CN112875659A - Method for realizing uniform fluorine doping of hexagonal boron nitride in situ - Google Patents
Method for realizing uniform fluorine doping of hexagonal boron nitride in situ Download PDFInfo
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Abstract
The invention provides a method for realizing uniform fluorine doping of hexagonal boron nitride in situ, and relates to preparation of hexagonal boron nitride and a method for carrying out element doping on the hexagonal boron nitride. The method adopts a fluorine-containing compound as a precursor, places a metal foil at the downstream position of the precursor as a growth substrate, and then quickly obtains the hexagonal boron nitride doped with uniform fluorine by utilizing a chemical vapor deposition method. The method provided by the invention realizes the high-quality and uniform fluorine-doped hexagonal boron nitride sample in situ by a simple, rapid and lossless means.
Description
Technical Field
The invention relates to the technical field of materials, in particular to a method for realizing uniform fluorine doping of hexagonal boron nitride in situ.
Background
In recent years, two-dimensional materials represented by graphene are attracting much research attention, and two-dimensional hexagonal boron nitride is a binary compound with a structure similar to that of graphene, and has also attracted extensive research interest due to its unique physical properties. Hexagonal boron nitride has excellent mechanical stability and thermal stability, is flat and has no dangling bond surface, is the best known two-dimensional insulator, has a wider band gap, can emit single photons from point defects, and has higher room-temperature proton conductivity, and the properties enable the hexagonal boron nitride to be widely applied to devices designed on the basis of two-dimensional insulator materials. The application of hexagonal boron nitride in the field of devices needs to be further widened depending on the interface energy band regulation design, and researches show that the hexagonal boron nitride can be converted into a broadband semiconductor material from an insulating material after being subjected to functional treatment and shows a room-temperature ferromagnetic effect. Therefore, the core difficulty in the comprehensive application of the two-dimensional material can be solved by adjusting and controlling physical properties such as a band gap structure, conductivity and the like by carrying out element doping on the hexagonal boron nitride to realize interface modification, the construction of an electronic device based on the full two-dimensional material is facilitated, and the development of future electronics is promoted.
Among the elements available for doping introduction, fluorine is an extremely active, extremely electronegative element, and when fluorine-containing substances come into contact with other molecules, hydrogen substitution reaction easily occurs, thereby fluorinating the other molecules. After the fluorination of the boron nitride, the energy band structure of the boron nitride is changed and partial semiconductor properties are shown, so that convenience is provided for subsequent device design and application. In the existing fluorine doping methods, strong acid solution such as perfluorosulfonic acid or gas such as xenon fluoride is often needed for assistance, and the methods can form a stable bonding structure in a boron nitride material, but have the problems that the preparation of large-area single-crystal two-dimensional materials cannot be realized, the quality of the materials cannot be guaranteed, and the like. Therefore, a stable and mild method capable of uniformly doping fluorine into boron nitride is urgently needed to be provided.
Disclosure of Invention
The invention firstly provides a method for realizing uniform fluorine doping of hexagonal boron nitride in situ.
A method for realizing uniform fluorine doping of hexagonal boron nitride in situ is characterized in that a metal foil and a fluorine-containing precursor are placed in chemical vapor deposition equipment, and high-quality uniform fluorine-doped hexagonal boron nitride grows on the metal foil; the chemical vapor deposition equipment comprises a tubular device, wherein the tubular device comprises an upstream area, a midstream area and a downstream area which are sequentially arranged along the gas flow direction; the method comprises the following steps:
placing a fluorine-containing precursor in a midstream region, placing a metal foil in a downstream region, placing a boron-nitrogen source in an upstream region, introducing inert gas, and then starting heating the midstream region and the downstream region;
(II) temperature in midstream regionWhen the temperature rises to 650-1100 ℃ and the temperature of the downstream area rises to 900-1100 ℃, H is introduced2Gas, annealing process is carried out;
after annealing, heating the boron nitrogen source in the upstream region, and growing in a normal pressure or low pressure environment;
and fourthly, after the growth is finished, cooling to room temperature in a normal pressure environment to obtain the hexagonal boron nitride uniformly doped with the fluorine element.
