WO2016190531A1 - 흑린 박막의 제조방법 및 이로부터 제조된 흑린 박막 - Google Patents

흑린 박막의 제조방법 및 이로부터 제조된 흑린 박막 Download PDF

Info

Publication number
WO2016190531A1
WO2016190531A1 PCT/KR2016/002977 KR2016002977W WO2016190531A1 WO 2016190531 A1 WO2016190531 A1 WO 2016190531A1 KR 2016002977 W KR2016002977 W KR 2016002977W WO 2016190531 A1 WO2016190531 A1 WO 2016190531A1
Authority
WO
WIPO (PCT)
Prior art keywords
thin film
black
ultra
film
lean
Prior art date
Application number
PCT/KR2016/002977
Other languages
English (en)
French (fr)
Inventor
권혁상
김정원
이은성
이태걸
Original Assignee
한국표준과학연구원
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from KR1020150074810A external-priority patent/KR101576573B1/ko
Priority claimed from KR1020150172253A external-priority patent/KR101851339B1/ko
Application filed by 한국표준과학연구원 filed Critical 한국표준과학연구원
Priority to US15/576,664 priority Critical patent/US10121658B2/en
Publication of WO2016190531A1 publication Critical patent/WO2016190531A1/ko

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02656—Special treatments
    • H01L21/02664—Aftertreatments
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02518—Deposited layers
    • H01L21/02521—Materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02612—Formation types
    • H01L21/02617—Deposition types
    • H01L21/0262—Reduction or decomposition of gaseous compounds, e.g. CVD
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02612—Formation types
    • H01L21/02617—Deposition types
    • H01L21/02631—Physical deposition at reduced pressure, e.g. MBE, sputtering, evaporation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/34—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies not provided for in groups H01L21/0405, H01L21/0445, H01L21/06, H01L21/16 and H01L21/18 with or without impurities, e.g. doping materials
    • H01L21/42—Bombardment with radiation
    • H01L21/423—Bombardment with radiation with high-energy radiation
    • H01L21/428—Bombardment with radiation with high-energy radiation using electromagnetic radiation, e.g. laser radiation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/02—Details
    • H01L31/0232—Optical elements or arrangements associated with the device
    • H01L31/02322—Optical elements or arrangements associated with the device comprising luminescent members, e.g. fluorescent sheets upon the device
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/054—Optical elements directly associated or integrated with the PV cell, e.g. light-reflecting means or light-concentrating means
    • H01L31/055—Optical elements directly associated or integrated with the PV cell, e.g. light-reflecting means or light-concentrating means where light is absorbed and re-emitted at a different wavelength by the optical element directly associated or integrated with the PV cell, e.g. by using luminescent material, fluorescent concentrators or up-conversion arrangements
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
    • H01L29/02—Semiconductor bodies ; Multistep manufacturing processes therefor
    • H01L29/12—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by the materials of which they are formed
    • H01L29/24—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by the materials of which they are formed including, apart from doping materials or other impurities, only semiconductor materials not provided for in groups H01L29/16, H01L29/18, H01L29/20, H01L29/22
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
    • H01L29/02—Semiconductor bodies ; Multistep manufacturing processes therefor
    • H01L29/30—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by physical imperfections; having polished or roughened surface
    • H01L29/34—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by physical imperfections; having polished or roughened surface the imperfections being on the surface
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
    • H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
    • H01L29/68—Types of semiconductor device ; Multistep manufacturing processes therefor controllable by only the electric current supplied, or only the electric potential applied, to an electrode which does not carry the current to be rectified, amplified or switched
    • H01L29/76—Unipolar devices, e.g. field effect transistors
    • H01L29/772—Field effect transistors
    • H01L29/78—Field effect transistors with field effect produced by an insulated gate
    • H01L29/786—Thin film transistors, i.e. transistors with a channel being at least partly a thin film
    • H01L29/78696—Thin film transistors, i.e. transistors with a channel being at least partly a thin film characterised by the structure of the channel, e.g. multichannel, transverse or longitudinal shape, length or width, doping structure, or the overlap or alignment between the channel and the gate, the source or the drain, or the contacting structure of the channel
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
    • H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
    • H01L31/0264—Inorganic materials
    • H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/02—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies
    • H01L33/26—Materials of the light emitting region
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/52—PV systems with concentrators

