KR20170043350A - Preparing method of 2-dimensional nanosheet by exfoliation of materials with layered structure using shear force and liquefied high impact - Google Patents
Preparing method of 2-dimensional nanosheet by exfoliation of materials with layered structure using shear force and liquefied high impact Download PDFInfo
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- KR20170043350A KR20170043350A KR1020150143003A KR20150143003A KR20170043350A KR 20170043350 A KR20170043350 A KR 20170043350A KR 1020150143003 A KR1020150143003 A KR 1020150143003A KR 20150143003 A KR20150143003 A KR 20150143003A KR 20170043350 A KR20170043350 A KR 20170043350A
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- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/26—Nozzle-type reactors, i.e. the distribution of the initial reactants within the reactor is effected by their introduction or injection through nozzles
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- C01B21/00—Nitrogen; Compounds thereof
- C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
- C01B21/064—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with boron
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Abstract
Description
More particularly, the present invention relates to a method of peeling a layered structure material by applying a force (shear stress) acting parallel to but opposite to a layered structure using a fluid collision method, And a method for producing a high-quality two-dimensional nanosheet having a large area.
In recent years, the properties of layered structures such as graphite, boron nitride (BN), molybdenum disulfide (MoS 2 ), and phosphorane have been observed as a two-dimensional nanosheet having a single layer or an aqueous layer As a result of the evaluation, it has been reported that it can exhibit properties superior to those of the bulk state material. Due to these excellent properties, various methods have been proposed or studied to more efficiently produce two-dimensional nanomaterials. Particularly, there have been various studies on a method for a simplified process which has a thinner thickness and a larger area while generating less defects in order to maximize the characteristics.
Firstly, a method of peeling a graphite into a graphene nanosheet by a physical method such as using a tape is known, but such a method is not suitable for mass production.
Also, a method of chemically obtaining two-dimensional nanosheets or oxides using an acid or a base solution is known. However, a number of defects may occur in the process of obtaining the nanosheet by reducing the oxide obtained by this method again. This can adversely affect the properties of the final product material and complicate the overall process.
In recent years, there has been known a method for producing a multilayered nanosheet by separating a layer by a method such as ultrasonic irradiation or ball milling while dispersing a layered structure material in a liquid phase. However, this method also has a problem that it is difficult to obtain a two-dimensional nanosheet having a sufficiently thin thickness and defects occur.
Accordingly, there is a continuing need for a process that can peel a material having a layered structure through a simplified process with a thinner and larger-sized two-dimensional nanosheet having few defects.
On the other hand, the method of peeling graphite as a layered structure material is disclosed in Korean Patent No. 10-1078734, but the above Korean Patent No. 10-1078734 is not only premised on a process condition using high temperature and high pressure, Dimensional nanosheet with a thinner thickness through first and second peeling due to shear stress and collision in a simplified process, which is different from the present invention .
In order to solve the above problems, the present invention provides a method for peeling a layered structure material into a two-dimensional nanosheet having a thinner thickness and a larger area through a simplified process and having reduced defect occurrence.
The present invention relates to a method for manufacturing a semiconductor device, comprising: dispersing a material having a layered structure in a solvent to form a dispersion; Introducing the dispersion into a fluid-impingement nano-atomizer equipped with a micro-nozzle having a diameter of 200 μm or less; Applying a shear stress to the charged dispersion and passing the dispersion through the micro-nozzle to peel off first; And a second peeling step in which the materials in the primary peeled dispersion are collided at a high speed, and having a nanoscale thickness of a single layer or an aqueous layer.
According to the present invention, a two-dimensional nanosheet can be manufactured by optimizing the peeling method in a state where the laminated material is more uniformly dispersed by using the dispersion solvent and the fluid collision method.
Therefore, according to the present invention, it is possible to omit the pre-treatment process or the post-treatment process of the conventional peeling process, which can minimize defects that may occur during the process. Further, according to the present invention, a two-dimensional nanosheet having a thinner thickness and a larger area can be easily produced at a high yield.
