KR102232618B1 - Manufacturing method for hexagonal boron nitride thin film and opto-electronic elements comprising thin film prepared from the same - Google Patents

Abstract

The present invention relates to a method of manufacturing a hexagonal boron nitride thin film and a photoelectric device having a thin film prepared therefrom, and in more detail, (S1) forming a graphene layer or a graphene oxide layer on a substrate; And (S2) heat treatment by an organometallic chemical vapor deposition (MOCVD) method while supplying a boron-containing precursor and a nitrogen-containing precursor on the graphene layer or the graphene oxide layer, and then hexagonal nitride on the graphene layer or the graphene oxide layer. It relates to a method for manufacturing a hexagonal boron nitride thin film including forming a boron thin film, and to a photoelectric device having a thin film prepared therefrom.

Description

TECHNICAL FIELD The manufacturing method of a hexagonal boron nitride thin film and an optoelectronic device having a thin film manufactured therefrom TECHNICAL FIELD

The present invention relates to a method of manufacturing a hexagonal boron nitride thin film and a photoelectric device having a thin film prepared therefrom, and more particularly, to a hexagonal nitride which can produce a high-quality multilayer thin film having a single crystal orientation in a large area. It relates to a method of manufacturing a boron thin film and a photoelectric device having a thin film manufactured therefrom.

Two-dimensional nanostructured materials are materials that have a certain planar shape and consist of one or several layers of atoms, and are considered one of the most active research fields in the fields of chemistry and materials. Research topics are diversifying.

Typical two-dimensional nanostructure materials include graphene and boron nitride, among which boron nitride has the formula of BN, boron atoms and nitrogen atoms form a planar two-dimensional hexagonal structure, and has a hexagonal structure similar to graphite. It is a material with high physical and chemical stability because its chemical and physical properties are similar to graphite. It is stable up to 3,000 ℃ in an inert atmosphere, and has high thermal shock resistance due to the high thermal conductivity of stainless steel, and there is no crack or damage even after repeated rapid heating and rapid cooling of 1,500 ℃. And, it is very excellent in high temperature lubricity and corrosion resistance.

In addition, the electrical resistance value is remarkably high. In particular, it can be used as an electrical insulating material in a wide temperature range due to the small change in the electrical resistance value at high temperature, and has the characteristic of emitting ultraviolet rays when an electric field is applied. In addition, boron nitride, like graphene, is impermeable to all gases and liquids, is transparent, and has excellent elasticity due to the spatial margin of a hexagonal honeycomb structure in which boron atoms and nitrogen atoms are connected like a net. The unique structure and physical properties of boron nitride can be applied as an insulator of a semiconductor material, an ultraviolet ray generator, a barrier film, and the like.

Recently, as the demand and interest in nanotechnology has increased, research is being conducted to obtain boron nitride in the form of nanosheets and nanotubes. Currently, methods for manufacturing hexagonal boron nitride (h-BN) nanosheets include mechanical peeling, liquid phase peeling, and chemical vapor deposition (CVD), and generally CVD method and liquid phase peeling method. It is used in the manufacture of this hexagonal boron nitride nanosheet.

The liquid phase peeling method is a method of separating multi-layer boron nitride from hexagonal boron nitride through ultrasonic treatment in a solvent, and has a disadvantage in that it is simple to manufacture but difficult to mass-produce. The CVD method is a method of depositing a catalytic metal on a substrate to form a thin metal film, flowing a gas containing boron and nitrogen at a high temperature of 1,000°C or higher, and cooling it to obtain a boron nitride nanosheet formed on the metal film. There is a disadvantage in that it is difficult to manufacture in an area.

Accordingly, an object of the present invention is to provide a method of manufacturing a hexagonal boron nitride thin film capable of manufacturing a high-quality multilayer hexagonal boron nitride thin film having a single crystal orientation in a large area.

Further, another object of the present invention is to provide a photoelectric device having a hexagonal boron nitride thin film manufactured through the above manufacturing method.

