KR20160150274A - Method for fabricating metallic nanowire electrode array - Google Patents

Method for fabricating metallic nanowire electrode array Download PDF

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KR20160150274A
KR20160150274A KR1020150114533A KR20150114533A KR20160150274A KR 20160150274 A KR20160150274 A KR 20160150274A KR 1020150114533 A KR1020150114533 A KR 1020150114533A KR 20150114533 A KR20150114533 A KR 20150114533A KR 20160150274 A KR20160150274 A KR 20160150274A
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metal
precursor
oxide
metal oxide
nanowire
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KR1020150114533A
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Korean (ko)
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이태우
이영준
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포항공과대학교 산학협력단
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/08—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • H01B13/0016—Apparatus or processes specially adapted for manufacturing conductors or cables for heat treatment
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • H01B13/0026—Apparatus for manufacturing conducting or semi-conducting layers, e.g. deposition of metal

Abstract

A method of manufacturing a metal nanowire electrode array is provided. The method of preparing a metal nanowire electrode array includes the steps of preparing a metal precursor / metal oxide precursor / organic polymer composite printing solution, preparing a metal precursor / metal oxide precursor / organic polymer composite nanowire pattern, and removing a polymer precursor / metal precursor / And a metal oxide precursor reduction step. Accordingly, a metal nanowire electrode array having a work function controlled and arranged in a large area can be manufactured by controlling the composition of the metal oxide precursor of the printing solution. Therefore, by using a metal nanowire electrode capable of work function control, a highly integrated electronic device having a large area can be manufactured with high efficiency in terms of process steps, time, and cost.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a method for fabricating a metallic nanowire electrode array,

The present invention relates to a method of manufacturing a metal nanowire electrode array, and more particularly, to a metal nanowire electrode array manufacturing method capable of work function control.

Nano-sized electrodes are essential for future ultra-high-density, ultra-small, transparent electronic devices, and the work function of metal electrodes has a very important effect on the performance of electronic devices. The metal has its own work function and there may be restrictions on the type of metal that can be selected due to cost and process reasons. In this case, the work function of the active layer and the electrode of the electronic device is not matched and the energy barrier the energy barrier and the contact resistance are increased, so that it may be difficult to fabricate a high-performance device. An additional post-treatment process is involved to control the work function of the metal electrode, and a high cost process based on photo resist is required to selectively control the work function of only the desired electrode. In addition, controlling the work function of the nano-sized electrode is much more difficult than controlling the work function of the conventional electrodes, so a breakthrough that can effectively overcome this is needed.

  The most typical method of controlling the work function of the metal electrode is to form a self-assembled monolayer (SAM) on the electrode. By controlling the work function through the SAM formed on the electrode, energy barrier with the activation layer can be reduced, and electronic devices having excellent performance can be manufactured.

  Another method is to add another type of thin metal layer over the metal layer or to adjust the work function through the formation of a thin metal oxide layer.

  The process has the following problems:

  1) The SAM material is an organic substance, which is very harmful to the human respiratory system and central nervous system, and is disadvantageous in that it is unstable to air or moisture.

2) The process of forming a thin metal layer or a thin metal oxide layer on a metal electrode is accompanied by an additional process, and in particular, an expensive vacuum process is required to selectively form additional layers on nano-sized electrodes.

Therefore, what is required is a method of controlling the work function of the metal nanoelectrode without additional processing.

Korean Patent Publication No. 10-2015-0047840

SUMMARY OF THE INVENTION It is an object of the present invention to provide a method of manufacturing a metal nanowire electrode array capable of controlling a work function by controlling the composition of a printing solution and aligning the metal nanowire electrode array with a large area.

One aspect of the present invention provides a method of fabricating a metal nanowire electrode array capable of work function control. A method of manufacturing a metal nanowire electrode array capable of controlling a work function includes preparing a printing solution by dissolving or mixing a metal precursor, a metal oxide precursor, and an organic polymer in distilled water or an organic solvent, dropping the printing solution onto a substrate, Forming a metal oxide precursor / organic polymer composite nanowire pattern; removing the organic polymer from the metal precursor / metal oxide precursor / organic polymer composite nanowire pattern and reducing the metal precursor and metal oxide precursor to form a metal / metal oxide And forming a composite nanowire pattern.

In addition, the metal precursor and the metal oxide precursor are each reduced to a metal and a semiconductive metal oxide after the reduction process.

The metal precursor may be selected from the group consisting of Au, Ag, Fe, Ni, Pt, Cu, Pd, Al, Ca, W, Zn, Li, Sn, Ti, Cr, Mo, It may be a precursor of one metal.

The semiconductive metal oxide may be at least one selected from the group consisting of zinc oxide, indium oxide, tin oxide, aluminum oxide, tungsten oxide, titanium oxide, vanadium oxide, physicodbium oxide, copper oxide, nickel oxide, iron oxide, chromium oxide, cobalt oxide, And at least one metal oxide selected from the group consisting of oxides, iron oxides, silver oxides, and mixtures thereof.

The metal oxide precursor includes a p-type metal oxide precursor or an n-type metal oxide precursor, and the work function can be controlled according to the ratio of the metal oxide precursor to the metal precursor.

When the metal oxide precursor includes a p-type metal oxide precursor, the work function of the metal oxide precursor increases as the ratio of the p-type metal oxide precursor to the metal precursor increases.

When the metal oxide precursor includes an n-type metal oxide precursor, the work function is lowered as the ratio of the n-type metal oxide precursor to the metal precursor increases.

The organic polymer may be at least one selected from the group consisting of polyvinyl alcohol, polyvinyl acetate, poly (p-phenylene vinylene), polyhydroxyethyl methacrylate, polyethylene oxide, polystyrene, polycaprolactone, polyacrylonitrile, Methacrylate), polyimide, poly (vinylidene fluoride), polyaniline, polyvinyl chloride, nylon, polyacrylic acid, polychlorostyrene, polydimethylsiloxane, polyetherimide, polyethersulfone, polyalkyl acrylate, polyethyl Acrylate, polyethylvinyl acetate, polyethyl-co-vinyl acetate, polyethylene terephthalate, polylactic acid-co-glycolic acid, polymethacrylate, polymethylstyrene, polystyrenesulfonate, polystyrene sulfonyl fluoride, polystyrene-co - acrylonitrile, polystyrene-co-butadiene, polystyrene-co-divinylbenzene, polylactide , Polyacrylamide, polybenzimidazole, polycarbonate, polydimethylsiloxane-co-polyethylene oxide, polyetheretherketone, polyethylene, polyethyleneimine, polyisoprene, polylactide, polypropylene, polysulfone, polyurethane, polyvinyl At least one selected from the group consisting of pyrrolidone and polyvinylcarbazole.

The organic solvent may be at least one selected from the group consisting of dichloroethylene, trichlorethylene, chloroform, chlorobenzene, dichlorobenzene, styrene, dimethylformamide, dimethylsulfoxide, xylene, toluene, cyclohexene, isopropyl alcohol, And at least one selected from the group consisting of methanol, tetrahydrofuran, isopropyl alcohol, terpineol, ethylene glycol, diethylene glycol, polyethylene glycol, acetonitrile, and acetone.

The metal precursor or the metal oxide precursor may be a nanoparticle, a nanowire, a nanofiber, a nanotube, a nanoflake, or a nanosheet dispersed in a compound dissolved in the organic solvent or an organic solvent.

