CN115341273A - 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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- 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
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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
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Abstract
The invention belongs to the technical field of preparation of bismuth telluride single crystals, and particularly relates to preparation of a large-size two-dimensional thermoelectric material bismuth telluride single crystal. For preparing large-size Bi 2 Te 3 The invention relates to a single crystal, which is based on a Chemical Vapor Deposition (CVD) method and uses a single-temperature-zone horizontal tube furnace to accurately control H through a hydrogen-assisted method 2 The proportion of the active component to the inert gas enhances the reducibility of Te to enable 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 increasing the growth rate, simultaneously reducing the adsorption energy of the substrate by using hydrogen, reducing the nucleation density, and further by precise controlSubstrate temperature (growth temperature) to ensure sufficient supply of Bi source and Te source, thereby realizing large-size Bi 2 Te 3 The preparation of the single crystal has low preparation cost and simple operation, and can be produced in batches.
Description
Technical Field
The invention belongs to the technical field of preparation of bismuth telluride single crystals, 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, and has topological and thermoelectric properties. Bi has a unique layered structure and a thermoelectric conversion property capable of operating at room temperature 2 Te 3 In recent years, attention is paid to the field of research of flexible wearable devices.
At present, bi is common 2 Te 3 The preparation method of the single crystal mainly comprises the following steps: (1) mechanical peeling method. The mechanical peeling method is generally to repeatedly peel off the bulk single crystal by using an adhesive tape with certain viscosity, and since the adhesive force of the adhesive tape to the single crystal is larger than the van der waals force between layers of the adhesive tape, the single crystal is easily peeled off at least by layers or even by a single layer, and the peeled single crystal nanosheet can be transferred to any target substrate for research. However, the method can only obtain single wafers of dozens of microns, and the appearance and the thickness of the sample are uncontrollable, so that the preparation cost is high, the time consumption is long, the yield is low, and the method is not beneficial to industrial application; (2) liquid phase synthesis method. The process generally involves dissolving one or more precursors in water or an organic solution to react and ultimately form the desired compound. For example, it has been studied to synthesize Bi having a diagonal line of about 1 μm easily by hydrothermal method 2 Te 3 The nanoplates have also been investigated by using BiCl 3 And Te as a precursor to prepare Bi 2 Te 3 Nanoparticles and nanowires. Although this method is high in yield, the lateral dimension of the product is 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 surface of the sample during the reaction also degrades the performance. And (3) molecular beam epitaxy. Under ultra-high vacuum (10) -8 Pa), the ultra-pure source material is heated to slowly sublimate, and the generated gaseous elements are condensed on the target substrate and mutually react to form a target product. Although this method can obtain a high-quality single crystal thin film, it requires an ultra-high vacuum growth environment due to molecular beam epitaxy andunder complex growth conditions such as precise temperature control, the growth equipment is often large and expensive, and the growth speed is slow, usually 1 μm/h, thereby greatly limiting the industrial application. And (4) Chemical Vapor Deposition (CVD). Usually, high-purity Bi is evaporated by heating in the center of a tube furnace 2 Te 3 And a powder source, wherein the vaporized gaseous source is transported to the substrate downstream of the tube furnace by taking inert gas as a carrier gas for growth. For example, there is a study 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 mu m is obtained on the substrate 2 Te 3 A nanosheet. It has also been studied to prepare Bi of 18 μm in lateral dimension and 12nm in thickness on a mica substrate by the same method 2 Te 3 And (5) a single chip. The method is that Bi 2 Te 3 The large size of (A) provides a basis for batch preparation. However, at present, bi is produced by CVD 2 Te 3 The process of (2) still has the following problems: (1) with Bi 2 Te 3 Powder is the source, since Bi 2 Te 3 Easy decomposition, the essence of the reaction process is Bi 2 Te 3 First decomposed into Bi and Te simple substances, and then transmitted to a substrate through air flow to carry out a combination reaction to generate Bi 2 Te 3 And (3) single crystal. However, because the reducibility of Te is weak, only a small part of Bi and Te react, the growth speed of the Te is slow, and the transverse size of the Te is small; (2) the untreated mica or silica surface has a large number of defects and dangling bonds, and the defects and dangling bonds have very large adsorption energy and are easy to form nucleation points, so that the nucleation density is high, and the transverse dimension and uniformity of the material are further limited. Thus, single wafers obtained by CVD have a maximum dimension of only 20 μm.