In order to achieve the above object, a method of manufacturing a hexagonal boron nitride thin film according to an aspect of the present invention includes: (S1) forming a graphene layer or a graphene oxide layer on a substrate; And (S2) heat treatment by an organometallic chemical vapor deposition (MOCVD) method while supplying a boron-containing precursor and a nitrogen-containing precursor on the graphene layer or the graphene oxide layer, and then hexagonal nitride on the graphene layer or the graphene oxide layer. And forming a boron thin film.

Here, the (S2) step, a first heat treatment step of heat treatment at a temperature of 1,000 to 1,200 ℃; A low temperature treatment step of heat treatment at a temperature of 700 to 900°C; And it may include a high-temperature treatment step of heat treatment at a temperature of 1,250 to 1,450 ℃.

In this case, the first heat treatment step may be performed for 1 to 5 minutes, the low temperature treatment step may be performed for 3 to 10 minutes, and the high temperature treatment step may be performed for 1 to 5 hours.

In addition, the step (S2) may be to supply the boron-containing precursor and the nitrogen-containing precursor in pulses so that the boron-containing precursor and the nitrogen-containing precursor are alternately supplied.

In this case, the pulse width of the pulse supply may be 1 to 10 seconds, and the pulse repetition interval may be 2 to 20 seconds.

Meanwhile, the substrate is sapphire (Al ₂ O ₃ ), silicon (Si), silicon carbide (SiC), gallium nitride (GaN), gallium arsenide (GaAs), zinc oxide (ZnO), gallium oxide (Ga ₂ O). ₃ ), lithium aluminum oxide (LiAlO ₂ ), aluminum nitride (AlN), germanium (Ge), silicon germanium (SiGe), lithium gallium oxide (LiGaO ₂ ), or magnesium aluminum oxide (MgAl ₂ O ₄ ). I can.

In addition, the boron-containing precursor may be (CH ₃ CH ₂ ) ₃ B, (CH ₃ ) ₃ B or a mixture thereof.

In addition, the nitrogen-containing precursor may be _{NH 3.}

Meanwhile, the photoelectric device according to another aspect of the present invention includes a hexagonal boron nitride thin film manufactured by the method of the present invention described above.

According to the method of manufacturing a hexagonal boron nitride thin film according to an embodiment of the present invention, a graphene layer or a graphene oxide layer formed on a substrate without directly forming a hexagonal boron nitride (h-BN) thin film on the substrate By forming an h-BN thin film on the substrate, crystal defects of the h-BN thin film caused by a difference in lattice constant from the substrate can be reduced, thereby producing a high-quality h-BN thin film.

In addition, unlike the case of manufacturing an h-BN thin film using a conventional metal catalyst, it is possible to manufacture a multilayer h-BN thin film having a single crystal orientation by using an organometallic chemical vapor deposition (MOCVD) method. have.

In addition, the h-BN thin film manufactured by the manufacturing method of the present invention has a high energy bandgap (6.5 eV), and thus can be used as a light-emitting and light-receiving device in a deep ultraviolet (Deep Ultra Violet) region.

Furthermore, it can be used as a substrate for a photoelectric device because it is flexible like graphene and has excellent mechanical and chemical stability.

The following drawings attached to the present specification illustrate preferred embodiments of the present invention, and serve to further understand the technical idea of the present invention together with the detailed description of the present invention to be described later. It is limited to and should not be interpreted.
1 is a diagram schematically showing a state in which an h-BN thin film layer is formed on a substrate according to an embodiment of the present invention.
2 is a diagram showing a method of supplying a pulse of a precursor according to an embodiment of the present invention.
3 is a view showing a change in temperature according to a growth time of an h-BN thin film according to an embodiment of the present invention.
4 is a TEM image of an h-BN thin film formed on a substrate according to an embodiment of the present invention.
5 is an ultraviolet-visible ray spectroscopy graph of an h-BN thin film formed on a substrate according to an embodiment and a comparative example of the present invention.
6 is a graph showing a comparison of the reactivity of an ultraviolet wavelength of a photodetector manufactured using an h-BN thin film formed on a substrate according to an embodiment of the present invention and a comparative example, and a view showing an electrode used for measurement thereof.

