CN112853492B - SnSe/CNT high-temperature flexible thermoelectric thin film material and preparation method thereof - Google Patents

SnSe/CNT high-temperature flexible thermoelectric thin film material and preparation method thereof Download PDF

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CN112853492B
CN112853492B CN201911184795.5A CN201911184795A CN112853492B CN 112853492 B CN112853492 B CN 112853492B CN 201911184795 A CN201911184795 A CN 201911184795A CN 112853492 B CN112853492 B CN 112853492B
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CN112853492A (en
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邰凯平
万晔
崔岩
赵洋
乔吉祥
康斯清
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Institute of Metal Research of CAS
Shenyang Jianzhu University
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Shenyang Jianzhu University
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    • 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
    • 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
    • C30B23/00—Single-crystal growth by condensing evaporated or sublimed materials
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    • C30B23/025—Epitaxial-layer growth characterised by the substrate
    • 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
    • C30B23/00—Single-crystal growth by condensing evaporated or sublimed materials
    • C30B23/02—Epitaxial-layer growth
    • C30B23/08—Epitaxial-layer growth by condensing ionised vapours
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    • H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
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    • 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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Abstract

The invention relates to the field of functional thin film materials, in particular to a SnSe/CNT high-temperature flexible thermoelectric thin film material and a preparation method thereof. The composite film is prepared by physical vapor deposition technology, so that a certain crystallographic direction of selenide grains is parallel to the axial direction of the CNT tube bundle, and the flexible composite film material with a nanoscale porous structure with certain out-of-plane orientation is formed. The material comprises a carbon nano tube film substrate and an SnSe functional film uniformly deposited on the surface of a carbon nano tube bundle, wherein the specific crystallographic direction of SnSe grains is parallel to the direction of a groove and an axis of the CNT tube bundle, and small-angle orientation tilt crystal boundaries are formed between adjacent grains to form a three-dimensional composite network with a nano porous structure. The SnSe/CNT high-temperature flexible thermoelectric material has relatively good thermoelectric property and flexibility, fills the gap of high-temperature flexible thermoelectric film materials, and provides a thought for the research of medium-high temperature flexible thermoelectric materials.

Description

SnSe/CNT high-temperature flexible thermoelectric thin film material and preparation method thereof
Technical Field
The invention relates to the field of functional thin film materials, in particular to a tin selenide (SnSe)/Carbon Nanotube (CNT) high-temperature flexible thermoelectric thin film material and a preparation method thereof.
Background
SnSe is surprising to the scientific community by exhibiting unexpectedly low thermal conductivity and high power factor, and it has become a very promising thermoelectric material. The thermoelectric material is a functional semiconductor material which can convert energy of two different forms, namely heat and electricity, without the assistance of other specific external force or devices, can fully utilize waste heat in daily production and life to generate electricity or perform micro-area high-heat-flux refrigeration, is an important research content in scientific and technological specialties such as high-efficiency resource utilization, waste heat and complementary energy recovery, micro-system heat management and the like in China at present, but the lower conversion efficiency is a prominent technical bottleneck of related industry development.
High thermoelectric performance requires a high power factor (S) 2 σ) and low thermal conductivity (κ). The electric transmission and heat transmission characteristics of the SnSe are excellent, and the SnSe has a unique crystal structure which causes extremely low heat conductivity, and is combined with a unique electronic structure to endow the SnSe with high power factor and excellent thermoelectric performance, so that the SnSe is a thermoelectric material with development potential, but the research on the thermoelectric performance is less at present. The carbon nano tube is widely paid attention to in recent years as a high-performance flexible thermoelectric material, and mainly benefits from extremely high flexibility and relatively ideal thermoelectric performance, and the performance of the carbon nano tube and polymer composite flexible thermoelectric material has obvious advantages in the field of organic thermoelectric materials, so that the carbon nano tube has great research value in the research of flexible thermoelectric composite materials and flexible thermoelectric devices.
Disclosure of Invention
The invention aims to provide a SnSe/CNT high-temperature flexible thermoelectric thin film material and a preparation method thereof, wherein a selenium (Se) compound (SnSe) thin film is deposited by a physical vapor phase method. The nano-scale composite thin film material is grown on a CNT substrate along a certain axial direction, and the nano-scale composite thin film material is synthesized, and the characteristics, heat conduction, electric conduction and thermoelectric force performances of the micro-scale composite thin film material are tested, so that the idea is provided for further researching materials in related fields, and the preparation is prepared for the application of high-temperature thermoelectric materials.
