CN114940483B - Ultra-fast preparation method of hexagonal boron nitride film - Google Patents
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Abstract
The invention relates to the field of hexagonal boron nitride film preparation, in particular to an ultrafast preparation method of a hexagonal boron nitride film, which is suitable for efficiently preparing the hexagonal boron nitride film. According to the invention, the high-temperature metal boride matrix is rapidly cooled (quenched) in liquid nitrogen, and in the quenching process, the liquid nitrogen is catalytically cracked into active nitrogen atoms, and then reacts with boron atoms on the surface of the matrix to grow the hexagonal boron nitride film. The preparation method has the advantages of simple process, high efficiency, low cost and good controllability, can prepare the hexagonal boron nitride film in batches, and lays a foundation for the application of the hexagonal boron nitride film in the fields of electronic devices, corrosion and wear resistant coatings, thermal management, ion transport and the like.
Description
Technical field:
the invention relates to the field of hexagonal boron nitride film preparation, in particular to an ultrafast preparation method of a hexagonal boron nitride film, which is suitable for efficiently preparing the hexagonal boron nitride film.
The background technology is as follows:
since the first time a scientist in the university of manchester in 2004 has obtained a graphene material having a single atomic layer and a few atomic layers in thickness by using a mechanical exfoliation method, a two-dimensional material represented by graphene has been attracting attention due to its atomic-level thickness, ultra-high specific surface area, and unique physicochemical properties that are very different from those of a bulk material. Among the many two-dimensional materials, two-dimensional hexagonal boron nitride is a typical insulator that has a similar crystal structure as graphene, also known as "white graphene". The two-dimensional hexagonal boron nitride has a plurality of excellent characteristics, such as wide band gap, high dielectric constant, high thermal conductivity, high mechanical strength, excellent thermal stability and the like, so that the two-dimensional hexagonal boron nitride has wide application prospects in deep ultraviolet detection, transparent dielectric films, gate insulating layers, thermal management, high-temperature oxidation corrosion resistance protection layers and the like.
Efficient preparation of hexagonal boron nitride films is a key to determine whether they can be practically used. Similar to the research of graphene, a micromechanical stripping method is the earliest method for preparing two-dimensional hexagonal boron nitride, and the method is used for obtaining high-quality two-dimensional hexagonal boron nitride by stripping hexagonal boron nitride blocks, but has extremely low preparation efficiency, and cannot obtain a large-area two-dimensional hexagonal boron nitride film, and a chemical vapor deposition method provides possibility for preparing the two-dimensional hexagonal boron nitride film in a large-area controllable manner. In general, the chemical vapor deposition method adopts metal matrixes such as copper, nickel and the like, and the two-dimensional hexagonal boron nitride film is prepared by cracking and recombining precursors such as ammonia borane, borazine and the like on the surface of a catalytic matrix at high temperature, so that the prepared hexagonal boron nitride film has high quality, can realize large-area preparation, has better controllability, but has longer preparation period and high preparation cost, and is difficult to obtain the two-dimensional hexagonal boron nitride film with small grain size.
The invention comprises the following steps:
the invention aims to provide an ultrafast preparation method of a hexagonal boron nitride film, which solves the problems of complex process, long production period, high cost and the like of the existing preparation method and lays a foundation for researching the intrinsic physical properties of the hexagonal boron nitride film and realizing the scale application of the hexagonal boron nitride film.
The technical scheme of the invention is as follows:
the ultra-fast preparation method of hexagonal boron nitride film adopts high-temperature metal boride matrix, and under inert protective atmosphere, the metal boride matrix is rapidly cooled in liquid nitrogen source through quenching, the liquid nitrogen source is catalytically cracked into nitrogen atoms in the quenching process, and then the nitrogen atoms react with boron atoms on the surface of the matrix to grow the hexagonal boron nitride film.
According to the ultra-fast preparation method of the hexagonal boron nitride film, the matrix is metal boride, and the matrix is any shape of foil, porous foam, powder or block; wherein: metal borides include, but are not limited to, feB, fe 2 B、Fe 83 B 17 、NiB 2 、NiB、Ni 4 B 3 、Ni 2 B、Ni 3 B、Ni 83 B 17 、CoB、Co 2 B or Co 82 B 18 。
According to the ultra-fast preparation method of the hexagonal boron nitride film, the liquid nitrogen source is liquid nitrogen.
