+

US20130270118A1 - Polycrystalline cuprous oxide nanowire array production method using low-temperature electrochemical growth - Google Patents

Polycrystalline cuprous oxide nanowire array production method using low-temperature electrochemical growth Download PDF

Info

Publication number
US20130270118A1
US20130270118A1 US13/978,416 US201213978416A US2013270118A1 US 20130270118 A1 US20130270118 A1 US 20130270118A1 US 201213978416 A US201213978416 A US 201213978416A US 2013270118 A1 US2013270118 A1 US 2013270118A1
Authority
US
United States
Prior art keywords
nanopore
solution
manufacturing
anodic oxidation
layer
Prior art date
Legal status (The legal status 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 status listed.)
Abandoned
Application number
US13/978,416
Inventor
Bae Ho Park
Sung Oong Kang
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
University Industry Cooperation Corporation of Konkuk University
Original Assignee
University Industry Cooperation Corporation of Konkuk University
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
Application filed by University Industry Cooperation Corporation of Konkuk University filed Critical University Industry Cooperation Corporation of Konkuk University
Assigned to KONKUK UNIVERSITY INDUSTRIAL COOPERATION CORP. reassignment KONKUK UNIVERSITY INDUSTRIAL COOPERATION CORP. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: KANG, SUNG OONG, PARK, BAE HO
Publication of US20130270118A1 publication Critical patent/US20130270118A1/en
Abandoned legal-status Critical Current

Links

Images

Classifications

    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D1/00Electroforming
    • C25D1/04Wires; Strips; Foils
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D1/00Electroforming
    • C25D1/006Nanostructures, e.g. using aluminium anodic oxidation templates [AAO]
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C16/00Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/06Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82BNANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
    • B82B3/00Manufacture or treatment of nanostructures by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C16/00Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02Anodisation
    • C25D11/04Anodisation of aluminium or alloys based thereon
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02Anodisation
    • C25D11/04Anodisation of aluminium or alloys based thereon
    • C25D11/045Anodisation of aluminium or alloys based thereon for forming AAO templates

