CN114249305A - Bismuth telluride-based thermoelectric film with stable wide-temperature-range performance and preparation method thereof - Google Patents
Bismuth telluride-based thermoelectric film with stable wide-temperature-range performance and preparation method thereof Download PDFInfo
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- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 70
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 70
- XSOKHXFFCGXDJZ-UHFFFAOYSA-N telluride(2-) Chemical compound [Te-2] XSOKHXFFCGXDJZ-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 55
- 238000000034 method Methods 0.000 claims abstract description 49
- 238000000137 annealing Methods 0.000 claims abstract description 48
- 230000008569 process Effects 0.000 claims abstract description 31
- 239000000758 substrate Substances 0.000 claims abstract description 26
- 230000008859 change Effects 0.000 claims abstract description 12
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 10
- 238000011065 in-situ storage Methods 0.000 claims abstract description 10
- 239000010408 film Substances 0.000 claims description 112
- 239000013078 crystal Substances 0.000 claims description 43
- 239000010409 thin film Substances 0.000 claims description 37
- 239000002131 composite material Substances 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 14
- 238000004544 sputter deposition Methods 0.000 claims description 11
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 6
- 229910052714 tellurium Inorganic materials 0.000 claims description 6
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 238000007738 vacuum evaporation Methods 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 238000010549 co-Evaporation Methods 0.000 claims description 3
- 239000011889 copper foil Substances 0.000 claims description 3
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 claims description 3
- 239000010453 quartz Substances 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 230000006872 improvement Effects 0.000 abstract description 7
- 230000001276 controlling effect Effects 0.000 abstract description 5
- 230000001105 regulatory effect Effects 0.000 abstract description 5
- 230000002349 favourable effect Effects 0.000 abstract description 4
- 238000000151 deposition Methods 0.000 description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 230000008021 deposition Effects 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000003599 detergent Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
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- 238000002791 soaking Methods 0.000 description 4
- 238000004506 ultrasonic cleaning Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000011161 development Methods 0.000 description 3
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- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 239000013077 target material Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000000412 dendrimer Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000007781 pre-processing Methods 0.000 description 2
- 239000012798 spherical particle Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B19/00—Selenium; Tellurium; Compounds thereof
- C01B19/007—Tellurides or selenides of metals
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- 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
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- H—ELECTRICITY
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- 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
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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Abstract
The invention relates to a bismuth telluride-based thermoelectric film with stable wide temperature range performance and a preparation method thereof, wherein a thermoelectric film is deposited on a substrate, the thermoelectric film is subjected to in-situ annealing under a control condition, and the annealed thermoelectric film is subjected to step cyclic annealing to finally prepare a thermoelectric film material with wide temperature range stability, wherein the change of an orientation structure is favorable for improving the thermoelectric performance of the material, the in-situ annealing is carried out on the thermoelectric film, so that the film material can fully grow in a growth environment, the internal stress and the film-based stress of the film are relieved, the structural stability of the film material is enhanced, and the step annealing process is favorable for regulating and controlling the carrier transport performance of the material according to the structural characteristics of the thermoelectric materials with different orientation structures, therefore, the bismuth telluride-based thermoelectric film material can realize the improvement of the thermoelectric performance, the film material has better performance and stability in a wide temperature range.
Description
Technical Field
The invention belongs to the technical field of thin film material preparation, and particularly relates to a bismuth telluride-based thermoelectric thin film with stable wide-temperature-range performance and a preparation method thereof.
Background
Due to its unique direct conversion characteristic between thermal energy and electrical energy, thermoelectric conversion technology has attracted extensive attention in the fields of microelectronic energy collection, power generation, refrigeration, sensing, and the like. In recent years, the record of the performance of thermoelectric block materials is continuously refreshed, and a solid foundation is laid for the development of the application technology of thermoelectric devices. However, the preparation and application technology of thermoelectric thin film materials in China at present lags behind the scientific development of thermoelectric bulk materials, and particularly, the wide temperature range performance stability of the thermoelectric thin film materials seriously restricts the further application of the thin film materials. From the aspect of a transport mechanism, the Seebeck coefficient and the wide temperature range performance of the electric conductivity of the thermoelectric material can be stably improved through the regulation and control of the electric transport performance of the material.