According to the ultra-fast preparation method of the hexagonal boron nitride film, the initial temperature of the high-temperature metal boride matrix is more than 700 ℃ and is lower than the gasification or decomposition temperature of the matrix, and the temperature is kept for 1-10 minutes.
In the preparation process, the protective atmosphere is a mixed gas of inert gas and hydrogen, the volume ratio of the inert gas to the hydrogen is 1:1, and the inert gas comprises one or more than two of helium, neon and argon.
According to the ultra-fast preparation method of the hexagonal boron nitride film, the thickness, the grain size and the crystallinity of the hexagonal boron nitride film are controlled by changing the components, the thickness and the initial temperature of a matrix.
The technical parameters of the hexagonal boron nitride film are as follows: the thickness is 0.7 nm-1000 nm, and the grain size is 1 nm-100 μm.
The ultra-fast preparation method of the hexagonal boron nitride film comprises the steps of utilizing a quenching method to grow the hexagonal boron nitride film on the surface of a substrate, and separating the hexagonal boron nitride film from the surface of the substrate by adopting an etching method or using the hexagonal boron nitride film and the substrate together; wherein the etchant comprises one or more than two of dilute nitric acid, dilute hydrochloric acid and dilute hydrochloric acid.
The design principle of the invention is as follows:
after the metal boride matrix is heated to a certain temperature, the metal boride matrix is placed in liquid nitrogen, and after the liquid nitrogen contacts with the high-temperature metal boride matrix, a large amount of nitrogen atoms can be generated by rapid catalytic decomposition, and then the hexagonal boron nitride film is grown by reaction with boron atoms on the surface of the matrix. Meanwhile, due to the rapid cooling effect of the liquid nitrogen, the temperature of the matrix can be rapidly reduced, namely quenching. When the substrate temperature is reduced to a certain degree, the boron nitride film stops growing. The growth rate is very fast because the substrate is in a high-concentration total nitrogen environment around the substrate in the growth process, and the growth of the boron nitride film occurs in the substrate cooling process, and the substrate cooling rate in liquid nitrogen is very fast.
The invention has the advantages and beneficial effects that:
1. the invention provides a brand-new ultra-fast preparation method of the hexagonal boron nitride film, which can complete the growth of the hexagonal boron nitride film within a few seconds and has the advantages of simple process, high efficiency, low requirements on equipment, convenient operation, low cost, easy performance regulation and batch preparation.
2. The invention can prepare hexagonal boron nitride film, powder, complex macroscopic body and other structures, can regulate and control the layer number and grain size, and can also be used for directly preparing hexagonal boron nitride and matrix composite materials.
3. The thickness of the obtained hexagonal boron nitride is 0.7-1000 nm, the grain size is 1-100 mu m, and the shape and the size depend on the shape and the size of a used matrix.
4. The invention lays a foundation for the application of the hexagonal boron nitride film in the fields of electronic devices, corrosion and wear resistant coatings, thermal management, ion transport and the like.
Description of the drawings:
fig. 1: schematic diagram of ultra-fast preparation of boron nitride film by quenching method.
Fig. 2: fe with a thickness of 5mm at an initial temperature of 1200 DEG C 2 And quenching the B matrix in liquid nitrogen to prepare the hexagonal boron nitride film. a is the Fe growing on 2 B transfer to SiO after substrate 2 Optical photomicrographs of hexagonal boron nitride film on Si substrate, b-plot transferred to SiO 2 Large area Raman mapping of hexagonal boron nitride film on Si substrate, c is transferred to SiO 2 Raman spectra of hexagonal boron nitride film on Si substrate (in the figure, the abscissa Raman Shift represents Raman Shift cm -1 The ordinate Intensity represents the relative Intensity a.u.), d-plot is the transfer to SiO 2 Atomic force microscope photograph of hexagonal boron nitride film on Si substrate.
