CN101956158A - Preparation method of rare earth doped Bi2Te3 based thermoelectric film material - Google Patents
Preparation method of rare earth doped Bi2Te3 based thermoelectric film material Download PDFInfo
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- CN101956158A CN101956158A CN2009101865135A CN200910186513A CN101956158A CN 101956158 A CN101956158 A CN 101956158A CN 2009101865135 A CN2009101865135 A CN 2009101865135A CN 200910186513 A CN200910186513 A CN 200910186513A CN 101956158 A CN101956158 A CN 101956158A
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Abstract
The invention relates to a rare earth doped Bi2Te3 based thermoelectric film material which is prepared by the steps of: adding rare earth elements during vacuum melting to obtain a Bi2-xTe3REx block thermoelectric material, wherein RE represents the rare earth elements, x is equal to 0.002-0.01, and the doped rare earth elements are light rare earth elements of La and Ce; and grinding the molten material into powder particles of 200-300 mu m to be used as a raw material of a flash evaporation method. The film is prepared by adopting the flash evaporation method, and the deposited film is annealed to obtain the rare earth doped Bi2-xTe3REx thermoelectric film material. The thermoelectric property of the rare earth doped Bi2-xTe3REx thermoelectric film material is superior to an undoped Bi2Te3 based thermoelectric film material, a doping principle is that the rare earth elements have properties similar to alkaline earth, and when the rare earth elements are added, a Bi position is easily replaced to be used as donor doping, which improves carrier concentration, thus the thermoelectric property of the Bi2Te3 based film material is improved.
Description
Technical field
The present invention relates to thermoelectric film material, be specifically related to a kind of rear-earth-doped Bi
2Te
3The base thermoelectric film material.
Background technology
Bi
2Te
3Sill is typical semiconductor refrigerating one of thermoelectric material, has wide practical use in microelectronics, photoelectron and many high-tech areas, gets more and more people's extensive concerning in recent years.Bi
2Te
3Base thermoelectric film material its thermoelectricity capability for practical application is still lower, awaits further raising.New approach has been opened up in the research that develops into high performance thermoelectric material of low-dimensionalization and optimum doping techniques, the low-dimensional thermoelectric material in the transmission of electronics and phonon by quantum size effect for the improvement significantly of thermoelectricity capability provides may.Thereby doping can be adjusted material carrier concentration and reduce the thermoelectricity capability that lattice thermal conductivity increases material.Present Bi
2Te
3The preparation method of base thermoelectric film material adopts the growth technology of expensive or complicated technology, as molecular beam epitaxy, electrochemical atomic layer epitaxy, metal-organic chemical vapor deposition equipment.The apparatus expensive of molecular beam epitaxy technique, production cost height.Although electrochemical atomic layer epitaxy does not need vacuum when the deposition thermal electric film, cost is lower, but influence factor is quite complicated, film performance not only is decided by very difficulty of thin-film material that the pH value of deposition current, voltage, temperature, solvent, solution and concentration, the factor affecting such as condition of surface, especially the electricity consumption chemistry atom-layer-epitaxial method that also are subjected to solution ion strength, electrode prepare ideal, complex component; There is the problem that can produce several respects such as poisonous source of the gas and apparatus expensive in prices of raw and semifnished materials costliness, the use in the metal-organic chemical vapor deposition equipment method.The above deposition method of what is more important all can't be realized rear-earth-doped Bi
2Te
3The preparation of base thermoelectric film material.
Summary of the invention
Its purpose of the present invention provides the rear-earth-doped Bi that a kind of technology is simple, cost is low with regard to being to overcome above defective
2Te
3Base thermoelectric film material preparation method, it is simple to have making method, safe and reliable pollution-free, cost is low, the advantage of easy handling, and because Doping Mechanism is that rare earth element has the similar character of alkaline-earth metal, after rare earth element adds, replace the Bi position easily, as donor doping, thereby the raising carrier concentration improves Bi
2Te
3The thermoelectricity capability of based film material.