Hereinafter, the present invention will be described in detail with reference to the drawings. The terms or words used in the specification and claims should not be construed as being limited to their usual or dictionary meanings, and the inventor may appropriately define the concept of terms in order to describe his own invention in the best way. It should be interpreted as a meaning and concept consistent with the technical idea of the present invention based on the principle that there is.

Therefore, the configuration described in the present specification is only the most preferred embodiment of the present invention and does not represent all the technical spirit of the present invention, so there are various equivalents and modifications that can replace them at the time of the present application. It should be understood that you can.

1 is a diagram schematically showing a state in which an h-BN thin film layer is formed on a substrate according to an embodiment of the present invention.

Referring to FIG. 1, a method of manufacturing a hexagonal boron nitride thin film according to an aspect of the present invention includes: (S1) forming a graphene layer or a graphene oxide layer 20 on a substrate 10; And (S2) heat treatment by an organometallic chemical vapor deposition (MOCVD) method while supplying a boron-containing precursor and a nitrogen-containing precursor on the graphene layer or the graphene oxide layer 20, and the graphene layer or the graphene oxide layer 20 ) And forming a hexagonal boron nitride thin film 30 on it.

Conventionally, a hexagonal boron nitride (h-BN) thin film was prepared by directly forming it on a substrate. At this time, crystal defects of the h-BN thin film occur due to the difference in lattice constant from the substrate, resulting in poor quality of the h-BN thin film. There was a problem.

However, according to the present invention, without directly forming the h-BN thin film 30 on the substrate 10, after transferring the graphene layer 20 on the substrate 10, the transferred graphene layer 20 By forming the h-BN thin film 30 on the substrate 10, crystal defects of the h-BN thin film 30 caused by a difference in lattice constant from the substrate 10 can be reduced, thereby manufacturing a high-quality h-BN thin film 30. .

Furthermore, unlike the case of manufacturing an h-BN thin film using a conventional metal catalyst, it is possible to manufacture a multilayer h-BN thin film having a single crystal orientation by using an organometallic chemical vapor deposition (MOCVD) method. I can.

In this case, the graphene layer 20 transferred onto the substrate 10 may be prepared by a chemical vapor deposition (CVD) method. In a more detailed description of the step of transferring the graphene layer 20 onto the substrate 10, after synthesizing graphene on the catalyst metal layer through a chemical vapor deposition (CVD) method, a carrier is formed on the graphene. After attaching to form a first structure, the catalyst metal layer is removed from the first structure to form a second structure, and then plasma treatment is performed on the target substrate, that is, the substrate 10 to which the graphene layer 20 is to be transferred. After that, the graphene of the second structure and the target substrate 10 are pressed to face each other to form a third structure, and then the graphene layer 20 is transferred onto the substrate 10 by removing the carrier. I can make it.

The graphene layer 20 is for controlling defects caused by a mismatch between the substrate 10 and the h-BN thin film 30. The inconsistency value of the lattice constant between the sapphire substrate and the h-BN thin film generally used is approximately 46.5%, and can be derived by the following equation.

Lattice constant mismatch value (%) = 100*(b-a)/a

(a: lattice constant of h-BN thin film, b: lattice constant of substrate)

On the other hand, the lattice constant mismatch between the graphene layer 20 and the h-BN thin film 30 is about 1.6%. In the present invention, by transferring the graphene layer 20 having little difference between the h-BN thin film 30 and the lattice constant on the substrate 10, and forming the h-BN thin film 30, high-quality thin film growth is achieved. It becomes possible.

