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WO2018143611A1 - Method for manufacturing large-area metal chalcogenide thin film, and method for manufacturing electronic device comprising metal chalcogenide thin film manufactured thereby - Google Patents

Method for manufacturing large-area metal chalcogenide thin film, and method for manufacturing electronic device comprising metal chalcogenide thin film manufactured thereby Download PDF

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WO2018143611A1
WO2018143611A1 PCT/KR2018/001166 KR2018001166W WO2018143611A1 WO 2018143611 A1 WO2018143611 A1 WO 2018143611A1 KR 2018001166 W KR2018001166 W KR 2018001166W WO 2018143611 A1 WO2018143611 A1 WO 2018143611A1
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thin film
polymer
metal chalcogen
precursor
formula
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French (fr)
Korean (ko)
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정운룡
기리아누팜
양희승
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POSTECH Academy Industry Foundation
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
    • B05D3/0254—After-treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/14—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by electrical means
    • B05D3/141—Plasma treatment
    • B05D3/142—Pretreatment
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/04—Pretreatment of the material to be coated
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/125—Process of deposition of the inorganic material
    • C23C18/1279—Process of deposition of the inorganic material performed under reactive atmosphere, e.g. oxidising or reducing atmospheres
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N70/00—Solid-state devices having no potential barriers, and specially adapted for rectifying, amplifying, oscillating or switching
    • H10N70/801—Constructional details of multistable switching devices
    • H10N70/881—Switching materials
    • H10N70/882—Compounds of sulfur, selenium or tellurium, e.g. chalcogenides

Definitions

  • the present invention provides a method for producing a high-quality large-area metal chalcogen thin film having a uniform thickness and composition by coating a polymer-precursor solution containing a polymer and a metal chalcogen compound precursor on a substrate, and then heat-treating the same.
  • the present invention relates to a method for manufacturing an electronic device including an area metal chalcogen thin film.
  • S sulfur
  • Se selenium
  • Te tellurium
  • metal chacogenides metals and chalcogenes. It is a nanomaterial with a structure similar to graphene as a compound of. Since the thickness is very thin as the thickness of the atomic layer, it has flexible and transparent properties, and electrically exhibits various properties such as semiconductors and conductors.
  • the metal chalcogenide of the semiconductor property has an electron band mobility of several hundred cm 2 / V ⁇ s while having an appropriate band gap, which is suitable for the application of semiconductor devices such as transistors, Has the potential.
  • the gas phase synthesis method can form a relatively uniform thin film compared to the solution synthesis method, but requires an expensive gas phase synthesis apparatus, and it is still difficult to synthesize a large area of the uniform properties.
  • the solution synthesis method can form a thin film at a relatively low cost, but in order to produce a uniform thin film through solution synthesis, nucleation on the volume of the solution must be suppressed and nucleation is selectively performed only on the substrate. The growth of crystals is suppressed and the crystals must grow only in the horizontal direction along the substrate.
  • the present invention is to solve the above problems of the prior art, an object of the present invention is to provide a method for producing a high-quality large-area metal chalcogen thin film of uniform thickness and composition at a low cost.
  • Another object of the present invention to provide a method for manufacturing an electronic device comprising a large area metal chalcogen thin film prepared as described above.
  • One aspect of the present invention for achieving the above object comprises the steps of preparing a polymer-precursor solution comprising a polymer and a metal chalcogen compound precursor; Coating the polymer-precursor solution on a substrate; And a step of heat-treating the substrate coated with the polymer-precursor solution.
  • the polymer may be ion-bonded with the metal chalcogenide precursor in a polymer-precursor solution.
  • the polymer may also be polyalkyleneimine.
  • polyalkyleneimine may be at least one selected from the group consisting of linear polyalkyleneimines, branched polyalkyleneimines, and dendrimer-type polyalkyleneimines.
  • linear polyalkyleneimine may be a polymer represented by Formula 1
  • the branched polyalkyleneimine may be a polymer represented by Formula 2
  • the dendrimer type polyalkyleneimine may be a polymer represented by Formula 3.
  • n is the number of repetitions of the repeating unit
  • p is any one of integers from 0 to 4,
  • the weight average molecular weight of the polymer represented by the formula 1 is 1,000 to 500,000
  • R 1 and R 2 are the same as or different from each other, and each independently a hydrogen atom or an aminoalkyl group of C2 to C5,
  • n are each the number of repetitions of the repeating unit
  • p is each independently an integer of 0 to 4,
  • the weight average molecular weight of the polymer represented by the formula 2 is 1,000 to 500,000
  • R 3 to R 18 are the same as or different from each other, and each independently a hydrogen atom or an aminoalkyl group of C1 to C5,
  • p is each independently an integer of 0 to 4,
  • the weight average molecular weight of the polymer represented by the formula 3 is 1,000 to 500,000.
  • the polymer may be linear-polyethyleneimine (L-PEI).
  • the precursor of the metal chalcogen compound is at least one metal selected from the group consisting of Mo, W, Sn, Bi, Sb and S, Se, and It may include one or more chalcogen elements selected from the group consisting of Te.
  • the precursor may be at least one selected from the group consisting of ammonium tetrathiomolybdate (ATM), ammonium tetrathiotungstate (ATT), ammonium molybate (AM), and ammonium bismuth citrate (BBC) .
  • ATM ammonium tetrathiomolybdate
  • ATT ammonium tetrathiotungstate
  • AM ammonium molybate
  • BCC ammonium bismuth citrate
  • the precursor may be ammonium tetrathiomolybdate (ATM).
  • the concentration of the metal chalcogen compound precursor may be 20 to 150mM with respect to the polymer-precursor solution.
  • the polymer-precursor solution may further include a polar aprotic solvent.
  • the polar aprotic solvent may be at least one selected from the group consisting of dimethylformamide (DMF), ethylene glycol (EG), and butylamine (butylamine).
  • DMF dimethylformamide
  • EG ethylene glycol
  • butylamine butylamine
  • the step of coating the polymer-precursor solution on a substrate is spin-coating, dip-coating, bar coating ( bar-coating).
  • the coating may be carried out in a thickness of 0.6 ⁇ 500 nm, preferably 1 ⁇ 500 nm.
  • the metal chalcogen thin film may have a large area of 500 mm 2 or more.
  • the metal chalcogen thin film may have a surface roughness of 0.5 to 1.0nm.
  • coating the polymer-precursor solution on a substrate may further include surface treating the substrate before coating the polymer-precursor solution on the substrate.
  • the surface treatment can also be carried out under piranha solution treatment and oxygen plasma.
  • the substrate is Si, SiO 2 , Ge, GaN, AlN, GaP, InP, GaAs, SiC, Al 2 O 3 , LiAlO 3 , MgO, It may include any one or more of glass, quartz, sapphire, graphite, graphene.
  • the substrate may be a polymer flexible substrate such as polyimide (PI).
  • PI polyimide
  • the heat treatment step may use a rapid thermal annealing system.
  • the heat treatment step may be performed at 400 ⁇ 1,000 °C.
  • the heat treatment step may be performed under a reducing atmosphere.
  • the reducing atmosphere may include argon gas and hydrogen gas.
  • Another aspect of the invention the step of producing a metal chalcogen thin film according to the method for producing a metal chalcogen thin film; And manufacturing an electronic device including the metal chalcogen thin film.
  • the metal chalcogen thin film may further comprise the step of separating from the substrate.
  • the electronic device may be a photometer.
  • the method for producing a metal chalcogenide thin film according to the present invention has an effect of providing a high quality thin film having a large area of 6 inches or more with a uniform thickness and composition through a low production cost and a simple process.
  • the electronic device including the large-area metal chalcogen thin film manufactured by the present invention is capable of modulating a band structure according to high charge mobility and thickness, and can implement a flexible substrate, thereby making a variety of high-performance transistors, optical devices, catalysts, energy materials, and the like. There is an effect that can be applied to the field.
  • FIG. 1 is a schematic view for explaining the concept of the present invention.
  • FIG. 2 is a schematic view showing step by step the manufacturing method of the present invention.
  • LiPEG 3 is a schematic view of a polymer (L-PEI) -precursor (ATM) thin film and a metal chalcogen (MoS 2 ) thin film formed on a substrate.
  • L-PEI polymer
  • ATM metal chalcogen
  • 5 is a photograph showing the change in color of the thin film according to the thickness change of the thin film.
  • FIG. 6 is a photograph of a 6-inch substrate formed with a MoS 2 thin film prepared according to the manufacturing method according to the present invention.
  • FIG. 7 is a 3-D atomic force microscope (AFM) image of the MoS 2 thin film according to FIG. 6.
  • FIG. 8A is a low magnification TEM image of the MoS 2 thin film according to FIG. 6,
  • FIG. 8B is a high resolution TEM (HR-TEM) image
  • FIG. 8C is a cross section of an HR-TEM image
  • FIG. 8D is for Mo and S atoms.
  • 9 is a graph measuring surface roughness of a thin film according to a change in precursor concentration.
  • 11A to 11D are graphs of photoreactivity measured according to thicknesses of MoS 2 thin films.
  • 13A to 13D are graphs of the photoelectric characteristics of the optical meter according to the embodiment of the present invention.
  • first and second to be used below may be used to describe various components, but the components are not limited by the terms. The terms are used only for the purpose of distinguishing one component from another.
  • first component may be referred to as the second component, and similarly, the second component may also be referred to as the first component.
  • a component when referred to as being “formed” or “laminated” on another component, it may be directly attached to, or laminated to, the front or one side on the surface of the other component, It will be understood that other components may exist in the.
  • the present invention relates to a method for producing a large-area metal chalcogenide thin film having a uniform thickness and composition by coating a polymer-precursor solution containing a polymer and a metal chalcogenide precursor on a substrate and then heat treatment.
  • FIG. 1 is a schematic view for explaining the concept of the present invention.
  • a basic concept of the present invention will be described with reference to FIG. 1.
  • nucleation on the volume of the solution is suppressed and nucleation is selectively performed only on the substrate, crystal growth in the vertical direction is suppressed, and crystal growth only in the horizontal direction along the substrate.
  • the conditions must be met.
  • the present invention is characterized by introducing a new concept of forming a polymer thin film layer on a substrate to ensure that all reactions occur only at the interface of the substrate.
  • the method for producing a large-area metal chalcogen thin film according to the present invention comprises the steps of: (a) preparing a polymer-precursor mixed solution comprising a polymer and a metal chalcogenide precursor; (b) coating the polymer-precursor solution onto a substrate; And (c) heat treating the substrate coated with the polymer-precursor solution.
  • the manufacturing method according to the present invention will be described in more detail step by step.
  • the polymer used in the present invention preferably uses a polymer having a low melting point. It is also desirable to use a water soluble polymer having a surface charge to enhance solubility and impart stability when dispersing the precursor in solution.
  • the precursor and the polymer should be capable of ion bonding, and the polymer should be able to be coated with a thin thickness in the coating.
  • a large-area thin film having a uniform thickness and composition can be obtained by introducing a polymer coating which is easy to manufacture a thin film of uniform thickness on a substrate.
  • the polymer is able to maintain a uniform coating on the substrate through improved wettability with the substrate.
  • the viscoelastic polymer layer that reacts with heat may be coated on the phase, and phase separation may be used to synthesize a metal chalcogenide film at a desired portion on the substrate.
  • the polymer side is a high viscosity liquid phase
  • the growth of metal chalcogen crystals becomes possible.
  • the metal chalcogenide source source, precursor, element
  • the concentration of the compound source participating in the reaction by controlling the type of polymer and the coating thickness. This makes it possible to suppress the crystal growth in the vertical direction and to limit the crystal growth only in the horizontal direction along the substrate.
  • a surfactant may be used as necessary to stabilize the surface of the crystal.
  • polyalkyleneimine may be used as the polymer.
  • the polyalkyleneimine may be at least one selected from the group consisting of linear polyalkyleneimines, branched polyalkyleneimines, and dendrimer-type polyalkyleneimines, but is not limited thereto.
  • the linear polyalkyleneimine may be represented by the following structural formula (1).
  • n is the number of repetitions of the repeating unit
  • p is any one of integers from 0 to 4,
  • the weight average molecular weight of the polymer represented by Structural Formula 1 is 1,000 to 500,000.
  • the branched polyalkyleneimine may be represented by the following Structural Formula 2.
  • R 1 and R 2 are the same as or different from each other, and each independently a hydrogen atom or an aminoalkyl group of C2 to C5,
  • n are each the number of repetitions of the repeating unit
  • p is each independently an integer of 0 to 4,
  • the weight average molecular weight of the polymer represented by the formula 2 is 1,000 to 500,000.
  • the dendrimer-type polyalkyleneimine may be represented by the following structural formula (3).
  • R 3 to R 18 are the same as or different from each other, and each independently a hydrogen atom or an aminoalkyl group of C1 to C5,
  • p is each independently an integer of 0 to 4,
  • the weight average molecular weight of the polymer represented by the formula 3 is 1,000 to 500,000.
  • L-PEI linear-polyethyleneimine
  • L-PEI acts electrostatically with a precursor, which will be described later, and decomposes at around 370 ° C.
  • polyalkyleneimine specifically L-PEI
  • the coating property of the precursor is ensured, there is an advantage that can be easily coated on a large large area substrate.
  • the precursor of the metal chalcogen compound is one or more metals selected from the group consisting of Mo, W, Sn, Bi, Sb and S, Se. And Te, but may include one or more chalcogen elements selected from the group consisting of Te.
  • the precursor may be used one or more selected from the group consisting of ammonium tetrathiomolybdate (ATM), ammonium tetrathiotungstate (ATT), ammonium molybate (AM), and BBC (ammonium bismuth citrate), but is not limited thereto. It doesn't happen. In addition, it is preferable to use ATM (ammonium tetrathiomolybdate).
  • ATM ammonium tetrathiomolybdate
  • the concentration of the metal chalcogenide precursor is preferably 15 to 1000 mMyl with respect to the polymer-precursor solution.
  • a polar aprotic solvent may include, but are not limited to, one or more selected from the group consisting of dimethylformamide (DMF), ethylene glycol (EG), and butylamine.
  • DMF dimethylformamide
  • EG ethylene glycol
  • butylamine butylamine
  • the polymer-precursor solution prepared as described above is coated on a large area substrate to form a polymer-precursor thin film.
  • the method of coating the polymer-precursor solution may be a known method, for example, spin-coating, dip-coating, bar-coating, and the like. Omit.
  • the substrate is at least one of Si, SiO 2 , Ge, GaN, AlN, GaP, InP, GaAs, SiC, Al 2 O 3 , LiAlO 3 , MgO, glass, quartz, sapphire, graphite, graphene It may include.
  • the substrate may use a flexible substrate.
  • the substrate is preferably subjected to surface treatment under oxygen plasma after cleaning in order to increase adhesion to the polymer-precursor solution.
  • the coating thickness of the polymer-precursor solution is preferably in the range of 2 ⁇ 900 nm. If the coating thickness is less than 2 nm, when pyrolysis is performed, there is a problem that the metal chalcogenide film is not continuous or partially coated due to dewetting.
  • the thin film coated with the polymer-precursor solution is heat-treated to remove the solvent and the polymer, and the precursor is reduced to form a metal chalcogen thin film on the large-area substrate. Accordingly, according to the present invention, it is possible to form a high quality thin film having a uniform thickness and composition even on a large area substrate of 6 inches or more.
  • FIG. 3 is a schematic diagram of a polymer (L-PEI) -precursor (ATM) thin film and a metal chalcogen (MoS 2 ) thin film formed on a substrate according to an embodiment of the present invention.
  • the reaction mechanism for converting the polymer-precursor thin film into the metal chalcogen thin film is as follows.
  • the heat treatment step is performed at about 700 ° C. without supply of additional sulfur under a reducing atmosphere in which 4 mol% of hydrogen and 96 mol% of argon gas are mixed.
  • the substrate is placed in a heat treatment chamber under vacuum at room temperature for about 30 minutes to remove oxygen and water molecules.
  • the mixed gas is then filled in the chamber and the temperature is raised to 400-1,000 ° C. in about 10 minutes using a rapid thermal annealing system.
  • ATM is converted to MoS 3 in the range of 120 to 260 ° C. and then to MoS 2 at 400 ° C. or higher to form a thin film as shown in FIG. 3.
  • the thickness of the polymer-precursor thin film can be controlled simply by controlling the concentration of the precursor in the polymer-precursor solution.
  • concentration of the precursor in the polymer-precursor solution The relationship between precursor concentration and thin film thickness is shown in FIG. 4. As shown in FIG. 4, it can be seen that the thickness of the thin film increases as the precursor concentration increases.
  • the black, red and blue lines represent the thickness of the polymer-precursor thin film, the thickness of the MoS 2 thin film and their thickness ratios, respectively.
  • the change in the color of the thin film with increasing thickness is shown in FIG. 5.
  • Another aspect of the present invention relates to a method for manufacturing an electronic device comprising a large-area metal chalcogen thin film produced by the above method.
  • the method of manufacturing the electronic device includes preparing a metal chalcogen thin film and manufacturing an electronic device including the metal chalcogen thin film of the large area prepared as described above.
  • the electronic device including the large-area metal chalcogen thin film manufactured according to the present invention is widely used in various fields such as catalysts, sensors, piezoelectrics, electrical energy storage, hydrogen storage, optoelectronics and transistors due to its wide bandgap control capability and high mechanical flexibility. Can be applied.
  • the solution 2 and solution 1 were mixed at a volume ratio of 5: 3, respectively, and 3 mL of ethanolamine was added thereto, followed by stirring for 30 minutes to prepare a precursor-polymer solution.
  • the prepared precursor-polymer solution was prepared by filtration using a 25 micron scan filter.
  • the 6-inch SiO 2 / Si (300 nm) substrate was treated with a piranha solution in which the ratio of sulfuric acid and hydrogen peroxide was mixed at 3: 1, and then washed with distilled water (DI water) and isopropyl alcohol, followed by 150W oxygen. Treatment was performed for 60 seconds in the plasma. The precursor-polymer solution was then spin coated onto the substrate at 3000 rpm for 60 seconds to 13 nm thick.
  • the substrate coated with the precursor-polymer solution was heat-treated at 130 ° C. for 10 minutes, and then heat-treated in an atmosphere of 96% Ar and 4% H 2 for 1 hour at 700 ° C. using a rapid thermal annealing system.
  • It was. 6 is a photograph of a substrate on which a MoS 2 thin film manufactured according to an embodiment of the present invention is formed.
  • a 3-D AFM image of the MoS 2 thin film is shown in FIG. 7. As can be seen in Figure 7 it can be seen that the average roughness of the MoS 2 thin film according to the present invention is very uniform, less than 1 nm.
  • FIG. 8 is a TEM image of the MoS 2 thin film shown in FIG. 6.
  • 8A is a low magnification TEM image showing the uniformity of the thin film over a large area.
  • 8B is a high resolution TEM image (HR-TEM), showing high crystallinity of the thin film.
  • 8C is a cross section of the HR-TEM image, with interlayer distance and thickness of 0.67 nm and 9 nm, respectively.
  • EDS energy-dispersive X-ray spectroscopic
  • 10A and 10B show XPS spectra of Mo 3d and S 2p of a large area MoS 2 thin film on a substrate. 229.6 and 232.7 eV binding energy of the Mo corresponds to Mo 3d 5/2 peak and Mo 3d 3/2 peak, respectively. Binding energy of S 162.5 and 163.7 eV corresponds to the S 3p 3/2 peak, and S 2p 1/2 peak, respectively. The binding energy coincides with the binding energy of the MoS 2 crystal.
  • the peak region of the XPS spectrum was integrated to obtain a stoichiometric ratio of Mo and S of 1: 1.96.
  • FIG. 10C Raman spectra for MoS 2 thin films of various thicknesses are shown in FIG. 10C.
  • the number of MoS 2 layers can be estimated by the difference ⁇ k between the Raman modes of E 2g and A 1g .
  • the ⁇ k 22 cm ⁇ 1 value at 20 mM indicates a stack of MoS 2 layers 2-3, which is in good agreement with the 2 nm thick thin film measured via atomic force microscopy (AFM).
  • AFM atomic force microscopy
  • 10D shows an X-ray diffraction (XRD) pattern of a MoS 2 thin film (thickness 270 nm) formed by bar coating from a 300-mM precursor solution.
  • the main peak read indicates the horizontal arrangement of MoS 2 layers in the thin film.
  • FIGS. 11A to 11D The photoreactivity of the MoS 2 thin film was measured and shown in FIGS. 11A to 11D.
  • Figures 11a to 11d it can be seen that the increase in the on-off current increases as the thickness of the MoS 2 thin film increases, but in the thin film having a thickness of 18 nm or more it can be seen that the current increase is reduced by one order. .
  • This phenomenon is common in metal chalcogenide compounds because the change in the semiconductor bandgap width is caused by the change in thickness.
  • the photoreactivity of the MoS 2 thin film according to the wavelength was measured and shown in FIG. 12. As can be seen in FIG. 12, when irradiating light through a laser of a single wavelength, even when irradiated with light of the same intensity, it can be seen that the photoreaction occurs. Rather, in the case of a single wavelength, the metal chalcogen absorbs light. It was confirmed that the increase of the current was large in a specific region.
  • the current (I) -voltage (V) characteristics of a photometer manufactured using a 9-nm thick MoS 2 thin film are shown in FIG. 13A.
  • FIG. 13C The photowitching behavior of the photometer with time-resolved photocurrent response is shown in FIG. 13C.
  • a green laser (532 nm, 1 mW) was irradiated at 3.0 v and repeated on-off at 10 second intervals. When the laser was turned on and off the current rapidly increased and restored between 8 nA and 25 ⁇ A.
  • the photocurrent response was measured at high time resolution for MoS 2 thin films of various thicknesses and is shown in FIG. 13D.
  • the response time ⁇ r and the erase time ⁇ d were substantially different. This substantial difference between ⁇ r and ⁇ d is presumed to be due to various defects that exist when the number of layers is small.
  • the photocurrent response was achieved within 1.0 ms above 6 nm in thickness. This may be attributed to the fact that the defect is reduced when the number of layers is 10 or more.
  • the method for producing a metal chalcogenide thin film according to the present invention has an effect of providing a high quality thin film having a large area of 6 inches or more with a uniform thickness and composition through a low production cost and a simple process.
  • the electronic device including the large-area metal chalcogen thin film manufactured by the present invention is capable of modulating a band structure according to high charge mobility and thickness, and can implement a flexible substrate, thereby making a variety of high-performance transistors, optical devices, catalysts, energy materials, and the like. There is an effect that can be applied to the field.