FIG. 1 is a schematic view showing a method of manufacturing a boron nitride (BN) nanosheet using shear stress according to the present invention
FIG. 2 is a detailed schematic view showing a process in which a boron nitride (BN) powder is peeled off into a nanosheet using the shear stress of FIG. 1
3 is an image obtained by observing the boron nitride (BN) powder used in the examples by Scanning Electron Microscopy (SEM).
FIG. 4 is an image of a BN nanosheet peeled off using the nanosheet manufacturing method shown in FIG. 1 by transmission electron microscopy (TEM).
FIG. 5 is an image of a boron nitride (BN) nanosheet peeled off using the nanosheet manufacturing method shown in FIG. 1 by a high-resolution transmission electron microscopy (HRTEM).
Hereinafter, the present invention will be described more specifically with reference to preferred embodiments. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in detail with reference to the accompanying drawings.
The present invention relates to a method for manufacturing a semiconductor device, comprising: dispersing a material having a layered structure in a solvent to form a dispersion; Introducing the dispersion into a fluid-impingement nano-atomizer equipped with a micro-nozzle having a diameter of 200 μm or less; Applying a shear stress to the charged dispersion and passing the dispersion through the micro-nozzle to peel off first; And a second peeling step in which the materials in the primary peeled dispersion are collided at a high speed, and having a nanoscale thickness of a single layer or an aqueous layer.
In one embodiment of the present application, the material having the layered structure is selected from the group consisting of graphite, boron nitride (BN), MoS 2 , MoSe 2 , WS 2 , WSe 2 , NbS 2 , NbSe 2 , ZrS 2 , (Phosphorene), and combinations thereof. However, the present invention is not limited thereto. These materials are stacked materials having a two-dimensional plate-like structure and can be used without limitation as long as they are peeled and have a single layer or a nanoscale thickness of an aqueous layer.
In one embodiment herein, the solvent is an aqueous solvent such as water or a solvent such as methanol, ethanol, acetone, butanol, isopropyl alcohol, N, N-dimethylformamide, ethylene glycol, dimethylacetamide , Formic acid ethyl acetate, acrylonitrile, and combinations thereof. However, the present invention is not limited thereto. A dispersion liquid can be prepared by dissolving or dispersing a material having a layered structure in a polar organic solvent having a polar functional group such as -OH, -COOH, -O-, -CN, -F.
In one embodiment of the present invention, the first separation step in which the dispersion passes through the micronozzles and the second separation step in which the materials in the dispersion liquid passing through the micronozzles collide are continuously performed. When a dispersion prepared by mixing a layered structure material in the water solvent or an organic solvent is passed through a fluid collision-type nano-atomizer equipped with a micro-nozzle having a diameter of 200 μm or less, shear stress is applied from the device, The nanosheets having a single layer or water layer are firstly peeled off, and then the primary peeled nanosheets are injected into the chamber containing the micro-nozzles to be dropped and moved so that high-speed collision between particles occurs. At this time, The second peeling occurs further. As a result, it is possible to obtain a nanosheet having a single layer or a water layer thinner than the nanosheet obtained from the first separation.
In one embodiment of the present invention, the nanoscale thickness of the single layer or the water layer is controlled by adjusting the type and concentration of the solvent and the number of times of passage and collision of the dispersion with the nozzle. The concentration of the solvent is 0.1% by weight to 10% by weight based on the weight of the total solution. The number of passes and the number of collisions of the dispersion is 5 times (pass) pass to 100 pass, but the present invention is not limited thereto. The concentration of the solvent may be, for example, from 0.1% to 10%, from 2% to 10%, from 4% to 10%, from 6% to 10% , 0.1% to 5%, or 0.1% to 3%, but is not limited thereto. However, when the number of passes and collisions of the nozzle is less than 5 passes, it is difficult to manufacture the two-dimensional nanosheet because the layered material does not peel off properly, and when the pass is more than 60 passes, And a defect may occur in the two-dimensional nanosheet generated by heat.