Definitions

  • the present invention relates to a monocrystalline copper oxide (I) nanowire array manufacturing method using low-temperature electrochemical growth, and more particularly, to a manufacturing method allowing easy vapor deposition at low temperatures and also a monocrystalline copper oxide (I) nanowire array manufacturing method using low-temperature electrochemical growth which retains characteristics such as large-area growth, high-crystallinity nanowire, uniform radial distribution, easy length, radius adjustment, and the like.
  • a nanowire is a wire structure with a diameter of the order of nanometer (nm). Due to its geometrical nanostructure having a high aspect ratio and a large surface area, the nanowire is an important nano material in a wide range of future industrial fields (e.g., a semiconductor memory field, an LED field, a solar cell field, a sensor field, a catalyst field, a battery electrode material field, etc.). As for a nano device having wire structures made of various nano materials as basic constituent units, the constituent units have the same structure and size and a monocrystalline nanowire assuring an electrical property and continuity of electron transport is very important.
  • a monocrystalline nanowire array obtained by a self-assembling process has been recognized as a main functional unit of a high-efficiency and high-integration nano device.
  • an electrochemical growth method using a nanopore membrane (AAO) as a nano molding flask is characterized by low costs and high efficiency and is capable of adjusting a size and a length of a nanowire ranging from nanometer to micrometer in a predetermined pattern.
  • AAO nanopore membrane
  • a monocrystalline copper oxide (I) nanowire array manufacturing method suggested in the present invention is a method for manufacturing a monocrystalline oxide nanowire array having high production yield a radius of which is very uniform and a length of which can be adjusted in the range of from several ten nanometers to several micrometers by inducing complex formation and a decomposition reaction within an electrochemical aqueous solution.
  • a monocrystalline copper oxide (I) nanowire array manufacturing method using low-temperature electrochemical growth in which the method includes: a step of manufacturing a nanopore alumina layer (anodized alumina (AAO)) from a high-purity aluminum (Al) sheet by using a two-step anodic oxidation method; and a step of manufacturing a monocrystalline copper oxide (I) nanowire array by using the nanopore alumina layer as a nanopore molding flask by means of a low-temperature electrochemical growth method.
  • AAO anodized alumina
  • the step of manufacturing a nanopore membrane from a high-purity aluminum (Al) sheet by using a two-step anodic oxidation method includes: a step of electrolytically polishing the high-purity aluminum sheet by applying direct current (DC) voltage thereto in an electrolytic polishing solution; a step of primary anodic oxidation for anodically oxidizing the electrolytically polished aluminum sheet in a sulfuric acid (H 2 SO 4 ) aqueous solution or an oxalic acid (H 2 C 2 O 4 ) aqueous solution; a step of etching and removing a porous alumina layer formed by the primary anodic oxidation process with a mixed solution of phosphoric acid (H 3 PO 4 ) and chromic acid (CrO 3 ); a step of secondary anodic oxidation for anodically oxidizing the alumina sheet, from which an alumina oxide layer is removed, in a sulfuric acid (H 2 SO 4 ) aqueous solution or an
  • the electrolytic polishing solution includes chloric acid (HClO 4 ) and ethanol at a volume ratio of 1:4.
  • the step of electrolytically polishing includes electrolytically polishing the high-purity aluminum sheet at a temperature of 10° C. for 4 minutes by applying direct current voltage of +20 V thereto in an electrolytic polishing solution.
  • the step of primary anodic oxidation includes anodically oxidizing the electrolytically polished aluminum sheet at a temperature of 10° C. for 12 hours by applying voltage of +20 V thereto in a 0.3 M sulfuric acid (H 2 SO 4 ) aqueous solution or a 0.3 M oxalic acid (H 2 C 2 O 4 ) aqueous solution.
  • the step of etching and removing a porous alumina layer formed by the primary anodic oxidation process with a mixed solution of phosphoric acid (H 3 PO 4 ) and chromic acid (CrO 3 ) includes etching and removing a porous alumina layer formed by the primary anodic oxidation process at a predetermined temperature with a mixed solution of phosphoric acid (H 3 PO 4 ) and 1.8 wt % of chromic acid (CrO 3 ).
  • the step of secondary anodic oxidation includes anodically oxidizing the aluminum sheet, from which an alumina oxide layer is removed, at a temperature of 10° C. for a desired time period by applying voltage of +20 V thereto in a 0.3 M sulfuric acid (H 2 SO 4 ) aqueous solution or a 0.3 M oxalic acid (H 2 C 2 O 4 ) aqueous solution.
  • the step of protecting the nanopore alumina layer from an etching process includes protecting the nanopore alumina layer from an etching process by coating a mixture of nitrocellulose and polyester thereon after the step of secondary anodic oxidation.
  • the step of forming a nanopore channel includes forming a nanopore channel by etching the nanopore alumina layer with 5 wt % of a phosphoric acid (H 3 PO 4 ) solution at a temperature of 30° C. for 15 minutes.
  • a phosphoric acid (H 3 PO 4 ) solution at a temperature of 30° C. for 15 minutes.
  • the step of depositing a Pt layer or an Au layer includes depositing a platinum (Pt) layer or a gold (Au) layer on one side surface of the nanopore membrane to a thickness of 200 nm or more.
  • the step of manufacturing a monocrystalline copper oxide (I) nanowire array by using the nanopore alumina layer as a nanopore molding flask includes: a step of manufacturing an electrochemical deposition solution by mixing copper nitrate hydrate (Cu(NO 3 ) 2 .2.5H 2 O) and hexamethylenetetramine; a step of stirring the electrochemical deposition solution and heating the electrochemical deposition solution in a boiling water bath; a step of stirring the electrochemical deposition solution at a predetermined temperature; a step of applying a predetermined current density to the nanopore molding flask in an electrochemical reaction solution; a step of washing an electrochemically grown nanowire with ethanol and deionized water and drying the nanowire; a step of performing a heat treatment to improve crystallinity of the nanowire; and a step of removing a nanopore membrane with an NaOH aqueous solution.
  • an electrochemical deposition solution by mixing copper nitrate hydrate (Cu(NO 3 ) 2 .2.5H 2 O) and
  • FIG. 1 is a schematic diagram of a low-temperature electrochemical reaction for manufacturing a monocrystalline copper oxide (I) nanowire array
  • FIGS. 2 to 4 provide scanning electron micrographs (SEMs) ( FIGS. 2 and 3 ) and an X-ray diffraction diagram ( FIG. 4 ) of monocrystalline copper oxide (I) nanowire arrays manufactured by an electrochemical deposition method using complex formation and a decomposition reaction;
  • FIGS. 5 and 6 provide transmission electron micrographs (TEMs) of manufactured monocrystalline copper oxide (I) nanowire arrays.
  • FIGS. 7 and 8 provide high resolution transmission electron micrographs (HRTEMs) of monocrystalline copper oxide (I) nanowires.
