Method for manufacturing boron nitride thin film, and boron nitride thin film

Abstract

To provide a method for manufacturing a boron nitride thin film, operated at low temperature and capable of reducing the risk of thermal damage to a substrate and energy consumption, and the boron nitride film.SOLUTION: A method for manufacturing a boron nitride thin film comprises steps of: supplying a precursor including a boron atom and a nitrogen atom to an energy control device; forming the excitation state of the precursor in the energy control device; and forming a material layer including boron nitride on a substrate. The main feature of the method is the use of the energy control device including a first electromagnetic wave source for radiating an electromagnetic wave having a specific wavelength range; and the method comprises some additional steps for further promoting the formation of the boron nitride thin film.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to a method for producing a thin film and the thin film itself, and more particularly to a method for producing a boron nitride thin film and a boron nitride thin film. The present invention is an invention in the field of thin films, and in particular to a method for producing a boron nitride thin film. [Background technology]

[0002] Boron nitride thin films have attracted widespread attention due to their unique mechanical, thermal, chemical, and electrical properties. These properties make them particularly suitable for use in high-temperature and high-pressure environments, for example in cutting tools, electronic devices, and protective coatings. Boron nitride thin films are typically synthesized using chemical vapor deposition (CVD) and physical vapor deposition (PVD) techniques, using precursors such as boron ureas and aminoboranes.

[0003] However, there are still challenges to synthesize high-quality BN thin films because of the difficulty in controlling the stoichiometry, phase, and microstructure of the thin films. For example, traditional chemical vapor deposition techniques require high-temperature environments, which may cause thermal damage to the substrate and increase energy consumption. On the other hand, physical vapor deposition techniques can be performed at low temperatures, but they have limited stoichiometry and phase control of the thin films. Summary of the Invention [Problem to be solved by the invention]

[0004] Although boron nitride thin films have many excellent properties, there are still many problems in their manufacturing process, making them difficult to put to practical use. Therefore, addressing these problems is a theme that has attracted the attention of those skilled in the art. The present invention aims to solve the above-mentioned problems, and provides a method for producing a boron nitride thin film and a boron nitride thin film itself. [Means for solving the problem]

[0005] In accordance with the objects and other objects of the present invention, the present invention provides a method for producing a boron nitride thin film, which includes the steps of: first, providing a precursor containing boron and nitrogen atoms to an energy control device; then forming an excited state of the precursor in the energy control device; the excited state containing boron and nitrogen atoms, some or all of whose ligands are in a bond-breaking state; and then forming a material layer containing boron nitride on a substrate. In this process, the energy control device includes a first electromagnetic wave source that emits electromagnetic waves within a specific wavelength range.

[0006] In certain embodiments, the precursor is selected from compounds having a 1:1 atomic ratio of boron to nitrogen. Additionally, the precursor may be borazine (B3H6N3), tris(dimethylamino)borane (TDMAB, CH 12 The compound is selected from compounds including boron borane (BN), tetramethylammonium borane, boron urea, aminoborane (BHN), and tris(ethylmethylamino)borane (TEMAB), all of which have a 1:1 atomic ratio of boron to nitrogen. Some embodiments also include forming a substrate bias to reduce particle deposition on the surface of the substrate. [Brief description of the drawings]

[0007] [Figure 1] 2 is a flow chart illustrating an embodiment of a method for forming a boron nitride layer on a substrate in accordance with the present invention. [Figure 2A] FIG. 1 illustrates an embodiment of an energy control device of the present invention. [Figure 2B] FIG. 2 illustrates another embodiment of the energy control device of the present invention. [Diagram 3] FIG. 2 is a diagram showing a substrate on which a boron nitride thin film is formed. [Figure 4] FIG. 2 is a schematic diagram showing the inside of a reaction chamber. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0008] With reference to the working steps shown in FIG. 1, the present invention provides a method for fabricating a boron nitride thin film on a substrate. The method of the present invention starts with supplying a precursor containing boron and nitrogen atoms to an energy control device, as shown in step S110. Here, the precursor is selected from compounds having an atomic ratio of boron to nitrogen of 1:1. The compounds include borazine (boron-nitrogen cyclic compound, B3H6N3), trimethylamine borane (C3H 12 The organic solvent may include one or more selected from the group consisting of tetramethylammonium borohydride, boron nitride, ammonia borane (BH6N), and triethylmethylamine borane (TEMAB).