In the preparing of the printing solution, the weight ratio of the metal precursor to the metal oxide precursor is 1: 1 to 1: 0.1, and the weight ratio of the metal precursor and the organic polymer is 1: 0.7 to 1: 0.1. .

The forming of the metal precursor / metal oxide precursor / organic polymer composite nanowire pattern may be performed by discharging the printing solution from a nozzle to which a voltage is applied at a position 10 to 20 mm vertically away from the substrate, And the substrate or the nozzle is moved while forming an aligned metal precursor / metal oxide precursor / organic polymer composite nanowire pattern.

The step of forming the metal precursor / metal oxide precursor / organic polymer composite nanowire pattern may be performed by using an electric field assisted robotic nozzle printing, electrospinning, ink jet printing, dip pen printing or electrohydraulic jet printing .

The step of forming the metal / metal oxide composite nanowire pattern includes a heat treatment step, a reducing agent treatment step or a light irradiation step.

The heat treatment may be performed at a temperature of 50 to 900 占 폚 for 5 minutes to 8 hours in a gas atmosphere containing at least one selected from the group consisting of air, oxygen, nitrogen, argon, and hydrogen. And the heating is performed five times.

The reducing agent treatment process may further include a treatment with a reducing agent such as hydrazine, formic acid, ascorbic acid, oxalic acid, carbon, carbon monoxide, formaldehyde, acetaldehyde, hydrogen, hydrogen compound, sulfur dioxide, sulfite, sodium sulfide, ammonium sulfide, , Magnesium, magnesium amalgam, calcium, calcium amalgam, aluminum, amalgam, zinc, zinc amalgam, phosphite, hypophosphite, phosphorous acid, iron sulfide, sodium, sodium compound, sodium borohydride, iron, iron compound, tin, Titanium, titanium compounds, chromium, chromium compounds, cysteine, acetylcysteine, cysteine HCI, thioglycolic acid, ammonium thioglycolate, ammonium chi-lactate, ethanolamine thioglycolate, cysteamine HCI, Glutathione, and a mixture thereof. Characterized in that the vapor of the raw material is used or immersed in a reducing agent.

Further, the light irradiation step is characterized by irradiating light in a wavelength range of 200 nm to 500 탆 for 0.001 second to 5 hours by using an excimer laser, an infrared laser, or a UV laser.

According to another aspect of the present invention, there is provided a light emitting diode. The light emitting diode includes an anode, a cathode, and a light emitting layer positioned between the anode and the cathode, and at least one of the anode and the cathode is a metal nanowire electrode array manufactured by the above-described manufacturing method.

According to another aspect of the present invention, there is provided a solar cell. The solar cell includes a positive electrode, a negative electrode, and a photoactive layer positioned between the positive electrode and the negative electrode, and at least one of the positive electrode and the negative electrode is a metal nanowire electrode array manufactured by the above-described manufacturing method .

According to another aspect of the present invention, there is provided an electrochemical cell. The electrochemical cell includes an anode, a cathode, and an active material layer positioned between the anode and the cathode, and at least one of the anode and the cathode is a metal nanowire electrode array manufactured by the above-described manufacturing method do.

According to another aspect of the present invention, there is provided a field effect transistor. The field effect transistor includes a gate electrode, a gate insulating layer, a source electrode, a drain electrode, and an organic, inorganic or organic hybrid semiconductor layer, and at least one of the gate electrode, the source electrode, Wherein the metal nanowire electrode array is a metal nanowire electrode array.

According to the present invention, firstly, work function can be controlled without additional process, and since the metal nanowire electrode can be manufactured in a large area, it is very efficient in terms of cost and time in the process.

Second, if a horizontal transistor, a light emitting diode (LED), a solar cell, or the like is manufactured using a metal nanowire electrode having a work function controlled according to the manufacturing method of the present invention, And the step can be reduced, and an electronic device having a very high transmittance in which the electrode is invisible can be manufactured.

The technical effects of the present invention are not limited to those mentioned above, and other technical effects not mentioned can be clearly understood by those skilled in the art from the following description.

1 is a process diagram showing a method of manufacturing a metal nanowire electrode array capable of work function control according to an embodiment of the present invention.
2 is a schematic diagram of an electric field assisted robotic nozzle printer.
3 is an SEM image showing the morphology of the silver / silver oxide precursor / organic polymer composite nanowire and the silver nanowire after heat treatment.
4 is a graph showing the work function of silver nanowires prepared according to Preparation Example 1. FIG.
Fig. 5 is a graph showing the analysis of surface components of silver nanowires prepared according to Production Example 1. Fig.
6 is a graph showing a current-voltage curve and resistivity of the silver nanowire fabricated according to Production Example 1. FIG.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings.

While the invention is susceptible to various modifications and alternative forms, specific embodiments thereof are shown by way of example in the drawings and will herein be described in detail. Rather, the intention is not to limit the invention to the particular forms disclosed, but rather, the invention includes all modifications, equivalents and substitutions that are consistent with the spirit of the invention as defined by the claims.

It will be appreciated that when an element such as a layer, region or substrate is referred to as being present on another element "on," it may be directly on the other element or there may be an intermediate element in between .

Although the terms first, second, etc. may be used to describe various elements, components, regions, layers and / or regions, such elements, components, regions, layers and / And should not be limited by these terms.

1 is a process diagram showing a method of manufacturing a metal nanowire electrode array capable of work function control according to an embodiment of the present invention.

Referring to FIG. 1, a method of manufacturing a metal nanowire electrode array capable of controlling work function according to the present invention includes the steps of preparing a metal precursor / metal oxide precursor / organic polymer composite printing solution (S110), a metal precursor / metal oxide precursor / Step (S120) of preparing an organic polymer composite nanowire pattern and removing the polymer and a metal precursor / metal oxide reduction step (S130). Therefore, as shown in (S140) in FIG. 1, a metal nanowire electrode array that can be formed by the present manufacturing method can be formed.

First, a metal precursor / metal oxide precursor / organic polymer composite printing solution is prepared (S110).

The printing solution may be prepared by dissolving or mixing the metal precursor, the metal oxide precursor and the organic polymer in distilled water or an organic solvent.

Wherein the metal precursor and the metal oxide precursor are each reduced to a metal and a semiconductive metal oxide after the reduction process.

For example, the metal precursor may be selected from the group consisting of Au, Ag, Fe, Ni, Pt, Cu, Pd, Al, Ca, W, Zn, Li, Sn, Ti, Cr, Mo, May be a precursor of any one of the metals.

For example, among the metal precursors, the copper precursor may be selected from the group consisting of copper acetate, copper acetate hydrate, copper acetylacetonate, copper isobutyrate, copper carbonate carbonate, copper chloride, copper chloride hydrate, copper ethylacetoacetate, copper 2-ethylhexanoate, copper fluoride, formic acid, Copper formate hydrate, Copper gluconate, Copper hexafluoroacetylacetonate, Copper hexafluoroacetylacetonate hydrate, Copper methoxide, Copper oxalate, Copper neodecanoate, copper nitrate hydrate, copper nitrate, copper nitrate, Copper perchlorate hydrate, Copper sulfate, Copper sulfate hydrate, Copper tartrate hydrate, Copper trifluoroacetylacetonate, Copper trifluoro methane sulfone, Copper perchlorate hydrate, Copper perchlorate hydrate, Copper sulfate, Copper sulfate hydrate, Copper tartrate hydrate, Copper trifluoromethanesulfonate, Tetraamminecopper sulfate hydrate, and combinations thereof.