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Abstract

The present invention relates to a method for manufacturing a large-area metal chalcogenide thin film and a device comprising the large-area metal chalcogenide thin film manufactured thereby, the method comprising the steps of: preparing a polymer-precursor solution; coating a substrate with the polymer-precursor solution; and heat-treating the substrate coated with the polymer-precursor solution. A high-quality, large-area metal chalcogenide thin film having a uniform thickness and composition can be manufactured at low cost according to the manufacturing method of the present invention.

Description

대면적 금속 칼코겐 박막의 제조방법 및 이에 의해 제조된 금속 칼코겐 박막을 포함하는 전자소자의 제조방법Method for manufacturing large area metal chalcogen thin film and method for manufacturing electronic device comprising metal chalcogen thin film produced thereby

본 발명은 고분자와 금속 칼코겐 화합물 전구체를 포함하는 고분자-전구체 용액을 기판 상에 코팅한 후 열처리함으로써 두께 및 조성이 균일한 고품질의 대면적 금속 칼코겐 박막을 제조하는 방법 및 이에 의해 제조된 대면적 금속 칼코겐 박막을 포함하는 전자소자의 제조방법에 관한 것이다.The present invention provides a method for producing a high-quality large-area metal chalcogen thin film having a uniform thickness and composition by coating a polymer-precursor solution containing a polymer and a metal chalcogen compound precursor on a substrate, and then heat-treating the same. The present invention relates to a method for manufacturing an electronic device including an area metal chalcogen thin film.

주기율표 16족에 속하는 원소 중 황(S), 셀레늄(Se), 텔루륨(Te)의 세 원소를 황족원소 또는 칼코겐(chalcogens)이라고 하며, 금속 칼코게나이드(metal chacogenide)는 금속과 칼코겐의 화합물로서 그래핀과 유사한 구조를 가지는 나노 재료이다. 그 두께는 원자 수 층의 두께로 매우 얇기 때문에 유연하고 투명한 특성을 가지며, 전기적으로는 반도체, 도체 등의 다양한 성질을 보인다.Among the elements belonging to group 16 of the periodic table, three elements of sulfur (S), selenium (Se), and tellurium (Te) are called sulfur elements or chalcogens, and metal chacogenides are metals and chalcogenes. It is a nanomaterial with a structure similar to graphene as a compound of. Since the thickness is very thin as the thickness of the atomic layer, it has flexible and transparent properties, and electrically exhibits various properties such as semiconductors and conductors.

특히, 반도체 성질의 금속 칼코게나이드의 경우 적절한 밴드갭(band gap)을 가지면서 수백 ㎠/V·s의 전자 이동도를 보이므로 트랜지스터 등의 반도체 소자의 응용에 적합하고 향후 유연 트랜지스터 소자에 큰 잠재력을 가지고 있다.In particular, the metal chalcogenide of the semiconductor property has an electron band mobility of several hundred cm 2 / V · s while having an appropriate band gap, which is suitable for the application of semiconductor devices such as transistors, Has the potential.

