KR101692514B1 - Formation method of large area, single crystal, single layered hexagonal boron nitride thin film on a substrate and hexagonal boron nitride thin film laminate thereby - Google Patents
Formation method of large area, single crystal, single layered hexagonal boron nitride thin film on a substrate and hexagonal boron nitride thin film laminate thereby Download PDFInfo
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- KR101692514B1 KR101692514B1 KR1020150133397A KR20150133397A KR101692514B1 KR 101692514 B1 KR101692514 B1 KR 101692514B1 KR 1020150133397 A KR1020150133397 A KR 1020150133397A KR 20150133397 A KR20150133397 A KR 20150133397A KR 101692514 B1 KR101692514 B1 KR 101692514B1
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Classifications
-
- H01L21/205—
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/34—Nitrides
- C23C16/342—Boron nitride
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/10—Details of semiconductor or other solid state devices to be connected
- H01L2924/102—Material of the semiconductor or solid state bodies
- H01L2924/1025—Semiconducting materials
- H01L2924/1026—Compound semiconductors
- H01L2924/1032—III-V
- H01L2924/10325—Boron nitride [BN], e.g. cubic, hexagonal, nanotube
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Vapour Deposition (AREA)
Abstract
The present invention relates to a method for producing a monocrystalline hexagonal boron nitride (h-BN) thin film on a substrate, and more particularly, to a method for producing a hexagonal boron nitride thin film. (b) heating a laminated substrate heated to a temperature not lower than the melting temperature of the second substrate; And (c) forming an h-BN thin film on the second substrate by a chemical vapor deposition method; and forming a single-layer h-BN thin film on the substrate, Layer of the h-BN thin film; and a substrate comprising a laminated structure of the h-BN thin film and the h-BN thin film.
Description
The present invention relates to a method for producing a hexagonal boron nitride (h-BN) thin film having a large area, a single crystal, or a single layer on a substrate by a chemical vapor deposition method.
More particularly, the present invention relates to a method of manufacturing a semiconductor device, comprising: (a) a substrate stacking step of positioning a second substrate on a first substrate; (b) heating a laminated substrate heated to a temperature not lower than the melting temperature of the second substrate; And (c) forming an h-BN thin film on the second substrate by a chemical vapor deposition method.
The present invention also relates to a method for efficiently separating the produced single-layer h-BN from a substrate and transferring a single-layer h-BN thin film to another substrate and a laminate including a single-layer h-BN thin film.
The hexagonal boron nitride (h-BN) has the chemical formula BN, the boron atom and the nitrogen atom form a planar two-dimensional hexagonal structure, and the hexagonal structure similar to graphite has chemical and physical properties. And are highly physically and chemically stable. It is stable up to 3,000 ℃ in an inert atmosphere, has a high thermal conductivity as high as stainless steel, has a high thermal shock resistance, and does not crack or break even after repeated rapid heating and quenching at about 1,500 ℃. And it has excellent high temperature lubrication and corrosion resistance. In addition, the electric resistance value is much higher. Especially, the electric resistance value is not changed at high temperature, so that it can be used as an electric insulating material in a wide temperature range and emits ultraviolet rays when an electric field is applied. In addition, boron nitride is transparent and has excellent stretchability due to the spatial allowance of a hexagonal honeycomb structure in which boron atoms and nitrogen atoms are connected like a net. The specific structure and physical properties of such boron nitride can be applied to an insulator of a semiconductor material and an ultraviolet ray generator.
Recently, as demand and interest in nanotechnology have increased, much research has been conducted to fabricate boron nitride in the form of nanosheets and nanotubes.