For achieving the above object, the technical solution used in the present invention is as follows:
At Bi
2Te
3Add rare earth element in the base thermoelectricity material, obtain Bi by vacuum melting and flash method
2-xTe
3The REx thermal electric film, wherein RE represents rare earth element, x=0.002-0.01.The rare earth element that is mixed is light rare earths La, Ce.
Concrete operations step of the present invention is as follows: raw material is pressed atomic ratio Bi
2-xTe
3After REx calculates and weighs, with pack into silica tube and vacuumize sealing of the powder for preparing, silica tube is put into process furnace, Heating temperature is 1373K, be 48h heat-up time, keep the silica tube slight vibration in the process of heating, slow cool to room temperature then grinds to form the block alloy of melting the powder particle that the is of a size of 200-300 μ m starting material as evaporation.
The powder particle of evaporation usefulness is packed in the powder feeder of flash method equipment, be evacuated to 2 * 10-6Torr, the well heater of the temperature of substrate below the substrate support folder controlled, and substrate temperature is heated to 473K, and the distance of evaporation source and substrate is 25cm.The material of evaporation source adopts tantalum piece, is heated to 1473K in advance.In evaporative process, thereby whole substrate support folder guarantees that the thickness of film is even, the about 3nm/s of sedimentation rate with the speed rotation of 15rpm.Sedimentary film thickness is between 50-1000nm.Sedimentary film is all carried out anneal, annealing temperature 473K, annealing time 1h.At the resistivity (ρ) and the Seebeck coefficient (S) of 300K MEASUREMENTS OF THIN, the thermoelectricity capability of film is estimated by thermoelectric (al) power factor formula: θ=S2/ ρ.
The present invention compared with prior art its advantage is,
1) it is simple to have a making method, and safe and reliable pollution-free, cost is low, the advantage of easy handling, and, after rare earth element adds, replace the Bi position easily because Doping Mechanism is that rare earth element has the similar character of alkaline-earth metal, as donor doping, thereby improve carrier concentration, improve Bi
2Te
3The thermoelectricity capability of based film material.
What 2) adopt is flash method, claims " moment " method of evaporation or " differential " method of evaporation again.It is that tiny alloy or compound particle are bit by bit delivered in the pyritous evaporation source successively, makes evaporated material realize that on evaporation source moment evaporates fully.Because flash method technology is simple, cost is low, can accurately control the chemical constitution of institute's deposit film, obtains the uniform film of composition, become preparation Bi
2Te
3The important process of base nanometer thermoelectric thin-film material.
Embodiment
Below by embodiment the present invention is described in further detail.
Embodiment 1
With raw material (Bi, Te and La) by atomic ratio Bi1.998Te3La0.002 calculate weigh after, the silica tube of packing into vacuumizes sealing and places process furnace, Heating temperature is 1373K, be 48h heat-up time, keep the silica tube slight vibration in the process of heating, slow cool to room temperature then grinds to form the block alloy of melting the powder particle that the is of a size of 200-300 μ m starting material as evaporation; Adopt flash method to realize the preparation of film, the about 3nm/s of sedimentation rate, film thickness are 200nm, and sedimentary film is carried out anneal, annealing temperature 473K, and annealing time 1h obtains rear-earth-doped Bi1.998Te3La0.002 thermoelectric film material.
Embodiment 2
With raw material (Bi, Te and La) by atomic ratio Bi1.996Te3La0.004 calculate weigh after, the silica tube of packing into vacuumizes sealing and places process furnace, Heating temperature is 1373K, be 48h heat-up time, keep the silica tube slight vibration in the process of heating, slow cool to room temperature then grinds to form the block alloy of melting the powder particle that the is of a size of 200-300 μ m starting material as evaporation; Adopt flash method to realize the preparation of film, the about 3nm/s of sedimentation rate, film thickness are 200nm, and sedimentary film is carried out anneal, annealing temperature 473K, and annealing time 1h obtains rear-earth-doped Bi1.996Te3La0.004 thermoelectric film material.
