KR20140103612A - A method for fabricating aligned oxide semiconductor wire patterns and electronic devices with the same - Google Patents

Abstract

Dissolving an oxide semiconductor precursor and an organic polymer in distilled water or an organic solvent to provide a composite solution of an oxide semiconductor precursor / organic polymer; Aligning the oxide semiconductor precursor / organic polymer composite wire on the substrate by dropping the solution of the oxide semiconductor precursor / organic polymer complex vertically from the substrate; And heating the aligned oxide semiconductor precursor / organic polymer composite wire to form a pattern of aligned oxide semiconductor wires.

Description

FIELD OF THE INVENTION [0001] The present invention relates to a method of manufacturing an aligned oxide semiconductor wire pattern and an electronic device using the same,

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of manufacturing an oxide semiconductor wire pattern in an aligned form and electronic devices using the same.

Conventional inorganic semiconductor nanowires, along with their excellent electrical properties and the demand for flexible electronic devices, have increased their utility value. In addition, due to the excellent properties of nano-sized materials such as high mobility and high integration, research on electronic devices using inorganic semiconductor nanowires is actively conducted.

As a representative method of fabricating semiconductors using inorganic semiconductor nanowires, a method of growing nanowires on a substrate by chemical vapor deposition has been used. When a silicon nano wire or a zinc oxide (ZnO) nanowire grown through the chemical vapor deposition method is used for a transistor, a transistor having a high charge mobility can be manufactured.

However, processes such as anodic aluminum oxide template, hydrothermal synthesis, electroless etching, etc., including the conventionally known chemical vapor deposition processes, have the following problems.

1) In order to manufacture an electronic device including an inorganic semiconductor nanowire as an active layer, the nanowire must be laid horizontally. Since the nanowire grown through a conventional process grows in a direction perpendicular to the substrate, the nanowire is separated from the substrate So that a separate process for dispersing them is required. In this process, the nanowires spread irregularly, making it impossible to fabricate a highly integrated large-area nanowire device array.

2) In order to fabricate a device including nanowires that are laid horizontally with respect to the substrate, an electrode must be deposited. Since the size of the nanowire is very small and irregular, expensive equipment such as E-beam evaporation should be used . Further, since it is necessary to set a position for directly depositing electrodes on individual nanowires, it is not suitable for mass production of electronic devices including nanowires.

Accordingly, there is a need for a method of manufacturing an electronic device including an inorganic semiconductor nanowire suitable for mass production by precisely adjusting the position and direction of the inorganic semiconductor nanowire and reducing manufacturing time.

The following references are the references of the present invention.

[1] H.-S. Lee et al., Biosensors and Bioelectronics, 24: 1801-1805 (2009).

[2] X. Yang et al., Inorganic Chem. Commu. 7, 176-178 (2004).

[3] H. Wu, and W. Pan, J. Am. Ceram. Soc., 89, 699-701 (2006).

An embodiment of the present invention provides a method of manufacturing an oxide semiconductor wire pattern capable of aligning an oxide semiconductor wire in a desired direction and a desired number with high speed and accuracy.

One embodiment of the present invention is a method

Dissolving an oxide semiconductor precursor and an organic polymer in distilled water or an organic solvent to provide a composite solution of an oxide semiconductor precursor / organic polymer;

Aligning the oxide semiconductor precursor / organic polymer composite wire on the substrate by dropping a complex solution of the oxide semiconductor precursor / organic polymer at a point 10 to 20 mm away from the substrate vertically;

Heating the aligned oxide semiconductor precursor / organic polymer composite wire to form a pattern of aligned oxide semiconductor wires

The present invention also provides a method of manufacturing an oxide semiconductor wire pattern.

The step of forming the oxide semiconductor wire pattern may include heating the oxide semiconductor precursor / organic polymer composite wire at a temperature of 100 ° C to 900 ° C for 10 minutes to 24 hours.

The step of aligning the ordered oxide semiconductor precursor / organic polymer composite wire may be performed by an electric field assisted robotic nozzle printer. The electric field assisted robotic nozzle printer comprises: i) a solution storage device for storing an oxide semiconductor precursor / organic polymer complex solution; ii) a nozzle device for discharging the solution supplied from the solution storage device; iii) a voltage applying device for applying a high voltage to the nozzle; iv) a collector for holding said substrate; v) a robot stage for moving the collector in a horizontal direction; vi) a micro-distance adjuster for moving the collector in a vertical direction; And vii) a lithotripter that supports the collector.

