CN112864300B - Bismuth telluride base alloy film-perovskite oxide heterojunction composite thermoelectric material and preparation and application thereof - Google Patents
Bismuth telluride base alloy film-perovskite oxide heterojunction composite thermoelectric material and preparation and application thereof Download PDFInfo
- Publication number
- CN112864300B CN112864300B CN201911195554.0A CN201911195554A CN112864300B CN 112864300 B CN112864300 B CN 112864300B CN 201911195554 A CN201911195554 A CN 201911195554A CN 112864300 B CN112864300 B CN 112864300B
- Authority
- CN
- China
- Prior art keywords
- bismuth telluride
- base alloy
- film
- thermoelectric material
- alloy film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 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 26
- 239000002131 composite material Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 6
- 239000010408 film Substances 0.000 claims abstract description 49
- 239000000758 substrate Substances 0.000 claims abstract description 25
- 239000010409 thin film Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract description 8
- 239000013077 target material Substances 0.000 claims description 14
- 238000000137 annealing Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000004544 sputter deposition Methods 0.000 claims description 5
- 238000005477 sputtering target Methods 0.000 claims description 5
- 229910002367 SrTiO Inorganic materials 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 4
- 239000012212 insulator Substances 0.000 abstract description 3
- 238000011946 reduction process Methods 0.000 abstract 1
- 239000002585 base Substances 0.000 description 21
- 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
- 229910052786 argon Inorganic materials 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 239000002344 surface layer Substances 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 2
- 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
- 230000000694 effects Effects 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 230000005679 Peltier effect Effects 0.000 description 1
- 230000005678 Seebeck effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000008021 deposition Effects 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
- 230000002349 favourable effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 238000004801 process automation Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910052712 strontium Inorganic materials 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
- 238000000427 thin-film deposition Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/80—Constructional details
- H10N10/85—Thermoelectric active materials
- H10N10/851—Thermoelectric active materials comprising inorganic compositions
- H10N10/852—Thermoelectric active materials comprising inorganic compositions comprising tellurium, selenium or sulfur
-
- C—CHEMISTRY; METALLURGY
- 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
-
- 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
-
- 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
- H10N10/855—Thermoelectric active materials comprising inorganic compositions comprising compounds containing boron, carbon, oxygen or nitrogen
Abstract
The invention provides a bismuth telluride base alloy film-perovskite oxide heterojunction composite thermoelectric material and preparation and application thereof, wherein the method comprises the following steps: the first step is to process the perovskite oxide substrate through a high-temperature reduction process, so that the substrate is changed into a surface conduction state from an insulator; and secondly, growing a bismuth telluride base 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 with 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 a high-efficiency and convenient process idea 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 thermoelectric, and particularly relates to preparation and application of a bismuth telluride alloy film-perovskite oxide semiconductor heterojunction composite thermoelectric material.
Background
Along with the increasing serious problems of global environmental pollution, energy shortage and the like, the development and utilization of new energy are particularly critical. The thermoelectric technology can realize conversion between heat energy and electric energy, and is widely focused 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, quick response, easy integration and the like, and has more application value in microelectronic devices.
Film and method for producing the sameThe thermoelectric device converts heat energy into electric energy mainly through the seebeck effect; and the Peltier effect is utilized to realize electric refrigeration and electric heating. Maximum output power for a thermoelectric energy conversion deviceWherein S is Seebeck coefficient, deltaT is temperature difference between two ends, R int Is the internal resistance of the device. The larger the seebeck coefficient and the lower the internal resistance, the higher the output power. However, the seebeck coefficient and conductivity of the material are both related to the carrier concentration: as the carrier concentration increases, the conductivity increases correspondingly, and the seebeck coefficient decreases. Thus, breaking the coupling between the two is a key to obtaining a large output power.