As can be seen from the above, bi is currently used 2 Te 3 The preparation method of the single crystal still has the problems of small product size, poor uniformity, uncontrollable thickness and the like, can not meet the requirements of low cost and batch production, and can not prepare Bi with large size and high uniformity 2 Te 3 Single crystal, thereby greatly limiting Bi 2 Se 3 The use of (1). Therefore, it is necessary to develop new Bi 2 Te 3 Single crystal preparationMethod for preparing large-size Bi by improving growth speed and reducing nucleation density 2 Te 3 And (3) single crystal.
Disclosure of Invention
In order to overcome the defects of 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, reduces the nucleation density and prepares large-size Bi by a hydrogen-assisted method 2 Te 3 And (3) single crystal.
In order to achieve the 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 comprises the following steps: with bismuth telluride (Bi) 2 Te 3 ) Powder (purity 99.99%) 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 variable-temperature area of the single-temperature-area horizontal tube furnace, 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 hydrogen-inert gas mixed 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 hydrogen-inert gas mixed gas, the flow rate of 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 hydrogen-inert gas mixture is a mixture of argon and hydrogen.
Preferably, the temperature rise rate of the central heating zone is 20-30 ℃/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 the variable temperature zone downstream from the central heating zone by 12 cm.
Preferably, the tube length of the single-temperature-zone horizontal tube furnace is 100cm, the outer diameter is 25mm, the tube wall thickness is 2.5mm, and the length of the central heating zone is 10cm.
Preferably, before the central heating zone begins to heat up, the internal pressure of the furnace tube is pumped to 10Pa, then 600sccm argon is filled to atmospheric pressure, and the gas is repeatedly washed to remove residual oxygen, then heating is started, and the mixed gas of hydrogen and inert gas is continuously filled in the whole heating process.
Preferably, in the hydrogen-inert gas mixture, the flow rate of the inert gas is 95sccm, and the flow rate of the hydrogen gas is 5sccm. The addition of a proper amount of hydrogen can effectively reduce the nucleation density, improve the 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 characterized in that on the basis of a Chemical Vapor Deposition (CVD) method, a single-temperature-zone horizontal tube furnace is used for accurately controlling H through a hydrogen-assisted method 2 The ratio of the Bi source to the inert gas reduces the nucleation density, increases the growth rate, and simultaneously ensures sufficient supply of the Bi source and the Te source by accurately controlling the substrate temperature (growth temperature), thereby realizing large-size Bi 2 Te 3 The preparation of the single crystal has low preparation cost and simple operation, and can be produced in batches. Specifically, the present 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 usually uses pure inert gas as carrier gas, however, for Bi 2 Te 3 In other words, CVD produces Bi due to its lower decomposition temperature (about 400 ℃ C.) 2 Te 3 The process of (A) is decomposition and combination, the reducibility of Te is very weak, only a small part of Bi and Te can generate combination reaction to generate Bi 2 Te 3 Therefore, the growth rate is slow, and the growth rate is only 0.4-6 μm/min. The invention adds hydrogen into 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 increasing Bi 2 Te 3 The growth rate of (2) promotes an increase in lateral dimension.
(2) The invention utilizes H 2 The auxiliary method effectively reduces the nucleation density. Conventional Bi 2 Te 3 SiO is generally used in the preparation process 2 Si and mica as growing Bi 2 Te 3 The substrate of (1). However, untreated SiO 2 The surface of the mica/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, so that the nucleation density is very high, 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 transverse size of the 2D material are nucleation density and growth speed, the nucleation density is too high, the more crystal boundaries exist in the material, the smaller the size of a single crystal is, and therefore the premise of large size is to reduce the nucleation density and improve the growth speed. The invention is through H 2 Can passivate the SiO 2 The dangling bonds on the surfaces of the/Si and the mica saturate the mica, so that the adsorption energy of the mica 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 high, the growth rate is slow, the source evaporation amount is small, the precursor supply is insufficient, and only small and thin products can be obtained; when the temperature is too high, the atom desorption on the surface of the substrate is enhanced, a large number of precursor particles cannot be adsorbed on the surface of the substrate, and the adsorption energy on the surface of the single crystal wafer is increased, so that Bi is added 2 Te 3 The single crystal tends to grow vertically, and the obtained product is small and thick and has low yield. When the hydrogen concentration is too low, the hydrogen hardly acts and it is difficult to promote Bi significantly 2 Te 3 Growing of (3); when the hydrogen concentration is too high, the corrosiveness of hydrogen itself will be to Bi 2 Te 3 The surface of the single crystal is corroded, so that holes are generated, and the quality of the crystal is reduced.