이러한 금속 칼코게나이드 박막을 효율적으로 이용하기 위하여는 대면적 기판 상에 균일하고 연속적인 박막 형성이 가능하고, 또한 유연 기판에 형성 가능한 제조 방법이 요구된다.In order to efficiently use such a metal chalcogenide thin film, a manufacturing method capable of forming a uniform and continuous thin film on a large area substrate and forming a flexible substrate is required.

한편 금속 칼코겐 박막을 형성하는 방법으로는 크게 기상합성 방법과 용액합성 방법으로 나눌 수 있다. 그러나 기상합성 방법은 용액합성 방법에 비하여 비교적 균일한 박막을 형성할 수 있으나 고가의 기상합성 장치가 필요하며, 균일한 성상의 대면적 합성에는 아직까지 많은 어려움을 겪고 있는 실정이다.On the other hand, as a method of forming a metal chalcogen thin film, it can be divided into gas phase synthesis method and solution synthesis method. However, the gas phase synthesis method can form a relatively uniform thin film compared to the solution synthesis method, but requires an expensive gas phase synthesis apparatus, and it is still difficult to synthesize a large area of the uniform properties.

또한 용액합성 방법은 비교적 저비용으로 박막을 형성할 수 있으나, 용액합성을 통해 균일한 박막을 제조하기 위하여는 용액 부피상에서의 핵생성은 억제되고 기판 위에서만 선택적으로 핵생성이 이루어져야 하며, 수직방향으로의 결정 성장은 억제되고 기판을 따라 수평방향으로만 결정이 성장하여야 한다.In addition, the solution synthesis method can form a thin film at a relatively low cost, but in order to produce a uniform thin film through solution synthesis, nucleation on the volume of the solution must be suppressed and nucleation is selectively performed only on the substrate. The growth of crystals is suppressed and the crystals must grow only in the horizontal direction along the substrate.

그러나, 일반적인 용액상에서 박막을 만들 경우에는 이와 같은 조건을 만족하기가 극히 어려우며, 현재까지 성공에 대한 보고도 없었다. 따라서, 용액합성 방법에 의한 금속 칼코겐 박막의 제조에 있어서 모든 반응이 기판의 계면에서만 발생하는 것을 보장하는 새로운 개념의 도입이 절실하게 요청되고 있는 실정이다.However, when the thin film is made in a general solution, it is extremely difficult to satisfy such conditions, and there have been no reports of success until now. Therefore, in the production of metal chalcogen thin film by the solution synthesis method, there is an urgent need to introduce a new concept that ensures that all reactions occur only at the interface of the substrate.

본 발명은 상기와 같은 종래 기술의 문제점을 해결하기 위한 것으로, 본 발명의 목적은 저렴한 비용으로 두께 및 조성이 균일한 고품질의 대면적 금속 칼코겐 박막을 제조하는 방법을 제공하는 것이다.The present invention is to solve the above problems of the prior art, an object of the present invention is to provide a method for producing a high-quality large-area metal chalcogen thin film of uniform thickness and composition at a low cost.

본 발명의 다른 목적은 상기와 같이 제조된 대면적 금속 칼코겐 박막을 포함하는 전자소자의 제조방법을 제공하는 것이다.Another object of the present invention to provide a method for manufacturing an electronic device comprising a large area metal chalcogen thin film prepared as described above.

상기와 같은 목적을 달성하기 위한 본 발명의 하나의 양상은, 고분자와 금속칼코겐 화합물 전구체를 포함하는 고분자-전구체 용액을 제조하는 단계; 상기 고분자-전구체 용액을 기판 상에 코팅하는 단계; 및 상기 고분자-전구체 용액이 코팅된 기판을 열처리하는 단계;를 포함하는 금속 칼코겐 박막의 제조방법에 관한 것이다.One aspect of the present invention for achieving the above object comprises the steps of preparing a polymer-precursor solution comprising a polymer and a metal chalcogen compound precursor; Coating the polymer-precursor solution on a substrate; And a step of heat-treating the substrate coated with the polymer-precursor solution.

본 발명의 일 구현예에 따른 금속 칼코겐 박막의 제조방법에 있어서, 상기 고분자는 고분자-전구체 용액에서 상기 금속칼코겐 화합물 전구체와 이온결합할 수 있다.In the method of manufacturing a metal chalcogen thin film according to an embodiment of the present invention, the polymer may be ion-bonded with the metal chalcogenide precursor in a polymer-precursor solution.

또한 고분자는 폴리알킬렌이민일 수 있다.The polymer may also be polyalkyleneimine.

또한 상기 폴리알킬렌이민은 선형 폴리알킬렌이민, 가지형 폴리알킬렌이민 및 덴드리머형 폴리알킬렌이민으로 이루어진 군에서 선택된 1종 이상일 수 있다.In addition, the polyalkyleneimine may be at least one selected from the group consisting of linear polyalkyleneimines, branched polyalkyleneimines, and dendrimer-type polyalkyleneimines.

또한 상기 선형 폴리알킬렌이민이 구조식 1로 표시되는 고분자이고, 상기 가지형 폴리알킬렌이민이 구조식 2로 표시되는 고분자이고, 상기 덴드리머형 폴리알킬렌이민이 구조식 3으로 표시되는 고분자일 수 있다. In addition, the linear polyalkyleneimine may be a polymer represented by Formula 1, the branched polyalkyleneimine may be a polymer represented by Formula 2, and the dendrimer type polyalkyleneimine may be a polymer represented by Formula 3.

[구조식 1][Formula 1]

Figure PCTKR2018001166-appb-I000001
Figure PCTKR2018001166-appb-I000001

상기 구조식 1에서,In the above formula 1,

m은 반복단위의 반복수이고,m is the number of repetitions of the repeating unit,

p는 0 내지 4의 정수 중 어느 하나이고,p is any one of integers from 0 to 4,

상기 구조식 1로 표시되는 고분자의 중량평균 분자량이 1,000 내지 500,000이고,The weight average molecular weight of the polymer represented by the formula 1 is 1,000 to 500,000,

[구조식 2][Formula 2]

Figure PCTKR2018001166-appb-I000002
Figure PCTKR2018001166-appb-I000002

상기 구조식 2에서,In the formula 2,

R1 및 R2는 서로 같거나 다르고, 각각 독립적으로 수소원자 또는 C2 내지 C5의 아미노알킬기이고,R 1 and R 2 are the same as or different from each other, and each independently a hydrogen atom or an aminoalkyl group of C2 to C5,

m 및 n은 각각 반복단위의 반복수이고,m and n are each the number of repetitions of the repeating unit,

p는 각각 독립적으로 0 내지 4의 정수 중 어느 하나이고,p is each independently an integer of 0 to 4,

상기 구조식 2로 표시되는 고분자의 중량평균 분자량이 1,000 내지 500,000이고,The weight average molecular weight of the polymer represented by the formula 2 is 1,000 to 500,000,

[구조식 3] [Formula 3]

Figure PCTKR2018001166-appb-I000003
Figure PCTKR2018001166-appb-I000003

상기 구조식 3에서,In the above formula 3,

R3 내지 R18은 서로 같거나 다르고, 각각 독립적으로 수소원자, 또는 C1 내지 C5의 아미노알킬기이고,R 3 to R 18 are the same as or different from each other, and each independently a hydrogen atom or an aminoalkyl group of C1 to C5,

p는 각각 독립적으로 0 내지 4의 정수 중 어느 하나이고,p is each independently an integer of 0 to 4,

상기 구조식 3으로 표시되는 고분자의 중량평균분자량이 1,000 내지 500,000이다.The weight average molecular weight of the polymer represented by the formula 3 is 1,000 to 500,000.

또한 상기 고분자가 L-PEI(linear-polyethyleneimine)일 수 있다.In addition, the polymer may be linear-polyethyleneimine (L-PEI).

본 발명의 일 구현예에 따른 금속 칼코겐 박막의 제조방법에 있어서, 상기 금속칼코겐 화합물의 전구체는 Mo, W, Sn, Bi, Sb로 이루어진 군에서 선택된 1종 이상의 금속과 S, Se, 및 Te로 이루어진 군에서 선택된 1종 이상의 칼코겐 원소를 포함할 수 있다.In the method for producing a metal chalcogen thin film according to an embodiment of the present invention, the precursor of the metal chalcogen compound is at least one metal selected from the group consisting of Mo, W, Sn, Bi, Sb and S, Se, and It may include one or more chalcogen elements selected from the group consisting of Te.

또한 상기 전구체는 ATM(ammonium tetrathiomolybdate), ATT(Ammonium tetrathiotungstate), AM(ammonium molybate), 및 BBC(ammonium bismuth citrate) 로 이루어진 군에서 선택되는 1종 이상일 수 있다. In addition, the precursor may be at least one selected from the group consisting of ammonium tetrathiomolybdate (ATM), ammonium tetrathiotungstate (ATT), ammonium molybate (AM), and ammonium bismuth citrate (BBC) .

또한 상기 전구체는 ATM(ammonium tetrathiomolybdate)일 수 있다.In addition, the precursor may be ammonium tetrathiomolybdate (ATM).

또한 상기 금속칼코겐 화합물 전구체의 농도는 고분자-전구체 용액에 대해서 20 내지 150mM일 수 있다.In addition, the concentration of the metal chalcogen compound precursor may be 20 to 150mM with respect to the polymer-precursor solution.

본 발명의 일 구현예에 따른 금속 칼코겐 박막의 제조방법에 있어서, 상기 고분자-전구체 용액은 극성 비양성자성 용매를 추가로 포함할 수 있다.In the method of manufacturing a metal chalcogen thin film according to an embodiment of the present invention, the polymer-precursor solution may further include a polar aprotic solvent.

또한 상기 극성 비양성자성 용매가 디메틸포름아미드(DMF), 에틸렌글리콜(EG), 및 부틸아민(butylamine)로 이루어진 군에서 선택된 1종 이상일 수 있다.In addition, the polar aprotic solvent may be at least one selected from the group consisting of dimethylformamide (DMF), ethylene glycol (EG), and butylamine (butylamine).

본 발명의 일 구현예에 따른 금속 칼코겐 박막의 제조방법에 있어서, 상기 고분자-전구체 용액을 기판 상에 코팅하는 단계는 스핀 코팅(spin-coating), 딥 코팅(dip-coating), 바 코팅(bar-coating) 중 어느 하나의 방법에 의해 수행될 수 있다.In the method of manufacturing a metal chalcogen thin film according to an embodiment of the present invention, the step of coating the polymer-precursor solution on a substrate is spin-coating, dip-coating, bar coating ( bar-coating).

또한 상기 코팅은 0.6~500 nm 두께, 바람직하게는 1~500 nm 두께로 수행될 수 있다.In addition, the coating may be carried out in a thickness of 0.6 ~ 500 nm, preferably 1 ~ 500 nm.

또한 상기 금속 칼코겐 박막은 면적이 500 mm2 이상의 대면적일 수 있다.In addition, the metal chalcogen thin film may have a large area of 500 mm 2 or more.

또한 상기 금속 칼코겐 박막은 표면조도가 0.5 내지 1.0nm일 수 있다.In addition, the metal chalcogen thin film may have a surface roughness of 0.5 to 1.0nm.

또한 상기 고분자-전구체 용액을 기판 상에 코팅하는 단계는, 상기 고분자-전구체 용액을 기판 상에 코팅하는 전에 기판을 표면처리하는 단계를 추가로 포함할 수 있다. In addition, coating the polymer-precursor solution on a substrate may further include surface treating the substrate before coating the polymer-precursor solution on the substrate.

또한 상기 표면처리가 피라냐 용액처리 및 산소 플라즈마 하에서 수행될 수 있다.The surface treatment can also be carried out under piranha solution treatment and oxygen plasma.

본 발명의 일 구현예에 따른 금속 칼코겐 박막의 제조방법에 있어서, 상기 기판이 Si, SiO2, Ge, GaN, AlN, GaP, InP, GaAs, SiC, Al2O3, LiAlO3, MgO, 유리, 석영, 사파이어, 그래파이트, 그래핀 중 어느 하나 이상을 포함할 수 있다.In the method of manufacturing a metal chalcogen thin film according to an embodiment of the present invention, the substrate is Si, SiO 2 , Ge, GaN, AlN, GaP, InP, GaAs, SiC, Al 2 O 3 , LiAlO 3 , MgO, It may include any one or more of glass, quartz, sapphire, graphite, graphene.

또한 상기 기판이 폴리이미드(PI)와 같은 고분자 플렉서블 기판일 수 있다.In addition, the substrate may be a polymer flexible substrate such as polyimide (PI).

