CN115341273B - Preparation of large-size two-dimensional thermoelectric material bismuth telluride single crystal - Google Patents
Preparation of large-size two-dimensional thermoelectric material bismuth telluride single crystal Download PDFInfo
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- 239000013078 crystal Substances 0.000 title claims abstract description 57
- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 38
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 35
- XSOKHXFFCGXDJZ-UHFFFAOYSA-N telluride(2-) Chemical compound [Te-2] XSOKHXFFCGXDJZ-UHFFFAOYSA-N 0.000 title claims abstract description 35
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- 238000006243 chemical reaction Methods 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 239000012159 carrier gas Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 4
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
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- 235000012431 wafers Nutrition 0.000 description 12
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- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 7
- 239000002243 precursor Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
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- DVGHHMFBFOTGLM-UHFFFAOYSA-L fluorogold Chemical compound F[Au][Au]F DVGHHMFBFOTGLM-UHFFFAOYSA-L 0.000 description 2
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- 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 1
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Classifications
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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
- C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
-
- 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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- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
The invention belongs to the technical field of bismuth telluride single crystal preparation, and particularly relates to preparation of a large-size two-dimensional thermoelectric material bismuth telluride single crystal. To prepare large-size Bi 2 Te 3 The invention uses a single temperature zone horizontal tube furnace to control H accurately by hydrogen assisted method based on Chemical Vapor Deposition (CVD) 2 The ratio of the noble gas to the inert gas enhances the reducibility of Te to lead H 2 First reacts with Te to generate H 2 Te gas due to H 2 Te has strong reducibility and can react with Bi to generate Bi 2 Te 3 Thereby improving the growth speed, reducing the adsorption energy of the substrate by utilizing hydrogen, reducing the nucleation density, ensuring sufficient Bi source and Te source supply by precisely controlling the substrate temperature (growth temperature), and further realizing large-size Bi 2 Te 3 The preparation of single crystals has low preparation cost and simple operation, and can be produced in batch.
Description
Technical Field
The invention belongs to the technical field of bismuth telluride single crystal preparation, and particularly relates to preparation of a large-size two-dimensional thermoelectric material bismuth telluride single crystal.
Background
Bismuth telluride (Bi) 2 Te 3 ) Is a typical layered semiconductor material with topological properties and thermoelectric properties. Bi due to its unique layered structure and thermoelectric conversion performance that can operate at room temperature 2 Te 3 In recent years there has been a great deal of interest in the field of flexible wearable device research.
Currently, common Bi 2 Te 3 The preparation method of the monocrystal mainly comprises the following steps: (1) mechanical stripping method. The mechanical peeling method is to repeatedly peel bulk single crystal by using adhesive tape with certain viscosity, and the single crystal is easily peeled due to the adhesion of the adhesive tape to the single crystal being greater than the interlayer Van der Waals forceAt least a layer, even a monolayer, of the exfoliated single crystal nanoplatelets can be transferred to any target substrate for investigation. However, the method can only obtain a single crystal wafer with a diameter of tens of micrometers, the shape and thickness of the sample are uncontrollable, the preparation cost is high, the time consumption is long, the yield is low, and the method is not beneficial to the industrial application; (2) liquid phase Synthesis method. The process typically involves dissolving one or more precursors in water or an organic solution to react to form the desired compound. For example, there is a study on easy synthesis of Bi having a diagonal of about 1 μm by hydrothermal method 2 Te 3 Nanoplates have also been studied by using BiCl 3 And Te as a precursor to prepare Bi 2 Te 3 Nanoparticles and nanowires. Despite the high yields of this method, the lateral dimensions of the product are only a few nanometers to a few micrometers, and it is difficult to obtain a few layers of product, and the solvent remaining on the sample surface during the reaction also reduces its performance. (3) molecular beam epitaxy. In ultra-high vacuum (10) -8 Pa), heating the ultrapure source material to sublimate slowly, and condensing and reacting the generated gaseous elements on