The step of aligning the ordered oxide semiconductor precursor / organic polymer composite wire comprises the steps of: i) supplying the oxide semiconductor precursor / organic polymer composite solution to the solution storage device; ii) discharging the oxide semiconductor precursor / organic polymer complex solution from the nozzle by applying a high voltage to the nozzle through the voltage application device of the electric field assisted robotic nozzle printer, And moving the collector on which the substrate is placed in a horizontal direction when the precursor / organic polymer composite solution is ejected.

The vertical distance between the collector and the nozzle may be 10 [mu] m to 20 [mu] m.

The substrate may be selected from the group consisting of an insulating material, a metal material, a carbon material, and a composite material of a conductor and an insulating film.

The oxide semiconductor precursor may be a zinc oxide precursor, an indium oxide precursor, a tin oxide precursor, a gallium oxide precursor, a tungsten oxide precursor, an aluminum oxide precursor, a titanium oxide precursor, a vanadium oxide precursor, a molybdenum oxide precursor, a copper oxide precursor, Precursors, iron oxide precursors, chromium oxide precursors, bismuth oxide precursors, and combinations thereof.

The zinc oxide precursor may be at least one 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) (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 ) (Zn (CH ₃ COCHCOCH ₃ ) ₂ ), zinc acetylacetonate hydrate (Zn (CH ₃ COCHCOCH ₃ ) ₂ .nH ₂ O), and combinations thereof, but is not limited thereto.

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. However, the present invention is not limited thereto.

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 But is not limited to this.

The gallium oxide precursor is gallium nitrate _{(Ga (NO 3) 3)} , gallium nitrate hydrate _{(Ga (NO 3) 3 ·} nH 2 O), gallium acetylacetonate _{(Ga (CH 3 COCHCOCH 3)} 3), gallium acetylacetonate carbonate hydrate _{(Ga (CH 3 COCHCOCH 3)} 3 · nH 2 O), gallium chloride _{(Ga 2 Cl 4, GaCl 3} ) , and may be selected from the group consisting of, but not limited to this.

The tungsten oxide precursor is tungsten carbide (WC), tungsten acid powder (H ₂ WO _4), chloride, tungsten (WCl _4, WCl _6), tungsten isopropoxide _{(W (OCH (CH 3)} 2) 6), tungsten Sodium nitrate (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, but is not limited thereto.

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 (CH ₃₎ O)), and it may be selected from the group consisting of, but not limited to this.

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 it may be selected from the group consisting of, but not limited to this.

The vanadium oxide precursor, vanadium isopropoxide _{(VO (OC 3 H 7)} 3), vanadium ammonium (NH ₄ VO _3), vanadium acetylacetonate _{(V (CH 3 COCHCOCH 3)} 3), vanadium acetylacetonate monohydrate _{(V (CH 3 COCHCOCH 3)} 3 · nH 2 O) , and may be selected from the group consisting of, but not limited to this.

Denyum the oxidized molybdenum denyum precursors include molybdenum isopropoxide _{(Mo (OC 3 H 7)} 5), chloride molybdate denyum isopropoxide _{(MoCl 3 (OC 3 H 7} ) 2), molybdenum having nyumsan ammonium (NH ₄ ) ₂ MoO ₄ ), ammonium molybdodenate hydrate ((NH ₄ ) ₂ MoO ₄ .nH ₂ O), and combinations thereof, but is not limited thereto.