In addition, the graphene oxide layer 20 may also replace the transferred graphene layer 20. The graphene oxide layer 20 is a graphene oxide nanosheet, a reduced graphene oxide nanosheet (in this case, the reduction method may be a thermal or chemical method, etc.), a chemically synthesized graphene nanosheet. It may be a sheet, and as a method of forming the graphene oxide layer 20 on the substrate 10, spray coating, spin coating, or the like may be used.

In addition, the transferred graphene layer 20 may be a single layer, or may be a multilayer of two or more or tens or more. At this time, the graphene layer 20 may have a thickness of several nm, and may have a thickness of several tens to several hundred nm.

The substrate 10 of the present invention is sapphire (Al ₂ O ₃ ), silicon (Si), silicon carbide (SiC), gallium nitride (GaN), gallium arsenide (GaAs), zinc oxide (ZnO), gallium oxide (Ga ₂ O ₃ ), lithium aluminum oxide (LiAlO ₂ ), aluminum nitride (AlN), germanium (Ge), silicon germanium (SiGe), lithium gallium oxide (LiGaO ₂ ), or magnesium aluminum oxide (MgAl ₂ O ₄ ) It may be selected from, but is not limited thereto, as long as the substrate can be stably maintained in a high temperature state of the high-temperature heat treatment step (1,250 to 1,450 °C) when the h-BN thin film 30 is grown. Therefore, any substrate having a melting point higher than the temperature of the high-temperature heat treatment step may be used, and a sapphire substrate may be preferably used.

On the other hand, the (S2) step, a first heat treatment step of heat treatment at a temperature of 1,000 to 1,200 ℃; A low temperature treatment step of heat treatment at a temperature of 700 to 900°C; And a high-temperature treatment step of heat-treating at a temperature of 1,250 to 1,450°C. Preferably, the first heat treatment step may be performed at a temperature of 1,050 to 1,150°C, the low temperature treatment step may be performed at a temperature of 750 to 850°C, and the high temperature treatment step may be performed at a temperature of 1,300 to 1,400°C. Preferably, the first heat treatment step may be performed at a temperature of about 1,100°C, the low temperature treatment step may be performed at a temperature of about 800°C, and the high temperature treatment step may be performed at a temperature of about 1,350°C.

In this case, the first heat treatment step, the low temperature treatment step, and the high temperature treatment step may be performed in a hydrogen atmosphere.

The first heat treatment step is performed to remove contaminants caused by organic substances that may occur during movement of the substrate 10 in a temperature range in which the substrate 10, the graphene layer, or the graphene oxide layer 20 is not thermally decomposed. .

And, the low-temperature treatment step, before the high-temperature treatment step, between the substrate 10 and the h-BN thin film 30 to be grown in the future, the interaction that can be generated by the coefficient of thermal expansion or Van der Waals (Van der Waals) force. It is performed to form an h-BN buffer layer to alleviate the interaction.

In addition, the high-temperature treatment step is a step in which the h-BN thin film 30 is substantially grown, and it is particularly important to maintain the high temperature.

In this case, the first heat treatment step may be performed for 1 to 5 minutes, the low temperature treatment step may be performed for 3 to 10 minutes, and the high temperature treatment step may be performed for 1 to 5 hours.

If the time of the first heat treatment step is shorter than the time, the removal of contaminants by organic substances may not be performed well. If the time is longer than the time, the substrate 10, the graphene layer, or the graphene oxide layer 20 It is not desirable because it may be damaged by heat and thermal decomposition may occur.

And, if the time of the low-temperature treatment step is shorter than the time, the thickness of the h-BN buffer layer may become too thin, but if the thickness of the h-BN buffer layer is too thin, it cannot serve as a buffer layer, and the time is longer than the above time. In this case, the thickness of the h-BN buffer layer, that is, the h-BN layer of low quality, becomes too thick, and the surface roughness of the h-BN thin film may be greatly increased, which is not preferable.