Currently, hexagonal boron nitride nanosheets can be produced by mechanical stripping, chemical vapor deposition (CVD) (Korean Laid-Open Patent Application No. 2013-0063410), low pressure chemical vapor deposition Pressure Chemical Vapor Deposition (LPCVD) method (Korean Patent Laid-Open Publication No. 2014-0115868). In general, the CVD method and the mechanical peeling method are used for producing hexagonal boron nitride nanosheet. i) The mechanical method is a method in which one or more layers of boron nitride in hexagonal boron nitride is removed in a solvent through ultrasonic treatment. However, this method is simple to manufacture but has a disadvantage in that mass production is difficult. ii) Generally, a CVD method is a method in which a catalyst metal is deposited on a substrate to form a thin metal film, then a gas containing boron and nitrogen is flowed at a high temperature of 1,000 ° C or higher and then cooled to obtain a boron nitride nanosheet Method has a disadvantage in that the process temperature is very high and is disadvantageous in terms of cost.
In general, the catalyst metal used in the chemical vapor deposition method has a polycrystalline structure, so that a small amount of grain, which is distinguished by the grain boundary, exists in a considerable amount on the surface of the catalyst. Such large amounts of grain and grain boundaries are one cause of degrading the surface quality of h-BN grown thereon. Thus, in Korean Patent Laid-Open Publication No. 2013-0063410, which is a prior art method for producing a hexagonal boron nitride sheet using chemical vapor deposition, firing and heat treatment are performed at a high temperature to induce rearrangement of atoms in the metal catalyst, Discloses a technique for producing a thin film of h-BN while supplying a nitrogen source and a boron source in vapor phase using a sheet-shaped metal catalyst having an increased grain size or a surface-polished metal catalyst.
However, this conventional technique is merely to increase the size of crystal grains by using heat treatment to a conventional metal catalyst having a small crystal grain size and to increase the surface roughness through surface polishing of the metal catalyst, The precursor of h-BN is grown according to the crystal grains of the metal surface, and defects occur while forming a thin film when the grains are aligned at different grain boundaries. In addition, it is difficult to precisely control the number of layers of the produced h-BN thin film, and it is still difficult to manufacture a large-sized h-BN thin film and to transfer the produced h-BN thin film to another substrate.
DISCLOSURE OF THE INVENTION The present invention has been made in order to solve the problems of the prior art described above, and it is an object of the present invention to provide a h-BN thin film which is produced by a chemical vapor deposition BN thin film of high quality without causing any influence on the quality of the h-BN thin film.
Further, it is intended to provide a method for manufacturing a large-area, single-crystal, single-layer h-BN thin film which can not be provided in the prior art.
It is also an object of the present invention to provide a method for efficiently peeling a manufactured high-quality uniform single-layer h-BN thin film from a metal catalyst base material and efficiently transferring the same on another substrate, and a laminate including a single-layer h-BN thin film.
According to an aspect of the present invention, there is provided a method of forming a single-layer h-BN thin film on a substrate, comprising the steps of: (a) depositing a second substrate on a first substrate; (b) heating a laminated substrate heated to a temperature not lower than the melting temperature of the second substrate; And (c) forming an h-BN thin film on the second substrate by chemical vapor deposition. The method for forming a single-layer h-BN thin film on a substrate includes:
And forming a third substrate on the h-BN thin film after the h-BN thin film forming step.
And separating the h-BN thin film from the second substrate in the aqueous solution after the third substrate formation step.
And an h-BN transfer step of transferring h-BN to the fourth substrate after the h-BN thin film separation step.
And a third substrate removing step of removing the third substrate after the h-BN transfer step.
And the melting temperature of the first base material is higher than the melting temperature of the second base material.
Wherein the first substrate is any one selected from the group consisting of zirconium (Zr), chromium (Cr), vanadium (V), rhodium (Rh), molybdenum (Mo), tantalum (Ta), and tungsten (W) The second substrate is made of gold (Au), copper (Cu), iron (Fe), manganese (Mn), nickel (Ni), cobalt (Co), palladium (Pd), titanium Lt; / RTI >
The third base material may be at least one selected from the group consisting of a polymer, an adhesive tape, a heat peeling tape, and a photoresist.
Separating the h-BN thin film by connecting a negative electrode to a first substrate or a second substrate and connecting a positive electrode to a separate counter electrode in an aqueous solution to use hydrogen generated at the interface between the second substrate and the h-BN thin film And separating the h-BN thin film.
The fourth substrate may be any one selected from the group consisting of a carbon grid, a flexible substrate, a conductor, a dielectric, or a semiconductive material.