the target substrate to form a target product. Although the method can obtain high-quality monocrystalline film, because of the complex growth conditions such as ultra-high vacuum growth environment, accurate temperature control and the like required by molecular beam epitaxy, the growth equipment is huge and expensive, and the growth speed is slow, usually 1 mu m/h, so that the industrialized application of the method is greatly limited. (4) Chemical Vapor Deposition (CVD). High-purity Bi is heated and evaporated in the center of a tube furnace 2 Te 3 And (3) a powder source, and transporting the evaporated gaseous source to a substrate downstream of the tube furnace to grow by taking inert gas as carrier gas. For example, there have been studies on SiO in an amorphous state by this method 2 Two-dimensional Bi with the thinnest thickness of 3nm and the maximum size of about 20 μm is obtained on the substrate 2 Te 3 A nano-sheet. Bi having a lateral dimension of 18 μm and a thickness of 12nm was also investigated on a mica substrate by the same method 2 Te 3 A single chip. The method is Bi 2 Te 3 Provides a basis for large-scale mass production. But at present CVD prepares Bi 2 Te 3 The following problems remain with the process of (a): (1) bi is used as 2 Te 3 The powder is the source, due to Bi 2 Te 3 Is easy to decompose, and the essence of the reaction process is Bi 2 Te 3 Firstly decomposing into Bi and Te simple substances, and then transmitting the Bi simple substances to a substrate through air flow to carry out a combination reaction to generate Bi 2 Te 3 And (3) single crystals. However, since Te is weak in reducibility, only a small part of Bi and Te react, the growth speed is slow, and the transverse size is small; (2) untreated mica or silica surfaces have a large number of defects and dangling bonds that have a very high adsorption energy and tend to form nucleation sites, resulting in a high nucleation density and thus limiting the lateral dimensions and uniformity of the material. The maximum size of single wafers currently obtained by CVD is only 20 μm.
From the above, it can be seen that Bi at present 2 Te 3 The preparation method of single crystals still has the problems of small product size, poor uniformity, uncontrollable thickness and the like, cannot meet the requirements of low cost and mass production, and cannot prepare Bi with large size and high uniformity 2 Te 3 Single crystal, thereby greatly restricting Bi 2 Se 3 Is used in the application of (a). Therefore, it is necessary to develop a new Bi 2 Te 3 Single crystal preparation method to increase growth speed, reduce nucleation density, and prepare large-size Bi 2 Te 3 And (3) single crystals.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a preparation method of a large-size two-dimensional thermoelectric material bismuth telluride single crystal, which improves the growth speed and reduces the nucleation density by a hydrogen-assisted method to prepare large-size Bi 2 Te 3 And (3) single crystals.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the invention provides a preparation method of a large-size two-dimensional thermoelectric material bismuth telluride single crystal, which specifically comprises the following steps: bismuth telluride (Bi) 2 Te 3 ) Powder (purity 99.99%) was used as a source, bismuth telluride was placed in the central heating zone of a single temperature zone horizontal tube furnace, and the substrate was placed in the downstream temperature change zone of the single temperature zone horizontal tube furnace, then central heating was controlledThe temperature of the zone is 400-600 ℃, bi source and Te source generated by evaporating bismuth telluride are transmitted to the substrate by taking the mixed gas of hydrogen and inert gas as carrier gas, bi and Te react under the action of hydrogen, and then large-size bismuth telluride (Bi) is generated on the substrate 2 Te 3 ) And in the single crystal, the flow rate of the inert gas in the mixed gas of the hydrogen and the inert gas is 50-100sccm, and the flow rate of the hydrogen is 2.5-15sccm.
Preferably, the temperature of the central heating zone is 500 ℃.
Preferably, the mixture of hydrogen and inert gas is a mixture of argon and hydrogen.
Preferably, the central heating zone has a heating rate of 20-30 deg.C/min.
Preferably, the substrate is a freshly peeled fluorophlogopite substrate.
Preferably, the reaction time is 1-10min, the carrier gas is kept unchanged after the reaction is finished, and the product is naturally cooled to room temperature along with the furnace.
Preferably, the substrate is placed in a downstream temperature change zone 12cm from the central heating zone.
Preferably, the length of the tube of the single-temperature zone horizontal tube furnace is 100cm, the outer diameter is 25mm, the thickness of the tube wall is 2.5mm, and the length of the central heating zone is 10cm.
Preferably, before the central heating area begins to heat, the pressure in the furnace tube is pumped to 10Pa, then 600sccm argon is filled to atmospheric pressure, and the gas washing is repeated to remove residual oxygen, and then heating is started, and the whole heating process is continuously filled with the hydrogen-inert gas mixture.