Among the metal precursors, the titanium precursor may be selected from the group consisting of titanium carbide, titanium chloride, titanium ethoxide, titanium fluoride, titanium hydride, titanium nitride titanium nitride, titanium chloride, titanium isopropoxide, titanium propoxide, titanium fluoride, titanium methoxide, titanium oxyacetylacetonate, Titanium oxyacetylacetonate, Titanium 2-ethylhexyloxide, Titanium butoxide, and combinations thereof.

Among the metal precursors, the precursors include silver hexafluorophosphate, silver neodecanoate, silver nitrate, silver trifluoromethanesulfonate, silver (silver silver acetate, silver carbonate, silver chloride, silver perchlorate, silver tetrafluoroborate, silver trifluoroacetate, and 2-ethylhexanoate Silver 2-ethylhexanoate, Silver fluoride, Silver perchlorate hydrate, Silver lactate, Silver acetylacetonate, Silver methanesulfonate, Hepta Silver heptafluorobutyrate, Silver chlorate, Silver pentafluoropropionate, Hydrogen fluoride, May be selected from the group consisting of silver hydrogenfluoride and combinations thereof.

  Among the metal precursors, the platinum precursor may be a platinum precursor selected from the group consisting of chloroplatinic acid hexahydrate, dihydrogen hexahydroxyplatinate, platinum acetylacetonate, platinum chloride, Platinum chloride hydrate, Platinum hexafluoroacetylacetonate, Tetraammineplatinum chloride hydrate, Tetraammineplatinum hydroxide hydrate, Tetraammineplatinum nitrate, Tetraammineplatinum nitrate, Tetraammineplatinum tetrachloroplatinate, Tetrachlorodiammine platinum, Dichlorodiammine platinum, Diammineplatinum dichloride, and the like. dichloride, and combinations thereof.

Among the metal precursors, the nickel precursor may be selected from the group consisting of Hexaamminenickel chloride, Nickel acetate, Nickel acetate hydrate, Nickel acetylacetonate, Nickel acetylacetonate hydrate acetylacetonate hydrate, nickel carbonyl, nickel chloride, nickel chloride hydrate, nickel fluoride, nickel fluoride hydrate, nickel hexafluoroacetylacetate Nickel hexafluoroacetylacetonate hydrate, Nickel hexafluoroacetylacetonate, Nickel hydroxide, Nickel hydroxyacetate, Nickel nitrate hydrate, Hyper perchlorate nickel hydrate Nickel perchlorate hydrate, Nickel perchlorate, Nickel sulfate hydrate, Nickel sulfate, Nickel tetrafluoroborate hydrate, Nickel tetrafluoroborate, Nickel trifluoroacetylacetonate hydrate, and the like. Nickel trifluoroacetylacetonate, Nickel trifluoromethanesulfonate, Nickel peroxide hydrate, Nickel peroxide, Nickel sulfate, Nickel, and the like. Nickel octanoate hydrate, Nickel carbonate, Nickel sulfamate hydrate, Nickel sulfamate, Nickel carbonate hydroxide hydrate, and combinations thereof. Lt; / RTI >

  Among the metal precursors, the gold precursor may include chlorocarbonylgold, hydrogen tetrachloroaurate, hydrogen tetrachloroaurate hydrate, chlorotriethylphosphine gold, chlorotrimethylphosphine gold ), Dimethyl (acetylacetonate) gold, gold (I) chloride, gold cyanide, gold sulfide, gold chloride hydrate, And combinations thereof.

Among the metal precursors, the aluminum precursor may be selected from the group consisting of aluminum chloride, aluminum fluoride, aluminum hexafluoroacetylacetonate, aluminum chloride hydrate, aluminum nitride, aluminum Aluminum trifluoromethanesulfonate, Triethylaluminum, Aluminum acetylacetonate, Aluminum hydroxide, Aluminum lactate, Aluminum nitrate hydrate, Aluminum 2-ethylhexanoate, aluminum perchlorate hydrate, aluminum sulfate hydrate, aluminum ethoxide, aluminum carbide, aluminum sulphate Aluminum sulfate, Aluminum acetate, aluminum acetate hydrate, aluminum sulfide, aluminum hydroxide hydrate, aluminum phenoxide, aluminum fluoride hydrate, aluminum But may be selected from the group consisting of aluminum tributoxide, aluminum diacetate, aluminum diacetate hydroxide, and combinations thereof.

Further, for example, the semiconductive metal oxide may be at least one selected from the group consisting of zinc oxide, indium oxide, tin oxide, aluminum oxide, tungsten oxide, titanium oxide, vanadium oxide, physbodenium oxide, copper oxide, nickel oxide, Cobalt oxide, magnesium oxide, iron oxide, silver oxide, and mixtures thereof. The metal oxide may be at least one selected from the group consisting of cobalt oxide, magnesium oxide, iron oxide,

For example, the zinc oxide precursor may be selected from the group consisting of zinc hydroxide (Zn (OH) 2 ), zinc acetate (Zn (CH 3 COO) 2 ), zinc acetate hydrate (Zn (CH 3 (COO) 2 .nH 2 O) ethyl zinc (Zn (CH 3 CH 2) 2), zinc nitrate (Zn (NO 3) 2) , zinc nitrate hydrate (Zn (NO 3) 2 · nH 2 O), zinc carbonate (Zn (CO 3)), Zinc acetylacetonate (Zn (CH 3 COCHCOCH 3 ) 2 ), zinc acetylacetonate hydrate (Zn (CH 3 COCHCOCH 3 ) 2 .nH 2 O), and combinations thereof.

The indium oxide precursor is indium nitrate hydrate (In (NO 3) 3 · nH 2 O), ethyl indium (In (CH 3 COO) 2 ), ethyl indium hydrate (In (CH 3 (COO) 2 · nH 2 O) chloride, indium (InCl, InCl 2, InCl 3 ), indium nitrate (In (NO 3) 3) , indium nitrate hydrate (In (NO 3) 3 · nH 2 O), indium acetylacetonate (In (CH 3 COCHCOCH 3 ) 2 ), indium acetylacetonate hydrate (In (CH 3 COCHCOCH 3 ) 2 .nH 2 O), and combinations thereof.

The tin oxide precursor may be at least one selected from the group consisting of tin acetate (Sn (CH 3 COO) 2 ), tin acetate hydrate (Sn (CH 3 (COO) 2 .nH 2 O), tin chloride (SnCl 2 , SnCl 4 ), tin chloride n · nH 2 O), tin acetylacetonate (Sn (CH 3 COCHCOCH 3) 2), tin acetylacetonate hydrate (Sn (CH 3 COCHCOCH 3) 2 · nH 2 O) , and selected from the group consisting of .

The tungsten oxide precursor is tungsten carbide (WC), tungsten acid powder (H 2 WO 4), chloride, tungsten (WCl 4, WCl 6), tungsten isopropoxide Forsythe (W (OCH (CH 3) 2) 6), tungsten sodium (Na 2 WO 4 ), tungsten sodium hydrate (Na 2 WO 4 .nH 2 O), ammonium tungstate ((NH 4 ) 6 H 2 W 12 O 40 ), ammonium tungstate ((NH 4 ) 6 H 2 W 12 O 40 .nH 2 O), tungsten ethoxide (W (OC 2 H 5 ) 6 ), and combinations thereof.

The aluminum oxide precursors are aluminum chloride (AlCl 3), aluminum nitrate (Al (NO 3) 3) , aluminum nitrate hydrate (Al (NO 3) 3 · nH 2 O), aluminum butoxide (Al (C 2 H 5 CH It may be selected from (CH 3) O)) and combinations thereof.