  • a high-integration and high-quality copper oxide nanowire array is manufactured by a low-temperature electrochemical reaction using complex formation and a decomposition reaction.
  • monocrystalline nanowires or nanowire arrays require high temperature and high pressure conditions or complicated and expensive manufacturing process and equipment.
  • monocrystalline nanowires manufactured according to the present invention are grown at a low temperature in an aqueous solution composed of a small amount (typically, in the unit of mg) of eco-friendly samples, the monocrystalline nanowires having very high crystallinity are arrayed and grown with uniform size and gap and adjusted length.
  • a monocrystalline copper oxide (I) nanowire array manufacturing method using low-temperature electrochemical growth is roughly divided into a step of manufacturing a nanopore membrane with desired size and thickness and a step of manufacturing a monocrystalline copper oxide (I) nanowire array using a low-temperature electrochemical growth method.
  • Example 1 was a step of manufacturing a nanopore membrane (anodized alumina (AAO)) from a high-purity aluminum (Al) sheet by using a two-step anodic oxidation method.
  • AAO anodized alumina
  • the high-purity aluminum sheet was electrolytically polished at a temperature of 10° C. for 4 minutes by applying direct current (DC) voltage of +20 V thereto in an electrolytic polishing solution (including chloric acid (HClO 4 ) and ethanol at a volume ratio of 1:4).
  • DC direct current
  • a porous alumina layer formed by the primary anodic oxidation was etched and removed with a mixed solution of 6 wt % of phosphoric acid (H 3 PO 4 ) and 1.8 wt % of chromic acid (CrO 3 ) at a temperature of 60° C. for 24 hours.
  • the nanopore alumina layer formed as described above was protected from an etching process by coating a mixture of nitrocellulose and polyester thereon.
  • the manufactured nanopore alumina layer was etched with 5 wt % of a phosphoric acid (H 3 PO 4 ) solution at a temperature of 30° C. for 15 minutes or more so as to form a nanopore channel.
  • a phosphoric acid H 3 PO 4
  • a platinum (Pt) layer or a gold (Au) layer was deposited on one side surface of the manufactured nanopore membrane to a thickness of 200 nm or more. These metal layers were used as working electrodes in an electrochemical growth reaction.
  • Example 2 was a step of manufacturing a monocrystalline copper oxide (I) nanowire array by using the nanopore alumina layer obtained from Example 1 as a nanopore molding flask.
  • a 20 mM aqueous solution was prepared by mixing copper nitrate hydrate (Cu(NO 3 ) 2 .2.5H 2 O) and hexamethylenetetramine.
  • the prepared electrochemical deposition solution was heated in a boiling water bath until a temperature thereof reached 80° C. with stirring at a speed of 100 rpm.
  • the electrochemical deposition solution was stirred at a speed of 100 rpm for 10 minutes.
  • an electrochemically grown nanowire was washed with ethanol and deionized water and then dried.
  • a heat treatment was performed onto the manufactured nanowire to further improve crystallinity of the nanowire at a temperature of 200° C. for 10 minutes.
  • a nanopore membrane was removed with a 1.0 M NaOH aqueous solution.
  • the electrochemical growth method for manufacturing a monocrystalline copper oxide (I) nanowire array as described above is based on the present inventors' patent application (Korean Patent Application No. 10-2009-0022569) relating to a method for forming a high-crystallinity copper oxide (I) thin film.
  • copper ions (Cu 2+ ) and hydroxyl ions (OH—) required to form copper oxide (I) are generated through complex formation and a decomposition reaction within an electrochemical aqueous solution, and two-dimensional nucleation and growth for monocrystalline growth is carried out effectively through an adsorption reaction between the formed complex and a specific growing surface of the copper oxide (I).
  • the copper ions (Cu 2+ ) generated through complex formation and a decomposition reaction are reduced to cuprous oxide ions (Cu + ) and grown to become a copper oxide (I) structure through a condensation reaction with the hydroxyl ions (OH—) on a conductive metal film.
  • high-density nanowires having very uniform radius are arrayed and grown at regular positions in a regular pattern.
  • Radiuses of the manufactured nanowires can be determined by a pore size of the nanopore membrane and lengths thereof can be adjusted by an electrochemical reaction time.
  • Radiuses of the monocrystalline copper oxide (I) nanowires manufactured by the above-described method can be adjusted in the range of about 20 nm to about 450 nm and lengths thereof can be readily adjusted in the range of from several ten nanometers to several micrometers.
  • Nanowires as shown in FIG. 3 have a small radius range of about 25 ⁇ 3 nm and are grown to a length of at least 3 ⁇ m.
  • such a nanowire array can be grown to have a large area of the order of centimeter and the area is determined by an area of a nanopore membrane.
  • FIG. 4 is an X-ray diffraction diagram of manufactured monocrystalline copper oxide (I) nanowire arrays. Incubation and growth directions of the manufactured nanowires are determined by crystallinity of a metal film (a working electrode) deposited on one side surface of a nanopore membrane.
  • a metal film a working electrode
  • the deposited metal film are incubated and grown in directions [111] and [200], and thus, the incubation and growth directions of the manufactured nanowires follow these two crystal growth directions.
  • the manufactured nanowires are straightly grown in a longitudinal direction and have very smooth surfaces.
  • High resolution transmission electron micrographs (HRTEMs) ( FIGS. 7 and 8 ) of the manufactured nanowires show that crystal lattices of the manufactured nanowires are uniformly arrayed with gaps of 0.247 nanometers and 0.210 nanometers, respectively.
  • the manufactured monocrystalline copper oxide (I) nanowires are incubated and grown in directions and [200].
  • the gaps of 0.247 nanometers and 0.210 nanometers between the crystal lattices respectively correspond to a surface (111) and a surface (200) of cubic copper oxide (I).
  • the manufacturing method of the present invention it is possible to manufacture a monocrystalline oxide nanowire array having high production yield, a radius of which is very uniform and a length of which can be adjusted in the range of from several ten nanometers to several micrometers, and also possible to achieve characteristics such as large-area growth, high-crystallinity nanowire, uniform radial distribution, and easy length and radius adjustment.
  • a monocrystalline oxide nanowire array having high production yield a radius of which is very uniform and a length of which can be adjusted in the range of from several ten nanometers to several micrometers, can be manufactured at low temperatures.
  • the present invention it is possible to achieve characteristics such as large-area growth, high-crystallinity nanowire, uniform radial distribution, and easy length and radius adjustment.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Metallurgy (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Nanotechnology (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