In order to achieve the purpose, the technical scheme of the invention is as follows:
the SnSe/CNT high-temperature flexible thermoelectric thin film material comprises a carbon nano tube thin film substrate and a SnSe functional thin film uniformly deposited on the surface of a carbon nano tube bundle, wherein the specific crystallographic direction of SnSe crystal grains is parallel to the direction of a groove and an axis of the CNT bundle, and small-angle orientation tilting crystal boundaries are formed between adjacent crystal grains, so that a three-dimensional composite network with a nano porous structure is formed; wherein, the thickness of the carbon nano tube film is 40-400nm, the nominal thickness of the SnSe functional film layer is 20-1000 nm, and when the nominal film thickness is 400nm, the volume fraction of the carbon nano tubes in the film material is less than 1%.
The nominal thickness of the SnSe layer is that the SnSe layer is deposited on SiO with a smooth surface under the same deposition condition 2 Thickness of the film on the substrate.
The specific crystallographic direction of the SnSe crystal grain is (400), and the small-angle orientation tilting crystal boundary is less than 10 degrees.
The SnSe/CNT high-temperature flexible thermoelectric thin film material is characterized in that a SnSe thin film layer uniformly wrapped on the surface of each bundle of carbon nanotubes consists of continuous nanoscale crystal grains, the SnSe functional thin film layer has higher crystallization quality, and the technical indexes for representing the higher crystallization quality are as follows: the mobility of the film is 30-50 cm 2 V -1 s -1 Observing the surface of the film by using a scanning electron microscope, wherein the SnSe crystal grows on the CNT substrate uniformly; the crystal grains show obvious ordered microstructure characteristics along the axial direction of the carbon nano tube bundle, and have XRD diffraction peaks with specific orientations (400).
The ordered microstructure of the SnSe/CNT high-temperature flexible thermoelectric thin film material enables the thin film material to have higher in-plane electrical conductivity, lower thermal conductivity and excellent out-of-plane bending flexible deformation performance; wherein, at the temperature of 720K, the in-plane electric conductivity is 10 to 35S/cm, the thermal conductivity range is 0.3 to 0.5Wm -1 K -1 (ii) a The technical indexes for characterizing the out-of-plane bending flexible deformation performance are as follows: the resistance value of the film changes along with the increase of the bending degree, and the increase range of the resistance value of the film is not more than 15 percent.
In the SnSe/CNT high-temperature flexible thermoelectric thin film material, the carbon nano tube thin film is formed by bundle-shaped carbon nano tubes which are randomly distributed in an oriented way and have the diameters of 5-50 nm, and the length of the carbon nano tube in the carbon nano tube thin film is 5-50 microns; the size of the carbon nano tube bundle can effectively control the grain size of the SnSe.
The preparation method of the SnSe/CNT high-temperature flexible thermoelectric thin film material comprises the steps of firstly placing a carbon nano tube thin film substrate on a metal deposition support, and then carrying out magnetron sputtering deposition on the carbon nano tube thin film to ensure that SnSe crystal grains with certain grain size and certain preferred orientation are deposited on the carbon nano tube thin film substrate so as to meet the requirement of uniformity of a functional thin film material; wherein the grain size range is 100-200 nm, and the out-of-plane preferred orientation is (400).
According to the preparation method of the SnSe/CNT high-temperature flexible thermoelectric thin film material, the SnSe/CNT high-temperature flexible thermoelectric thin film material is in a self-supporting state, is free from substrate effect influence, is cut into any geometric shape by using a femtosecond laser micro-nano processing method and is transferred to various types of substrates, and the preparation method is beneficial to preparation of thermoelectric devices with various structures.
The preparation method of the SnSe/CNT high-temperature flexible thermoelectric thin film material comprises the following steps:
(S1) surface treatment:
cleaning the surface of the substrate, sequentially leaching the substrate for 10 to 15 minutes by using alcohol, acetone and deionized water, and heating and baking the substrate for 10 to 30 minutes at 373K to 423K in a vacuum environment;
fixing the CNT substrate on a metal bracket by using electrostatic force, fixing the metal bracket on a coated sample plate by using silver colloid, and baking at 373K-423K for 10-30 minutes;
(S2) depositing a tin selenide film layer on the surface of the substrate:
placing the cleaned substrate and the CNT substrate on a film coating sample disc, and depositing in a magnetron deposition system in a co-sputtering mode, wherein the growth conditions are as follows: the sputtering target material is commercial block SnSe and SnSe 2 The vacuum degree of the back bottom of the target material is (4-6) multiplied by 10 -4 Pa, high-purity argon with the working gas of 0.2-2 Pa, the growth heating temperature range of 673K-923K and the deposition power of 40-60W.