The bismuth telluride-based material is taken as the thermoelectric material with the optimal performance in the room temperature area at present, and the research on the performance of the bismuth telluride-based material in all aspects is highly regarded by experts. In the fifth and sixty years of the 20 th century, the performance of the bismuth telluride-based thermoelectric material is greatly improved. However, in the last 50 years, the research on the bismuth telluride-based thermoelectric material has been very slow. Based on the development of nanotechnology, thin film technology is gradually applied to the thermoelectric field, and meanwhile, thin film thermoelectric materials provide huge space for enhancing thermoelectric figure of merit. A great deal of research shows that the microstructure regulation of the material has great influence on the thermoelectric performance. The carrier transport performance of the material can be effectively regulated and controlled by regulating and controlling the nano structure in the film, controlling the diffusion of metal elements and the like, and the purpose of high-precision carrier regulation and control is realized, so that the performance stability of the material in a larger temperature range is further regulated and controlled.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a bismuth telluride-based thermoelectric film with stable wide-temperature-range performance and a preparation method thereof. The bismuth telluride-based thin film material can realize the stability of the structure and the electrical property within the temperature range of 300-500K. The invention realizes the regulation and control of the structure and the performance stability of the thin film material under the condition of basically not changing the electrical and thermal properties of the material by the stepped annealing design of the thermoelectric thin film in the inert atmosphere.
The technical scheme adopted by the invention is as follows:
a preparation method of a bismuth telluride-based thermoelectric film with stable wide-temperature-range performance is characterized by comprising the following steps:
(1) preparing a layer of thermoelectric film on a substrate;
(2) carrying out in-situ annealing treatment on the thermoelectric film in the step (1);
(3) and (3) performing multi-step cyclic annealing treatment on the thermoelectric film subjected to the in-situ annealing treatment in the step (2) to obtain the bismuth telluride-based thermoelectric film with stable wide-temperature-range performance.
In the step (1), the thermoelectric film is prepared by adopting a method of co-sputtering a thermoelectric material and a tellurium target, and the thickness is 50-5000 nm.
In the step (1), the thermoelectric film is any one of (015) a crystal plane preferred orientation particle stacking film, (015) a crystal plane preferred orientation inclined laminated composite film, (00l) a crystal plane and (015) a crystal plane composite orientation film, and (00l) a crystal plane preferred orientation laminated film.
In the step (1), the substrate is any one or a mixture of more of silicon, quartz, aluminum nitride and copper foil.
The preparation of the thermoelectric film in the step (1) can adopt any one of a magnetron sputtering process and a vacuum evaporation process, and the process specifically comprises the following steps: the alternating current of the co-sputtering Te target connected with the radio frequency target is 40-80A, and the voltage is 0.25-0.60 kV; the control current for co-evaporation of the crucible with Te particles was 30A.
In the step (2), the annealing treatment specifically comprises: performing in-situ annealing treatment at 400 deg.C and 0.5-3Pa for 10-50 min.
The annealing of the stable thermoelectric film in the step (3) adopts a multi-step cyclic annealing process, and the annealing process specifically comprises the following steps: performing step annealing treatment for 10-50min under the conditions of 100-400 ℃ and 0.5-3Pa in the atmosphere of inert gases such as Ar and He, naturally cooling, and repeating the steps for 1-10 times.
In the step (3), the structure of the bismuth telluride-based thermoelectric film is still maintained to be any one of (015) crystal face preferred orientation particle stacking film, (015) crystal face preferred orientation inclined layered composite film, (00l) crystal face and (015) crystal face composite orientation film, and (00l) crystal face preferred orientation layered film.