The titanium oxide precursor may be selected from the group consisting of titanium isopropoxide (Ti (OCH (CH 3 ) 2 ) 4 ), titanium chloride (TiCl 4 ), titanium ethoxide (Ti (OC 2 H 5 ) 4 ), titanium butoxide OC 4 H 9 ) 4 ), and combinations thereof.

The vanadium oxide precursor, vanadium isopropoxide Forsythe (VO (OC 3 H 7) 3), vanadium ammonium (NH 4 VO 3), vanadium acetylacetonate (V (CH 3 COCHCOCH 3) 3), vanadium acetylacetonate hydrate It may be selected from (V (CH 3 COCHCOCH 3) 3 · nH 2 O) and combinations thereof.

The oxidation molybdenum precursor is molybdenum isopropoxide Forsythe (Mo (OC 3 H 7) 5), chloride, molybdenum isopropoxide Forsythe (MoCl 3 (OC 3 H 7 ) 2), having the molybdenum nyumsan ammonium (( NH 4 ) 2 MoO 4 ), ammonium molybdodenate hydrate ((NH 4 ) 2 MoO 4 .nH 2 O), and combinations thereof.

The copper oxide precursor may be at least one selected from the group consisting of copper chloride (CuCl, CuCl 2 ), copper chloride hydrate (CuCl 2 .nH 2 O), copper acetate (Cu (CO 2 CH 3 ), Cu (CO 2 CH 3 ) 2 ) (Cu (CO 2 CH 3) 2 · nH 2 O), copper acetyl acetonate (Cu (C 5 H 7 O 2) 2), copper nitrate hydrate (Cu (NO 3) 2 · nH 2 O), copper ( I) bromide (CuBr, CuBr 2 ), Copper (II) carbonate (CuCO 3 · Cu (OH) 2), Copper (I) sulfide (Cu 2 S, CuS), Copper (II) phthalocyanine ((C 32 H 16 N 8 ) Cu), and combinations thereof.

The nickel oxide precursor of nickel chloride (NiCl 2), nickel chloride hydrate (NiCl 2 · nH 2 O) , nickel acetate hydrate (Ni (OCOCH 3) 2 · 4H 2 O), nickel nitrate hydrate (Ni (NO 3) 2 · 6H 2 O), nickel acetylacetonate (Ni (C 5 H 7 O 2) 2), nickel hydroxide (Ni (OH) 2), nickel phthalocyanine (C 32 H 16 N 8 Ni ), nickel carbonate monohydrate (NiCO 3 · 2Ni (OH) 2 · nH 2 O), and combinations thereof.

The iron oxide precursor is iron acetate (Fe (CO 2 CH 3) 2), iron chloride (FeCl 2, FeCl 3), ferric chloride hydrate (FeCl 3 · nH 2 O) , iron acetylacetonate (Fe (C 5 H 7 O 2 3) 3), nitric acid withdrawal cargo (Fe (NO 3) 3 · 9H 2 O), iron phthalocyanine (C 32 H 16 FeN 8) , cheolok live hydrate (Fe (C 2 O 4) · nH 2 O, Fe 2 (C 2 O 4 ) 3 6H 2 O), and combinations thereof.

The chromium oxide precursor may be chromium chloride (CrCl 2 , CrCl 3 ), chromium chloride hydrate (CrCl 3 .nH 2 O), chromium carbide (Cr 3 C 2 ), chromium acetylacetonate (Cr (C 5 H 7 O 2 ) 3), nitric acid, chromium hydrate (Cr (NO 3) 3 · nH 2 O), chromium hydroxide acetate (CH 3 CO 2) 7 Cr 3 (OH) 2, chromium acetate monohydrate ([(CH 3 CO 2) 2 Cr · H 2 O] 2 ), and combinations thereof.

Wherein the bismuth precursor is chloride, bismuth (BiCl 3), nitric acid, bismuth hydrate (Bi (NO 3) 3 · nH 2 O), bismuth acetate ((CH 3 CO 2) 3 Bi), bismuth carbonate ((BiO) 2 CO 3 ), And combinations thereof.

In addition, the metal oxide precursor may include a p-type metal oxide precursor or an n-type metal oxide precursor. For example, the p-type semiconductive metal oxide may comprise copper oxide, nickel oxide or cobalt oxide. The n-type semiconductive metal oxide may also include zinc oxide, indium oxide, tin oxide, or tungsten oxide.

Therefore, the work function can be controlled according to the kind and ratio of the metal oxide precursor to the metal precursor.

Thus, by controlling the ratio of the metal oxide precursor to the metal precursor of the printing solution, that is, the ratio of the metal and semiconductive metal oxide contained in the finally prepared metal nanowire electrode array can be controlled. Thus, the work function of the metal itself may be raised or lowered by the added p-type or n-type metal oxide to ultimately determine the work function of the metal nanowire electrode array.

For example, when the metal oxide precursor includes a p-type metal oxide precursor, the work function of the metal nanowire electrode array increases as the ratio of the p-type metal oxide precursor to the metal precursor increases.

Also, when the metal oxide precursor includes an n-type metal oxide precursor, the work function of the metal nanowire electrode array is lowered as the ratio of the n-type metal oxide precursor to the metal precursor is increased.

For example, when the amount of the precursor of the copper oxide, which is the precursor of the p-type metal oxide compared to the metal precursor, is increased, the work function is greatly increased. When the amount of the precursor of the zinc oxide, which is the n-type metal oxide, .

For example, the organic polymer may be selected from the group consisting of polyvinyl alcohol (PVA), polyvinyl acetate (PVAc), poly (p-phenylene vinylene) (PPV), polyhydroxyethyl methacryl (PEMA), polystyrene (PS), polycaprolactone (PCL), polyacrylonitrile (PAN), poly (methyl methacrylate) (PMMA), polyimide, poly Polyvinyl chloride (PVC), nylon, polyacrylic acid, polychlorostyrene, polydimethylsiloxane, polyetherimide, polyethersulfone, polyalkyl acrylate, polyethylacrylate, Polyacrylic acid, polymethacrylic acid, polymethylstyrene, polystyrenesulfonic acid salt, polystyrene sulfonyl fluoride, polystyrene-co-arc, polyvinyl acetate, polyethylvinyl acetate, polyethyl-co-vinyl acetate, polyethylene terephthalate, polylactic acid- Polystyrene-co-butadiene, polystyrene-co-divinylbenzene, polylactide, polyacrylamide, polybenzimidazole, polycarbonate, polydimethylsiloxane-co-polyethylene oxide, polyetheretherketone, polyethylene, polyethylene And at least one selected from the group consisting of polyimide, polyimide, polyimide, polyimide, polyimide, imine, polyisoprene, polylactide, polypropylene, polysulfone, polyurethane, polyvinylpyrrolidone (PVP), and polyvinylcarbazole .

The organic solvent may be at least one selected from the group consisting of dichloroethylene, trichlorethylene, chloroform, chlorobenzene, dichlorobenzene, styrene, dimethylformamide, dimethylsulfoxide, xylene, toluene, cyclohexene, isopropyl alcohol, And at least one selected from the group consisting of methanol, tetrahydrofuran, isopropyl alcohol, terpineol, ethylene glycol, diethylene glycol, polyethylene glycol, acetonitrile, and acetone.

The metal precursor or the metal oxide precursor may be a nanoparticle, a nanowire, a nanofiber, a nanotube, a nanoflake, or a nanosheet dispersed in a compound dissolved in the organic solvent or an organic solvent.