The single-layer h-BN is a single crystal, and may be several millimeters in size.
The h-BN thin film laminate according to the present invention is provided with a laminate including a single-layer h-BN thin film manufactured according to the above-described method and a substrate having a laminated structure with the single-layer h-BN thin film.
In the present invention, crystal grains of a large-area, single-crystal, single-layer h-BN are formed on the surface of a flat liquid metal catalyst without crystal grains and are freely moved and rearranged on the surface of the liquid phase. Particularly, the h-BN is arranged in accordance with a large area of crystal grains generated as the surface of the gold catalyst solidifies while being slowly cooled. The grain size is several millimeters in diameter and the surface is very smooth, which is the optimal h-BN growth condition. However, the h-BN thin film is not affected by the crystal grains of the gold catalyst, and the h-BN is formed as a single layer under such growth conditions. Since the h-BN thin film can be transferred without damage by using the polymer, the gold catalyst can be used repeatedly .
It is possible to apply h-BN thin film having high crystallinity by growing h-BN, which is uniform in atomic thickness, as an anti-oxidation coating and a substrate for two-dimensional material by using inherent insulating property of h- The catalyst can be repeatedly used by removing the catalyst from the catalyst without any damage, which is economically effective.
FIG. 1 is a conceptual view illustrating a change in shape of gold as a metal catalyst according to an embodiment of the present invention. FIG.
2 is a conceptual view showing a substrate stacking step of placing a second substrate on a first substrate according to an embodiment of the present invention.
FIG. 3 is a conceptual diagram illustrating formation of a single-layer h-BN in the h-BN thin film forming step according to the reaction time on a second substrate according to an embodiment of the present invention.
FIG. 4 illustrates a third substrate forming step of forming a third substrate on the h-BN thin film after the h-BN thin film forming step according to an embodiment of the present invention and a second substrate forming step of forming a h-BN thin film Thin film separation step.
FIG. 5 is an image observed with field emission scanning electrons (FE-SEM) of (a) island-shaped h-BN and (b) thin film type h-BN prepared according to an embodiment of the present invention.
FIG. 6 is a graph illustrating the crystal orientation direction of a h-BN thin film manufactured according to an embodiment of the present invention by transferring the thin film to a carbon grid and measuring a wide range by SAED.
FIG. 7 is an image of a surface of a prepared h-BN thin film according to the number of times of re-use of a gold-tungsten substrate used according to an embodiment of the present invention, using a field emission scanning electron (FE-SEM).
FIG. 8 is a graph showing the bonding structure of h-BN and the bonded atoms of the h-BN thin film prepared according to one embodiment of the present invention on a copper grid and measured by HR-TEM.
9 shows the thickness and surface roughness of transferred h-BN according to an embodiment of the present invention through AFM.
Hereinafter, the present invention will be described in detail. The terms and words used in the present specification and claims should not be construed as limited to ordinary or dictionary terms and the inventor may appropriately define the concept of the term in order to best describe its invention It should be construed as meaning and concept consistent with the technical idea of the present invention.
A method of forming a single-layer h-BN thin film on a substrate according to an aspect of the present invention includes the steps of: (a) depositing a second substrate on a first substrate; (b) heating a laminated substrate heated to a temperature not lower than the melting temperature of the second substrate; And (c) forming an h-BN thin film on the second substrate by chemical vapor deposition.
And forming a third substrate on the h-BN thin film after the h-BN thin film forming step.
And separating the h-BN thin film from the second substrate in the aqueous solution after the third substrate formation step.
And an h-BN transfer step of transferring h-BN to the fourth substrate after the h-BN thin film separation step.
And a third substrate removing step of removing the third substrate after the h-BN transfer step.
And the melting temperature of the first base material is higher than the melting temperature of the second base material.
The first substrate is characterized in that the first substrate is selected from the group consisting of Zr, Cr, V, Rh, Mo, And the second substrate may be at least one selected from the group consisting of Au, Cu, Fe, Mn, Ni, Co, Pd, Ti, Pt). ≪ / RTI >
The third base material may be at least one selected from the group consisting of a polymer, an adhesive tape, a heat peeling tape, and a photoresist.