There are provided a monocrystalline copper oxide (I) nanowire array manufacturing method using low-temperature electrochemical growth, and more particularly, to a manufacturing method allowing easy vapor deposition at low temperatures and also a monocrystalline copper oxide (I) nanowire array manufacturing method using low-temperature electrochemical growth which retains characteristics such as large-area growth, high-crystallinity nanowire, uniform radial distribution, easy length, radius adjustment, and the like.
A monocrystalline copper oxide (I) nanowire array manufacturing method of the present invention includes a step of manufacturing a nanopore alumina layer (anodized alumina (AAO)) from a high-purity aluminum (Al) sheet by using a two-step anodic oxidation method; and a step of manufacturing a monocrystalline copper oxide (I) nanowire array by using the nanopore alumina layer as a nanopore molding flask by means of a low-temperature electrochemical growth method.

Description

    FIELD OF THE INVENTION
  • The present invention relates to a monocrystalline copper oxide (I) nanowire array manufacturing method using low-temperature electrochemical growth, and more particularly, to a manufacturing method allowing easy vapor deposition at low temperatures and also a monocrystalline copper oxide (I) nanowire array manufacturing method using low-temperature electrochemical growth which retains characteristics such as large-area growth, high-crystallinity nanowire, uniform radial distribution, easy length, radius adjustment, and the like.
  • BACKGROUND OF THE INVENTION
  • Typically, a nanowire is a wire structure with a diameter of the order of nanometer (nm). Due to its geometrical nanostructure having a high aspect ratio and a large surface area, the nanowire is an important nano material in a wide range of future industrial fields (e.g., a semiconductor memory field, an LED field, a solar cell field, a sensor field, a catalyst field, a battery electrode material field, etc.). As for a nano device having wire structures made of various nano materials as basic constituent units, the constituent units have the same structure and size and a monocrystalline nanowire assuring an electrical property and continuity of electron transport is very important.
  • In particular, a monocrystalline nanowire array obtained by a self-assembling process has been recognized as a main functional unit of a high-efficiency and high-integration nano device. Among various monocrystalline nanowire array manufacturing methods, an electrochemical growth method using a nanopore membrane (AAO) as a nano molding flask is characterized by low costs and high efficiency and is capable of adjusting a size and a length of a nanowire ranging from nanometer to micrometer in a predetermined pattern.
  • Until the present, a technology for manufacturing monocrystalline nanowires or nanowire arrays requires high temperature and high pressure conditions or complicated and expensive manufacturing process and equipment.
  • BRIEF SUMMARY OF THE INVENTION
  • A monocrystalline copper oxide (I) nanowire array manufacturing method suggested in the present invention is a method for manufacturing a monocrystalline oxide nanowire array having high production yield a radius of which is very uniform and a length of which can be adjusted in the range of from several ten nanometers to several micrometers by inducing complex formation and a decomposition reaction within an electrochemical aqueous solution.
  • According to an aspect of the present invention, there is provided a monocrystalline copper oxide (I) nanowire array manufacturing method using low-temperature electrochemical growth, in which the method includes: a step of manufacturing a nanopore alumina layer (anodized alumina (AAO)) from a high-purity aluminum (Al) sheet by using a two-step anodic oxidation method; and a step of manufacturing a monocrystalline copper oxide (I) nanowire array by using the nanopore alumina layer as a nanopore molding flask by means of a low-temperature electrochemical growth method.
  • The step of manufacturing a nanopore membrane from a high-purity aluminum (Al) sheet by using a two-step anodic oxidation method includes: a step of electrolytically polishing the high-purity aluminum sheet by applying direct current (DC) voltage thereto in an electrolytic polishing solution; a step of primary anodic oxidation for anodically oxidizing the electrolytically polished aluminum sheet in a sulfuric acid (H2SO4) aqueous solution or an oxalic acid (H2C2O4) aqueous solution; a step of etching and removing a porous alumina layer formed by the primary anodic oxidation process with a mixed solution of phosphoric acid (H3PO4) and chromic acid (CrO3); a step of secondary anodic oxidation for anodically oxidizing the alumina sheet, from which an alumina oxide layer is removed, in a sulfuric acid (H2SO4) aqueous solution or an oxalic acid (H2C2O4) aqueous solution; a step of protecting the nanopore alumina layer from an etching process by coating a mixture of nitrocellulose and polyester thereon after the step of secondary anodic oxidation; a step of forming a nanopore channel by etching the nanopore alumina layer at a predetermined temperature with a phosphoric acid (H3PO4) solution; and a step of depositing a platinum (Pt) layer or a gold (Au) layer on one side surface of the nanopore membrane.
  • The electrolytic polishing solution includes chloric acid (HClO4) and ethanol at a volume ratio of 1:4.
  • The step of electrolytically polishing includes electrolytically polishing the high-purity aluminum sheet at a temperature of 10° C. for 4 minutes by applying direct current voltage of +20 V thereto in an electrolytic polishing solution.
  • The step of primary anodic oxidation includes anodically oxidizing the electrolytically polished aluminum sheet at a temperature of 10° C. for 12 hours by applying voltage of +20 V thereto in a 0.3 M sulfuric acid (H2SO4) aqueous solution or a 0.3 M oxalic acid (H2C2O4) aqueous solution.
  • The step of etching and removing a porous alumina layer formed by the primary anodic oxidation process with a mixed solution of phosphoric acid (H3PO4) and chromic acid (CrO3) includes etching and removing a porous alumina layer formed by the primary anodic oxidation process at a predetermined temperature with a mixed solution of phosphoric acid (H3PO4) and 1.8 wt % of chromic acid (CrO3).
  • The step of secondary anodic oxidation includes anodically oxidizing the aluminum sheet, from which an alumina oxide layer is removed, at a temperature of 10° C. for a desired time period by applying voltage of +20 V thereto in a 0.3 M sulfuric acid (H2SO4) aqueous solution or a 0.3 M oxalic acid (H2C2O4) aqueous solution.
  • The step of protecting the nanopore alumina layer from an etching process includes protecting the nanopore alumina layer from an etching process by coating a mixture of nitrocellulose and polyester thereon after the step of secondary anodic oxidation.
  • The step of forming a nanopore channel includes forming a nanopore channel by etching the nanopore alumina layer with 5 wt % of a phosphoric acid (H3PO4) solution at a temperature of 30° C. for 15 minutes.
  • The step of depositing a Pt layer or an Au layer includes depositing a platinum (Pt) layer or a gold (Au) layer on one side surface of the nanopore membrane to a thickness of 200 nm or more.
  • The step of manufacturing a monocrystalline copper oxide (I) nanowire array by using the nanopore alumina layer as a nanopore molding flask includes: a step of manufacturing an electrochemical deposition solution by mixing copper nitrate hydrate (Cu(NO3)2.2.5H2O) and hexamethylenetetramine; a step of stirring the electrochemical deposition solution and heating the electrochemical deposition solution in a boiling water bath; a step of stirring the electrochemical deposition solution at a predetermined temperature; a step of applying a predetermined current density to the nanopore molding flask in an electrochemical reaction solution; a step of washing an electrochemically grown nanowire with ethanol and deionized water and drying the nanowire; a step of performing a heat treatment to improve crystallinity of the nanowire; and a step of removing a nanopore membrane with an NaOH aqueous solution.
  • BRIEF DESCRIPTION OF THE DRAWINGS
  • The above and other objects, features and advantages of the present invention will become more apparent to those of ordinary skill in the art by describing in detail exemplary embodiments thereof with reference to the accompanying drawings, in which:
  • FIG. 1 is a schematic diagram of a low-temperature electrochemical reaction for manufacturing a monocrystalline copper oxide (I) nanowire array;
  • FIGS. 2 to 4 provide scanning electron micrographs (SEMs) (FIGS. 2 and 3) and an X-ray diffraction diagram (FIG. 4) of monocrystalline copper oxide (I) nanowire arrays manufactured by an electrochemical deposition method using complex formation and a decomposition reaction;
  • FIGS. 5 and 6 provide transmission electron micrographs (TEMs) of manufactured monocrystalline copper oxide (I) nanowire arrays; and
  • FIGS. 7 and 8 provide high resolution transmission electron micrographs (HRTEMs) of monocrystalline copper oxide (I) nanowires.
  • DETAILED DESCRIPTION OF EXEMPLARY EMBODIMENTS
  • Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings.