Definitions

  • NAME OF THE INVENTION A method for producing a black lean thin film and a green thin film manufactured therefrom
  • the present invention relates to a method of manufacturing a thin film and a black lean thin film produced therefrom. Specifically, a thin black lean thin film is formed by active oxygen in a chamber and the accompanying black lean oxide film is removed by water to remove the black lean thin film. To manufacture.
  • Two-dimensional material is considered as a substitute for molybdenum disulfide, which has a band gap, and black phosphorus is an allotrope of the same causal element but with different properties. Its shape is similar to graphite.
  • graphene lacks a direct electron band gap between the electron band and the conduction band.
  • black lean has not only a direct band gap, but also the band gap can be adjusted according to the thickness, thus operating in a wide wavelength range from visible light to near infrared light.
  • the band 3 ⁇ 4 is a material-specific physics that is close to zero, and current flows easily.
  • the present invention has been made to solve the above problems, and has a chamber for forming an ultra thin film with high air and reaction rate, and irradiated with ultraviolet rays in the chamber to react oxygen and ultraviolet rays. It is to provide a black lean ultra thin film and a method of manufacturing a black lean ultra thin film which is formed by etching a green thin film through the active oxygen generated as a result, and removing the black lean oxide thin film produced as a by-product with water washing.
  • One aspect of the present invention provides a method for forming a thin film of black phosphorus; and ultraviolet light in a chamber.
  • the black lean thin film is made from pure black lean.
  • It may be a black thin film formed by a mechanical peeling method or a chemical vapor deposition method.
  • One aspect of the present invention may be a method of manufacturing an ultrathin thin film, further comprising: removing the black oxide film by treating the ultrathin film having identified the etching with water.
  • One aspect of the present invention is a method of determining the thickness of the black phosphorus thin film from which the black phosphorus oxide film is removed using at least one selected from an optical image, a Raman spectrum, an atomic force microscope, and a scanning tunneling microscope. It may be a manufacturing method of an ultra-thin film.
  • An aspect of the present invention provides an optical image of the formed black phosphorus ultrathin film.
  • It may be a method of manufacturing an ultra-thin black thin film, further comprising the step of confirming the etching using any one or more selected from the Raman spectrum.
  • the chamber is configured to enable continuous inflow and outflow of oxygen, and may be introduced at 100 to 600 sccm into the chamber.
  • the black lean ultrathin film produced by the above production method may have a surface roughness in the range of 1 nm or less at a 10 m X lO ⁇ m area.
  • the ultrathin film may be an ultrathin film having a thickness of 3 nm or less.
  • the black ultrathin film has one or two photoluminescence at wavelengths of 700 to 1000 nm.
  • PL having a photoluminescence (PL) peak and comprising any one or more selected from a single PL peak by a single monolayer of chromium at 780 to 830 nm and a single PL peak by a biatomic layer at 880 to 950 nm Peaks.
  • PL photoluminescence
  • Or it relates to an optoelectronic device including an ultra-thin film.
  • the ultrathin film has a surface roughness at an area of 10 X 10.
  • It may have a range of less than 1 nm and a thickness of more than 8 nm. In one embodiment of the present invention, it is also directed to a field effect transistor comprising the ultrathin film.
  • One aspect of the present invention relates to a method for producing a black lean thin film by treating the black lean thin film with water to remove the black lean oxide film.
  • the present invention utilizes free radicals in the chamber to remove black phosphorus by etching the thin film.
  • the production of ultra thin films has the advantage of producing an efficient and desired thickness of black thin film.
  • the present invention can also provide a black thin film having excellent electric element characteristics by surface cleaning.
  • the present invention takes advantage of the photoluminescent properties of black phosphorus ultrathin photodiodes
  • Figure L illustrates a method for producing a black lean ultra thin film according to the present invention.
  • FIG 2 shows an optical image of an ultrathin film according to the present invention.
  • FIG. 3 shows an AFM measurement surface of a black lean ultra thin film according to the present invention.
  • FIG. 5 shows the Raman spectrum signal size ratio of black lean ultra thin film formation according to the present invention.
  • FIG. 6 shows Raman spectrum peak differences in formation of ultra-thin films according to the present invention.
  • FIG. 7 shows the PL spectrum of a single atom layer and a binary atom black phosphorus ultra thin film according to the present invention.
  • FIG 8 shows a transistor device fabricated using a black thin film according to the present invention.
  • FIG. 9 is a graph evaluating the electrical characteristics of a thin film according to the present invention.
  • pure black phosphorus refers to the bulk of a crystalline state. It means hot.
  • a black phosphorous thin film means a thin film manufactured from pure blacks by mechanical, physical or chemical methods.
  • a black phosphorous ultrathin film refers to an ultra-thin black film manufactured by controlling the thickness by etching oxygen thin film by active oxygen, specifically 0.5 nm that can be used in optoelectronic devices. It can include black ultrathin thin films of 3 nm to 3 nm, ultra thin thin films of 3 nm to 8 nm, or more than 8 nm of ultra thin films that can be used in field effect transistors, and can have a thickness of up to 500 nm. The thickness may be less than 100 nm, more preferably less than 50 nm, and less than 30 nm may be more desirable for ultra-thin devices.
  • the black phosphorus of the present invention is a black phosphorus, an allotrope of the same causal element, but of different nature, containing a metallic gloss in iron gray, and having a similar appearance to graphite. It is a semiconducting material consisting of a layered layer of graphene.
  • Black phosphors have a direct band gap, and the band gap can be adjusted from about 0.3 to 1.5 eV depending on the thickness.
  • Black thin ultra thin films with a thickness of 3 nm or less have excellent variable light emission characteristics and are advantageous for optoelectronic device use, and when it is more than 8 nm, electron mobility is excellent, which is advantageous for use in field effect transistors and the like.
  • a method of manufacturing an ultra-thin film comprises: forming a black lean thin film; and irradiating ultraviolet rays in a chamber, using a reactive oxygen generated through reaction with irradiated ultraviolet rays and oxygen, Forming an ultra-thin black film by etching.
  • the green thin film which is used as a base material for the production of ultrathin black films, may be manufactured from pure blacks by mechanical, physical or chemical methods.
  • the black thin film may be manufactured by the following manufacturing method, but is not limited thereto. Any known method for producing a black thin film from pure pristine may be a mechanical, physical or chemical method. Not only can it be applied independently, but also can be combined and applied. Similarly, the method of manufacturing a thin film should be interpreted as being applicable to one or more of the following embodiments or combinations of the two or more embodiments described below. For clarity of understanding, these details, which apply to any one embodiment and / or combinations of two or more aspects, may be referred to collectively as the general aspects of the present invention.
  • the mechanical exfoliation method may be a method of separating pure green into layers by using an adhesive material, specifically, using a scotch tape. It may include a method of mechanical peeling.
  • a solvent peeling method may be used to disperse and isolate black phosphorus (pristine).
  • the solvent stripping method may be performed by mixing a pure or pristine with a solvent to prepare a dispersion, and stirring the dispersion or irradiating ultrasonic waves to obtain pure black phosphorus. It may include a method of manufacturing a thin film by peeling (pristine).
  • Alcohol and aprotic solvent may be selected as the solvent, and as the alcohol, one or more alcohols selected from C1 to C8 may be used.
  • the protic solvent one or more selected from the group consisting of tetrahydrofuran, nucleic acid, methylene chloride, and toluene can be used.
  • a dispersion containing the above-mentioned black lean thin film is known means such as filtration and centrifugation. After the solvent is separated, a thin film can be produced.
  • a chemical vapor deposition method is to deposit a catalyst metal on a substrate to form a thin metal film, and then, after cooling the black phosphor gas at a high temperature, the thin thin film formed on the metal film is formed. It may be how to get it.
  • the method of manufacturing a black thin film whose thickness is reduced from pure pristine by the mechanical, physical or chemical method is difficult to precisely control the thickness of the thin film, and the surface roughness of the thin film is not uniform or large in large area. Contains defects. Even if the thin black film is manufactured by the mechanical, physical or chemical method, the black thin film manufactured by the above method may not be able to adjust the thickness of the thin film to an ultra thin film of 3 nm or less, and the thin film may be uneven or defective. There is a problem in that the operation to the optoelectronic device or the field transistor is limited.
  • the black thin super thin film means that the black thin film is etched by active oxygen to be adjusted to a desired thickness.
  • the process of manufacturing an ultra-thin film due to the unstable problem due to the high reaction velocity of the thin film air is to be carried out in the chamber. Can be.
  • the ultra-thin film manufacturing apparatus is formed to be sealed, and may include a chamber formed to enable the inflow and discharge of oxygen, and a sample table formed in the chamber, and the black thin film positioned thereon.
  • the ultra-thin film manufacturing apparatus may include an ultraviolet ray irradiation portion for irradiating ultraviolet rays to generate active oxygen in the chamber.
  • the chamber includes an ultraviolet ray inflow portion to which ultraviolet rays are introduced to one side, and the ultraviolet ray inflow portion is ultraviolet ray. It is desirable to be in a position where irradiation can be performed without this interference and where a thin film can be etched without difficulty.
  • the ultraviolet inflow portion is provided with quartz having excellent transmittance of ultraviolet rays.
  • the quartz has a thickness of 0.1 to 0.5 mm, in order to use a high magnification objective lens with a small working distance when observing by using an optical image or a Raman spectrometer.
  • Silver is not limited to the quartz described above, it is a matter of course that various examples of materials are possible as long as the transmittance of ultraviolet rays is excellent and the observation is available through the objective lens.
  • the formation of ultra-thin black film is performed by etching black phosphorus by irradiating ultraviolet rays in the chamber and using active oxygen generated in the process of generating ozone through reaction of irradiated ultraviolet rays with oxygen.
  • oxygen (0 2 ) gas When oxygen (0 2 ) gas is injected together with irradiation of ultraviolet rays in the chamber, oxygen gas can be repeatedly decomposed and combined with ozone (o 3 ) and monoatomic active oxygen (o) by the energy of ultraviolet rays.
  • the active oxygen is an oxygen that is significantly richer in chemical reaction than oxygen, and may serve as an oxidizing agent for etching the surface of the thin film.
  • ultrathin thin film In the formation of ultrathin thin film, ozone and active oxygen are formed by the reaction of oxygen and ultraviolet rays in the chamber, and the ultrathin thin film can be formed by etching the black thin film by active oxygen.
  • the etching reaction may be sequentially performed according to the surface area size of the surface defects on the black thin film, that is, the small defects of several hundred nanometers or less may be firstly etched due to the selective reaction, and the size of the etching defects may be larger. It can be etched from the edge and removed.
  • ultra-thin black films is preferred to introduce oxygen into the chamber at about 100 to 600 seem (standard cubic centimeter per minute) and to maintain 1 atm using only oxygen in the chamber, but is not limited thereto. .
  • the temperature inside the chamber is 15 to 45 ° C. and the ultraviolet rays to be irradiated is 180 to 250 nm. Depending on the wavelength, the desired thickness can be adjusted according to the amount of light irradiated. Forming an ultra-thin film by irradiating at an output of 10 to 30 mW is not desirable, but it is not desirable.
  • the thickness of the ultrathin black film according to the present invention depends on the amount of ozone and free radical production.
  • the wavelength of light can be in the range of 180 to 250 nm, and 189 nm of light may be desirable to decompose the double bond of oxygen to generate free radicals.