Fig. 3: co with a thickness of 5mm at an initial temperature of 1200 DEG C 2 And quenching the B matrix in liquid nitrogen to prepare the hexagonal boron nitride film. Graph a shows Co grown on 2 B transfer to SiO after substrate 2 Optical photomicrographs of hexagonal boron nitride film on Si substrate, b-plot transferred to SiO 2 Large area Raman mapping of hexagonal boron nitride film on Si substrate, c is transferred to SiO 2 Raman spectra of hexagonal boron nitride film on Si substrate (in the figure, the abscissa Raman Shift represents Raman Shift cm -1 The ordinate Intensity represents the relative Intensity a.u.), d-plot is the transfer to SiO 2 Atomic force microscope photograph of hexagonal boron nitride film on Si substrate, e-picture is transmission electron microscope photograph of hexagonal boron nitride film, f-picture is hexagonalSelected area electron diffraction patterns of square boron nitride films.
The specific embodiment is as follows:
in the specific implementation process, the metal boride matrix is heated to a preset temperature under the protection of gas, the adopted heating method comprises high-frequency electromagnetic induction heating, resistance wire heating, electric heating furnace heating and the like, then the high-temperature matrix is placed into liquid nitrogen for rapid cooling (quenching), the liquid nitrogen is catalytically cracked into nitrogen atoms in the quenching process, and then the nitrogen atoms react with boron atoms on the surface of the matrix to grow the hexagonal boron nitride film. It is subsequently etched away from the substrate surface or used directly with the substrate.
The invention is further described below by way of examples and figures.
Example 1
First, this embodiment will be Fe 2 B alloy matrix (20 mm multiplied by 10mm multiplied by 5mm, purity is 99.99 wt%) is placed on the upper portion of high-frequency induction heating coil, in order to prevent oxide on the surface of matrix from affecting growth of hexagonal boron nitride film, in the mixed atmosphere of argon gas and hydrogen gas (volume ratio of argon gas and hydrogen gas is 1:1) the high-temp. 1200 deg.C is annealed for 5 min, then placed in liquid nitrogen and quickly cooled (quenched), in the course of quenching the hexagonal boron nitride film is grown in Fe 2 B alloy substrate surface, wait for Fe 2 And (5) cooling the alloy matrix to room temperature and taking out.
Then, fe with a hexagonal boron nitride film was coated with an ethyl lactate solution of polymethyl methacrylate (PMMA) (polymethyl methacrylate 4 wt.%) 2 And (3) uniformly spin-coating the surface of the alloy matrix for 60s at a rotation speed of 2000 rpm by using a spin coater, and then baking at 180 ℃ for 20 minutes and naturally cooling. Fe to be covered with PMMA/hexagonal boron nitride 2 Soaking the B alloy matrix in dilute nitric acid solution with the depth of 2wt% for 2 hours until the PMMA/hexagonal boron nitride composite film and Fe are obtained 2 After the B alloy matrix is separated, the PMMA/hexagonal boron nitride composite film is transferred to SiO 2 And (3) dissolving and removing PMMA on the Si matrix by using acetone at the temperature of 70 ℃ to finish the transfer of the hexagonal boron nitride film. Wherein SiO is 2 The Si matrix is SiO deposited on the surface of the monocrystalline Si sheet with nano-scale thickness 2 Film, siO 2 The thickness of the film was 290nm.
The uniformity, the number of layers and the domain size of the hexagonal boron nitride film are characterized by utilizing an optical microscope, an atomic force microscope and a Raman spectrometer, so that the obtained hexagonal boron nitride film is a few-layer film, the average thickness is 2nm, the average domain size is 48nm, and the crystallization quality in the domain is good.
Example 2
First, this embodiment will be Fe 83 B 17 The alloy substrate (20 mm multiplied by 10mm multiplied by 5mm, the purity is 99.99 wt%) is placed on the upper portion of high-frequency induction heating coil, in order to prevent the oxide on the surface of the substrate from affecting the growth of hexagonal boron nitride film, in the mixed atmosphere of argon gas and hydrogen gas (volume ratio of argon gas and hydrogen gas is 1:1) the high-temperature annealing for 5 min at 1200 deg.C is implemented, then placed in liquid nitrogen and quickly cooled (quenched), in the course of quenching the hexagonal boron nitride film is grown in Fe 83 B 17 Alloy substrate surface, to be Fe 83 B 17 And cooling the alloy matrix to room temperature and taking out.