Separating the h-BN thin film by connecting a negative electrode to a first substrate or a second substrate and connecting a positive electrode to a separate counter electrode in an aqueous solution to use hydrogen generated at the interface between the second substrate and the h-BN thin film And separating the h-BN thin film.
The fourth substrate may be any one selected from the group consisting of a flexible substrate, a conductor, a dielectric, and a semiconductive material.
The single-layer h-BN is a single crystal, and may be several millimeters in size. More preferably a single crystal having a size of several millimeters.
The h-BN thin film laminate according to the present invention is provided with a laminate including a single-layer h-BN thin film manufactured according to the above-described method and a substrate having a laminated structure with the single-layer h-BN thin film.
First, the metal that can be used as the first substrate and the second substrate includes at least one of zirconium (Zr), chromium (Cr), vanadium (V), rhodium (Rh), molybdenum (Mo), tantalum (Ta), tungsten (W) Selected from the group consisting of Au, Au, Cu, Fe, Mn, Ni, Co, Pd, Ti and Pt. One or more metals or alloys.
More preferably, in the selection of the first base material and the second base material, any combination of metals can be used in which the melting temperature of the first base material is higher than the melting temperature of the second base material.
More preferably, the first substrate has a melting temperature of 1,800 ° C or higher, and the second substrate has a melting temperature of 1,000-1,800 ° C.
For example, the first substrate is selected from the group consisting of zirconium (Zr), chromium (Cr), vanadium (V), rhodium (Rh), molybdenum (Mo), tantalum (Ta), and tungsten One or more metals or alloys may be used.
For example, the second base material may be at least one selected from the group consisting of Au, Cu, Fe, Mn, Ni, Co, Pd, Ti, (Pt) may be used.
Table 1 shows the types of metals usable as the first substrate and the melting temperatures of the metals, and Table 2 shows the types of metals usable as the second substrate and the melting temperatures of the metals.
Fig. 1 shows that when the sheet-like metal corresponding to the second substrate is heated to the melting temperature or higher of the metal, the form changes from a sheet-like sheet shape to a spherical shape when there is no support. Particularly, gold (Au), which is a second base material according to an embodiment of the present invention and is a metal catalyst for producing h-BN, has a spherical shape capable of minimizing surface tension by melting when heated to a melting temperature of 1,063 ° C or higher The shape changes.
First, the base material lamination step of (a) placing the second base material on the first base material is a step of laminating the first base material such as zirconium (Zr), chromium (Cr), vanadium (V), rhodium (Rh) (Au), copper (Cu), iron (Fe), manganese (Mo), tantalum (Ta), and tungsten (W) on a sheet made of one or more metals or alloys selected from the group consisting of molybdenum Is a step of laminating a sheet made of at least one metal or alloy selected from the group consisting of Mn, Ni, Cobalt, Pd, Ti and Pt.
(b) heating the laminated substrate heating the substrate laminated at a temperature not lower than the melting temperature of the second substrate, wherein the second substrate comprises at least one of gold (Au), copper (Cu), iron (Fe), manganese (Mn) ), Cobalt (Co), palladium (Pd), titanium (Ti) and platinum (Pt). As described above with reference to FIG. 1, when the second substrate is heated to a temperature higher than the melting temperature, the shape of the second substrate changes from a sheet shape to a sphere shape. When the first substrate is laminated on the first substrate, Phase is changed from the solid state to the liquid state while maintaining the shape of the plate.
That is, in one embodiment of the present invention, the limitation that the shape of the tungsten substrate can not be retained by being in a liquid state beyond the melting point of gold (Au), which is a catalyst used in the production of h-BN, The h-BN of a single-layer single-layer large-sized single-layer is grown on the surface of gold in the liquid phase, so that it can be manufactured with excellent reproducibility as a uniform sheet form of atomic thickness.
(c) forming the h-BN thin film on the second substrate by the chemical vapor deposition method comprises forming the h-BN thin film on the first substrate at a temperature higher than the melting temperature of the second substrate, BN thin film on a second substrate by a chemical vapor deposition method using a gaseous nitrogen source and a boron source on a liquid second substrate.