본 발명의 일 구현예에 따른 금속 칼코겐 박막의 제조방법에 있어서, 상기 열처리 단계는 급속 열처리 시스템(rapid thermal annealing system)을 이용할 수 있다.In the method of manufacturing a metal chalcogen thin film according to an embodiment of the present invention, the heat treatment step may use a rapid thermal annealing system.

또한 상기 열처리 단계는 400~1,000℃ 에서 수행될 수 있다.In addition, the heat treatment step may be performed at 400 ~ 1,000 ℃.

또한 상기 열처리 단계는 환원성 분위기 하에서 수행될 수 있다.In addition, the heat treatment step may be performed under a reducing atmosphere.

또한 상기 환원성 분위기는 아르곤 가스 및 수소 가스를 포함할 수 있다.In addition, the reducing atmosphere may include argon gas and hydrogen gas.

본 발명의 또 하나의 양상은, 상기 금속 칼코겐 박막의 제조방법에 따라 금속 칼코겐 박막을 제조하는 단계; 및 상기 금속 칼코겐 박막을 포함하는 전자 소자를 제조하는 단계;를 포함하는 전자 소자의 제조방법에 관한 것이다.Another aspect of the invention, the step of producing a metal chalcogen thin film according to the method for producing a metal chalcogen thin film; And manufacturing an electronic device including the metal chalcogen thin film.

본 발명의 일 구현예에 따른 전자 소자의 제조방법에 있어서, 전자 소자를 제조하는 단계 전에, 상기 금속 칼코겐 박막을 기판으로부터 분리하는 단계를 추가로 포함할 수 있다.In the method of manufacturing an electronic device according to an embodiment of the present invention, before the step of manufacturing the electronic device, the metal chalcogen thin film may further comprise the step of separating from the substrate.

또한 상기 전자 소자가 광검침기일 수 있다.In addition, the electronic device may be a photometer.

본 발명에 따른 금속 칼코겐 박막의 제조방법은 낮은 생산 단가와 간단한 공정을 통해 두께와 조성이 균일한 6인치 이상 대면적의 고품질 박막을 제공할 수 있는 효과가 있다.The method for producing a metal chalcogenide thin film according to the present invention has an effect of providing a high quality thin film having a large area of 6 inches or more with a uniform thickness and composition through a low production cost and a simple process.

또한 본 발명에 의해 제조된 대면적 금속 칼코겐 박막을 포함하는 전자소자는 높은 전하이동도와 두께에 따른 밴드구조 변조가 가능하고 유연 기판을 구현할 수 있어 고성능 트랜지스터, 광소자, 촉매, 에너지 재료 등 다양한 분야에 응용될 수 있는 효과가 있다.In addition, the electronic device including the large-area metal chalcogen thin film manufactured by the present invention is capable of modulating a band structure according to high charge mobility and thickness, and can implement a flexible substrate, thereby making a variety of high-performance transistors, optical devices, catalysts, energy materials, and the like. There is an effect that can be applied to the field.

도 1은 본 발명의 개념을 설명하기 위한 모식적 도면이다.1 is a schematic view for explaining the concept of the present invention.

도 2는 본 발명의 제조방법을 단계별로 도시한 모식적 도면이다.2 is a schematic view showing step by step the manufacturing method of the present invention.

도 3은 기판 상에 형성된 고분자(L-PEI)-전구체(ATM) 박막과 금속 칼코겐 (MoS2) 박막의 모식적 도면이다. 3 is a schematic view of a polymer (L-PEI) -precursor (ATM) thin film and a metal chalcogen (MoS 2 ) thin film formed on a substrate.

도 4는 전구체 농도와 박막 두께와의 관계를 나타낸 그래프이다.4 is a graph showing the relationship between precursor concentration and thin film thickness.

도 5는 박막 두께 변화에 따른 박막 색깔의 변화를 나타내는 사진이다.5 is a photograph showing the change in color of the thin film according to the thickness change of the thin film.

도 6은 본 발명에 따른 제조방법에 따라 제조된 MoS2 박막이 형성된 6 인치 기판의 사진이다.6 is a photograph of a 6-inch substrate formed with a MoS 2 thin film prepared according to the manufacturing method according to the present invention.

도 7은 도 6에 따른 MoS2 박막의 3-D AFM(atomic force microscope) 이미지이다.7 is a 3-D atomic force microscope (AFM) image of the MoS 2 thin film according to FIG. 6.

도 8a는 도 6에 따른 MoS2 박막의 저배율의 TEM 이미지이고, 도 8b는 고해상 TEM(HR-TEM) 이미지이며, 도 8c는 HR-TEM 이미지의 단면이고, 도 8d는 Mo 및 S 원자에 대한 TEM의 단면 스캐닝 이미지이다.FIG. 8A is a low magnification TEM image of the MoS 2 thin film according to FIG. 6, FIG. 8B is a high resolution TEM (HR-TEM) image, FIG. 8C is a cross section of an HR-TEM image, and FIG. 8D is for Mo and S atoms. Cross section scanning image of TEM.

도 9는 전구체 농도 변화에 따른 박막의 표면 조도를 측정한 그래프이다.9 is a graph measuring surface roughness of a thin film according to a change in precursor concentration.

도 10은 XPS(X-ray photoelectron spectroscopy) 및 라만 분광법에 의해 MoS2 박막을 분석한 그래프이다.10 is a graph analyzing the MoS 2 thin film by X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy.

도 11a 내지 도 11d는 MoS2 박막의 두께에 따른 광반응성을 측정한 그래프이다.11A to 11D are graphs of photoreactivity measured according to thicknesses of MoS 2 thin films.

도 12는 파장에 따른 MoS2 박막의 광반응성을 측정한 그래프이다.12 is a graph measuring photoreactivity of MoS 2 thin film with wavelength.

도 13a 내지 도 13d는 본 발명의 실시예에 따른 광 검침기의 광전 특성을 측정한 그래프이다.13A to 13D are graphs of the photoelectric characteristics of the optical meter according to the embodiment of the present invention.

본 발명은 다양한 변환을 가할 수 있고 여러 가지 실시예를 가질 수 있는 바, 특정 실시예들을 예시하고 상세한 설명에 상세하게 설명하고자 한다. 그러나, 이는 본 발명을 특정한 실시 형태에 대해 한정하려는 것이 아니며, 본 발명의 사상 및 기술 범위에 포함되는 모든 변환, 균등물 내지 대체물을 포함하는 것으로 이해되어야 한다. 본 발명을 설명함에 있어서 관련된 공지 기술에 대한 구체적인 설명이 본 발명의 요지를 흐릴 수 있다고 판단되는 경우 그 상세한 설명을 생략한다.As the invention allows for various changes and numerous embodiments, particular embodiments will be illustrated and described in detail in the detailed description. However, this is not intended to limit the present invention to specific embodiments, it should be understood to include all transformations, equivalents, and substitutes included in the spirit and scope of the present invention. In the following description of the present invention, if it is determined that the detailed description of the related known technology may obscure the gist of the present invention, the detailed description thereof will be omitted.

또한, 이하에서 사용될 제1, 제2 등과 같이 서수를 포함하는 용어는 다양한 구성요소들을 설명하는데 사용될 수 있지만, 상기 구성요소들은 상기 용어들에 의해 한정되지는 않는다. 상기 용어들은 하나의 구성요소를 다른 구성요소로부터 구별하는 목적으로만 사용된다. 예를 들어, 본 발명의 권리 범위를 벗어나지 않으면서 제1 구성요소는 제2 구성요소로 명명될 수 있고, 유사하게 제2 구성요소도 제1 구성요소로 명명될 수 있다. In addition, terms including ordinal numbers such as first and second to be used below may be used to describe various components, but the components are not limited by the terms. The terms are used only for the purpose of distinguishing one component from another. For example, without departing from the scope of the present invention, the first component may be referred to as the second component, and similarly, the second component may also be referred to as the first component.

또한, 어떤 구성요소가 다른 구성요소 상에 "형성되어" 있다거나 "적층되어" 있다고 언급된 때에는, 그 다른 구성요소의 표면 상의 전면 또는 일면에 직접 부착되어 형성되어 있거나 적층되어 있을 수도 있지만, 중간에 다른 구성요소가 더 존재할 수도 있다고 이해되어야 할 것이다.In addition, when a component is referred to as being "formed" or "laminated" on another component, it may be directly attached to, or laminated to, the front or one side on the surface of the other component, It will be understood that other components may exist in the.

단수의 표현은 문맥상 명백하게 다르게 뜻하지 않는 한, 복수의 표현을 포함한다. 본 출원에서, "포함하다" 또는 "가지다" 등의 용어는 명세서상에 기재된 특징, 숫자, 단계, 동작, 구성요소, 부품 또는 이들을 조합한 것이 존재함을 지정하려는 것이지, 하나 또는 그 이상의 다른 특징들이나 숫자, 단계, 동작, 구성요소, 부품 또는 이들을 조합한 것들의 존재 또는 부가 가능성을 미리 배제하지 않는 것으로 이해되어야 한다.Singular expressions include plural expressions unless the context clearly indicates otherwise. In this application, the terms "comprise" or "have" are intended to indicate that there is a feature, number, step, operation, component, part, or combination thereof described in the specification, and one or more other features. It is to be understood that the present invention does not exclude the possibility of the presence or the addition of numbers, steps, operations, components, components, or a combination thereof.

이하, 본 발명의 금속 칼코겐 박막의 제조방법에 대하여 상세히 설명하기로 한다. 다만, 이는 예시로서 제시되는 것으로, 이에 의해 본 발명이 제한되지는 않으며 본 발명은 후술할 청구범위의 범주에 의해 정의될 뿐이다.Hereinafter, a method of manufacturing the metal chalcogen thin film of the present invention will be described in detail. However, this is presented as an example, by which the present invention is not limited and the present invention is defined only by the scope of the claims to be described later.

본 발명은 고분자와 금속 칼코겐 화합물 전구체를 포함하는 고분자-전구체 용액을 기판 상에 코팅한 후 열처리함으로써 두께 및 조성이 균일한 대면적의 금속 칼코겐 박막을 제조하는 방법에 관한 것이다. The present invention relates to a method for producing a large-area metal chalcogenide thin film having a uniform thickness and composition by coating a polymer-precursor solution containing a polymer and a metal chalcogenide precursor on a substrate and then heat treatment.

도 1은 본 발명의 개념을 설명하기 위한 모식적 도면이다. 이하에서는 도 1을 참조하여 본 발명의 기본적인 개념에 대하여 설명한다.1 is a schematic view for explaining the concept of the present invention. Hereinafter, a basic concept of the present invention will be described with reference to FIG. 1.

용액 합성을 통해 균일한 박막을 제조하기 위해서는 용액 부피상에서의 핵생성은 억제되고 기판 위에서만 선택적으로 핵생성이 이루어지며, 수직방향으로의 결정 성장은 억제되고 기판을 따라 수평방향으로만 결정이 성장하는 조건을 만족하여야 한다.To produce a uniform thin film through solution synthesis, nucleation on the volume of the solution is suppressed and nucleation is selectively performed only on the substrate, crystal growth in the vertical direction is suppressed, and crystal growth only in the horizontal direction along the substrate. The conditions must be met.

그러나, 일반적인 용액상에서 박막을 만들 경우에는 이와 같은 조건을 만족하기가 극히 어렵다. 따라서 본 발명에서는 모든 반응이 기판의 계면에서만 발생하는 것을 보장하기 위하여 기판 위에 고분자 박막층을 형성하는 새로운 개념을 도입함에 발명의 특징이 있다.However, when the thin film is made in a general solution, it is extremely difficult to satisfy such a condition. Therefore, the present invention is characterized by introducing a new concept of forming a polymer thin film layer on a substrate to ensure that all reactions occur only at the interface of the substrate.

도 2는 본 발명의 제조방법을 단계별로 도시한 모식적 도면이다. 도 2를 참조하면, 본 발명에 따른 대면적 금속 칼코겐 박막의 제조방법은 (a) 고분자와 금속 칼코겐 화합물 전구체를 포함하는 고분자-전구체 혼합 용액을 제조하는 단계; (b)상기 고분자-전구체 용액을 기판 상에 코팅하는 단계; 및 (c)상기 고분자-전구체 용액이 코팅된 기판을 열처리하는 단계를 포함한다. 이하에서는 본 발명에 따른 제조방법을 단계별로 보다 상세하게 설명한다.2 is a schematic view showing step by step the manufacturing method of the present invention. 2, the method for producing a large-area metal chalcogen thin film according to the present invention comprises the steps of: (a) preparing a polymer-precursor mixed solution comprising a polymer and a metal chalcogenide precursor; (b) coating the polymer-precursor solution onto a substrate; And (c) heat treating the substrate coated with the polymer-precursor solution. Hereinafter, the manufacturing method according to the present invention will be described in more detail step by step.

