CN105483790B - A kind of method that bismuth selenide thermal electric film is prepared with bismuth oxide - Google Patents

A kind of method that bismuth selenide thermal electric film is prepared with bismuth oxide Download PDF

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Publication number
CN105483790B
CN105483790B CN201510943219.XA CN201510943219A CN105483790B CN 105483790 B CN105483790 B CN 105483790B CN 201510943219 A CN201510943219 A CN 201510943219A CN 105483790 B CN105483790 B CN 105483790B
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film
bismuth
thermal electric
precursor thin
electrode
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CN105483790A (en
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刘科高
李静
刘慧�
苏沫林
徐勇
石磊
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Shandong Jianzhu University
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D9/00—Electrolytic coating other than with metals
    • C25D9/04—Electrolytic coating other than with metals with inorganic materials
    • C25D9/08—Electrolytic coating other than with metals with inorganic materials by cathodic processes
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/48—After-treatment of electroplated surfaces
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/54—Electroplating of non-metallic surfaces
    • 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

Abstract

A kind of method that bismuth selenide thermal electric film is prepared with bismuth oxide, belong to thermoelectric film material preparing technical field, the present invention obtains as follows, tin dioxide conductive glass substrate is cleaned first, then by Bi2O3、SeO2It is put into dust technology, precursor thin-film is obtained on electro-conductive glass piece with electrodeposition process, spontaneously dries, it is put into the tube furnace added with hydrazine hydrate, precursor thin-film sample is not contacted with hydrazine hydrate, is heated in airtight tube type stove, finally take out sample to be dried, obtain bismuth selenide thermal electric film.The present invention does not need high vacuum condition, requires low to instrument and equipment, production cost is low, and production efficiency is high, easily operated.Gained bismuth selenide thermal electric film has preferable continuity and uniformity, principal phase Bi2Se3Phase, it is possible to achieve inexpensive large-scale industrial production.

