WO2018143611A1 - Procédé de fabrication de film mince de chalcogénure métallique de grande surface, et procédé de fabrication de dispositif électronique comprenant un film mince de chalcogénure métallique ainsi fabriqué - Google Patents

Procédé de fabrication de film mince de chalcogénure métallique de grande surface, et procédé de fabrication de dispositif électronique comprenant un film mince de chalcogénure métallique ainsi fabriqué 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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PCT/KR2018/001166
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Korean (ko)
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정운룡
기리아누팜
양희승
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포항공과대학교 산학협력단
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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

La présente invention concerne un procédé de fabrication d'un film mince de chalcogénure métallique de grande surface et un dispositif comprenant le film mince de chalcogénure métallique de grande surface ainsi fabriqué, le procédé comprenant les étapes consistant à : préparer une solution de précurseur de polymère ; revêtir un substrat avec la solution de précurseur de polymère ; et traiter thermiquement le substrat revêtu de la solution de précurseur de polymère. Un film mince de chalcogénure métallique de grande surface et de grande qualité ayant une épaisseur et une composition uniformes peut être fabriqué à faible coût selon le procédé de fabrication de la présente invention.
PCT/KR2018/001166 2017-02-02 2018-01-26 Procédé de fabrication de film mince de chalcogénure métallique de grande surface, et procédé de fabrication de dispositif électronique comprenant un film mince de chalcogénure métallique ainsi fabriqué WO2018143611A1 (fr)

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KR10-2017-0014784 2017-02-02

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CN113088922A (zh) * 2021-03-31 2021-07-09 西北工业大学 一种晶圆级绝对单层过渡金属硫族化合物的制备方法和应用
US20210273158A1 (en) * 2018-12-26 2021-09-02 Industry-University Cooperation Foundation Hanyang University Erica Campus Memory device and manufacturing method therefor

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KR102042680B1 (ko) * 2018-04-18 2019-11-08 한국과학기술연구원 레이저를 이용한 전이금속 칼코겐 화합물의 대면적 및 선택적 고속 합성 방법 및 이에 따라 합성된 전이금속 칼코겐 화합물
KR20200094462A (ko) 2019-01-30 2020-08-07 한양대학교 산학협력단 금속 칼코겐 화합물 박막의 제조방법
KR102256513B1 (ko) 2019-04-09 2021-05-27 한양대학교 산학협력단 금속 칼코겐 화합물 박막의 제조방법

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CN113088922A (zh) * 2021-03-31 2021-07-09 西北工业大学 一种晶圆级绝对单层过渡金属硫族化合物的制备方法和应用

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