Preferably, the metal foil is not subjected to any surface treatment, i.e. metal foils obtained from open commercial sources are used directly in the process without any surface pre-treatment.
Preferably, the method comprises the steps of:
placing the metal foil and the fluorine-containing precursor on a quartz plate, placing the quartz plate into a quartz tube of chemical vapor deposition equipment, placing a boron-nitrogen source outside a zone heated by a muffle furnace at the front end of the quartz tube, winding a heating belt around the zone, introducing inert gas, and then starting to heat;
(II) when the temperature of the fluorine-containing precursor region rises to 650-1100 ℃, and the temperature of the metal foil region rises to 900-1100 ℃, H is introduced2Gas, H2Carrying out an annealing process with the flow rate of 2-50 sccm;
after annealing, heating the boron nitrogen source at the front end of the quartz tube by a heating belt, and growing in a normal pressure or low pressure environment for 1 s-60 min;
and fourthly, after the growth is finished, cooling to room temperature in a normal pressure environment to obtain the hexagonal boron nitride uniformly doped with the fluorine element.
Preferably, the method comprises the steps of:
placing a metal foil which is not subjected to any surface treatment and a fluorine-containing precursor on a quartz plate, wherein the metal foil is positioned at the downstream position and is placed in a quartz tube of chemical vapor deposition equipment, placing a boron-nitrogen source outside a muffle furnace heating area at the front end of the quartz tube, winding a heating belt around the boron-nitrogen source, introducing Ar with the flow rate of more than 300sccm, and then starting to heat up, wherein the heating process lasts for 40-90 min;
(II) when the temperature of the fluorine-containing precursor region rises to 650-1100 ℃, and the temperature of the metal foil region rises to 900-1100 ℃, H is introduced2Gas, H2The flow rate is 2-50 sccm, the Ar flow rate is kept unchanged, and the annealing process is carried out for 30-100 min;
and thirdly, after the annealing is finished, heating a boron-nitrogen source at the front end of the quartz tube through a heating belt to perform normal-pressure or low-pressure growth, wherein the temperature is 50-150 ℃, and adjusting H2The flow is 0.2-50 sccm, the Ar flow is kept unchanged, and the growth time is 1 s-60 min;
(IV) after the growth is finished, turning off the heating power supply, turning off the heating belt, and enabling the system to be in a normal-pressure environment with Ar and H2And naturally cooling the metal foil to room temperature for protecting gas, and growing high-quality hexagonal boron nitride uniformly doped with the fluorine element on the metal foil, namely completing the low-cost in-situ preparation of the hexagonal boron nitride uniformly doped with the fluorine element.
Preferably, the fluorine-containing precursor is a fluoride, including CaF2、BaF2、MgF2、AlF3LiF, NaF, KF, cryolite, Na3AlF6One or more of (a). Preferably, the metal is copper, platinum, nickel or gold.
Preferably, the heating process in the first step is not conducted with H2。
Preferably, the temperature rise, the annealing treatment and the cooling in the first step, the second step and the fourth step are all carried out under the condition of normal pressure, and the growth process in the third step is carried out under the condition of normal pressure or low pressure.
Preferably, in the third step, the fluorine-containing precursor releases fluorine at high temperature, and diffuses to the metal foil on which boron nitride grows through the diffusion process in the air flow, so that the uniform fluorine doping of hexagonal boron nitride growing on the metal foil is realized in situ.
Preferably, the first step comprises the steps of: placing a metal foil which is purchased from a public way and is not subjected to any surface treatment and a fluorine-containing precursor on a quartz plate, placing the metal foil at a downstream position into chemical vapor deposition equipment, introducing Ar with the flow rate of more than 300sccm,the working pressure is atmospheric (i.e. one atmosphere or about 1X 10)5Pa), and then starting to heat up, wherein the heating process lasts for 40-90 min.