In one embodiment of the invention, an acid may be added to the solvent to impart functional groups to the surface. The acid added may be selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, hydrobromic acid, hydroiodic acid, acetic acid, glyoxylic acid, toluenic acid, 4-nitrobenzoic acid, malic acid, malonic acid, oxalic acid, succinic acid, But are not limited to, at least one selected from the group consisting of hydrochloric acid, trifluoroacetic acid, butyric acid, tartaric acid, phthalic acid, benzoic acid, citric acid, salicylic acid, mandelic acid, and combinations thereof.
In one embodiment of the present invention, the surface of the nanosheet is treated with an acid such as a carboxyl group, a hydroxyl group, an amide group, a glycidyl group, an isocyanate group, an epoxide group, a cyclic ether group, a sulfide group, Toners, and combinations thereof. However, the present invention is not limited thereto.
The above-described method of manufacturing a two-dimensional nanosheet may include a step of passing through a nozzle of a pass and a step of removing the nanosheet from the dispersion containing the peeled nanosheet after the separation by the impact. At this time, the recovery of the two-dimensional nanosheets can be carried out by centrifugation, vacuum filtration or pressure filtration, and the drying can be performed by vacuum drying at a temperature of about 30 ° C to about 100 ° C.
BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail with reference to examples. 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 embodiments described below. Embodiments of the present invention are provided to more fully describe the present invention to those skilled in the art.
Example
(1 wt% based on the weight of the solvent) of hexagonal boron nitride (h-BN) powder was dispersed in a mixed solvent of 100 vol% of water or 50 vol% of water and 50 vol% of ethanol as a polar organic solvent To prepare a dispersion. The dispersion thus prepared was put into a fluid counter collision system (CNNT Co.) equipped with a micro-nozzle having a diameter of 200 mu m to carry out a first peeling through a micro-nozzle, The peeled nanosheets were moved into the chamber to carry out the second peeling. (5, 10, 15, 20, 30, 40, 50, 60 pass) in total from 5 pass to 60 pass And the pressure was set to 170 MPa. Detailed conditions of the examples are shown in Table 1 below.
The process of peeling the h-BN powder particles of the above embodiment into two-dimensional nanosheets can be easily understood through the schematic diagrams of FIGS. 1 and 2. FIG. As shown in Figs. 1 and 2, a micro-nozzle is mounted at the end of the dispersion supply part of the fluid-impingement nano-atomization apparatus, and the micro-nozzle is inserted into the chamber including the part of the dispersion liquid supply part. The dispersion containing the h-BN powder particles is put into the apparatus for the first peeling, and the shear stress is applied when the dispersion liquid is moved from the end of the apparatus feeding section to the micronozzles. At this time, the first peeling is performed. As shown in Fig. 2, when the h-BN powder particles of the three-dimensional structure pass through the micro-nozzle, the shear stress acts in a direction parallel to each other but acts in the opposite direction. The h-BN powder particles in the form of a three-dimensional block are exfoliated into nanosheets having a two-dimensional plate-like structure by receiving a stress.
3 is an image of the h-BN powder particles observed by a scanning electron microscope. 5 μm scale, and it was confirmed that the thickness of the h-BN powder before peeling reached a size of several hundred nanometers.
FIG. 4 is an image of a BN nanosheet obtained by peeling h-BN by using the above-mentioned shear stress-induced nanosheet manufacturing method by a transmission electron microscope. As a result of observing the scale of 200 nm and 5 nm, it was confirmed that BN nanosheets having a thickness of several micrometers and a thickness of several nanometers were peeled off. The two-dimensional nanosheet to be peeled by the present invention is characterized in that defects are minimized during peeling. The BN nano-sheet peeled off without a large defect on the surface can be seen in Fig.
FIG. 5 is an image of a BN nanosheet obtained by peeling h-BN using the above-described method for producing nanosheet using shear stress, with a high-resolution transmission electron microscope. As shown in FIG. 4, it was confirmed that a BN nanosheet having a thickness of several nanometers and a minimal defect was obtained.
Claims (7)
Introducing the dispersion into a fluid-impingement nano-atomizer equipped with a micro-nozzle having a diameter of 200 μm or less;
Applying a shear stress to the charged dispersion and passing the dispersion through the micro-nozzle to peel off first; And
A step of subjecting the materials in the primary peeled dispersion to high-speed collision and secondary peeling
And having a nanoscale thickness of a single layer or an aqueous layer.