  • the stronger the light intensity the thinner the ultrathin film obtained in a unit time can be.
  • the thickness of the ultrathin film of the present invention is not obtained only at a specific dosage of light, or at a specific intensity of light. Various combinations of the two variables are possible to obtain, and such combinations are of course included in the scope of the present invention.
  • the black lean ultra thin film manufacturing apparatus generates ozone and active oxygen directly by reaction of oxygen and ultraviolet rays in the process of etching black lean, and forms an ultra thin thin film using the same to separate activities. There is no need to install an oxygen generator, which lowers the manufacturing cost.
  • the above-described ultrathin thin film manufacturing apparatus is only one embodiment for generating free radicals in the present invention, but the method for producing ultrathin thin film of the present invention is not limited thereto, and the free radicals are produced by active oxygen by generating free radicals. If the thin film can be etched, various variations are possible in the size and shape of the chamber, the supply and discharge of oxygen, and such modifications are, of course, included in the present invention.
  • the formed black phosphorus ultrathin film is an optical image
  • the method may further include verifying the etching using one or more selected from the Raman spectrometers.
  • the etching of the ultra-thin film may be performed by using an optical image or a Raman spectrometer, but it may be etched by black phosphorus. If this is not done, it is necessary to perform etching of the black lean thin film again. Therefore, it is efficient to check whether the etch is performed in the chamber with the ultra thin film.
  • the method may further include removing the black phosphorus oxide film by treating the black phosphorus ultrathin film having been identified with the etching.
  • the black phosphorus oxide film may further include a liquid oxide film (absorb water) generated by active oxygen. a P x O y) as, heukrin oxide film and the surface of the ultra-thin heukrin washed with water in the present invention as a non-limiting embodiment The fault can be eliminated.
  • the treatment of the black super thin film with water not only selectively removes the green oxide film existing on the surface of the super thin film, but also makes the surface flat and has an advantage of providing a thin film of uniform thickness.
  • a method for removing an oxide film is not limited.
  • Specific examples include, but are not limited to, washing with a thin ultra thin film, washing with a direct spray of water or washing with a cleaning device.
  • the water used for washing may be distilled or deionized water, but is not limited to the examples above to maintain the nature of the water.
  • a method of using the cleaning device is, for example, a rotary cleaning device (spin type).
  • an ultra-thin film is placed on a rotatable chuck, and water is sprayed to remove oxides and foreign substances while rotating the chuck in one direction.
  • the temperature of washing the ultrathin thin film with water may be 1 ° C to 70 ° C, and the contact time with water may be 10 seconds to 10 hours.
  • the black oxide film present in the ultra-thin film can be selectively removed, and preferably can be removed as quickly as possible in the temperature range of 5 ° C. to 50 ° C. If it is out of range, the oxide may not be completely removed or may be quickly etched away, which may be undesirable.Also, ultra thin films and water may remove the oxide from 10 seconds to 10 hours of contact time, preferably within 20 seconds. The contact time of 5 minutes can be effectively removed. If the contact time is removed, the oxide film may not be removed, the black etch may be etched, or the process efficiency may be deteriorated.
  • the present invention in order to form an ultra-thin film, may be etched through free radicals, washed with water, and then irradiated again with ultraviolet rays to repeat the free radical etch process.
  • the washing process many variations are possible, such as skipping the washing process arbitrarily.
  • ultra-thin thicknesses are produced by oxygen, moisture, and light during rapid exposure to produce ultra-thin films below 3 nm.
  • additional or omitted cleaning steps may be required, and surface protection layer formation may be required, particularly for the fabrication and characterization of stable electrical devices.
  • the method for producing a black lean thin film omits the step of etching the thin film using active oxygen, and the black thin film is treated with water to remove the black lean oxide film to produce the black lean thin film.
  • the method may also be included.
  • the steps to determine the thickness of the oxide film has been removed hokrin heukrin ultra thin film; can contain reuldeo.
  • the thickness of the ultra-thin film is selected from the optical image, the Raman spectroscopy, the atomic force microscope (AFM), and the scanning tunneling microscope (STM). It is advisable to check the thickness of the thin film using more than one.
  • the present invention is to provide an ultra-thin film manufactured by the above-described method.
  • the black lean ultra thin film of the present invention may be a black lean ultra thin film laminated with 1 to 5 layers, and may have a thickness of 3 nm or less. Thin ultrathin films with a thickness of less than 3 nm can be used for optoelectronic devices because of their excellent light emission or light absorption characteristics by near-infrared to visible light.
  • a device for mutually changing electrical energy it may include a photodiode, a light emitting diode, a solar cell, a photodetector, an optical switch, and the like.
  • scanning tunneling Microscope STM
  • STM scanning Tunneling Microscope
  • atomic force microscopy can accurately measure the thickness of a thin film of black phosphor by directly measuring the force between atoms using the tip of the tip, which is formed of metal or semiconductor, which is a very thin surface.
  • the ultrathin film of the present invention can measure surface roughness (roughness) by atomic force microscope (AFM), and surface roughness may be less than 1 nm in an area of 10 ⁇ ⁇ 10.
  • AFM atomic force microscope
  • the ultra-thin membranes of the present invention can be measured by Raman spectroscopy, which can be measured by phonons in accordance with the manner of vibration movement when a black atom has a constant lattice structure.
  • heukrin of the invention is ultra thin film can be measured a 'g mode, 2g B, a-mode oscillating in one direction parallel with the lattice plane that oscillates in one direction perpendicular to the lattice plane through Raman spectroscopy.
  • the ultra-thin films of the present invention can also measure photoluminescence (PL) characteristics.
  • PL photoluminescence
  • This method utilizes a phenomenon in which the electrons of the specimen are excitated by irradiating light at a particular wavelength of the specimen. The emission of light can be measured as it comes to a steady state.
  • the black phosphorus ultrathin film of the present invention has one or two PL peaks at wavelengths of 700 to 1000 nm, single PL peaks by black single atom layers at 750 to 810 mn, and biatomic layers at 870 to 930 nm. It is characterized by having a PL peak containing one or more selected from a single PL peak.
  • an ultra-thin film of a single atom layer and a two atom layer is removed.
  • the monolayer PL was measured at about 780 nm and the biatomic layer PL was measured at approximately 900 nm. These ultra-thin films are photodiodes,
  • optoelectronic devices such as light emitting diodes, solar cells, photodetectors and optical switches.
  • the ultrathin thin film of the present invention may be an ultrathin thin film having a thickness of 8 nm or more.
  • the ultra-thin film When the ultra-thin film is 8 nm or more, it has a 0.3 eV bulk band gap, and may have excellent electron mobility, and may have electron mobility of more than 1000 cmWs, and is affected by surface characteristics.
  • These black phosphorus ultrathin films can be high quality or ultrathin thin films with excellent electrical properties and can be used as field effect transistors.
  • the root mean squared roughness was calculated from three-dimensional surface images measured at 10 / m X 10 j3 ⁇ 4 m.
  • the laser power was measured below 0.1 mW.
  • Pure black lean (bulk crystal 99.99%, smart elements) was mechanically peeled on a 285 nm thick Si0 2 / Si substrate using scotch tape (3M) to prepare a black lean thin film.
  • the optical cell has a Q.17 mm thickness at which ultraviolet light can be introduced at the top. It was equipped with quartz glass (077 Vitreosil® Optical Fused Quartz). The optical sal infused 0 2 gas at 500 sccm to maintain 1 atmosphere of oxygen.
  • Ultraviolet rays were UV-irradiated by a pencil-type mercury lamp (Oriel, 6035), and the lamp power was 19 mW at 200 nm. : 14.6 ⁇ 8.1 nm, B: 26.3 ⁇ 20.1 nm).
  • a black lean thin film is formed on the Si0 2 / Si substrate, and is generated by ultraviolet irradiation.
  • the black phosphorus ultrathin film etched with active oxygen was immersed in a beaker of deionized water and washed for 1 minute.
  • the device for transistor measurement was fabricated by lithography method and the electronic device characteristics were measured in vacuum.
  • the manufactured device was immersed in a beaker of deionized water and washed for 1 minute.
  • FIG. 2 is an optical image result according to Example 1 of the present invention.
  • FIG. 3 is a result of measuring AFMs for regions A and B of FIG. 2.
  • FIG. 2A and FIG. 3D show mechanical peeling. It was a very thin film caused by an ultra-thin film. The image was obtained within 20 minutes after mechanical peeling, but it can be seen that the surface is uneven. The surface roughness of pure pristine was determined to be 5.1 nm in the A region and 5.4 nm in the B region.
  • the thickness of the oxide film is about 174 nm in the B region.
  • the oxide film can be removed by deionized water, which is shown in c of FIG. 2 and f of FIG.
  • the thickness change after washing in the first rough condition was about 5.5 nm, and the smooth surface of the ultrathin film could be confirmed. It was confirmed to be less than 1 nm in the m X 10 area.
  • FIG. 5 shows the signal size ratios of 8 and Si bands in the Raman spectrum of FIG. 4 according to UV irradiation time.
  • the ultra-thin film has a thickness of about 3 nm or less.
  • FIG. 6 shows the peak difference values of 8 3 ⁇ 4 and A 2 g bends of the black phosphorus ultrathin film of FIG. 4.
  • the ultra thin film of 3 nm or more in thickness means no significant difference in the peak difference value.However, the peak difference rapidly increased over 20 minutes of UV irradiation time, which is below 3 nm. It means to become angry.
  • a super atomic thin film of 2 atomic layers was formed, and at 31 minutes of UV irradiation, a super atomic thin film of a single atomic layer was formed.
  • FIG. 7 shows the PL spectra of the monoatomic and biatomic black phosphorus thin films prepared by Example 1.
  • the single PL and biatomic ultrathin films have strong characteristic PL peaks at 782 nm and 896 nm, respectively.
  • the biatomic black ultrathin films are 488 nm.
  • a strong characteristic PL peak of about 1,000 photon counts was obtained at 0.01 mW power and 60 seconds.
  • the single monolayer is about 780 nm and the biatomic layer is about 900 nm.
  • the green thin film produced only by mechanical peeling shows PL in the mid-infrared region, but the single- or double-atom black ultrathin film obtained by UV irradiation of the present invention exhibits a strong PL spectrum in the near-infrared and visible region. Therefore, the black thin film manufactured by conventional mechanical peeling method has bulk characteristics with many defects on the surface, while the single atomic and two-atomic black ultra thin layers of the present invention are defect-free and have a uniform surface area. It can be confirmed that it is a high quality ultra thin film material.
  • FIG. 8 shows an optical image of a transistor device using a 30 nm thick black thin film prepared in Example 5.
  • the dark field images of (left) and (right) before and after washing with water are shown. It can be seen that a significant amount of green oxide film is present on the device before washing with deionized water, but all the green oxide film is removed after washing with deionized water.
  • the electrical characteristics of the transistor element are measured by measuring the amount of current flowing through the two metal electrodes according to the change of the gate electrode after connecting the gate electrode to Si under Si0 2 after applying the electrode. Specifically, the result before the deionized water washing is shown in black oxide film. As a result, as shown in the figure, the low current value for the voltage change is shown, but the result after dewatering and washing shows that the amount of current increases and the device characteristics are significantly improved.
  • the washing step by water thus comprises a black lean thin film or a black lean ultra thin film.
  • the green thin film was etched with active oxygen to adjust to the desired ultra thin film thickness, the Raman was confirmed to have a thickness of less than 3 nm, and the PL photoluminescent property was confirmed.
  • the oxide film By removing the oxide film, a uniform surface of the black thin film was formed to confirm the improvement of the electrical device characteristics.