In the preparation method of the SnSe/CNT high-temperature flexible thermoelectric thin film material, preferably, the working gas pressure in the step (S2) is 0.4 to 0.6Pa.
The design idea of the invention is as follows:
firstly, the research on high-temperature thermoelectric thin-film materials is few, and tin selenide has excellent electric transmission and heat transmission performance and extremely low heat conductivity, and is endowed with ultrahigh power factor and excellent thermoelectric performance by combining a unique electronic structure, so that single crystals of the tin selenide become potential high-temperature thermoelectric materials due to the excellent thermoelectric performance at a high-temperature stage; secondly, the CNT film material has good flexibility, excellent chemical stability and thermal stability; in order to fully exert the advantages of the composite material, the brittle tin selenide material is structurally flexible, and is connected and compounded with CNT in a nanoscale by using a magnetron sputtering technology, so that a defect-free and impurity-free high-quality interface is formed, and the stability of the composite structure is ensured; finally, the tin selenide crystal grains present a highly ordered growth structure along the axial direction of the carbon nano tube bundle, namely the close-packed crystallographic directions of the adjacent crystal grains are parallel to the grooves and the axial direction of the carbon nano tube bundle, and the composite structure material has excellent flexible deformation performance and very wide application prospect.
Based on the design guidance thought, the SnSe/CNT high-temperature flexible thermoelectric thin film material is successfully prepared, and the components, the micro-ordered structure, the macro-physical property and the mechanical property of the composite thin film can be accurately controlled by adjusting the magnetron sputtering process parameters due to the flexibility, the nano-scale effect and the high-temperature stability of the carbon nano-thin film substrate. In addition, the prepared composite film has the performance advantage at high temperature, so that the composite film has the possibility of high-temperature thermoelectric device application
The invention has the following advantages and beneficial effects:
1. the composite film material has excellent flexible deformation performance due to the scale effect caused by low dimension in the thickness direction; the small-angle tilting crystal boundary between the nano-scale crystal grains (the phase difference between adjacent crystal grains is less than 10 degrees) greatly improves the electrical property of the material; as a self-supporting film, the flexibility of the film is further improved and is not influenced by the matrix effect.
2. The invention combines the metal compound functional material and the nanometer effect of the flexible carbon nanotube film, and regulates and controls the components and the microstructure of the film material by optimizing the deposition process conditions, so that the film material has the optimal electrical property and flexible deformation property. Meanwhile, the tin selenide thin film material and the flexible carbon nano tube are tightly wrapped, the SnSe/CNT high-temperature flexible thermoelectric thin film material with strong bonding force, high crystallinity and good flexibility is prepared, and a material basis is provided for the application of the SnSe/CNT high-temperature flexible thermoelectric thin film material in the aspects of flexibility and high temperature.
3. According to the invention, the tin selenide film coating is carried out on the carbon nano tube film, so that the bending flexibility of the SnSe/CNT high-temperature flexible thermoelectric film material is ensured, and the thermoelectric performance of the SnSe/CNT high-temperature flexible thermoelectric film material in a high-temperature stage is also ensured.
4. The SnSe/CNT high-temperature flexible thermoelectric thin film material has the advantages that the crystallographic plane with low index and easy elastoplastic slip is parallel to the free surface of the composite thin film, the crystallographic close arrangement direction of adjacent crystal grains, namely the easy slip direction with elastoplastic deformation is parallel to the axial direction of the carbon nano tube and the tube bundle groove, and the elastoplastic deformation in the out-of-plane direction of the thin film and the transfer between the adjacent nano crystal grains are facilitated.
Drawings
FIG. 1 is SEM image of SnSe/CNT high-temperature flexible thermoelectric thin film material.
Fig. 2 is an XRD pattern of SnSe thin film material with preferred orientation (400). In the figure, the abscissa 2 θ represents the diffraction angle (deg.) and the ordinate intensity represents the relative intensity.
Fig. 3 is a schematic diagram of a metal scaffold supporting carbon nanotubes (unit cm, ratio 1. Wherein, (a) carbon nanotubes are tiled on the metal bracket, and (b) the size of the metal bracket is marked. In the figure, 1 is a metal support, 2 is a carbon nanotube.
Detailed Description
In the specific implementation process, the invention provides a method for preparing a high-temperature flexible selenide thermoelectric thin film material and regulating and controlling the performance. The metal bracket is used for bearing CNT, and the CNT film is used for preparing the SnSe/CNT composite film material by utilizing a magnetron sputtering deposition technology under the air pressure of 0.2-2 Pa and the temperature of 673-923K, so that a certain crystallographic direction of selenide crystal grains is parallel to the axial direction of the CNT tube bundle, and the flexible composite film material with a nanoscale porous structure with certain out-of-plane orientation is formed. The performance of the film is further researched, and the element content in the film is controlled by controlling the target power and the deposition time, so that the requirements of regulating and controlling the grain size, the crystallization quality and a certain out-of-plane orientation in the film material are met. The film prepared by the invention has better crystallization quality and certain out-of-plane orientation, and the flexible performance of the flexible substrate to the material is greatly improved. The invention provides an innovative method for preparing the high-temperature thermoelectric thin film material on one hand, and provides a new effective way for regulating and controlling the performance of the flexible thin film thermoelectric material on the other hand.
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention. It is understood that the embodiments described are part of the invention, and not all of them. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
Example 1
In this embodiment, the method for preparing the SnSe/CNT high-temperature flexible thermoelectric thin film material includes the following steps:
(S1) surface treatment:
cleaning the surface of a substrate (such as a silicon dioxide sheet), sequentially rinsing for 12 minutes by using alcohol, acetone and deionized water, and then heating and baking for 20 minutes at 398K under a vacuum environment;
fixing a substrate (such as CNT) on a metal bracket by using electrostatic force, fixing the metal bracket on a film-coated sample plate by using silver adhesive, and baking for 20 minutes at 398K;
as shown in fig. 3, the metal support has a structure of 5 small frames carved out of a copper plate of 4cm × 3 cm: 3 pieces of 3cm multiplied by 1cm are arranged side by side along the vertical direction, 1 piece of 1cm multiplied by 1cm and 1 piece of 2cm multiplied by 1cm are opposite along the transverse direction, the adopted metal material is copper, and the size is shown in the schematic diagram in detail. The carbon nanotubes 2 can be spread on the metal support 1 by electrostatic force, which is convenient for operation.
(S2) depositing a selenide (SnSe) thin film layer on the surface of the substrate/base:
placing the cleaned substrate on a film coating sample disc, and depositing in a magnetron deposition system in a co-sputtering mode under the growth conditions that: the sputtering target material is commercial block tin selenide and tin diselenide target material, and the backing vacuum degree is 5 multiplied by 10 -4 Pa, high-purity argon (with the volume purity of 99.999%) with the working gas of 0.5Pa, the growth heating temperature range of 773K, and the deposition power of the selenium (Se) compound of 50W, thereby forming the SnSe/CNT high-temperature flexible thermoelectric thin film material. The element content in the film is controlled by controlling the target power and the deposition time, so that the requirements of regulating and controlling the grain size, the crystallization quality and a certain out-of-plane orientation in the film material are met.
The SnSe/CNT high-temperature flexible thermoelectric thin film material comprises a carbon nano tube thin film matrix and a SnSe functional thin film uniformly deposited on the surface of a carbon nano tube bundle, wherein the specific crystallographic direction of SnSe crystal grains is parallel to the direction of a groove and an axis of the CNT tube bundle, and small-angle orientation tilting crystal boundaries are formed between adjacent crystal grains, so that a three-dimensional composite network with a nano porous structure is formed; wherein, the thickness of the carbon nanotube film is 40-400 nm (40 nm in this embodiment), and the nominal thickness of the SnSe functional film layer is 20-1000 nm (400 nm in this embodiment); the volume fraction of carbon nanotubes in the composite thin film material was less than 1% (0.9% in this example) when the nominal film thickness was 400 nm. Wherein, the meaning of the specific crystallographic direction is that the film grows along a certain crystallographic axis, which is (400) orientation in this embodiment.
Meanwhile, the SnSe film is subjected to the test of electric conductivity, seebeck thermoelectric coefficient and thermal conductivity. The data acquisition and analysis of thermoelectric performance use German Netzsch SBA-458 instrument, and the process of morphology analysis and thermoelectric performance test is as follows:
(S1) microscopic morphology analysis of nanoscale tin selenide/carbon nanotube (SnSe/CNT) thin film material:
as shown in FIG. 1, the surface of the thin film was observed using a scanning electron microscope, and the composition of the thin film sample was analyzed using EDS, and the carbon nanotube thin film was randomly orientedThe bundle carbon nano-tube with the diameter of 5-50 nm, the length of the carbon nano-tube in the carbon nano-tube film is 5-50 microns; the SnSe thin film layer uniformly wrapped on the surface of each bundle of carbon nano tubes consists of continuous nano-scale crystal grains, and the size of the SnSe crystal grains can be effectively controlled by the size of the carbon nano tube bundles. As can be seen from FIG. 1, the SnSe crystal grows uniformly on the CNT substrate, the SnSe functional thin film layer has higher crystallization quality, and the mobility of the thin film is 40cm 2 V -1 s -1 。
In this embodiment, snSe grains having a grain size of 150nm, a preferred orientation of (400), and a small angle orientation tilt grain boundary of less than 10 ° are deposited on the carbon nanotube film substrate.
As shown in FIG. 2, the film is qualitatively analyzed by XRD to characterize the crystal quality and preferred orientation of the SnSe film thermoelectric film, and as can be seen from FIG. 2, only the diffraction peak with (400) orientation exists in the spectrum, indicating that the film has strong preferred orientation. The SnSe crystal grains present obvious ordered microstructure characteristics along the axial direction of the carbon nano tube bundle, and the technical index for representing the obvious ordered microstructure characteristics is an XRD diffraction peak with specific orientation (400).
(S2) testing the Seebeck thermoelectric coefficient and the electric conductivity of the nanoscale tin selenide (SnSe) thin film material:
in the embodiment, the geometric parameters of the sample to be tested are input into a Netzsch SBA-458 test system, the measurement temperature range is RT-773K, and the test standard is executed according to the related thermoelectric material test standard. Within the test temperature range, the in-plane conductivity is 0-35S/cm, the Seebeck coefficient is 400-600 mu VK -1 . Thus, it can be seen that the ordered microstructure results in a thin film material having a high in-plane conductivity.
(S3) testing the thermal conductivity of the nanoscale tin selenide/carbon nanotube (SnSe/CNT) thin film material:
in the embodiment, the thermal conductivity is tested by using self-built 3 omega method film thermal conductivity test equipment, and the test result is 0.3-0.5W m -1 K -1 . Thus, it can be seen that the ordered microstructure results in a thin film material having a lower thermal conductivity.
(S4) testing the flexibility performance of the nanoscale tin selenide/carbon nanotube (SnSe/CNT) thin film material:
in this embodiment, a flexible thermoelectric performance test device is used for testing, and the technical indexes for characterizing the out-of-plane bending flexible deformation performance are as follows: the resistance value of the film is changed in different degrees along with different bending degrees, the smaller the change degree is, the better the flexibility performance of the film is, and the resistance value increase range is about 8% along with the increase of the bending degree in the film flexibility performance test of the embodiment. Thus, it can be seen that the ordered microstructure gives the film material excellent out-of-plane bending flexibility deformation properties.
The results of the examples show that the nanoscale tin selenide/carbon nanotube (SnSe/CNT) high-temperature thermoelectric thin film material has good thermoelectric property and flexibility. Compared with a flexible multiphase mixed thermoelectric material, the tin selenide/carbon nanotube (SnSe/CNT) high-temperature thermoelectric film material has the advantages that the organic material and inorganic material laminated structure design is carried out through a physical vapor deposition technology, the flexibility of an organic substrate is utilized, the flexibility of the composite film is improved, an organic and inorganic interface layer which is easy to regulate and control is formed between an organic matter and an inorganic matter, the charge transmission can be regulated and controlled, the phonon can be sufficiently scattered to regulate and control the lattice thermal conductivity to realize the optimization of thermoelectric performance, and the material has great scientific research value in the field of research and application of high-temperature thermoelectric.
The above details are provided for the SnSe/CNT high-temperature flexible thermoelectric material and the preparation method thereof. The principles and embodiments of the present invention are explained in detail using specific examples, and the above descriptions of the embodiments are only used to help understanding the method and core ideas of the present invention. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.

Claims (5)

1. A preparation method of a SnSe/CNT high-temperature flexible thermoelectric thin film material is characterized by comprising a carbon nano tube thin film matrix and a SnSe functional thin film uniformly deposited on the surface of a carbon nano tube bundle, wherein the specific crystallographic direction of SnSe crystal grains is parallel to the direction of a groove and an axis of the carbon nano tube bundle, and small-angle orientation tilting crystal boundaries are formed between adjacent crystal grains, so that a three-dimensional composite network with a nano porous structure is formed; wherein, the thickness of the carbon nano tube film is 40-400nm, the nominal thickness of the SnSe functional film layer is 20-1000 nm, and when the nominal film thickness is 400nm, the volume fraction of the carbon nano tubes in the film material is less than 1%;
the SnSe thin film layer uniformly wrapped on the surface of each bundle of carbon nano tubes consists of continuous nano-scale crystal grains, the SnSe functional thin film layer has higher crystallization quality, and the technical indexes representing the higher crystallization quality are as follows: the mobility of the film is 30-50 cm 2 V -1 s -1 Observing the surface of the film by using a scanning electron microscope, wherein the SnSe crystal grows on the CNT substrate uniformly; the crystal grains show obvious ordered microstructure characteristics along the axial direction of the carbon nano tube bundle, and have XRD diffraction peaks with specific orientation (400);
the ordered microstructure enables the film material to have higher in-plane electrical conductivity, lower thermal conductivity and excellent out-of-plane bending flexible deformation performance; wherein, at the temperature of 720K, the in-plane electric conductivity is 10 to 35S/cm, the thermal conductivity range is 0.3 to 0.5Wm -1 K -1 (ii) a The technical indexes for characterizing the out-of-plane bending flexible deformation performance are as follows: the resistance value of the film changes along with the increase of the bending degree, and the increase range of the resistance value of the film is not more than 15 percent;
the specific crystallographic direction of the SnSe crystal grains is (400), and the small-angle orientation tilting crystal boundary is less than 10 degrees;
the carbon nano tube film is composed of bundle-shaped carbon nano tubes which are randomly distributed in orientation and have the diameters of 5-50 nm, and the length of the carbon nano tubes in the carbon nano tube film is 5-50 microns; the size of the carbon nano tube bundle can effectively control the grain size of SnSe;
the preparation method of the SnSe/CNT high-temperature flexible thermoelectric thin film material comprises the steps of firstly placing a carbon nano tube thin film substrate on a metal deposition support, and then carrying out magnetron sputtering deposition on the carbon nano tube thin film to ensure that SnSe crystal grains with certain grain size and certain preferred orientation are deposited on the carbon nano tube thin film substrate so as to meet the requirement of uniformity of a functional thin film material; wherein the grain size range is 100-200 nm, and the out-of-plane preferred orientation is (400).
2. The method for preparing the SnSe/CNT high-temperature flexible thermoelectric thin film material according to claim 1, wherein the SnSe/CNT high-temperature flexible thermoelectric thin film material is in a self-supporting state without substrate effect influence, and can be cut into any geometric shape and transferred to various types of substrates by a micro-nano processing method of femtosecond laser, thereby facilitating the preparation of thermoelectric devices with various structures.
3. The method for preparing the SnSe/CNT high-temperature flexible thermoelectric thin film material according to claim 1, which comprises the following steps:
(S1) surface treatment:
cleaning the surface of the substrate, sequentially leaching the substrate for 10 to 15 minutes by using alcohol, acetone and deionized water, and heating and baking the substrate for 10 to 30 minutes at 373K to 423K in a vacuum environment;
fixing the CNT substrate on a metal bracket by using electrostatic force, fixing the metal bracket on a film coating sample disc by using silver colloid, and baking for 10-30 minutes at 373K-423K;
(S2) depositing a tin selenide film layer on the surface of the substrate:
placing the cleaned substrate and the CNT substrate on a film coating sample disk, and depositing in a magnetron deposition system in a co-sputtering mode, wherein the growth conditions are as follows: the sputtering target material is commercial block SnSe and SnSe 2 The vacuum degree of the back bottom of the target material is (4-6) multiplied by 10 -4 Pa, high-purity argon with the working gas of 0.2-2 Pa, the growth heating temperature range of 673K-923K and the deposition power of 40-60W.
4. The method for preparing the SnSe/CNT high-temperature flexible thermoelectric thin film material according to claim 3, wherein the working gas pressure in the step (S2) is preferably 0.4 to 0.6Pa.
5. The method of claim 1 for making a SnSe/CNT high temperature flexible thermoelectric thin film materialCharacterized in that the nominal thickness of the SnSe layer is that the SnSe layer is deposited on SiO with a flat surface under the same deposition condition 2 Thickness of the film on the substrate.
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