(a)고분자-전구체 용액을 제조하는 단계:(a) preparing a polymer-precursor solution:

균일한 박막제조를 위해서는 전구체의 균일한 코팅이 중요하다. 이를 위하여 본 발명에 사용되는 고분자는 녹는점이 낮은 고분자를 사용하는 것이 좋다. 또한 전구체를 용액에 분산할 때 용해도를 향상시키고 안정성을 부여하기 위해 표면 전하를 지니고 있는 수용성 고분자를 이용하는 것이 바람직하다. 또한 전구체와 고분자는 이온 결합을 할 수 있어야 하며 고분자는 코팅에 있어 얇은 두께로 코팅이 가능해야 한다.Uniform coating of precursors is important for uniform thin film production. To this end, the polymer used in the present invention preferably uses a polymer having a low melting point. It is also desirable to use a water soluble polymer having a surface charge to enhance solubility and impart stability when dispersing the precursor in solution. In addition, the precursor and the polymer should be capable of ion bonding, and the polymer should be able to be coated with a thin thickness in the coating.

본 발명에 따른 금속 칼코겐 박막의 제조방법은, 기판 위에 균일한 두께의 박막 제조가 쉬운 고분자 코팅을 도입함으로써 두께와 조성이 균일한 대면적 박막을 얻을 수 있게 된다. 본 발명에 있어서, 상기 고분자는 기판과의 젖음성 향상을 통해 기판 위에서 균일한 코팅을 유지할 수 있게 된다. 또한 만일 고분자 층이 기판 위에서 디웨팅(dewetting)이 발생할 경우, 또 열에 반응하는 점탄성 고분자층을 위에 코팅하여 상분리를 이용, 기판상 원하는 부분에서 금속 칼코겐 필름이 합성되도록 조절할 수 있다. In the method for producing a metal chalcogen thin film according to the present invention, a large-area thin film having a uniform thickness and composition can be obtained by introducing a polymer coating which is easy to manufacture a thin film of uniform thickness on a substrate. In the present invention, the polymer is able to maintain a uniform coating on the substrate through improved wettability with the substrate. In addition, if the polymer layer is dewetting on the substrate, the viscoelastic polymer layer that reacts with heat may be coated on the phase, and phase separation may be used to synthesize a metal chalcogenide film at a desired portion on the substrate.

본 발명의 제조방법에 따르면, 고분자 측이 고점도의 액상이기 때문에 금속 칼코겐 결정의 성장이 가능하게 된다. 또한 금속 칼코겐 화합물 소스(source, 전구체, 원소)가 고분자 박막 층에 녹아 들어간 후, 기판의 표면 위에서 선택적으로 반응이 진행되는 것이 가능하다.  According to the production method of the present invention, since the polymer side is a high viscosity liquid phase, the growth of metal chalcogen crystals becomes possible. In addition, after the metal chalcogenide source (source, precursor, element) is dissolved in the polymer thin film layer, it is possible to selectively react on the surface of the substrate.

또한 고분자의 종류 및 코팅 두께의 조절을 통해 반응에 참여하는 화합물 소스의 농도 조절이 가능하게 된다. 이에 의해 수직방향으로의 결정 성장은 억제하고 기판을 따라 수평방향으로만 결정을 성장하도록 제한 할 수 있게 된다. 이때 필요에 따라 결정의 표면을 안정화시킬 수 있는 계면활성화제를 사용할 수도 있다.In addition, it is possible to control the concentration of the compound source participating in the reaction by controlling the type of polymer and the coating thickness. This makes it possible to suppress the crystal growth in the vertical direction and to limit the crystal growth only in the horizontal direction along the substrate. In this case, a surfactant may be used as necessary to stabilize the surface of the crystal.

본 발명의 제조방법에 있어서, 상기 고분자로는 폴리알킬렌이민을 사용할 수 있다.In the production method of the present invention, polyalkyleneimine may be used as the polymer.

상기 폴리알킬렌이민은 선형 폴리알킬렌이민, 가지형 폴리알킬렌이민 및 덴드리머형 폴리알킬렌이민으로 이루어진 군에서 선택된 1종 이상일 수 있으나, 이에 한정되는 것은 아니다. The polyalkyleneimine may be at least one selected from the group consisting of linear polyalkyleneimines, branched polyalkyleneimines, and dendrimer-type polyalkyleneimines, but is not limited thereto.

본 발명의 제조방법에 있어서, 상기 선형 폴리알킬렌이민은 하기 구조식 1로 표시될 수 있다. In the production method of the present invention, the linear polyalkyleneimine may be represented by the following structural formula (1).

[구조식 1][Formula 1]

Figure PCTKR2018001166-appb-I000004
Figure PCTKR2018001166-appb-I000004

상기 구조식 1에서,In the above formula 1,

m은 반복단위의 반복수이고,m is the number of repetitions of the repeating unit,

p는 0 내지 4의 정수 중 어느 하나이고,p is any one of integers from 0 to 4,

상기 구조식 1로 표시되는 고분자의 중량평균 분자량이 1,000 내지 500,000이다.The weight average molecular weight of the polymer represented by Structural Formula 1 is 1,000 to 500,000.

본 발명에 있어서, 상기 가지형 폴리알킬렌이민은 하기 구조식 2로 표시될 수 있다.In the present invention, the branched polyalkyleneimine may be represented by the following Structural Formula 2.

[구조식 2][Formula 2]

Figure PCTKR2018001166-appb-I000005
Figure PCTKR2018001166-appb-I000005

상기 구조식 2에서,In the formula 2,

R1 및 R2는 서로 같거나 다르고, 각각 독립적으로 수소원자 또는 C2 내지 C5의 아미노알킬기이고,R 1 and R 2 are the same as or different from each other, and each independently a hydrogen atom or an aminoalkyl group of C2 to C5,

m 및 n은 각각 반복단위의 반복수이고,m and n are each the number of repetitions of the repeating unit,

p는 각각 독립적으로 0 내지 4의 정수 중 어느 하나이고,p is each independently an integer of 0 to 4,

상기 구조식 2로 표시되는 고분자의 중량평균 분자량이 1,000 내지 500,000이다.The weight average molecular weight of the polymer represented by the formula 2 is 1,000 to 500,000.

본 발명에 있어서, 상기 덴드리머형 폴리알킬렌이민은 하기 구조식 3으로 표시될 수 있다. In the present invention, the dendrimer-type polyalkyleneimine may be represented by the following structural formula (3).

[구조식 3] [Formula 3]

Figure PCTKR2018001166-appb-I000006
Figure PCTKR2018001166-appb-I000006

상기 구조식 3에서,In the above formula 3,

R3 내지 R18은 서로 같거나 다르고, 각각 독립적으로 수소원자, 또는 C1 내지 C5의 아미노알킬기이고,R 3 to R 18 are the same as or different from each other, and each independently a hydrogen atom or an aminoalkyl group of C1 to C5,

p는 각각 독립적으로 0 내지 4의 정수 중 어느 하나이고,p is each independently an integer of 0 to 4,

상기 구조식 3으로 표시되는 고분자의 중량평균분자량이 1,000 내지 500,000이다.The weight average molecular weight of the polymer represented by the formula 3 is 1,000 to 500,000.

본 발명의 바람직한 구현예에 따르면, 상기 고분자로는 L-PEI(linear-polyethyleneimine)을 사용하는 것이 좋다. L-PEI는 후술할 전구체와 정전기적으로 작용하며 370℃ 부근에서 분해된다. 폴리알킬렌이민, 구체적인 예로 L-PEI를 사용할 경우, 전구체와 고분자간의 복합체를 만들기가 용이하며, 전구체가 열에 의해 금속 칼코겐 화합물로 변하기 전에 모두 열분해 되어 최종물질에는 남지 않는다. 또한 전구체의 코팅성을 확보하게 하여 큰 대면적 기판에도 쉽게 코팅이 가능하다는 장점이 있다. According to a preferred embodiment of the present invention, it is preferable to use L-PEI (linear-polyethyleneimine) as the polymer. L-PEI acts electrostatically with a precursor, which will be described later, and decomposes at around 370 ° C. In the case of using polyalkyleneimine, specifically L-PEI, it is easy to form a complex between a precursor and a polymer, and all are pyrolyzed before the precursor is converted into a metal chalcogenide by heat, leaving no residue in the final material. In addition, the coating property of the precursor is ensured, there is an advantage that can be easily coated on a large large area substrate.

본 발명에 따른 금속 칼코겐 박막의 제조방법에 있어서, 상기 금속칼코겐 화합물의 전구체는 Mo, W, Sn, Bi, Sb로 이루어진 군에서 선택된 1종 이상의 금속과 S, Se. 및 Te로 이루어진 군에서 선택된 1종 이상의 칼코겐 원소를 포함할 수 있으나 이에 한정되는 것은 아니다.In the method for producing a metal chalcogen thin film according to the present invention, the precursor of the metal chalcogen compound is one or more metals selected from the group consisting of Mo, W, Sn, Bi, Sb and S, Se. And Te, but may include one or more chalcogen elements selected from the group consisting of Te.

본 발명에 있어서, 상기 전구체는 ATM(ammonium tetrathiomolybdate), ATT(Ammonium tetrathiotungstate), AM(ammonium molybate), 및 BBC(ammonium bismuth citrate)로 이루어진 군에서 선택되는 1종 이상을, 사용할 수 있으나, 이에 한정되는 것은 아니다. 또한 바람직하게는 ATM(ammonium tetrathiomolybdate)을 사용하는 것이 좋다. In the present invention, the precursor may be used one or more selected from the group consisting of ammonium tetrathiomolybdate (ATM), ammonium tetrathiotungstate (ATT), ammonium molybate (AM), and BBC (ammonium bismuth citrate), but is not limited thereto. It doesn't happen. In addition, it is preferable to use ATM (ammonium tetrathiomolybdate).

본 발명의 제조방법에 따르면, 상기와 같은 고분자 및 전구체를 각각 용매에 용해시킨 후 상기 고분자가 용해된 용액과 전구체가 용해된 용액을 5:4 내지 8:3의 부피비로 혼합하며, 나머지 부피를 에탄올 아민(Ethanolamine)를 첨가하여 고분자-전구체 용액을 제조한다. 에탄올 아민(Ethanolamine)은 전구체와 고분자가 복합화를 이룰때, L-PEI와 함께 전구체와 빠르게 결합하여 용액이 젤레이션(gelation)되는 현상을 막으며 안정성을 향상시키는 역할을 할 수 있다. 이때 박막의 표면 조도를 균일하게 하기 위하여 상기 금속칼코겐 화합물 전구체의 농도는 고분자-전구체 용액에 대해서 15 내지 1000 mM일인 것이 바람직하다. According to the production method of the present invention, after dissolving the polymer and the precursor as described above in a solvent, the solution in which the polymer is dissolved and the solution in which the precursor is dissolved are mixed in a volume ratio of 5: 4 to 8: 3, the remaining volume Ethanol amine is added to prepare a polymer-precursor solution. Ethanol amine (Ethanolamine) when the precursor and the polymer is complexed, it can quickly combine with the precursor with L-PEI to prevent the gelation (gelation) of the solution and play a role in improving the stability. In this case, in order to make the surface roughness of the thin film uniform, the concentration of the metal chalcogenide precursor is preferably 15 to 1000 mMyl with respect to the polymer-precursor solution.

본 발명에 있어서, 상기 용매로는 극성 비양성자성 용매를 사용하는 것이 바람직하다. 상기 극성 비양성자성 용매의 예로는, 이에 한정되는 것은 아니나, 디메틸포름아미드(DMF), 에틸렌글리콜(EG), 및 부틸아민(butylamine)로 이루어진 군에서 선택된 1종 이상을 사용할 수 있다.In the present invention, it is preferable to use a polar aprotic solvent as the solvent. Examples of the polar aprotic solvent may include, but are not limited to, one or more selected from the group consisting of dimethylformamide (DMF), ethylene glycol (EG), and butylamine.

(b) 고분자-전구체 용액을 기판 상에 코팅하는 단계: (b) coating the polymer-precursor solution onto the substrate:

이어서, 상기와 같이 준비된 고분자-전구체 용액을 대면적 기판 상에 코팅하여 고분자-전구체 박막을 형성한다. 상기 고분자-전구체 용액을 코팅하는 방법은 공지의 방법, 예를 들어 스핀 코팅(spin-coating), 딥 코팅(dip-coating), 바 코팅(bar-coating) 등을 사용할 수 있으며 이에 대한 상세한 설명은 생략한다. Subsequently, the polymer-precursor solution prepared as described above is coated on a large area substrate to form a polymer-precursor thin film. The method of coating the polymer-precursor solution may be a known method, for example, spin-coating, dip-coating, bar-coating, and the like. Omit.