The invention has the beneficial effects that:
the preparation method of the bismuth telluride-based thermoelectric film with stable wide temperature range performance comprises the following steps of firstly depositing a thermoelectric film on a substrate, then carrying out in-situ annealing treatment on the thermoelectric film under a control condition, and finally carrying out step annealing treatment on the thermoelectric film after annealing treatment to finally prepare the thermoelectric film material with stable wide temperature range, wherein the steps of the thermoelectric film material are as follows: the method comprises the steps of inducing an orientation structure of a thin film material from the initial growth stage of the thin film to prepare a thermoelectric thin film material with a specific orientation structure, wherein the change of the orientation structure is favorable for improving the thermoelectric performance of the material, and the in-situ annealing treatment is carried out on the thermoelectric thin film, so that the thin film material can fully grow in a growth environment, the internal stress and the film-based stress of the thin film are simultaneously relieved, the structural stability of the thin film material is enhanced, and the stepped annealing process is favorable for regulating and controlling the carrier transport performance of the material aiming at the structural characteristics of the thermoelectric material with different orientation structures, so that the bismuth telluride-based thermoelectric thin film material can realize the controllable regulation of the thin film structure and the performance stability in a wide temperature range; according to the invention, by means of the orientation structure design and the stepped annealing treatment of the thermoelectric thin film material, the thin film material is finally realized to have better performance and stability in a wide temperature range under the condition of improving the thermoelectric performance.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a SEM surface view of a film of (015) crystal plane-preferentially-oriented particles according to example 1 of the present invention;
FIG. 2 is an SEM surface view of a film of a (015) crystal plane preferred orientation inclined layered composite structure according to example 2 of the present invention;
FIG. 3 is an SEM surface view of a film of a composite structure of (00l) plane and (015) plane orientation according to example 3 of the present invention;
FIG. 4 is a SEM surface view of a film of a (00l) crystal plane preferred orientation layer structure according to example 4 of the present invention;
FIG. 5 is a SEM surface view of a film having an unstable structure according to a comparative example of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail below. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the examples given herein without any inventive step, are within the scope of the present invention.
Example 1
The embodiment provides a bismuth telluride-based thermoelectric film with stable wide-temperature-range performance, which is a (015) crystal plane preferred orientation particle stacking film and is prepared by the following method:
(1) taking silicon as a substrate, and preprocessing the substrate, specifically: sequentially soaking the substrate in liquid detergent, deionized water, ethanol and acetone for ultrasonic cleaning to obtain a pretreated substrate;
depositing a layer of bismuth telluride-based thermoelectric film with the thickness of 50nm on a substrate by adopting a magnetron sputtering co-sputtering process, wherein the co-sputtering process comprises the following specific conditions:
the air pressure is 1.0Pa, the deposition temperature is 40 ℃, and the deposition time is 10 min; fixing the bismuth telluride base target material on a direct current power supply: the current of the direct current is 100mA, and the voltage is 0.3 kV; fixing the tellurium target on a radio frequency power supply: the alternating current had a current of 40mA and a voltage of 0.25 kV.
(2) Annealing the bismuth telluride-based thermoelectric film in the step (1) for 10min at the temperature of 100 ℃ and under the pressure of 0.5 Pa;
(3) performing a multi-step cyclic annealing process on the bismuth telluride-based thermoelectric film annealed in the step (2) by using a vacuum annealing furnace to obtain the bismuth telluride-based thermoelectric film with stable wide-temperature-range performance;
the annealing process comprises the following specific conditions:
ar gas is used as atmosphere, the air pressure is 0.5Pa, the temperature is 40 ℃, the annealing time is 10min, and the cycle time is 1.
Obtaining the bismuth telluride-based thermoelectric film with stable wide-temperature-range performance according to the steps, wherein the conductivity of the bismuth telluride-based thermoelectric film is 1 multiplied by 104s m-1Seebeck coefficient of 100. mu. V K-1Thermal conductivity of 0.45W m-1K-1The performance can not be increased or reduced along with the change of the temperature, the stability is kept in the temperature range of 300-500K, and the numerical change rate is less than 5 percent.
An SEM surface image of the (015) crystal plane preferred orientation particle film is shown in FIG. 1, which shows: the film is formed by stacking spherical particles with uniform size, the conductivity of the film is reduced due to more interfaces of the particle stacked film, and the Seebeck coefficient of the material is lower due to poorer crystal form integrity.
Example 2
The embodiment provides a bismuth telluride-based thermoelectric film with stable wide-temperature-range performance, which is a (015) crystal plane preferred orientation inclined layered composite structure film and is prepared by the following method:
(1) taking quartz as a substrate, and preprocessing the substrate, specifically: sequentially soaking the substrate in liquid detergent, deionized water, ethanol and acetone for ultrasonic cleaning to obtain a pretreated substrate;
depositing a layer of bismuth telluride-based thermoelectric film with the thickness of 5000nm on a substrate by adopting a magnetron sputtering co-sputtering process, wherein the co-sputtering process comprises the following specific conditions:
the air pressure is 1.0Pa, the deposition temperature is 250 ℃, and the deposition time is 5 h; fixing the bismuth telluride base target material on a direct current power supply: the current of the direct current is 100mA, and the voltage is 0.3 kV; fixing the tellurium target on a radio frequency power supply: the alternating current had a current of 60mA and a voltage of 0.50 kV.