In addition, if the time of the high-temperature treatment step is shorter than the time, the growth of the h-BN thin film 30 may not be performed properly, and even if it is longer than the time, the h-BN thin film 30 The thickness does not increase significantly, and it is uneconomical and is not desirable.

On the other hand, in the step (S2), when supplying a boron-containing precursor and a nitrogen-containing precursor on the graphene layer or the graphene oxide layer 20, hydrogen gas may be used as a carrier for transporting the precursors. When hydrogen gas is used as a carrier, it is preferable that the h-BN thin film 30 can be better grown in a plate-like structure. When an inert gas other than hydrogen gas is used as a carrier, the atoms of the other inert gas have an atomic size larger than that of hydrogen, and as a result, it may be somewhat difficult for the h-BN thin film to grow in a plate-like structure.

In addition, the step (S2) may be to supply the boron-containing precursor and the nitrogen-containing precursor in pulses so that the boron-containing precursor and the nitrogen-containing precursor are alternately supplied.

In this case, the pulse width of the pulse supply may be 1 to 10 seconds, and the pulse repetition interval may be 2 to 20 seconds.

If the boron-containing precursor and the nitrogen-containing precursor are not alternately supplied, but are supplied simultaneously, unwanted pre-reaction may occur between the gaseous precursors in a high-temperature atmosphere, and contamination by oxygen atoms or carbon atoms may occur. Can't do it.

In addition, the boron-containing precursor may be (CH ₃ CH ₂ ) ₃ B, (CH ₃ ) ₃ B or a mixture thereof, but is not limited thereto.

Meanwhile, according to another aspect of the present invention, there is provided a light-emitting and light-receiving device including an h-BN thin film manufactured by the manufacturing method of the present invention described above. The h-BN thin film manufactured according to the present invention has a high energy bandgap (6.5 eV), and thus can be used as a light-emitting and light-receiving device in a deep ultraviolet (Deep Ultra Violet) region.

Further, according to another aspect of the present invention, there is provided an optoelectronic device including an h-BN thin film manufactured by the method of the present invention described above.

Hereinafter, examples will be described in detail to illustrate the present invention in detail. However, the embodiments according to the present invention may be modified in various other forms, and the scope of the present invention should not be construed as being limited to the embodiments described below. The embodiments of the present invention are provided to more completely describe the present invention to those of ordinary skill in the art.

1. Preparation of hexagonal boron nitride (h-BN) thin film

(1) Examples

_{After the graphene is synthesized by heat treatment (chemical vapor deposition, CVD) while introducing CH 4} as a carbon source on the Ni catalyst metal layer, the first structure is formed by attaching a carrier of a polymethyl methacrylate coating film to the formed graphene. After formation, the second structure was formed by removing the Ni catalyst metal layer from the first structure.

Subsequently, after plasma treatment is performed on the sapphire substrate, the graphene of the second structure and the sapphire substrate are pressed to face each other to form a third structure, and then the carrier of the polymethyl methacrylate coating film is removed. The graphene layer was transferred onto the sapphire substrate.

At this time, the transferred graphene layer was composed of a total of 4 layers.

Subsequently, while supplying the boron-containing precursor trimethylboron ((CH ₃ ) ₃ B) and the nitrogen-containing precursor ammonia (NH ₃ ) onto the graphene layer using hydrogen gas as a carrier, organometallic chemical vapor deposition (MOCVD) By heat treatment by the method, a hexagonal boron nitride thin film was formed on the graphene layer.

At this time, the total flow rate of the precursor gases and the hydrogen gas was 10 slm (standard liter per minute), and the flow rate of trimethylboron ((CH ₃ ) ₃ B) was 2.9 μmol/min, ammonia. The flow rate was adjusted to be 500 to 8,000 sccm (standard cubic centimeter per minute).

Then, each pulse was supplied so that the trimethylboron and the ammonia were alternately supplied.