Bismuth telluride (Bi) 2 Te 3 ) The base alloy is used as a semiconductor with a narrow band gap (0.13 eV), has excellent thermoelectric performance near room temperature, is widely applied to traditional thermoelectric devices, but has a smaller Seebeck coefficient (< 250 mu V/K) and limits the improvement of output voltage. In addition, after being prepared into a film, the internal resistance is high, so that the output power is generally less than 200nw. In contrast, perovskite-type oxides are typically wide bandgap semiconductors, which generally have a relatively high seebeck coefficient, but also cannot achieve a relatively high output power due to their higher electrical and thermal conductivities than conventional thermoelectric materials. Conventional methods increase thin film thermoelectric device output power by increasing thermoelectric leg pairs and increasing thin film thickness, but these methods generally require complex processes.
Disclosure of Invention
The bismuth telluride base alloy film-perovskite oxide semiconductor heterojunction composite thermoelectric material is used for solving the problems of low seebeck coefficient and high internal resistance of the conventional film thermoelectric material, and can be applied to improving the output power of a film thermoelectric device. By constructing a heterojunction composite material system on a real space, the excellent conductivity of the bismuth telluride base alloy film and the higher Seebeck coefficient of the perovskite oxide substrate are effectively combined, the coupling between the resistance and the Seebeck coefficient existing in a single thermoelectric material system is broken through, and the film thermoelectric material with high Seebeck coefficient and low internal resistance is obtained, so that the output power of the device is improved.
In one aspect, the present invention provides a composite thermoelectric material comprising a bismuth telluride based alloy thin film and a perovskite oxide; and the bismuth telluride base alloy film and the perovskite type oxide are compounded to form a heterojunction structure.
Based on the above technical scheme, preferably, the perovskite type oxide has a general formula of ABO 3 A is an alkali metal element or a rare earth element; b is a transition metal element.
Based on the above technical scheme, preferably, the A is Sr, ba, ca or La; and B is Ti, mn, co and the like.
Based on the above technical scheme, preferably, the perovskite oxide is SrTiO 3 、BaTiO 3 、LaMnO 3 Etc.
Based on the technical scheme, preferably, the thickness of the bismuth telluride base alloy film is 1-2000nm.
Based on the technical scheme, preferably, the bismuth telluride base alloy is p-type Bi x Sb 2-x Te 3 (0.ltoreq.x.ltoreq.2) or n-type Bi 2 Te 3-y Se y (0＜y≤3)。
The invention also provides a preparation method of the heterojunction structure composite thermoelectric material, which comprises the following steps:
(1) Perovskite oxide is used as a substrate, and H is carried out at 700-1200 DEG C 2 Annealing for 1-12h under the atmosphere;
(2) Depositing a bismuth telluride base alloy film on the surface of the perovskite oxide obtained through the treatment in the step (1) by a magnetron sputtering method to obtain the composite thermoelectric material, wherein the structure of the composite thermoelectric material is shown in figure 1; the deposition conditions are as follows: and the bismuth telluride base alloy target and the tellurium target are adopted for co-sputtering, the direct current power supply is adopted for the bismuth telluride base alloy target, the temperature of a heating substrate is 100-350 ℃, and the film thickness can be regulated by controlling the sputtering power and the growth time.
Based on the above technical scheme, preferably, the magnetron sputtering conditions are: when the bismuth telluride base alloy film is p-type Bi x Sb 2-x Te 3 Film: bi with the purity of 99.99 weight percent x Sb 2-x Te 3 Co-sputtering target material and Te target material, bi x Sb 2-x Te 3 The target material adopts a direct current power supply, and the power is 30W; the Te target adopts a radio frequency power supply, the power is 40W, the temperature of a heating substrate is 300 ℃, the flow rate of argon is 30sccm, and the growth time is 1-15000s.