Preferably, in the mixed gas of hydrogen and inert gas, the flow rate of the inert gas is 95sccm, and the flow rate of the hydrogen is 5sccm. The addition of a proper amount of hydrogen can effectively reduce nucleation density, improve growth speed and is beneficial to the synthesis of large-size single crystal wafers.
Compared with the prior art, the invention has the beneficial effects that:
the invention discloses a preparation method of a large-size two-dimensional thermoelectric material bismuth telluride single crystal, which is based on a Chemical Vapor Deposition (CVD) method and uses a single-temperature-zone horizontal tube furnace to pass hydrogenGas-assisted method for precisely controlling H 2 The proportion of the inert gas to the inert gas reduces the nucleation density, improves the growth speed, ensures sufficient Bi source and Te source supply by precisely controlling the substrate temperature (growth temperature), and further realizes large-size Bi 2 Te 3 The preparation of single crystals has low preparation cost and simple operation, and can be produced in batch. Specifically, the invention has the following advantages:
(1) The invention utilizes H 2 The auxiliary method effectively improves the growth speed. Conventional Bi 2 Te 3 The preparation process is usually carried out with pure inert gas as carrier gas, however for Bi 2 Te 3 In other words, CVD prepares Bi due to its lower decomposition temperature (about 400 ℃ C.) 2 Te 3 The process is that decomposition is carried out before chemical combination, the reducibility of Te is very weak, and only a small part of Bi and Te can be subjected to chemical combination reaction to generate Bi 2 Te 3 Therefore, the growth rate is slow, and the growth rate is only 0.4-6 mu m/min. The hydrogen is added into the inert gas to enhance the reducibility of Te, H 2 First reacts with Te to generate H 2 Te gas, H 2 Te has strong reducibility and can react with Bi to generate Bi 2 Te 3 Thereby improving Bi 2 Te 3 The growth rate of (c) promotes an increase in lateral dimensions.
(2) The invention utilizes H 2 The auxiliary method effectively reduces the nucleation density. Traditional Bi 2 Te 3 SiO is generally used in the preparation process 2 Si and mica as growth Bi 2 Te 3 Is a substrate of a substrate (a). However, untreated SiO 2 The surface of the/Si has a large number of dangling bonds and defects, the dangling bonds and the defects have very strong adsorption energy, precursor particles can be adsorbed and nucleated, the very high nucleation density is caused, and potassium ions on the surface of the mica substrate also have higher adsorption energy. In the CVD growth process, the most important factors influencing the lateral dimension of the 2D material are nucleation density and growth speed, the larger the nucleation density is, the more grain boundaries exist in the material, the smaller the size of the single crystal is, so the precondition of the large size is to reduce the nucleation density and increase the growth speed. The invention is realized by H 2 Can passivate SiO 2 The dangling bond on the surface of the Si and the mica is saturated, so that the adsorption energy is reduced, the nucleation density is reduced, and the large-size growth of the 2D single crystal is promoted.
(3) The invention realizes large-size growth by controlling the temperature of the heating center and the flow of the carrier gas. When the temperature is too low, the nucleation density is larger, the growth rate is slower, the source evaporation amount is smaller, the precursor supply is insufficient, and only a small and thin product can be obtained at the moment; when the temperature is too high, the atomic desorption of the surface of the substrate is enhanced, a large amount of precursor particles cannot be adsorbed on the surface of the substrate, and the adsorption energy of the surface of the single crystal wafer is increased, so that Bi 2 Te 3 The single crystal wafer tends to grow vertically, and the obtained product is small and thick, and the yield is low. When the hydrogen concentration is too low, the hydrogen hardly acts, and it is difficult to significantly promote Bi 2 Te 3 Is grown in the presence of a seed; when the hydrogen concentration is too high, the corrosiveness of hydrogen itself may be reduced to Bi 2 Te 3 The surface of the single crystal is corroded, so that holes are generated, and the crystal quality is reduced.