[0009] Borazine is a colorless liquid at room temperature and is known to be used as a precursor for preparing boron nitride thin films due to its high thermal stability. Tris(dimethylamino)borane is known to be highly reactive and volatile, making it suitable for chemical vapor deposition processes. Tetramethylammonium borohydride is an air-stable compound and can be used as a single source precursor for boron nitride thin films. Boron urea is stable under normal conditions and can be used as a precursor for synthesizing boron nitride nanotubes. Aminoborane is a solid at room temperature and can be used as a precursor for synthesizing boron nitride nanotubes and nanosheets. Tris(ethylmethylamino)borane is a stable compound under normal conditions and can be used as a precursor for synthesizing boron nitride thin films. In the present invention, these compounds are used alone or in combination.

[0010] An embodiment of the energy control device of the present invention will be described in detail with reference to FIG. 1 and FIG. 2A. The energy control device 100 includes a power source 101, a first electromagnetic wave source 102, and a propagation device 103 that emits electromagnetic waves, such as a waveguide or an antenna. The power source 101 provides energy to the first electromagnetic wave source 102 to generate electromagnetic waves. The first electromagnetic wave source 102 is a device that generates electromagnetic waves at a specified wavelength and energy level, and the propagation device 103 directs the electromagnetic waves toward the precursor. The energy control device 100 further includes a control system 104 that adjusts the wavelength and energy of the electromagnetic waves. In this embodiment, the control system 104 includes a microprocessor 104a or other type of controller, and a sensor 104b that monitors the wavelength and energy of the electromagnetic waves. The microprocessor 104a adjusts the operation of the first electromagnetic wave source 102 based on the readings of the sensor 104b to maintain the electromagnetic waves at the desired wavelength and energy level. The energy control device 100 also includes a cooling system 105 and a safety system 106. A cooling system 105 is provided to cool the components of the energy control device 100 and prevent overheating. A safety system 106 is a device for ensuring the safety of the energy control device 100 during operation, and automatically shuts down the device if abnormal operation is detected. Furthermore, the energy control device 100 is provided with channels (not shown) for introducing and discharging precursors.

[0011] In one embodiment of the method, the precursors are introduced into the energy control device 100 under certain temperature conditions. In this embodiment, the temperature is maintained in the range of 25° C. to 400° C. The precursors are introduced into the energy control device 100 by an inert carrier gas, which can be argon, helium, nitrogen, or a combination of these gases. The inert gas is selected depending on its ability to keep the precursors stable and its compatibility with the precursors and the energy control device 100. In this fabrication process, the flow rate of the inert carrier gas can be adjusted to optimize the formation of excited states of the precursors. A high flow rate is used to quickly introduce the precursors into the energy control device, while a low flow rate is used to ensure sufficient interaction between the precursors and the electromagnetic waves. The flow rate can also be adjusted based on the temperature and pressure changes in the energy control device. This allows for dynamic control of the process to form high quality boron nitride thin films on the substrate.

[0012] In one embodiment, the molar fraction of the precursor containing boron and nitrogen atoms in the inert carrier gas is 0.5% to 10%. The flow rate of the inert carrier gas entering the energy control device 100 is set to 20 to 40 sccm (standard cubic centimeters per minute), the vapor pressure in the energy control device 100 is set to 20 torr to 60 torr, and the average residence time of the inert carrier gas is 10 seconds to 100 seconds.

[0013] Continuing to refer to FIG. 1 and FIG. 2A, in step S120, the precursor is brought to a high energy state, i.e., an "excited state", via the energy control device 100. The excited state includes cases where boron and nitrogen atoms are in an excited state, and cases where some or all of the ligands are in a bond-disconnected state. In one embodiment, the first electromagnetic wave source 102 of the energy control device 100 emits controlled electromagnetic waves with a wavelength in the range of 180 nm to 500 nm and an energy in the range of 100 W to 600 W. As another specific embodiment, in addition to the components shown in FIG. 2A, the energy control device 100' includes a second electromagnetic wave source 107 as shown in FIG. 2B. The wavelength range of the second electromagnetic wave source 107 is between 0.5 nm to 180 nm, and the output is 100 W to 600 W. The wavelength of the electromagnetic wave of the second electromagnetic wave source 107 is shorter than that of the first electromagnetic wave source 102. Shorter wavelengths correspond to more energetic photons. These higher energy photons can more effectively excite the precursors and more efficiently form excited states. By adjusting the first electromagnetic wave source 102 and the second electromagnetic wave source 107, the formation of the excited states of the precursors can be optimized.