본 발명에 따르면 상기 기판은 Si, SiO2, Ge, GaN, AlN, GaP, InP, GaAs, SiC, Al2O3, LiAlO3, MgO, 유리, 석영, 사파이어, 그래파이트, 그래핀 중 어느 하나 이상을 포함할 수 있다. According to the invention the substrate is at least one of Si, SiO 2 , Ge, GaN, AlN, GaP, InP, GaAs, SiC, Al 2 O 3 , LiAlO 3 , MgO, glass, quartz, sapphire, graphite, graphene It may include.

본 발명에 따르면 특히 상기 기판은 플렉서블 기판을 사용할 수 있다. According to the present invention, in particular, the substrate may use a flexible substrate.

또한 상기 기판은 고분자-전구체 용액과의 접착력을 높이기 위하여 세정 후 산소 플라즈마 하에서 표면처리를 하는 것이 바람직하다. In addition, the substrate is preferably subjected to surface treatment under oxygen plasma after cleaning in order to increase adhesion to the polymer-precursor solution.

본 발명의 제조방법에 있어서, 상기 고분자-전구체 용액의 코팅 두께는 2~900 nm 범위인 것이 바람직하다. 코팅 두께가 2 nm 미만이면 열분해가 이루어졌을 때, 금속 칼코겐 필름이 연속적이지 않거나 디웨팅이 발생하여 부분적으로 코팅이 안 되는 문제가 있다. In the production method of the present invention, the coating thickness of the polymer-precursor solution is preferably in the range of 2 ~ 900 nm. If the coating thickness is less than 2 nm, when pyrolysis is performed, there is a problem that the metal chalcogenide film is not continuous or partially coated due to dewetting.

(c) 고분자-전구체 용액이 코팅된 기판을 열처리하는 단계:(c) heat-treating the substrate coated with the polymer-precursor solution:

이어서 상기와 같이 고분자-전구체 용액이 코팅된 박막을 열처리함으로써 용매 및 고분자를 제거하고 전구체를 환원시켜 대면적의 기판 상에 금속 칼코겐 박막을 형성한다. 이에 의하여 본 발명에 따르면 6 인치 이상의 대면적 기판에도 두께와 조성이 균일한 고품질의 박막을 형성하는 것이 가능하다.Subsequently, the thin film coated with the polymer-precursor solution is heat-treated to remove the solvent and the polymer, and the precursor is reduced to form a metal chalcogen thin film on the large-area substrate. Accordingly, according to the present invention, it is possible to form a high quality thin film having a uniform thickness and composition even on a large area substrate of 6 inches or more.

도 3은 본 발명의 일 구현예에 따라 기판 상에 형성된 고분자(L-PEI)-전구체(ATM) 박막과 금속 칼코겐 (MoS2) 박막의 모식적 도면이다. 고분자-전구체 박막이 금속 칼코겐 박막으로 전환하는 반응 메커니즘은 다음과 같다.3 is a schematic diagram of a polymer (L-PEI) -precursor (ATM) thin film and a metal chalcogen (MoS 2 ) thin film formed on a substrate according to an embodiment of the present invention. The reaction mechanism for converting the polymer-precursor thin film into the metal chalcogen thin film is as follows.

(NH4)2MoS4 → 2NH3 + H2S + MoS3 (1)(NH 4 ) 2 MoS 4 → 2NH 3 + H 2 S + MoS 3 (1)

MoS3 + H2 → MoS2 + H2S (2)MoS 3 + H 2 → MoS 2 + H 2 S (2)

본 발명의 제조방법에 따르면, 상기 열처리 단계는 4 몰%의 수소와 96 몰%의 아르곤 가스가 혼합된 환원성 분위기 하에 추가적인 황의 공급 없이 약 700℃에서 수행된다. According to the preparation method of the present invention, the heat treatment step is performed at about 700 ° C. without supply of additional sulfur under a reducing atmosphere in which 4 mol% of hydrogen and 96 mol% of argon gas are mixed.

먼저 합성된 금속 칼코겐 박막의 산화를 방지하기 위하여 기판을 열처리 챔버 내에서 상온의 진공 하에 약 30분 정도 놓아두어 산소 및 물 분자를 제거한다. 이어서 챔버에 상기와 같은 혼합 가스를 채우고 급속 열처리 시스템(rapid thermal annealing system)을 이용하여 약 10분 이내에 400~1,000℃까지 온도를 상승시킨다. 여기에서 본 발명에 따르면 ATM은 120~260℃ 범위에서 MoS3로 전환되며 이어서 400℃ 이상에서 MoS2로 전환되어 도 3에 도시된 바와 같은 박막이 형성된다.First, in order to prevent oxidation of the synthesized metal chalcogen thin film, the substrate is placed in a heat treatment chamber under vacuum at room temperature for about 30 minutes to remove oxygen and water molecules. The mixed gas is then filled in the chamber and the temperature is raised to 400-1,000 ° C. in about 10 minutes using a rapid thermal annealing system. According to the present invention, ATM is converted to MoS 3 in the range of 120 to 260 ° C. and then to MoS 2 at 400 ° C. or higher to form a thin film as shown in FIG. 3.

본 발명의 제조방법에 있어서, 고분자-전구체 박막의 두께, 따라서 MoS2 박막의 두께는 고분자-전구체 용액에서 전구체의 농도를 조절함으로써 간단하게 조절할 수 있다. 전구체 농도와 박막 두께와의 관계를 도 4에 도시하였다. 도 4에 도시된 바와 같이 전구체 농도가 증가할수록 박막 두께가 증가함을 알 수 있다. 흑색, 적색, 청색 라인은 각각 고분자-전구체 박막의 두께, MoS2 박막의 두께 및 이들의 두께 비율을 나타낸다. 두께가 증가함에 따른 박막 색깔의 변화를 도 5에 도시하였다. In the production method of the present invention, the thickness of the polymer-precursor thin film, and thus the thickness of the MoS 2 thin film, can be controlled simply by controlling the concentration of the precursor in the polymer-precursor solution. The relationship between precursor concentration and thin film thickness is shown in FIG. 4. As shown in FIG. 4, it can be seen that the thickness of the thin film increases as the precursor concentration increases. The black, red and blue lines represent the thickness of the polymer-precursor thin film, the thickness of the MoS 2 thin film and their thickness ratios, respectively. The change in the color of the thin film with increasing thickness is shown in FIG. 5.

본 발명의 또 하나의 양상은 상기와 같은 방법에 의해 제조되는 대면적 금속 칼코겐 박막을 포함하는 전자소자의 제조방법에 관한 것이다. 상기 전자소자의 제조방법은, 이상 설명한 바와 같이 금속 칼코겐 박막을 제조하는 단계 및 상기와 같이 제조된 대면적의 금속 칼코겐 박막을 포함하여 전자 소자를 제조하는 단계를 포함한다.Another aspect of the present invention relates to a method for manufacturing an electronic device comprising a large-area metal chalcogen thin film produced by the above method. As described above, the method of manufacturing the electronic device includes preparing a metal chalcogen thin film and manufacturing an electronic device including the metal chalcogen thin film of the large area prepared as described above.

본 발명에 따라 제조되는 상기 대면적 금속 칼코겐 박막을 포함하는 전자 소자는 광범위한 밴드갭 조절 능력 및 높은 기계적 유연성으로 인하여 촉매, 센서, 압전기, 전기적 에너지 저장, 수소 저장, 광전자 및 트랜지스터 등 다양한 분야에 적용될 수 있다.The electronic device including the large-area metal chalcogen thin film manufactured according to the present invention is widely used in various fields such as catalysts, sensors, piezoelectrics, electrical energy storage, hydrogen storage, optoelectronics and transistors due to its wide bandgap control capability and high mechanical flexibility. Can be applied.

[실시예]EXAMPLE

이하, 본 발명을 실시예를 들어 더욱 상세하게 설명하도록 한다. 그러나 이는 예시를 위한 것으로서 이에 의하여 본 발명의 범위가 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to Examples. However, this is for illustrative purposes and the scope of the present invention is not limited thereby.

전구체-고분자 용액의 제조Preparation of Precursor-Polymer Solution

0.1g의 L-PEI 고분자(Mw = 10,000)를 10 mL의 DMF(99.8%)에 60℃에서 빠르게 교반하여 녹였다(용액 1). 또한 전체 용액 용량 대비 100 mM 의 ATM(ammonium thiomolybdate, 99.98%)을 7.5 mL DMF에 울트라소니케이터를 이용하여 50℃에서 30분간 용해시켰다(용액 2). 0.1 g of L-PEI polymer (Mw = 10,000) was dissolved in 10 mL of DMF (99.8%) by rapid stirring at 60 ° C (solution 1). In addition, 100 mM ATM (ammonium thiomolybdate, 99.98%) relative to the total solution volume was dissolved in 7.5 mL DMF using an ultrasonicator at 50 ° C. for 30 minutes (solution 2).

상기 용액 2 및 용액 1을 각각 5:3의 부피비로 혼합한 뒤 3 mL의 에탄올아민을 첨가하여 30분간 교반하여 전구체-고분자 용액을 제조하였다.The solution 2 and solution 1 were mixed at a volume ratio of 5: 3, respectively, and 3 mL of ethanolamine was added thereto, followed by stirring for 30 minutes to prepare a precursor-polymer solution.

제조된 전구체-고분자 용액은 25 마이크로미터의 주사 필터를 이용하여 걸러내어 준비하였다. The prepared precursor-polymer solution was prepared by filtration using a 25 micron scan filter.

MoS2MoS2 박막의 합성 Synthesis of thin film

6인치 SiO2/Si(300 nm)의 기판을 황산과 과산화수소수의 비율을 3:1로 혼합한 피라냐 용액으로 처리한 뒤, 증류수(DI water)와 이소프로필 알코올을 이용하여 세정한 뒤 150W 산소 플라즈마에서 60초간 처리하였다. 이어서 상기 기판 상에 3000rpm에서 60초간 전구체-고분자 용액을 13nm 두께로 스핀 코팅하였다. The 6-inch SiO 2 / Si (300 nm) substrate was treated with a piranha solution in which the ratio of sulfuric acid and hydrogen peroxide was mixed at 3: 1, and then washed with distilled water (DI water) and isopropyl alcohol, followed by 150W oxygen. Treatment was performed for 60 seconds in the plasma. The precursor-polymer solution was then spin coated onto the substrate at 3000 rpm for 60 seconds to 13 nm thick.

이어서 상기 전구체-고분자 용액이 코팅된 기판을 130℃에서 10분간 열처리한 뒤 급속 열처리 시스템(rapid thermal annealing system)을 이용하여 700℃에서 1시간 동안 96 %의 Ar과 4 %의 H2 분위기에서 열처리하였다. 도 6은 본 발명의 실시예에 따라 제조된 MoS2 박막이 형성된 기판의 사진이다. 상기 MoS2 박막의 3-D AFM 이미지를 도 7에 도시하였다. 도 7에서 알 수 있는 바와 같이 본 발명에 따른 MoS2 박막의 평균 조도는 1 nm 미만으로 매우 균일함을 확인할 수 있다.Subsequently, the substrate coated with the precursor-polymer solution was heat-treated at 130 ° C. for 10 minutes, and then heat-treated in an atmosphere of 96% Ar and 4% H 2 for 1 hour at 700 ° C. using a rapid thermal annealing system. It was. 6 is a photograph of a substrate on which a MoS 2 thin film manufactured according to an embodiment of the present invention is formed. A 3-D AFM image of the MoS 2 thin film is shown in FIG. 7. As can be seen in Figure 7 it can be seen that the average roughness of the MoS 2 thin film according to the present invention is very uniform, less than 1 nm.

도 8은 도 6에 도시된 MoS2 박막의 TEM 이미지이다. 도 8a는 저배율의 TEM 이미지로서, 넓은 면적에 걸쳐 박막의 균일성을 보여준다. 도 8b는 고해상 TEM 이미지(HR-TEM)로서, 박막의 높은 결정성을 보여준다. 도 8c는 HR-TEM 이미지의 단면으로서, 층간 거리 및 두께는 각각 0.67 nm 및 9 nm이다. 도 8d는 Mo 및 S 원자에 대하여 STEM-HAADF(high angle annular dark-field)에 의해 TEM의 단면 스캐닝을 사용하여 얻은 이미지 및 EDS(energy-dispersive X-ray spectroscopic) 분석 결과이다. 원자비율은 전체 탐지 영역에 걸쳐 화학양론적으로 부합하며(Mo:S=1:2) 이는 MoS2 박막의 성공적인 형성을 의미한다.FIG. 8 is a TEM image of the MoS 2 thin film shown in FIG. 6. 8A is a low magnification TEM image showing the uniformity of the thin film over a large area. 8B is a high resolution TEM image (HR-TEM), showing high crystallinity of the thin film. 8C is a cross section of the HR-TEM image, with interlayer distance and thickness of 0.67 nm and 9 nm, respectively. 8D is an image and energy-dispersive X-ray spectroscopic (EDS) analysis results obtained using cross-sectional scanning of TEM by high angle annular dark-field (STEM-HAADF) for Mo and S atoms. The atomic ratio is stoichiometrically consistent across the entire detection range (Mo: S = 1: 2), indicating successful formation of MoS 2 thin films.

