CN112864300A - Bismuth telluride-based alloy thin film-perovskite type oxide heterojunction composite thermoelectric material and preparation and application thereof - Google Patents
Bismuth telluride-based alloy thin film-perovskite type oxide heterojunction composite thermoelectric material and preparation and application thereof Download PDFInfo
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- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 36
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 36
- XSOKHXFFCGXDJZ-UHFFFAOYSA-N telluride(2-) Chemical compound [Te-2] XSOKHXFFCGXDJZ-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 239000000956 alloy Substances 0.000 title claims abstract description 35
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 35
- 239000000463 material Substances 0.000 title claims abstract description 28
- 239000002131 composite material Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 239000010409 thin film Substances 0.000 claims abstract description 36
- 239000010408 film Substances 0.000 claims abstract description 35
- 239000000758 substrate Substances 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 15
- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract description 8
- 239000013077 target material Substances 0.000 claims description 18
- 229910002370 SrTiO3 Inorganic materials 0.000 claims description 11
- 238000004544 sputter deposition Methods 0.000 claims description 9
- 238000000137 annealing Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 229910002328 LaMnO3 Inorganic materials 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- 229910002113 barium titanate Inorganic materials 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- 229910052723 transition metal Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 230000008859 change Effects 0.000 abstract description 4
- 239000012212 insulator Substances 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 4
- 238000011946 reduction process Methods 0.000 abstract 1
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 239000002585 base Substances 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 229910002367 SrTiO Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000002344 surface layer Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000005679 Peltier effect Effects 0.000 description 1
- 230000005678 Seebeck effect Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- 230000005619 thermoelectricity Effects 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
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- 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
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/0623—Sulfides, selenides or tellurides
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
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- 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
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- 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
- H10N10/855—Thermoelectric active materials comprising inorganic compositions comprising compounds containing boron, carbon, oxygen or nitrogen
Abstract
The invention provides a bismuth telluride-based alloy thin film-perovskite type oxide heterojunction composite thermoelectric material and preparation and application thereof, wherein the method comprises the following steps: firstly, processing a perovskite type oxide substrate through a high-temperature reduction process to change the substrate from an insulator to a surface conductive state; and secondly, growing a bismuth telluride-based alloy film on the surface of the substrate by a magnetron sputtering method to prepare the heterojunction. The method can combine the large Seebeck coefficient of the perovskite type oxide substrate and the excellent conductivity of the bismuth telluride base alloy film to prepare the composite material with high Seebeck coefficient and low internal resistance. The invention provides an efficient and convenient process thought for improving the performance of the thin-film thermoelectric material and the performance of the thin-film thermoelectric device.
Description
Technical Field
The invention belongs to the technical field of thermoelectricity, and particularly relates to preparation and application of a bismuth telluride alloy film-perovskite type oxide semiconductor heterojunction composite thermoelectric material.
Background
With the increasing problems of global environmental pollution, energy shortage and the like, the development and utilization of new energy are particularly critical. Thermoelectric technology can realize the conversion between heat energy and electric energy, and is widely concerned at home and abroad as a clean renewable energy source. The thermoelectric device has the advantages of small volume, light weight, no noise, environmental friendliness and the like, and has great application potential in the fields of waste heat recovery, aerospace, thermal management, sensors and the like. Compared with bulk thermoelectric materials, the thin film thermoelectric device has the advantages of small volume, fast response, easy integration and the like, and has higher application value in microelectronic devices.
The thin film thermoelectric device mainly converts heat energy into electric energy through the Seebeck effect; the electric refrigeration and the electric heating are realized by using the Peltier effect. Maximum output power for a thermoelectric energy conversion device
Wherein S is a Seebeck coefficient, Delta T is a temperature difference between two ends, RintIs the internal resistance of the device. The larger the seebeck coefficient and the lower the internal resistance, the higher the output power. But the seebeck coefficient and the conductivity of the material are both related to the carrier concentration: as the carrier concentration increases, the conductivity increases and the seebeck coefficient decreases accordingly. Therefore, breaking the coupling between the two is the key to obtain large output power.