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 _{(Cu (NO 3) 2)} , copper nitrate hydrate (Cu (NO _{3) 2 · nH 2 O)} , copper bromide (CuBr, CuBr _2), copper carbonate _{(CuCO 3 · Cu (OH)} 2), copper sulfide (Cu ₂ S, CuS), copper phthalocyanine (C ₃₂ H ₁₆ N ₈ (Cu (CO ₂ CF ₃ ) ₂ ), copper isobutyrate (C ₈ H ₁₄ CuO ₄ ), copper ethyl acetoacetate (C ₁₂ H ₁₈ CuO ₆ ), copper 2-ethylhexano ([CH ₃ (CH ₂ ) ₃ CH (C ₂ H ₅ ) CO ₂ ] ₂ Cu), copper fluoride (CuF ₂ ), formic acid copper hydrate ((HCO ₂ ) ₂ Cu? H ₂ O), copper gluconate _{(C 12 H 22 CuO 14)} , a copper-hexahydro flow acetylacetonate _{(Cu (C 5 HF 6 O} 2) 2), copper-hexahydro Floro acetylacetonate monohydrate _{(Cu (C 5 HF 6 O} 2) 2? H ₂ O), Lee methoxide _{(Cu (OCH 3) 2)} , copper neodecanoate _{(C 10 H 19 O 2 Cu} ), perchlorate, copper hydrate (Cu (ClO _{4) 2 and} 6H ₂ O), copper sulfate (CuSO _4), copper sulfate hydrate _{(CuSO 4 H 2 O?)} , tartaric acid copper hydrate ^{(? [- CH (OH)} CO 2] 2 Cu H 2 O), with a copper triple acetylacetonate _{(Cu (C 5 H 4 F} 3 O 2) ₂ ), copper triflouromethanesulfonate ((CF ₃ SO ₃ ) ₂ Cu), tetraamine copper sulfate hydrate (Cu (NH ₃ ) ₄ SO _{4 -2} O), and combinations thereof But is not limited thereto.

.

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, but is not limited thereto.

.

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, but is not limited thereto.

.

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, but is not limited thereto.

.

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, but is not limited thereto.

.

The organic polymer may be at least one selected from the group consisting of polyvinyl alcohol (PVA), polyethylene oxide (PEO), polystyrene (PS), polycaprolactone (PCL), polyacrylonitrile (PAN), poly (methyl methacrylate) Polyvinylidene fluoride (PVDF), polyaniline (PANI), polyvinyl chloride (PVC), nylon, poly (acrylic acid), poly (chlorostyrene), poly (dimethylsiloxane) Poly (ethyl acrylate), poly (ethyl vinyl acetate), poly (ethyl-co-vinyl acetate), poly (ethylene terephthalate), poly (lactic acid- Poly (styrene sulfonate), poly (styrene-co-acrylonitrile), poly (styrene-co (meth) acrylate) -Butadiene), poly (styrene-co-divinylbenzene), poly (vinyl acetate), poly Poly (vinyl alcohol), polyacrylamide, polybenzimidazole, polycarbonate, poly (dimethylsiloxane-co-polyethylene oxide), poly (etheretherketone), polyethylene, polyethyleneimine, polyisoprene, polylactide But are not limited to, polypropylene, polysulfone, polyurethane, poly (vinylpyrrolidone), poly (phenylenevinylene), poly (vinylcarbazole), and combinations thereof.

.

The organic solvent is selected from the group consisting of dichloroethylene, trichlorethylene, chloroform, chlorobenzene, dichlorobenzene, dichloromethane, styrene, dimethylformamide, dimethylsulfoxide, tetrahydrofuran, xylene, toluene, cyclohexene, 2 But are not limited to, methoxyethanol, ethanolamine, acetonitrile, butyl alcohol, isopropyl alcohol, ethanol, methanol and acetone, and combinations thereof.

.

The diameter of the oxide semiconductor wire may be 10 nm to 1000 μm, more specifically 50 nm to 5 μm. The length of the oxide semiconductor wire can be as long as a desired length to be more than several tens of km or more at a length of at least 10 nm, and more specifically at a length of 1 μm to 1 km .

Another embodiment of the present invention provides a pressure sensor comprising an aligned oxide semiconductor wire fabricated by the above-described fabrication method.

Another embodiment of the present invention provides an optical sensor comprising an arrayed oxide semiconductor wire made by the above-described fabrication method.

Another embodiment of the present invention provides a CMOS (Complementary Metal-Oxide-Semiconductor) sensor including aligned oxide semiconductor wires manufactured by the above-described manufacturing method.

Another embodiment of the present invention provides a solar cell comprising an aligned oxide semiconductor wire produced by the above-described manufacturing method.

Another embodiment of the present invention provides a light emitting transistor comprising an aligned oxide semiconductor wire manufactured by the above-described manufacturing method.

Another embodiment of the present invention provides a laser device comprising an aligned oxide semiconductor wire manufactured by the above-described manufacturing method.

Yet another embodiment of the present invention provides a memory comprising aligned oxide semiconductor wires made by the above-described fabrication method.

Another embodiment of the present invention provides a piezoelectric device comprising an aligned oxide semiconductor wire manufactured by the above-described manufacturing method.