When the bismuth telluride base alloy film is n-type Bi 2 Te 3-y Se y Film: bi with the purity of 99.99 weight percent 2 Te 3- y Se y Co-sputtering target material and Te target material, bi 2 Te 3-y Se y A direct current power supply is adopted, and the power is 35W; te adopts a radio frequency power supply, and the power is 20W. The temperature of the heated substrate is 300 ℃, the flow rate of argon is 30sccm, and the growth time is 1-15000s.
The invention also provides a thin film thermoelectric device, which comprises the heterostructure thermoelectric material. The thickness of the bismuth telluride base alloy is adjusted, and the open-circuit voltage and the internal resistance of the heterojunction can be adjusted, so that the output power is adjusted.
Advantageous effects
(1) Perovskite-type oxides are typically insulating as a substrate for thin film growth. After high-temperature annealing treatment, the surface layer is reduced, the insulator is changed into a surface layer conductive state, and the resistance is changed in a gradient way from the surface to the inside, so that a higher Seebeck coefficient can be provided for the heterojunction, and the output voltage is improved. Compared with a single bismuth telluride base alloy film, the seebeck coefficient of the composite material is greatly improved.
(2) And growing a bismuth telluride base alloy film on the surface of the reduced perovskite oxide by using a magnetron sputtering method. The film has excellent conductivity, is tightly combined with the perovskite oxide substrate, is favorable for electron transport, 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 size of the Seebeck coefficient and the internal resistance can be adjusted by changing the thickness of the bismuth telluride base alloy film, so that the output power of the heterojunction is adjusted.
(4) The heterojunction composite material has a seebeck coefficient which is far higher than that of the bismuth telluride base alloy film, although the seebeck coefficient is reduced compared with that of the single perovskite oxide. By combining the large seebeck coefficient of the perovskite type oxide substrate and the excellent conductivity of the bismuth telluride-based thin film, a 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 diagram of a bismuth telluride based alloy thin film-perovskite oxide heterojunction structure; the surface layer is a bismuth telluride base alloy film grown by magnetron sputtering, and the middle is a reduced perovskite oxide conductive layer.
FIG. 2 (a) shows Bi of different thicknesses in example 1 0.5 Sb 1.5 Te 3 Thin film deposition on the surface of insulating strontium titanate (Bi 0.5 Sb 1.5 Te 3 /SrTiO 3 ) Reduction of strontium titanate surface (Bi) 0.5 Sb 1.5 Te 3 /SrTiO 3-x ) The seebeck coefficient of (c) varies with film thickness; FIG. 2 (b) is Bi 0.5 Sb 1.5 Te 3 /SrTiO 3-x And Bi (Bi) 0.5 Sb 1.5 Te 3 /SrTiO 3 The internal resistance of (c) varies with film thickness.
FIG. 3 shows Bi having a thickness of 80nm in example 1 0.5 Sb 1.5 Te 3 /SrTiO 3 、Bi 0.5 Sb 1.5 Te 3 /SrTiO 3-x And reducing the strontium titanate substrate (SrTiO) 3-x ) And the seebeck coefficient.
FIG. 4 (a) shows Bi of 80nm thickness in example 1 0.5 Sb 1.5 Te 3 /SrTiO 3-x ，SrTiO 3-x ，Bi 0.5 Sb 1.5 Te 3 /SrTiO 3 Output power test results at 60K temperature difference; fig. 4 (b) is an enlarged view of the dotted line block in fig. 4 (a).
FIG. 5 shows the structure of example 1, when Bi 0.5 Sb 1.5 Te 3 And when the film thickness is 80nm, the output power and the I-V curve diagram are shown in different temperature differences.
FIG. 6 shows Bi in example 2 2 Te 2.7 Se 0.3 /SrTiO 3 、Bi 2 Te 2.7 Se 0.3 /SrTiO 3-x 、SrTiO 3-x Schematic of the resistance and seebeck coefficient of (c).
FIG. 7 shows Bi of 100nm thickness in example 2 2 Te 2.7 Se 0.3 /SrTiO 3-x And outputting a power schematic diagram under different temperature differences.