The invention uses metal foil as a growth substrate, uses a fluorine-containing precursor to be arranged at the midstream position of chemical vapor deposition equipment, and then uses a chemical vapor deposition method to quickly obtain the hexagonal boron nitride doped with uniform fluorine. The method provided by the invention solves the technical problem of in-situ preparation of the uniform fluorine-doped hexagonal boron nitride, and realizes rapid in-situ preparation of a high-quality uniform fluorine-doped hexagonal boron nitride sample by a very simple method.
The invention has the advantages that:
1. the invention selects the metal foil as the growth substrate, does not need to carry out complex surface pretreatment on the substrate, greatly simplifies the growth process, shortens the growth period and greatly reduces the preparation cost;
2. according to the invention, the high-quality uniform fluorine-doped hexagonal boron nitride can be rapidly prepared in situ only by placing the metal foil at the downstream position of the fluorine-containing precursor, and no other special treatment is needed;
3. the method is simple and effective, has short preparation period, and is beneficial to the practical application and industrial production of the hexagonal boron nitride doped with uniform fluorine.
Drawings
FIG. 1 is a schematic diagram of the rapid in-situ preparation of uniform fluorine-doped hexagonal boron nitride by chemical vapor deposition according to the present invention.
Fig. 2 is an optical microscope picture of a sample of uniformly fluorine doped hexagonal boron nitride prepared according to the present invention.
Fig. 3 is a scanning electron microscope picture of a uniform fluorine doped hexagonal boron nitride sample prepared in accordance with the present invention.
Fig. 4 is a raman spectrum of hexagonal boron nitride prepared according to the present invention, showing that the prepared sample is hexagonal boron nitride doped with uniform fluorine.
FIG. 5 is an X-ray diffraction pattern of hexagonal boron nitride prepared in accordance with the present invention, showing that the sample prepared was fluorine-doped hexagonal boron nitride.
Detailed Description
The present invention will be described in further detail with reference to specific examples, which are conventional unless otherwise specified. The starting materials are commercially available from the open literature unless otherwise specified, and the metal foils are cut to size and then directly placed into the CVD system for growth.
The first implementation mode comprises the following steps: method for realizing uniform fluorine doping of hexagonal boron nitride in situ
This embodiment is carried out in the apparatus shown in FIG. 1. As shown in fig. 1, the apparatus comprises a tubular apparatus comprising an upstream region, a midstream region, and a downstream region arranged in sequence along the gas flow direction (from left to right in fig. 1), wherein the fluorine-containing precursor is located in the midstream region, the metal foil is located in the downstream region, and the boron nitrogen source is located in the upstream region.
In a specific embodiment, the upstream region is a region outside the region heated by the muffle furnace at the front end of the tubular device, and a heating belt is wound around the tubular device in the region. In a specific embodiment, the tube device comprises a quartz tube.
In a specific embodiment, the boron nitrogen source comprises NH3BH3(ii) a The fluorine-containing precursor comprises CaF2、BaF2、MgF2、AlF3LiF, NaF, KF, cryolite, Na3AlF6One or more of (a). The fluorine-containing precursor may be a powder or a wafer. The metal foil is made of copper, platinum, nickel or gold.