Another embodiment of the present invention provides a battery comprising an aligned oxide semiconductor wire produced by the above-described manufacturing method.

Another embodiment of the present invention provides a logic circuit comprising an aligned oxide semiconductor wire fabricated by the above-described fabrication method.

Another embodiment of the present invention provides a ring oscillator comprising an aligned oxide semiconductor wire fabricated by the above-described fabrication method.

It is possible to manufacture various electronic devices using oxide semiconductor wires in a quick and simple manner by providing a method of aligning the oxide semiconductor wires in a desired position, direction, and shape. Particularly, according to the present invention, it is possible to manufacture a large-area, high-performance electronic device array with higher speed and accuracy.

FIG. 1 is a schematic view showing a process for manufacturing an oxide semiconductor wire pattern according to an embodiment of the present invention.
FIG. 2 is a schematic view of an electric field assisted robotic nozzle printer used in manufacturing an oxide semiconductor precursor / organic polymer composite wire pattern, according to an embodiment of the present invention.
3A and 3B are SEM photographs showing ordered zinc oxide nanowire patterns.
4 is a graph showing output voltage characteristics of an inverter fabricated using an aligned zinc oxide nanowire pattern and a copper oxide nanowire pattern.

Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited thereto, and the present invention is only defined by the scope of the following claims.

One embodiment of the present invention provides a method of manufacturing an oxide semiconductor wire pattern in an ordered form.

The term "aligned" wire as used herein refers to a wire whose position and orientation have been adjusted as desired.

A method of manufacturing an oxide semiconductor wire pattern according to an embodiment of the present invention includes the steps of: dissolving an oxide semiconductor precursor and an organic polymer in distilled water or an organic solvent to provide a composite solution of an oxide semiconductor precursor / organic polymer; Aligning the oxide semiconductor precursor / organic polymer composite wire on the substrate by dropping a complex solution of the oxide semiconductor precursor / organic polymer at a point 10 to 20 mm away from the substrate vertically; And heating the aligned oxide semiconductor precursor / organic polymer composite wire to form a pattern of aligned oxide semiconductor wires.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic view of a process for manufacturing an oxide semiconductor wire pattern for explaining an embodiment of the present invention, specifically providing (110) a composite solution of an oxide semiconductor precursor / organic polymer; (120) aligning the oxide semiconductor precursor / organic polymer composite wire on the substrate by dropping the oxide semiconductor precursor / organic polymer composite solution; And heating the aligned oxide semiconductor precursor / organic polymer composite wire to form a pattern of aligned oxide semiconductor wires (130).

The substrate may be selected from the group consisting of an insulating material, a metal material, a carbon material, a composite material of a conductor and an insulating film, and combinations thereof. For example, the insulating material may be a glass plate, a plastic film, paper, fabric, wood, etc. The metal material may be copper, aluminum, titanium, gold, silver, stainless steel, As the material, graphene, carbon nanotubes, graphite amorphous carbon and the like can be used. As the conductor / insulating film composite material, a semiconductor wafer substrate, a silicon (Si) / silicon dioxide (SiO ₂ ) ) / Aluminum oxide (Al ₂ O ₃ ) substrate can be used.

Since an oxide semiconductor has a wide band gap, it is a material that receives light as a very important material as an electron and an optoelectronic material. One embodiment of the present invention provides a method of aligning the oxide semiconductor wires to obtain a pattern.

Specifically, a method of aligning the oxide semiconductor wires is as follows.

First, a solution containing an oxide semiconductor precursor and an organic polymer is prepared.

The oxide semiconductor precursor may be a zinc oxide precursor, an indium oxide precursor, a tin oxide precursor, a gallium oxide precursor, a tungsten oxide precursor, an aluminum oxide precursor, a titanium oxide precursor, a vanadium oxide precursor, a molybdenum oxide precursor, a copper oxide precursor, Precursors, iron oxide precursors, chromium oxide precursors, bismuth oxide precursors, and combinations thereof.

Examples of the zinc oxide precursor include zinc hydroxide (Zn (OH) ₂ ), zinc acetate (Zn (CH ₃ COO) ₂ ), zinc acetate hydrate (Zn (CH ₃ (COO) ₂ .nH ₂ O) (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 ) (Zn (CH ₃ COCHCOCH ₃ ) ₂ ), zinc acetylacetonate hydrate (Zn (CH ₃ COCHCOCH ₃ ) ₂ .nH ₂ O), and combinations thereof, but are not limited thereto.