Detailed Description
The following examples are provided for clarity of illustration of the effects of the invention, but the scope of the invention shall include the full contents of the claims and not be limited to the embodiments alone.
Example 1
1. Commercial strontium titanate (SrTiO) 3 ) The single crystal was used as a substrate, and the dimensions were 10.0 mm. Times.2.0 mm. Times.0.5 mm. By 1000 ℃, H 2 Annealing for 8h in the atmosphere to generate oxygen vacancies, which are converted from an insulator to a surface-layer conductive conductor (SrTiO 3-x ) The thickness of the conductive layer is about 10 μm.
2. Depositing p-type Bi on the strontium titanate surface obtained in the step 1 by a magnetron sputtering method 0.5 Sb 1.5 Te 3 Thin films forming heterojunction structures as shown in fig. 1. The growth conditions are as follows: bi with purity of 99.99wt% 0.5 Sb 1.5 Te 3 Co-sputtering target material and Te target material, bi 0.5 Sb 1.5 Te 3 The target material adopts a direct current power supply, and the power is 30W; the Te target adopts a radio frequency power supply with the power of 40W. The temperature of the heating substrate is 300 ℃, the flow rate of argon is 30sccm, the film growth rate is 8nm/min, the film thickness can be regulated by controlling the growth time, and the film with the thickness of 1-2000nm can be grown in the time range of 1-15000s.
As shown in FIG. 2 (a), bi increases with the film thickness 0.5 Sb 1.5 Te 3 /SrTiO 3-x The seebeck coefficient gradually decreases but remains negative. Bi (Bi) 0.5 Sb 1.5 Te 3 /SrTiO 3 The Seebeck coefficient is kept at a normal positive value at 110. Mu.V/K.
As shown in FIG. 2 (b) is Bi 0.5 Sb 1.5 Te 3 /SrTiO 3-x (dotted line) and Bi 0.5 Sb 1.5 Te 3 /SrTiO 3 (solid line) internal resistance change schematic diagram, internal resistance gradually decreases as film thickness increases, bi 0.5 Sb 1.5 Te 3 /SrTiO 3-x The internal resistance of the heterojunction is smaller than Bi 0.5 Sb 1.5 Te 3 /SrTiO 3 Internal resistance of (3).
Comparative example 1
Reduction of strontium titanate SrTiO 3-x The internal resistance of the substrate is 12.4kΩ and the Seebeck coefficient is-860 μV/K. At a temperature difference of 60K, the output power was 57nW.
Comparative example 2
When the sputtering time is 600s, p-type Bi of 80nm is grown on the insulating strontium titanate substrate 0.5 Sb 1.5 Te 3 A thin film was produced in the same manner as in example 1 to obtain Bi 0.5 Sb 1.5 Te 3 /SrTiO 3 The composite thermoelectric material has Seebeck coefficient of 110 μV/K, internal resistance of 580 Ω, and output power of 16nW at 60K.
As shown in FIG. 3, bi 0.5 Sb 1.5 Te 3 /SrTiO 3-x The heterojunction overall reduced in resistance to 230 Ω with a seebeck coefficient of-510 μv/K, and although the seebeck coefficient was reduced for the reduction of strontium titanate, the internal resistance was reduced by a greater extent, as shown in fig. 4, with an output power that was 1100% higher compared to the reduction of strontium titanate. Compared with Bi 0.5 Sb 1.5 Te 3 For 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=60K), and the output power is increased by 4400%.
As shown in FIG. 5, bi of 80nm thickness 0.5 Sb 1.5 Te 3 /SrTiO 3-x The 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 and is consistent with the internal resistance of 230 omega, which indicates that the internal resistance of the thin film thermoelectric device can be kept stable along with the change of temperature.