In one specific embodiment, the boron-nitrogen source NH is respectively placed in an upstream region, a midstream region and a downstream region in sequence in a chemical vapor deposition device3BH3The preparation method comprises the following steps of:
firstly, placing a metal foil which is not subjected to any surface treatment and a fluorine-containing precursor on a quartz plate, placing the metal foil at a downstream position into a quartz tube of chemical vapor deposition equipment, placing a boron-nitrogen source outside a muffle furnace heating area at the front end of the quartz tube, winding a heating tape around the boron-nitrogen source, introducing Ar with the flow rate of more than 300sccm, and processingThe pressure is normal pressure (i.e. one atmosphere or about 1X 10)5Pa), then starting to heat up, wherein the heating process lasts for 40-90 min;
secondly, when the temperature of the fluorine-containing precursor region rises to 650-1100 ℃, and the temperature of the metal foil region rises to 900-1100 ℃, H is introduced2Gas, H2The flow rate is 2-50 sccm, the Ar flow rate is kept unchanged, and the annealing process is carried out for 30-100 min;
thirdly, after the annealing is finished, heating the boron-nitrogen source in the upstream area to 50-110 ℃ through a heating zone to carry out normal-pressure or low-pressure growth, and adjusting H2The flow is 0.2-50 sccm, the Ar flow is kept unchanged, and the growth time is 1 s-60 min;
fourthly, after the growth is finished, the heating power supply is closed, the heating belt is closed, and Ar and H are added under the normal pressure environment2Naturally cooling to room temperature for protecting gas, and growing high-quality hexagonal boron nitride uniformly doped with fluorine element on the metal foil in situ, namely completing the low-cost in-situ preparation of the hexagonal boron nitride uniformly doped with fluorine.
It should be noted that: if the metal foil is surface-treated, it can also be applied to the method having the above-described steps to obtain hexagonal boron nitride uniformly doped with fluorine.
The first, second and fourth steps of the method are carried out under normal pressure, namely one atmosphere or about 1 × 105Pa, the growth process in the third step is carried out under the condition of normal pressure or low pressure.
In the second step, no heating operation is carried out on the upstream area, namely, the area is not heated by using a heating furnace, and the heating belt is in an unheated state.
In the third step, after the annealing is finished, the temperature of the fluorine-containing precursor region is still maintained at 650-1100 ℃, the temperature of the metal foil region is still maintained at 900-1100 ℃, namely, the temperature of the fluorine-containing precursor region and the metal foil region is not reduced after the annealing is finished.
In the third step, the fluorine-containing precursor releases fluorine element at high temperature, and diffuses to the metal foil on which the boron nitride grows through the diffusion process in the air flow, so that the hexagonal boron nitride growing in situ on the metal foil is uniformly doped with the fluorine element.
The optical diagram of the single crystal hexagonal boron nitride sample prepared by the method is shown in figure 2, the shape of the boron nitride single crystal is triangular, and the size can reach 100 mu m. The Raman spectrum (the laser wavelength is 532nm) of the single crystal hexagonal boron nitride sample prepared by the method is shown in figure 4, and the Raman spectrum shows that the sample has a very obvious boron nitride characteristic peak, which indicates that the prepared sample is high-quality boron nitride. In addition, as shown in FIG. 5, the X-ray diffraction pattern shows that there is a clear fluorine signal, indicating that boron nitride is doped with fluorine.
The embodiment has the following beneficial effects:
1. in the embodiment, the easily-obtained metal foil is used as the growth substrate, and the uniform fluorine-doped hexagonal boron nitride can be obtained at a high repetition rate.
2. The method takes the common fluorine-containing substrate and powder as the precursor, does not need other special treatment, and reduces the growth cost.
3. The growth duration of the embodiment is only 1 s-60 min, the growth period is short, and the time and the cost are saved.
4. The hexagonal boron nitride grown by the method has high quality, few defects and uniform element doping, and has a very good application prospect in future electronics.
