CN110172735B - Single crystal tin selenide thermoelectric film and preparation method thereof - Google Patents
Single crystal tin selenide thermoelectric film and preparation method thereof Download PDFInfo
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- MFIWAIVSOUGHLI-UHFFFAOYSA-N selenium;tin Chemical compound [Sn]=[Se] MFIWAIVSOUGHLI-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 239000013078 crystal Substances 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- 239000000758 substrate Substances 0.000 claims abstract description 116
- 239000006185 dispersion Substances 0.000 claims abstract description 28
- 239000007788 liquid Substances 0.000 claims abstract description 28
- 238000004544 sputter deposition Methods 0.000 claims abstract description 26
- 238000001035 drying Methods 0.000 claims abstract description 25
- 239000011261 inert gas Substances 0.000 claims abstract description 22
- 239000011248 coating agent Substances 0.000 claims abstract description 21
- 238000000576 coating method Methods 0.000 claims abstract description 21
- 238000004140 cleaning Methods 0.000 claims abstract description 18
- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract description 16
- 238000010438 heat treatment Methods 0.000 claims abstract description 14
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 238000005477 sputtering target Methods 0.000 claims abstract description 8
- 239000013077 target material Substances 0.000 claims abstract description 8
- 239000010409 thin film Substances 0.000 claims description 36
- 239000011521 glass Substances 0.000 claims description 34
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 24
- 239000010408 film Substances 0.000 claims description 24
- 229910052710 silicon Inorganic materials 0.000 claims description 24
- 239000010703 silicon Substances 0.000 claims description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 23
- 229910021389 graphene Inorganic materials 0.000 claims description 23
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 14
- 239000010445 mica Substances 0.000 claims description 14
- 229910052618 mica group Inorganic materials 0.000 claims description 14
- 239000007789 gas Substances 0.000 claims description 9
- 229910052786 argon Inorganic materials 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 238000011049 filling Methods 0.000 claims description 6
- 239000001307 helium Substances 0.000 claims description 6
- 229910052734 helium Inorganic materials 0.000 claims description 6
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000000151 deposition Methods 0.000 claims description 4
- 230000008021 deposition Effects 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 4
- 239000000463 material Substances 0.000 abstract description 27
- 230000008901 benefit Effects 0.000 abstract description 3
- 230000001276 controlling effect Effects 0.000 description 13
- 230000009286 beneficial effect Effects 0.000 description 10
- 238000002207 thermal evaporation Methods 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 5
- 239000008187 granular material Substances 0.000 description 4
- 238000004528 spin coating Methods 0.000 description 4
- 238000001514 detection method Methods 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 238000005457 optimization Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000013590 bulk material Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
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- 238000005265 energy consumption Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000004549 pulsed laser deposition Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
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- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B23/00—Single-crystal growth by condensing evaporated or sublimed materials
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/46—Sulfur-, selenium- or tellurium-containing compounds
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Abstract
The invention relates to a single crystal tin selenide thermoelectric film and a preparation method thereof, belonging to the field of thermoelectric materials. The preparation method of the single crystal tin selenide thermoelectric film comprises the following steps: taking a substrate, placing the substrate in a cleaning solution, ultrasonically cleaning for 10min, drying for 2h at the temperature of 60-150 ℃ after cleaning, taking out and naturally cooling; putting the processed substrate on a spin coater, dripping dispersion liquid on the surface of the substrate, spin-throwing for 10-60s, taking out the substrate after spin-throwing, and drying at 200 ℃ for 5-10min to obtain a buffer layer substrate; and putting the tin selenide sputtering target material and the prepared buffer layer substrate into a high-vacuum multifunctional magnetron sputtering coating instrument, vacuumizing, heating the buffer layer substrate, introducing inert gas, and sputtering for 20-60min to obtain the single crystal tin selenide thermoelectric film. The preparation method has the advantages that the preparation process is simple, and the prepared single-crystal tin selenide thermoelectric film has good single-crystal property and high power factor.
Description
Technical Field
The invention belongs to the field of thermoelectric materials, and particularly relates to a single-crystal tin selenide thermoelectric thin film and a preparation method thereof.