The gaseous nitrogen source and the boron source can be supplied at a constant flow rate and can be supplied in an inert atmosphere or a reducing atmosphere. The inert atmosphere may be an inert gas such as argon or helium, and the reducing atmosphere may be formed using hydrogen gas.
The nitrogen source is not particularly limited as long as it is capable of supplying a nitrogen element in the vapor phase, and may include at least one selected from NH 3 , N 2, and the like. The boron source is not particularly limited as long as it can supply a boron element in the vapor phase. BH 3 , BF 3 , BCl 3 , B 2 H 6 , (CH 3 ) 3 B, (CH 3 CH 2 ) 3 B , A borazine compound, and the like.
The nitrogen source and the boron source need only be supplied in the gaseous phase. The raw material itself need not be in a gaseous state. It is also possible to vaporize the nitrogen and boron-containing materials in the solid phase in the outer vessel. As a source of nitrogen and boron in the solid phase, ammonia-borane (NH 3 -BH 3 ) compounds can be used.
The crystal grains of a single layer of h-BN are formed on the surface of the flat second substrate without the crystal grains in the liquid phase by the nitrogen source and the boron source, and rearrangement is performed while moving freely on the liquid second substrate surface . Since the surface of the second substrate is hardened in the gradually cooling step, the h-BN is formed according to the large crystal grains generated. The grain size of the crystal grains is several millimeters in diameter and the surface is very smooth. h-BN growth condition, and under these growth conditions, h-BN can grow as a single layer. On the other hand, since the surface of the second substrate has a very smooth surface at the stage of gradually cooling the substrate after the molten state, it is possible to omit the polishing process of the surface as in the prior art, and to produce a high quality h- .
FIG. 3 is a conceptual diagram showing the growth of h-BN only in a single layer even when the growth time of h-BN is increased in the step of forming h-BN thin film. In the chemical vapor deposition method, only h- The results were confirmed by scanning electron microscopy (SEM) and atomic force microscopy (AFM).
The third substrate forming step of forming the third substrate on the h-BN thin film after the h-BN thin film forming step is a step of forming the third substrate on the formed h-BN thin film. The third substrate to be formed is at least one selected from the group consisting of a polymer, an adhesive tape, a heat peeling tape and a photoresist, and the polymer is at least one selected from the group consisting of polyethylene terephthalate (PET), polyethylene sulfone (PES), polyethylene naphthalate (PC), polymethyl methacrylate (PMMA), polyimide (PI), ethylene vinyl acetate (EVA), polypropylene terephthalate (PPT), polyethylene terephthalate glycerol (PETG), polycyclohexylenedimethylene terephthalate (CPC), cyclopentadiene polymer (CPD), polyarylate (PAR), cyclic olefin polymer (COP), dicyclopentadiene polymer (DCPD) ), Polyetherimide (PEI), polydimethylsilonane (PDMS), silicone resin, fluororesin, and modified epoxy resin.
As a method of forming the polymer as the third base material, a known polymer coating method such as spraying, dip coating and spin coating can be used by mixing the polymer with a solvent. If necessary, a monomer and a crosslinking agent may be mixed to form a h- BN thin film, polymer can be formed on the h-BN thin film by polymerization and crosslinking. Further, in the case of an adhesive tape or a heat peeling tape, the third base material can be formed by pressing each tape.
Such a third substrate is used for supporting the h-BN from the laminate of the first substrate and the second substrate to the efficient h-BN thin film separation step or the h-BN transfer step for transferring the produced h-BN thin film to the fourth substrate After separating the h-BN thin film from the first and second substrates, the third substrate may be removed by using a solvent or heat to separate the h-BN thin film separately. Alternatively, the h- -BN transcription step or may be removed after the h-BN transcription step.
The h-BN thin film separating step of separating the h-BN thin film from the second substrate in the aqueous solution after the third substrate forming step comprises the steps of applying a minus voltage to the laminate having the third substrate formed thereon in an alkali solution atmosphere, By applying a positive voltage to the counter metal of the second base material, separating the interface with the h-BN thin film from hydrogen generated on the surface of the second base material.