Bismuth telluride (Bi)2Te3) The base alloy is used as a narrow-band gap (0.13eV) semiconductor, has excellent thermoelectric performance near room temperature, is widely applied to traditional thermoelectric devices, but has a small Seebeck coefficient (less than 250 muV/K) and limits the improvement of the output voltage. In addition, after being prepared into a film, the internal resistance is high, so that the output power is generally less than 200 nw. In contrast, perovskite-type oxides are generally wide band gap semiconductors, generally having a high seebeck coefficient, but cannot achieve high output power due to their higher electrical resistivity and thermal conductivity than conventional thermoelectric materials.The traditional method increases the output power of the thin film thermoelectric device by increasing the number of pairs of thermoelectric legs and increasing the thickness of the thin film, but the methods generally need complicated processes.
Disclosure of Invention
The invention prepares a bismuth telluride-based alloy thin film-perovskite type oxide semiconductor heterojunction composite thermoelectric material, is used for solving the problems of low Seebeck coefficient and high internal resistance of the conventional thin film thermoelectric material, and can be applied to improving the output power of a thin film thermoelectric device. By constructing a heterojunction composite material system in a real space, the excellent conductivity of the bismuth telluride-based alloy thin film is effectively combined with the higher Seebeck coefficient of the perovskite type oxide substrate, the coupling between the resistance and the Seebeck coefficient existing in a single thermoelectric material system is broken through, the thin film thermoelectric material with the high Seebeck coefficient and the low internal resistance is obtained, and the output power of the device is improved.
The invention provides a composite thermoelectric material, which comprises a bismuth telluride base alloy thin film and a perovskite type oxide; the bismuth telluride-based alloy thin film and the perovskite type oxide are compounded to form a heterojunction structure.
Based on the technical scheme, preferably, the general formula of the perovskite oxide is ABO3A is an alkali metal element or a rare earth element; b is a transition metal element.
Based on the technical scheme, preferably, A is Sr, Ba, Ca or La; and B is Ti, Mn, Co and the like.
Based on the technical scheme, preferably, the perovskite type oxide is SrTiO3、BaTiO3、LaMnO3And the like.
Based on the technical scheme, the thickness of the bismuth telluride-based alloy thin film is preferably 1-2000 nm.
Based on the technical scheme, preferably, the bismuth telluride-based alloy is p-type BixSb2-xTe3(x is more than or equal to 0 and less than or equal to 2) or n-type Bi2Te3-ySey(0＜y≤3)。
The invention also provides a preparation method of the composite thermoelectric material with the heterojunction structure, which comprises the following steps:
(1) perovskite type oxide is used as a substrate, and the temperature is 700-1200 ℃ and H2Annealing for 1-12h under the atmosphere;
(2) depositing a bismuth telluride-based alloy thin film on the surface of the perovskite oxide obtained by the processing in the step (1) by a magnetron sputtering method to obtain the composite thermoelectric material, wherein the structure is shown in figure 1; the deposition conditions were: the bismuth telluride-based alloy target and the tellurium target are co-sputtered, the bismuth telluride-based alloy target adopts a direct-current power supply, the heating substrate temperature is 100-350 ℃, and the film thickness can be adjusted by controlling the sputtering power and the growth time.
Based on the above technical scheme, preferably, the magnetron sputtering conditions are as follows: when the bismuth telluride-based alloy thin film is p-type BixSb2-xTe3Film formation: bi with the purity of 99.99wt percentxSb2-xTe3Co-sputtering of target material and Te target material, BixSb2-xTe3The target material adopts a direct current power supply, and the power is 30W; the Te target material adopts a radio frequency power supply, the power is 40W, the temperature of a heating substrate is 300 ℃, the flow of argon is 30sccm, and the growth time is 1-15000 s.
When the bismuth telluride-based alloy thin film is n-type Bi2Te3-ySeyFilm formation: bi with the purity of 99.99wt percent2Te3- ySeyCo-sputtering of target material and Te target material, Bi2Te3-ySeyA direct-current power supply is adopted, and the power is 35W; te adopts a radio frequency power supply with the power of 20W. The substrate temperature was 300 deg.C, the argon flow was 30sccm, and the growth time was 1-15000 s.