In addition, in the step of preparing the printing solution (S110), the weight ratio of the metal precursor to the metal oxide precursor is 1: 1 to 1: 0.1, and the weight ratio of the metal precursor and the organic polymer is 1: 0.7 to 1: .

Therefore, the work function of the finally formed metal nanowire electrode array can be controlled by controlling the weight ratio of the metal precursor and the metal oxide precursor within a range of 1: 1 to 1: 0.1.

On the other hand, when the weight ratio of the metal oxide precursor to the metal precursor is more than 1: 1 and the amount of the metal oxide is increased, it may be difficult to use as an electrode because of low conductivity and semiconductivity may be large. Further, when the weight ratio of the metal oxide precursor to the metal precursor is less than 1: 0.1, and the amount of the metal oxide is less, the influence of controlling the work function may be small.

Also, when the weight ratio of the organic polymer to the metal precursor is more than 1: 0.7 and the amount of the organic polymer is increased, the nanowire may not be continuously connected and the organic polymer may be broken when the organic polymer is removed by the heat treatment process. In addition, when the reducing agent treatment process is used, the polymer remains as it is and only the metal and metal oxide precursors grow into the respective nanoparticles. When the proportion of the polymer is large, the nanoparticles do not continuously connect and exist in a dispersed form. Further, when the weight ratio of the organic polymer to the metal precursor is less than 1: 0.1, the amount of the organic polymer is less, which makes it difficult to continuously print the nanowire.

Next, a metal precursor / metal oxide precursor / organic polymer composite nanowire pattern is prepared (S120).

The step of forming the metal precursor / metal oxide precursor / organic polymer composite nanowire pattern may form the metal precursor / metal oxide precursor / organic polymer composite nanowire pattern by dropping the printing solution onto the substrate.

For example, in the step of forming the metal precursor / metal oxide precursor / organic polymer composite nanowire pattern, the printing solution is ejected from a nozzle to which a voltage is applied at a point 10 to 20 mm away from the substrate vertically, And the substrate or the nozzle is moved and formed to form an aligned metal precursor / metal oxide precursor / organic polymer composite nanowire pattern while being dropped onto a substrate.

In addition, the step of forming the metal precursor / metal oxide precursor / organic polymer composite nanowire pattern may be performed using an electric field assisted robot nozzle printing, electrospinning, inkjet printing, dip pen printing or electrohydraulic jet printing .

For example, the step of forming a metal precursor / metal oxide precursor / organic polymer composite nanowire pattern using the electric field assisted robotic nozzle printer shown in FIG. 2 will be described. After the printing solution is loaded into the syringe 10 and discharged from the nozzle 30 by the syringe pump 20, a droplet is formed at the end of the nozzle 30. When a voltage in the range of 0.1 kV to 30 kV is applied to the nozzle 30 using the high voltage generator 40, the droplet is not scattered by the electrostatic force between the charge formed on the droplet and the collector 50, And adheres to the substrate on the collector 50.

At this time, as the droplet increases, a metal precursor / metal oxide precursor / organic polymer composite nanowire having a length longer in one direction than the other direction from the droplet may be formed. The width of the metal precursor / metal oxide precursor / organic polymer composite nanowire can be adjusted to 10 nm to 100 탆 by adjusting the applied voltage and the nozzle size. In addition, by moving the collector 50, the metal precursor / metal oxide precursor / organic polymer composite nanowire can be arranged in a desired position in the desired direction on the substrate by a desired number.

Therefore, the metal precursor / metal oxide precursor / organic polymer composite nanowire can be formed to have a line width of 10 nm to 10 탆 and a circular, semicircular or elliptical cross section

An electric field assisted robotic nozzle printer used for forming a metal precursor / metal oxide precursor / organic polymer composite nanowire pattern will be described later in more detail with reference to FIG.

Referring again to FIG. 1, a polymer removal and a metal precursor / metal oxide reduction step are then performed (S 130).

For example, the organic polymer may be removed from the metal precursor / metal oxide precursor / organic polymer composite nanowire pattern, and the metal precursor and the metal oxide precursor may be reduced to form a metal / metal oxide composite nanowire pattern.

For example, the step of forming the metal / metal oxide composite nanowire pattern may include a heat treatment process, a reducing agent treatment process, or a light irradiation process.

For example, the heat treatment process may be carried out in a temperature range of 50 to 900 占 폚 for 5 minutes to 8 hours in a gas atmosphere containing at least one selected from the group consisting of air, oxygen, nitrogen, argon, Followed by heating five times to five times. Through this heat treatment process, organic polymer removal and precursor reduction can be performed.

Accordingly, the aligned organic nanowire electrode array can be obtained because the organic polymer is decomposed by the heat treatment process, the metal precursor is converted into metal, and the metal oxide precursor is converted into the semiconducting metal oxide. Therefore, the metal nanowire at this time will be a nanowire to which semiconductive metal oxide is added to the metal.

For example, the reducing agent treatment process can be carried out using a reducing agent such as hydrazine, formic acid, ascorbic acid, oxalic acid, carbon, carbon monoxide, formaldehyde, acetaldehyde, hydrogen, hydrogen compounds, sulfur dioxide, sulfites, sodium sulfide, sodium polysulfide, Alkali metal, magnesium, magnesium amalgam, calcium, calcium amalgam, aluminum, aluminum amalgam, zinc, zinc amalgam, phosphite, hypophosphite, phosphorous acid, iron sulfide, sodium, sodium compound, sodium borohydride, iron, iron compound, tin, tin A cysteine, a cysteine, a cysteine, a thioglycolic acid, an ammonium thioglycolate, an ammonium chi-lactate, an ethanolamine thioglycolate, a cysteamine H At least one member selected from the group consisting of citrate, glutaric acid, and mixtures thereof Characterized in that the vapor of the reducing agent is used or is immersed in the reducing agent. Accordingly, the metal precursor and the metal oxide precursor can be reduced in a metal precursor / metal oxide precursor / organic polymer composite nanowire pattern through a reducing agent treatment process.

For example, the light irradiation process is characterized in that light irradiation is performed for 0.001 second to 5 hours in a wavelength range of 200 nm to 500 μm by using an excimer laser, an infrared laser, or a UV laser. Accordingly, the organic polymer can be removed by heat and the precursor can be reduced according to the wavelength and intensity of the light irradiated in the light irradiation process. In some cases, only the precursor may be reduced by leaving the organic polymer as it is.

Therefore, as shown in (S140) in FIG. 1, a metal nanowire electrode array that can be formed by the present manufacturing method can be formed. In this case, the nanowire of the metal nanowire electrode array means metal and metal oxide.

2 is a schematic diagram of an electric field assisted robotic nozzle printer.

The electric field assisted robotic nozzle printer of FIG. 2 is used in manufacturing a metal nanowire electrode array capable of work function control according to the present invention.

2, the electric field assisted robotic nozzle printer 1 includes a solution storage device 10, a discharge regulator 20, a nozzle 30, a voltage application device 40, a collector 50, A stage 60, an etch stop 61, and a micro-distance adjuster 70.

The solution storage device 10 stores the metal precursor / organic polymer composite solution and supplies the solution to the nozzle 30 so that the nozzle 30 can discharge the solution.

The solution storage device 10 may be in the form of a syringe. The solution storage device 10 may be made of plastic, glass, or stainless steel.

The storage capacity of the solution storage device 10 may be selected within a range of about 1 쨉 l to about 5,000 ml. Preferably, it can be selected within the range of about 10 μl to about 50 ml.