[0014] Referring to FIG. 1 and FIG. 3, FIG. 3 illustrates a boron nitride thin film formed on a substrate. In step S130, an excited state precursor is induced on at least one surface of the substrate 20. The key to this step is that the precursor is in an excited state. This excited state precursor is in a bond-broken state of the boron and nitrogen atoms, or some or all of the ligands of these atoms. This bond-broken state means that the boron and nitrogen atoms are excited and ready to chemically react with other atoms and molecules. This state is achieved by exposing the precursor to a specific energy condition provided by an energy control device.

[0015] When the excited precursors are introduced to the substrate 20, the excited boron and nitrogen atoms begin to form a new material layer 21 on the substrate, as shown in step S140. This new material layer 21 includes boron nitride, i.e., a boron nitride thin film. The specific properties of the formed boron nitride thin film are determined by the arrangement of the boron and nitrogen atoms on the substrate. In summary, step S130 is mainly to introduce the excited precursors to the substrate and form a material layer including boron nitride on the substrate. The temperature of the substrate 20 in this process is maintained at about 400° C. or less.

[0016] The material layer 21 may include hexagonal boron nitride (h-BN), cubic boron nitride (c-BN), or amorphous boron nitride (a-BN). The different types of crystal structures of boron nitride in the material layer, e.g., h-BN, c-BN, or a-BN, result from different atomic arrangements of the boron and nitrogen atoms in the material layer. These different crystal structures result in different physical and chemical properties that may be advantageous for various applications. For example, h-BN has a layered structure similar to graphite and is very useful as a lubricant. On the other hand, c-BN has a structure similar to diamond, is very hard, and is very useful as a cutting tool. Amorphous boron nitride has a unique disordered structure and has unique physical and chemical properties not found in materials with ordered structures.

[0017] Therefore, amorphous boron nitride may exhibit superior performance in certain specialized applications, such as in high temperature or pressure environments, or where high wear and corrosion resistance is required. Furthermore, the disordered structure of amorphous boron nitride provides excellent thermal and chemical stability, allowing it to maintain its structure and performance even at high temperatures or in chemically harsh environments. For this reason, amorphous boron nitride is widely used in various industrial applications, such as high performance lubricants, wear resistant materials, and corrosion resistant coatings.

[0018] In this embodiment, the material of the substrate 20 is selected from metals, metal alloys, ceramics, polymers, or combinations thereof. Specifically, the material of the metal substrate is selected from aluminum, copper, steel, or combinations thereof. The material of the metal alloy substrate is selected from stainless steel, brass, bronze, or combinations thereof. The material of the ceramic substrate is selected from alumina, zirconia, silicon carbide, or combinations thereof. The material of the polymer substrate is selected from polyethylene, polypropylene, polystyrene, or combinations thereof. The selection of the substrate material is determined by various factors, such as the required properties of the boron nitride thin film, the application of the product, and the conditions under which the product will be used.

[0019] For example, when selecting a substrate material that provides high mechanical strength and excellent wear resistance, a person skilled in the art may choose to use stainless steel or alumina as the substrate material, so that the boron nitride layer formed is strongly bonded to the substrate and can maintain its performance for a long period of time even under harsh operating conditions. On the other hand, when excellent chemical stability in a specific environment is required, zirconia or silicon carbide may be selected as the substrate material, so that the boron nitride layer formed does not deteriorate even in a chemically harsh environment and can provide stable performance.

[0020] It is noted that the substrate 20 may be treated or coated prior to depositing the boron nitride thin film to enhance adhesion between the material layer 21 and the substrate 20. For example, the substrate may be cleaned, roughened, or coated with a primer or adhesion promoter. Additionally, in one embodiment, an electric field, referred to as a substrate bias, may be applied to the substrate 20 to reduce the deposition of charged particles on the surface of the substrate 20. The substrate bias may be either a positive bias or a negative bias depending on the polarity of the charged particles. For example, a positive bias is set if the charged particles are primarily positively charged, and conversely, a negative bias is set if the charged particles are primarily negatively charged.