Embodiment 3
With raw material (Bi, Te and La) by atomic ratio Bi1.994Te3La0.006 calculate weigh after, the silica tube of packing into vacuumizes sealing and places process furnace, Heating temperature is 1373K, be 48h heat-up time, keep the silica tube slight vibration in the process of heating, slow cool to room temperature then grinds to form the block alloy of melting the powder particle that the is of a size of 200-300 μ m starting material as evaporation; Adopt flash method to realize the preparation of film, the about 3nm/s of sedimentation rate, film thickness are 200nm, and sedimentary film is carried out anneal, annealing temperature 473K, and annealing time 1h obtains rear-earth-doped Bi1.994Te3La0.006 thermoelectric film material.
Embodiment 4
With raw material (Bi, Te and La) by atomic ratio Bi1.992Te3La0.008 calculate weigh after, the silica tube of packing into vacuumizes sealing and places process furnace, Heating temperature is 1373K, be 48h heat-up time, keep the silica tube slight vibration in the process of heating, slow cool to room temperature then grinds to form the block alloy of melting the powder particle that the is of a size of 200-300 μ m starting material as evaporation; Adopt flash method to realize the preparation of film, the about 3nm/s of sedimentation rate, film thickness are 200nm, and sedimentary film is carried out anneal, annealing temperature 473K, and annealing time 1h obtains rear-earth-doped Bi1.992Te3La0.008 thermoelectric film material.
Embodiment 5
With raw material (Bi, Te and La) by atomic ratio Bi1.99Te3La0.01 calculate weigh after, the silica tube of packing into vacuumizes sealing and places process furnace, Heating temperature is 1373K, be 48h heat-up time, keep the silica tube slight vibration in the process of heating, slow cool to room temperature then grinds to form the block alloy of melting the powder particle that the is of a size of 200-300 μ m starting material as evaporation; Adopt flash method to realize the preparation of film, the about 3nm/s of sedimentation rate, film thickness are 200nm, and sedimentary film is carried out anneal, annealing temperature 473K, and annealing time 1h obtains rear-earth-doped Bi1.99Te3La0.01 thermoelectric film material.
Embodiment 6
With raw material (Bi, Te and Ce) by atomic ratio Bi1.998Te3Ce0.002 calculate weigh after, the silica tube of packing into vacuumizes sealing and places process furnace, Heating temperature is 1373K, be 48h heat-up time, keep the silica tube slight vibration in the process of heating, slow cool to room temperature then grinds to form the block alloy of melting the powder particle that the is of a size of 200-300 μ m starting material as evaporation; Adopt flash method to realize the preparation of film, the about 3nm/s of sedimentation rate, film thickness are 200nm, and sedimentary film is carried out anneal, annealing temperature 473K, and annealing time 1h obtains rear-earth-doped Bi1.998Te3Ce0.002 thermoelectric film material.
Embodiment 7
With raw material (Bi, Te and Ce) by atomic ratio Bi1.996Te3Ce0.004 calculate weigh after, the silica tube of packing into vacuumizes sealing and places process furnace, Heating temperature is 1373K, be 48h heat-up time, keep the silica tube slight vibration in the process of heating, slow cool to room temperature then grinds to form the block alloy of melting the powder particle that the is of a size of 200-300 μ m starting material as evaporation; Adopt flash method to realize the preparation of film, the about 3nm/s of sedimentation rate, film thickness are 200nm, and sedimentary film is carried out anneal, annealing temperature 473K, and annealing time 1h obtains rear-earth-doped Bi1.996Te3RE0.004 thermoelectric film material.