광 검침기(Photodetector)의 제조 Manufacture of Photodetector

MoS2 박막이 형성된 기판 위에 6 % Poly(methyl methacrylate)/chloroform (PMMA sol.)를 이용하여 스핀 코팅하고 180℃에서 15분간 열처리 한 후, 30 wt% KOH 용액에 담궈 SiO2 기판으로부터 MoS2 박막을 분리하였다. 이어서, HfO2가 코팅된 웨이퍼로 전사하고 물로 여러 차례 세척한 뒤, PMMA를 디클로로메탄을 이용하여 제거하였다. 이어서 금속 SUS 마스크를 씌워 thermal evaporator를 이용하여 금으로 전극을 형성하여 2-검침(probe) 광 검침기(전극 채널 길이=500 ㎛, 활성층 면적=0.5 ㎟)를 제조하였다.Using a 6% Poly (methyl methacrylate) / chloroform (PMMA sol.) On the substrate is formed MoS 2 thin film spin-coated and heat-treated at 180 ℃ 15 bungan, MoS 2 thin film from the soak SiO 2 substrate in 30 wt% KOH solution Was separated. The HfO 2 coated wafer was then transferred and washed several times with water, after which PMMA was removed using dichloromethane. Subsequently, an electrode was formed of gold using a metal SUS mask and then thermal evaporator to prepare a 2-probe photometer (electrode channel length = 500 μm, active layer area = 0.5 mm 2).

[[ 시험예Test Example ]]

전구체 농도에 따른 전구체 박막과 Precursor thin film according to precursor concentration and MoS2MoS2 박막의 표면 조도 측정 Surface roughness measurement of thin film

전구체 농도 변화에 따른 전구체 박막과 MoS2 박막의 표면 조도를 측정하여 도 9에 도시하였다. 도 9에서 알 수 있는 바와 같이 전구체의 농도가 증가할수록 박막의 표면 조도가 증가함을 확인할 수 있었다.Surface roughnesses of the precursor thin film and the MoS 2 thin film according to the precursor concentration change were measured and shown in FIG. 9. As can be seen in Figure 9 it was confirmed that as the concentration of the precursor increases the surface roughness of the thin film.

MoS2MoS2 박막의 화학양론적 분석 Stoichiometric Analysis of Thin Films

합성된 MoS2 박막의 정밀한 화학양론, 미반응 전구체의 양 및 박막의 산화 여부를 평가하기 위하여 XPS(X-ray photoelectron spectroscopy) 및 라만 분광법에 의해 MoS2 박막을 분석하여 도 10에 도시하였다.The MoS 2 film by XPS (X-ray photoelectron spectroscopy) and Raman spectroscopy, to assess whether the amount of the oxide thin film and the precise stoichiometry, the unreacted precursors of the synthesized MoS 2 thin film is shown in Figure 10 by analysis.

도 10A 및 10B는 기판 상 대면적 MoS2 박막의 Mo 3d 및 S 2p의 XPS 스펙트럼을 도시한다. Mo의 결합에너지 229.6 및 232.7 eV는 각각 Mo 3d5 /2 피크 및 Mo 3d3 /2 피크에 대응한다. S의 결합에너지 162.5 및 163.7 eV는 각각 S 3p3 /2 피크 및 S 2p1 /2 피크에 대응한다. 상기 결합에너지는 MoS2 결정의 결합에너지와 일치한다. XPS 스펙트럼의 피크 영역을 통합하여 Mo와 S의 화학양론적 비율 1:1.96을 얻었다.10A and 10B show XPS spectra of Mo 3d and S 2p of a large area MoS 2 thin film on a substrate. 229.6 and 232.7 eV binding energy of the Mo corresponds to Mo 3d 5/2 peak and Mo 3d 3/2 peak, respectively. Binding energy of S 162.5 and 163.7 eV corresponds to the S 3p 3/2 peak, and S 2p 1/2 peak, respectively. The binding energy coincides with the binding energy of the MoS 2 crystal. The peak region of the XPS spectrum was integrated to obtain a stoichiometric ratio of Mo and S of 1: 1.96.

다양한 두께의 MoS2 박막에 대한 라만 스펙트럼을 도 10C에 도시하였다. MoS2 박막의 두께가 2 nm 에서 32 nm 로 증가함에 따라 E2g 피크 위치가 383 cm-1 에서 380 cm- 1 로 점진적으로 증가하고, A1g 피크 위치가 402 cm-1 에서 404 cm- 1 로 이동하였다. MoS2 층의 개수는 E2g 와 A1g 의 라만 모드 사이의 차(△k)에 의해 예상할 수 있다. 20mM에서 △k=22 cm-1 수치는 MoS2 층 2-3의 적층을 나타내며, 이는 AFM(atomic force microscopy)를 통해 측정된 2 nm 두께 박막과 잘 일치한다. 도 10D는 300-mM 전구체 용액으로부터 바 코팅에 의해 형성된 MoS2 박막(두께 270 nm)의 XRD(X-ray diffraction) 패턴을 도시한다. 검침된 주 피크는 박막 내에서 MoS2 층들의 수평적 배열을 나타낸다.Raman spectra for MoS 2 thin films of various thicknesses are shown in FIG. 10C. As the thickness of the MoS 2 thin film increased from 2 nm to 32 nm, the E 2g peak position gradually increased from 383 cm -1 to 380 cm - 1 , and the A 1g peak position from 402 cm -1 to 404 cm - 1 Moved. The number of MoS 2 layers can be estimated by the difference Δk between the Raman modes of E 2g and A 1g . The Δk = 22 cm −1 value at 20 mM indicates a stack of MoS 2 layers 2-3, which is in good agreement with the 2 nm thick thin film measured via atomic force microscopy (AFM). FIG. 10D shows an X-ray diffraction (XRD) pattern of a MoS 2 thin film (thickness 270 nm) formed by bar coating from a 300-mM precursor solution. The main peak read indicates the horizontal arrangement of MoS 2 layers in the thin film.

MoS2MoS2 박막의 두께에 따른  Depending on the thickness of the film 광반응성Photoreactivity 측정 Measure

MoS2 박막의 두께에 따른 광반응성을 측정하여 도 11a 내지 도 11d에 도시하였다. 도 11a 내지 도 11d에서 알 수 있는 바와 같이 MoS2 박막의 두께가 증가할수록 On-Off 전류 증가폭이 크게 나타나는 것을 확인할 수 있으나, 18 nm 이상의 두께의 박막에서는 전류 증가폭이 1 오더 감소하는 것을 확인할 수 있었다. 이러한 현상은 금속 칼코겐 화합물에서 일반적이며, 두께의 변화에 따른 반도체 밴드갭 폭의 변화가 이루어지기 때문이다. The photoreactivity of the MoS 2 thin film was measured and shown in FIGS. 11A to 11D. As can be seen in Figures 11a to 11d it can be seen that the increase in the on-off current increases as the thickness of the MoS 2 thin film increases, but in the thin film having a thickness of 18 nm or more it can be seen that the current increase is reduced by one order. . This phenomenon is common in metal chalcogenide compounds because the change in the semiconductor bandgap width is caused by the change in thickness.

파장에 따른 According to the wavelength MoS2MoS2 박막의  Thin film 광반응성Photoreactivity 측정 Measure

파장에 따른 MoS2 박막의 광반응성을 측정하여 도 12에 도시하였다. 도 12에서 알 수 있는 바와 같이 단일파장의 레이저를 통해 빛을 조사하였을 경우 동일한 세기의 빛을 조사한 경우에도, 광반응을 하는 것을 확인할 수 있으며, 오히려 단일 파장일 경우, 금속 칼코겐이 빛을 흡수하는 특정영역에서 전류의 증가폭이 크게 나타난 것을 확인하였다. The photoreactivity of the MoS 2 thin film according to the wavelength was measured and shown in FIG. 12. As can be seen in FIG. 12, when irradiating light through a laser of a single wavelength, even when irradiated with light of the same intensity, it can be seen that the photoreaction occurs. Rather, in the case of a single wavelength, the metal chalcogen absorbs light. It was confirmed that the increase of the current was large in a specific region.

광 검침기의 광전 특성 평가Evaluation of Photoelectric Properties of Photometers

9-nm 두께의 MoS2 박막을 사용하여 제조된 광 검침기의 전류(I)-전압(V) 특성을 도 13a에 도시하였다. 다양한 조명 전력(30-140 ㎼) 하에서 백색 광원을 소자에 수직으로 조사하였다. 암흑 상태 전류는 3 V 바이어스 전압에서 8 nA 이었다. 전류는 30 ㎼일 때 1.47 μA 에서 140 ㎼일 때 13.5 μA로 증가하였다(온-오프 비율=~ 10-4). The current (I) -voltage (V) characteristics of a photometer manufactured using a 9-nm thick MoS 2 thin film are shown in FIG. 13A. The white light source was irradiated perpendicular to the device under various illumination powers (30-140 Hz). Dark state current was 8 nA at 3 V bias voltage. The current increased from 1.47 μA at 30 mA to 13.5 μA at 140 mA (on-off ratio = -10 −4 ).

MoS2 박막 두께에 따른 온-오프 비율 의존성을 532 nm 녹색 레이저 하에서 측정하여 도 13b에 도시하였다. MoS2 박막의 두께가 2 nm에서 9 nm로 증가함에 따라 온-오프 비율이 ~101에서 ~104으로 증가하였다. 이어서 32 nm에서 ~102으로 감소하였다. 이 결과를 기초로 광 검침기의 활성층으로 9-nm 두께의 MoS2 박막을 선택하였다.The on-off ratio dependence on the MoS 2 thin film thickness was measured in 532 nm green laser and shown in FIG. 13B. On MoS 2 as the thickness of the thin film increased from 2 nm to 9 nm - increase in the off-rate was 10 1 to 10 4. It was then reduced to ˜10 2 at 32 nm. Based on this result, a 9-nm-thick MoS 2 thin film was selected as the active layer of the photometer.

시분해 광전류 응답(time-resolved photocurrent response)에 의한 광 검침기의 광전 거동(photoswitching behavior)을 도 13c에 도시하였다. 녹색 레이저(532 nm, 1 mW)를 3.0 v에서 조사하였으며, 10초 간격으로 온-오프를 반복하였다. 레이저가 켜지고 꺼질 때 전류는 8 nA와 25 μA 사이에서 급하게 증가하고 복원되었다.The photowitching behavior of the photometer with time-resolved photocurrent response is shown in FIG. 13C. A green laser (532 nm, 1 mW) was irradiated at 3.0 v and repeated on-off at 10 second intervals. When the laser was turned on and off the current rapidly increased and restored between 8 nA and 25 μA.

다양한 두께의 MoS2 박막에 대해 고 시간 해상(high time resolution) 하에서 광전류 응답을 측정하여 도 13d에 도시하였다. 2 nm 두께에서 응답 시간(τr)과 소거 시간(τd )이 실질적으로 상이했다. 이러한 τr와 τd 의 실질적인 차이는 층의 개수가 적을 때 존재하는 여러 결점(defects)에서 기인하는 것으로 추정된다. 그러나, 두께가 6 nm이상에서 광전류 응답은 1.0 ms 이내에서 달성되었다. 이는 층의 개수가 10 이상일 경우 결점이 감소되는 것에서 기인하는 것으로 볼 수 있다.The photocurrent response was measured at high time resolution for MoS 2 thin films of various thicknesses and is shown in FIG. 13D. At 2 nm thickness, the response time τ r and the erase time τ d were substantially different. This substantial difference between τ r and τ d is presumed to be due to various defects that exist when the number of layers is small. However, the photocurrent response was achieved within 1.0 ms above 6 nm in thickness. This may be attributed to the fact that the defect is reduced when the number of layers is 10 or more.