As shown in FIG. 4, the h-BN thin film is separated by the hydrogen gas generated at the interface between the second substrate and the h-BN thin film, so that the h-BN thin film is not separated by external physical force or other means, And the laminate of the first substrate and the second substrate can be efficiently separated without causing damage to the surface. In addition, the laminated sheet of the first base material and the second base material remaining after the separation of the h-BN thin film is washed and repeatedly used for manufacturing the h-BN thin film.
The h-BN transfer step of transferring h-BN to the fourth substrate after the h-BN thin film separation step comprises transferring the h-BN to be brought into contact with the transfer target fourth substrate on the surface of the separated h-BN thin film to be. Wherein the fourth substrate is any one of a carbon grid, a flexible substrate, a conductor, a dielectric, or a semiconductor material, and more preferably the flexible substrate is at least one selected from the group consisting of polyethylene terephthalate (PET), polyethylene sulfone (PES), polyethylene naphthalate Wherein the conductive material is one of graphene, the dielectric material is any one of MoS 2 and BCN, the semiconductive material is silicon or silicon Wafer. In addition, the method of transferring may be performed by a dry process, a wet process, or a roll-to-roll process, but is not limited thereto.
After the h-BN transfer step, the third substrate removal step of removing the third substrate is a step of removing the third substrate using a solvent or heat. When the third base material is a material soluble in a solvent such as a polymer or a photoresist, it can be removed using a solvent. In the case of an adhesive tape, a physical method can be used. In the case of a heat peeling tape, Can be removed.
The h-BN thin film laminate according to the present invention is provided with a laminate comprising a h-BN thin film of one layer manufactured according to the above-described method and a substrate forming a laminated structure of the h-BN thin film.
The substrate constituting the laminated structure may be at least one substrate selected from the group consisting of the first substrate, the second substrate, the third substrate, or the fourth substrate.
Hereinafter, embodiments of the present invention will be described in detail. However, the embodiments according to the present invention can be modified into various other forms, and the scope of the present invention should not be construed as being limited to the following embodiments. Embodiments of the invention are provided to more fully describe the present invention to those skilled in the art.
Example 1: Formation of a gold (Au) catalyst on a tungsten substrate (see FIGS. 1 and 2)
(Au), which is a catalyst used in the production of h-BN, is melted as shown in Fig. 1 when a temperature higher than the melting point of 1,063 ° C is applied, thereby changing to a sphere shape that minimizes the surface tension. 2, a gold (Au) substrate as a
The tungsten substrate, which is the first substrate (1), is sized to fit into the quartz tube of the CVD equipment. In this experiment, a size of 2 cm x 3 cm was used. Since the gold (Au) substrate as the
Example 2: Preparation of h-BN thin film (see Fig. 3)
A hexagonal boron nitride thin film (h-BN thin film) (3) was formed on the formed gold-tungsten sheet by chemical vapor deposition as shown in FIG.
Boron (H 3 B 3 N 3 H 3 ) was used as a nitrogen source and boron source, which are precursors of h-BN, to produce h-BN thin films. Borazin is a type of unsaturated boron nitride with a hexagonal structure similar to h-BN, consisting of 3 nitrogen atoms and 3 boron atoms in one molecule. Its melting point is 57 ℃ and its boiling point is 55 ℃. Therefore, it is preferable to use the borazine in a liquid state at room temperature, so that the temperature is kept at -10 ° C. by using a cooler so that the vapor pressure is kept unaffected by the temperature. In the subzero temperature, It is possible to control the flow rate by using hydrogen as a precursor for producing the h-BN thin film by feeding the diluted borazine in the gaseous state by introducing hydrogen into the liquid state of the borazine because it does not occur. There is an advantage that solid impurities are not generated.