Material having the layered structure of graphite (graphite), boron nitride (BN), the MoS 2, MoSe 2, WS 2 , WSe 2, NbS 2, NbSe 2, ZrS 2, phosphine tarpaulins (Phosphorene), and combinations thereof Wherein the nanoparticles are at least one selected from the group consisting of polyvinyl alcohol, polyvinyl alcohol, and polyvinyl alcohol.
The solvent is selected from the group consisting of water, methanol, ethanol, acetone, butanol, isopropyl alcohol, N, N-dimethylformamide, ethylene glycol, dimethylacetamide, ethyl acetate formate, acrylonitrile, Wherein the nanoparticles are at least one selected from the group consisting of nanoparticles and combinations thereof.
Wherein the first separation step in which the dispersion liquid passes through the micro-nozzle and the second separation step in which the materials in the dispersion liquid passing through the micro-nozzle collide with each other are continuously performed.
The concentration of the solvent is in the range of 0.1 wt% to 10 wt%, and the number of pass and collision of the dispersion in the nozzle is 5 pass to 60 pass. The concentration of the solvent, Wherein the nanoscale thickness of the single layer or the water layer is adjusted.
Wherein an acid is added to the solvent so that a functional group can be imparted to the surface of the two-dimensional nanosheet.
Wherein the surface of the nanosheet is coated with a compound selected from the group consisting of a carboxyl group, a hydroxyl group, an amide group, a glycidyl group, an isocyanate group, an epoxide group, a cyclic ether group, a sulfide group, an acetal group, a lactone group, Wherein the functional group is capable of introducing at least two functional groups.
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Cited By (4)
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| CN109205578A (en) * | 2018-08-09 | 2019-01-15 | 上海交通大学 | A kind of method of microwave-assisted liquid phase stripped laminar material preparation two-dimensional nano piece |
| CN109231177A (en) * | 2018-08-30 | 2019-01-18 | 昆明理工大学 | A method of phosphorus alkene is prepared using nano-cellulose colloidal solution up-stripping black phosphorus |
| CN110152587A (en) * | 2018-02-13 | 2019-08-23 | 华瑞墨石丹阳有限公司 | High-speed jet percussion device and the method for preparing two-dimension nano materials using the device |
| JP2019532001A (en) * | 2016-09-30 | 2019-11-07 | ザ リージェンツ オブ ザ ユニバーシティ オブ カリフォルニア | Continuous production of exfoliated 2D layered material by compressed flow |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101378734B1 (en) * | 2013-01-22 | 2014-04-04 | 주식회사 제이오 | Apparatus and method for exfoliating graphite using high temperature and high pressure medium |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2019532001A (en) * | 2016-09-30 | 2019-11-07 | ザ リージェンツ オブ ザ ユニバーシティ オブ カリフォルニア | Continuous production of exfoliated 2D layered material by compressed flow |
| US11472158B2 (en) | 2016-09-30 | 2022-10-18 | The Regents Of The University Of California | Continuous production of exfoliated 2D layered materials by compressive flow |
| CN110152587A (en) * | 2018-02-13 | 2019-08-23 | 华瑞墨石丹阳有限公司 | High-speed jet percussion device and the method for preparing two-dimension nano materials using the device |
| CN109205578A (en) * | 2018-08-09 | 2019-01-15 | 上海交通大学 | A kind of method of microwave-assisted liquid phase stripped laminar material preparation two-dimensional nano piece |
| CN109205578B (en) * | 2018-08-09 | 2021-07-13 | 上海交通大学 | Method for preparing two-dimensional nanosheet by stripping layered material through microwave-assisted liquid phase |
| CN109231177A (en) * | 2018-08-30 | 2019-01-18 | 昆明理工大学 | A method of phosphorus alkene is prepared using nano-cellulose colloidal solution up-stripping black phosphorus |
| CN109231177B (en) * | 2018-08-30 | 2021-07-16 | 昆明理工大学 | Method for preparing phosphene by using nano-cellulose colloidal solution to assist stripping of black phosphorus |
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