(2) Annealing the bismuth telluride-based thermoelectric film in the step (1) for 30min at 250 ℃ under the condition of 1.0 Pa;
(3) performing a multi-step cyclic annealing process on the bismuth telluride-based thermoelectric film annealed in the step (2) by using a vacuum annealing furnace to obtain the bismuth telluride-based thermoelectric film with stable wide-temperature-range performance;
the annealing process comprises the following specific conditions:
atmosphere is He gas, pressure is 1.5Pa, temperature is 100 deg.C for 10min, 150 deg.C for 15min and 250 deg.C for 30min, and cycle number is 4.
Obtaining the bismuth telluride-based thermoelectric film with stable wide-temperature-range performance according to the steps, wherein the conductivity of the bismuth telluride-based thermoelectric film is 6 multiplied by 104s m-1Seebeck coefficient of 180. mu. V K-1Thermal conductivity of 1.00W m-1K-1The performance can not be increased or reduced along with the change of the temperature, the stability is kept in the temperature range of 300-500K, and the numerical change rate is less than 5 percent.
As shown in fig. 2, it is an SEM surface image of the (015) crystal plane preferred orientation inclined lamellar composite structure film, which shows: the film is formed by stacking inclined flaky sheets with uniform size, and the conductivity and Seebeck coefficient of the material are improved due to the improvement of the crystal form integrity of the material.
Example 3
The embodiment provides a bismuth telluride-based thermoelectric film with stable wide-temperature-range performance, wherein the bismuth telluride-based thermoelectric film is a film with a composite orientation structure of a (00l) crystal face and a (015) crystal face, and the bismuth telluride-based thermoelectric film is prepared by adopting the following method:
(1) the method comprises the following steps of taking aluminum nitride as a substrate, and pretreating the substrate, wherein the method specifically comprises the following steps: sequentially soaking the substrate in liquid detergent, deionized water, ethanol and acetone for ultrasonic cleaning to obtain a pretreated substrate;
depositing a layer of bismuth telluride-based thermoelectric film with the thickness of 500nm on a substrate by adopting a vacuum evaporation process, wherein the vacuum evaporation process specifically comprises the following conditions:
the air pressure is 1.0 x 10-3Pa, the deposition temperature is 300 ℃, and the deposition time is 30 min; controlling the current of the crucible filled with the bismuth telluride particles to be 100A; the control current for the crucible containing tellurium particles was 30A.
(2) Annealing the bismuth telluride-based thermoelectric film in the step (1) for 30min at the temperature of 300 ℃ and under the pressure of 2.0 Pa;
(3) performing a multi-step cyclic annealing process on the bismuth telluride-based thermoelectric film annealed in the step (2) by using a vacuum annealing furnace to obtain the bismuth telluride-based thermoelectric film with stable wide-temperature-range performance;
the annealing process comprises the following specific conditions:
ar gas is used as atmosphere, the air pressure is 2.0Pa, the temperature is kept at 100 ℃ for 10min, the temperature is kept at 150 ℃ for 15min and 250 ℃ for 30min, the temperature is kept at 300 ℃ for 50min, and the cycle frequency is 10 times.
Obtaining the bismuth telluride-based thermoelectric film with stable wide-temperature-range performance according to the steps, wherein the conductivity of the bismuth telluride-based thermoelectric film is 15 multiplied by 104s m-1Seebeck coefficient of 220. mu. V K-1Thermal conductivity of 1.50W m- 1K-1The performance can not be increased or reduced along with the change of the temperature, the stability is kept in the temperature range of 300-500K, and the numerical change rate is less than 5 percent.
FIG. 3 is an SEM surface diagram of the film with the (00l) crystal plane and (015) crystal plane oriented composite structure, and the SEM surface diagram shows that: the film is formed by piling inclined flaky sheets with uniform size, the inclination angle of the film is reduced, the gap between the sheets is reduced, the compactness of the film is enhanced, the electrical conductivity of the material is greatly improved, the Seebeck coefficient is also improved, and the thermal conductivity is correspondingly increased due to the large improvement of the electrical conductivity.