2 is a diagram showing a method of supplying a pulse of a precursor. Referring to FIG. 2, the flow of trimethylboron has a period in which the supply is made for 4 seconds, the supply is cut off for 8 seconds, the supply is made again for 4 seconds, and then the supply is cut off again for 8 seconds. In the case of ammonia, the supply is made for 4 seconds at the midpoint of the time when the supply of trimethylboron is blocked, and then the supply is cut off for 8 seconds, whereby the two precursor gases are alternately supplied with each other. At this time, there is a depletion region in which ammonia is not supplied for 4 seconds before and after the supply of trimethylboron is performed for 2 seconds, respectively.

And, to describe the MOCVD method in more detail, PHAETHON 100U (Top Engineering Co., Ltd.) equipment was used. First, the first heat treatment was performed at 1,100°C for about 3 minutes, and then the temperature was lowered to about 800°C. After performing the heat treatment for 5 minutes, the temperature was raised again and the heat treatment was performed at a temperature of 1,350° C. for about 2 hours to form an h-BN thin film. The change in temperature according to the growth time of the h-BN thin film is shown in FIG. 3. At this time, the pressure inside the MOCVD equipment was maintained to be about 30 to 400 torr.

(2) Comparative example

An h-BN thin film was formed in the same manner as in Example except that the graphene layer was not transferred and the h-BN thin film was directly formed on the sapphire substrate.

2. TEM image measurement of hexagonal boron nitride (h-BN) thin film

Using a spherical aberration correction transmission electron microscope (Cs-Corrected Transmission Electron Microscope, model name: JEM-ARM 200F, hereinafter TEM) equipment, a TEM image of the h-BN thin film prepared according to the Example was obtained.

4 shows a TEM image of an h-BN thin film formed on a substrate by a method according to an embodiment. Referring to FIG. 4, it can be seen that the sapphire substrate, the graphene layer transferred on the sapphire substrate, and the h-BN thin film formed on the transferred graphene layer are distinguished from each other. The transferred graphene layer was observed as a four-layer thin film, and the formed h-BN thin film was rotated about 60° on the transferred graphene layer to confirm that it had a multilayer Bernal Staking (ABAB) structure of about 30 to 35 nm thickness. .

In addition, as a result of SAED (Selected Area Electron Diffraction) analysis, it was confirmed that the transferred graphene layer and the formed h-BN thin film had a hexagonal structure.

In addition, the In-Plane Lattice Constant of the h-BN thin film using DFT (Density Functional Theory) is 0.256 nm, and the In-Plane Lattice Constant of the graphene layer is 0.24 nm, which is similar to the theoretical value. Was confirmed.

3. Comparison of properties of hexagonal boron nitride (h-BN) thin films

5 is an ultraviolet-visible ray spectroscopy graph of an h-BN thin film formed on a substrate according to an embodiment and a comparative example of the present invention.

Referring to FIG. 5, both Examples and Comparative Examples have a high transmittance of about 98% at a wavelength in the 300 to 800 nm region, and h-BN according to the Example compared to the Comparative Example at a wavelength in the 200 to 300 nm region. It was confirmed that the absorption rate of the thin film increased rapidly.

In addition, as a result of calculating the optical bandgap using Tauc's equation based on the results of ultraviolet-visible light analysis, the h-BN thin film according to the embodiment was 5.65 eV, and the h-BN thin film according to the comparative example It was confirmed that it was 5.57 eV. This is similar to the optical band gap (5.56 to 5.92 eV) of the multilayer h-BN thin film known by other previous studies.

6 is a graph showing a comparison of the reactivity of an ultraviolet wavelength of a photodetector manufactured using an h-BN thin film formed on a substrate according to an embodiment of the present invention and a comparative example, and a view showing an electrode used for measurement thereof.

A photodetector was fabricated using the h-BN thin film formed according to the example and the comparative example of the present invention, and an electrode was formed by depositing Ni/Au at 50 nm on the h-BN thin film, respectively, and metal-semiconductor-metal ( MSM) structure, the length of the electrode was 300 ㎛, the width of the electrode was 10 ㎛, the distance between the electrode and the electrode was manufactured to be 5 ㎛.

