CN105439106A - Method for preparing bismuth selenide thermoelectric thin film with bismuth sulfate - Google Patents
Method for preparing bismuth selenide thermoelectric thin film with bismuth sulfate Download PDFInfo
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- CN105439106A CN105439106A CN201510943168.0A CN201510943168A CN105439106A CN 105439106 A CN105439106 A CN 105439106A CN 201510943168 A CN201510943168 A CN 201510943168A CN 105439106 A CN105439106 A CN 105439106A
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- CN
- China
- Prior art keywords
- thin film
- bismuth
- film
- precursor thin
- bismuth selenide
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Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B19/00—Selenium; Tellurium; Compounds thereof
- C01B19/04—Binary compounds including binary selenium-tellurium compounds
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/01—Manufacture or treatment
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/80—Constructional details
- H10N10/85—Thermoelectric active materials
- H10N10/851—Thermoelectric active materials comprising inorganic compositions
- H10N10/852—Thermoelectric active materials comprising inorganic compositions comprising tellurium, selenium or sulfur
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/20—Materials for coating a single layer on glass
- C03C2217/28—Other inorganic materials
- C03C2217/287—Chalcogenides
- C03C2217/289—Selenides, tellurides
Abstract
The invention discloses a method for preparing a bismuth selenide thermoelectric thin film with bismuth sulfate, and belongs to the technical field of thermoelectric thin film material preparation. The bismuth selenide thermoelectric thin film is obtained through the following steps: firstly, cleaning a stannic oxide conductive glass substrate, then putting Bi2(SO4)3 and SeO2 into dilute nitric acid, and thus obtaining a precursor thin film on the conductive glass substrate by an electrodeposition method; naturally drying the precursor thin film, putting the precursor thin film in a tube furnace with diamide hydrate, making the precursor thin film sample in no contact with diamide hydrate, and heating in the airtight tube furnace; and finally, taking out the sample, drying the sample, and thus obtaining the bismuth selenide thermoelectric thin film. The method does not need a high vacuum condition, has low requirements on instruments and equipment, and is low in production cost, high in production efficiency and easy to operate. The obtained bismuth selenide thermoelectric thin film has relatively good continuity and uniformity, a main phase is a Bi2Se3 phase, and the low-cost and large-scale industrialized production can be achieved.
Description
Technical field
The invention belongs to thermal electric film preparing technical field, particularly relate to a kind of method that bismuth sulfate prepares bismuth selenide thermal electric film.
Background technology
The energy, material and information are three large pillars of modern technologies.Along with the demand of the social development energy increases, and Nonrenewable energy resources reserves are in continuous minimizing, therefore to the reasonable development of the energy especially renewable energy source with utilize ever more important.Before 20th century, the main energy sources source of China is coal, and renewable energy source accounts for total energy consumption less than 1%.Coal can discharge CO after combustion as traditional fossil energy
2isothermal chamber gas, and then cause the stubborn problems such as global warming, and coal is non-renewable, coal in China occupancy volume per person also not enough world occupancy volume per person 1/2, therefore it can not for a long time as China's main energy sources source.
Thermoelectric generation technology is a kind of new-type and eco-friendly Energy conversion technology, and wherein thermoelectric material is thermoelectric material again, heat energy and electric energy can be made to carry out directly mutually transforming, the conversion of convenient energy and storage.The energy utilization that fossil energy is taken as the leading factor causes the problem such as Greenhouse effect and depletion of the ozone layer more serious, and thermoelectric material can alleviate this two large problems as a kind of Energy conversion material.The heat that the used heat waste gas produced in industrial or agricultural and solar radiation produce can be converted to electric energy by thermoelectric material, namely utilizes thermo-electric generation, temperature-difference refrigerating also can be utilized to replace freonll-11 and reduce its destruction to ozonosphere.
Bi
2se
3belong to V
2-VI
3race, be low-gap semiconductor, energy gap is about 0.24eV.Bi
2te
3also there is good thermoelectricity capability, but due to global tellurium ore reserves limited, and to reduce, face exhausted danger, Bi
2se
3with Bi
2te
3compare and have wider temperature use range, and the temperature value of its optimum performance usually at room temperature, selenium ore deposit is abundanter than tellurium ore reserves simultaneously, therefore, uses Bi in recent years
2se
3replace Bi
2te
3research become focus gradually.