  • In the present invention, a high-integration and high-quality copper oxide nanowire array is manufactured by a low-temperature electrochemical reaction using complex formation and a decomposition reaction.
  • Typically, a technology for manufacturing monocrystalline nanowires or nanowire arrays requires high temperature and high pressure conditions or complicated and expensive manufacturing process and equipment. Although, however, monocrystalline nanowires manufactured according to the present invention are grown at a low temperature in an aqueous solution composed of a small amount (typically, in the unit of mg) of eco-friendly samples, the monocrystalline nanowires having very high crystallinity are arrayed and grown with uniform size and gap and adjusted length.
  • According to an example of the present invention, a monocrystalline copper oxide (I) nanowire array manufacturing method using low-temperature electrochemical growth is roughly divided into a step of manufacturing a nanopore membrane with desired size and thickness and a step of manufacturing a monocrystalline copper oxide (I) nanowire array using a low-temperature electrochemical growth method.
  • The present invention will be described in detail with reference to the following Examples, but the scope of the present invention is not limited to these Examples.
  • Example 1
  • Example 1 was a step of manufacturing a nanopore membrane (anodized alumina (AAO)) from a high-purity aluminum (Al) sheet by using a two-step anodic oxidation method.
  • In other words, after a high-purity aluminum sheet having a desired size was prepared, the high-purity aluminum sheet was electrolytically polished at a temperature of 10° C. for 4 minutes by applying direct current (DC) voltage of +20 V thereto in an electrolytic polishing solution (including chloric acid (HClO4) and ethanol at a volume ratio of 1:4).
  • Primary anodic oxidation was performed onto the electrolytically polished aluminum sheet at a temperature of 10° C. for 12 hours by applying voltage of +20 V thereto in a 0.3 M sulfuric acid (H2SO4) aqueous solution or a 0.3 M oxalic acid (H2C2O4) aqueous solution.
  • A porous alumina layer formed by the primary anodic oxidation was etched and removed with a mixed solution of 6 wt % of phosphoric acid (H3PO4) and 1.8 wt % of chromic acid (CrO3) at a temperature of 60° C. for 24 hours.
  • Secondary anodic oxidation was performed onto the aluminum sheet, from which an alumina oxide layer was removed, at a temperature of 10° C. for a desired time period by applying voltage of +20 V thereto in a 0.3 M sulfuric acid (H2SO4) aqueous solution or a 0.3 M oxalic acid (H2C2O4) aqueous solution.
  • The nanopore alumina layer formed as described above was protected from an etching process by coating a mixture of nitrocellulose and polyester thereon.
  • The manufactured nanopore alumina layer was etched with 5 wt % of a phosphoric acid (H3PO4) solution at a temperature of 30° C. for 15 minutes or more so as to form a nanopore channel.
  • A platinum (Pt) layer or a gold (Au) layer was deposited on one side surface of the manufactured nanopore membrane to a thickness of 200 nm or more. These metal layers were used as working electrodes in an electrochemical growth reaction.
  • Example 2
  • Example 2 was a step of manufacturing a monocrystalline copper oxide (I) nanowire array by using the nanopore alumina layer obtained from Example 1 as a nanopore molding flask. A 20 mM aqueous solution was prepared by mixing copper nitrate hydrate (Cu(NO3)2.2.5H2O) and hexamethylenetetramine.
  • Then, the prepared electrochemical deposition solution was heated in a boiling water bath until a temperature thereof reached 80° C. with stirring at a speed of 100 rpm.
  • Further, when the temperature of the electrochemical deposition solution reached 80° C., the electrochemical deposition solution was stirred at a speed of 100 rpm for 10 minutes.
  • Thereafter, a predetermined current density of 1 mA/cm2 was applied to the prepared nanopore molding flask in an electrochemical reaction solution for a desired time period.
  • Subsequently, an electrochemically grown nanowire was washed with ethanol and deionized water and then dried.
  • Then, a heat treatment was performed onto the manufactured nanowire to further improve crystallinity of the nanowire at a temperature of 200° C. for 10 minutes. Herein, a nanopore membrane was removed with a 1.0 M NaOH aqueous solution.
  • The electrochemical growth method for manufacturing a monocrystalline copper oxide (I) nanowire array as described above is based on the present inventors' patent application (Korean Patent Application No. 10-2009-0022569) relating to a method for forming a high-crystallinity copper oxide (I) thin film.
  • To be specific, as illustrated in FIG. 1, copper ions (Cu2+) and hydroxyl ions (OH—) required to form copper oxide (I) are generated through complex formation and a decomposition reaction within an electrochemical aqueous solution, and two-dimensional nucleation and growth for monocrystalline growth is carried out effectively through an adsorption reaction between the formed complex and a specific growing surface of the copper oxide (I).
  • The copper ions (Cu2+) generated through complex formation and a decomposition reaction are reduced to cuprous oxide ions (Cu+) and grown to become a copper oxide (I) structure through a condensation reaction with the hydroxyl ions (OH—) on a conductive metal film.
  • As can be seen from FIG. 2, high-density nanowires having very uniform radius are arrayed and grown at regular positions in a regular pattern.
  • Radiuses of the manufactured nanowires can be determined by a pore size of the nanopore membrane and lengths thereof can be adjusted by an electrochemical reaction time.
  • Radiuses of the monocrystalline copper oxide (I) nanowires manufactured by the above-described method can be adjusted in the range of about 20 nm to about 450 nm and lengths thereof can be readily adjusted in the range of from several ten nanometers to several micrometers. Nanowires as shown in FIG. 3 have a small radius range of about 25±3 nm and are grown to a length of at least 3 μm.
  • Further, such a nanowire array can be grown to have a large area of the order of centimeter and the area is determined by an area of a nanopore membrane.
  • FIG. 4 is an X-ray diffraction diagram of manufactured monocrystalline copper oxide (I) nanowire arrays. Incubation and growth directions of the manufactured nanowires are determined by crystallinity of a metal film (a working electrode) deposited on one side surface of a nanopore membrane.
  • In other words, as can be seen from FIG. 4, the deposited metal film are incubated and grown in directions [111] and [200], and thus, the incubation and growth directions of the manufactured nanowires follow these two crystal growth directions.
  • As can be seen from FIGS. 5 and 6, the manufactured nanowires are straightly grown in a longitudinal direction and have very smooth surfaces.
  • Crystallinities of the manufactured nanowires were observed by using a high resolution transmission electron microscope (HRTEM).
  • High resolution transmission electron micrographs (HRTEMs) (FIGS. 7 and 8) of the manufactured nanowires show that crystal lattices of the manufactured nanowires are uniformly arrayed with gaps of 0.247 nanometers and 0.210 nanometers, respectively.
  • It can be seen from a distance between crystal faces that the manufactured monocrystalline copper oxide (I) nanowires are incubated and grown in directions and [200]. Herein, the gaps of 0.247 nanometers and 0.210 nanometers between the crystal lattices respectively correspond to a surface (111) and a surface (200) of cubic copper oxide (I).
  • Therefore, according to the manufacturing method of the present invention, it is possible to manufacture a monocrystalline oxide nanowire array having high production yield, a radius of which is very uniform and a length of which can be adjusted in the range of from several ten nanometers to several micrometers, and also possible to achieve characteristics such as large-area growth, high-crystallinity nanowire, uniform radial distribution, and easy length and radius adjustment.
  • According to the present invention, a monocrystalline oxide nanowire array having high production yield, a radius of which is very uniform and a length of which can be adjusted in the range of from several ten nanometers to several micrometers, can be manufactured at low temperatures.
  • According to the present invention, it is possible to achieve characteristics such as large-area growth, high-crystallinity nanowire, uniform radial distribution, and easy length and radius adjustment.
  • The above description of the present invention is provided for the purpose of illustration, and those skilled in the art can made various changes, modifications, and substitutions without changing essential features of the present invention. Thus, the accompanying drawings are provided not to limit but to explain a technical conception of the present invention, and a range of the technical conception of the present invention is not limited by the accompanying drawings.
  • The scope of the present invention is defined by the following claims, and it shall be understood that all technical conceptions conceived from the meaning and scope of the claims and their equivalents are included in the scope of the present invention.