In order to find out the reactivity of the ultraviolet wavelength of the photodetector manufactured as described above, the dark current (I _{dark ) measured in a dark room atmosphere according to the reverse voltage and the photocurrent (I photo} ) using a 4 W power lamp having a wavelength of 254 nm are used. It was measured.

The dark current of the photodetector fabricated according to the example was found to be 5.70×10 ^-13 A, and the photocurrent was 6.46×10 ^-11 A when a reverse voltage of -100 V was applied, and the dark current of the photo detector fabricated by the comparative example was 4.10. ×10 ^-13 A, photocurrent was confirmed to be ^{1.57 × 10 -12 A.}

Finally, as a result of calculating the ratio (I _photo /I _dark ) of the photocurrent (I _{photo ) to the dark} current (I dark), it was confirmed that the photodetector prepared according to the Example exhibited about 30 times higher reactivity.

On the other hand, the embodiments of the present invention disclosed in the specification and drawings are only presented specific examples to aid understanding, and are not intended to limit the scope of the present invention. It is apparent to those of ordinary skill in the art that other modifications based on the technical idea of the present invention may be implemented in addition to the embodiments disclosed herein.

10: substrate
20: graphene layer or graphene oxide layer
30: hexagonal boron nitride thin film (h-BN thin film)

Claims (9)

(S1) transferring the graphene layer onto the substrate; And
(S2) heat treatment by an organometallic chemical vapor deposition (MOCVD) method while supplying a boron-containing precursor and a nitrogen-containing precursor on the graphene layer to form a hexagonal boron nitride thin film on the graphene layer,
The step (S2) is a method of manufacturing a hexagonal boron nitride thin film comprising forming an h-BN buffer layer through a low temperature treatment step of heat treatment at a temperature of 700 to 900°C. The method of claim 1,
The step (S2) may include a first heat treatment step of heat treatment at a temperature of 1,000 to 1,200°C; And further comprising a high-temperature treatment step of heat treatment at a temperature of 1,250 to 1,450 ℃,
The h-BN buffer layer is a method of manufacturing a hexagonal boron nitride thin film, characterized in that formed between the substrate and the hexagonal boron nitride thin film. The method of claim 2,
The first heat treatment step is performed for 1 minute to 5 minutes,
The low temperature treatment step is performed for 3 to 10 minutes,
The high-temperature treatment step is a method of manufacturing a hexagonal boron nitride thin film, characterized in that it is made for 1 to 5 hours. The method of claim 1,
In the step (S2), the boron-containing precursor and the nitrogen-containing precursor are supplied in a pulse so that the boron-containing precursor and the nitrogen-containing precursor are alternately supplied. Way. The method of claim 4,
The method of manufacturing a hexagonal boron nitride thin film, characterized in that the pulse width of the pulse supply is 1 to 10 seconds, and the pulse repetition interval is 2 to 20 seconds. The method of claim 1,
The substrate is sapphire (Al ₂ O ₃ ), silicon (Si), silicon carbide (SiC), gallium nitride (GaN), gallium arsenide (GaAs), zinc oxide (ZnO), gallium oxide (Ga ₂ O ₃ ) , Lithium aluminum oxide (LiAlO ₂ ), aluminum nitride (AlN), germanium (Ge), silicon germanium (SiGe), lithium gallium oxide (LiGaO ₂ ), or magnesium aluminum oxide (MgAl ₂ O ₄ ). Method for producing a hexagonal boron nitride thin film. The method of claim 1,
The boron-containing precursor is (CH ₃ CH ₂ ) ₃ B, (CH ₃ ) ₃ B, or a mixture thereof. The method of claim 1,
The nitrogen-containing precursor is a method of manufacturing a hexagonal boron nitride thin film, characterized in that _{NH 3.} A photoelectric device comprising a hexagonal boron nitride thin film manufactured by the method of any one of claims 1 to 8.

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