The growth conditions of h-BN were as follows: a gold (Au) substrate as a
Example 3: Isolation of h-BN thin film (see Figs. 4 to 6)
The h-BN thin film was coated with a polymer as the third base material (4), a negative voltage was applied in an alkaline solution atmosphere, and a positive voltage was applied to the counter metal to separate h-BN from hydrogen generated in the metal. The gold-tungsten sheet from which the h-BN was removed was repeatedly used.
The separation process of the grown h-BN thin film (bubbling transfer process) is as follows. Place the h-BN / gold / tungsten base material on the cleaned PET film and stick it with a Scotch tape near the edge to coat only the upper part of the h-BN with the polymer as the third base material (4). The polymer used as the third substrate (4) used in the separation process of the thin film is a mixture of 950 PMMA A9 and anisole in a volume ratio of 1: 1. 950 PMMA A9 is a product in which PMMA is dissolved in anisole at 9 ~ 11 wt%, and the concentration of the polymer coating solution is 4 ~ 6 wt%. The polymer coating solution was dropped on the h-BN thin film and spin-coated at a speed of 2500 rpm for 1 minute using a spin coater. After the spin coating, the solvent was evaporated in an oven at 80 ° C for about 1 hour, and the tape portion was removed. The aqueous solution used for the separation of the h-BN thin film was prepared by applying a minus voltage to the h-BN / gold / tungsten substrate under the conditions of 10 V and 1.8 A voltage and current using a 500 mL 0.25M sodium hydroxide aqueous solution, (Platinum) by applying a positive voltage to separate the h-BN thin film from the hydrogen generated on the surface of the gold (Au) substrate.
Example 4: Transcription of h-BN thin film
The removed PMMA / h-BN thin film laminate floats on the surface of the aqueous sodium hydroxide solution. Therefore, the PMMA / h-BN thin film laminate is removed using clean PET or glass substrate, transferred to distilled water and repeatedly washed three times with sodium hydroxide Remove the aqueous solution. Washing with distilled water was carried out for 20 minutes. After washing, the pH of the distilled water was compared using litmus paper to confirm that no base was present. The cleaned PMMA / h-BN thin film laminate was transferred to a substrate of a desired fourth base material in a clean state. In the fourth base material to be transferred, a PMMA / h-BN thin film laminate was prepared by using a plate of SiO 2 / Si, Si, Quartz, PET, / h-BN and the substrate are placed in an oven at 80 ° C, and the moisture is evaporated for about one hour, so that the h-BN sticks to the substrate of the fourth substrate better.
The third reference, PMMA, was removed by using acetone and the remaining h-BN thin film was heat-treated at 450 ° C, 700 sccm argon, 300 sccm hydrogen and atmospheric pressure for 5 hours using an additional heat treatment equipment. PMMA was completely removed by pyrolysis.
Experiment result
Fig. 5 (a) shows the island-shaped h-BN prepared by the above method, and Fig. 5 (b) shows the result of observation of the surface of h-BN in the form of a thin film by a field emission scanning electron microscope (FE-SEM) The h-BN grows in a flake form by nucleation and is gradually aggregated and aligned to form a film. FIG. 5 (a) FIG. 5 (b) is an image of the film type h-BN. The surface of the h-BN prepared according to the present invention was found to be smooth, uniform, and large-sized.
FIG. 6 is a graph showing the results of (a) measurement of a broad range of SAED (b) after transferring the h-BN thin film produced according to an embodiment of the present invention to a carbon grid, All the single crystals are shown.
7 shows the surface of the prepared h-BN thin film according to the number of times of reuse ((a) 2 times, (b) 5 times, (c) 10 times) of the gold-tungsten substrate used according to one embodiment of the present invention It can be seen that the gold-tungsten sheet can be reused repeatedly with the image observed by field emission scanning electron (FE-SEM).
FIG. 8 is a graph showing the bonding structure of h-BN and the bonded atoms of the h-BN thin film prepared according to one embodiment of the present invention on a copper grid and measured by HR-TEM.
FIG. 9 is a graph showing the surface roughness (a) and the thickness (b) of the transferred h-BN according to an embodiment of the present invention measured through AFM, and the surface roughness value (Rq) It can be seen that the surface is smooth, uniform and large-sized, and the thickness of the h-BN thin film is 0.4 nm, which indicates that a single-layer h-BN thin film is formed.