Landscapes

  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • General Physics & Mathematics (AREA)
  • Computer Hardware Design (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Power Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Electromagnetism (AREA)
  • Optics & Photonics (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Thin Film Transistor (AREA)

Abstract

본 발명은 흑린 박막의 제조방법 및 그로부터 제조된 흑린 박막에 관한 것으로， 상세하게는 챔버 내에서 활성산소에 의하여 흑린 초박막을 형성하고, 수반되는 흑린 산화막을 물로 제거하여 흑린 초박막을 제조하는 것이다. 본 발명의 흑린 초박막은 대면적에서 실질적으로 결함이 없고 평탄한 표면을 가지며, 1 nm 이하의 표면조도 특성을 가짐으로써 광전자소자 및 전계 효과 트랜지스터에 높은 응용성을 나타낸다.

Description

명세서
발명의명칭:흑린박막의제조방법및이로부터제조된혹린박막 기술분야
[1] 본발명은혹린박막의제조방법및이로부터제조된흑린박막에관한것으로， 상세하게는챔버내에서활성산소에의하여흑린초박막을형성하고，수반되는 흑린산화막을물로제거하여흑린초박막을제조하는것이다.
배경기술
[2] 미래형웨어러블전자기기나，투명디스플레이등을구현하려면휘어지고
늘어나면서도성능은뛰어난전자소자개발이필수다.
[3] 실리콘이후，차세대전자소자를만들소재로그래핀과이황화몰리브덴등
2차원물질이꼽히고있는데,최근밴드갭을가지는이황화몰리브덴을대체 가능한물질로평가받는혹린 (검은인， black phosphorus)은인과원소는같지만 성질이다른동소체로서，철회색에금속광택을포함하며，걸의모양이흑연과 비슷한물질이다.
[4] 특히,그래핀이가전자대와전도대사이에직접전자밴드갭이부족해
대표적인반도체인실리콘을대체하는데한계가있는반면,흑린은직접 밴드갭도가지고있을뿐만아니라,두께에따라서밴드갭의조절이가능하므로 가시광선에서근적외선까지폭넓은파장범위에서도작동이가능한장점을 가진다.
[5] 상기밴드 ¾이란，물질고유의물리량으로 0에가까우면전류가쉽게흘러
도체가되며,값이클수록전류가쉽게흐르지않아절연체가된다.따라서만약 밴드갭의크기를자유자재로조절할수있다면물질의전기적성질을도체에서 부도체에이르기까지조작하는것이가능하다.
[6J 트랜지스터의작동전압을낮추고생성되는열을감소시키기위해서원자
수준의매우얇은트랜지스터를디자인해야만하는데,흑린은이를층족할수 있는차세대물질로많은연구가이뤄지고있다.
[7] 그러나혹린은공기중반응속도가높아안정적이지못하여자연산화막이 생성되는데이는시간이지남에따라서흑린표면또는계면에서의전류량 흐름을저해함으로써 ,전자소자특성을악화시키는문제점이발생하므로 전자소자에흑린박막을사용하기위해서는효과적인산화막제거방법이 반드시요구된다.
[8] 한편，약 0.3 eV의벌크밴드에너지를가지는혹린은두께에무관하게직접 천이 (direct transition)를통한높은광발광특성을가지고특히 3 nm이하에서는 근적외선에서부터가시광선영역까지가변밴드에너지조절이가능하다.현재 기계적박리법에의한흑린박막형성이가능한데이방법으로는자연산화막 형성으로인해혹린초박막제조에큰어려움이존재한다. 발명의상세한설명
기술적과제
[9] 본발명은상기와같은문제점을해결하기위하여안출된것으로서,공기와 반응속도가높은혹린박막을초박막으로형성하기위해챔버를구비하고，상기 챔버내에자외선을조사하여，산소와자외선의반응으로발생되는활성산소를 통하여혹린박막을식각하여흑린초박막을형성하고，부산물로생성되는흑린 산화막을물세척으로제거해서제조되는흑린초박막의제조방법및흑린 초박막을제공하는것이다
과제해결수단
[10] 본발명의일양태는흑린박막을형성하는단계;및챔버내에자외선을
조사하여，조사된자외선과산소와의반응을통해발생되는활성산소를 이용하여흑린박막을식각함으로써흑린초박막을형성하는단계;를포함하는 혹린초박막의제조방법에관한것이다.
[11] 본발명의일양태에있어서 ,상기흑린박막은순수한흑린으로부터
기계적으로박리하는방법또는화학적기상증착방법에의해형성되는흑린 박막일수있다.
[12] 본발명의일양태는상기식각을확인한혹린초박막을물로처리하여흑린 산화막을제거하는단계;를더포함하는것인혹린초박막의제조방법일수 있다.
[13] 본발명의일양태는상기흑린산화막이제거된흑린초박막을광학이미지, 라만스펙트럼，원자힘현미경및주사터널링현미경에서선택되는어느하나 이상을이용하여두께를확인하는단계;를더포함하는것인혹린초박막의 제조방법일수있다.
[14] 본발명의일양태는상기형성된흑린초박막을광학이미지및
라만스펙트럼에서선택되는어느하나이상을이용하여식각올확인하는 단계;를더포함하는것인흑린초박막의제조방법일수있다.
[15] 본발명의일양태에있어서，상기챔버는연속적으로산소의유입및배출이 가능하도록형성되며,챔버내부에 100내지 600 sccm으로산소를유입하는것일 수있다.
[16] 본발명의일양태에있어서，상기제조방법에의해제조된흑린초박막은 10 m X lO ^m면적에서표면조도가 1 nm이하의범위를가질수있다.
[17] 본발명의일양태에있어서，혹린초박막은 3 nm이하의두께를가지는혹린 초박막일수있다.본발명의일구체양태로,상기흑린초박막은파장 700내지 1000 nm에서 1또는 2개의광발광 (photoluminescence:이하 PL)피크를가지며, 780내지 830 nm에서흑린단일원자층에의한단일 PL피크및 880내지 950 nm에서혹린 2원자층에의한단일 PL피크에서선택된어느하나또는둘 이상을포함하는 PL피크를가질수있다.또한본발명의일구체양태로，상기 혹린초박막을포함하는광전자소자에관한것이다.
[1 8] 본발명의일양태에있어서，혹린초박막은 10 X 10 면적에서표면조도가
1 nm이하의범위및 8 nm이상의두께를가지는것일수있다.또한본발명의일 구체양태로,상기혹린초박막을포함하는전계효과트랜지스터에관한것이다.
[19] 본발명의일양태는흑린박막을물로처리하여，흑린산화막올제거하는흑린 박막의제조방법에관한것이다.
발명의효과
[20] 본발명은챔버내에활성산소를이용하여혹린박막의식각을통해흑린
초박막을제조함으로써，효율적이고원하는두께의흑린박막을제조할수있는 장점이있다.또한본발명은표면세척으로우수한전기소자특성을갖는흑린 초박막을제공할수있다.
[21] 특히본발명은흑린초박막의광발광특성을이용하여광다이오드,
발광다이오드，태양전지,광검출기，광스위치등을포함하는
광전자소자 (optoelectronic device)에웅용할수있으며,우수한전자이동도로 인하여전계효과트랜지스터 (field effect transistor)에웅용할수있다.
도면의간단한설명
[22] 도 L은본발명에따른흑린초박막의제조방법을도식화한것이다.
[23] 도 2는본발명에따른혹린초박막의광학이미지를나타낸것이다.
[24] 도 3은본발명에따른흑린초박막의 AFM측정표면을나타낸것이다.
[25] 도 4는본발명에따른혹린초박막형성의라만스펙트럼을나타낸것이다.
[26] 도 5는본발명에따른흑린초박막형성의라만스펙트럼신호크기비율을 나타낸것이다.
[27] 도 6은본발명에따른혹린초박막형성의라만스펙트럼피크차이를나타낸 것이다.
[28] 도 7은본발명에따른단일원자층, 2원자층흑린초박막의 PL스펙트럼을 나타낸것이다.
[29] 도 8은본발명에따른흑린박막을이용하여제작한트랜지스터소자의
광학이미지이다 ·
[30] 도 9는본발명에따른혹린박막의전기적특성을평가한그래프이다.
발명의실시를위한형태
[31] 이하，첨부한도면들을참조하여본발명을상세히설명한다.이때사용되는 기술용어및과학용어에있어서다른정의가없다면，이발명이속하는기술 분야에서통상의지식을가진자가통상적으로이해하고있는의미를가지며， 하기의설명에서본발명의요지를불필요하게흐릴수있는공지기능및 구성에대한설명은생략한다.
[32]
[33] 본발명의용어에있어，순수한흑린 (pristine)이란，벌크 (bulk)한결정체상태의 혹린을의미한다.
[34] 본발명의용어에있어 ,혹린박막 (black phosphorous thin film)이란，순수한 흑린 (pristine)으로부터기계적，물리적또는화학적방법으로제조되는박막을 의미한다.