Example 4
The embodiment provides a bismuth telluride-based thermoelectric film with stable wide-temperature-range performance, wherein the bismuth telluride-based thermoelectric film is a (00l) crystal plane preferred orientation layered structure film, and the bismuth telluride-based thermoelectric film is prepared by adopting the following method:
(1) the method comprises the following steps of taking a copper foil as a substrate, and pretreating the substrate, wherein the method specifically comprises the following steps: sequentially soaking the substrate in liquid detergent, deionized water, ethanol and acetone for ultrasonic cleaning to obtain a pretreated substrate;
depositing a silicon dioxide insulating layer with the thickness of 200nm on a substrate by adopting a magnetron sputtering process, and depositing a bismuth telluride-based thermoelectric film with the thickness of about 1000nm on the insulating layer by adopting a magnetron sputtering co-sputtering process, wherein the co-sputtering process comprises the following specific conditions:
the air pressure is 3.0Pa, the deposition temperature is 400 ℃, and the deposition time is 5 h; fixing the bismuth telluride base target material on a direct current power supply: the current of the direct current is 100mA, and the voltage is 0.3 kV; fixing the tellurium target on a radio frequency power supply: the alternating current had a current of 80mA and a voltage of 0.60 kV.
(2) Annealing the bismuth telluride-based thermoelectric film in the step (1) for 50min at the temperature of 400 ℃ and under the pressure of 3.0 Pa;
(3) performing a multi-step cyclic annealing process on the bismuth telluride-based thermoelectric film annealed in the step (2) by using a vacuum annealing furnace to obtain the bismuth telluride-based thermoelectric film with stable wide-temperature-range performance;
the annealing process comprises the following specific conditions:
ar gas is used as atmosphere, the air pressure is 3.0Pa, the temperature is kept at 100 ℃ for 10min, the temperature is kept at 150 ℃ for 15min and 250 ℃ for 30min, the temperature is kept at 400 ℃ for 50min, and the cycle frequency is 5 times.
Obtaining the bismuth telluride-based thermoelectric film with stable wide-temperature-range performance according to the steps, wherein the conductivity of the bismuth telluride-based thermoelectric film is 3 multiplied by 104s m-1Seebeck coefficient of 300. mu. V K-1Thermal conductivity of 1.20W m-1K-1The performance can not be increased or reduced along with the change of the temperature, the stability is kept in the temperature range of 300-500K, and the numerical change rate is less than 5 percent.
An SEM surface image of the film of the (00l) crystal plane preferred orientation layer structure is shown in FIG. 4, which shows that: the film is composed of flaky slices with uniform size, and the conductivity and Seebeck coefficient of the material are improved due to the improvement of the crystal form integrity of the material.
Comparative example
This comparative example provides a bismuth telluride-based thermoelectric film, which is different from example 4 only in that: the differences of post-annealing processes are as follows:
the bismuth telluride-based thin film is directly annealed for 50min at the temperature of 400 ℃ without adopting a multi-step cyclic annealing process, and the prepared bismuth telluride-based thin film does not have a stable structure.
Fig. 5 is an SEM surface image of the thin film having an unstable structure, showing: as the elements on the surface of the film volatilize to form a large number of dendritic compounds, the structure of the film is thoroughly destroyed, and the performance is greatly reduced.
Examples of the experiments
The SEM surface structures of the bismuth telluride-based thermoelectric thin film materials obtained in examples 1 to 4 and comparative example are as follows.
An SEM surface image of the (015) crystal plane preferred orientation particle film is shown in FIG. 1, which shows: the film is formed by stacking spherical particles with uniform size, the conductivity of the film is reduced due to more interfaces of the particle stacked film, and the Seebeck coefficient of the material is lower due to poorer crystal form integrity.
As shown in fig. 2, it is an SEM surface image of the (015) crystal plane preferred orientation inclined lamellar composite structure film, which shows: the film is formed by stacking inclined flaky sheets with uniform size, and the conductivity and Seebeck coefficient of the material are improved due to the improvement of the crystal form integrity of the material.
FIG. 3 is an SEM surface diagram of the film with the (00l) crystal plane and (015) crystal plane oriented composite structure, and the SEM surface diagram shows that: the film is formed by piling inclined flaky sheets with uniform size, the inclination angle of the film is reduced, the gap between the sheets is reduced, the compactness of the film is enhanced, the electrical conductivity of the material is greatly improved, the Seebeck coefficient is also improved, and the thermal conductivity is correspondingly increased due to the large improvement of the electrical conductivity.