Embodiment 8
With raw material (Bi, Te and Ce) by atomic ratio Bi1.994Te3Ce0.006 calculate weigh after, the silica tube of packing into vacuumizes sealing and places process furnace, Heating temperature is 1373K, be 48h heat-up time, keep the silica tube slight vibration in the process of heating, slow cool to room temperature then grinds to form the block alloy of melting the powder particle that the is of a size of 200-300 μ m starting material as evaporation; Adopt flash method to realize the preparation of film, the about 3nm/s of sedimentation rate, film thickness are 200nm, and sedimentary film is carried out anneal, annealing temperature 473K, and annealing time 1h obtains rear-earth-doped Bi1.994Te3Ce0.006 thermoelectric film material.
Embodiment 9
With raw material (Bi, Te and Ce) by atomic ratio Bi1.992Te3Ce0.008 calculate weigh after, the silica tube of packing into vacuumizes sealing and places process furnace, Heating temperature is 1373K, be 48h heat-up time, keep the silica tube slight vibration in the process of heating, slow cool to room temperature then grinds to form the block alloy of melting the powder particle that the is of a size of 200-300 μ m starting material as evaporation; Adopt flash method to realize the preparation of film, the about 3nm/s of sedimentation rate, film thickness are 200nm, and sedimentary film is carried out anneal, annealing temperature 473K, and annealing time 1h obtains rear-earth-doped Bi1.992Te3Ce0.008 thermoelectric film material.
Embodiment 10
With raw material (Bi, Te and Ce) by atomic ratio Bi1.99Te3Ce0.01 calculate weigh after, the silica tube of packing into vacuumizes sealing and places process furnace, Heating temperature is 1373K, be 48h heat-up time, keep the silica tube slight vibration in the process of heating, slow cool to room temperature then grinds to form the block alloy of melting the powder particle that the is of a size of 200-300 μ m starting material as evaporation; Adopt flash method to realize the preparation of film, the about 3nm/s of sedimentation rate, film thickness are 200nm, and sedimentary film is carried out anneal, annealing temperature 473K, and annealing time 1h obtains rear-earth-doped Bi1.99Te3Ce0.01 thermoelectric film material.
Comparative Examples
(Bi Te) presses atomic ratio Bi with raw material
2Te
3After calculating is weighed, the silica tube of packing into vacuumizes sealing and places process furnace, Heating temperature is 1373K, be 48h heat-up time, keep the silica tube slight vibration in the process of heating, slow cool to room temperature then grinds to form the block alloy of melting the powder particle that the is of a size of 200-300 μ m starting material as evaporation; Adopt flash method to realize the preparation of film, the about 3nm/s of sedimentation rate, film thickness are 200nm, and sedimentary film is carried out anneal, annealing temperature 473K, and annealing time 1h obtains Bi
2Te
3Thermoelectric film material.
The tabulation of thermoelectric (al) power factor calculation result
| Example | Materials chemistry is formed | Thermoelectric (al) power factor θ (* 10-6W/mK2) |
| Embodiment 1 | Bi1.998Te3La0.002? | 1280? |
| Embodiment 2 | Bi1.996Te3La0.004? | 1360? |
| Embodiment 3 | Bi1.994Te3La0.006? | 1390? |
| Embodiment 4 | Bi1.992Te3La0.008? | 1530? |
| Embodiment 5 | Bi1.99Te3La0.01? | 1670? |
| Embodiment 6 | Bi1.998Te3Ce0.002? | 1230? |
| Embodiment 7 | Bi1.996Te3Ce0.004? | 1340? |
| Embodiment 8 | Bi1.994Te3Ce0.006? | 1380? |
| Embodiment 9 | Bi1.992Te3Ce0.008? | 1420? |
| Embodiment 10 | Bi1.99Te3Ce0.01? | 1510? |
| Comparative Examples | Bi 2Te 3 | 1170? |
Claims (3)
1. rear-earth-doped Bi
2Te
3The preparation method of base thermoelectric film material is characterized in that, may further comprise the steps:
(1) chemical constitution of material is Bi
2-xTe
3RE
x, wherein RE is a rare earth element, x=0.002-0.01.Raw material is pressed atomic ratio Bi
2-xTe
3RE
xAfter calculating is weighed, with pack into silica tube and vacuumize sealing of the powder for preparing, silica tube is put into process furnace, Heating temperature is 1373K, be 48h heat-up time, keep the silica tube slight vibration in the process of heating, slow cool to room temperature then grinds to form the block alloy of melting the powder particle that the is of a size of 200-300 μ m starting material as evaporation.