[35] 본발명의용어에있어，혹린초박막 (black phosphorous ultrathin film)이란， 활성산소에의하여혹린박막을식각하여두께를조절하여제조되는흑린 초박막을의미한다구체적으로광전자소자에웅용될수있는 0.5 nm내지 3 nm의흑린초박막， 3 nm내지 8 nm의흑린초박막,전계효과트랜지스터에 웅용될수있는 8 nm이상의혹린초박막을포함할수있으며,최대 500 nm 두께를가질수있다.바람직하게는 8 nm이상의흑린초박막의두께는 100 nm 이하，더욱바람직하게는 50 nm이하일수있으며，초박막소자로는 30 nm이하가 더바람직할수있다.
[36]
[37] 본발명의흑린이란，검은인 (black phosphorus)으로인과원소는같지만성질이 다른동소체로서，철회색에금속광택을포함하며,겉의모양이흑연과비슷한 물질이다.혹린은몇층의인으로구성된반도체성재료로그래핀처럼층구조를 이루고있다.혹린은밴드 ¾이없어전류의흐름을통제하기어려운그래핀을 대체할차세대반도체소재로관심을받고있다.
[38] 흑린은두께에따라서밴드갭의조절이가능하므로가시광선에서
근적외선까지폭넓은파장범위에서도작동이가능하며，우수한
광웅답성 (photoresponsivity)과 1000 cmWs이상의전자이동도 (electron mobility)를나타낸다.
[39] 흑린은직접밴드갭 (direct band gap)성질을가지고있으며，두께에따라서약 0.3내지 1.5 eV까지밴드갭이조절이가능하다. 3 nm이하의두께가얇은흑린 초박막은가변광발광특성이우수하여광전자소자웅용에유리하며， 8 nm 이상일때는전자이동도가우수하여전계효과트랜지스터 (field effect transistor)등의웅용에유리하다.
[40]
[41] 본발명의일양태에있어서，혹린초박막의제조방법은흑린박막을형성하는 단계;및챔버내에자외선을조사하여,조사된자외선과산소와의반웅을통해 발생되는활성산소를이용하여흑린박막을식각함으로써흑린초박막을 형성하는단계;를포함할수있다.
[42] 흑린초박막을제조하기위한기초재료로서사용되는혹린박막은순수한 흑린 (pristine)으로부터기계적，물리적또는화학적방법으로제조되는것일수 있다.
[43] 구체적으로，흑린박막은후술하는제조방법에의해제조될수있으나이에 제한되지아니하며,순수한혹린 (pristine)으로부터흑린박막을제조하는공지의 방법이라면기계적，물리적또는화학적방법일수있으며，상기방법들이 독립적으로적용될수있을뿐만아니라서로결합되어적용될수있음은 물론이다.마찬가지로혹린박막의제조방법은후술하는일양태또는둘이상의 양태들이결합하여도출되는예들에모두적용되는것으로해석되어야하며， 이때，보다명료한이해를위해，임의의일양태및 /또는둘이상의양태들이 결합된예들에모두적용되는이러한내용들을본발명의일반적양태로 통칭하며상술할수있다.
[44] 혹린박막을제조하는일양태에있어서，기계적박리 (exfoliation)방법은순수한 흑린 (pristine)을접착성소재를이용하여혹린을층별로분리하는방법일수 있으며,구체적으로스카치테이프등을이용하여기계적으로박리하는방법을 포함할수있다.
[45] 혹린박막올제조하는다른일양태에있어서，용매중에순수한
흑린 (pristine)을분산하여박리하는용매박리방법을포함할수있다.상기용매 박리방법은순수한혹린 (pristine)을용매에흔합하여분산체를제조하고，상기 분산체를교반하거나초음파를조사하여순수한흑린 (pristine)을박리함으로써 혹린박막을제조하는방법을포함할수있다.상기용매로는알코올및 비양성자성용매가선택될수있으며，상기알코올로는 C1내지 C8에서 선택되는 1종이상의알코올을사용할수있으며，비양성자성용매로는 테트라하이드로퓨란，핵산，메틸렌클로라이드,틀루엔으로이루어진군에서 선택되는 1종이상을사용할수있다.박리된상기흑린박막을포함하는 분산체는여과，원심분리등의공지의수단을통해용매를분리한후,혹린 박막을제조할수있다.
[46] 혹린박막올제조하는다른일양태에있어서,화학적기상증착방법이란기판 위에촉매금속을증착하여얇은금속막을형성한후,고온에서흑린기체를 홀려준뒤,넁각시켜금속막위에형성된혹린박막을얻는방법일수있다.
[47] 상기기계적，물리적또는화학적방법을통해순수한혹린 (pristine)으로부터 두께가감소된흑린박막의제조방법은，혹린박막두께의정밀한조절이 어렵고,대면적에서박막의표면조도가일정치않거나많은결함을포함한다. 상기기계적，물리적또는화학적방법을통해박막형태의흑린을제조하더라도 상기제조방법에의해제조된흑린박막은박막의두께를 3 nm이하의초박막 형태로조절하기불가능할수있고,불균일하거나결함을가진박막이얻어지게 되어광전자소자또는전계트랜지스터로의웅용이제한된다는문제점이있다.
[48] 따라서,흑린박막의두께를정밀하게조절하고，대면적에서박막의
표면조도를최소화하며，실질적으로결함이존재하지않는혹린초박막및혹린 초박막의제조방법을제공한다.흑린초박막은활성산소에의하여흑린박막을 식각하여원하는두께로조절하여제조되는것을의미한다.
[49]
[50] 본발명의일양태에있어서,혹린박막이공기중반웅속도가높아안정적이지 못한문제점으로인하여혹린초박막을제조하는공정은챔버내에서이루어질 수있다.
[51] 혹린초박막제조장치는밀폐가능하도록형성되며,산소의유입및배출이 가능하도록형성된챔버와상기챔버내에형성되며，흑린박막이위치되는 시료대를포함할수있다.
[52] 아울러，혹린초박막제조장치는상기챔버내에활성산소를생성하기위해 자외선을조사하는자외선조사부를포함할수있다.상기챔버는일측에 자외선이유입되는자외선유입부를포함하며，상기자외선유입부는자외선이 간섭없이조사가가능한위치및혹린박막의식각여부를어려움없이확인할 수있는위치에구비되는것이바람직하다.
[53] 상기자외선유입부는자외선의투과율이우수한석영이구비되는것이
바람직하다.이때，석영은 0.1내지 0.5 mm의두께를가지는것이바람직하며, 이는광학이미지또는라만분광기를이용하여관찰시，작업거리가작은 고배율의대물렌즈를사용하기위함이다.상기자외선유입부의재질은상기에 기재된석영에한정하지않고,자외선의투과율이우수하고,대물렌즈를통한 관찰이용이하다면다양한재질의실시예가가능함은물론이다.
[54]
[55] 본발명의일양태에있어서，흑린초박막의형성은상기챔버내에자외선을 조사하여，조사된자외선과산소와의반응을통해오존을생성하는과정에서 발생되는활성산소를이용하여흑린을식각함으로써，얇은두께를가지는흑린 초박막을형성할수있다
[56] 상기챔버내에자외선의조사와함께산소 (02)가스를주입하면，자외선이 가지는에너지에의해산소가스가오존 (o3)및단원자활성산소 (o)로분해및 결합을반복할수있다.상기활성산소는산소에비해뚜렷하게화학반웅성이 풍부한산소로，혹린박막의표면을식각하는산화제역할을할수있다.
[57] 흑린초박막의형성은챔버내에서산소와자외선의반웅에의해오존및 활성산소를형성하고，활성산소에의하여흑린박막을식각함으로써,혹린 초박막을형성할수있다.
[58] 상기식각반웅은흑린박막상의표면결함의표면적크기에따라순차적으로 식각이수행될수있다.즉，수백나노미터이하의작은결함은상기반웅이 선택적으로발생하여먼저식각될수있으며，그이상의크기는가장자리부터 식각되어제거될수있다.
[59] 상기식각반웅의순차적반웅특성에의해흑린박막상에존재하는표면 결함이실질적으로대부분제거될수있으며，표면조도역시 10 /ffli x 10；圆 면적에서 l mn이하의범위로정밀하게조절될수있다.
[60] 또한，흑린초박막의형성은챔버내부에약 100내지 600 seem (standard cubic centimeter per minute)으로산소를유입하고,챔버내산소만으로 1기압을 유지하도록하는것이바람직하나，이에제한되는것은아니다.
[61] 상기챔버내부의온도는 15내지 45°C,조사하는자외선은 180내지 250 nm 파장에의한것이며，빛의조사량에따라원하는두께를조절할수있으며， 10 내지 30 mW의출력으로조사하여혹린초박막을형성하는것이부반웅없이 균일하게반웅하여바람직하나이에제한되는것은아니다.
[62] 본발명에따른흑린초박막의두께는，오존및활성산소생성량에따른
흑린과의반웅정도에비례할수있다.빛의파장은 180내지 250 nm의범위일수 있으며,산소의이중결합을분해하여활성산소를생성하기위해서는 189 nm의 빛이바람직할수있다.빛의조사량이높아지거나빛의세기가강할수록 단위시간에얻어지는혹린초박막의두께는보다작아질수있다.그러나본 발명의혹린초박막의두께가빛의특정조사량,빛의특정세기에만얻어지는 것이아니며，흑린초박막의특정두께를얻기위해상기 2가지변수의다양한 조합이가능하며，이러한조합예역시본발명의범위에포함되는것은 물론이다.