이상, 본 발명의 바람직한 구현예들에 대하여 설명하였으나, 해당 기술 분야에서 통상의 지식을 가진 자라면 특허청구범위에 기재된 본 발명의 사상으로부터 벗어나지 않는 범위 내에서, 구성 요소의 부가, 변경, 삭제 또는 추가 등에 의해 본 발명을 다양하게 수정 및 변경시킬 수 있을 것이며, 이 또한 본 발명의 권리범위 내에 포함된다고 할 것이다. 예를 들어, 단일형으로 설명되어 있는 각 구성 요소는 분산되어 실시될 수도 있으며, 마찬가지로 분산된 것으로 설명되어 있는 구성 요소들도 결합된 형태로 실시될 수 있다. 본 발명의 범위는 상기 상세한 설명보다는 후술하는 특허청구범위에 의하여 나타내어지며, 특허청구범위의 의미 및 범위 그리고 그 균등 개념으로부터 도출되는 모든 변경 또는 변형된 형태가 본 발명의 범위에 포함되는 것으로 해석되어야 한다.As mentioned above, preferred embodiments of the present invention have been described, but those skilled in the art may add, change, delete, or eliminate the elements within the scope not departing from the spirit of the present invention described in the claims. The present invention may be variously modified and changed by addition, etc., which will also be included within the scope of the present invention. For example, each component described as a single type may be implemented in a distributed manner, and similarly, components described as distributed may be implemented in a combined form. The scope of the present invention is shown by the following claims rather than the above description, and all changes or modifications derived from the meaning and scope of the claims and their equivalents should be construed as being included in the scope of the present invention. do.

본 발명에 따른 금속 칼코겐 박막의 제조방법은 낮은 생산 단가와 간단한 공정을 통해 두께와 조성이 균일한 6인치 이상 대면적의 고품질 박막을 제공할 수 있는 효과가 있다.The method for producing a metal chalcogenide thin film according to the present invention has an effect of providing a high quality thin film having a large area of 6 inches or more with a uniform thickness and composition through a low production cost and a simple process.

또한 본 발명에 의해 제조된 대면적 금속 칼코겐 박막을 포함하는 전자소자는 높은 전하이동도와 두께에 따른 밴드구조 변조가 가능하고 유연 기판을 구현할 수 있어 고성능 트랜지스터, 광소자, 촉매, 에너지 재료 등 다양한 분야에 응용될 수 있는 효과가 있다.In addition, the electronic device including the large-area metal chalcogen thin film manufactured by the present invention is capable of modulating a band structure according to high charge mobility and thickness, and can implement a flexible substrate, thereby making a variety of high-performance transistors, optical devices, catalysts, energy materials, and the like. There is an effect that can be applied to the field.

Claims (20)

고분자와 금속칼코겐 화합물 전구체를 포함하는 고분자-전구체 용액을 제조하는 단계;Preparing a polymer-precursor solution comprising a polymer and a metal chalcogenide precursor; 상기 고분자-전구체 용액을 기판 상에 코팅하는 단계; 및Coating the polymer-precursor solution on a substrate; And 상기 고분자-전구체 용액이 코팅된 기판을 열처리하는 단계;를 포함하는,Comprising: heat-treating the substrate coated with the polymer-precursor solution; 금속 칼코겐 박막의 제조방법.Method for producing a metal chalcogen thin film. 제1항에 있어서,The method of claim 1, 상기 고분자가 상기 고분자-전구체 용액에서 상기 금속칼코겐 화합물 전구체와 이온결합하는 것을 특징으로 하는 금속 칼코겐 박막의 제조방법.Method for producing a metal chalcogenide thin film, characterized in that the polymer is ion-bonded with the metal chalcogenide precursor in the polymer-precursor solution. 제1항에 있어서,The method of claim 1, 상기 고분자가 폴리알킬렌이민인 것을 특징으로 하는 금속 칼코겐 박막의 제조방법.Method for producing a metal chalcogen thin film, characterized in that the polymer is polyalkyleneimine. 제3항에 있어서,The method of claim 3, 상기 폴리알킬렌이민이 선형 폴리알킬렌이민, 가지형 폴리알킬렌이민 및 덴드리머형 폴리알킬렌이민으로 이루어진 군에서 선택된 1종 이상인 것을 특징으로 하는 금속 칼코겐 박막의 제조방법.And said polyalkyleneimine is at least one selected from the group consisting of linear polyalkyleneimines, branched polyalkyleneimines and dendrimer type polyalkyleneimines. 제4항에 있어서,The method of claim 4, wherein 상기 선형 폴리알킬렌이민이 구조식 1로 표시되는 고분자이고, 상기 가지형 폴리알킬렌이민이 구조식 2로 표시되는 고분자이고, 상기 덴드리머형 폴리알킬렌이민이 구조식 3으로 표시되는 고분자인 것을 특징으로 하는 금속 칼코겐 박막의 제조방법.The linear polyalkyleneimine is a polymer represented by formula 1, wherein the branched polyalkyleneimine is a polymer represented by formula 2, and the dendrimer type polyalkyleneimine is a polymer represented by formula 3 Method for producing a metal chalcogen thin film. [구조식 1][Formula 1]
Figure PCTKR2018001166-appb-I000007
Figure PCTKR2018001166-appb-I000007
 상기 구조식 1에서,In the above formula 1, m은 반복단위의 반복수이고,m is the number of repetitions of the repeating unit, p는 0 내지 4의 정수 중 어느 하나이고,p is any one of integers from 0 to 4, 상기 구조식 1로 표시되는 고분자의 중량평균 분자량이 1,000 내지 500,000이고,The weight average molecular weight of the polymer represented by the formula 1 is 1,000 to 500,000, [구조식 2][Formula 2]
Figure PCTKR2018001166-appb-I000008
Figure PCTKR2018001166-appb-I000008
 상기 구조식 2에서,In the formula 2, R1 및 R2는 서로 같거나 다르고, 각각 독립적으로 수소원자 또는 C2 내지 C5의 아미노알킬기이고,R 1 and R 2 are the same as or different from each other, and each independently a hydrogen atom or an aminoalkyl group of C2 to C5, m 및 n은 각각 반복단위의 반복수이고,m and n are each the number of repetitions of the repeating unit, p는 각각 독립적으로 0 내지 4의 정수 중 어느 하나이고,p is each independently an integer of 0 to 4, 상기 구조식 2로 표시되는 고분자의 중량평균 분자량이 1,000 내지 500,000이고,The weight average molecular weight of the polymer represented by the formula 2 is 1,000 to 500,000, [구조식 3] [Formula 3]
Figure PCTKR2018001166-appb-I000009
Figure PCTKR2018001166-appb-I000009
 상기 구조식 3에서,In the above formula 3, R3 내지 R18은 서로 같거나 다르고, 각각 독립적으로 수소원자, 또는 C1 내지 C5의 아미노알킬기이고,R 3 to R 18 are the same as or different from each other, and each independently a hydrogen atom or an aminoalkyl group of C1 to C5, p는 각각 독립적으로 0 내지 4의 정수 중 어느 하나이고,p is each independently an integer of 0 to 4, 상기 구조식 3으로 표시되는 고분자의 중량평균분자량이 1,000 내지 500,000이다.The weight average molecular weight of the polymer represented by the formula 3 is 1,000 to 500,000. 제3항에 있어서,The method of claim 3, 상기 고분자가 L-PEI(linear-polyethyleneimine)인 것을 특징으로 하는 금속 칼코겐 박막의 제조방법.Method for producing a metal chalcogen thin film, characterized in that the polymer is linear-polyethyleneimine (L-PEI). 제1항에 있어서,The method of claim 1, 상기 금속칼코겐 화합물의 전구체가 Mo, W, Sn, Bi 및 Sb로 이루어진 군에서 선택된 1종 이상의 금속과 S, Se 및 Te로 이루어진 군에서 선택된 1종 이상의 칼코겐 원소를 포함하는 것을 특징으로 하는 금속 칼코겐 박막의 제조방법.The precursor of the metal chalcogen compound is characterized in that it comprises at least one metal selected from the group consisting of Mo, W, Sn, Bi and Sb and at least one chalcogen element selected from the group consisting of S, Se and Te Method for producing a metal chalcogen thin film. 제7항에 있어서,The method of claim 7, wherein 상기 전구체가 ATM(ammonium tetrathiomolybdate), ATT(Ammonium tetrathiotungstate), AM(ammonium molybate), 및 BBC(ammonium bismuth citrate)로 이루어진 군에서 선택되는 1종 이상을 포함하는 것을 특징으로 하는 금속 칼코겐 박막의 제조방법.Preparation of the metal chalcogen thin film, characterized in that the precursor comprises at least one selected from the group consisting of ammonium tetrathiomolybdate (ATM), ammonium tetrathiotungstate (ATT), ammonium molybate (AM), and BBC (ammonium bismuth citrate) Way. 제8항에 있어서,The method of claim 8, 상기 전구체가 ATM(ammonium tetrathiomolybdate)인 것을 특징으로 하는 금속 칼코겐 박막의 제조방법.Method for producing a metal chalcogen thin film, characterized in that the precursor is ATM (ammonium tetrathiomolybdate). 제1항에 있어서, The method of claim 1, 상기 금속칼코겐 화합물 전구체의 농도가 고분자-전구체 용액에 대해서 20 내지 150mM인 것을 특징으로 하는 것을 특징으로 하는 금속 칼코겐 박막의 제조방법.Method for producing a metal chalcogen thin film, characterized in that the concentration of the metal chalcogen compound precursor is 20 to 150mM with respect to the polymer-precursor solution. 제1항에 있어서,The method of claim 1, 상기 고분자-전구체 용액이 극성 비양성자성 용매를 추가로 포함하는 것을 특징으로 하는 금속 칼코겐 박막의 제조방법.Method for producing a metal chalcogen thin film, characterized in that the polymer-precursor solution further comprises a polar aprotic solvent. 제10항에 있어서,The method of claim 10, 상기 극성 비양성자성 용매가 디메틸포름아미드(DMF), 에틸렌글리콜(EG), 및 부틸아민(butylamine)로 이루어진 군에서 선택된 1종 이상인 것을 특징으로 하는 금속 칼코겐 박막의 제조방법.Wherein said polar aprotic solvent is at least one member selected from the group consisting of dimethylformamide (DMF), ethylene glycol (EG), and butylamine (butylamine). 제1항에 있어서The method of claim 1 상기 코팅이 1~500 nm 두께로 수행되는 것을 특징으로 하는 금속 칼코겐 박막의 제조방법.Method for producing a metal chalcogen thin film, characterized in that the coating is performed with a thickness of 1 ~ 500 nm. 제1항에 있어서The method of claim 1 상기 금속 칼코겐 박막은 면적이 500 mm2 이상의 대면적인 것을 특징 특징으로 하는 금속 칼코겐 박막의 제조방법.The metal chalcogen thin film is a manufacturing method of a metal chalcogen thin film, characterized in that the large area of 500 mm 2 or more. 제14항에 있어서, The method of claim 14, 상기 금속 칼코겐 박막은 표면조도가 0.5 내지 1.0nm인 것을 특징으로 하는 금속 칼코겐 박막의 제조방법.The metal chalcogen thin film manufacturing method of the metal chalcogen thin film, characterized in that the surface roughness is 0.5 to 1.0nm. 제1항에 있어서,The method of claim 1, 상기 고분자-전구체 용액을 기판 상에 코팅하는 단계는,Coating the polymer-precursor solution on a substrate, 상기 고분자-전구체 용액을 기판 상에 코팅하는 전에 기판을 산소 플라즈마로 표면처리하는 단계를 추가로 포함하는 것을 특징으로 하는 금속 칼코겐 박막의 제조방법.And surface treating the substrate with oxygen plasma prior to coating the polymer-precursor solution on the substrate. 제1항에 있어서,The method of claim 1, 상기 열처리 단계가 400~1,000℃ 에서 수행되는 것을 특징으로 하는 금속 칼코겐 박막의 제조방법.Method for producing a metal chalcogen thin film, characterized in that the heat treatment step is carried out at 400 ~ 1,000 ℃. 제1항에 있어서,The method of claim 1, 상기 열처리 단계가 환원성 분위기 하에서 수행되는 것을 특징으로 하는 금속 칼코겐 박막의 제조방법.Method for producing a metal chalcogen thin film, characterized in that the heat treatment step is carried out in a reducing atmosphere. 제1항의 금속 칼코겐 박막의 제조방법에 따라 금속 칼코겐 박막을 제조하는 단계; 및Preparing a metal chalcogen thin film according to the method of manufacturing a metal chalcogen thin film of claim 1; And 상기 금속 칼코겐 박막을 포함하는 전자 소자를 제조하는 단계;를 Manufacturing an electronic device comprising the metal chalcogen thin film; 포함하는 전자 소자의 제조방법.Method of manufacturing an electronic device comprising. 제19항에 있어서,The method of claim 19, 전자 소자를 제조하는 단계 전에, 상기 금속 칼코겐 박막을 기판으로부터 분리하는 단계를 추가로 포함하는 것을 특징으로 하는 전자 소자의 제조방법.Before the step of manufacturing the electronic device, further comprising the step of separating the metal chalcogen thin film from the substrate.
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