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, but is not limited thereto.

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 But is not limited to.

The gallium oxide precursor is gallium nitrate _{(Ga (NO 3) 3)} , gallium nitrate hydrate _{(Ga (NO 3) 3 ·} nH 2 O), gallium acetylacetonate _{(Ga (CH 3 COCHCOCH 3)} 3), gallium acetylacetonate carbonate hydrate _{(Ga (CH 3 COCHCOCH 3)} 3 · nH 2 O), gallium chloride _{(Ga 2 Cl 4, GaCl 3} ) and can be selected from the group consisting of, but not limited to this.

The tungsten oxide precursor is tungsten carbide (WC), tungsten acid powder (H ₂ WO _4), chloride, tungsten (WCl _4, WCl _6), tungsten isopropoxide _{(W (OCH (CH 3)} 2) 6), tungsten Sodium nitrate (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, but is not limited thereto.

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 (CH ₃₎ O)), and it can be selected from the group consisting of, but not limited to this.

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 it can be selected from the group consisting of, but not limited to this.

The vanadium oxide precursor, vanadium isopropoxide _{(VO (OC 3 H 7)} 3), vanadium ammonium (NH ₄ VO _3), vanadium acetylacetonate _{(V (CH 3 COCHCOCH 3)} 3), vanadium acetylacetonate monohydrate _{(V (CH 3 COCHCOCH 3)} 3 · nH 2 O) and can be selected from the group consisting of, but not limited to this.

Denyum the oxidized molybdenum denyum precursors include molybdenum isopropoxide _{(Mo (OC 3 H 7)} 5), chloride molybdate denyum isopropoxide _{(MoCl 3 (OC 3 H 7} ) 2), molybdenum having nyumsan ammonium (NH ₄ ) ₂ MoO ₄ ), ammonium molybdodenate hydrate ((NH ₄ ) ₂ MoO ₄ .nH ₂ O), and combinations thereof, but are not limited thereto.

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 _{(Cu (NO 3) 2)} , copper nitrate hydrate (Cu (NO _{3) 2 · nH 2 O)} , copper bromide (CuBr, CuBr _2), copper carbonate _{(CuCO 3 · Cu (OH)} 2), copper sulfide (Cu ₂ S, CuS), copper phthalocyanine (C ₃₂ H ₁₆ N ₈ (Cu (CO ₂ CF ₃ ) ₂ ), copper isobutyrate (C ₈ H ₁₄ CuO ₄ ), copper ethyl acetoacetate (C ₁₂ H ₁₈ CuO ₆ ), copper 2-ethylhexano ([CH ₃ (CH ₂ ) ₃ CH (C ₂ H ₅ ) CO ₂ ] ₂ Cu), copper fluoride (CuF ₂ ), formic acid copper hydrate ((HCO ₂ ) ₂ Cu? H ₂ O), copper gluconate _{(C 12 H 22 CuO 14)} , a copper-hexahydro flow acetylacetonate _{(Cu (C 5 HF 6 O} 2) 2), copper-hexahydro Floro acetylacetonate monohydrate _{(Cu (C 5 HF 6 O} 2) 2? H ₂ O), Lee methoxide _{(Cu (OCH 3) 2)} , copper neodecanoate _{(C 10 H 19 O 2 Cu} ), perchlorate, copper hydrate (Cu (ClO _{4) 2 and} 6H ₂ O), copper sulfate (CuSO _4), copper sulfate hydrate _{(CuSO 4 H 2 O?)} , tartaric acid copper hydrate ^{(? [- CH (OH)} CO 2] 2 Cu H 2 O), with a copper triple acetylacetonate _{(Cu (C 5 H 4 F} 3 O 2) ₂ ), copper triflouromethanesulfonate ((CF ₃ SO ₃ ) ₂ Cu), tetraamine copper sulfate hydrate (Cu (NH ₃ ) ₄ SO _{4 -2} O), and combinations thereof But is not limited to.

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, but is not limited thereto.

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, but is not limited thereto.

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, but is not limited thereto.

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, but is not limited thereto.