Drawings
FIG. 1 shows the preparation of two-dimensional Bi 2 Te 3 Schematic of an apparatus for single crystal material;
FIG. 2 shows the large-size Bi prepared in example 1 2 Te 3 Optical microscopy pictures of single-wafer (a is high power optical view, b is low power optical view);
FIG. 3 shows Bi prepared in example 1 2 Te 3 A high resolution transmission electron microscope image of a single wafer;
FIG. 4 shows Bi prepared in example 1 2 Te 3 Element distribution diagram of single chip;
FIG. 5 shows Bi prepared in example 1 2 Te 3 Raman spectra of single-crystal wafers;
FIG. 6 shows Bi prepared in example 2 2 Te 3 Optical microscopy pictures of single-wafer;
FIG. 7 shows Bi prepared in example 3 2 Te 3 Optical microscopy pictures of single-wafer;
FIG. 8 shows Bi prepared in example 4 2 Te 3 Single wafer optical microscopeA picture;
FIG. 9 shows Bi prepared in comparative example 1 2 Te 3 Optical microscopy pictures of single-wafer.
Detailed Description
The following describes the invention in more detail. The description of these embodiments is provided to assist understanding of the present invention, but is not intended to limit the present invention. In addition, the technical features of the embodiments of the present invention described below may be combined with each other as long as they do not collide with each other.
The experimental methods in the following examples, unless otherwise specified, are conventional, and the experimental materials used in the following examples, unless otherwise specified, are commercially available.
Example 1 preparation of two-dimensional thermoelectric Material bismuth telluride Single Crystal
(1) As shown in FIG. 1, a single temperature zone horizontal tube furnace (ThermoFisher, TF 55035C-1) was used, the tube length was 100cm, the outer diameter was 25mm, the tube wall thickness was 2.5mm, the constant temperature zone range (i.e., central heating zone) was 10cm, the central temperature was set to 500℃and the heating rate was 30℃per minute. Bismuth telluride powder (purity > 99.99%) is used as Bi source and Te source, and the powder is placed in a central heating zone; using fluorogold mica sheets as a deposition substrate, and placing the fluorogold mica sheets in a downstream temperature change area 12cm away from a central temperature area;
(2) Before the reaction, a mechanical pump is utilized to perform pre-vacuumizing to about 10Pa, then 600sccm Ar is filled to atmospheric pressure, and gas washing is performed repeatedly to remove residual oxygen;
(3) Beginning heating, continuously introducing 95sccm Ar and 5sccm H 2 Keeping the temperature for 5 minutes after the temperature reaches 500 ℃, keeping the carrier gas unchanged after the reaction is finished, cooling the product to room temperature along with a furnace, and obtaining the two-dimensional Bi from the fluorous-mica sheet 2 Te 3 A single chip.
FIG. 2 reflects Bi 2 Te 3 Morphology of the single crystal wafer, see Bi obtained 2 Te 3 The monocrystal is uniform hexagon, the size is large and can reach 241 mu m, and the thickness can reach a single layer (1.1 nm); FIG. 3 is Bi 2 Te 3 The high-resolution transmission electron microscope photograph of the single crystal wafer shows that the single crystal wafer has a lattice structure which is regularly arranged, and the interplanar spacing is 0.22nm; FIG. 4 is Bi 2 Te 3 The element component analysis result of the single crystal wafer shows that Bi elements and Te elements are uniformly distributed; FIG. 4 is Bi 2 Te 3 Raman spectrum of single-chip, showing three characteristic peaks, 61cm respectively -1 ,101cm -1 ,132cm -1 . The synthesized product is bismuth telluride monocrystal, and has good crystallinity.
Example 2 preparation of two-dimensional thermoelectric Material bismuth telluride Single Crystal
The specific preparation method is the same as in example 1, except that: the center temperature was set at 400 ℃.
The morphology is shown in FIG. 6, and the obtained Bi is shown in the following 2 Te 3 The thickness of the single crystal is relatively thin, and the size is about 20-30 μm, which is significantly smaller than that of example 1.
Example 3 preparation of two-dimensional thermoelectric Material bismuth telluride Single Crystal
The specific preparation method is the same as in example 1, except that: the center temperature was set at 600 ℃.
The morphology is shown in FIG. 7, and the obtained Bi is shown in the following 2 Te 3 The thickness of the single crystal is relatively thin, and the size is about 30-40 μm, which is significantly smaller than that of example 1.
Example 4 preparation of two-dimensional thermoelectric Material bismuth telluride Single Crystal
The specific preparation method is the same as in example 1, except that: introducing 85sccm Ar and 15sccm H 2 。
The morphology is shown in FIG. 8, and it is obvious that due to H 2 The corrosiveness caused by higher content leads to Bi 2 Te 3 The surface has voids, and the crystal quality is significantly reduced compared with example 1.