Drawings
FIG. 1 is a scheme for preparing two-dimensional Bi 2 Te 3 A schematic illustration of an apparatus for single crystal material;
FIG. 2 shows large-sized Bi prepared in example 1 2 Te 3 Optical microscope pictures of the single wafer (a is a high power optical image, and b is a low power optical image);
FIG. 3 shows Bi prepared in example 1 2 Te 3 High resolution transmission electron microscopy images of single wafers;
FIG. 4 shows Bi prepared in example 1 2 Te 3 An elemental profile of the single wafer;
FIG. 5 shows Bi prepared in example 1 2 Te 3 Raman spectrum of the single chip;
FIG. 6 shows Bi prepared in example 2 2 Te 3 Optical microscopy of single wafers;
FIG. 7 shows Bi prepared in example 3 2 Te 3 Optical microscopy of single wafers;
FIG. 8 shows Bi prepared in example 4 2 Te 3 Optical microscopy of single wafers;
FIG. 9 shows Bi prepared in comparative example 1 2 Te 3 Optical microscopy pictures of single wafers.
Detailed Description
The following further describes embodiments of the present invention. It should be noted that the description of the embodiments is provided to help understanding of the present invention, but the present invention is not limited thereto. In addition, the technical features involved in the respective embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
The experimental procedures in the following examples were carried out by conventional methods unless otherwise specified, and the test materials used in the following examples were commercially available by conventional methods unless otherwise specified.
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 at 500 ℃ and the temperature rise rate was 30 ℃/min. Bismuth telluride powder (purity is more than 99.99%) is used as a Bi source and a Te source, and the powder is placed in a central heating area; adopting fluorophlogopite sheets as a deposition substrate, and placing the deposition substrate in a downstream temperature-changing area 12cm away from a central temperature area;
(2) Before the reaction, a mechanical pump is used for pre-vacuumizing to about 10Pa, then 600sccm Ar is filled to atmospheric pressure, and gas washing is repeated to remove residual oxygen;
(3) Heating was started and 95sccm Ar and 5sccm H were continuously added throughout the process 2 When the temperature reaches 500 ℃, preserving the heat for 5 minutes, keeping the carrier gas unchanged after the reaction is finished, cooling the product to room temperature along with the furnace, and obtaining the two-dimensional Bi from the fluorophlogopite sheet 2 Te 3 And (3) a single wafer.
FIG. 2 reflects Bi 2 Te 3 Morphology of the single wafer, it can be seen that the Bi obtained 2 Te 3 The single crystal is in a uniform hexagon shape, the size is large and can reach 241 mu m, and the thickness can reach a single layer (1.1 nm); FIG. 3 shows Bi 2 Te 3 The high-resolution transmission electron microscope photo of the single crystal wafer shows that the single crystal wafer presents a regularly arranged lattice structure, and the spacing between crystal planes is 0.22nm; FIG. 4 shows Bi 2 Te 3 The element component analysis result of the single chip shows that the Bi element and the Te element are uniformly distributed; FIG. 4 shows Bi 2 Te 3 The Raman spectrum of the single chip shows three characteristic peaks which are respectively 61cm -1 ，101cm -1 ，132cm -1 . The synthesized product is bismuth telluride single crystal and has good crystallinity.
EXAMPLE 2 preparation of two-dimensional thermoelectric Material bismuth telluride Single Crystal
The specific preparation method is the same as that of example 1, except that: the core temperature was set at 400 ℃.
The morphology is shown in FIG. 6, which shows that Bi is obtained 2 Te 3 The thickness of the single crystal is thin, with dimensions of about 20-30 μm, significantly smaller than in example 1.
EXAMPLE 3 preparation of two-dimensional thermoelectric Material bismuth telluride Single Crystal
The specific preparation method is the same as that of example 1, except that: the core temperature was set at 600 ℃.