The invention also provides a thin film thermoelectric device comprising the heterostructure thermoelectric material. The thickness of the bismuth telluride base alloy is adjusted, the open-circuit voltage and the internal resistance of the heterojunction can be adjusted, and therefore the output power is adjusted.
Advantageous effects
(1) The perovskite oxide is generally insulating as a substrate for thin film growth. After high-temperature annealing treatment, the surface layer is reduced and is changed into a surface layer conducting state from an insulator, and the resistance changes in a gradient manner from the surface to the inside, so that a higher Seebeck coefficient can be provided for a heterojunction, and the output voltage is improved. Compared with a single bismuth telluride-based alloy film, the Seebeck coefficient of the composite material is greatly improved.
(2) And growing the bismuth telluride-based alloy film on the surface of the reduced perovskite oxide by a magnetron sputtering method. The film has excellent conductivity, is tightly combined with the perovskite type oxide substrate, is beneficial to electron transportation, effectively improves the conductivity of the composite material, and greatly reduces the internal resistance of the composite material compared with two independent materials.
(3) The Seebeck coefficient and the internal resistance can be adjusted by changing the thickness of the bismuth telluride base alloy film, thereby adjusting the output power of the heterojunction.
(4) Although the Seebeck coefficient of the heterojunction composite material is reduced compared with that of a single perovskite type oxide, the Seebeck coefficient of the heterojunction composite material is still far higher than that of the bismuth telluride base alloy thin film. By combining the large Seebeck coefficient of the perovskite type oxide substrate and the excellent conductivity of the bismuth telluride based thin film, the thin film device with high output voltage and low internal resistance is obtained, and the output power of the thin film thermoelectric device is improved.
Drawings
FIG. 1 is a schematic structural view of a bismuth telluride-based alloy thin film-perovskite-type oxide heterojunction; the surface layer is a bismuth telluride-based alloy film grown by magnetron sputtering, and the middle part is a reduced perovskite type oxide conducting layer.
FIG. 2(a) shows Bi of different thicknesses in example 10.5Sb1.5Te3Film deposition on insulating strontium titanate surface (Bi)0.5Sb1.5Te3/SrTiO3) Reduced strontium titanate surface (Bi)0.5Sb1.5Te3/SrTiO3-x) The seebeck coefficient of (a) varies with the film thickness; FIG. 2(b) shows Bi0.5Sb1.5Te3/SrTiO3-xAnd Bi0.5Sb1.5Te3/SrTiO3The internal resistance of (a) varies with the film thickness.
FIG. 3 shows Bi of 80nm thickness in example 10.5Sb1.5Te3/SrTiO3、Bi0.5Sb1.5Te3/SrTiO3-xAnd reduced strontium titanate substrate (SrTiO)3-x) Internal resistance and seebeck coefficient.
FIG. 4(a) shows Bi of 80nm thickness in example 10.5Sb1.5Te3/SrTiO3-x，SrTiO3-x，Bi0.5Sb1.5Te3/SrTiO3The output power test result under the temperature difference of 60K; fig. 4(b) is an enlarged view of a dotted line box in fig. 4 (a).
FIG. 5 shows that in example 1, Bi is present0.5Sb1.5Te3The output power and I-V curve are shown schematically under different temperature differences when the thickness of the film is 80 nm.
FIG. 6 shows Bi in example 22Te2.7Se0.3/SrTiO3、Bi2Te2.7Se0.3/SrTiO3-x、SrTiO3-xResistance and seebeck coefficient of (a).
FIG. 7 shows Bi of 100nm thickness in example 22Te2.7Se0.3/SrTiO3-xAnd outputting power under different temperature differences.
Detailed Description
The following examples are provided for clearly illustrating the effects of the present invention, but the scope of the present invention should include the full contents of the claims, not limited to the embodiments only.
Example 1
1. Commercial strontium titanate (SrTiO)3) The single crystal was used as a substrate and had dimensions of 10.0mm × 2.0mm × 0.5 mm. Passing through 1000 ℃ C, H2Annealing for 8h in atmosphere to generate oxygen vacancy, and converting the insulator into a conductor (SrTiO) with conductive surface3-x) The conductive layer is about 10 μm thick.