Background
The thermoelectric material is a functional material which realizes direct interconversion between heat energy and electric energy by utilizing the interaction and transport characteristics of current carriers and phonons of a solid material, and waste heat can be directly converted into electric energy based on the thermoelectric material thermoelectric power generation technology, so that the use efficiency of energy is improved. Thermoelectric refrigerators made with thermoelectric materials have the advantages that mechanical compression refrigerators have a competitive advantage: the size is small, the weight is light, no mechanical rotating part is arranged, the operation is noiseless, no liquid or gaseous medium exists, the problem of environmental pollution does not exist, the accurate temperature control can be realized, the response speed is high, and the service life of the device is long. Today, the environmental pollution and the energy crisis are becoming more serious, thermoelectric materials are materials with wide application prospects.
The thermoelectric property of the SnSe material is obviously improved in single crystal and polycrystalline block materials through regulating and controlling the layered structure of the SnSe material. But simultaneously, the layered structure regulation of the SnSe bulk material is limited by a plurality of aspects such as complex preparation process, poor mechanical property of the material and the like. The thin film material has stronger controllability and more obvious quantum scale effect in the aspect of regulating and controlling the layered structure. The prior methods for preparing the SnSe film comprise thermal evaporation, pulsed laser deposition, chemical vapor deposition and the like, but the methods generally have the defects of complex preparation process, low yield, high cost, high energy consumption and the like, and the prepared polycrystalline film has low performance and is not suitable for large-scale process production and application
Disclosure of Invention
The invention provides a single-crystal tin selenide thermoelectric thin film and a preparation method thereof, aiming at solving the technical problems, the preparation process is simple, the parameter control and optimization are easier, the production period is shorter, the cost is lower, the yield is higher, and the prepared single-crystal tin selenide thermoelectric thin film has good single crystal property and high power factor.
The technical scheme for solving the technical problems is as follows: a preparation method of a single-crystal tin selenide thermoelectric thin film comprises the following steps:
s1, taking the substrate, placing the substrate in a cleaning solution for ultrasonic cleaning for 10min, drying the substrate for 2h at the temperature of 60-150 ℃ after cleaning, taking out and naturally cooling the substrate;
s2, putting the substrate processed in the step S1 on a spin coater, dripping 0.3-1mL of dispersion liquid on the surface of the substrate, spin-drying at the rotating speed of 0-4000r/min for 10-60S, taking out the substrate after spin-drying, and drying at 200 ℃ for 5-10min to obtain a buffer layer substrate;
s3, placing the tin selenide sputtering target material on a target platform of a deposition cavity of the high-vacuum multifunctional magnetron sputtering coating instrument, placing the buffer layer substrate prepared in the step S2 on a sample platform of the deposition cavity of the high-vacuum multifunctional magnetron sputtering coating instrument, vacuumizing, heating the buffer layer substrate, introducing inert gas, and sputtering for 20-60min to obtain the single-crystal tin selenide thermoelectric film.
The preparation method of the invention has the beneficial effects that: the preparation method is simpler, the parameter control and optimization are easier, the production period is shorter, the cost is lower, the yield is higher, the single crystal tin selenide thermoelectric thin film prepared has good single crystal property and high power factor, and the single crystal tin selenide thermoelectric power factor is greatly improved.
On the basis of the technical scheme, the invention can be further improved as follows.
Further, the substrate in the step S1 is one of ordinary glass, mica, and a silicon wafer.
The beneficial effect of adopting the further scheme is that: the substrate has wide application and selection range, and is beneficial to mass production.
Further, the cleaning solution in step S1 is one or a mixture of two of anhydrous ethanol and deionized water.
The beneficial effect of adopting the further scheme is that: can effectively remove oil stains and impurities.
Further, the dispersion liquid in the step S2 is a graphene oxide dispersion liquid of 1 to 5 mg/mL.
The beneficial effect of adopting the further scheme is that: the dispersion effect is better.
Further, the step S3 of evacuating is to evacuate until the vacuum degree is less than 10Pa, fill inert gas until the pressure reaches 100Pa to complete the gas cleaning, evacuate again until the vacuum degree is less than 6 × 10-4Pa。
The beneficial effect of adopting the further scheme is that: air exchange is carried out firstly and then vacuum pumping is carried out, so that oxygen interference is avoided.
Further, the buffer layer substrate is heated to 200-280 ℃ in the step S3.
The beneficial effect of adopting the further scheme is that: the prepared single crystal tin selenide thermoelectric film has better performance.