Claims (12)

1. A monocrystalline copper oxide (I) nanowire array manufacturing method using low-temperature electrochemical growth, the method comprising:
a step of manufacturing a nanopore alumina layer (anodized alumina (AAO)) from a high-purity aluminum (Al) sheet by using a two-step anodic oxidation method; and
a step of manufacturing a monocrystalline copper oxide (I) nanowire array by using the nanopore alumina layer as a nanopore molding flask by means of a low-temperature electrochemical growth method.
2. The method of claim 1, wherein the step of manufacturing a nanopore membrane from a high-purity aluminum (Al) sheet by using a two-step anodic oxidation method includes:
a step of electrolytically polishing the high-purity aluminum sheet by applying direct current voltage thereto in an electrolytic polishing solution;
a step of primary anodic oxidation for anodically oxidizing the electrolytically polished aluminum sheet in a sulfuric acid (H2SO4) aqueous solution or an oxalic acid (H2C2O4) aqueous solution;
a step of etching and removing a porous alumina layer formed by the primary anodic oxidation with a mixed solution of phosphoric acid (H3PO4) and chromic acid (CrO3);
a step of secondary anodic oxidation for anodically oxidizing the alumina sheet, from which an alumina oxide layer is removed, in a sulfuric acid (H2SO4) aqueous solution or an oxalic acid (H2C2O4) aqueous solution;
a step of protecting the nanopore alumina layer from an etching process by coating a mixture of nitrocellulose and polyester thereon after the step of secondary anodic oxidation;
a step of forming a nanopore channel by etching the nanopore alumina layer at a predetermined temperature with a phosphoric acid (H3PO4) solution; and
a step of depositing a platinum (Pt) layer or a gold (Au) layer on one side surface of the nanopore membrane.
3. The method of claim 2, wherein the electrolytic polishing solution includes chloric acid (HClO4) and ethanol at a volume ratio of 1:4.
4. The method of claim 2, wherein the step of electrolytically polishing includes electrolytically polishing the high-purity aluminum sheet at a temperature of 10° C. for 4 minutes by applying direct current voltage of +20 V thereto in an electrolytic polishing solution.
5. The method of claim 2, wherein the step of primary anodic oxidation includes anodically oxidizing the electrolytically polished aluminum sheet at a temperature of 10° C. for 12 hours by applying voltage of +20 V thereto in a 0.3 M sulfuric acid (H2SO4) aqueous solution or a 0.3 M oxalic acid (H2C2O4) aqueous solution.
6. The method of claim 2, wherein the step of etching and removing a porous alumina layer formed by the primary anodic oxidation with a mixed solution of phosphoric acid (H3PO4) and chromic acid (CrO3) includes etching and removing a porous alumina layer formed by the primary anodic oxidation at a predetermined temperature with a mixed solution of phosphoric acid (H3PO4) and 1.8 wt % of chromic acid (CrO3).
7. The method of claim 2, wherein the step of secondary anodic oxidation includes anodically oxidizing the aluminum sheet, from which an alumina oxide layer is removed, at a temperature of 10° C. for a desired time period by applying voltage of +20 V thereto in a 0.3 M sulfuric acid (H2SO4) aqueous solution or a 0.3 M oxalic acid (H2C2O4) aqueous solution.
8. The method of claim 2, wherein the step of protecting the nanopore alumina layer from an etching process includes protecting the nanopore alumina layer from an etching process by coating a mixture of nitrocellulose and polyester thereon after the step of secondary anodic oxidation.
9. The method of claim 2, wherein the step of forming a nanopore channel includes forming a nanopore channel by etching the nanopore alumina layer with 5 wt % of a phosphoric acid (H3PO4) solution at a temperature of 30° C. for 15 minutes.
10. The method of claim 2, wherein the step of depositing a Pt layer or an Au layer includes depositing a platinum (Pt) layer or a gold (Au) layer on one side surface of the nanopore membrane to a thickness of 200 nm or more.
11. The method of claim 1, wherein the step of manufacturing a monocrystalline copper oxide (I) nanowire array by using the nanopore alumina layer as a nanopore molding flask includes:
a step of manufacturing an electrochemical deposition solution by mixing copper nitrate hydrate (Cu(NO3)22.5H2O) and hexamethylenetetramine;
a step of stirring the electrochemical deposition solution and heating the electrochemical deposition solution in a boiling water bath;
a step of stirring the electrochemical deposition solution at a predetermined temperature;
a step of applying a predetermined current density to the nanopore molding flask in an electrochemical reaction solution;
a step of washing an electrochemically grown nanowire with ethanol and deionized water and drying the nanowire;
a step of performing a heat treatment to improve crystallinity of the nanowire; and
a step of removing a nanopore membrane with an NaOH aqueous solution.
12. A monocrystalline copper oxide (I) nanowire array manufactured by the manufacturing method according to claim 1.
US13/978,416 2011-01-07 2012-01-04 Polycrystalline cuprous oxide nanowire array production method using low-temperature electrochemical growth Abandoned US20130270118A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
KR1020110001703A KR101332422B1 (en) 2011-01-07 2011-01-07 Templated electrochemical growth of single-crystal Cu2O nanowire arrays
KR10-2011-0001703 2011-01-07
PCT/KR2012/000076 WO2012093847A2 (en) 2011-01-07 2012-01-04 Polycrystalline cuprous oxide nanowire array production method using low-temperature electrochemical growth