Description

A kind of method that bismuth selenide thermal electric film is prepared with bismuth oxide
Technical field
The invention belongs to thermal electric film preparing technical field, more particularly to one kind to prepare bismuth selenide thermal electric film with bismuth oxide Method.
Background technology
The energy, material and information are three big pillars of modern technologies.Increase with the demand of the social development energy, without Regenerative resource reserves are but constantly being reduced, therefore reasonable development to the energy especially regenerative resource and utilization are more heavy Will.Before 20th century, Chinese main energy sources source is coal, and regenerative resource accounts for total energy consumption less than 1%.Coal is made CO can be discharged after combustion for traditional fossil energy2Isothermal chamber gas, and then cause the stubborn problems such as global warming, and And coal is non-renewable, coal in China occupancy volume per person is also insufficient the 1/2 of world occupancy volume per person, therefore it can not long-term conduct China main energy sources source.
Thermoelectric generation technology is a kind of new-type and environment-friendly energy conversion technology, and wherein thermoelectric material is called thermoelectric Material, heat energy can be made to carry out directly mutually conversion, the conversion and storage of convenient energy with electric energy.Fossil energy is leading energy Source is more serious using the problems such as causing greenhouse effects and depletion of the ozone layer, and thermoelectric material can delay as a kind of energy conversion material Solve this two large problems.Thermoelectric material can change heat caused by caused used heat waste gas in industrial or agricultural and solar radiation For electric energy, i.e., using thermo-electric generation, temperature-difference refrigerating can also be utilized to replace freon and reduce its destruction to ozone layer.
Bi2Se3Belong to V2-Ⅵ3Race, is low-gap semiconductor, and energy gap is about 0.24eV.Bi2Te3Also have good Thermoelectricity capability, but because global tellurium ore reserves is limited, and reduce, face the danger of exhaustion, Bi2Se3With Bi2Te3 Compared to broader temperature use range, and the temperature value of its optimum performance is generally at room temperature, while selenium ore deposit is than tellurium ore deposit Rich reserves, therefore, Bi are used in recent years2Se3Substitute Bi2Te3Research be increasingly becoming focus.
Bi2Se3The preparation method of film mainly has chemical vapor deposition, SILAR method, pulse laser to sink Product, electrodeposition process etc..Wherein electrodeposition process cost is low, workable, easily realizes industrialization, and electrodeposition process prepares Bi2Se3It is thin Film has Research Significance.
Method is the same as previously described, and other methods also have the defects of different.Related to the present invention also has following document：
[1] Vasiliy O. Pelenovich, Renzheng Xiao, Yong Liu, Panke Liu, Mingkai Li, Yunbing He, Dejun Fu, Characterization of Bi2Se3:Fe epitaxial films grown by pulsed laser deposition, Thin Solid Films 577 (2015) 119–123.
Essentially describe the Bi prepared with pulsed laser deposition by raw material of bismuth meal2Se3:Fe epitaxial films and to its structure, Pattern and electrical property are studied.
[2] Mei Liu, Fu Yan Liu, Bao Yuan Man, Dong Bi, Xue You Xu, Multi- layered nanostructure Bi2Se3 grown by chemical vapor deposition in selenium- rich atmosphere, Applied Surface Science 317 (2014) 257–261.
Essentially describe the Bi for preparing multi-layer nano structure with chemical vapour deposition technique in selenium-rich atmosphere2Se3。
[3] B.R. Sankapal, C.D. Lokhande, Photoelectrochemical characterization of Bi2Se3 thin films deposited by SILAR technique, Materials Chemistry and Physics 73 (2002) 151–155.
Essentially describe and Bi is prepared by raw material of bismuth nitrate with SILAR method2Se3Film, and carry out Structure, pattern and performance evaluation.
[4] Li Xiaolong, Xue Zhen, The effect of electrochemical conditions on morphology and properties of Bi2Se3 thick films by electrodeposition, Materials Letters 129 (2014) 1–4.
Electrochemical conditions are essentially described to the Bi that is prepared using bismuth nitrate as raw material electro-deposition2Se3The shadow of pattern and performance Ring.
[5] Chengjing Xiao, Junyou Yang, Wen Zhu, Jiangying Peng, Jiansheng Zhang, Electrodeposition and characterization of Bi2Se3 thin films by electrochemicalatomic layer epitaxy (ECALE), Electrochimica Acta 54 (2009) 6821–6826.
Essentially describe and prepare Bi by raw material electrochemical atomic layer epitaxy method of bismuth nitrate2Se3Film and its performance characterization.
[6] A.P. Torane, C.H. Bhosale, Preparation and characterization of electrodeposited Bi2Se3 thin films from nonaqueous medium, Materials Research Bulletin 36 (2001) 1915–1924.
Essentially describe and prepare Bi by raw material electro-deposition of bismuth nitrate in non-aqueous media2Se3Film, and have studied difference Influence of the bath composition to structure and pattern.
The content of the invention
The present invention in order to solve it is existing preparation selenizing bismuth thin film existing for problem, invented one kind bismuth oxide preparation selenizing The method of bismuth thermal electric film.
Heat treatment prepares selenizing bismuth thin film after the present invention uses electro-deposition, uses tin dioxide conductive glass as substrate, with Bi2O3, SeO2For raw material, using dust technology as solvent, electric depositing solution is prepared by fixed molar ratio, first using transistor constant potential Instrument prepares precursor thin-film under certain potentials and time, using hydrazine hydrate as reducing agent, is heated in airtight tube type stove, before making Target product is obtained after driving body thin film heat treatment.
The specific preparation method of the present invention is included following steps in sequence：
A. the cleaning of tin dioxide conductive glass substrate is carried out, the sheet glass that size is 20mm × 20mm is put into volume ratio Acetone：Distilled water=5：In 1 solution, ultrasonic wave cleaning 30min；Substrate is put into ethanol again, ultrasonic wave cleaning 30min；Again By glass substrate sonic oscillation 30min in distilled water；Glass substrate obtained above is emitted on to be sent into glass dish and dried In case, drying is for film at 100 DEG C.
B. by Bi2O3, SeO2It is put into dust technology, obtains uniform and stable electric depositing solution.Specifically, can be by 3.4 ~6.8 parts of Bi2O3, 1.0~2.0 parts of SeO2It is put into 1800.0~3600.0 parts of dust technologies, dissolves the material in solution.
C. electric depositing solution described in step b is poured into three electrode assemblies, using saturated calomel electrode as reference electrode, platinum electricity Extremely auxiliary electrode, tin dioxide conductive glass are Electrode, use transistor potentiostat in the case where sedimentation potential is -0.4V Normal temperature deposition film, sedimentation time 20min, natural drying obtain precursor thin-film sample.
D. precursor thin-film sample obtained by step c is placed on support, precursor thin-film and hydrazine hydrate is put into tubular type In stove, precursor thin-film sample is not contacted with hydrazine hydrate, and hydrazine hydrate is put into as 40.0~50.0 parts.By diamond heating extremely Between 250~400 DEG C, 1~3h of soaking time, room temperature taking-up is then cooled to.
E. by step d gains, after spontaneously drying its normal temperature, that is, bismuth selenide thermal electric film is obtained.
The present invention does not need high vacuum condition, requires low to instrument and equipment, production cost is low, and production efficiency is high, is easy to grasp Make.Gained bismuth selenide thermal electric film has preferable continuity and uniformity, principal phase Bi2Se3Phase, it is possible to achieve the big rule of low cost The industrialized production of mould.
Embodiment
Embodiment 1
A. the cleaning of tin dioxide conductive glass substrate：Cleaning glass substrate is carried out as previously described, and substrate size is 20mm ×20mm。
B. by 3.4 parts of Bi2O3, 1.0 parts of SeO2It is put into 1800.0 parts of dust technologies, dissolves the material in solution.
C. above-mentioned electric depositing solution is poured into three electrode assemblies, using saturated calomel electrode as reference electrode, platinum electrode is Auxiliary electrode, tin dioxide conductive glass are Electrode, use transistor potentiostat normal temperature in the case where sedimentation potential is -0.4V Deposition film, sedimentation time 20min, natural drying obtain precursor thin-film sample.
D. precursor thin-film sample obtained by step c is placed on support, precursor thin-film and hydrazine hydrate is put into tubular type In stove, precursor thin-film sample is not contacted with hydrazine hydrate, and hydrazine hydrate is put into as 40.0 parts.By diamond heating to 350 DEG C, Soaking time 2h, then it is cooled to room temperature taking-up.
E. by step d gains, normal temperature natural drying is carried out, obtains bismuth selenide thermal electric film.