Test one: in the experiment, the method for rapidly preparing the uniformly fluorine-doped hexagonal boron nitride in situ by using the fluorine-containing precursor comprises the following steps
The method comprises the following steps:
firstly, placing a metal copper foil without any surface treatment and NaF powder on a quartz plate, wherein the NaF powder is positioned at a midstream position, the metal copper foil is positioned at a downstream position, placing the metal copper foil into a quartz tube of chemical vapor deposition equipment, placing a boron nitrogen source outside a muffle furnace heating area at the front end of the quartz tube (namely an upstream area), winding a heating belt around the boron nitrogen source, introducing Ar, wherein the flow rate is 500sccm, the working pressure is 1 multiplied by 105Pa, then starting heating up, wherein the heating up process lasts for 60 min;
secondly, the temperature of the NaF area is raised to 850 ℃, and the metallic copper is addedWhen the temperature of the foil area rises to 1020 ℃, H is introduced2Gas, H2The flow is 10sccm, the Ar flow is kept unchanged, and the annealing process is carried out, wherein the annealing duration is 40 min;
thirdly, after the annealing is finished, the air pump is opened, and the BH at the front end of the quartz tube starts to be heated through the heating belt3NH3Heating the reactant at 75 deg.C, growing at low pressure, and regulating H2The flow rate is 30sccm, the Ar flow rate is kept unchanged, and the growth time is 20 min;
fourthly, after the growth is finished, the heating power supply is closed, the heating belt is closed, the air pump is closed, argon is introduced, and Ar and H are added after the air pump is inflated to normal pressure2Naturally cooling to room temperature for protecting gas, and growing high-quality hexagonal boron nitride uniformly doped with fluorine element in situ on the metal copper foil, namely completing the low-cost in-situ preparation of the hexagonal boron nitride uniformly doped with fluorine.
The hexagonal boron nitride prepared by the test has uniform doping, high quality and triangular shape.
And (2) test II: the method for rapidly preparing the uniformly fluorine-doped hexagonal boron nitride in situ by using the fluorine-containing precursor in the test is carried out according to the following steps:
firstly, metal copper foil without any surface treatment and BaF2The wafer is placed on a quartz plate, BaF2The wafer is positioned at the midstream position, the metal copper foil is positioned at the downstream position, the wafer is placed in a quartz tube of chemical vapor deposition equipment, a boron-nitrogen source is arranged outside a muffle furnace heating area at the front end of the quartz tube (namely an upstream area), a heating belt is wound around the boron-nitrogen source, Ar is introduced, the flow rate is 500sccm, the working pressure is 1 multiplied by 105Pa, then starting heating up, wherein the heating up process lasts for 60 min;
II, BaF2The temperature of the area is raised to 1000 ℃, and H is introduced when the temperature of the area of the metal copper foil is raised to 1020 DEG C2Gas, H2The flow is 10sccm, the Ar flow is kept unchanged, and the annealing process is carried out, wherein the annealing duration is 40 min;
thirdly, after the annealing is finished, the air pump is opened, and the BH at the front end of the quartz tube starts to be heated through the heating belt3NH3The reactants are heated at 75 ℃ to carry outLow pressure growth, regulation of H2The flow rate is 30sccm, the Ar flow rate is kept unchanged, and the growth time is 20 min;
fourthly, after the growth is finished, the heating power supply is closed, the heating belt is closed, the air pump is closed, argon is introduced, and Ar and H are added after the air pump is inflated to normal pressure2And naturally cooling to room temperature for protecting gas, and growing high-quality hexagonal boron nitride uniformly doped with fluorine on the metal copper foil, namely completing the low-cost in-situ preparation of the uniformly fluorine-doped hexagonal boron nitride.
The hexagonal boron nitride prepared by the test has uniform doping, high quality and triangular shape.