The morphology is shown in FIG. 7, which shows that the Bi obtained 2 Te 3 The thickness of the single crystal is thin, and the dimension is about 30-40 μm, which is obviously smaller than that of the embodiment 1.
Example 4 preparation of two-dimensional thermoelectric Material bismuth telluride Single Crystal
The specific preparation method is the same as that of example 1, except that: 85sccm of Ar and 15sccm of H are introduced 2 。
The morphology is shown in FIG. 8, which is clearly seen due to H 2 The higher content of Bi due to its corrosive nature 2 Te 3 The surface was porous, and the crystal quality was remarkably reduced as 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 that of example 1, except that: 100sccm of pure Ar was introduced.
The morphology is shown in FIG. 9, and it is clearly seen that Bi is obtained in comparison with example 1 2 Te 3 The nucleation density of the single crystal is very large, about 10-20 μm in size, significantly smaller than example 1, and the uniformity is poor.
The obvious advantages of the present invention are evident from comparing the nucleation density, growth rate and size of the products of example 1 and comparative example 1. The nucleation density of the product of example 1 is 3200/mm 2 Compared with the comparative example 1, the growth speed is one order of magnitude less than that of the comparative example 1, the growth speed is 48 mu m/min, and the growth speed is one order of magnitude higher than that of the comparative example 1, so that the size of a final product can reach 240 mu m, and the size is the Bi reported at present 2 Te 3 The largest dimension.
TABLE 1 Bi of example 1 and comparative example 1 2 Te 3 Comparison 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 accurately controls H 2 The ratio of the Bi to Ar is increased, thereby reducing the nucleation density, increasing the growth speed and further promoting the large-size Bi 2 Te 3 The growth of (2) achieves an order of magnitude improvement. Meanwhile, by precisely controlling the substrate temperature (growth temperature), sufficient supply of Bi source and Te source is ensured, and thus a large-sized single crystal Bi of 240 μm in size is obtained at the maximum growth rate 2 Te 3 . In addition, the method has low preparation cost and simple operation, and can be used for batch production.
The embodiments of the present invention have been described in detail, 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 in these embodiments without departing from the principles and spirit of the invention, and the scope of protection is still within the scope of the invention.
Claims (10)
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 hydrogen-inert gas mixed gas as a 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 the inert gas flow rate is 50-100sccm and the hydrogen flow rate is 2.5-15sccm in the hydrogen-inert gas mixed gas.
2. The method for preparing a large-sized two-dimensional thermoelectric material bismuth telluride single crystal as claimed in claim 1, wherein the temperature of the central heating zone is 500 ℃.
3. The method for preparing the large-size two-dimensional thermoelectric material bismuth telluride single crystal as claimed in 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 as in claim 1, wherein the temperature rise rate of the central heating zone is 20-30 ℃/min.
5. The method for preparing the large-size two-dimensional thermoelectric material bismuth telluride single crystal as claimed in claim 1, wherein the substrate is a freshly peeled fluorophlogopite substrate.
6. The method for preparing the large-size two-dimensional thermoelectric material bismuth telluride single crystal as in claim 1, wherein 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.
7. The method for preparing a large-size two-dimensional thermoelectric material bismuth telluride single crystal as claimed in claim 1, wherein the substrate is placed in a downstream temperature-varying region 12cm from the central heating region.
8. The method for preparing a large-size two-dimensional thermoelectric material bismuth telluride single crystal as in claim 1, wherein the tube length of the single-temperature-zone horizontal tube furnace is 100cm, the outer diameter is 25mm, the tube wall thickness is 2.5mm, and the length of the central heating zone is 10cm.
9. The method for preparing the large-size two-dimensional thermoelectric material bismuth telluride single crystal as claimed in claim 1, wherein before the temperature of the central heating zone is raised, the internal pressure of the furnace tube is firstly pumped to 10Pa, then 600sccm argon is filled to atmospheric pressure, and the gas is repeatedly washed to remove residual oxygen, then heating is started, and hydrogen-inert gas mixture is continuously introduced in the whole heating process.
10. The method for preparing the large-size two-dimensional thermoelectric material bismuth telluride single crystal as claimed in claim 1, wherein a flow rate of the inert gas is 95sccm and a flow rate of the hydrogen is 5sccm in the hydrogen-inert gas mixture.
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