(2) during the powder particle that will evaporate usefulness is packed the powder feeder of flash method equipment into, be evacuated to 2 * 10
-6Torr, the well heater of the temperature of substrate below the substrate support folder controlled, and substrate temperature is heated to 473K, and the distance of evaporation source and substrate is 25cm.The material of evaporation source adopts tantalum piece, is heated to 1473K in advance.In evaporative process, thereby whole substrate support folder guarantees that the thickness of film is even, the about 3nm/s of sedimentation rate with the speed rotation of 15rpm.Sedimentary film thickness is between 50-1000nm.Sedimentary film is all carried out anneal, annealing temperature 473K, annealing time 1h.
2. a kind of rear-earth-doped Bi according to claim 1
2Te
3The base thermoelectric film material, it is characterized in that: the described rare earth element that mixes is a light rare earths.
3. a kind of rear-earth-doped Bi according to claim 2
2Te
3The base thermoelectric film material, it is characterized in that: described light rare earths is La, Ce.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103390721A (en) * | 2012-05-10 | 2013-11-13 | 三星电子株式会社 | Thermoelectric material, and thermoelectric element, thermoelectric module and thermoelectric apparatus including the thermoelectric material |
| CN103436729A (en) * | 2013-09-02 | 2013-12-11 | 中国科学院宁波材料技术与工程研究所 | Thermoelectric material and preparation method thereof |
| CN104134720A (en) * | 2014-07-10 | 2014-11-05 | 上海大学 | Preparation method of organic and inorganic hybridization perovskite material growing by single-source flash evaporation method and plane solar cell of material |
| CN104495763A (en) * | 2014-12-12 | 2015-04-08 | 上海申和热磁电子有限公司 | Preparation method of bismuth-telluride-base thermoelectric material |
| CN113502534A (en) * | 2021-06-22 | 2021-10-15 | 中国工程物理研究院材料研究所 | Preparation method of Ce-doped topological insulator bismuth telluride single crystal film |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1267338C (en) * | 2003-09-25 | 2006-08-02 | 浙江大学 | Prepn of Bi2Te3-base nano thermoelectric material powder containing RE element |
| CN101220513B (en) * | 2007-09-28 | 2010-12-08 | 北京科技大学 | Thermal treatment method for improving type N polycrystal Bi2Te3thermoelectricity capability |
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2009
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103390721A (en) * | 2012-05-10 | 2013-11-13 | 三星电子株式会社 | Thermoelectric material, and thermoelectric element, thermoelectric module and thermoelectric apparatus including the thermoelectric material |
| CN103390721B (en) * | 2012-05-10 | 2018-04-06 | 三星电子株式会社 | Thermoelectric material and the thermoelectric element, electrothermal module and thermoelectric device for including it |
| CN103436729A (en) * | 2013-09-02 | 2013-12-11 | 中国科学院宁波材料技术与工程研究所 | Thermoelectric material and preparation method thereof |
| CN103436729B (en) * | 2013-09-02 | 2016-01-20 | 中国科学院宁波材料技术与工程研究所 | A kind of thermoelectric material and preparation method thereof |
| CN104134720A (en) * | 2014-07-10 | 2014-11-05 | 上海大学 | Preparation method of organic and inorganic hybridization perovskite material growing by single-source flash evaporation method and plane solar cell of material |
| CN104495763A (en) * | 2014-12-12 | 2015-04-08 | 上海申和热磁电子有限公司 | Preparation method of bismuth-telluride-base thermoelectric material |
| CN113502534A (en) * | 2021-06-22 | 2021-10-15 | 中国工程物理研究院材料研究所 | Preparation method of Ce-doped topological insulator bismuth telluride single crystal film |
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