As described above, the method for producing the h-BN thin film using the gold catalyst and the tungsten substrate according to an embodiment of the present invention is in a liquid state above the melting point of the gold (Au) catalyst used in the production of h-BN Since the tungsten substrate, which is the first substrate, serves to stably support the limit that can not maintain the shape, h-BN of a single-layer single-layer large-area monolayer grows on the gold surface of the liquid, . The h-BN of a single-crystal single-layer single-layer produced by this method can be used as a device and a growth substrate by being used as a template of another two-dimensional material because the inherent insulating property can be manifested. In addition, the present invention is economically effective because the gold catalyst can be repeatedly used by removing the h-BN and the gold catalyst without damaging it.
1: first substrate, 2: second substrate, 3: h-BN thin film, 4: third substrate
Claims (13)
(a) a substrate stacking step of positioning a second substrate on a first substrate;
(b) heating a laminated substrate heated to a temperature not lower than the melting temperature of the second substrate;
(c) forming an h-BN thin film on the second substrate;
(d) forming a third substrate on the h-BN thin film after the h-BN thin film forming step; And
(e) separating the h-BN thin film from the second substrate in the aqueous solution after the third substrate forming step, characterized in that it comprises a step of separating the h-BN thin film from the second substrate Way.
Further comprising an h-BN transfer step of transferring h-BN to the fourth substrate after the h-BN thin film separation step.
Further comprising a third substrate removing step for removing the third substrate after the h-BN transfer step.
Wherein the melting temperature of the first substrate is higher than the melting temperature of the second substrate.
Wherein the first substrate is any one selected from the group consisting of zirconium (Zr), chromium (Cr), vanadium (V), rhodium (Rh), molybdenum (Mo), tantalum (Ta), and tungsten (W) The second substrate is made of gold (Au), copper (Cu), iron (Fe), manganese (Mn), nickel (Ni), cobalt (Co), palladium (Pd), titanium Lt; RTI ID = 0.0 > h-BN < / RTI > thin film on a substrate.
Wherein the third substrate is at least one selected from the group consisting of a polymer, an adhesive tape, a heat peeling tape, and a photoresist.
In the h-BN thin film separation step, a negative electrode is connected to the first substrate or the second substrate, a positive electrode is connected to a separate counter electrode in the aqueous solution, and hydrogen generated at the interface between the second substrate and the h- lt; RTI ID = 0.0 > h-BN < / RTI > thin film.
Wherein the fourth substrate is any one selected from the group consisting of a carbon grid, a flexible substrate, a conductor, a dielectric, or a semiconductive material.
Wherein the single-layer h-BN is a single crystal.
Wherein the single-layer h-BN is a single crystal of several millimeters in size.
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| KR102072580B1 (en) | 2018-11-06 | 2020-02-03 | 한국과학기술연구원 | Method for manufacturing hexagonal boron nitride thin film, method for manufacturing multi-layered structure and method for manufacturing switching element using the same |
| US10629696B1 (en) | 2018-11-06 | 2020-04-21 | Korea Institute Of Science And Technology | Method for forming hexagonal boron nitride thin film, method for forming multi-layered structure and method for manufacturing switching element using the same |
| CN111986999A (en) * | 2019-05-23 | 2020-11-24 | 台湾积体电路制造股份有限公司 | Method of forming semiconductor device |
| KR20200135716A (en) * | 2019-05-23 | 2020-12-03 | 타이완 세미콘덕터 매뉴팩쳐링 컴퍼니 리미티드 | Single-crystal hexagonal boron nitride layer and method forming same |
| KR102378230B1 (en) * | 2019-05-23 | 2022-03-25 | 타이완 세미콘덕터 매뉴팩쳐링 컴퍼니 리미티드 | Single-crystal hexagonal boron nitride layer and method forming same |
| US11289582B2 (en) | 2019-05-23 | 2022-03-29 | Taiwan Semiconductor Manufacturing Company, Ltd. | Single-crystal hexagonal boron nitride layer and method forming same |
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