Bi
2se
3the preparation method of film mainly contains chemical vapour deposition, SILAR method, pulsed laser deposition, electrodip process etc.Wherein electrodip process cost is low, workable, easily realizes industrialization, and electrodip process prepares Bi
2se
3film has Research Significance.
Method is the same as previously described, and other method also has different defects.Related to the present invention also has as Publication about Document:
[1]VasiliyO.Pelenovich,RenzhengXiao,YongLiu,PankeLiu,MingkaiLi,YunbingHe,DejunFu,CharacterizationofBi
2Se
3:Feepitaxialfilmsgrownbypulsedlaserdeposition,ThinSolidFilms577(2015)119–123.
Essentially describing with pulsed laser deposition with bismuth meal is Bi prepared by raw material
2se
3: Fe epitaxial film is also studied its structure, pattern and electrical property.
[2]MeiLiu,FuYanLiu,BaoYuanMan,DongBi,XueYouXu,Multi-layerednanostructureBi
2Se
3grownbychemicalvapordepositioninselenium-richatmosphere,AppliedSurfaceScience317(2014)257–261.
Essentially describe the Bi preparing multi-layer nano structure in rich selenium atmosphere with chemical Vapor deposition process
2se
3.
[3]B.R.Sankapal,C.D.Lokhande,PhotoelectrochemicalcharacterizationofBi
2Se
3thinfilmsdepositedbySILARtechnique,MaterialsChemistryandPhysics73(2002)151–155.
Essentially describing with SILAR method with Bismuth trinitrate is that Bi prepared by raw material
2se
3film, and carry out finishing structure, pattern and performance analysis.
[4]LiXiaolong,XueZhen,TheeffectofelectrochemicalconditionsonmorphologyandpropertiesofBi
2Se
3thickfilmsbyelectrodeposition,MaterialsLetters129(2014)1–4.
Essentially describe electrochemical conditions to taking Bismuth trinitrate as Bi prepared by raw material galvanic deposit
2se
3the impact of pattern and performance.
[5]ChengjingXiao,JunyouYang,WenZhu,JiangyingPeng,JianshengZhang,ElectrodepositionandcharacterizationofBi
2Se
3thinfilmsbyelectrochemicalatomiclayerepitaxy(ECALE),ElectrochimicaActa54(2009)6821–6826.
Essentially describe with Bismuth trinitrate is that raw material electrochemical atomic layer epitaxy legal system is for Bi
2se
3film and performance characterization thereof.
[6]A.P.Torane,C.H.Bhosale,PreparationandcharacterizationofelectrodepositedBi
2Se
3thinfilmsfromnonaqueousmedium,MaterialsResearchBulletin36(2001)1915–1924.
Essentially describe in non-aqueous media is that Bi is prepared in raw material galvanic deposit with Bismuth trinitrate
2se
3film, and have studied the impact of different electrolytes composition on structure and pattern.
Summary of the invention
The present invention existingly prepares bismuth selenide thermal electric film Problems existing to solve, and has invented a kind of method that bismuth sulfate prepares bismuth selenide thermal electric film.
The present invention adopts galvanic deposit postheat treatment to prepare bismuth selenide film, adopts tin dioxide conductive glass to be substrate, with Bi
2(SO
4)
3, SeO
2for raw material, take dust technology as solvent, by fixed molar ratio preparation electric depositing solution, transistor potentiostat is first adopted to prepare precursor thin-film under certain potentials and time, take hydrazine hydrate as reductive agent, heat in airtight tube type stove, after making precursor thin-film thermal treatment, obtain target product.
Concrete preparation method of the present invention comprises the step of following order:
A. carrying out the cleaning of tin dioxide conductive glass substrate, is that volume ratio acetone put into by the sheet glass of 20mm × 20mm by size: the solution of distilled water=5:1, ultrasonic cleaning 30min; Again substrate is put into ethanol, ultrasonic cleaning 30min; In distilled water, glass substrate is used sonic oscillation 30min again; Being emitted in glass dish by glass substrate obtained above sends in baking oven, dries for masking at 100 DEG C.
B. by Bi
2(SO
4)
3, SeO
2put into dust technology, obtain uniform and stable electric depositing solution.Specifically, can by 5.0 ~ 10.0 parts of Bi
2(SO
4)
3, 1.0 ~ 2.0 parts of SeO
2put into 1800.0 ~ 3600.0 parts of dust technology, make the substance dissolves in solution.
C. electric depositing solution described in step b is poured in three electrode devicies, take saturated calomel electrode as reference electrode, platinum electrode is supporting electrode, tin dioxide conductive glass is Electrode, adopt transistor potentiostat normal temperature deposit film under sedimentation potential is-0.4V, depositing time is 20min, and seasoning obtains precursor thin-film sample.
D. be placed on support by step c gained precursor thin-film sample, precursor thin-film and hydrazine hydrate are put into tube furnace, and precursor thin-film sample does not contact with hydrazine hydrate, and it is 40.0 ~ 50.0 parts that hydrazine hydrate is put into.By between diamond heating to 250 ~ 400 DEG C, soaking time 1 ~ 3h, then cool to room temperature takes out.
E. by steps d gains, after making its normal temperature seasoning, bismuth selenide thermal electric film is namely obtained.
The present invention does not need high vacuum condition, and require low to plant and instrument, production cost is low, and production efficiency is high, easy handling.Gained bismuth selenide thermal electric film has good continuity and homogeneity, and principal phase is Bi
2se
3phase, can realize low cost large-scale industrial production.
Accompanying drawing explanation
Nothing
Embodiment
Embodiment 1
A. the cleaning of tin dioxide conductive glass substrate: carry out cleaning glass substrate as previously mentioned, substrate size is 20mm × 20mm.
B. by 5.0 parts of Bi
2(SO
4)
3, 1.0 parts of SeO
2put into 1800.0 parts of dust technology, make the substance dissolves in solution.
C. above-mentioned electric depositing solution is poured in three electrode devicies, take saturated calomel electrode as reference electrode, platinum electrode is supporting electrode, tin dioxide conductive glass is Electrode, adopt transistor potentiostat normal temperature deposit film under sedimentation potential is-0.4V, depositing time is 20min, and seasoning obtains precursor thin-film sample.
D. be placed on support by step c gained precursor thin-film sample, precursor thin-film and hydrazine hydrate are put into tube furnace, and precursor thin-film sample does not contact with hydrazine hydrate, and it is 40.0 parts that hydrazine hydrate is put into.By diamond heating to 350 DEG C, soaking time 2h, then cool to room temperature takes out.
E. by steps d gains, carry out normal temperature seasoning, obtain bismuth selenide thermal electric film.
Claims (4)
1. prepare a method for bismuth selenide thermal electric film with bismuth sulfate, comprise the step of following order:
A. the cleaning of tin dioxide conductive glass substrate;
B. by 5.0 ~ 10.0 parts of Bi
2(SO
4)
3, 1.0 ~ 2.0 parts of SeO
2put into the dust technology of 1800.0 ~ 3600.0 parts, make the substance dissolves in solution;
C. adopt electrodip process to be deposited on conductive glass sheet by solution described in step b and obtain precursor thin-film, seasoning, obtain precursor thin-film sample;
D. be placed on support by step c gained precursor thin-film sample, precursor thin-film sample does not contact with hydrazine hydrate, and precursor thin-film and hydrazine hydrate are put into tube furnace; By between diamond heating to 250 ~ 400 DEG C, soaking time 1 ~ 3h, then cool to room temperature takes out;
E. by steps d gains, carry out seasoning, obtain bismuth selenide thermal electric film.
2. a kind of bismuth sulfate prepares the method for bismuth selenide thermal electric film as claimed in claim 1, it is characterized in that, clean described in step a, is be 20mm × 20mm by conductive glass substrate size, put into volume ratio acetone: the solution of distilled water=5:1, ultrasonic cleaning 30min; Again substrate is put into ethanol, ultrasonic cleaning 30min; In distilled water, glass substrate is used sonic oscillation 30min again; Being emitted in glass dish by glass substrate obtained above sends in baking oven, dries for masking at 100 DEG C.
3. a kind of bismuth sulfate prepares the method for bismuth selenide thermal electric film as claimed in claim 1, it is characterized in that, described in step c, being added by solution in three electrode devicies, take saturated calomel electrode as reference electrode, and platinum electrode is supporting electrode, tin dioxide conductive glass is Electrode, adopt transistor potentiostat normal temperature deposit film under sedimentation potential is-0.4V, depositing time is 20min, and seasoning obtains precursor thin-film sample.
4. a kind of bismuth sulfate prepares the method for bismuth selenide thermal electric film as claimed in claim 1, it is characterized in that, puts into 40.0 ~ 50.0 parts of hydrazine hydrates in tube furnace described in steps d.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510943168.0A CN105439106B (en) | 2015-12-17 | 2015-12-17 | A kind of method that bismuth selenide thermal electric film is prepared with bismuth sulfate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510943168.0A CN105439106B (en) | 2015-12-17 | 2015-12-17 | A kind of method that bismuth selenide thermal electric film is prepared with bismuth sulfate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105439106A true CN105439106A (en) | 2016-03-30 |
| CN105439106B CN105439106B (en) | 2018-01-12 |
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|---|---|---|---|
| CN201510943168.0A Expired - Fee Related CN105439106B (en) | 2015-12-17 | 2015-12-17 | A kind of method that bismuth selenide thermal electric film is prepared with bismuth sulfate |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101214933A (en) * | 2008-01-10 | 2008-07-09 | 华中科技大学 | Process for preparing metal selenide thin film |
| CN101420010A (en) * | 2008-11-28 | 2009-04-29 | 天津大学 | Liquid phase electric deposit N type or P type thin-film thermoelectric material and production method thereof |
| EP2072644A1 (en) * | 2007-12-21 | 2009-06-24 | ETH Zürich, ETH Transfer | Device and method for the electrochemical deposition of chemical compounds and alloys with controlled composition and or stoichiometry |
| CN101630701A (en) * | 2008-12-03 | 2010-01-20 | 山东建筑大学 | Method for preparing copper-indium-selenium optoelectronic thin film material of solar cell |
| CN102603201A (en) * | 2011-09-29 | 2012-07-25 | 山东建筑大学 | Method for preparing cuprous selenide thin film |
| CN102603202A (en) * | 2012-03-12 | 2012-07-25 | 山东建筑大学 | Method for preparing tin selenide photoelectric thin film |
-
2015
- 2015-12-17 CN CN201510943168.0A patent/CN105439106B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2072644A1 (en) * | 2007-12-21 | 2009-06-24 | ETH Zürich, ETH Transfer | Device and method for the electrochemical deposition of chemical compounds and alloys with controlled composition and or stoichiometry |
| CN101214933A (en) * | 2008-01-10 | 2008-07-09 | 华中科技大学 | Process for preparing metal selenide thin film |
| CN101420010A (en) * | 2008-11-28 | 2009-04-29 | 天津大学 | Liquid phase electric deposit N type or P type thin-film thermoelectric material and production method thereof |
| CN101630701A (en) * | 2008-12-03 | 2010-01-20 | 山东建筑大学 | Method for preparing copper-indium-selenium optoelectronic thin film material of solar cell |
| CN102603201A (en) * | 2011-09-29 | 2012-07-25 | 山东建筑大学 | Method for preparing cuprous selenide thin film |
| CN102603202A (en) * | 2012-03-12 | 2012-07-25 | 山东建筑大学 | Method for preparing tin selenide photoelectric thin film |
Non-Patent Citations (1)
| Title |
|---|
| A.P. TORANE ET AL.: "Preparation and characterization of electrodeposited Bi2Se3 thin films", 《MATERIALS CHEMISTRY AND PHYSICS》 * |
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| CN105439106B (en) | 2018-01-12 |
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Granted publication date: 20180112 Termination date: 20181217 |