Example 2
1. The commercial strontium titanate single crystal was used as a substrate and had a size of 10.0mm×2.0mm×0.5mm. By 1000 ℃, H 2 Annealing for 8h in atmosphere to generate oxygen vacancies, and forming an insulatorIs converted into a conductor with internal resistance of 12.4kΩ, and the seebeck coefficient is-860 μV/K. At a temperature difference of 60K, the output power was 57nW.
2. Magnetron sputtering growth of n-type Bi 2 Te 2.7 Se 0.3 The conditions of the film are: bi with the purity of 99.99 weight percent 2 Te 2.7 Se 0.3 Co-sputtering target material and Te target material, bi 2 Te 2.7 Se 0.3 A direct current power supply is adopted, and the power is 35W; te adopts a radio frequency power supply, and the power is 20W. The temperature of the heating substrate is 300 ℃, the flow rate of argon is 30sccm, the growth rate of the film is 8nm/min, the thickness of the film can be regulated by controlling the growth time, and the film with the thickness of 1-2000nm can be grown in the time range of 1-15000s. The output voltage and the internal resistance of the thin film thermoelectric device can be adjusted by adjusting the thickness of the bismuth telluride base alloy thin film, so that the output power is adjusted.
Comparative example 3
As shown in FIG. 6, bi was obtained by growing on an insulating strontium titanate substrate when the sputtering time was 750s and the film thickness was 100nm 2 Te 2.7 Se 0.3 The seebeck coefficient of the film is-90 mu V/K, the internal resistance is 550 omega, and the output power is 13nW when the temperature difference is 60K.
When Bi is 2 Te 2.7 Se 0.3 When the film is deposited on the reduced strontium titanate substrate, the overall resistance is reduced to 220 omega, the Seebeck coefficient is-390 mu V/K, compared with Bi with the same thickness on the insulating strontium titanate substrate 2 Te 2.7 Se 0.3 For the film, the resistance is reduced by 60%, the seebeck coefficient is improved by 330%, the output power is 412nW (delta T=60K), and the output power is increased by 3000%.
As shown in FIG. 7, bi of 100nm thickness 2 Te 2.7 Se 0.3 /SrTiO 3-x The 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 and is consistent with the internal resistance 220 omega, which indicates that the internal resistance of the thin film thermoelectric device can be kept 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 base alloy thin film-perovskite oxide heterojunction. The perovskite oxide surface is reduced in the annealing process, so that the seebeck coefficient of the perovskite oxide is large, and the excellent conductivity of the bismuth telluride base alloy film is combined, the barrier between the seebeck coefficient and the resistance is broken through in real space, and the output power of the film is effectively improved. And the process automation degree is high, the prepared film has small volume, high output power and high power density. Provides a good idea for improving the performance of the thin film device.
Claims (4)
1. A composite thermoelectric material, characterized by: the composite thermoelectric material comprises a bismuth telluride base alloy film and perovskite type oxide; the bismuth telluride base alloy film and the perovskite type oxide are compounded to form a heterojunction structure;
the perovskite oxide is SrTiO 3 、BaTiO 3 、LaMnO 3 ；
The bismuth telluride base alloy is p-type Bi x Sb 2-x Te 3 Or n-type Bi 2 Te 3-y Se y ；0＜x≤2；0＜y＜3；
The preparation method of the composite thermoelectric material comprises the following steps:
(1) Perovskite oxide is used as a substrate, and H is carried out at 700-1200 DEG C 2 Annealing for 1-12h under the atmosphere;
(2) And (3) growing the bismuth telluride base alloy 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.
2. The composite thermoelectric material according to claim 1, characterized in that the thickness of the bismuth telluride-based alloy thin film is 1-2000nm.