2. Depositing p-type Bi on the surface of the strontium titanate obtained in the step 1 by a magnetron sputtering method0.5Sb1.5Te3Thin film to form a heterojunction structure as shown in figure 1. The growth conditions were: bi of purity of 99.99 wt%0.5Sb1.5Te3Co-sputtering of target material and Te target material, Bi0.5Sb1.5Te3Target material miningUsing a direct current power supply with the power of 30W; the Te target material adopts a radio frequency power supply, and the power is 40W. The temperature of the heating substrate is 300 ℃, the argon flow is 30sccm, the growth rate of the film is 8nm/min, the thickness of the film can be adjusted by controlling the growth time, and the film with the thickness of 1-2000nm can be grown within the time range of 1-15000 s.
As shown in FIG. 2(a), Bi increases with the film thickness0.5Sb1.5Te3/SrTiO3-xThe seebeck coefficient gradually decreases but remains negative. Bi0.5Sb1.5Te3/SrTiO3The Seebeck coefficient was at 110 μ V/K, which remained a conventional positive value.
Shown as Bi in FIG. 2(b)0.5Sb1.5Te3/SrTiO3-x(dotted line) and Bi0.5Sb1.5Te3/SrTiO3(solid line) schematic diagram of the change of internal resistance, the internal resistance gradually decreases as the film thickness increases, Bi0.5Sb1.5Te3/SrTiO3-xThe internal resistance of the heterojunction is less than that of Bi0.5Sb1.5Te3/SrTiO3Internal resistance of (2).
Comparative example 1
Reduced strontium titanate SrTiO3-xThe internal resistance of the substrate is 12.4K omega, and the Seebeck coefficient is-860 mu V/K. At a temperature difference of 60K, the output power is 57 nW.
Comparative example 2
When the sputtering time is 600s, 80nm of p-type Bi grows on the insulating strontium titanate substrate0.5Sb1.5Te3Film preparation procedure was the same as in example 1 to obtain Bi0.5Sb1.5Te3/SrTiO3The Seebeck coefficient of the composite thermoelectric material is 110 mu V/K, the internal resistance is 580 omega, and the output power is 16nW when the temperature difference is 60K.
As shown in FIG. 3, Bi0.5Sb1.5Te3/SrTiO3-xThe heterojunction has a reduced resistance of 230 Ω as a whole and a seebeck coefficient of-510 μ V/K, and although the seebeck coefficient is reduced for the reduced strontium titanate, the reduction of the internal resistance is greater, as shown in fig. 4, the output power is increased by 1100% compared with the reduced strontium titanate. Compared with Bi0.5Sb1.5Te3For the film, the internal resistance of the composite material is reduced by 60%, the Seebeck coefficient is increased by 400%, the output power is 722nW (delta T is 60K), and the output power is increased by 4400%.
Bi of 80nm thickness, as shown in FIG. 50.5Sb1.5Te3/SrTiO3-xThe output power of the heterojunction increases with increasing temperature difference. The output current and the open-circuit voltage have good linear relation under different temperature differences: the slope is 230, which is consistent with the internal resistance 230 omega, which shows that the internal resistance of the thin film thermoelectric device can keep stable along with the temperature change.
Example 2
1. Commercial strontium titanate single crystals were used as substrates, with dimensions of 10.0mm by 2.0mm by 0.5 mm. Passing through 1000 ℃ C, H2Annealing for 8h in the atmosphere to generate oxygen vacancy, converting the insulator into a conductor with the internal resistance of 12.4K omega, and the Seebeck coefficient is-860 mu V/K. At a temperature difference of 60K, the output power is 57 nW.
2. Magnetron sputtering growth of n-type Bi2Te2.7Se0.3The film conditions were: bi with the purity of 99.99wt percent2Te2.7Se0.3Co-sputtering of target material and Te target material, Bi2Te2.7Se0.3A direct-current power supply is adopted, and the power is 35W; te adopts a radio frequency power supply with the power of 20W. The temperature of the heating substrate is 300 ℃, the argon flow is 30sccm, the growth rate of the film is 8nm/min, the thickness of the film can be adjusted by controlling the growth time, and the film with the thickness of 1-2000nm can be grown within the time range of 1-15000 s. The output voltage and the internal resistance of the thin film thermoelectric device can be adjusted by adjusting the thickness of the bismuth telluride-based alloy thin film, so that the output power is adjusted.