And (3) test III: the method for rapidly preparing the uniformly fluorine-doped hexagonal boron nitride in situ by using the fluorine-containing precursor in the test is carried out according to the following steps:
firstly, metal platinum foil without any surface treatment and BaF2The wafer is placed on a quartz plate, BaF2The wafer is positioned at the midstream position, the metal platinum foil is positioned at the downstream position, the wafer is placed in a quartz tube of chemical vapor deposition equipment, a boron-nitrogen source is arranged outside a muffle furnace heating area at the front end of the quartz tube (namely an upstream area), a heating belt is wound around the boron-nitrogen source, Ar is introduced, the flow rate is 500sccm, the working pressure is 1 multiplied by 105Pa, then starting heating up, wherein the heating up process lasts for 60 min;
II, BaF2The zone temperature is increased to 1000 ℃, when the zone temperature of the metal platinum foil is increased to 1020 ℃, H is introduced2Gas, H2The flow is 10sccm, the Ar flow is kept unchanged, and the annealing process is carried out, wherein the annealing duration is 40 min;
thirdly, after the annealing is finished, the air pump is opened, and the BH at the front end of the quartz tube starts to be heated through the heating belt3NH3Heating the reactant at 75 deg.C, growing at low pressure, and regulating H2The flow rate is 30sccm, the Ar flow rate is kept unchanged, and the growth time is 20 min;
fourthly, after the growth is finished, the heating power supply is closed, the heating belt is closed, the air pump is closed, argon is introduced, and Ar and H are added after the air pump is inflated to normal pressure2Naturally cooling to room temperature for protecting gas, and growing high-quality uniform doping on the metal platinum foilThe hexagonal boron nitride of fluorine element is used, namely the low-cost in-situ preparation of the hexagonal boron nitride doped with uniform fluorine is completed.
The hexagonal boron nitride prepared by the test has uniform doping, high quality and triangular shape.
And (4) testing: the method for rapidly preparing the uniformly fluorine-doped hexagonal boron nitride in situ by using the fluorine-containing precursor in the test is carried out according to the following steps:
firstly, placing a metal copper foil without any surface treatment and NaF powder on a quartz plate, wherein the NaF powder is positioned at a midstream position, the metal copper foil is positioned at a downstream position, placing the metal copper foil into a quartz tube of chemical vapor deposition equipment, placing a boron nitrogen source outside a muffle furnace heating area at the front end of the quartz tube (namely an upstream area), winding a heating belt around the boron nitrogen source, introducing Ar, wherein the flow rate is 500sccm, the working pressure is 1 multiplied by 105Pa, then starting heating up, wherein the heating up process lasts for 60 min;
secondly, when the temperature of the NaF area rises to 850 ℃ and the temperature of the metal platinum foil area rises to 1020 ℃, H is introduced2Gas, H2The flow is 10sccm, the Ar flow is kept unchanged, and the annealing process is carried out, wherein the annealing duration is 40 min;
thirdly, after the annealing is finished, heating BH at the front end of the quartz tube by a heating belt3NH3Heating the reactant at 75 deg.C, growing at normal pressure, and regulating H2The flow rate is 30sccm, the Ar flow rate is kept unchanged, and the growth time is 20 min;
fourthly, after the growth is finished, the heating power supply is closed, the heating belt is closed, and Ar and H are added under the normal pressure environment2Naturally cooling to room temperature for protecting gas, and growing high-quality hexagonal boron nitride uniformly doped with fluorine element in situ on the metal platinum foil, namely completing the low-cost in-situ preparation of the hexagonal boron nitride uniformly doped with fluorine.
The hexagonal boron nitride prepared by the test has uniform doping, high quality and triangular shape.
Claims (10)
1. A method for realizing uniform fluorine doping of hexagonal boron nitride in situ is characterized in that a metal foil and a fluorine-containing precursor are placed in chemical vapor deposition equipment, and high-quality hexagonal boron nitride uniformly doped with fluorine is grown in situ on the metal foil; the chemical vapor deposition equipment comprises a tubular device, wherein the tubular device comprises an upstream area, a midstream area and a downstream area which are sequentially arranged along the gas flow direction; the method comprises the following steps:
firstly, placing a fluorine-containing precursor in a midstream region, placing a metal foil in a downstream region, placing a boron-nitrogen source in an upstream region, introducing inert gas, and then starting heating the midstream region and the downstream region;
(II) when the temperature of the midstream region rises to 650-1100 ℃ and the temperature of the downstream region rises to 900-1100 ℃, introducing H2 Gas, annealing process is carried out;
after annealing, heating the boron nitrogen source in the upstream region, and growing in a normal pressure or low pressure environment;
and (IV) after the growth is finished, cooling to room temperature in a normal pressure environment to obtain the hexagonal boron nitride uniformly doped with the fluorine element.