Comparative example 1 preparation of two-dimensional thermoelectric Material bismuth telluride Single Crystal
The specific preparation method is the same as in example 1, except that: 100sccm of pure Ar was introduced.
The morphology is shown in FIG. 9, and it is evident that Bi is obtained as compared with example 1 2 Te 3 Nucleation of single crystalsThe density is very high, the size is about 10-20 μm, significantly less than example 1, and the uniformity is poor.
It is apparent from the nucleation density, growth rate and size of the products of comparative example 1 and comparative example 1 that there are significant advantages to the present invention. The nucleation density of the product of example 1 is 3200/mm 2 An order of magnitude smaller than comparative example 1, a growth rate of 48 μm/min, an order of magnitude higher than comparative example 1, and thus the final product size can reach 240. Mu.m, which is the Bi reported so far 2 Te 3 Maximum size.
TABLE 1 Bi for example 1 and comparative example 1 2 Te 3 Contrast of Single Crystal growth
As can be seen from the above examples and comparative examples, the preparation method of the two-dimensional thermoelectric material bismuth telluride single crystal provided by the invention adopts a hydrogen-assisted method and precisely controls H 2 The ratio of Ar to the silicon dioxide to reduce nucleation density, improve growth speed and promote large-size Bi 2 Te 3 An order of magnitude improvement is achieved. At the same time, by precisely controlling the substrate temperature (growth temperature), sufficient Bi source and Te source supply are ensured, and thus a large-sized single crystal Bi having a size of 240 μm is obtained at the maximum growth rate 2 Te 3 . In addition, the preparation method has low preparation cost and simple operation, and can be used for mass production.
The embodiments of the present invention have been described in detail above, but the present invention is not limited to the described embodiments. It will be apparent to those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, and yet fall within the scope of the invention.
Claims (9)
1. A preparation method of a large-size two-dimensional thermoelectric material bismuth telluride single crystal is characterized in that bismuth telluride powder is used as a source, bismuth telluride is placed in a central heating area of a single-temperature area horizontal tube furnace, a substrate is placed in a downstream temperature changing area of the single-temperature area horizontal tube furnace, then the temperature of the central heating area is controlled to be 400-600 ℃, a Bi source and a Te source generated by bismuth telluride evaporation are transmitted to the substrate by taking a mixed gas of hydrogen and inert gas as carrier gas, bi and Te react under the action of hydrogen, and then the large-size bismuth telluride single crystal is generated on the substrate, wherein in the mixed gas of the hydrogen and the inert gas, the flow of the inert gas is 95sccm, and the flow of the hydrogen is 5sccm.
2. The method for preparing a large-sized two-dimensional thermoelectric material bismuth telluride single crystal according to claim 1, wherein the temperature of the central heating zone is 500 ℃.
3. The method for preparing a large-size two-dimensional thermoelectric material bismuth telluride single crystal according to claim 1, wherein the hydrogen-inert gas mixture is a mixture of argon and hydrogen.
4. The method for preparing a large-size two-dimensional thermoelectric material bismuth telluride single crystal according to claim 1, wherein the heating rate of the central heating zone is 20-30 ℃/min.
5. The method for preparing a large-size two-dimensional thermoelectric material bismuth telluride single crystal according to claim 1, wherein the substrate is a freshly peeled fluorophlogopite substrate.
6. The method for preparing a large-size two-dimensional thermoelectric material bismuth telluride single crystal according to claim 1, wherein the reaction time is 1-10min, carrier gas is kept unchanged after the reaction is finished, and the product is naturally cooled to room temperature along with a furnace.
7. The method for preparing a large-sized two-dimensional thermoelectric material bismuth telluride single crystal according to claim 1, wherein the substrate is placed in a downstream temperature change zone 12cm from the central heating zone.
8. The method for preparing a bismuth telluride single crystal as claimed in claim 1, wherein the single temperature zone horizontal tube furnace has a tube length of 100cm, an outer diameter of 25mm, a tube wall thickness of 2.5mm, and a central heating zone length of 10cm.
9. The method for preparing a bismuth telluride single crystal as claimed in claim 1, wherein before the central heating zone is heated, the pressure in the furnace tube is pumped to 10Pa, 600sccm argon is then introduced to atmospheric pressure, and the gas is repeatedly purged to remove residual oxygen, and then heating is started, wherein the whole heating process is continuously introduced with a hydrogen-inert gas mixture.
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