[63]
[64] 상기에기재된바와같이，본발명에따른흑린초박막제조장치는흑린의식각 과정에서산소와자외선의반웅에의해오존및활성산소를직접생성하고이를 이용하여혹린초박막을형성함으로써，별도의활성산소발생장치의구비가 필요하지않아，제조단가를낮출수있는장점이있다.
[65] 상술한혹린초박막제조장치는본발명에서활성산소를발생시키기위한일 실시양태에불과할뿐본발명의흑린초박막의제조방법이이에제한받지는 아니하며 ,활성산소를발생시켜활성산소에의해혹린박막을식각할수있다면 챔버의크기및형태，산소의공급과배출등에서다양한변형이가능하며 이러한변형예역시본발명에포함되는것은물론이다.
[66]
[67] 본발명의일양태에있어서，상기형성된흑린초박막을광학이미지및
라만분광기에서선택되는어느하나이상을이용하여식각을확인하는단계;를 더포함할수있다.
[68] 아울러,혹린초박막의식각확인은정확한식각여부를확인하기위해,
자외선이조사되는시간대에따른식각여부를상대적으로확인하여，정확한 식각여부를확인할수있다ᅳ이때,상기혹린초박막의식각확인은광학이미지 또는라만분광기를이용하여식각여부를확인하되,흑린에식각이수행되지 않았을경우，다시흑린박막의식각을수행해야하므로，상기챔버내에혹린 초박막을구비한상태에서식각의여부를확인하는것이효율적이고
바람직하나，이에한정하지는않는다.
[69]
[70] 본발명의일양태에있어서,상기식각을확인한흑린초박막을물로처리하여 흑린산화막을제거하는단계;를더포함할수있다.상기흑린산화막은 활성산소에의해발생한액상의산화막 (물을흡수한 PxOy)으로서，본발명에서는 비한정적인구체예로서물로세척하여흑린초박막의흑린산화막및표면 결함을제거할수있다.
[71] 상기흑린초박막을물로처리함으로써혹린초박막의표면에존재하는혹린 산화막이선택적으로제거될뿐만아니라표면이평탄해지며，균일한두께의 혹린박막을얻을수있는장점이있다.
[72]
[73] 본발명의일양태에있어서，혹린산화막을제거하는방법은비한정적인
구체예로서，혹린초박막을물에넣어세척하는방법，혹린초박막에물을직접 분사하여세척하는방법,세정장치를이용하여세척하는방법등이 있으나，이에 제한되는것은아니다.
[74] 본발명의일양태에있어서，세척에사용되는물은증류수또는탈이온수일수 있으나물의성질을유지하는범위에서상기예에제한되는것은아니다.
[75] 상기세정장치를이용하는방법은예를들면,회전식세정장치 (spin type
cleaner)를통하여,회전이가능한척 (chuck)상에혹린초박막을배치하고，척을 일방향으로회전시키면서물을분사하여산화막및이물질을제거할수있다.
[76] 혹린초박막을물과접촉시킬경우，흑린초박막을물로세척하는온도는 1°C 내지 70°C일수있으며，물과의접촉시간은 10초내지 10시간일수있다. l°C내지 70oC의온도범위에서혹린초박막에존재하는흑린산화막이선택적으로제거될 수있으며，바람직하게는 5°C내지 50°C의온도범위에서가장빠르게선택적으로 제거될수있다.상기온도범위를벗어날경우산화막의제거가완벽하게 이뤄지지않거나,혹린까지빠르게식각되어바람직하지않을수있다.혹린 초박막과물은 10초내지 10시간의접촉시간에서혹린산화막을제거할수 있으며，바람직하게는 20초내지 5분간의접촉시간에서효과적으로제거될수 있다.상기접촉시간을벗어날경우산화막이제거되지않거나，흑린까지 식각되거나공정효율성이떨어질수있어바람직하지않을수있다.
[77] 본발명은일양태에있어서，혹린초박막을형성하기위하여활성산소를통해 식각한후，물로세척과정을수행한다음，다시자외선조사를하여활성산소 식각과정을재수행할수있으며,이를반복적으로여러번수행할수있고, 임의로세척과정을생략하는등의다양한변형이가능하다.바람직하게, 3 nm 이하혹린초박막을제조하기위해,대기노출시산소，수분그리고빛에의해 식각이빠르게진행되므로초박막두께에따라세척단계가추가또는생략될수 있으며，특히안정한전기소자의제조및특성측정을위해서는표면보호막층 형성이요구될수있다.
[78] 본발명의일양태에있어서,흑린박막의제조방법은활성산소를이용하여 혹린박막을식각하는단계를생략하고，혹린박막을물로처리하여,흑린 산화막을제거하여흑린박막을제조하는방법또한포함할수있다.
[79]
[80] 본발명의일양태에있어서，상기혹린산화막이제거된흑린초박막의두께를 확인하는단계;를더포함할수 '있다. [81 ] 이때，상기혹린초박막의두께확인은산화막이제거된혹린초박막을 광학이미지，라만분광기,원자힘현미경 (Atomic Force Microscope, AFM), 주사터널링현미경 (Scanning Tunneling Microscope, STM)중선택되는어느하나 이상올이용하여혹린박막의두께를확인하는것이바람직하다.
[82]
[83] 본발명은상기전술한방법을통해제조되는혹린초박막을제공하는것이다.
[84] 본발명의흑린초박막은 1층내지 5층으로적층된흑린초박막일수있으며 , 3 nm이하의두께를가지는것일수있다. 3 nm이하의두께가얇은혹린초박막은 근적외선에서가시광영역까지밴드갭류닝에의해발광또는광흡수특성이 우수하여광전자소자에웅용될수있다.광전자소자란광에너지및
전기에너지를상호변화시키는소자로서 ,광다이오드，발광다이오드,태양전지 , 광검출기，광스위치등을포함할수있다.
[85]
[86] 또한본발명에의해제조된흑린박막을원자힘현미경 (Atomic Force
Microscope, AFM),주사터널'링현미경 (Scanning Tunneling Microscope, STM)등을 이용하여두께와표면조도를확인할수있다.
[87] 특히，원자힘현미경 (AFM)은표면을매우가는금속또는반도체인실리콘으로 형성되는팁의끝을이용하여원자간의힘을직접측정함으로써，정확한흑린 박막의두께를측정할수있다.
[88] 본발명의혹린초박막은원자힘현미경 (AFM)으로표면조도 (거칠기)를측정할 수있으며， 10 ΛΏ Χ 10 면적에서표면조도가 1 nm이하일수있다.
[89]
[90] 본발명의혹린초박막은라만분광기 (Raman spectroscopy)를통하여두께를 측정할수있는데，이는흑린원자가일정한격자구조를가지고있을때，진동 운동의방식에따른포논 (phonon)에의해측정될수있다.본발명의흑린 초박막은라만분광기를통해격자평면에수직한방향으로진동하는 A'g모드， 격자평면과평행한방향으로진동하는 B2g, A 모드를측정할수있다.
[91]
[92] 또한본발명의혹린초박막은광발광 (photoluminescence: PL)특성을측정할수 있다.이러한방법은시편의특정파장의광을조사하여발광올유도하는현상을 이용하여 ,시편의전자가여기 (excitation)되었다가평형상태 (steady state)로 오면서빛의방출을측정할수있다.
[93] 본발명의흑린초박막은파장 700내지 1000 nm에서 1또는 2개의 PL피크를 가지며 , 750내지 810 mn에서흑린단일원자층에의한단일 PL피크및 870내지 930 nm에서혹린 2원자층에의한단일 PL피크에서선택된어느하나또는둘 이상올포함하는 PL피크를가지는것을특징으로한다.
[94] 본발명의일실시예에의하면，단일원자층및 2원자층의혹린초박막을
제조할수있으며，단일원자층의 PL은약 780 nm에서측정되었고 2원자층의 PL은약 900 nm로측정되었다ᅳ이러한혹린초박막은광다이오드,
발광다이오드,태양전지，광검출기，광스위치둥의광전자소자 (optoelectronic device)에웅용될수있다.
[95]
[96] 본발명의혹린초박막은 8 nm이상의두께를가지는혹린초박막일수있다. 혹린초박막이 8 nm이상일때는약 0.3 eV벌크밴드갭을가지며,동시에 전자이동도 (electron mobility)가우수할수있으며，구체적으로 1000 cmWs 이상의전자이동도를가질수있으며，표면특성에영향을받는전자소자웅용에 용이하게사용할수있다.이러한흑린초박막은전기적특성이우수한고품질의 혹린초박막일수있으며,전계효과트랜지스터 (field effect transistor)등으로 웅용할수있다.
[97]
[98] 이하실시예를통해본발명을더욱상세히설명한다.다만하기실시예는본 발명을상세히설명하기위한하나의참조일뿐이며，본발명이이에한정되는 것은아니다.
[99]
[100] [특성평가]
[101] 1. AFM측정법:
[102] AFM (Park system XE-70)측정은실온에서스캐닝속도으4 Hz으로
수행하였다.표면조도 (거칠기)는 AFM장비.와같이구매한 XEI
프로그램 (version 1.6.5)을사용하여, 10 / m X 10 j¾m크기에서측정된 3차원표면 이미지로부터표면단차의제곱평균값 (RMS roughness: root mean squared roughness)을계산하여측정하였다.