Comparative example 3
As shown in FIG. 6, when the sputtering time was 750s and the film thickness was 100nm, Bi was grown on the insulating strontium titanate substrate2Te2.7Se0.3The Seebeck coefficient of the film was-90. mu.V/K, the internal resistance was 550. omega. and the output was 13nW at a temperature difference of 60K.
When Bi is present2Te2.7Se0.3When the film is deposited on the reduced strontium titanate substrate, the resistance is reduced to 220 omega, Seebeck coefficient of-390 muV/K, compared to Bi of the same thickness on an insulating strontium titanate substrate2Te2.7Se0.3For the film, the resistance was reduced by 60%, the seebeck coefficient was improved by 330%, the output was 412nW (Δ T60K), and the output was increased by 3000%.
Bi of 100nm thickness, as shown in FIG. 72Te2.7Se0.3/SrTiO3-xThe output power of the heterojunction increases with increasing temperature difference. The output current and the open-circuit voltage have good linear relation under different temperature differences: the slope is 220, which is consistent with the internal resistance of 220 omega, which shows that the internal resistance of the thin film thermoelectric device can keep stable along with the temperature change.
The invention provides a method for improving the output power of a thin film device by preparing a bismuth telluride-based alloy thin film-perovskite type oxide heterojunction. The surface of the perovskite type oxide is reduced through the annealing process, the large Seebeck coefficient of the perovskite type oxide is combined with the excellent electric conductivity of the bismuth telluride base alloy film, the barrier between the Seebeck coefficient and the resistance is broken through in a real space, and the output power of the film is effectively improved. And the process has high automation degree, and the prepared film has small volume, large output power and high power density. Provides a good idea for improving the performance of the thin film device.
Claims (9)
1. A composite thermoelectric material, characterized by: the composite thermoelectric material comprises a bismuth telluride-based alloy thin film and a perovskite type oxide; the bismuth telluride-based alloy thin film and the perovskite type oxide are compounded to form a heterojunction structure.
2. The composite thermoelectric material according to claim 1, wherein the perovskite oxide has a general formula of ABO3A is an alkali metal element or a rare earth element; b is a transition metal element.
3. The composite thermoelectric material according to claim 2, wherein a is Sr, Ba, Ca, or La; and B is Ti, Mn or Co.
4. The composite thermoelectric material according to claim 1, wherein the perovskite-type oxide is SrTiO3、BaTiO3、LaMnO3。
5. The composite thermoelectric material according to claim 1, wherein the thickness of the bismuth telluride-based alloy thin film is 1 to 2000 nm.
6. The composite thermoelectric material according to claim 1, wherein the bismuth telluride-based alloy is p-type BixSb2- xTe3Or n-type Bi2Te3-ySey；0≤x≤2；0＜y≤3。
7. A method of making the composite thermoelectric material of claim 1, comprising the steps of:
(1) perovskite type oxide is used as a substrate, and the temperature is 700-1200 ℃ and H2Annealing for 1-12h under the atmosphere;
(2) growing the bismuth telluride-based alloy thin film on the surface of the perovskite oxide treated in the step (1) by using a magnetron sputtering method to obtain the composite thermoelectric material.
8. The production method according to claim 7,
when the bismuth telluride-based alloy thin film is p-type BixSb2-xTe3Film formation: using commercial BixSb2-xTe3Co-sputtering of target material and Te target material, BixSb2-xTe3The target material adopts a direct current power supply, the Te target material adopts a radio frequency power supply, and the heating substrate temperature is 100-;
when the bismuth telluride-based alloy thin film is n-type Bi2Te3-ySeyFilm formation: using commercial Bi2Te3-ySeyCo-sputtering of target material and Te target material, Bi2Te3-ySeyAdopts a direct current power supply and a radio frequency power supply for the Te target materialThe heating substrate temperature is 100-350 ℃.
9. A thin film thermoelectric device comprising the composite thermoelectric material according to any one of claims 1 to 6.
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