Further, in the step S3, the volume flow of the inert gas is controlled to be 15-25 Sccm.
The beneficial effect of adopting the further scheme is that: the control of the air pressure intensity of sputtering is facilitated.
Further, in the step S3, the sputtering air pressure of the high-vacuum multifunctional magnetron sputtering coating instrument is controlled to be 1.2-2.7Pa, the sputtering power is 80-100W, and the rotating speed is 15-30 r/min.
The beneficial effect of adopting the further scheme is that: the prepared single crystal tin selenide thermoelectric film has better performance.
Further, the inert gas is one or a mixture of two of helium and argon in any proportion.
The beneficial effect of adopting the further scheme is that: the inert gas is more convenient to use.
The invention also provides the single-crystal tin selenide thermoelectric thin film prepared by the preparation method of the single-crystal tin selenide thermoelectric thin film.
Drawings
FIG. 1 is an XRD pattern for example 4 of the present invention;
FIG. 2 is an XRD pattern for examples 1-4 of the present invention;
FIG. 3 is a surface view of a scanning electron microscope in example 4 of the present invention;
FIG. 4 is a cross-sectional view of a scanning electron microscope according to example 4 of the present invention;
FIG. 5 is a surface view of a scanning electron microscope according to example 5 of the present invention;
FIG. 6 is a cross-sectional view of a scanning electron microscope according to example 5 of the present invention;
FIG. 7 is a linear plot of conductivity measurements for examples 1-4 of the present invention;
FIG. 8 is a linear graph of Seebeck coefficients for examples 1 to 4 of the present invention;
FIG. 9 is a graph of power factor versus thermodynamic temperature T for examples 1-4 of the present invention;
FIG. 10 is a linear plot of the conductivity of tin selenide films prepared by thermal evaporation;
FIG. 11 is a linear plot of Seebeck coefficient for tin selenide films prepared by thermal evaporation;
FIG. 12 is a graph of power factor versus thermodynamic temperature T for tin selenide films prepared by thermal evaporation.
Detailed Description
The principles and features of this invention are described below in conjunction with the following drawings, which are set forth by way of illustration only and are not intended to limit the scope of the invention.
Example 1
The embodiment provides a preparation method of a single-crystal tin selenide thermoelectric thin film, which comprises the following steps:
s1, placing the common glass substrate into a mixed solution of absolute ethyl alcohol and deionized water, carrying out ultrasonic cleaning for 10min at room temperature to remove oil stains and impurities on the surface of the common glass substrate, taking out the common glass substrate after cleaning, placing the common glass substrate in an oven, heating the common glass substrate to 120 ℃, drying the common glass substrate for 2h at atmospheric pressure, taking out the common glass substrate, and naturally cooling the common glass substrate to room temperature;
s2, placing the common glass substrate processed in the step S1 on a sample platform of a spin coater, shaking a container filled with the graphene oxide dispersion liquid to make the common glass substrate uniform before the graphene oxide dispersion liquid is dripped, dripping 0.3mL of 5mg/mL graphene oxide dispersion liquid on the surface of the common glass substrate to make the graphene oxide dispersion liquid completely cover the upper surface of the common glass substrate, then spin-casting the common glass substrate for 30S at a rotating speed of 1500r/min, taking out the common glass substrate after spin-casting, placing the common glass substrate on a drying platform, and drying the common glass substrate for 5min at 200 ℃ to obtain a buffer layer substrate;
s3, putting a 99.99% tin selenide sputtering target material purchased from Zhongnuo New materials (Beijing) science and technology Limited company and the buffer layer substrate prepared in the step S2 into a high-vacuum multifunctional magnetron sputtering coating instrument, vacuumizing until the vacuum degree is less than 10Pa, filling inert gas argon until the air pressure reaches 100Pa to complete one-time gas washing, vacuumizing again until the vacuum degree is less than 5Pa, and continuously vacuumizing by using a molecular pump until the vacuum degree is 6 multiplied by 10-4Pa, heating the substrate to 280 deg.C, and keeping the vacuum degree below 6.0 × 10-4And Pa, introducing the inert gas argon again, controlling the volume flow of the introduced inert gas to be 20Sccm, and controlling a gate valve of the high-vacuum multifunctional magnetron sputtering coating instrument to enable the sputtering pressure to be 1.2Pa, set the sputtering power to be 80W and the rotating speed to be 15r/min, and performing sputtering for 20min to obtain the single-crystal tin selenide thermoelectric film.