In the case of the solution storage device 10 made of stainless steel, there is a gas inlet (not shown) for injecting gas into the solution storage device 10 so that the solution is discharged out of the solution storage device .

On the other hand, a plurality of solution storage devices 10 for forming the metal precursor / organic composite nanofibers having the core shell structure may be formed.

The discharge regulator 20 is a portion for applying pressure to the solution in the solution storage device 10 to discharge the metal / organic polymer composite solution in the solution storage device 10 through the nozzle 30 at a constant rate.

As this discharge regulator 20, a pump or a gas pressure regulator may be used.

The discharge regulator 20 can regulate the discharge speed of the solution within the range of 1 nl / min to 50 ml / min.

When a plurality of solution storage devices 10 are used, each solution storage device 10 is provided with a separate discharge controller 20 so that it can operate independently.

A gas pressure regulator (not shown) may be used as the discharge regulator 20 in the case of the solution storage device 10 made of stainless steel.

The nozzle 30 is a part through which the solution of the metal precursor / organic polymer composite is discharged from the solution storage device 10 and the solution discharged forms a drop at the end of the nozzle 30 . The diameter of the nozzle 30 may range from about 1 [mu] m to about 1.5 mm.

The nozzle 30 may include a single nozzle, a dual-concentric nozzle, or a triple-concentric nozzle.

When forming a metal precursor / organic composite nanofiber having a core shell structure, two or more kinds of organic solutions can be discharged using a double nozzle or a triple nozzle. In this case, two or three solution storage devices 10 may be connected to the double or triple nozzles.

The voltage application device 40 may include a high voltage generating device for applying a high voltage to the nozzle 30.

The voltage application device 40 may be electrically connected to the nozzle 30 through the solution storage device 10, for example.

Voltage application device 40 may apply a voltage of about 0.1 kV to about 30 kV. There is an electric field between the nozzle 30 to which the high voltage is applied by the voltage applying device 40 and the collector 50 which is grounded and the droplet formed at the end of the nozzle 30 by the electric field becomes the Taylor cone, And the nanofibers are continuously formed at the ends.

The collector 50 is a portion where nanofibers formed from the solution discharged from the nozzle 30 are aligned. The collector 50 is flat and movable on a horizontal plane by the robot stage 60 beneath it. The collector 50 is grounded to have a grounding characteristic relative to the high voltage applied to the nozzle 30. [

Reference numeral 51 denotes that the collector 50 is grounded. The collector 50 may be made of a conductive material, for example, a metal, and may have a flatness within a range of 0.5 μm to 10 μm (the degree of flatness, when the flatness of a completely horizontal surface has a value of 0, Represents the maximum error value from the plane).

The robot stage 60 is a means for moving the collector 50. The robot stage 60 is driven by a servo motor and can move at a precise speed.

The robot stage 60 can be controlled to move in two directions, for example, x-axis and y-axis on a horizontal plane.

The robot stage 60 can move the distance in a range of 100 nm or more and 100 cm or less, for example, within a range of 10 탆 or more and 20 cm or less.

The moving speed of the robot stage 60 may range from 1 mm / min to 60,000 mm / min.

The robot stage 60 may be installed on a base plate 61, and may have a plan view of 0.5 to 5 탆. The distance between the nozzle 30 and the collector 50 can be adjusted to be constant by the plan view of the stone crystal tablet 61 at this time.

The stone stone tablet 61 can control the precision of the metal precursor / organic composite nano fiber pattern by suppressing the vibration generated by the operation of the robot stage.

The micro distance adjuster 70 is a means for adjusting the distance between the nozzle 30 and the collector 50. The distance between the nozzle 30 and the collector 50 can be adjusted by moving the solution storage device 10 and the nozzle 30 vertically by the micro distance adjuster 70. [

The micro distance adjuster 70 may include a jog 71 and a micrometer 72. The jog 71 can be used to roughly adjust the distance in mm or cm, and the fine adjuster 72 can be used to adjust a fine distance of at least 10 μm.

The distance between the nozzle 30 and the collector 50 can be precisely adjusted by the fine adjuster 72 after the nozzle 30 approaches the collector 50 with the jog 71. [

The distance between the nozzle 30 and the collector 50 by the micro distance adjuster 70 can be adjusted in the range of 10 mu m to 20 mm.

Meanwhile, the electric field assisted robotics nozzle printer 100 may be placed in the housing.

The housing may be formed of a transparent material. The housing is hermetically sealed and can inject gas into the housing through a gas inlet (not shown). The gas to be injected may be nitrogen, dry air or the like, and the metal precursor / organic polymer complex solution, which is easily oxidized by moisture by the injection of the gas, can be stably maintained.

Also, a ventilator and a lamp may be installed in the housing. The role of the ventilator is to regulate the evaporation rate of the solvent when the nanofibers are formed by controlling the vapor pressure in the housing. In robotic nozzle printing, which requires rapid evaporation of the solvent, the speed of the ventilator can be controlled to help evaporate the solvent. The evaporation rate of the solvent affects the morphological and electrical properties of the metal precursor / organic composite nanofiber. If the evaporation rate of the solvent is too fast, the solution will dry out at the nozzle tip before the nanofibers of the metal precursor / organic complex are formed, causing the nozzle to clog. If the evaporation rate of the solvent is too slow, the nanofibers of the solid metal precursor / organic polymer complex are not formed and are placed in the collector in liquid form. The liquid metal precursor / organic polymer composite solution can not be used for the fabrication of the device because it does not have characteristic electrical properties of the nanofibers.

Thus, since the evaporation rate of the solvent affects the formation of nanofibers, the ventilator plays an important role in nanofiber formation.

A light emitting diode including a metal nanowire electrode array according to an embodiment of the present invention will be described.

The light emitting diode includes an anode, a cathode, and a light emitting layer positioned between the anode and the cathode, and at least one of the anode and the cathode is connected to the metal nanowire electrode array manufactured by the above- .

A solar cell including a metal nanowire electrode array according to an embodiment of the present invention will be described.

The solar cell includes a positive electrode, a negative electrode, and a photoactive layer positioned between the positive electrode and the negative electrode, and at least one of the positive electrode and the negative electrode is formed of the metal nanowire electrode Arrays.

In addition, when the solar cell is an organic solar cell, it may further include at least one of a hole extraction layer, an exciton blocking layer, and an electron extraction layer.

An electrochemical cell including a metal nanowire electrode array according to an embodiment of the present invention will be described.

The solar cell includes a positive electrode, a negative electrode, and an active material layer positioned between the positive electrode and the negative electrode, wherein at least one of the positive electrode and the negative electrode is a metal nanowire electrode manufactured by the above- Arrays.

A field effect transistor including a metal nanowire electrode array according to an embodiment of the present invention will be described. Such a field effect transistor may be an organic or inorganic semiconductor based field effect transistor.

Such a field effect transistor may include a gate electrode, a gate insulating layer, a source electrode, a drain electrode, and a semiconductor layer. At least one of the gate electrode, the source electrode, and the drain electrode is a metal nanowire electrode array fabricated by the metal nanowire electrode array manufacturing method described above.

The structure of the transistor element can be classified according to the position of the gate electrode. A bottom gate structure leading to the substrate, and a top gate structure having the gate electrode upward. Further, the structure of the transistor element can be classified according to the position of the source / drain electrode. If the source / drain electrode is located below the semiconductor layer, it may be classified as a bottom contact, and if the source / drain electrode is positioned on the semiconductor layer, it may be classified as a top contact element.