Then, fe with a hexagonal boron nitride film was coated with an ethyl lactate solution of polymethyl methacrylate (PMMA) (polymethyl methacrylate 4 wt.%) 83 B 17 The alloy substrate surface is uniformly spin-coated for 60s by a spin coater at 2000 rpm, and then is baked at 180 ℃ for 20 minutes and naturally cooled. Fe to be covered with PMMA/hexagonal boron nitride 83 B 17 Soaking the alloy matrix in 2% dilute nitric acid solution for 2h, and obtaining the PMMA/hexagonal boron nitride composite film and Fe 83 B 17 After the alloy matrix is separated, the PMMA/hexagonal boron nitride composite film is transferred to SiO 2 And (3) dissolving and removing PMMA on the Si matrix by using acetone at the temperature of 70 ℃ to finish the transfer of the hexagonal boron nitride film. Wherein SiO is 2 The Si matrix is SiO deposited on the surface of the monocrystalline Si sheet with nano-scale thickness 2 Film, siO 2 The thickness of the film was 290nm.
The uniformity, the number of layers and the domain size of the hexagonal boron nitride film are characterized by utilizing an optical microscope, an atomic force microscope and a Raman spectrometer, so that the obtained hexagonal boron nitride film is a few-layer film, the average thickness is 3nm, the average domain size is 60nm, and the crystallization quality in the domain is good.
Example 3
Firstly, in the embodiment, a FeB alloy substrate (20 mm multiplied by 10mm multiplied by 5mm, the purity is 99.99 wt%) is placed on the upper part of a high-frequency induction heating coil, in order to avoid the influence of oxide on the surface of the substrate on the growth of a hexagonal boron nitride film, the alloy substrate is annealed at a high temperature of 1300 ℃ for 5 minutes in a mixed atmosphere of argon and hydrogen (the volume ratio of the argon to the hydrogen is 1:1) in advance, then the alloy substrate is placed in liquid nitrogen for rapid cooling (quenching), the hexagonal boron nitride film grows on the surface of the FeB alloy substrate in the quenching process, and the alloy substrate is taken out after the temperature of the FeB alloy substrate is reduced to room temperature.
Then, the surface of the FeB alloy substrate on which the hexagonal boron nitride film was grown was covered with a solution of polymethyl methacrylate (PMMA) in ethyl lactate (polymethyl methacrylate 4 wt%), spin-coated uniformly at 2000 rpm for 60 seconds using a spin coater, and then baked at 180℃for 20 minutes and then cooled naturally. Soaking a FeB alloy matrix covered with PMMA/hexagonal boron nitride in 2% dilute nitric acid solution for 2h, and transferring the PMMA/hexagonal boron nitride composite film to SiO after the PMMA/hexagonal boron nitride composite film is separated from the FeB alloy matrix 2 And (3) dissolving and removing PMMA on the Si matrix by using acetone at the temperature of 70 ℃ to finish the transfer of the hexagonal boron nitride film. Wherein SiO is 2 The Si matrix is SiO deposited on the surface of the monocrystalline Si sheet with nano-scale thickness 2 Film, siO 2 The thickness of the film was 290nm.
The uniformity, the number of layers and the domain size of the hexagonal boron nitride film are characterized by utilizing an optical microscope, an atomic force microscope and a Raman spectrometer, so that the obtained hexagonal boron nitride film is a few-layer film, the average thickness is 10nm, the average domain size is 100nm, and the crystallization quality in the domain is good.
Example 4
First, the present embodiment will be Co 2 A B alloy substrate (20 mm. Times.10 mm. Times.5 mm, purity: 99.99 wt%) was placed on top of the high-frequency induction heating coil, and in order to avoid the influence of the oxide on the surface of the substrate on the growth of the hexagonal boron nitride film, a mixed atmosphere of argon and hydrogen (argonThe volume ratio of gas to hydrogen is 1:1), annealing is carried out for 5 minutes at 1200 ℃ and then the annealing is carried out in liquid nitrogen for rapid cooling (quenching), and the hexagonal boron nitride film grows on Co during the quenching process 2 B alloy substrate surface, waiting for Co 2 And (5) cooling the alloy matrix to room temperature and taking out.
Then, co with hexagonal boron nitride film was coated with a solution of polymethyl methacrylate (PMMA) in ethyl lactate (polymethyl methacrylate 4 wt.%) 2 And (3) uniformly spin-coating the surface of the alloy matrix for 60s at a rotation speed of 2000 rpm by using a spin coater, and then baking at 180 ℃ for 20 minutes and naturally cooling. Co to be covered with PMMA/hexagonal boron nitride 2 Soaking the B alloy matrix in 2% dilute nitric acid solution for 2h, and obtaining PMMA/hexagonal boron nitride composite film and Co 2 After the B alloy matrix is separated, the PMMA/hexagonal boron nitride composite film is transferred to SiO 2 And (3) dissolving and removing PMMA on the Si matrix by using acetone at the temperature of 70 ℃ to finish the transfer of the hexagonal boron nitride film. Wherein SiO is 2 The Si matrix is SiO deposited on the surface of the monocrystalline Si sheet with nano-scale thickness 2 Film, siO 2 The thickness of the film was 290nm.
The uniformity, the number of layers and the domain size of the hexagonal boron nitride film are characterized by utilizing an optical microscope, an atomic force microscope and a Raman spectrometer, so that the obtained hexagonal boron nitride film is 1-2 layers of films, the average thickness is 1.2nm, the average domain size is 60nm, and the crystallization quality in the domain is good.
Example 5
First, the present embodiment will be Co 82 B 18 Alloy substrate (20 mm x 10mm x 5mm, purity 99.99 wt%) is placed on the upper portion of high-frequency induction heating coil, in order to prevent oxide on the surface of the substrate from affecting growth of hexagonal boron nitride film, in the mixed atmosphere of argon gas and hydrogen gas (volume ratio of argon gas and hydrogen gas is 1:1) the high-temp. annealing for 5 min at 1100 deg.C is implemented, then it is placed in liquid nitrogen and quickly cooled (quenched), in the course of quenching the hexagonal boron nitride film is grown on Co 82 B 18 Alloy substrate surface to Co 82 B 18 And cooling the alloy matrix to room temperature and taking out.
Then, by means of aggregationEthyl lactate solution of methyl methacrylate (PMMA) (polymethyl methacrylate 4 wt%) was coated on Co with hexagonal boron nitride film 82 B 18 The alloy substrate surface is uniformly spin-coated for 60s by a spin coater at 2000 rpm, and then is baked at 180 ℃ for 20 minutes and naturally cooled. Co to be covered with PMMA/hexagonal boron nitride 82 B 18 Soaking the alloy matrix in 2% dilute nitric acid solution for 2h, and obtaining PMMA/hexagonal boron nitride composite film and Co 82 B 18 After the alloy matrix is separated, the PMMA/hexagonal boron nitride composite film is transferred to SiO 2 And (3) dissolving and removing PMMA on the Si matrix by using acetone at the temperature of 70 ℃ to finish the transfer of the hexagonal boron nitride film. Wherein SiO is 2 The Si matrix is SiO deposited on the surface of the monocrystalline Si sheet with nano-scale thickness 2 Film, siO 2 The thickness of the film was 290nm.
The uniformity, the number of layers and the domain size of the hexagonal boron nitride film are characterized by utilizing an optical microscope, an atomic force microscope and a Raman spectrometer, so that the obtained hexagonal boron nitride film is a single-layer film, the average thickness is 0.7nm, the average domain size is 20nm, and the crystallization quality in the domain is good.
Example 6
First, the present embodiment uses Ni 2 B alloy matrix (20 mm multiplied by 10mm multiplied by 5mm, purity is 99.99 wt%) is placed on the upper portion of high-frequency induction heating coil, in order to prevent oxide on the surface of matrix from affecting growth of hexagonal boron nitride film, in the mixed atmosphere of argon gas and hydrogen gas (volume ratio of argon gas and hydrogen gas is 1:1) the high-temp. annealing for 5 min at 1100 deg.C is implemented, then it is placed in liquid nitrogen and quickly cooled (quenched), in the course of quenching the hexagonal boron nitride film is grown on Ni film 2 B alloy substrate surface, wait Ni 2 And (5) cooling the alloy matrix to room temperature and taking out.
Then, ni on which a hexagonal boron nitride film was grown was covered with an ethyl lactate solution of polymethyl methacrylate (PMMA) (polymethyl methacrylate 4 wt.%) 2 And (3) uniformly spin-coating the surface of the alloy matrix for 60s at a rotation speed of 2000 rpm by using a spin coater, and then baking at 180 ℃ for 20 minutes and naturally cooling. Ni to be covered with PMMA/hexagonal boron nitride 2 Soaking the B alloy matrix in 2% dilute nitric acid solution for 2h until PMMA/hexagonal boron nitride composite film and Ni are obtained 2 After the B alloy matrix is separated, the PMMA/hexagonal boron nitride composite film is transferred to SiO 2 And (3) dissolving and removing PMMA on the Si matrix by using acetone at the temperature of 70 ℃ to finish the transfer of the hexagonal boron nitride film. Wherein SiO is 2 The Si matrix is SiO deposited on the surface of the monocrystalline Si sheet with nano-scale thickness 2 Film, siO 2 The thickness of the film was 290nm.
The uniformity, the number of layers and the domain size of the hexagonal boron nitride film are characterized by utilizing an optical microscope, an atomic force microscope and a Raman spectrometer, so that the obtained hexagonal boron nitride film is a single-layer film, the average thickness is 0.7nm, the average domain size is 25nm, and the crystallization quality in the domain is good.
Example 7
Firstly, the embodiment adopts a common vertical furnace (the bottom of a quartz tube of the vertical furnace is connected with a metal container filled with liquid nitrogen by a flange) to realize the ultra-fast preparation of hexagonal boron nitride powder. The upper end of the vertical furnace is provided with a mixed atmosphere air inlet of argon and hydrogen, and Co is added into the furnace 2 And (3) placing the powder B in a molybdenum boat, placing the powder B in the center of a hearth by using a push-pull rod (the temperature of the center of the hearth is always kept at 1200 ℃), and after the powder B rises to 1200 ℃ in a mixed atmosphere of argon and hydrogen (the volume ratio of the argon to the hydrogen is 1:1), enabling the powder B to fall into a metal container filled with liquid nitrogen to be rapidly cooled (quenched), and completing the growth of hexagonal boron nitride powder in the quenching process. After the liquid nitrogen is volatilized, obtaining Co coated with boron nitride 2 And (B) powder.
Then, the boron nitride coated Co 2 The powder B is put into 2 percent of dilute hydrochloric acid solution until Co 2 And (3) completely dissolving the powder B, filtering to obtain hexagonal boron nitride powder, and drying the hexagonal boron nitride powder in a vacuum oven at the constant temperature of 90 ℃ to obtain the hexagonal boron nitride powder. The quality, uniformity and layer number of the hexagonal boron nitride powder are characterized by utilizing an optical microscope, a scanning electron microscope and a Raman spectrometer, and the obtained hexagonal boron nitride powder is few layers of hexagonal boron nitride, has an average thickness of 2nm and has higher quality.
As shown in fig. 1, a schematic diagram of ultra-fast preparation of hexagonal boron nitride film by quenching method is provided. And heating the metal boride matrix to a preset temperature under an inert protective atmosphere (argon is mixed with hydrogen to isolate water from oxygen), then placing the high-temperature metal boride matrix in liquid nitrogen, rapidly cooling (quenching) to room temperature, and rapidly growing a hexagonal boron nitride film on the surface of the matrix.
As shown in FIG. 2, the hexagonal boron nitride film obtained in example 1 was a few layers, the average thickness was 2nm, and the average domain size was 48nm.
As shown in FIG. 3, the hexagonal boron nitride film obtained in example 4 was 1 to 2 layers, the average thickness was 1.2nm, and the average domain size was 60nm.
The results show that the hexagonal boron nitride film can be rapidly grown by adopting a high-temperature metal boride matrix and rapidly cooling (quenching) the metal boride matrix in liquid nitrogen, and then the hexagonal boron nitride film is obtained by etching the matrix or is directly used together with the matrix. The film and powder can be prepared by using matrixes with different shapes, and the number of layers and grain size of the hexagonal boron nitride can be regulated and controlled by changing the components, thickness and initial temperature of the matrixes. The invention has the characteristics of simple process, high efficiency, low requirement on equipment, convenient operation, low cost, adjustable product thickness and grain size, suitability for large-area preparation and batch preparation, and the like. The invention lays a foundation for the application of the hexagonal boron nitride film in the fields of electronic devices, corrosion and wear resistant coatings, thermal management, ion transport and the like.
Claims (7)
1. The ultra-fast preparation method of the hexagonal boron nitride film is characterized in that a high-temperature metal boride matrix is adopted, the metal boride matrix is rapidly cooled in a liquid nitrogen source through quenching in an inert protective atmosphere, the liquid nitrogen source is catalytically cracked into nitrogen atoms in the quenching process, and then the nitrogen atoms react with boron atoms on the surface of the matrix to grow the hexagonal boron nitride film;
the metal boride matrix is in any shape of foil, porous foam, powder or block, and the metal boride is FeB or Fe 2 B、Fe 83 B 17 、NiB 2 、NiB、Ni 4 B 3 、Ni 2 B、Ni 3 B、Ni 83 B 17 、CoB、Co 2 B or Co 82 B 18 。
2. The ultra-fast preparation method of a hexagonal boron nitride film according to claim 1, wherein the liquid nitrogen source is liquid nitrogen.
3. The ultra-fast preparation method of the hexagonal boron nitride film according to claim 1, wherein the initial temperature of the high-temperature metal boride substrate is more than 700 ℃ and is lower than the gasification or decomposition temperature of the substrate, and the temperature is kept for 1-10 minutes.
4. The ultra-fast preparation method of the hexagonal boron nitride film according to claim 1, wherein in the preparation process, the protective atmosphere is a mixed gas of inert gas and hydrogen, the volume ratio of the inert gas to the hydrogen is 1:1, and the inert gas is one or more than two of helium, neon and argon.
5. The ultra-fast preparation method of the hexagonal boron nitride film according to claim 1, wherein the control of the thickness, grain size and crystallinity of the hexagonal boron nitride film is achieved by changing the composition, thickness and starting temperature of the matrix.
6. The ultra-fast preparation method of the hexagonal boron nitride film according to claim 5, wherein the technical parameters of the hexagonal boron nitride film are as follows: the thickness is 0.7nm to 1000nm, and the grain size is 1nm to 100 μm.
7. The ultra-fast preparation method of the hexagonal boron nitride film according to claim 1, wherein the hexagonal boron nitride film grown on the surface of the substrate by the quenching method is separated from the surface of the substrate by the etching method or is used together with the substrate; wherein the etchant is one or more of dilute nitric acid, dilute hydrochloric acid and dilute hydrochloric acid.
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| CN106082148A (en) * | 2016-06-21 | 2016-11-09 | 江苏大学 | A kind of method utilizing liquid nitrogen gasification preparation two dimension hexagonal boron nitride nanosheet |
| CN111377418A (en) * | 2020-03-23 | 2020-07-07 | 河北工业大学 | Synthesis method of porous hexagonal boron nitride |
| CN114275746A (en) * | 2022-01-04 | 2022-04-05 | 山东晶亿新材料有限公司 | Hexagonal boron nitride nanosheet and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106082148A (en) * | 2016-06-21 | 2016-11-09 | 江苏大学 | A kind of method utilizing liquid nitrogen gasification preparation two dimension hexagonal boron nitride nanosheet |
| CN111377418A (en) * | 2020-03-23 | 2020-07-07 | 河北工业大学 | Synthesis method of porous hexagonal boron nitride |
| CN114275746A (en) * | 2022-01-04 | 2022-04-05 | 山东晶亿新材料有限公司 | Hexagonal boron nitride nanosheet and preparation method thereof |
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