The embodiment also provides the single-crystal tin selenide thermoelectric thin film prepared by the preparation method, and the single-crystal tin selenide thermoelectric thin film is mainly applied to the thermoelectric technical field, and has high power factor and high electrical conductivity.
Example 2
The embodiment provides a preparation method of a single-crystal tin selenide thermoelectric thin film, which comprises the following steps:
s1, placing the common glass substrate into a mixed solution of absolute ethyl alcohol and deionized water, carrying out ultrasonic cleaning for 10min at room temperature to remove oil stains and impurities on the surface of the common glass substrate, taking out the common glass substrate after cleaning, placing the common glass substrate in an oven, heating the common glass substrate to 120 ℃, drying the common glass substrate for 2h at atmospheric pressure, taking out the common glass substrate, and naturally cooling the common glass substrate to room temperature;
s2, placing the common glass substrate processed in the step S1 on a sample platform of a spin coater, shaking a container filled with the graphene oxide dispersion liquid to make the common glass substrate uniform before the graphene oxide dispersion liquid is dripped, dripping 0.3mL of 5mg/mL graphene oxide dispersion liquid on the surface of the common glass substrate to make the graphene oxide dispersion liquid completely cover the upper surface of the common glass substrate, then spin-casting the common glass substrate for 30S at a rotating speed of 2000r/min, taking out the common glass substrate after spin-casting, placing the common glass substrate on a drying platform, and drying the common glass substrate for 5min at 200 ℃ to obtain a buffer layer substrate;
s3, putting a 99.99% tin selenide sputtering target material purchased from Zhongnuo New materials (Beijing) science and technology Limited company and the buffer layer substrate prepared in the step S2 into a high-vacuum multifunctional magnetron sputtering coating instrument, vacuumizing until the vacuum degree is less than 10Pa, filling inert gas argon until the air pressure reaches 100Pa to complete one-time gas washing, vacuumizing again until the vacuum degree is less than 5Pa, and continuously vacuumizing by using a molecular pump until the vacuum degree is 6 multiplied by 10-4Pa, heating the substrate to sputtering temperature of 220 deg.C and maintaining vacuum degree less than 6.0 × 10-4And Pa, introducing the inert gas argon again, controlling the volume flow of the introduced inert gas to be 15Sccm, controlling a gate valve of the high-vacuum multifunctional magnetron sputtering coating instrument to enable the sputtering pressure to be 1.2Pa, setting the sputtering power to be 80W and the rotating speed to be 15r/min, and sputtering for 60min to obtain the single crystal tin selenide thermoelectric film.
The embodiment also provides the single-crystal tin selenide thermoelectric thin film prepared by the preparation method, and the single-crystal tin selenide thermoelectric thin film is mainly applied to the thermoelectric technical field, and has high power factor and high electrical conductivity.
Example 3
The embodiment provides a preparation method of a single-crystal tin selenide thermoelectric thin film, which comprises the following steps:
s1, placing the mica substrate into a mixed solution of absolute ethyl alcohol and deionized water, ultrasonically cleaning for 10min at room temperature to remove oil stains and impurities on the surface of the mica substrate, taking out the mica substrate after cleaning, placing the mica substrate in an oven, heating the oven to 150 ℃, drying for 2h at atmospheric pressure, taking out and naturally cooling to room temperature;
s2, placing the mica substrate processed in the step S1 on a sample platform of a spin coater, shaking a container filled with the graphene oxide dispersion liquid to make the mica substrate uniform before dropping the graphene oxide dispersion liquid, then dropping 0.5mL of 3mg/mL graphene oxide dispersion liquid on the surface of the mica substrate to make the graphene oxide dispersion liquid completely cover the upper surface of the mica substrate, then spin-throwing the mica substrate at the rotating speed of 3000r/min for 30S, taking the mica substrate out after spin-throwing, placing the mica substrate on a drying platform, and drying the mica substrate at the temperature of 200 ℃ for 8min to obtain a buffer layer substrate;
s3, putting a 99.99% tin selenide sputtering target material purchased from Zhongnuo New materials (Beijing) science and technology Limited company and the buffer layer substrate prepared in the step S2 into a high-vacuum multifunctional magnetron sputtering coating instrument, vacuumizing until the vacuum degree is less than 10Pa, filling inert gas argon until the air pressure reaches 100Pa to complete one-time gas washing, vacuumizing again until the vacuum degree is less than 5Pa, and continuously vacuumizing by using a molecular pump until the vacuum degree is 6 multiplied by 10-4Pa, heating the substrate to sputtering temperature of 250 deg.C and maintaining vacuum degree less than 6.0 × 10-4And Pa, introducing the inert gas argon again, controlling the volume flow of the introduced inert gas to be 23Sccm, controlling a gate valve of the high-vacuum multifunctional magnetron sputtering coating instrument to enable the sputtering pressure to be 1.5Pa, setting the sputtering power to be 100W and the rotating speed to be 30r/min, and sputtering for 30min to obtain the single crystal tin selenide thermoelectric film.