An SEM surface image of the film of the (00l) crystal plane preferred orientation layer structure is shown in FIG. 4, which shows that: the film is composed of flaky slices with uniform size, and the conductivity and Seebeck coefficient of the material are improved due to the improvement of the crystal form integrity of the material.
Fig. 5 is an SEM surface image of the thin film having an unstable structure, showing: as the elements on the surface of the film volatilize to form a large number of dendritic compounds, the structure of the film is thoroughly destroyed, and the performance is greatly reduced.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.
Claims (10)
1. A preparation method of a bismuth telluride-based thermoelectric film with stable wide-temperature-range performance is characterized by comprising the following steps:
(1) preparing a layer of thermoelectric film on a substrate;
(2) carrying out in-situ annealing treatment on the thermoelectric film in the step (1);
(3) and (3) performing multi-step cyclic annealing treatment on the thermoelectric film subjected to the in-situ annealing treatment in the step (2) to obtain the bismuth telluride-based thermoelectric film with stable wide-temperature-range performance.
2. The method for preparing the bismuth telluride-based thermoelectric thin film with the stable wide temperature range performance as claimed in claim 1, wherein in the step (1), the thermoelectric thin film is prepared by a method of co-sputtering a thermoelectric material and a tellurium target, and the thickness is 50-5000 nm.
3. The method for preparing the bismuth telluride-based thermoelectric film having the wide temperature range and stable performance according to claim 1, wherein in the step (1), the thermoelectric film is any one of (015) a crystal plane preferred orientation particle stacked film, (015) a crystal plane preferred orientation inclined laminar composite film, (001) a crystal plane and (015) a crystal plane composite orientation film, and (001) a crystal plane preferred orientation laminar film.
4. The method for preparing the bismuth telluride-based thermoelectric film with the stable wide temperature range performance as claimed in claim 1, wherein in the step (1), the substrate is one or a mixture of more of silicon, quartz, aluminum nitride and copper foil.
5. The method for preparing the bismuth telluride-based thermoelectric film with the stable wide temperature range performance as claimed in claim 1, wherein in the step (1), the bismuth telluride-based thermoelectric film can be prepared by any one of a magnetron sputtering co-sputtering process and a vacuum evaporation co-evaporation process, and the process specifically comprises the following steps: the alternating current of the co-sputtering Te target connected with the radio frequency target is 40-80A, and the voltage is 0.25-0.60 kV; the control current for co-evaporation of the crucible with Te particles was 30A.
6. The method for preparing the bismuth telluride-based thermoelectric thin film having the stable wide temperature range performance as claimed in claim 1, wherein in the step (2), the annealing treatment specifically comprises: performing in-situ annealing treatment at 400 deg.C and 0.5-3Pa for 10-50 min.
7. The method for preparing the bismuth telluride-based thermoelectric thin film with the stable wide temperature range performance as claimed in claim 1, wherein the annealing of the stable thermoelectric thin film in the step (3) in the step (1) adopts a multi-step cyclic annealing process, and the annealing process specifically comprises the following steps: performing step annealing treatment for 10-50min under the conditions of 100-400 ℃ and 0.5-3Pa in the atmosphere of inert gases such as Ar and He, naturally cooling, and repeating the steps for 1-10 times.
8. The bismuth telluride-based thermoelectric thin film having stable wide temperature range properties, prepared by the method according to any one of claims 1 to 7.
9. The wide-temperature-range performance-stable bismuth telluride-based thermoelectric thin film according to claim 8, wherein the thermoelectric thin film is a bismuth telluride-based thermoelectric thin film having a special orientation structure, and the special orientation structure is a (015) preferred crystal plane orientation particle stacking structure, a (015) preferred crystal plane orientation inclined layered composite structure, a (00l) and (015) crystal plane composite orientation structure, and a (00l) preferred crystal plane orientation layered structure.
10. The bismuth telluride-based thermoelectric thin film having stable wide temperature range properties as claimed in claim 8, wherein the bismuth telluride-based thermoelectric thin film has an electrical conductivity of 1 to 15 x 104S m-1Seebeck coefficient of 100--1The thermal conductivity is 0.45-1.50W m-1K-1The performance can not be increased or reduced along with the change of the temperature, the stability is kept in the temperature range of 300-500K, and the numerical change rate is less than 5 percent.
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