[103]
[104] 2.라만분석법:
[105] Home-built confocal Raman system(EMCCD, Tunable Ar ion laser, 457-514 nm)을 사용하여라만분석 (Raman analysis)을하였다.
[106]
[107] 3. PL측정법:
[108] Nd:YAG(532 nm), Tunable Ar ion laser(488 nm)에서측정하였으며,흑린의
손상을줄이기위해레이저출력은 0.1 mW이하로측정하였다.
[109]
[110] [실시예 1]
[111] 순수한흑린 (bulk crystal 99.99%, smart elements)을 285 nm두께의 Si02 /Si기판 위에서 scotch tape (3M)을이용하여기계적으로박리하여흑린박막을 제조하였다.
[112] 자외선처리를위해,흑린박막을내부용적 40 ml의광학셀의시료대에
위치시켰다.광학셀은상부에자외선이유입될수있는 Q.17 mm의두께의 석영글래스 (077 Vitreosil® Optical Fused Quartz)로구비되었다.광학샐은 500 sccm으로 02가스를유입하여 1기압산소환경을유지하였다.
[113] 자외선은펜슬형수은램프 (Oriel, 6035)에의해 UV조사되었으며，램프전력은 200 nm에서 19 mW이었다.자외선의조사시간올 30분동안조사하여약 6 nm 두께가식각된혹린초박막 (A: 14.6→ 8.1 nm, B: 26.3→ 20.1 nm)을제조하였다.
[114] 상기 Si02/Si기판위에흑린박막이형성되고，자외선조사에의해생성된
활성산소로식각된흑린초박막을탈이온수가든비커에담근후 1분간 세척하였다.
[1 15]
[1 16] [실시예 2]
[1 17] 자외선조사시간을 10분동안조사한것을제외하고는모든공정을실시예 1과 동일하게진행하여，흑린초박막을제조하였다.
[118]
[119] [실시예 3]
[120] 자외선조사시간을 20분동안조사한것올제외하고는모든공정을실시예 1과 동일하게진행하여,흑린초박막을제조하였다.
[121]
[122] [실시예 4]
[123] 자외선조사시간을 31분동안조사한것을제외하고는모든공정을실시예 1과 동일하게진행하여,흑린초박막을제조하였다.
[124]
[125] [비교예 1]
[126] 자외선을조사하지않은것을제외하고는모든공정을실시예 1과동일하게 진행하여，흑린박막을제조하였다.
[ 127]
[128] [실시예 5]혹린박막의트랜지스터소자제작
[129] 혹린 bulk crystal (99.99%, smart elements)을 285 nm두께의 Si02 /Si기판위에서 scotch tape (3M)을이용하여기계적으로박리하였다.
[130] 그리고 30 nm두께의흑린박막에대해서전자범리소그래피 (e-beam
lithography)방법을통하여트랜지스터측정을위한소자를제작하였고 전자소자특성은진공내에서측정되었다.
[131] 상기제작한소자를탈이온수가든비커에담근후 1분간세척하였다.
[132]
[133] [평가결과]
[134] 도 2는본발명의실시예 1에따른광학이미지결과이다.또한도 3은도 2의 A와 B지역에대한 AFM을측정한결과이다.도 2의 a및도 3의 d는기계적인 박리에의한혹린초박막올나타낸것이다.기계적박리후 20분이내에 이미지를얻었지만，표면이고르지못한것을알수있다.이러한거칠기는흑린 표면에생성된산화물로부터기인한것으로,순수한흑린 (pristine)의표면조도는 측정결과 A지역은 5.1 nm B지역은 5.4 nm로측정되었다.
[135] 도 2의 b및도 3의 e는자외선조사후，활성산소가혹린과반웅하여,혹린
산화막이생긴이미지로혹린산화막의두께는 B지역이약 174 nm로
측정되었으며,이는흑린의높은친수성으로인해산화막이물을흡수하여 표면의두께가크게변화한것을알수있었다.혹린산화막은탈이온수에의해 제거될수있으며，이는도 2의 c및도 3의 f에나타내었다.처음혹린상태에서 세척후두께변화는약 5.5 nm로확인하였으며，혹린초박막의매끈한표면을 확인할수있었다.표면조도는 10 ; m X 10 면적에서 1 nm이하로확인되었다.
[136]
[137] 도 4는본발명의실시예 1내지 4에의해제조된혹린초박막의라만
스펙트럼 (A'g, B2g, A2 g)의결과를나타내었으며， UV조사시간에따른흑린 초박막의라만피크의위치변화를확인하였다. UV조사시간에따라흑린 초박막의두께가감소하였으며,혹린초박막의두께가감소됨에따라 8와 Si 라만밴드신호크기비율의변화와 B2g와 A2 g밴드의피크위치가변화하였고， 상기위치가변화된 B2g와 A2 g벤드의피크차이값을통해단일층의초박막을 확인할수있었다.
[138] 도 5는도 4의라만스펙트럼중 8와 Si밴드의신호크기비율을 UV조사 시간에따라관찰한것으로 , 0.1이하의경우혹린초박막은약 3 nm이하의 두께를확인하였다.
[139] 도 6은상기도 4의흑린초박막의 8¾와 A2 g벤드의피크차이값을 UV
조사시간에따라도시한것이다 . UV조사시간 20분미만에서는두께 3 nm 이상의혹린초박막을의미하며피크차이값에큰변화가없었다.그러나 UV 조사시간 20분이상에서는피크차이값이급격하게증가하였으며，이는점차 3 nm이하로혹린초박막화되는것을의미한다. UV조사시간 30분에서는 2 원자층의혹린초박막이형성되었고， UV조사시간 31분에서는단일원자층의 혹린초박막이형성되었다.
[140]
[141] 도 7은실시예 1에의해제조된단일원자층과 2원자층의흑린초박막의 PL 스펙트럼을도시하고있다.스펙트럼에서는단일원자층과 2원자층이각각 기여하는 2개의 PL피크가명확하게얻어졌으며，디컨벌루션 (deconvolution)에 의해피크를분리함으로써단일원자층과 2원자층초박막은각각 782 nm, 896 nm에서강한특성 PL피크가얻어졌다.구체적으로， 2원자층흑린초박막은 488 nm, 0.01 mW출력및 60초에서약 1,000 photon counts의강한특성 PL피크가 얻어졌다.
[142] 혹린단일원자층은약 780 nm, 2원자층은약 900 nm에서 PL스펙트럼의
중앙값을가지고있다고알려져있으므로,이를통하여초박막혹린표면내 PL 신호크기를감쇄하는나노미터수준의표면결함이없음을확인할수있다. [143] 한편，기계적박리법으로만제조된혹린박막은중적외선영역의 PL을 보이지만，본발명의 UV조사에의해얻어진단일원자층또는 2원자층흑린 초박막은근적외선과가시광영역에서강한 PL스펙트럼을나타내었다.따라서 통상적인기계적박리법에의해제조된흑린박막은표면위많은결함을가진 벌크특성을보이는데반하여，본발명의단일원자층과 2원자층흑린초박막은 대면적에서결함이없고균일한표면의고품질초박막물질임을확인할수있다.
[144]
[145] 도 8은실시예 5에의해제조된 30 nm두께의흑린박막을이용한트랜지스터 소자의광학이미지를나타낸것이다.물로세척하기전 (좌)및후 (우)의암 시야 (Dark field)이미지를보여주며탈이온수세척전에는상당량의혹린 산화막이소자상에존재하지만탈이은수세척후에는혹린산화막이모두 제거된것을확인할수있다.
[146] 도 9는도 8에도시된바와같이，두금속전극에플러스그리고마이너스
전극을인가후 Si02아래 Si에게이트전극을연결후게이트전극변화에따른 두금속전극으로흐르는전류양을측정하여트랜지스터소자의전기적특성을 보여주고있다.구체적으로，탈이온수세척전의결과는흑린산화막으로인해 그림과같이전압변화에대해서낮은전류값을보이는데반해,탈이은수세척 후의결과는전류양이증가하며소자특성이현저히향상됨을나타내었다.
[147] 이로써물에의한세척단계는흑린박막또는흑린초박막을포함하는
트랜지스터소자등의다양한전기소자에서혹린산화막에의한전기소자의 전기적특성의급격한저하를해결할수있는수단임을확인하였다.
[148]
[149] 혹린박막의두께및균일한표면의제어는차세대소재를위한핵심전제
조건이다.본발명은혹린박막을활성산소로식각하여원하는초박막두께로 조절하고，라만으로 3 nm이하의두께를확인및 PL로우수한광발광특성을 확인하였다.또한혹린박막을물로처리하여흑린산화막을제거함으로써，흑린 박막의균일한표면을이루어전기소자특성향상을확인하였다.
[150]
[151] 이상과같이，본발명은비록한정된실시예와도면에의해설명되었으나，본 발명은이것에의해한정되지않으며，본발명이속하는기술분야에서통상의 지식을가진자에의해본발명의기술사상과아래에기재될청구범위의 균등범위내에서다양한수정및변형가능함은물른이다.
[152]

