol/L earlier, and adds thermal agitation, the HCl solution with 1mol/L is adjusted to sediment completely dissolve simultaneously, namely has been made into required growth solution; Heat resistant glass substrate or silicon substrate are dried in vacuum drying chamber with Ultrasonic Cleaning is totally rear in distilled water and absolute ethyl alcohol, and under ultraviolet light, shine 7min; Again substrate be impregnated in the SC (NH of 60 ℃ 0.02mol/L 2) 27min in the solution takes out then substrate and naturally dries, under ultraviolet light, shine 7min again after, substrate is positioned in the growth solution deposition takes out after 24 hours, in 60 ℃ of lower vacuum drying; With after drying substrate under the Ar atmosphere protection in 400 ℃ of heat treatments 0.5 hour, namely can obtain Sb as shown in Figure 2 2S 3Film.
Embodiment 3: at first with antimony chloride SbCl 3Be dissolved in the antimony chloride solution that is mixed with 0.1mol/L in the distilled water, regulate antimony chloride solution until the precipitation dissolving with the HCl solution of 1mol/L again; With thiocarbamide 8C (NH 2) 2It is for subsequent use to be dissolved in two kinds of thiourea solutions that are mixed with 0.1mol/L and 0.02mol/L in the distilled water; Press SbCl 3: SC (NH 2) 2=2: 3 mol ratio preparation SbCl 3And SC (NH 2) 2Mixed solution, during preparation, the thiourea solution with 0.1mol/L slowly is added drop-wise in the antimony chloride solution of 0.1mol/L earlier, and adds thermal agitation, the HCl solution with 1mol/L is adjusted to sediment completely dissolve simultaneously, namely has been made into required growth solution; Heat resistant glass substrate or silicon substrate are dried in vacuum drying chamber with Ultrasonic Cleaning is totally rear in distilled water and absolute ethyl alcohol, and under ultraviolet light, shine 10min; Again substrate be impregnated in the SC (NH of 60 ℃ 0.02mol/L 2) 210min in the solution takes out then substrate and naturally dries, under ultraviolet light, shine 10min again after; Substrate is positioned over deposition taking-up after 36 hours in the growth solution, in 80 ℃ of lower vacuum drying; With after drying substrate under the Ar atmosphere protection in 500 ℃ of heat treatments 2 hours, namely can obtain Sb as shown in Figure 3 2S 3Film.

Claims (4)

1, a kind of Sb 2S 3The preparation method of thermal electric film is characterized in that:
1) at first with antimony chloride SbCl 3Be dissolved in the antimony chloride solution that is mixed with 0.1mol/L in the distilled water, regulate antimony chloride solution up to resolution of precipitate with the HCl solution of 1mol/L again;
2) with thiocarbamide SC (NH 2) 2It is for subsequent use to be dissolved in two kinds of thiourea solutions that are mixed with 0.1mol/L and 0.02mol/L in the distilled water;
3) press SbCl 3: SC (NH 2) 2=2: 3 mol ratio preparation SbCl 3And SC (NH 2) 2Mixed solution, during preparation, the thiourea solution with 0.1mol/L slowly is added drop-wise in the antimony chloride solution of the 0.1mol/L after HCl solution is regulated earlier, and adds thermal agitation, HCl solution with 1mol/L is adjusted to sediment completely dissolve simultaneously, namely has been made into required growth solution;
4) heat resistant glass substrate or silicon substrate are dried in vacuum drying chamber with Ultrasonic Cleaning is totally rear in distilled water and absolute ethyl alcohol, and under ultraviolet light, shine 5-10min;
5) again substrate be impregnated in the SC (NH of 60 ℃ 0.02mol/L 2) 25-10min in the solution takes out then substrate and naturally dries, under ultraviolet light, shine 5-10min again after, substrate is positioned in the growth solution deposition takes out after 12-36 hour, in 50-80 ℃ of lower vacuum drying;
6) general's substrate after drying in 300-500 ℃ of heat treatment 0.5-2 hour, namely can obtain Sb under the Ar atmosphere protection 2S 3Film.
2, Sb according to claim 1 2S 3The preparation method of thermal electric film is characterized in that: at first with antimony chloride SbCl 3Be dissolved in the antimony chloride solution that is mixed with 0.1mol/L in the distilled water, regulate antimony chloride solution until the precipitation dissolving with the HCl solution of 1mol/L again; With thiocarbamide SC (NH 2) 2It is for subsequent use to be dissolved in two kinds of thiourea solutions that are mixed with 0.1mol/L and 0.02mol/L in the distilled water; Press SbCl 3: SC (NH 2) 2=2: 3 mol ratio preparation SbCl 3And SC (NH 2) 2Mixed solution, during preparation, the thiourea solution with 0.1mol/L slowly is added drop-wise in the antimony chloride solution of the 0.1mol/L after HCl solution is regulated earlier, and adds thermal agitation, HCl solution with 1mol/L is adjusted to sediment completely dissolve simultaneously, namely has been made into required growth solution; Heat resistant glass substrate or silicon substrate are dried in vacuum drying chamber with Ultrasonic Cleaning is totally rear in distilled water and absolute ethyl alcohol, and under ultraviolet light, shine 5min; Again substrate be impregnated in the SC (NH of 60 ℃ 0.02mol/L 2) 25min in the solution takes out then substrate and naturally dries, under ultraviolet light, shine 5min again after, substrate is positioned in the growth solution deposition takes out after 12 hours, in 50 ℃ of lower vacuum drying; With after drying substrate under the Ar atmosphere protection in 300 ℃ of heat treatments 1 hour, can obtain Sb 2S 3Film.
3, Sb according to claim 1 2S 3The preparation method of thermal electric film is characterized in that: at first with antimony chloride SbCl 3Be dissolved in the antimony chloride solution that is mixed with 0.1mol/L in the distilled water, regulate antimony chloride solution until the precipitation dissolving with the HCl solution of 1mol/L again; With thiocarbamide SC (NH 2) 2It is for subsequent use to be dissolved in two kinds of thiourea solutions that are mixed with 0.1mol/L and 0.02mol/L in the distilled water; Press SbCl 3: SC (NH 2) 2=2: 3 mol ratio preparation SbCl 3And SC (NH 2) 2Mixed solution, during preparation, the thiourea solution with 0.1mol/L slowly is added drop-wise in the antimony chloride solution of the 0.1mol/L after HCl solution is regulated earlier, and adds thermal agitation, HCl solution with 1mol/L is adjusted to sediment completely dissolve simultaneously, namely has been made into required growth solution; Heat resistant glass substrate or silicon substrate are dried in vacuum drying chamber with Ultrasonic Cleaning is totally rear in distilled water and absolute ethyl alcohol, and under ultraviolet light, shine 7min; Again substrate be impregnated in the S C (NH of 60 ℃ 0.02mol/L 2) 27min in the solution takes out then substrate and naturally dries, under ultraviolet light, shine 7min again after, substrate is positioned in the growth solution deposition takes out after 24 hours, in 60 ℃ of lower vacuum drying; With after drying substrate under the Ar atmosphere protection in 400 ℃ of heat treatments 0.5 hour, can obtain Sb 2S 3Film.
4, Sb according to claim 1 2S 3The preparation method of thermal electric film is characterized in that: at first with antimony chloride SbCl 3Be dissolved in the antimony chloride solution that is mixed with 0.1mol/L in the distilled water, regulate antimony chloride solution until the precipitation dissolving with the HCl solution of 1mol/L again; With thiocarbamide SC (NH 2) 2It is for subsequent use to be dissolved in two kinds of thiourea solutions that are mixed with 0.1mol/L and 0.02mol/L in the distilled water; Press SbCl 3: SC (NH 2) 2=2: 3 mol ratio preparation SbCl 3And SC (NH 2) 2Mixed solution, during preparation, the thiourea solution with 0.1mol/L slowly is added drop-wise in the antimony chloride solution of the 0.1mol/L after HCl solution is regulated earlier, and adds thermal agitation, HCl solution with 1mol/L is adjusted to sediment completely dissolve simultaneously, namely has been made into required growth solution; Heat resistant glass substrate or silicon substrate are dried in vacuum drying chamber with Ultrasonic Cleaning is totally rear in distilled water and absolute ethyl alcohol, and under ultraviolet light, shine 10min; Again substrate be impregnated in the SC (NH of 60 ℃ 0.02mol/L 2) 210min in the solution takes out then substrate and naturally dries, under ultraviolet light, shine 10min again after; Substrate is positioned over deposition taking-up after 36 hours in the growth solution, in 80 ℃ of lower vacuum drying; With after drying substrate under the Ar atmosphere protection in 500 ℃ of heat treatments 2 hours, can obtain Sb 2S 3Film.
CNB2006100431563A 2006-07-13 2006-07-13 Preparation method of Sb2S3 thermal electric film Expired - Fee Related CN100432290C (en)

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CN104830275A (en) * 2015-01-12 2015-08-12 刘艳娇 Thermoelectric thin film
CN104830271A (en) * 2015-01-12 2015-08-12 刘艳娇 Preparation method of thermoelectric thin film
CN105489384B (en) * 2016-01-11 2018-04-10 三峡大学 A kind of C/Sb2S3Preparation method of the laminated film to electrode material

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05274579A (en) * 1992-03-27 1993-10-22 Fujitsu Denso Ltd Guard system
CN1465740A (en) * 2002-06-14 2004-01-07 上海化工研究院 Method for preparing vacuum film-coating zinc sulfide
CN1624196A (en) * 2004-12-07 2005-06-08 浙江大学 Method of synthesizing ferrous disulfide film by electro deposition oxidation and hot sulfurization
US20050276980A1 (en) * 2004-06-09 2005-12-15 Tory Plastics (America), Inc. Co-extruded high refractive index coated embossable film

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05274579A (en) * 1992-03-27 1993-10-22 Fujitsu Denso Ltd Guard system
CN1465740A (en) * 2002-06-14 2004-01-07 上海化工研究院 Method for preparing vacuum film-coating zinc sulfide
US20050276980A1 (en) * 2004-06-09 2005-12-15 Tory Plastics (America), Inc. Co-extruded high refractive index coated embossable film
CN1624196A (en) * 2004-12-07 2005-06-08 浙江大学 Method of synthesizing ferrous disulfide film by electro deposition oxidation and hot sulfurization

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