2. The method of claim 1, wherein the fluorine-containing precursor is a powder or a wafer.
3. The method of claim 1, wherein the metal foil is free of any surface treatment.
4. Method according to claim 1, characterized in that it comprises the following steps:
placing the metal foil and a fluorine-containing precursor on a quartz plate, placing the fluorine-containing precursor in a midstream region, placing the metal foil in a downstream region, placing the metal foil in a quartz tube of chemical vapor deposition equipment, placing a boron-nitrogen source outside a region heated by a muffle furnace at the front end of the quartz tube, winding a heating belt around the region, introducing inert gas, and then starting to heat; the region outside the region heated by the muffle furnace at the front end of the quartz tube is an upstream region;
(II) increasing the temperature to 65 ℃ in the midstream regionIntroducing H when the temperature of the downstream area is increased to 900-1100 ℃ at the temperature of 0-1100 DEG C2 Gas, H2Carrying out an annealing process with the flow rate of 2-50 sccm;
after annealing is finished, heating a boron nitrogen source at the front end of the quartz tube through a heating belt to grow in a normal-pressure or low-pressure environment for 1 s-60 min;
and (IV) after the growth is finished, cooling to room temperature in a normal pressure environment to obtain the hexagonal boron nitride uniformly doped with the fluorine element.
5. Method according to claim 1, characterized in that it comprises the following steps:
placing a metal foil without any surface treatment and a fluorine-containing precursor on a quartz plate, placing the fluorine-containing precursor in a midstream region, placing the metal foil in a downstream region, placing the metal foil in a quartz tube of chemical vapor deposition equipment, placing a boron nitrogen source outside a muffle furnace heating region at the front end of the quartz tube, winding a heating belt around the boron nitrogen source, introducing Ar with the flow rate of more than 300sccm, and then starting to heat up, wherein the heating process lasts for 40-90 min; the region outside the region heated by the muffle furnace at the front end of the quartz tube is an upstream region;
(II) when the temperature in the midstream region rises to 650-1100 ℃ and the temperature in the downstream region rises to 900-1100 ℃, introducing H2 Gas, H2The flow rate is 2-50 sccm, the Ar flow rate is kept unchanged, and the annealing process is carried out for 30-100 min;
after annealing, starting to heat the boron-nitrogen source at the front end of the quartz tube through a heating band to perform normal pressure or low pressure growth, and adjusting H2The flow is 0.2-50 sccm, the Ar flow is kept unchanged, and the growth time is 1 s-60 min;
(IV) after the growth is finished, the heating power supply is closed, the heating belt is closed, and Ar and H are added under the normal pressure environment2Naturally cooling to room temperature for protecting gas, and growing high-quality hexagonal boron nitride uniformly doped with fluorine on the metal foil in situ to finish the preparation of the single crystal hexagonal boron nitride uniformly doped with the fluorine at low cost.
6. The method of claim 1, wherein the fluorine-containing precursor is a fluoride, including CaF2、BaF2、MgF2、AlF3LiF, NaF, KF, cryolite, Na3AlF6One or more of (a).
7. The method of claim 1, wherein the metal foil is made of copper, platinum, nickel or gold.
8. The method of claim 4 or 5, wherein the in-situ grown boron nitride has a thickness of 0.3nm to 10 cm.
9. The method of claim 4 or 5, wherein the warming process in step one does not block H2。
10. The method according to claim 4 or 5, wherein the heating, annealing and cooling in the first, second and fourth steps are performed under normal pressure, and the growth in the third step is performed under normal pressure or low pressure.
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