For example, in the case of a bottom gate-bottom contact device, a gate insulating layer located on the gate electrode, a source electrode and a drain electrode located on the gate insulating layer, and a source electrode and a drain electrode on the gate insulating layer, And an organic semiconductor layer positioned to be in contact with the organic semiconductor layer.

The semiconductor layer may be an organic semiconductor layer, an inorganic semiconductor layer, or an organic hybrid semiconductor layer.

The organic semiconductor generally includes low molecular weight, oligomer, and polymer semiconductor of known conjugate structure. But are not limited to, for example, pentacene, tetracene, TIPS-pentacene, polythiophene and derivatives thereof, polyfluorene and derivatives thereof, polyacetylene and derivatives thereof, polyphenylene and derivatives thereof .

The inorganic semiconductor may be selected from the group consisting of silicon (Si), Group 4 crystals such as silicon or germanium, Group 3-5 compounds such as gallium arsenide (GaAs), Group 2-6 compounds such as CdS, And all inorganic semiconductors that are not organic materials such as fins.

In addition, a hole injecting layer, a hole transporting layer, an electron transporting layer, an exciton blocking layer, a hole blocking layer, and an electron injecting layer (electron injecting layer) an injection layer, and the like.

Production Example 1

A high work function silver nanowire electrode array having an area of 7 cm x 7 cm was fabricated using a manufacturing method of a large area metal nanowire electrode array capable of work function control according to an embodiment of the present invention.

A silver precursor (21 wt%), a metal precursor (21 wt%), a copper oxide precursor (6.25 wt%) as a p-type metal oxide precursor, and an organic polymer PVP (10 wt%) were dissolved in dimethylformamide and tetrahydrofuran, / Copper oxide precursor / PVP composite printing solution was prepared.

The prepared printing solution was placed in a syringe of an electric field assisted robotic nozzle printer, and the solution was discharged from the nozzle while applying a voltage of about 0.5 kV to the nozzle. A silver precursor / copper oxide precursor / PVP complex nanowire pattern was formed on the substrate of the collector moved by the robot stage.

At this time, the diameter of the used nozzle was 100 mu m, the distance between the nozzle and the collector was 7 mm, and the applied voltage was 0.5 kV. The moving distance in the Y axis direction of the robot stage was 200 mu m, and the moving distance in the X axis direction was 15 cm. The size of the collector was 20 cm x 20 cm, and the size of the substrate on the collector was 7 cm x 7 cm. The substrate was a silicon (Si) wafer in which a silicon oxide film (SiO 2 ) was coated to a thickness of 300 nm.

  The ordered silver precursor / copper oxide precursor / PVP composite nanowire pattern was heated in a furnace at 350 ° C for 30 minutes or 1 hour to form a silver nanowire pattern with ordered copper oxide addition.

Production Example 2

A low work function silver nanowire electrode array having an area of 7 cm x 7 cm was fabricated using a manufacturing method of a large area metal nanowire electrode array capable of work function control according to an embodiment of the present invention.

The silver precursor (21 wt%) which is a metal precursor, the zinc oxide precursor (6.25 wt%) which is an n-type metal oxide precursor and the organic polymer PVP (10 wt%) were dissolved in dimethylformamide and tetrahydrofuran, Zinc oxide precursor / PVP composite printing solution was prepared.

The prepared printing solution was placed in a syringe of an electric field assisted robotic nozzle printer, and the solution was discharged from the nozzle while applying a voltage of about 0.5 kV to the nozzle. A silver precursor / zinc oxide precursor / PVP complex nanowire pattern was formed on the substrate of the collector moved by the robot stage.

At this time, the diameter of the used nozzle was 100 mu m, the distance between the nozzle and the collector was 7 mm, and the applied voltage was 0.5 kV. The moving distance in the Y axis direction of the robot stage was 200 mu m, and the moving distance in the X axis direction was 15 cm. The size of the collector was 20 cm x 20 cm, and the size of the substrate on the collector was 7 cm x 7 cm. The substrate was a silicon (Si) wafer in which a silicon oxide film (SiO 2 ) was coated to a thickness of 300 nm.

The ordered silver precursor / zinc oxide precursor / PVP nanowire pattern was heated in a furnace at 350 DEG C for 30 minutes or 1 hour to form a silver nanowire pattern with added zinc oxide.

3 is an SEM image showing the morphology of the silver precursor / copper oxide precursor / organic polymer composite nanowire and the silver nanowire after heat treatment.

Referring to FIG. 3, silver nanowires were formed when the silver / silver oxide precursor / organic composite nanowire was heat-treated as in Production Example 1.

4 is a graph showing the work function of silver nanowires prepared according to Preparation Example 1. FIG.

In Fig. 4, the work function of silver nanowires was analyzed using the Calvin probe method.

Referring to FIG. 4, it can be seen that the nanowire in air has a work function of 5.1 eV increased by 0.4 eV as compared to the work function (4.7 eV) of the Calvin probe tip made of gold (Au). It has a very high work function improved by the copper oxide component compared to the work function (4.3 eV) of silver nanowires in the previously reported vacuum.

Fig. 5 is a graph showing the analysis of surface components of silver nanowires prepared according to Production Example 1. Fig.

FIG. 5 is XPS data obtained by analyzing surface components of silver nanowires and surface components of silver thin films formed by vapor deposition.

Referring to FIG. 5, it can be seen that a copper oxide component exists on the surface of the silver nanowire, unlike the silver thin film.

6 is a graph showing a current-voltage curve and resistivity of the silver nanowire fabricated according to Production Example 1. FIG.

Referring to FIG. 6, the electrical resistivity of the silver nanowire is 5.7 μΩ · cm.

According to the present invention, firstly, work function can be controlled without additional process, and since the metal nanowire electrode can be manufactured in a large area, it is very efficient in terms of cost and time in the process.

Second, if a horizontal transistor, a light emitting diode (LED), and a solar cell are manufactured using a metal nanowire electrode array having a work function controlled according to the manufacturing method of the present invention, The cost and the step can be reduced, and an electronic device having a very high transmittance can be manufactured in which the electrode is invisible.

In this case, it can be applied to LED, solar cell, organic LED (OLED), inorganic LED, organic / inorganic hybrid perovskite LED, organic PV (OPV), inorganic PV and organic hybrid perovskite PV.

It should be noted that the embodiments of the present invention disclosed in the present specification and drawings are only illustrative of specific examples for the purpose of understanding and are not intended to limit the scope of the present invention. It will be apparent to those skilled in the art that other modifications based on the technical idea of the present invention are possible in addition to the embodiments disclosed herein.