[0021] The purpose of setting the substrate bias is to improve the quality of the deposited boron nitride by eliminating charged particles that may interfere with the deposition process. When the substrate is biased, the electric field affects the movement of the charged particles, making it more difficult for these particles to deposit directly on the substrate surface. This reduces the random deposition of charged particles on the substrate surface, resulting in a smoother and more uniform layer of material 21. Thus, setting the substrate bias can improve the quality of the boron nitride thin film.

[0022] Please also refer to FIG. 4, which shows a schematic diagram of the inside of the reaction chamber. In one embodiment, step S130 is carried out in a reaction chamber 200 equipped with a plasma source 210. This design aims to increase the formation rate of boron nitride. In this process, the plasma source 210 in the reaction chamber 200 plays an important role. The main function of the plasma source 210 is to generate plasma, which is a gas that contains an equal number of positive and negative charges in an electrically unbalanced state. In this state, the atoms or molecules of the gas are ionized by the energy of the plasma source 210 to form charged particles. These charged particles have high energy and can undergo further chemical reactions with the precursors.

[0023] During the chemical reaction, the charged particles combine with boron and nitrogen atoms in the precursor to form boron nitride. This chemical reaction takes place within the reaction chamber 200 and under the influence of the plasma source 210. Furthermore, the plasma source 210 can take a variety of forms, such as direct current (DC) plasma, radio frequency (RF) plasma, electron cyclotron resonance (ECR) plasma, or a combination of these. Each plasma source type has specific operating conditions and advantages. For example, DC plasma sources are the most common type and use direct current voltage to generate the plasma. RF plasma sources use radio frequency voltage to generate the plasma, operate at low pressures, and can generate high plasma densities. ECR plasma sources use magnetic fields to generate the plasma, operate at very low pressures, and can generate very high plasma densities.

[0024] In this embodiment, the energy output of the plasma source 210 is set to more than 300 W. This energy setting allows the plasma source to effectively generate plasma and provide enough energy to ionize the atoms or molecules of the gas to form charged particles. This energy setting can also be adjusted according to the requirements of a particular application. Furthermore, the plasma is composed of at least one gas selected from argon, helium, nitrogen, hydrogen, ammonia, or combinations thereof. These gases are selected for their ability to effectively generate plasma and their compatibility with the precursors and reaction chamber. For example, argon and helium are the most commonly used plasma gases because they have high ionization energy and generate high density plasma. Nitrogen and hydrogen can be used when a specific chemical reaction is required in the plasma. Ammonia can be used when a chemical reaction involving nitrogen is required in the plasma.

[0025] In summary, the method for producing boron nitride thin films of the present invention has several important advantages over existing methods for depositing boron nitride thin films. First, the method of the present invention produces thin films at low temperatures, which can significantly reduce the risk of thermal damage to the substrate and reduce energy consumption. This low-temperature production method is not only more efficient, but also more environmentally friendly. In addition, the method of the present invention includes several additional options to further enhance the formation of the boron nitride thin film. For example, applying a substrate bias can reduce the deposition of charged particles on the substrate surface and improve the quality of the boron nitride layer. Furthermore, the inclusion of a plasma source in the reaction chamber can increase the rate of boron nitride formation and improve production efficiency. These optional steps make the method for producing thin films of boron nitride more flexible and can be tailored to specific needs.

[0026] As described above, the contents of the present invention have been disclosed based on the preferred embodiments, but they are not intended to limit the present invention. Those skilled in the art can make appropriate changes and modifications without departing from the spirit and scope of the present invention. Therefore, the protection scope of the present invention should be determined by the claims.

Claims

1. (a) providing a precursor comprising boron atoms and nitrogen atoms to an energy control device; (b) forming an excited state of the precursor in the energy control device; (c) forming a layer of material comprising boron nitride on the substrate; the excited state of the precursor comprises a boron atom and a nitrogen atom, or a boron ligand and a nitrogen ligand in a bond dissociation state; The energy control device includes a first electromagnetic wave source that emits electromagnetic waves in a specific wavelength range.

2. 2. The method for producing a boron nitride thin film according to claim 1, wherein the precursor is selected from compounds having an atomic ratio of boron and nitrogen of 1:

1.

3. 3. The method for producing a boron nitride thin film according to claim 2, wherein the precursor contains one or more precursors selected from the group consisting of borazine, trimethylamine borane, tetramethylammonium borane, boron nitride, ammonia borane, and tris(ethylmethylamino)borane, each of which has an atomic ratio of boron to nitrogen of 1:

1.

4. 2. The method for producing a boron nitride thin film according to claim 1, wherein the material constituting the substrate includes at least one selected from the group consisting of metals, metal alloys, ceramics, polymers, and combinations thereof.

5. 2. The method of claim 1, wherein the material layer comprises hexagonal boron nitride, cubic boron nitride, or amorphous boron nitride.

6. 2. The method for producing a boron nitride thin film according to claim 1, wherein in step (a), the precursor is supplied to an energy control device at a temperature of 25°C to 400°C.

7. 7. The method for producing a boron nitride thin film according to claim 6, wherein the precursor is supplied to the energy control device using an inert carrier gas.

8. 8. The method for producing a boron nitride thin film according to claim 7, wherein the inert carrier gas is at least one selected from the group consisting of argon, helium, nitrogen, and combinations thereof.

9. 8. The method for producing a boron nitride thin film according to claim 7, wherein a molar concentration of said precursor in said inert carrier gas is 0.5% or more and 10% or less.

10. 8. The method for producing a boron nitride thin film according to claim 7, wherein the flow rate of said inert carrier gas to said energy control device is 20 sccm or more and 40 sccm or less.

11. 8. The method for producing a boron nitride thin film according to claim 7, wherein the pressure inside the energy control device is 20 torr or more and 60 torr or less.

12. 8. The method for producing a boron nitride thin film according to claim 7, wherein the average residence time of the inert carrier gas in the energy control device is from 10 seconds to 100 seconds.

13. 2. The method for producing a boron nitride thin film according to claim 1, wherein the first electromagnetic wave source emits electromagnetic waves having a wavelength of 180 nm or more and 500 nm or less and a power of 100 W or more and 600 W or less.

14. 14. The method for producing a boron nitride thin film according to claim 13, wherein the energy control device further comprises a second electromagnetic wave source that radiates electromagnetic waves having a wavelength of 0.5 nm or more and 180 nm or less and a power of 100 W or more and 600 W or less.

15. 2. The method of claim 1, wherein step (c) further comprises forming a substrate bias on the surface of the substrate to reduce particle deposition on the surface of the substrate.

16. 2. The method for producing a boron nitride thin film according to claim 1, further comprising maintaining the temperature of the substrate at 400° C. or less in the step (c).

17. 2. The method for producing a boron nitride thin film according to claim 1, further comprising providing a reaction chamber including a plasma source for increasing the rate of formation of the boron nitride in the step (c).

18. 18. The method for producing a boron nitride thin film according to claim 17, wherein the plasma source is one or more selected from the group consisting of direct current plasma, high frequency plasma, electron cyclotron resonance plasma, or a combination thereof, and the energy of the plasma emitted from the plasma source exceeds 300 W.

19. 15. The method for producing a boron nitride thin film according to claim 14, wherein the plasma contains at least one gas selected from argon, helium, nitrogen, hydrogen, ammonia, or a combination thereof.

20. A boron nitride thin film formed on a substrate by a method comprising the following steps (a) to (c): (a) providing a precursor comprising boron atoms and nitrogen atoms to an energy control device; (b) forming an excited state of the precursor in the energy control device; (c) forming a layer of material comprising boron nitride on the substrate; the excited state of the precursor comprises a boron atom and a nitrogen atom, or a boron ligand and a nitrogen ligand in a bond dissociation state; The energy control device is characterized in that it includes a first electromagnetic wave source that emits electromagnetic waves in a specific wavelength range, and a second electromagnetic wave source that emits electromagnetic waves with a wavelength shorter than the wavelength of the electromagnetic waves emitted by the first electromagnetic wave source.

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