3. The composite thermoelectric material according to claim 1, wherein,
when the bismuth telluride base alloy film is p-type Bi x Sb 2-x Te 3 Film: by commercial Bi x Sb 2-x Te 3 Target material and Te target materialCo-sputtering, bi x Sb 2-x Te 3 The target adopts a direct current power supply, the Te target adopts a radio frequency power supply, and the temperature of a heating substrate is 100-350 ℃;
when the bismuth telluride base alloy film is n-type Bi 2 Te 3-y Se y Film: by commercial Bi 2 Te 3-y Se y Co-sputtering target material and Te target material, bi 2 Te 3-y Se y The Te target material adopts a radio frequency power supply by adopting a direct current power supply, and the temperature of a heating substrate is 100-350 ℃.
4. A thin film thermoelectric device comprising the composite thermoelectric material of any one of claims 1-3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911195554.0A CN112864300B (en) | 2019-11-28 | 2019-11-28 | Bismuth telluride base alloy film-perovskite oxide heterojunction composite thermoelectric material and preparation and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911195554.0A CN112864300B (en) | 2019-11-28 | 2019-11-28 | Bismuth telluride base alloy film-perovskite oxide heterojunction composite thermoelectric material and preparation and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112864300A CN112864300A (en) | 2021-05-28 |
| CN112864300B true CN112864300B (en) | 2024-02-02 |
Family
ID=75995978
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911195554.0A Active CN112864300B (en) | 2019-11-28 | 2019-11-28 | Bismuth telluride base alloy film-perovskite oxide heterojunction composite thermoelectric material and preparation and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112864300B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117156940B (en) * | 2023-10-30 | 2024-01-09 | 北京中育神州数据科技有限公司 | Method for optimizing thermoelectric performance by utilizing heterogeneous thermoelectric material |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1836341A (en) * | 2004-03-01 | 2006-09-20 | 松下电器产业株式会社 | Thermoelectric conversion device, and cooling method and power generating method using the device |
| CN102482766A (en) * | 2009-06-30 | 2012-05-30 | 欧-弗莱克斯科技有限公司 | Method for producing thermoelectric layers |
| CN105355771A (en) * | 2015-10-16 | 2016-02-24 | 中国科学院上海硅酸盐研究所 | High-power-factor zinc oxide thermoelectric material and preparation method therefor |
| CN106784279A (en) * | 2016-12-22 | 2017-05-31 | 北京科技大学 | A kind of preparation method of high-performance doped strontium titanates oxide thermoelectricity film |
| CN108231991A (en) * | 2017-11-24 | 2018-06-29 | 浙江大学 | A kind of p-type bismuth telluride-base thermoelectric material to generate electricity near room temperature solid-state refrigeration and waste heat |
| CN109554674A (en) * | 2018-10-09 | 2019-04-02 | 中国科学院电工研究所 | A kind of preparation method of the bismuth telluride thermal electric film with heterojunction structure |
| CN110098313A (en) * | 2019-04-22 | 2019-08-06 | 武汉科技大学 | A kind of preparation method of preferred orientation p-type bismuth telluride-base polycrystalline bulk thermoelectric material |
-
2019
- 2019-11-28 CN CN201911195554.0A patent/CN112864300B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1836341A (en) * | 2004-03-01 | 2006-09-20 | 松下电器产业株式会社 | Thermoelectric conversion device, and cooling method and power generating method using the device |
| CN102482766A (en) * | 2009-06-30 | 2012-05-30 | 欧-弗莱克斯科技有限公司 | Method for producing thermoelectric layers |
| CN105355771A (en) * | 2015-10-16 | 2016-02-24 | 中国科学院上海硅酸盐研究所 | High-power-factor zinc oxide thermoelectric material and preparation method therefor |
| CN106784279A (en) * | 2016-12-22 | 2017-05-31 | 北京科技大学 | A kind of preparation method of high-performance doped strontium titanates oxide thermoelectricity film |