The embodiment also provides the single-crystal tin selenide thermoelectric thin film prepared by the preparation method, and the single-crystal tin selenide thermoelectric thin film is mainly applied to the thermoelectric technical field, and has high power factor and high electrical conductivity.
Example 4
The embodiment provides a preparation method of a single-crystal tin selenide thermoelectric thin film, which comprises the following steps:
s1, placing the silicon wafer substrate into a mixed solution of absolute ethyl alcohol and deionized water, ultrasonically cleaning for 10min at room temperature to remove oil stains and impurities on the surface of the silicon wafer substrate, taking out the silicon wafer substrate after cleaning, placing the silicon wafer substrate in an oven, heating the oven to 80 ℃, drying for 2h at atmospheric pressure, taking out the silicon wafer substrate, and naturally cooling to room temperature;
s2, placing the silicon wafer substrate processed in the step S1 on a sample platform of a spin coater, shaking a container filled with the graphene oxide dispersion liquid to make the container uniform before dropping the graphene oxide dispersion liquid, then dropping 1mL of graphene oxide dispersion liquid with the concentration of 4mg/mL on the surface of the silicon wafer substrate to make the graphene oxide dispersion liquid completely cover the upper surface of the silicon wafer substrate, then spin-throwing the silicon wafer substrate at the rotating speed of 4000r/min for 30S, taking the silicon wafer substrate out after spin-throwing, placing the silicon wafer substrate on a drying platform, and drying the silicon wafer substrate at the temperature of 200 ℃ for 10min to obtain a buffer layer substrate;
s3, putting a 99.99% tin selenide sputtering target material purchased from Zhongnuo New materials (Beijing) science and technology Limited company and the buffer layer substrate prepared in the step S2 into a high-vacuum multifunctional magnetron sputtering coating instrument, vacuumizing until the vacuum degree is less than 10Pa, filling inert gas helium into the instrument until the air pressure reaches 100Pa to complete primary gas washing, vacuumizing again until the vacuum degree is less than 5Pa, and continuously vacuumizing by using a molecular pump until the vacuum degree is 6 multiplied by 10-4Pa, heating the substrate to 280 deg.C, and keeping the vacuum degree below 6.0 × 10-4And Pa, introducing helium gas into the reactor again, controlling the volume flow of the introduced inert gas to be 25Sccm, controlling a gate valve of the high-vacuum multifunctional magnetron sputtering coating instrument to enable the sputtering pressure to be 2.5Pa, setting the sputtering power to be 100W and the rotating speed to be 15r/min, and sputtering for 30min to obtain the single-crystal tin selenide thermoelectric film.
The embodiment also provides the single-crystal tin selenide thermoelectric thin film prepared by the preparation method, and the single-crystal tin selenide thermoelectric thin film is mainly applied to the thermoelectric technical field, and has high power factor and high electrical conductivity.
Example 5
The embodiment provides a preparation method of a single-crystal tin selenide thermoelectric thin film, which comprises the following steps:
s1, placing the silicon wafer substrate into a mixed solution of absolute ethyl alcohol and deionized water, ultrasonically cleaning for 10min at room temperature to remove oil stains and impurities on the surface of the silicon wafer substrate, taking out the silicon wafer substrate after cleaning, placing the silicon wafer substrate in an oven, heating the oven to 120 ℃, drying for 2h at atmospheric pressure, taking out the silicon wafer substrate, and naturally cooling to room temperature;
s2, placing the silicon wafer substrate processed in the step S1 on a sample platform of a spin coater, shaking a container filled with the graphene oxide dispersion liquid to make the container uniform before dropping the graphene oxide dispersion liquid, then dropping 0.8mL of 5mg/mL graphene oxide dispersion liquid on the surface of the silicon wafer substrate to make the graphene oxide dispersion liquid completely cover the upper surface of the silicon wafer substrate, keeping the rotation speed of 0r/min, standing for 30S, taking out the silicon wafer substrate, placing the silicon wafer substrate on a drying platform, and drying for 8min at 200 ℃ to obtain a buffer layer substrate;
s3, putting a 99.99% tin selenide sputtering target material purchased from Zhongnuo New materials (Beijing) science and technology Limited company and the buffer layer substrate prepared in the step S2 into a high-vacuum multifunctional magnetron sputtering coating instrument, vacuumizing until the vacuum degree is less than 10Pa, filling inert gas helium into the instrument until the air pressure reaches 100Pa to complete primary gas washing, vacuumizing again until the vacuum degree is less than 5Pa, and continuously vacuumizing by using a molecular pump until the vacuum degree is 6 multiplied by 10-4Pa, heating the substrate to sputtering temperature 260 deg.C and maintaining vacuum degree less than 6.0 × 10-4And Pa, introducing helium gas into the reactor again, controlling the volume flow of the introduced inert gas to be 20Sccm, controlling a gate valve of the high-vacuum multifunctional magnetron sputtering coating instrument to enable the sputtering pressure to be 2.0Pa, setting the sputtering power to be 80W and the rotating speed to be 20r/min, and sputtering for 50min to obtain the single-crystal tin selenide thermoelectric film.
The embodiment also provides the single-crystal tin selenide thermoelectric thin film prepared by the preparation method, and the single-crystal tin selenide thermoelectric thin film is mainly applied to the thermoelectric technical field, and has high power factor and high electrical conductivity.
XRD examination of examples 1 to 4 showed that peaks of (200), (400), (600) and (800) crystal orientations were observed clearly in FIGS. 1 and 2, indicating that the preferred orientation of the a-axis was clear and a single crystal thin film was formed. When a single crystal thin film is not formed, the peak in the a-axis direction is not conspicuous, and peaks in other crystal orientations such as (111), (201), (311), and the like also appear.
Then, the scanning electron microscope examination is performed on the example 4 and the example 5, as shown in fig. 3-6, wherein fig. 3 and 4 are the example 4, and fig. 5 and 6 are the example 5. In the drawings, a and b are front scanning electron micrographs, and c and d are cross-sectional scanning electron micrographs. As can be seen from fig. 3 to 6, the growth mode of the single crystal tin selenide film prepared by the preparation method is lamellar growth, the surface is formed by tightly arranging 70 to 100nm particles, and the graphene oxide has a hexagonal honeycomb structure, so that the shape of the SnSe film particles is similar to a hexagon and the distribution is uniform. The overall height fluctuation of the surface nano-particles is about 6-7nm, the particles are distributed and stacked along layers, and the minimum stacking height is 1-2 nm.
The electrical properties of examples 1-4 were measured, specifically using a conductivity meter to measure conductivity, and using a resistance measurement system zem to measure the Seebeck coefficient and the relationship between the power factor and the thermodynamic temperature T, with the results shown in FIGS. 7-9.
Meanwhile, the relation between the conductivity, the Seebeck coefficient and the power factor of the tin selenide film prepared by the thermal evaporation method in the existing preparation method and the thermodynamic temperature T is detected, and the relation is shown in figures 10-12. Specifically, the thermal evaporation method is a process of placing a substrate or a workpiece to be coated in a vacuum chamber, heating a coating material to evaporate and gasify the coating material to deposit the coating material on the surface of a substrate or the workpiece and form a film or a coating, and specifically comprises the steps of uniformly mixing powder of elemental selenium and elemental tin in a ratio of 1:1, applying an external force of 4 tons, keeping for 1 minute to prepare SnSe granular materials, cutting the granular materials into small blocks serving as evaporation source materials, adding the heat source materials in an evaporation coating device to evaporate and gasify the granular materials to deposit the granular materials on the substrate, and controlling evaporation time to obtain the required film thickness.
It should be noted that the above-mentioned detection of the relationship between the conductivity, the Seebeck coefficient and the power factor and the thermodynamic temperature T is performed by the existing detection methods known to those skilled in the art.
According to the above detection, it can be seen from the comparison between fig. 7 and fig. 10 that the conductivity of the single-crystal tin selenide thermoelectric thin film prepared by the preparation method is 12S at the temperature of 550Kcm-1The conductivity of the tin selenide thermoelectric film prepared by the thermal evaporation method is 3Scm at the temperature of 550K-1For thermoelectric materials, a higher electrical conductivity indicates a better conductivity of the material. As can be seen from comparison between FIGS. 8 and 11, the Seebeck coefficient of the single-crystal tin selenide thermoelectric thin film prepared by the preparation method is 330 μ VK at a temperature of 550K-1The Seebeck coefficient of the tin selenide thermoelectric film prepared by the thermal evaporation method is 180 mu VK at the temperature of 550K-1. As can be seen from the comparison between FIG. 9 and FIG. 12, the thermoelectric power factor of the single-crystal tin selenide prepared by the preparation method is 1.6 mu Wcm at 550K-1K-2The power factor of the tin selenide thermoelectric film prepared by the thermal evaporation method is 1 mu Wcm at the temperature of 550K-1K-2. For thermoelectric materials, based on
The higher the electrical conductivity and seebeck coefficient of the material, the higher the resulting power factor, the higher the thermoelectric conversion efficiency, and the less the loss.
The single-crystal tin selenide thermoelectric thin film prepared by the preparation method can be obtained from the results, the whole preparation process is simpler, the parameter control and optimization are easier, the production period is shorter, the cost is lower, the yield is higher, the single-crystal tin selenide thermoelectric thin film prepared by the preparation method has good single crystal property, and the power factor is obviously higher than that of the tin selenide thermoelectric thin film prepared by the existing thermal evaporation method, so that the single-crystal tin selenide thin film prepared by the preparation method has better thermoelectric conversion efficiency.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (5)
1. A preparation method of a single-crystal tin selenide thermoelectric film is characterized by comprising the following steps:
s1, taking the substrate, placing the substrate in a cleaning solution for ultrasonic cleaning for 10min, drying the substrate for 2h at the temperature of 60-150 ℃ after cleaning, taking out and naturally cooling the substrate;
s2, putting the substrate processed in the step S1 on a spin coater, dropwise adding 0.3-1mL of dispersion liquid on the surface of the substrate, wherein the dispersion liquid is 1-5mg/mL of graphene oxide dispersion liquid, spin-drying at 2000r/min for 30S, taking out the substrate after spin-drying, and drying at 200 ℃ for 5-10min to obtain a buffer layer substrate;
s3, placing the tin selenide sputtering target material on a target platform of a deposition cavity of the high-vacuum multifunctional magnetron sputtering coating instrument, placing the buffer layer substrate prepared in the step S2 on a sample platform of the deposition cavity of the high-vacuum multifunctional magnetron sputtering coating instrument, vacuumizing until the vacuum degree is less than 10Pa, filling inert gas until the air pressure reaches 100Pa to complete gas washing, vacuumizing again until the vacuum degree is less than 6 multiplied by 10- 4And Pa, heating the buffer layer substrate to 200-280 ℃, introducing inert gas with the volume flow of 15-25Sccm, and sputtering for 20-60min at the sputtering pressure of 1.2-2.7Pa, the sputtering power of 80-100W and the rotation speed of 15-30r/min to obtain the single-crystal tin selenide thermoelectric film.
2. The method for preparing a single crystal tin selenide thermoelectric thin film as claimed in claim 1, wherein the substrate in the step S1 is one of ordinary glass, mica and silicon wafer.
3. The method for preparing a single-crystal tin selenide thermoelectric thin film as claimed in claim 1, wherein the cleaning solution in the step S1 is one or a mixture of any two of absolute ethyl alcohol and deionized water.
4. The method for preparing a single crystal tin selenide thermoelectric thin film according to any one of claims 1 to 3, wherein the inert gas is one or a mixture of any two of helium and argon.
5. A single-crystal tin selenide thermoelectric thin film manufactured by the method for manufacturing a single-crystal tin selenide thermoelectric thin film as claimed in any one of claims 1 to 4.
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