Publications (1)

Publication Number Publication Date
US20130270118A1 true US20130270118A1 (en) 2013-10-17

Family

ID=46457840

Family Applications (1)

Application Number Title Priority Date Filing Date
US13/978,416 Abandoned US20130270118A1 (en) 2011-01-07 2012-01-04 Polycrystalline cuprous oxide nanowire array production method using low-temperature electrochemical growth

Country Status (4)

Country Link
US (1) US20130270118A1 (en)
JP (1) JP5942115B2 (en)
KR (1) KR101332422B1 (en)
WO (1) WO2012093847A2 (en)

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103754925A (en) * 2014-01-13 2014-04-30 复旦大学 Cuprous oxide nanowire porous film as well as preparation method and application thereof
CN104087997A (en) * 2014-06-16 2014-10-08 北京工业大学 Method for preparing regular small-aperture anodized aluminum template through mixed acid variable pressure two-stage oxidation
CN104628411A (en) * 2015-02-05 2015-05-20 宁波大学 A super-macroporous material loaded with copper oxide nanowires
US9324766B2 (en) 2014-08-14 2016-04-26 Samsung Display Co., Ltd. Display device and method for manufacturing the same
US9373821B2 (en) 2013-09-30 2016-06-21 Samsung Display Co., Ltd. Display apparatus
US20160181121A1 (en) * 2013-07-25 2016-06-23 The Board Of Trustees Of The Leland Stanford Junior University Electro-assisted transfer and fabrication of wire arrays
WO2016138385A1 (en) * 2015-02-26 2016-09-01 Board Of Regents, The University Of Texas System Two-dimensional nanosheets and methods of making and use thereof
CN106493391A (en) * 2016-12-12 2017-03-15 中国科学技术大学 A kind of method of purification of copper nano-wire
CN111676498A (en) * 2020-06-24 2020-09-18 河北工业大学 A kind of preparation method of cuprous oxide electrode
CN112164597A (en) * 2020-09-28 2021-01-01 桂林理工大学 Copper oxide nano array electrode, copper oxide nano array non-solid water system flexible energy storage device and preparation method thereof
US10910232B2 (en) 2017-09-29 2021-02-02 Samsung Display Co., Ltd. Copper plasma etching method and manufacturing method of display panel

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101745080B1 (en) * 2015-04-17 2017-06-09 연세대학교 산학협력단 Manufacturing Method for Alumina Based Light Diffuser, and Light Diffuser Manufactured Thereby
KR101795866B1 (en) * 2015-11-20 2017-11-09 연세대학교 산학협력단 Nanowire bundle array, membrane comprising the same and method for manufacturing of the membrane and steam generator using the membrane
CN105621353B (en) * 2015-12-31 2017-04-05 中山大学 A kind of large-area nano graphic method based on multi-layered anode alumina formwork
CN108063187B (en) * 2017-12-18 2021-01-26 苏州大学 A kind of aluminum nanoparticle array, preparation method and application thereof
CN119571399A (en) * 2024-12-16 2025-03-07 兰州大学 Method for preparing magnetic metal nickel tapered nanowire

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070289945A1 (en) * 2006-06-16 2007-12-20 Fujifilm Corporation Microstructure and method of manufacturing the same
US20090243584A1 (en) * 2008-03-25 2009-10-01 Guigen Zhang Fabrication of microstructures integrated with nanopillars along with their applications as electrodes in sensors
US20100163419A1 (en) * 2008-12-31 2010-07-01 Korea University Research And Business Foundation Method for fabricating multi-component nanowires

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007224364A (en) * 2006-02-23 2007-09-06 Fujifilm Corp Microstructure and its production method
KR101031019B1 (en) * 2009-03-10 2011-04-25 삼성전기주식회사 Method for producing a metal electrode having a transition metal oxide coating layer and the metal electrode produced thereby
KR101069738B1 (en) * 2009-03-17 2011-10-05 건국대학교 산학협력단 Method for forming copper oxide
JP5271790B2 (en) * 2009-04-24 2013-08-21 公益財団法人神奈川科学技術アカデミー Aluminum base material for stamper manufacture, and method for manufacturing stamper

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070289945A1 (en) * 2006-06-16 2007-12-20 Fujifilm Corporation Microstructure and method of manufacturing the same
US20090243584A1 (en) * 2008-03-25 2009-10-01 Guigen Zhang Fabrication of microstructures integrated with nanopillars along with their applications as electrodes in sensors
US20100163419A1 (en) * 2008-12-31 2010-07-01 Korea University Research And Business Foundation Method for fabricating multi-component nanowires

Non-Patent Citations (7)

* Cited by examiner, † Cited by third party
Title
Chen-Un Yu, Chi-Chang Hu, Allen Bai, Yong-Feng Yang, Pore-size dependence of AAO films on surface roughness of Al-1050 sheets controlled by electropolishing coupled with fractional factorial design, Surface and Coatings Technology, Volume 201, Issues 16-17, 21 May 2007, Pages 7259-7265 *
Control of the Anodic Aluminum Oxide Barrier Layer Opening Process by Wet Chemical Etching Catherine Y. Han,†,‡, Gerold A. Willing,†,�, Zhili Xiao,|| and, and H. Hau Wang* Langmuir 2007 23 (3), 1564-1568 *
Facile Electrochemical Synthesis of Hexagonal Cu2O Nanotube Arrays and Their Application Jin-Hui Zhong, Gao-Ren Li, Zi-Long Wang, Yan-Nan Ou, and Ye-Xiang Tong Inorganic Chemistry 2011 50 (3), 757-763 *
Hexagonal pore arrays with a 50–420 nm interpore distance formed by self-organization in anodic aluminaLi, A. P. and Müller, F. and Birner, A. and Nielsch, K. and Gösele, U., Journal of Applied Physics, 84, 6023-6026 (1998) *
O. Jessensky, F. M�ller, and U. G�sele, Self-Organized Formation of Hexagonal Pore Structures in Anodic AluminaJ. Electrochem. Soc. 1998 145(11): 3735-374 *
Sun-Kyu Hwang, Soo-Hwan Jeong, Hee-Young Hwang, Ok-Joo Lee, Kun-Hong Lee, "Fabrication of highly ordered pore array in anodic aluminum oxide" Korean Journal of Chemical Engineering, May 2002, Volume 19, Issue 3, pp 467-473 *
Translation of cited KR2010-0104265 *