Claims

청구범위
[청구항 1] 흑린박막을형성하는단계;및
챔버내에자외선을조사하여，조사된자외선과산소와의반웅을통해 발생되는활성산소를이용하여흑린박막을식각함으로써혹린초박막을 형성하는단계 ;
를포함하는것인흑린초박막의제조방법 .
[청구항 2] 제 1항에있어서,
상기흑린박막은순수한혹린으로부터기계적으로박리하는방법또는 화학적기상증착방법에의해흑린박막을형성하는것인혹린초박막의 제조방법.
[청구항 3] 제 1항에있어서,
상기형성된흑린초박막을광학이미지및라만분광기에서선택되는 어느하나이상을이용하여식각을확인하는단계;를더포함하는것인 흑린초박막의제조방법.
[청구항 4] 제 3항에있어서，
상기식각을확인한흑린초박막을물로처리하여혹린산화막을 제거하는단계;를더포함하는것인흑린초박막의제조방법.
[청구항 5] 제 4항에있어서，
상기혹린산화막이제거된흑린초박막을광학이미지,라만분광기, 원자힘현미경및주사터널링현미경에서선택되는어느하나이상을 이용하여두깨를확인하는단계;를더포함하는것인혹린초박막의 제조방법.
[청구항 6] 제 1항에있어서,
상기챔버는연속적으로산소의유입및배출이가능하도록형성되는 것인혹린초박막의제조방법 .
[청구항 7] 제 6항에있어서，
상기챔버내부에 loo내지 600 sccm으로산소를유입하는것인흑린 초박막의제조방법.
[청구항 8] 제 1항내지제 7항에서선택되는어느한항의제조방법으로제조되며，
10；圆 X 10 면적에서표면조도가 1 nm이하의범위인혹린초박막.
[청구항 9] 제 8항에있어서,
상기혹린초박막은 3 nm이하의두께인혹린초박막.
[청구항 10] 제 9항에있어서,
상기혹린초박막은파장 700내지 1000 nm에서 1또는 2개의 PL피크를 가지며 , 750내지 810 nm에서혹린단일원자층에의한단일 PL피크및 870내지 930 nm에서흑린 2원자층에의한단일 PL피크에서선택된 어느하나또는둘이상을포함하는 PL피크를가지는것인흑린초박막. [청구항 1 1 ] 제 9항의흑린초박막을포함하는광전자소자.
[청구항 12] 제 1항내지제 7항에서선택되는어느한항의제조방법으로제조되며
10 im X 10 면적에서표면조도가 1 nm이하의범위및 8 nm이상의 두께를가지는것인혹린초박막.
[청구항 13] 제 12항의흑린초박막을포함하는전계효과트랜지스터.
[청구항 14] 혹린박막을물로처리하여，혹린산화막을제거하는것인흑린박막의 제조방법.
PCT/KR2016/002977 2015-05-28 2016-03-24 흑린 박막의 제조방법 및 이로부터 제조된 흑린 박막 WO2016190531A1 (ko)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US15/576,664 US10121658B2 (en) 2015-05-28 2016-03-24 Method of fabricating black phosphorus ultrathin film and black phosphorus ultrathin film thereof

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR10-2015-0074810 2015-05-28
KR1020150074810A KR101576573B1 (ko) 2015-05-28 2015-05-28 오존 생성을 이용한 흑린 박막 제조 방법 및 이를 위한 제조 장치
KR1020150172253A KR101851339B1 (ko) 2015-12-04 2015-12-04 산화막 제거 및 활성산소 처리를 통한 고품질의 흑린 박막 제조방법
KR10-2015-0172253 2015-12-04

Publications (1)

Publication Number Publication Date
WO2016190531A1 true WO2016190531A1 (ko) 2016-12-01

Family

ID=57392784

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2016/002977 WO2016190531A1 (ko) 2015-05-28 2016-03-24 흑린 박막의 제조방법 및 이로부터 제조된 흑린 박막

Country Status (2)

Country Link
US (1) US10121658B2 (ko)
WO (1) WO2016190531A1 (ko)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10727050B1 (en) * 2016-06-15 2020-07-28 Northrop Grumman Systems Corporation Wafer-scale catalytic deposition of black phosphorus
AU2019295411A1 (en) 2018-06-26 2021-01-07 Royal Melbourne Institute Of Technology Sensor and method for discriminating between wavelength regions using the sensor
US10858253B2 (en) 2018-12-26 2020-12-08 United States Of America As Represented By The Secretary Of The Air Force Method and apparatus for producing a nanometer thick film of black phosphorus
CN111627991A (zh) * 2020-05-07 2020-09-04 中国人民解放军国防科技大学 一种基于黑磷制备顶栅型场效应管的方法及场效应管
CN111533096B (zh) * 2020-05-27 2020-11-10 中钢集团南京新材料研究院有限公司 一种黑磷纳米片及其制备方法与应用
CN113134370B (zh) * 2021-03-19 2023-06-16 洛阳师范学院 一种三元异质结光催化抗菌材料及制备方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20030086660A (ko) * 2002-05-06 2003-11-12 삼성전자주식회사 반도체 제조설비의 케미컬온도 제어장치 및 그 제어방법
KR20060077681A (ko) * 2004-12-30 2006-07-05 매그나칩 반도체 유한회사 광촉매를 이용한 에싱 방법 및 에싱 장치

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20160304352A1 (en) * 2013-12-05 2016-10-20 National University Of Singapore Graphene tape
EP3130936B1 (en) * 2015-08-12 2022-03-16 Nokia Technologies Oy A charge-carrier hall-effect sensor
US9702748B2 (en) * 2015-10-14 2017-07-11 International Business Machines Corporation Graphene-based magnetic hall sensor for fluid flow analysis at nanoscale level
US10648959B2 (en) * 2016-05-05 2020-05-12 University Of Southern California Black phosphorus gas sensor

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20030086660A (ko) * 2002-05-06 2003-11-12 삼성전자주식회사 반도체 제조설비의 케미컬온도 제어장치 및 그 제어방법
KR20060077681A (ko) * 2004-12-30 2006-07-05 매그나칩 반도체 유한회사 광촉매를 이용한 에싱 방법 및 에싱 장치

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
DOGANOV, ROSTISLAV A. ET AL.: "Transport Properties of Pristine Few-layer Black Phosphorus by Van Der Waals Passivation in an Inert Atmosphere.", NATURE COMMUNICATIONS, vol. 6, 10 April 2015 (2015-04-10), pages 1 - 7, XP055334174 *
FAVRON, ALEXANDRE ET AL.: "Exfoliating Pristine Black Phosphorus Down to the Monolayer: Photo-oxidation and Electronic Confinement.", ARXIV:1408.0345V2, 2014, pages 1 - 34, XP055334178, Retrieved from the Internet <URL:hitp://arxiv.cirg/abs/1408.0345v2> *
ZHANG, SHUANG ET AL.: "Extraordinary Photoluminescence and Strong Temperature/ Angle-Dependent Raman Responses in Few-Layer Phosphorene.", ACS NANO, vol. 8, no. 9, 4 September 2014 (2014-09-04), pages 9590 - 9596, XP055334176 *

Also Published As

Publication number Publication date
US20180138039A1 (en) 2018-05-17
US10121658B2 (en) 2018-11-06

Similar Documents

Publication Publication Date Title
US10121658B2 (en) Method of fabricating black phosphorus ultrathin film and black phosphorus ultrathin film thereof
Krzywiecki et al. Zinc oxide as a defect-dominated material in thin films for photovoltaic applications–experimental determination of defect levels, quantification of composition, and construction of band diagram
Yanilmaz et al. Nitrogen doping for facile and effective modification of graphene surfaces
Favron et al. Exfoliating pristine black phosphorus down to the monolayer: photo-oxidation and electronic confinement effects
US8617651B2 (en) Low work function diamond surface and radiation energy converters using same
Huang et al. Rapid and scalable production of high-quality phosphorene by plasma–liquid technology
Gong et al. Emergence of photoluminescence on bulk MoS 2 by laser thinning and gold particle decoration
Kim et al. In situ thickness control of black phosphorus field-effect transistors via ozone treatment
JP5002803B2 (ja) ダイヤモンドライクカーボン膜の製造方法
Hou et al. Photoluminescence of monolayer MoS 2 modulated by water/O 2/laser irradiation
Kopani et al. Effect of etching time on structure of p-type porous silicon
Kim et al. Facile dry surface cleaning of graphene by UV treatment
Kopani et al. Morphology and FT IR spectra of porous silicon
US20240093407A1 (en) Systems and methods for disassembling two-dimensional van der waals crystals into macroscopic monolayers and reassembling into artificial lattices
KR101851339B1 (ko) 산화막 제거 및 활성산소 처리를 통한 고품질의 흑린 박막 제조방법
Ji et al. Exciton-dominant photoluminescence of MoS 2 by a functionalized substrate
RU2413330C1 (ru) Способ получения атомно-тонких монокристаллических пленок
US7994602B2 (en) Titanium dioxide thin film systems
Kim et al. First-Principles Calculation Guided High-Purity Layer Control of 4 in. MoS2 by Plasma RIE
Ray Facile fabrication of defect-induced 2D-stanene/stanene-oxide nano-sheet structure material through etching of SnO x thin film by the process of successive Ar+ ion sputtering
Comanescu et al. Metal-Reduced Graphene Oxide Heterostructures on Glass substrate: Preparation and Characterization
Dantas et al. ZnO nanowires growth from thin zinc films for field emission purposes
Sheglov et al. A novel tip-induced local electrical decomposition method for thin GeO films nanostructuring
Giangrisostomi et al. Inhomogeneity of Cleaved Bulk MoS
Intilla Study of ZnO properties applied to thin film transistors

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 16800171

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 15576664

Country of ref document: US

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 16800171

Country of ref document: EP

Kind code of ref document: A1