10: Solution storage device 20: Discharge regulator
30: nozzle 40: voltage applying device
50: collector 51: grounding device
60: robot stage 61:
70: Micro distance adjuster 71: Jog

Claims (21)

Preparing a printing solution by dissolving or mixing the metal precursor, the metal oxide precursor, and the organic polymer in distilled water or an organic solvent;
Dropping the printing solution onto a substrate to form a metal precursor / metal oxide precursor / organic polymer composite nanowire pattern; And
The work function control including a step of removing the organic polymer from the metal precursor / metal oxide precursor / organic polymer composite nanowire pattern and reducing the metal precursor and the metal oxide precursor to form a metal / metal oxide composite nanowire pattern A method of manufacturing a metal nanowire electrode array. The method according to claim 1,
Wherein the metal precursor and the metal oxide precursor are reduced to metal and semiconducting metal oxides, respectively, after the reduction process. The method according to claim 1,
Wherein the metal precursor is selected from the group consisting of Au, Ag, Fe, Ni, Pt, Cu, Pd, Al, Ca, W, Zn, Li, Sn, Ti, Cr, Mo, A method of manufacturing a metal nanowire electrode array capable of work function control which is a precursor of metal. 3. The method of claim 2,
Wherein the semiconductive metal oxide is selected from the group consisting of zinc oxide, indium oxide, tin oxide, aluminum oxide, tungsten oxide, titanium oxide, vanadium oxide, physbodenium oxide, copper oxide, nickel oxide, iron oxide, chromium oxide, cobalt oxide, Wherein the metal nanowire electrode array comprises at least one metal oxide selected from the group consisting of iron oxide, iron oxide, iron oxide, iron oxide, iron oxide, iron oxide, iron oxide, iron oxide, iron oxide, The method according to claim 1,
Wherein the metal oxide precursor comprises a p-type metal oxide precursor or an n-type metal oxide precursor,
Wherein the work function can be controlled according to the ratio of the metal oxide precursor to the metal precursor. 6. The method of claim 5,
When the metal oxide precursor comprises a p-type metal oxide precursor,
Wherein the work function is increased as the ratio of the p-type metal oxide precursor to the metal precursor is increased. 6. The method of claim 5,
When the metal oxide precursor comprises an n-type metal oxide precursor,
Wherein the work function is lowered as the ratio of the n-type metal oxide precursor to the metal precursor is increased. The method according to claim 1,
Wherein the organic polymer is selected from the group consisting of polyvinyl alcohol, polyvinyl acetate, poly (p-phenylene vinylene), polyhydroxyethyl methacrylate, polyethylene oxide, polystyrene, polycaprolactone, polyacrylonitrile, Polyacrylic acid, polyacrylic acid, polychlorostyrene, polydimethylsiloxane, polyetherimide, polyethersulfone, polyalkyl acrylate, polyethylacrylate (polyvinylidene fluoride), polyvinylidene fluoride, polyaniline, polyvinyl chloride, nylon, , Polyvinyl acetate, polyethyl-co-vinyl acetate, polyethylene terephthalate, polylactic acid-co-glycolic acid, polymethacrylate, polymethylstyrene, polystyrenesulfonate, polystyrene sulfonyl fluoride, polystyrene- Rhenitrile, polystyrene-co-butadiene, polystyrene-co-divinylbenzene, polylactide, poly Acrylamide, polybenzimidazole, polycarbonate, polydimethylsiloxane-co-polyethylene oxide, polyetheretherketone, polyethylene, polyethyleneimine, polyisoprene, polylactide, polypropylene, polysulfone, polyurethane, polyvinylpyrrole And at least one selected from the group consisting of gold, silver, gold, silver, gold, silver, gold, silver, gold, silver, gold, silver, gold, silver, gold, silver, gold, The method according to claim 1,
The organic solvent is selected from the group consisting of dichloroethylene, trichlorethylene, chloroform, chlorobenzene, dichlorobenzene, styrene, dimethylformamide, dimethylsulfoxide, xylene, toluene, cyclohexene, isopropyl alcohol, Wherein the work function-controllable metal comprises at least one selected from the group consisting of tetrahydrofuran, isopropyl alcohol, terpineol, ethylene glycol, diethylene glycol, polyethylene glycol, acetonitrile, and acetone. A method of manufacturing a line electrode array. The method according to claim 1,
Wherein the metal precursor or the metal oxide precursor is a nanoparticle, a nanowire, a nanofiber, a nanotube, a nanoflake, or a nanosheet dispersed in an organic solvent or a compound dissolved in the organic solvent. A method of manufacturing a line electrode array. The method according to claim 1,
Wherein the weight ratio of the metal precursor to the metal oxide precursor is 1: 1 to 1: 0.1, and the weight ratio of the metal precursor to the organic polymer is 1: 0.7 to 1: 0.1. A method of manufacturing a metal nanowire electrode array capable of work function control. The method according to claim 1,
The step of forming the metal precursor / metal oxide precursor / organic polymer composite nanowire pattern includes:
The printing solution is discharged from a nozzle to which a voltage is applied at a position 10 to 20 mm away from the substrate vertically. The substrate or the nozzle is moved while being dropped onto the substrate, and the aligned metal precursor / metal oxide precursor / organic polymer complex And forming a nanowire pattern on the surface of the metal nanowire. The method according to claim 1,
The step of forming the metal precursor / metal oxide precursor / organic polymer composite nanowire pattern is performed using an electric field assisted robotic nozzle printing, electrospinning, inkjet printing, dip pen printing or electrohydraulic jet printing method A method of manufacturing a metal nanowire electrode array capable of work function control. The method according to claim 1,
Wherein the step of forming the metal / metal oxide composite nanowire pattern includes a heat treatment process, a reducing agent treatment process, or a light irradiation process. 14. The method of claim 13,
The heat treatment process is performed in a temperature range of 50 to 900 占 폚 for 5 minutes to 8 hours in a gas atmosphere containing at least one selected from the group consisting of air, oxygen, nitrogen, argon, and hydrogen, Wherein the metal nanowire electrode array is heated by heating the metal wire. 14. The method of claim 13,
The reducing agent treatment process may be carried out in the presence of a reducing agent such as hydrazine, formic acid, ascorbic acid, oxalic acid, carbon, carbon monoxide, formaldehyde, acetaldehyde, hydrogen, hydrogen compound, sulfur dioxide, sulfite, sodium sulfide, polysulfide, ammonium sulfide, , Magnesium amalgam, calcium, calcium amalgam, aluminum, aluminum amalgam, zinc, zinc amalgam, phosphite, hypophosphite, phosphorous acid, iron sulfide, sodium, sodium compound, sodium borohydride, iron, iron compound, tin, Titanium compounds, chromium, chromium compounds, cysteine, acetylcysteine, cysteine HCI, thioglycolic acid, ammonium thioglycolate, ammonium chi-lactate, ethanolamine thioglycolate, cysteamine HCI, glutathione and And a mixture thereof, and a reducing agent containing at least one selected from the group consisting of The method controls the work function is a metal nanowire electrode array, comprising a step of using a vapor deposition or a reducing agent. 14. The method of claim 13,
The work function controllable metal nanowire electrode array manufacturing method according to any one of claims 1 to 3, wherein the light irradiation step comprises irradiating light in a wavelength range of 200 nm to 500 m for 0.001 second to 5 hours by using an excimer laser, an infrared laser, Way. An anode, a cathode, and a light-emitting layer positioned between the anode and the cathode,
Wherein at least one of the positive electrode and the negative electrode is a metal nanowire electrode array manufactured by the manufacturing method according to any one of claims 1 to 17. A positive electrode, a negative electrode, and a photoactive layer positioned between the positive electrode and the negative electrode,
Wherein at least one of the positive electrode and the negative electrode is a metal nanowire electrode array manufactured by the manufacturing method according to any one of claims 1 to 17. An anode, a cathode, and an active material layer disposed between the anode and the cathode,
Wherein at least one of the positive electrode and the negative electrode is a metal nanowire electrode array manufactured by the manufacturing method according to any one of claims 1 to 17. A gate electrode, a gate insulating layer, a source electrode, a drain electrode, and an organic, inorganic or organic hybrid semiconductor layer,
Wherein at least one of the gate electrode, the source electrode, and the drain electrode is a metal nanowire electrode array manufactured by the manufacturing method according to any one of claims 1 to 17.
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