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20160181121A1 (en) * 2013-07-25 2016-06-23 The Board Of Trustees Of The Leland Stanford Junior University Electro-assisted transfer and fabrication of wire arrays
US10037896B2 (en) * 2013-07-25 2018-07-31 The Board Of Trustees Of The Leland Stanford Junior University Electro-assisted transfer and fabrication of wire arrays
US9373821B2 (en) 2013-09-30 2016-06-21 Samsung Display Co., Ltd. Display apparatus
CN103754925A (en) * 2014-01-13 2014-04-30 复旦大学 Cuprous oxide nanowire porous film as well as preparation method and application thereof
CN104087997A (en) * 2014-06-16 2014-10-08 北京工业大学 Method for preparing regular small-aperture anodized aluminum template through mixed acid variable pressure two-stage oxidation
US9324766B2 (en) 2014-08-14 2016-04-26 Samsung Display Co., Ltd. Display device and method for manufacturing the same
US9502655B2 (en) 2014-08-14 2016-11-22 Samsung Display Co., Ltd. Display device and method for manufacturing the same
CN104628411A (en) * 2015-02-05 2015-05-20 宁波大学 A super-macroporous material loaded with copper oxide nanowires
WO2016138385A1 (en) * 2015-02-26 2016-09-01 Board Of Regents, The University Of Texas System Two-dimensional nanosheets and methods of making and use thereof
CN106493391A (en) * 2016-12-12 2017-03-15 中国科学技术大学 A kind of method of purification of copper nano-wire
US10910232B2 (en) 2017-09-29 2021-02-02 Samsung Display Co., Ltd. Copper plasma etching method and manufacturing method of display panel
CN111676498A (en) * 2020-06-24 2020-09-18 河北工业大学 A kind of preparation method of cuprous oxide electrode
CN112164597A (en) * 2020-09-28 2021-01-01 桂林理工大学 Copper oxide nano array electrode, copper oxide nano array non-solid water system flexible energy storage device and preparation method thereof

Also Published As

Publication number Publication date
WO2012093847A3 (en) 2012-11-08
KR101332422B1 (en) 2013-12-02
JP5942115B2 (en) 2016-06-29
KR20120080325A (en) 2012-07-17
WO2012093847A2 (en) 2012-07-12
JP2014507561A (en) 2014-03-27

Similar Documents

Publication Publication Date Title
US20130270118A1 (en) Polycrystalline cuprous oxide nanowire array production method using low-temperature electrochemical growth
JP7281445B2 (en) Formation of functional material layer on conductive substrate
Zhang et al. Two-dimensional layered MoS 2: rational design, properties and electrochemical applications
Xu et al. Preparation of II-VI group semiconductor nanowire arrays by dc electrochemical deposition in porous aluminum oxide templates
Wu et al. Electrochemical synthesis and applications of oriented and hierarchically quasi-1D semiconducting nanostructures
Chen et al. Fabrication and characterization of highly-ordered valve-metal oxide nanotubes and their derivative nanostructures
KR101896266B1 (en) Ionic diode membrane comprising tapered nanopore and method for preparing thereof
KR20100075032A (en) Manufacturing method of self-organized anodic titanium oxide nanotube arrays and control of the anodic titanium oxide nanotube thereby
CN101870453A (en) Fabrication method of semiconductor nanopillar array structure
CN103628106A (en) Method for preparing indium/tellurium porous nanowire array
Mebed et al. Electrochemical fabrication of 2D and 3D nickel nanowires using porous anodic alumina templates
US10662550B2 (en) Diamond nanostructures with large surface area and method of producing the same
Zhang et al. Electrochemical behaviors of hierarchical copper nano-dendrites in alkaline media
Nazemi et al. Aluminium oxide nanowires synthesis from high purity aluminium films via two-step anodization
KR101710421B1 (en) Photo-electrode composed of CuO/ZnO nanorod-nanobranch structure and method of forming the structure
RU2526066C1 (en) Method of obtaining thread-like nanocrystals of semiconductors
Bao et al. Controllable fabrication of one-dimensional ZnO nanoarrays and their application in constructing silver trap structures
Perillo et al. Formation of TiO2 nanopores by anodization of Ti-Films
Yang et al. Advances of the research evolution on aluminum electrochemical anodic oxidation technology
CN113526541B (en) A method for electrochemical reduction-assisted preparation of ultrathin zinc oxide nanosheets
Duan et al. Structural and optical properties of porous ZnO nanorods synthesized by a simple two-step method
Lyu et al. Cyanide-free preparation of gold nanowires: controlled crystallinity, crystallographic orientation and enhanced field emission
Shoja et al. Growth of TiO2 nanotube arrays in semiconductor porous anodic alumina templates
Li et al. Synthesis of ZnO nanotube arrays by annealing Zn nanowire arrays in anodic alumina membrane
CN103422155A (en) Method for preparing compact single crystal ZnO nanowire in porous template

Legal Events

Date Code Title Description
AS Assignment

Owner name: KONKUK UNIVERSITY INDUSTRIAL COOPERATION CORP., KO

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:PARK, BAE HO;KANG, SUNG OONG;REEL/FRAME:030742/0063

Effective date: 20130704

STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION

点击 这是indexloc提供的php浏览器服务,不要输入任何密码和下载