Claims (1)

  1. A kind of 1. method that bismuth selenide thermal electric film is prepared with bismuth oxide, by forming following steps in sequence：
    A. the cleaning of tin dioxide conductive glass substrate：It is 20mm × 20mm by electro-conductive glass substrate size, is put into volume ratio third Ketone：Distilled water=5：In 1 solution, ultrasonic wave cleaning 30min；Substrate is put into ethanol again, ultrasonic wave cleaning 30min；Exist again By glass substrate sonic oscillation 30min in distilled water；Glass substrate obtained above is emitted in glass dish and is sent into baking oven In, drying is for film at 100 DEG C；
    B. by 3.4 parts of Bi2O3, 1.0 parts of SeO2It is put into 1800.0 parts of dust technologies, dissolves above-mentioned substance, it is molten forms electro-deposition Liquid；
    C. above-mentioned electric depositing solution is poured into three electrode assemblies, using saturated calomel electrode as reference electrode, platinum electrode is auxiliary Electrode, tin dioxide conductive glass are Electrode, use transistor potentiostat normal temperature in the case where sedimentation potential is -0.4V to deposit Film, sedimentation time 20min, natural drying obtain precursor thin-film sample；
    D. precursor thin-film sample obtained by step c is placed on support, precursor thin-film sample and hydrazine hydrate is put into tubular type In stove, precursor thin-film sample is not contacted with hydrazine hydrate, and hydrazine hydrate is put into as 40.0 parts, by diamond heating to 350 DEG C, Soaking time 2h, then it is cooled to room temperature taking-up；
    E. by step d gains, normal temperature natural drying is carried out, obtains bismuth selenide thermal electric film.
CN201510943219.XA 2015-12-17 2015-12-17 A kind of method that bismuth selenide thermal electric film is prepared with bismuth oxide Expired - Fee Related CN105483790B (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101613867A (en) * 2009-07-25 2009-12-30 天津大学 Galvanic deposit Bi 2Te 3The preparation method of mixed with thin-film thermoelectric material
CN102020253A (en) * 2010-11-09 2011-04-20 北京大学 Topological insulator material and preparation method thereof
CN104480508A (en) * 2014-12-24 2015-04-01 北京化工大学 Preparation method of porous and laminar Bi2Te3 nano thermoelectric film

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI500825B (en) * 2013-05-02 2015-09-21 Nat Univ Tsing Hua Method for producing nano sheet array structure of v-vi group semiconductor

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101613867A (en) * 2009-07-25 2009-12-30 天津大学 Galvanic deposit Bi 2Te 3The preparation method of mixed with thin-film thermoelectric material
CN102020253A (en) * 2010-11-09 2011-04-20 北京大学 Topological insulator material and preparation method thereof
CN104480508A (en) * 2014-12-24 2015-04-01 北京化工大学 Preparation method of porous and laminar Bi2Te3 nano thermoelectric film

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Electrodeposition and characterization of thermoelectric Bi2Se3 thin films;Xiao-long Li et al.;《International Journal of Minerals, Metallurgy and Materials》;20100101;第17卷(第1期);第104页右栏第2部分 实验程序 *
电化学沉积三元热电材料之技术开发;陈彦翔;《台湾师范大学机电科技研究所学位论文》;http://www.airitilibrary.com/Publication/alDetailedMesh?docid=U0021-1610201315211343#;20100101;摘要 *

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