| CN108231991A (en) * | 2017-11-24 | 2018-06-29 | 浙江大学 | A kind of p-type bismuth telluride-base thermoelectric material to generate electricity near room temperature solid-state refrigeration and waste heat |
| CN109554674A (en) * | 2018-10-09 | 2019-04-02 | 中国科学院电工研究所 | A kind of preparation method of the bismuth telluride thermal electric film with heterojunction structure |
| CN110098313A (en) * | 2019-04-22 | 2019-08-06 | 武汉科技大学 | A kind of preparation method of preferred orientation p-type bismuth telluride-base polycrystalline bulk thermoelectric material |
Non-Patent Citations (1)
| Title |
|---|
| 多晶碲化铋基热电材料制备及性能测试;郭亮等;《研究与设计》;全文 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112864300A (en) | 2021-05-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Singh et al. | The effect of doping on thermoelectric performance of p-type SnSe: Promising thermoelectric material | |
| Liu et al. | Composition dependent metal-semiconductor transition in transparent and conductive La-doped BaSnO3 epitaxial films | |
| Takayama et al. | Multi-layered-stack thermoelectric generators using p-type Sb2Te3 and n-type Bi2Te3 thin films by radio-frequency magnetron sputtering | |
| Zhou et al. | Enhancing the thermoelectric performance of ZnO epitaxial films by Ga doping and thermal tuning | |
| GB2416244A (en) | Thermoelectric element and thermoelectric module | |
| Ashfaq et al. | Tailoring the thermoelectric properties of sol-gel grown CZTS/ITO thin films by controlling the secondary phases | |
| Saini et al. | On-chip thermoelectric module comprised of oxide thin film legs | |
| Yasukawa et al. | Thermoelectric properties and figure of merit of perovskite-type Ba1− xLaxSnO3 with x= 0.002–0.008 | |
| Wan et al. | Synergetic enhancement of thermoelectric performance in a Bi 0.5 Sb 1.5 Te 3/SrTiO 3 heterostructure | |
| Hsu et al. | A new p-Ni1− xO: Li/n-Si heterojunction solar cell fabricated by RF magnetron sputtering | |
| US7435896B2 (en) | Thermoelectric conversion material, thermoelectric conversion element using the material, cooling device and electric apparatus using the element, and electric power generation method and cooling method using the element | |
| CN106399937A (en) | Method for preparing preferred-orientation bismuth telluride thermoelectric thin film | |
| CN112864300B (en) | Bismuth telluride base alloy film-perovskite oxide heterojunction composite thermoelectric material and preparation and application thereof | |
| CN106498354A (en) | A kind of method for preparing hexagonal Spiral morphology Tellurobismuthite. thermal electric film | |
| CN109554674A (en) | A kind of preparation method of the bismuth telluride thermal electric film with heterojunction structure | |
| JP6587125B2 (en) | Oxide semiconductor thin film, semiconductor element, photoelectric conversion element, solar cell, and method for manufacturing oxide semiconductor thin film | |
| CN101969096B (en) | Nanostructured thermoelectric material and device and production method thereof | |
| KR101537974B1 (en) | Porous Organic Thermoelectric Device | |
| CN101645464B (en) | TbMnO p-n heterojunction having two-way rectifying characteristic and preparation method thereof | |
| US7417186B2 (en) | Thermoelectric conversion material, thermoelectric conversion element using the same, and electronic apparatus and cooling device comprising the element | |
| Saini et al. | Effect of Oxygen Pressure on Thermoelectric Properties of p-Type CuAlO 2 Films Fabricated by Pulsed Laser Deposition | |
| Jeon et al. | Experimental Study on Zinc Oxide Thin Film-Based Thermoelectric Energy Harvester Under Plane-Vertical Temperature Gradients | |
| Serralta-Macías et al. | Energy storage performance in lead-free antiferroelectric 0.92 (Bi0. 54Na0. 46) TiO3-0.08 BaTiO3 ultrathin films by pulsed laser deposition | |
| JP2016008324A (en) | P-type copper nitride semiconductor thin film | |
| KR102296386B1 (en) | The method for preparation of transparent thermoelectric materials and transparent and flexible thermoelectric generators using the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |