KR101733491B1 - Three dimensional materials quantum dots doped with molecules including hetero atoms and methods of forming the same - Google Patents
Three dimensional materials quantum dots doped with molecules including hetero atoms and methods of forming the same Download PDFInfo
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Abstract
As quantum dots of a three-dimensional material having a laminated structure, graphene quantum dots doped with hetero atoms, boron nitride doped with hetero atoms, or quantum dots doped with hetero atoms, which are inorganic chalcogenide quantum dots doped with hetero atoms, / RTI > Since the quantum dots of the three-dimensional material doped with a molecule containing the heteroatom are formed without injecting a stripper, a doping gas, or an organic material, the quantum dot can be excellent in quality, can realize various colors, And can be applied to various fields such as a semiconductor device, an energy device, or a light emitting device because a hetero element is doped to improve properties and electrical properties.
Description
The present invention relates to a molecule-doped three-dimensional material quantum dot including a hetero-element and a method of manufacturing the same. More particularly, the present invention relates to a quantum dot of a molecule-doped three-dimensional material including a hetero-element, which is prepared by using a vaporization of a solvent after intercalation of a solvent into a three-dimensional material having a three-dimensional structure, .
Graphene is a material that has a hexagonal shape of carbon atoms and has a two-dimensional planar structure. It is composed of graphite having a three-dimensional structure, carbon nanotubes having a one-dimensional structure, fullerene having a zero- ) And other physical properties. The single layer graphene film reported to date has a surface area of about 2600 m 2 / g and an electron mobility of 15,000 to 200,000 cm 2 / Vs, which are different from those of conventional carbon materials. In particular, the electron transfer rate in graphene films is close to the speed of light because electrons flow as if there is no mass in the graphene film.
Graphene quantum dots are small pieces of graphene, generally within 20 nm in size, have a non-zero band gap, and have an edge site effect ) Have photoluminescence characteristics.
Graphene quantum dots are generally prepared by oxidizing graphite to produce graphene oxide and then hydrothermal reaction. Graphite is a material in which graphene is bonded in which a carbon atom is bonded in a hexagonal ring structure. Carbon atoms forming graphene have a sp 2 bond, and the graphene layer is formed by neighboring graphene layers and van der Waals) and it is difficult to cut graphite into smaller quantum dots. Therefore, existing researchers fabricated graphene graphene by hydrothermal reaction to produce graphene quantum dots by weakening bond between graphene plane and layer. However, this method is disadvantageous in that the quality of the quantum dots produced is deteriorated due to chemical oxidation of the structure of graphite in a strong acidic solution. In addition, there are problems in that the yield is reduced as the graphene quantum dot is subjected to several steps and each step is performed.
In order to increase the yield of graphene quantum dots, many researchers have studied graphene quantum dots by irradiating hydrothermal reaction or microwaves under the conditions of producing graphite oxide graphene. Such a manufacturing method has a merit that the process is simple because there is no step of preparing the graphene oxide. However, since the strong acid solution is used similarly to the above-described method, various oxygen functional groups are bonded to the graphene quantum dot, .
Studies have also been carried out to extract graphene quantum dots from carbon materials other than graphite. Carbon fibers are subjected to high-temperature carbonization or graphitization to increase the crystallinity of the fibers and to develop a graphitic structure inside the fibers. When high temperature carbonized or graphitized carbon fibers are melted with a strong acidic solution, only the graphitic structure remains. When the carbonization or graphitization temperature is controlled, the size of the graphitic structure can be controlled. It is known that when the size of the graphite structure extracted by this method is small, it has a quantum dot characteristic. However, this method also has a disadvantage in that the yield of the quantum dots is low because the quality of the quantum dots is deteriorated due to the strong acid solution and only a small amount of quantum dots can be extracted from the expensive carbon fiber. Techniques for extracting quantum dots contained in coal have also been reported, but they have the same disadvantages as those for extracting quantum dots from carbon fibers.
As described above, the technique for producing graphene quantum dots has a problem in that the quality of graphene quantum dots is poor and the yield is low because a strong acid solution is used to scrape the graphene structure small.
Recently, researches on graphene quantum dots doped with carbon, such as nitrogen, oxygen, chlorine, and sulfur, have been actively conducted. It has been reported that the quantum yield of a graphene quantum dot doped with a hetero element other than carbon can realize various colors and improve the semiconductor property and the electrical property. Therefore, there is a study on the method of doping a graphene quantum dot with a hetero-element and its characteristics. In this method, a method of doping a gas or an organic material by oxidation and a method of doping a graphene quantum dot, And then synthesizing them into graphene quantum dots. However, it is pointed out that the method of doping an oxidized graphene quantum dot by using a gas or an organic material is low in doping yield and quantum dot quality, and is expensive and time consuming. The method of bonding organic materials to grow graphene quantum dots is relatively simple, but it is pointed out as a disadvantage that it is more expensive and can not be mass-produced than peeling the graphite.
In addition, as described above, the technique of manufacturing a quantum dot and the technique of doping a hetero-element here use a strong acidic or basic solution to sculpt the structure of a three-dimensional material to a small size, so that the quality of the quantum dot is deteriorated. There is a low problem. In addition, the method of doping the quantum dots with gaseous or organic materials and doping the hetero-elements has a problem in that the doping yield is low and an additional process is required, which increases the production cost and increases the process time.
Embodiments of the present invention aim to provide a quantum dot of a molecule-doped three-dimensional material including a high-quality hetero-element.
In another embodiment of the present invention, quantum dots of the three-dimensional material are efficiently formed by using a three-dimensional material having a three-dimensional laminated structure, and a molecule containing a heteroatom is doped into quantum dots of the three- The present invention provides a method for providing a plurality of data streams.
In one embodiment of the present invention, as a quantum dot of a three-dimensional material having a laminated structure,
A graphene quantum dot doped with a molecule containing a heteroatom, a boron nitride quantum dot doped with a molecule containing a heteroatom, and a molecular chalcogenide quantum dot doped with a molecule containing a heteroatom. A quantum dot of a three-dimensional material doped with a molecule containing a heteroatom is provided.
In an exemplary embodiment, the inorganic chalcogenide may be molybdenum disulfide.
In an exemplary embodiment, the heteroelement may be at least one selected from the group consisting of nitrogen, oxygen, sulfur, chlorine, fluorine, boron and phosphorus.
In an exemplary embodiment, the quantum dot of the three-dimensional material may have luminescent properties.
In an exemplary embodiment, the graphene quantum dot may have a thickness in the range of 0.1 nm to 200 nm and an area in the range of 1 nm 2 to 10 5 nm 2 .
In an exemplary embodiment, the molecules comprising the heteroatom may be formed by decomposition from the solvent simultaneously with the vaporization of the solvent used to form the quantum dots of the three-dimensional material, or by reaction between the decomposition products of the solvent .
In an exemplary embodiment, the molecule comprising the heteroelement is selected from the group consisting of Methyl 5-oxo-L-prolinate, 5- (hydroxymethyl) -1-methyl- (2E) -N-Hydroxy-4-methyl-2-pyrrolidinone, methyl-3-penten-2-imine, 1-butylpyrrolidin-2-one, 1- pyrrolidinyl) methanol, and 3-hydroxy-3-phenylpropyl carbamate.
In another embodiment of the present invention, there is provided a quantum dot of a three-dimensional material having a laminated structure, wherein the three-dimensional material is represented by the following
[Chemical Formula 1]
M n + 1 AX n
Wherein M is at least one element selected from the group consisting of Se, Ti, V, Cr, Zr, Nb, Mo, And tantalum (Ta), and A may be any one selected from the group consisting of Al, Si, P, S, Ga, (As), cadmium (Cd), indium (In), tin (Sn), lead (Pb), and X may be any one selected from the group consisting of carbon or nitrogen And n may be an integer within the range of 1 to 3.)
In another embodiment of the present invention, there is provided a process for producing a three-dimensional material, comprising: a first step of mixing a three-dimensional material and a solvent in a reaction vessel and depositing the solvent between the layers of the three-dimensional material; And applying heat and pressure to the reaction vessel to vaporize the solvent, separate the layers of the three-dimensional material from each other, and separate the molecules to produce quantum dots of the three-dimensional material, A second step of doping quantum dots of the three-dimensional material; A method of forming a quantum dot of a molecule-doped three-dimensional material including a hetero-element containing a hetero atom is provided.
In an exemplary embodiment, in the first step, the process of forming the mixture may be performed under conditions of pressure and temperature below the vaporization point of the solvent.
In an exemplary embodiment, the molecules comprising the heteroatom may be formed by decomposition from the solvent simultaneously with the vaporization of the solvent used to form the quantum dots of the three-dimensional material, or by reaction between the decomposition products of the solvent .
In an exemplary embodiment, the solvent is selected from the group consisting of water, ethanol, acetone, carbon tetrachloride, benzene, N-methyl-2-pyrrolidone, NMP, dimethylformamide, dimethylsulfoxide , DMSO), liquid carbon dioxide, carbon disulfide, liquid ammonia, and 1,1,1,2,3,4,4,5,5,5-dicarfluoropentane (1,1,1,2,3,4,4 , 5,5,5-decafluoropentane, nonafluorobutyl methyl ether, perfluorononane, and the like may be used.
In an exemplary embodiment, the solvent may be an aqueous phosphoric acid solution, an ammonia borane aqueous solution, or an aqueous boric acid solution.
In an exemplary embodiment, the molecule comprising the heteroatom is selected from the group consisting of methyl (2S) -5-oxopyrrolidine-2-carboxylate, 5- Methylpyrrolidin-2-one, (2E) -N-hydroxy-4-methyl-3-penten- (2E) -N-Hydroxy-4-methyl-3-penten-2-imine, N-Butyl-2-pyrrolidinone, (1-ethylpyrrolidinyl) (1-ethyl-2-pyrrolidinyl) methanol), 5- (hydroxymethyl) -1-methylpyrrolidin-2- 3-hydroxy-3-phenylpropyl carbamate. The term " 3-hydroxy-3-phenylpropyl carbamate "
In an exemplary embodiment, the heteroelement may be at least one selected from the group consisting of nitrogen, oxygen, sulfur, chlorine, fluorine, boron and phosphorus.
In an exemplary embodiment, the three-dimensional material may be at least one selected from the group consisting of a carbon material, boron nitride, and inorganic chalcogenide.
In an exemplary embodiment, the three-dimensional material may be represented by the following formula (1).
[Chemical Formula 1]
M n + 1 AX n
M is any one selected from the group consisting of Se, Ti, V, Cr, Zr, Nb, Mo, Hf and Ta; A is at least one selected from the group consisting of Al, Si, P, S, Ga, Ge , As, Cd, In, Sn, Tiu, and Pb, and X may be carbon and / or nitrogen, and n may be an integer within 1 to 3.)
In an exemplary embodiment, in the second step, the temperature and pressure of the reaction vessel containing the mixture may each be higher than the temperature and pressure of the vaporization point of the solvent.
In an exemplary embodiment, in the second step, the distance between the molecules of the solvent may be distanced as the solvent vaporizes to form a gap between the molecules of the three-dimensional material.
In an exemplary embodiment, the quantum dot of the three-dimensional material may have a thickness in the range of 0.1 nm to 200 nm and an area in the range of 1 nm 2 to 10 5 nm 2 .
In an exemplary embodiment, the yield of quantum dots of the three-dimensional material may be between 5% and 95%.
In an exemplary embodiment, the quantum dots of the three-dimensional material may be dispersed in the solvent in a concentration of from 0.001 mg / ml to 100 mg / ml.
In an exemplary embodiment, the method further comprises a fourth step of separating the quantum dots of the three-dimensional material according to size,
In the fourth step, the quantum dots of the three-dimensional material are separated by centrifugal separation, and the centrifugal separator used for the centrifugal separation may maintain the rotation rate in the range of 1000 rpm to 1,000,000 rpm.
The quantum dots of a molecule-doped three-dimensional material including a hetero-element according to an embodiment of the present invention are formed not only by the removal of the exfoliation material, the doping gas, or the organic material but also the defect of the structure is small and the hetero- The doping of the molecules can be excellent.
In addition, the quantum dot of a molecule-doped three-dimensional material including a hetero-element according to an embodiment of the present invention may exhibit various characteristics depending on the type and amount of the doped heterogeneous material, and thus can be applied to various fields.
In addition, since the quantum dots of the three-dimensional material doped with the molecules including the hetero elements can be easily separated according to the respective properties and are dispersed in the solution containing the quantum dots, the semiconductor devices, It can be applied to various fields easily.
In addition, the method of forming a quantum dot of a molecule-doped three-dimensional material including a hetero element according to an embodiment of the present invention may be applied to a peeling material such as a metal ion or a polymer, The process can be simplified by not injecting chemicals or the like.
In addition, the method of forming a quantum dot of a molecule-doped three-dimensional material including a hetero-element according to an embodiment of the present invention is characterized in that doping of a hetero-element requires no additional steps such as addition of a gas or an organic material, The solvent is decomposed to induce quantum dot formation and hetero-element doping at the same time, thereby facilitating the process.
FIG. 1 is a schematic view showing a method of manufacturing a graphene quantum dot doped with a hetero-element according to an embodiment of the present invention.
FIG. 2 is a graph showing a Raman spectrum of a lower layer of graphene quantum dots doped with hetero atoms prepared according to an embodiment of the present invention.
FIG. 3 is a graph showing a Raman spectrum of a graphene quantum dot middle layer doped with hetero atoms prepared according to an embodiment of the present invention.
FIG. 4 is a graph showing a photoluminescence (PL) spectrum according to centrifugal rotation speed of a hetero-element-doped graphene quantum dot layer prepared according to an embodiment of the present invention.
FIGS. 5A and 5B are TEM images of TEM images of a hetero-element-doped graphene quantum dot layer prepared according to an embodiment of the present invention. FIG.
FIGS. 6A and 6B are graphs showing X-ray photoelectron spectroscopy (XPS) spectra of graphene quantum dots doped with hetero atoms prepared according to an embodiment of the present invention.
FIG. 7 is a photograph showing a dispersed image of graphene quantum dots doped with hetero atoms prepared according to an embodiment of the present invention.
8 is a photograph showing a luminescence image of a graphene quantum dot doped with a hetero-element produced according to an embodiment of the present invention.
9 is a graph showing PL spectra of graphene quantum dots doped with hetero-elements prepared according to Example 2. Fig.
10A and 10B are photographs showing TEM images of graphene quantum dots doped with hetero-elements prepared according to Example 3, respectively.
11 is a photograph showing a Raman spectrum of a graphene quantum dot doped with a hetero-element produced according to Example 3. Fig.
12 is a graph showing PL spectra of graphene quantum dots prepared according to Example 4. FIG.
13A and 13B are dispersion and emission images of a solution containing a molybdenum disulfide quantum dot prepared according to Example 5, respectively.
14 is a PL spectrum of a molybdenum disulfide quantum dot prepared according to Example 5. Fig.
15A and 15B are photographs showing an atomic force microscope image and a thickness distribution diagram of a molybdenum disulfide quantum dot prepared according to Example 5, respectively.
16 is a photograph showing X-ray photoelectron spectroscopy of a molybdenum disulfide quantum dot prepared according to Example 5. Fig.
Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. Although the embodiments of the present invention have been described with reference to the accompanying drawings, it is to be understood that the same is by way of illustration and example only and is not to be construed as limiting the scope of the present invention.
The term " three-dimensional material " as used herein means a material having a three-dimensional laminated structure, and means a material having a three-dimensional laminated structure such as graphite, boron nitride, inorganic chalcogenide, MAX phases, do.
In this specification, inorganic chalcogenide refers to chalcogen (X) and molybdenum (Mo), tungsten (WS), niobium (Nb), and the like, such as sulfur (S), selenium A material containing a bond between a transition metal (M) such as rhenium (Re), nickel (Ni), vanadium (V) ≪ / RTI >
In the present specification, a MAX phase material means a material having a structure of Mn + 1A Xn, and a material in which a layer is piled up to form a three-dimensional structure. M is an early transition metal and may be any one selected from the group consisting of Se, Ti, V, Cr, Zr, Nb, Mo, Hf and Ta; , S, Ga, Ge, As, Cd, In, Sn, Tiu, and Pb. Also, X may be carbon and / or nitrogen.
As used herein, a two-dimensional material refers to a material formed by partly delaminating a three-dimensional material, and having a thickness of about 0.1 nm to 200 nm and an area ranging from about 0.1 μm 2 to about 106 μm 2 .
In this specification, a quantum dot of a three-dimensional material means a three-dimensional material having a small size of three-dimensional material and generally having a size within 20 nm.
As used herein, the carbon material means a substance collectively referred to as a material containing carbon such as graphite and carbon nanotube.
A quantum dot of a three-dimensional material doped with a molecule containing a heteroatom
The present invention relates to a quantum dot of a three-dimensional material, which is a quantum dot of a three-dimensional material, which is a graphene quantum dot doped with a molecule containing a hetero element or an inorganic chalcogenide quantum dot doped with a molecule containing a hetero element.
In an exemplary embodiment, the quantum dot of the three-dimensional material may be a graphene quantum dot, a boron nitride quantum dot, or an inorganic chalcogenide quantum dot.
The inorganic chalcogenide may have a structure in which two atoms of a chalcogen are bonded to one atom of a transition metal, and the transition metal may be, for example, molybdenum (Mo), tungsten (WS), niobium (Nb) (S), selenium (Se), tellurium (Te), and the like. The chalcogen may be at least one selected from the group consisting of Re, Ni, V, At least one selected. For example, the inorganic chalcogenide may include molybdenum disulfide or the like.
Alternatively, in an exemplary embodiment, the quantum dots of the three-dimensional material may be quantum dots of a MAX phase material represented by
[Chemical Formula 1]
M n + 1 AX n
Wherein M is at least one element selected from the group consisting of Se, Ti, V, Cr, Zr, Nb, Mo, And tantalum (Ta), and A may be any one selected from the group consisting of Al, Si, P, S, Ga, (As), cadmium (Cd), indium (In), tin (Sn), lead (Pb), and X may be any one selected from the group consisting of carbon or nitrogen And n may be an integer within the range of 1 to 3.)
In an exemplary embodiment, the heteroelement may be nitrogen, oxygen, sulfur, chlorine, phosphorus, boron, fluorine, etc. and may be present in a solvent used in the step of stripping the three-dimensional material to form the quantum dots of the three- .
In an exemplary embodiment, the solvent is a substance having surface energy similar to that of graphite, and specifically, the solvent may include at least one selected from the group including polar solvents, organic solvents, and inorganic solvents.
Examples of the polar solvent include water, ethanol, acetone and the like. Examples of the organic solvent include non-polar solvents such as carbon tetrachloride, benzene, n-hexane and the like, (N-methyl-2-pyrrolidone, NMP), dimethylformamide (DMF), dimethyl sulfoxide (DMSO), and the like. Examples of the inorganic solvent include liquid carbon dioxide, carbon disulfide, and liquid ammonia. In addition, 1,1,1,2,3,4,4,5,5,5-dicafluoropentane (1,1,1,2,3,4,4,5,5,5-decafluoropentane), Nonafluorobutyl methyl ether, and perfluorononane may be used.
Alternatively, the solvent may be an aqueous phosphoric acid solution, an ammonia borane aqueous solution or an aqueous boric acid solution.
According to an embodiment of the present invention, at a temperature and a pressure higher than the vaporization point of the solvent, the solvent vaporizes and decomposes itself, or the solvent molecules react with each other to form new molecules.
Accordingly, a molecule containing a heteroatom can be formed and doped to the quantum dots of the three-dimensional material. In an exemplary embodiment, the solvent comprises a heteroatom such as nitrogen, oxygen, sulfur, chlorine, fluorine, phosphorus, boron and the like, so that the molecule containing the heteroatom may also contain nitrogen, oxygen, sulfur, chlorine, Boron, and the like. The quantum dots of the three-dimensional material are doped with one or more elements selected from the group consisting of nitrogen, oxygen, sulfur, chlorine, fluorine, phosphorus, boron and the like as the molecules including the hetero element are doped into the quantum dots of the three- Can be doped.
In an exemplary embodiment, the molecules containing the heteroatom may be doped into the quantum dots upon formation of the quantum dots of the three-dimensional material by the molecules themselves.
For example, if the solvent is NMP, the molecule containing the heteroatom may be selected from the group consisting of Methyl 5-oxo-L-prolinate, 5- (hydroxymethyl) -1- Methyl-2-pyrrolidinone, (2E) -N-hydroxy-4-methyl-3-pentene- Hydroxy-4-methyl-3-penten-2-imine, 1-butylpyrrolidin-2-one, 1- Ethyl-2-pyrrolidinyl) methanol, 3-hydroxy-3-phenylpropyl carbamate, and the like.
In an exemplary embodiment, the quantum dots of the three-dimensional material is a thickness of 0.1nm to 200 nm range and 1nm 2 To 10 < 5 > nm < 2 >.
In an exemplary embodiment, the quantum dots of the three-dimensional material exhibit luminescence characteristics, and the quantum dots of the three-dimensional material are blue when the size is smaller and red when the size is larger. In addition, the higher the doping ratio of the molecule containing the heteroatom, the more blue, and the higher the doping ratio of the molecule containing the heteroatom, the more reddish it may be.
The quantum dot of a molecule-doped three-dimensional material including a hetero-element according to an embodiment of the present invention may be formed with high quality because it is formed without the removal of a stripper, a doping gas, or an organic material.
In addition, the quantum dots of the three-dimensional material doped with the molecules containing the hetero elements may implement various colors.
In addition, the quantum dots of the three-dimensional material doped with the molecules containing the hetero elements can be prevented from being stacked with other quantum dots because the molecules containing the hetero atoms generated in the decomposition of the solvent are bonded to the quantum dots. In addition, the quantum dots of the three-dimensional material produced according to the present invention are small in size and can be uniformly controlled. Accordingly, the dispersibility of the quantum dots of the three-dimensional material doped with the molecules containing the hetero elements can be improved.
In addition, the quantum dot of a molecule-doped three-dimensional material including a hetero-element according to an embodiment of the present invention may exhibit various characteristics depending on the kind of the hetero atoms.
For example, the quantum dot of a molecule-doped three-dimensional material including a hetero-element according to an embodiment of the present invention has a wide band gap and has a semiconductor characteristic, so that it can be applied to various electronic devices. In addition, when the hetero-element is oxygen, the quantum dot of the three-dimensional material has high dispersibility with respect to the hydrophilic solvent, so that it can be used to produce a conductive ink having a high concentration. When the heteroelement is at least one selected from the group consisting of nitrogen, fluorine, sulfur, etc., the quantum dots of the three-dimensional material lower the energy that the quantum dot oxygen atoms of the three-dimensional material adsorb or desorb on the carbon surface, It can be utilized as a reaction catalyst for producing electrons by reducing oxygen molecules. In addition, by using the semiconductor characteristics of the quantum dots of the three-dimensional material, it is possible to increase the hole transfer speed in the solar cell.
Accordingly, since the quantum dots of the three-dimensional material have various physical or chemical properties, they can be applied to various fields such as semiconductor devices, energy devices, light emitting devices, and the like.
Method for manufacturing quantum dots of three-dimensional material doped with molecules containing hetero elements
A method of manufacturing a quantum dot of a molecule-doped three-dimensional material comprising hetero elements according to embodiments of the present invention includes mixing a three-dimensional material and a solvent in a reaction vessel to form a mixture, A first step of inserting the solvent; And applying heat and pressure to the reaction vessel to vaporize the solvent to separate and separate layers of the three-dimensional material and form quantum dots of the three-dimensional material, and to form quantum dots of the three- A second step of doping a molecule containing an element; .
Each step will be described below.
1 is a schematic view showing a method of forming a quantum dot of a molecule-doped three-dimensional material including a hetero-element according to an embodiment of the present invention.
Referring to FIG. 1, first, a three-dimensional material and a solvent are mixed in a reaction vessel and the solvent is inserted between layers of the three-dimensional material (first step).
In an exemplary embodiment, the three-dimensional material may comprise a carbon material having a three-dimensional laminated structure, a boron nitride, and an inorganic chalcogenide. The carbon material may be at least one selected from the group consisting of artificial graphite, high crystalline graphite, expanded graphite, graphite graphite, microcrystalline graphite, and a carbon material containing small-sized highly crystalline carbon such as graphene quantum dot, The inorganic chalcogenide may include, for example, molybdenum disulfide or the like
Alternatively, in an exemplary embodiment, the three-dimensional material may be a MAX phase material represented by the following formula (1).
[Chemical Formula 1]
Mn + 1AXn
Wherein M is at least one element selected from the group consisting of Se, Ti, V, Cr, Zr, Nb, Mo, And tantalum (Ta), and A may be any one selected from the group consisting of Al, Si, P, S, Ga, (As), cadmium (Cd), indium (In), tin (Sn), lead (Pb), and X may be any one selected from the group consisting of carbon or nitrogen And n may be an integer within the range of 1 to 3.)
In an exemplary embodiment, the solvent may comprise at least two or more selected from the group comprising polar solvents, apolar solvents, organic solvents and inorganic solvents. The polar solvent may be, for example, water ethanol, acetone, and the non-polar solvent may be carbon tetrachloride, benzene, n-hexane, and the like. Examples of the organic solvent include N-methyl-2-pyrrolidine (NMP), dimethylformamide (DMF), dimethyl sulfoxide (DMSO) ), And the like, and the inorganic solvent may be, for example, liquid carbon dioxide, carbon disulfide, liquid ammonia, and the like.
Further, it is also possible to use 1,1,1,2,3,4,4,5,5,5-dicafluoropentane (1,1,1,2,3,4,4,5,5,5-decafluoropentane), nona A solution containing at least one selected from the group consisting of nonafluorobutyl methyl ether and perfluorononane may be used as the solvent. Alternatively, an aqueous solution of phosphoric acid, an aqueous ammonia borane solution, a solution of boric acid An aqueous solution or the like may be used.
The solvent may include heteroatoms such as nitrogen, oxygen, sulfur, chlorine, phosphorus, boron, fluorine, and the like.
In an exemplary embodiment, when a three-dimensional material and a solvent are mixed, a direct mixing process or an indirect mixing process may be performed and mixed. The direct mixing process can be performed, for example, using mechanical and electrical mixing processes, and the indirect mixing process can be performed using, for example, ultrasonic waves or microwaves.
In an exemplary embodiment, the first step may be performed under conditions of pressure and temperature below the vaporization point of the solvent.
In an exemplary embodiment, the solvent in the first step may be intermixed with a three-dimensional material and intercalated between layers of molecules within the three-dimensional material, such that the three-dimensional material has a structure in which the solvent is intercalated between layers As shown in Fig.
Thereafter, heat and pressure are applied to the reaction vessel to vaporize the solvent to separate the layers of the three-dimensional material from each other and to separate the quantum dots of the three-dimensional material, and at the same time, And a molecule containing a heteroatom is doped (Step 2).
First, heat and pressure may be applied to the mixture including the solvent and the three-dimensional material so that the phase change of the solvent present in the reaction vessel takes place.
In the second step, the temperature and the pressure of the reaction vessel may be higher than the temperature and pressure of the vaporization point of the solvent, respectively.
The second step involves a phase change process of the solvent to the gas, and when the reaction vessel in which the mixture is present is gradually heated and pressurized, the distance between the molecules of the solvent existing between the layers of the three- It is possible to form a gap between the three-dimensional material molecules. Then, when the heat and pressure inside the reaction vessel in which the mixture is present exceeds the heat and pressure of the vaporization point of the solvent in the mixture, the solvent vaporizes and the gap between the molecules of the three-dimensional material becomes larger, The three-dimensional material may be peeled off and at the same time cleaved to form quantum dots of the three-dimensional material. At this time, a part of the three-dimensional material may be partly peeled off to form a two-dimensional material having a two-dimensional structure.
In an exemplary embodiment, as the solvent is vaporized, the quantum dots of the three-dimensional material are formed and the solvent molecules are decomposed on their own, and the decomposed solvent molecules react with each other to form a molecule containing a different element . At this time, the molecules including the heteroatom can be doped into the quantum dots of the three-dimensional material. Accordingly, a quantum dot of a three-dimensional material doped with molecules including a hetero element can be formed. Further, a part of the three-dimensional material may remain in the reaction vessel without reacting with the solvent.
In an exemplary embodiment, the mixture is subjected to the second step of a three-dimensional material and from about 0.1nm to 200 nm range with the thickness of about 0.1μm and the area of 2 to 10 6 μm 2 in the range of from about 0.1 to 200nm range and a thickness And may include quantum dots of a three-dimensional material having an area ranging from about 1 nm 2 to 10 5 nm 2 .
In an exemplary embodiment, graphene and graphene quantum dots of various sizes can be formed depending on the type of solvent, and since they contain more energy than when the solvent has a high vaporization point, a wider range of graphene and graphene quantum dots Can be formed.
Thereafter, the step of separating the unreacted three-dimensional material, the two-dimensional material, and the quantum dots of the three-dimensional material that have not reacted with the solvent may be further performed (third step).
Specifically, the unreacted three-dimensional material, the two-dimensional material, and the quantum dots of the three-dimensional material can be separated by a centrifugation method or an extraction method using a filter having a diameter of about 10 to 100 or 100 nm.
The solution containing the mixture prepared in the second step may be divided into an upper layer, an intermediate layer and a lower layer. The upper layer may have quantum dots of a three-dimensional material having various sizes, the middle layer may have quantum dots of a three-dimensional material and a two-dimensional material, and the lower layer may contain unreacted three-dimensional materials and two-dimensional materials. The upper layer, the middle layer and the lower layer can be separated by centrifugation or a filter having a diameter of about 10 to 100 and 100 nm.
Thus, a two-dimensional material having a thickness of about 0.1 nm to 200 nm and an area in the range of about 0.1 μm 2 to 10 6 μm 2 , a thickness of about 0.1 nm to 200 nm, and a thickness of about 1 nm 2 to 10 5 nm 2 Quantum dots of a three-dimensional material having an area can be obtained.
The method of forming a graphene quantum dot according to an embodiment of the present invention may further include a step of separating the quantum dots of the separated three-dimensional material according to their sizes through a third step. (Step 4)
Specifically, the quantum dots of the three-dimensional material obtained through the first to third steps can be centrifuged and separated according to their sizes. When centrifuging the quantum dots of a plurality of three-dimensional materials, the centrifuge can maintain a number of revolutions of about 1,000 rpm to 1,000,000 rpm, preferably a number of revolutions of about 10,000 rpm to 150,000 rpm, Can maintain a rotational speed of about 30,000 rpm to about 110,000 rpm.
When using a method of manufacturing quantum dots of a molecule-doped three-dimensional material containing a hetero-element according to an exemplary embodiment, the quantum dot of the three-dimensional material can be produced with a yield of 5% to 95%.
In the exemplary embodiment, since the quantum dots of the molecule-doped three-dimensional material obtained through the first through fourth steps have luminescence characteristics and have excellent electrical characteristics, the transparent electrodes, the organic light emitting diode (OLED) , An organic solar cell (OPV), or an electrode of an electric device or a semiconductor material. In addition, the quantum dots of the three-dimensional material doped with the molecules containing the heteroatom may be dispersed in the remaining solvent at a concentration of about 0.001 mg / ml to 100 mg / ml, thereby exhibiting excellent dispersibility.
The method of forming a quantum dot of a three-dimensional material according to the exemplary embodiment uses the condensation and vaporization characteristics of a solvent without requiring a peeling material such as a metal ion or a polymer as essential elements for peeling the three-dimensional material, .
Further, since no additional chemicals are added to the manufacturing process, the quantum dots of the three-dimensional material according to the manufacturing method can have excellent quality.
Finally, the quantum dots of the three-dimensional material prepared by the above method can be separated by a simple method such as a centrifugal separation method, and can be easily applied to each application field of high quality since they are produced in a form dispersed in a solution.
Hereinafter, the present invention will be described in more detail with reference to Examples. It is to be understood by those skilled in the art that these embodiments are only for illustrating the present invention and that the scope of the present invention is not construed as being limited by these embodiments.
Example 1
The graphite was mixed with the NMP solvent at a ratio of about 1: 70, followed by stirring for about 2 hours. The prepared mixture was put into a reaction vessel capable of being pressurized and heated and heated to about 300 DEG C, at which time the pressure was raised to about 100 atm. The mixture was allowed to react for 24 hours under the above conditions to form graphene quantum dots and to dope a molecule containing nitrogen and oxygen in NMP solvent. Then, it was analyzed by dividing it into lower layer, middle layer and upper layer.
Example 2
The graphene quantum dots were formed by the same process except for heating and mixing at about 50 캜 for 3 hours before the heating and pressurizing process in Example 1, followed by separation.
Example 3
In Example 1, graphene quantum dots were formed by the same process except that a surfactant was added to a mixture of graphite and a solvent, followed by separation.
Example 4
The graphene quantum dots were prepared in the same manner as in Example 1 except that ethanol was used as another organic solvent .
Example 5
The molybdenum disulfide powder was mixed with the ethyl alcohol solvent at a concentration of 0.1 mg / ml and then stirred for about 2 hours to prepare a mixture of the solvent and the molybdenum disulfide. The prepared mixture was placed in a pressurizable and heatable reactor and heated to 300 DEG C, and the pressure was increased to about 250 atm. Thereafter, the reaction was carried out for 10 hours under a high temperature / high pressure reaction, and the resultant was centrifuged several times at about 8000 rpm to prepare molybdenum disulfide quantum dots.
Experimental Example 1
The physical properties of molecule-doped graphene quantum dots prepared through Example 1 were measured by various methods and are shown in FIGS. 2 to 7. FIG.
FIGS. 2 and 3 are graphs showing Raman spectra of the graphene quantum dot bottom layer and middle layer portion, respectively, prepared according to an embodiment of the present invention. Referring to FIG. 2, the lower layer showed a Raman spectrum similar to that of graphite, which was considered to be unreacted residual graphite. 3, it is observed that the graph of the Raman spectra of the middle layer is gentle, and thus it can be confirmed that multi-layer graphene of several micrometers size and graphene quantum dots are mixed.
Since graphene quantum dots are formed in the upper layer and quantum dots in various sizes are mixed in the upper layer, quantum dots are separated by size using a centrifuge. FIG. 4 is a graph showing a PL spectrum according to centrifugal rotation speed of an upper layer of graphene quantum dot prepared according to an embodiment of the present invention. FIG. Referring to FIG. 4, it can be seen that the PL spectra are shifted toward shorter wavelengths because graphene quantum dots having a small size are formed at a high centrifugation speed (110,000 rpm). FIGS. 5A and 5B are TEM images of graphene quantum dots according to centrifugal rotation speeds of the graphene quantum dot upper layer produced according to an embodiment of the present invention. FIG. Referring to FIGS. 5A and 5B, it can be reconfirmed that small-sized quantum dots are present when centrifugation at a high speed such as 110,000 rpm as in the PL spectrum of FIG. 4 is performed.
6A and 6B are graphs showing XPS spectra of graphene quantum dots prepared according to one embodiment of the present invention. 6A and 6B, it was confirmed that the solvent was decomposed and doped with nitrogen and oxygen atoms on the graphene quantum dot.
7 and 8 are photographs showing a dispersion image and a luminescence image of a graphene quantum dot doped with a molecule containing nitrogen prepared according to Example 1, respectively. FIG. 7 is a graph showing the results of separation of graphene quantum dots according to Example 1 from grapevines having a size of about 10,000 nm, 30,000 nm, 50,000 nm, 70,000 nm, 90,000 nm and 11,000 nm from the left side, It is the photograph which measured dispersion excellence. 7, it was observed that the graphene quantum dot prepared according to Example 1 was easily dispersed in a solvent regardless of its size.
FIG. 8 is a graph showing the results of separation of graphene quantum dots prepared according to Example 1 from grapevines having a size of about 10,000 nm, 30,000 nm, 50,000 nm, 70,000 nm, 90,000 nm and 11,000 nm from the left, This is a photograph measuring the luminance. Referring to FIG. 8, the graphene quantum dots doped with the molecules prepared according to Example 1 exhibit a blue color with a smaller size and a red color with a larger size.
Experimental Example 2
The PL spectra of the graphene quantum dots formed in Example 2 were observed and are shown in Fig.
As shown in FIG. 9, as the mixing time before heating and pressing increases, the amount of the solvent inserted between the graphite layers is increased, and thus graphene quantum dots having a smaller size are formed, so that the PL spectrum is shifted to a shorter wavelength .
Experimental Example 3
The PL spectra of the graphene quantum dots prepared in Example 3 were observed, and TEM images thereof were shown in Figs. 10a and 10b. Raman spectra of the graphene quantum dots prepared in Example 3 are shown in Fig.
10A, 10B, and 11, it was difficult to observe the graphene quantum dots by using the surfactant used. However, as shown in FIGS. 10A and 10B and FIG. 11, it was confirmed that high quality graphene having a size of several micrometers larger than graphene quantum dot was observed.
Experimental Example 4
PL spectra of the graphene quantum dots prepared according to Example 4 were observed and are shown in Fig.
12, PL spectra were observed even when ethanol was used under the same conditions, showing different characteristics from those obtained when NMP was used as a solvent. At this time, it was confirmed that the graphene quantum dots were doped with oxygen molecules. As a result, it was confirmed that the quantum dots of the three-dimensional material having various properties can be formed by varying the solvent conditions.
Experimental Example 5
The luminescence characteristics of the molybdenum disulfide quantum dots produced according to Example 5 were observed and shown in FIGS. 13A and 13B, and the PL spectra results of the molybdenum disulfide quantum dots were shown in FIG. In addition, the morphological characteristics of the molybdenum disulfide quantum dots were observed and shown in FIGS. 15A and 15B, and the composition of the molybdenum disulfide quantum dots was examined.
13A and 13B, it was confirmed that the molybdenum disulfide quantum dot showed luminescence characteristics in a dark place. In particular, as shown in FIG. 14, when the wavelength of the irradiation light was about 380 nm, it was confirmed that the light-emitting characteristic was exhibited at a wavelength of about 430 nm.
15A, the average thickness of the quantum dots is about 6.5 nm, which is very thin, and the size is also in the range of 10 to 20 nm, which is relatively uniform.
The composition of the quantum dots was analyzed using an X-ray photoelectron spectrometer. As shown in FIG. 16, it was confirmed that molybdenum dioxide quantum dots were formed with a S / Mo ratio of about 1.9, and it was confirmed that there were no other impurities I could.
Claims (23)
A graphene quantum dot doped with a molecule containing a heteroatom, a boron nitride quantum dot doped with a molecule containing a heteroatom, and a molecular chalcogenide quantum dot doped with a molecule containing a heteroatom. ,
The molecule containing the heterogeneous element is selected from the group consisting of methyl 5-oxo-L-prolinate, 5- (hydroxymethyl) -1-methyl-2-pyrrolidinone (5- (2E) -N-Hydroxy-4-methyl-3-penten-2-yl] 2-imine, 1-butylpyrrolidin-2-one, 1-ethyl-2-pyrrolidinyl) methanol and 3 A quantum dot of a molecule-doped three-dimensional material comprising a hetero-element comprising at least one selected from the group consisting of 3-hydroxy-3-phenylpropyl carbamate.
Wherein the heteroelement is a quantum dot of a molecule-doped three-dimensional material comprising at least one heteroatom selected from the group consisting of nitrogen, oxygen, sulfur, chlorine, fluorine, boron and phosphorus.
Wherein the quantum dot of the three-dimensional material has a light emitting property.
Wherein the graphene quantum dot has a thickness in the range of 0.1 nm to 200 nm and an area in the range of 1 nm 2 to 10 5 nm 2 .
Wherein the molecules comprising the heteroatom are formed by the decomposition of the solvent or the decomposition products of the solvent simultaneously with the vaporization of the solvent used to form the quantum dots of the three dimensional material Quantum dots of doped three-dimensional material.
A molecule containing a heteroatom is a doped inorganic chalcogenide quantum dot,
The inorganic chalcogenide is a quantum dot of a three-dimensional material doped with a molecule containing a hetero element which is molybdenum disulfide.
Wherein the three-dimensional material is represented by the following formula (1)
A quantum dot of a molecule-doped three-dimensional material comprising a heteroatom, the molecule comprising a heteroatom being doped.
[Chemical Formula 1]
M n + 1 AX n
Wherein M is at least one element selected from the group consisting of Se, Ti, V, Cr, Zr, Nb, Mo, And tantalum (Ta), and A may be any one selected from the group consisting of Al, Si, P, S, Ga, (As), cadmium (Cd), indium (In), tin (Sn) and lead (Pb). X may be at least one selected from the group consisting of carbon or nitrogen And n may be an integer within the range of 1 to 3.)
A step of vaporizing the solvent by applying heat and pressure to the reaction vessel to separate and separate layers of the three-dimensional material, generating quantum dots of the three-dimensional material, and separating the molecule containing the heterogeneous element formed by decomposition as the solvent vaporizes A second step of doping quantum dots of the three-dimensional material; / RTI >
Wherein the three-dimensional material comprises at least one heteroatom selected from the group consisting of a carbon material, boron nitride, and inorganic chalcogenide.
In the first step, the process for forming the mixture comprises a hetero-element carried out under a pressure and temperature condition less than the vaporization point of the solvent.
Wherein the molecules comprising the heteroatom are formed by the reaction between the decomposition products of the solvent or the decomposition products of the solvent simultaneously with the vaporization of the solvent used to form the quantum dots of the three- Method of forming quantum dots of doped three dimensional materials.
The solvent may be selected from the group consisting of water, ethanol, acetone, carbon tetrachloride, benzene, n-hexane, N-methyl-2-pyrrolidone (NMP), dimethylformamide (Dimethyl sulfoxide, DMSO), liquid carbon dioxide, carbon disulfide, liquid ammonia, 1,1,1,2,3,4,4,5,5,5-dicafluoropentane (1,1,1,2,3, 4,4,5,5,5-Decafluoropentane, Nonafluorobutyl methyl ether, and Perfluorononane. The molecule containing the hetero atom is at least one selected from the group consisting of 4,4,5,5,5-decafluoropentane, nonafluorobutyl methyl ether, and perfluorononane. A method for forming quantum dots of a doped three - dimensional material.
Wherein the solvent is an aqueous phosphoric acid solution, an ammonia borane aqueous solution, or an aqueous boric acid solution.
The molecule containing the heteroatom may be selected from the group consisting of methyl (2S) -5-oxopyrrolidine-2-carboxylate (methyl (2S) -5-oxopyrrolidine- Methyl-3-penten-2-imine ((2E) -N- (4-methylpyrrolidin- N-butyl-2-pyrrolidinone, (1-ethylpyrrolidinyl) methanol ((1-Ethyl-2 -pyrrolidinyl) methanol), 5- (hydroxymethyl) -1-methylpyrrolidin-2-one and 3- (3-hydroxy-3-phenylpropyl carbamate). 2. The method of claim 1,
Wherein the heteroelement comprises a heteroatom selected from the group consisting of nitrogen, oxygen, sulfur, chlorine, fluorine, boron and phosphorus.
A step of vaporizing the solvent by applying heat and pressure to the reaction vessel to separate and separate layers of the three-dimensional material, generating quantum dots of the three-dimensional material, and separating the molecule containing the heterogeneous element formed by decomposition as the solvent vaporizes A second step of doping quantum dots of the three-dimensional material; / RTI >
Wherein the three-dimensional material is represented by the following formula (1).
[Chemical Formula 1]
M n + 1 AX n
Wherein M is at least one element selected from the group consisting of Se, Ti, V, Cr, Zr, Nb, Mo, And tantalum (Ta), and A may be any one selected from the group consisting of Al, Si, P, S, Ga, (As), cadmium (Cd), indium (In), tin (Sn) and lead (Pb). X may be at least one selected from the group consisting of carbon or nitrogen And n may be an integer within the range of 1 to 3.)
Wherein in the second step, the temperature and pressure of the reaction vessel containing the mixture are each higher than the temperature and pressure of the vaporization point of the solvent, respectively.
Wherein in the second step, a distance between the molecules of the solvent is increased as the solvent vaporizes to form a gap between the molecules of the three-dimensional material, / RTI >
Wherein the quantum dot of the three-dimensional material has a thickness in the range of 0.1 nm to 200 nm and an area in the range of 1 nm 2 to 10 5 nm 2 .
Wherein a yield of the quantum dots of the three-dimensional material is 5% to 95%.
Wherein the quantum dots of the three-dimensional material are dispersed in the solvent in a concentration of 0.001 mg / ml to 100 mg / ml.
Further comprising a fourth step of separating the quantum dots of the three-dimensional material according to sizes,
In the fourth step, the quantum dots of the three-dimensional material are separated by centrifugation, and the centrifuge used for the centrifugation is maintained at a rotation speed in the range of 1000 rpm to 1,000,000 rpm. Method of forming quantum dots of dimensional materials.
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