Examples of the organic polymer include polyvinyl alcohol (PVA), polyethylene oxide (PEO), polystyrene (PS), polycaprolactone (PCL), polyacrylonitrile (PAN), poly (methyl methacrylate) (Polyvinylidene fluoride) (PVDF), polyaniline (PANI), polyvinyl chloride (PVC), nylon, poly (acrylic acid), poly (chlorostyrene), poly (dimethylsiloxane) Poly (ethyl acrylate), poly (ethyl vinyl acetate), poly (ethyl-co-vinyl acetate), poly (ethylene terephthalate), poly (lactic acid- poly (styrenesulfonyl fluoride), poly (styrene-co-acrylonitrile), poly (styrene-co-glycolic acid) (co-butadiene), poly (styrene-co-divinylbenzene), poly Poly (ethylene oxide), poly (etheretherketone), polyethylene, polyethyleneimine, polyisoprene, polyimide, polyimide, polyimide, (Polyvinylidene fluoride), poly (lactide), poly (lactide), poly (lactide), polypropylene, polysulfone, polyurethane, poly It is not limited.

In the preparation of the solution, water or an organic solvent may be used as the solvent. Examples of the organic solvent include dichloroethylene, trichlorethylene or chloroform, chlorobenzene, dichlorobenzene, dichloromethane, styrene, dimethylformamide, Methyl alcohol, isopropyl alcohol, ethanol, methanol, acetone, or a mixture thereof may be used, but not limited thereto, for example, methylene chloride, methylene chloride, methylsulfoxide, tetrahydrofuran, xylene, toluene, cyclohexene, 2-methoxyethanol, ethanolamine, acetonitrile, It is not.

The mixing ratio of the oxide semiconductor precursor and the organic polymer may be a weight ratio of 10: 90 to 97: 3. More specifically, it may be a weight ratio of 70:30 to 90:10. When the mixing ratio of the oxide semiconductor precursor and the organic polymer is within the above range, the finally obtained oxide semiconductor wire can be formed with a uniform diameter without breaking. Since the organic polymer is decomposed by heating, if the proportion of the organic polymer exceeds 90% by weight, the amount of oxide semiconductor remaining after heating is insufficient, resulting in a problem that the wires are not uniformly formed and are cut off. If the proportion of the organic polymer is less than 3% by weight, the viscosity of the oxide semiconductor precursor-organic polymer solution is too low to cause a problem that the oxide semiconducting precursor / organic polymer composite wire pattern is not formed properly by the electric field assistant robotic nozzle printer .

The concentration of the oxide semiconductor precursor and the organic polymer solution may be 1 to 30 wt%. When the mixing ratio of the oxide semiconductor precursor and the organic polymer is within the above range and the concentration of the oxide semiconductor precursor and the organic polymer solution is within the above range, the viscosity of the solution is sufficient and the electric field assistant robot nozzle printer A wire pattern can be formed. If the concentration of the solute in the oxide semiconductor precursor and the organic polymer solution is less than 1 wt%, the viscosity may be too low to form a droplet of the solution rather than the wire. If the concentration of the oxide semiconductor precursor and the organic polymer solution exceeds 30% by weight, the viscosity may be too high and the solution may not be properly discharged through the electric field assisted robotic nozzle printer.

By dropping the solution of the oxide semiconductor precursor / organic polymer complex at a position vertically 10 μm to 20 mm away from the substrate using the solution of the oxide semiconductor precursor / organic polymer complex, the oxide semiconductor precursor / organic polymer complex Polymer composite wires can be aligned.

As the distance to which the oxide semiconductor precursor / organic polymer complex solution is dropped is farther from the substrate, the speed of the aligned wires in the horizontal direction increases as the solution of the oxide semiconductor precursor / organic polymer complex drops, . Thus, the wire is disturbed, making it difficult to align the wire in the desired direction or parallel. However, by dropping a complex solution of an oxide semiconductor precursor / organic polymer at a distance of 10 占 퐉 to 20 占 퐉 from the substrate, the present invention can suppress the warping of the wire and arrange the wire in a desired direction. FIGS. 3A and 3B show SEM photographs of zinc oxide nanowires formed on a substrate, and nanowires aligned in a parallel direction can be identified.

The step of aligning the ordered oxide semiconductor precursor / organic polymer composite wire may be performed by an electric field assisted robotic nozzle printer. The electric field assisted robotic nozzle printer comprises i) a solution storage device for containing an oxide semiconductor precursor / organic polymer complex solution; ii) a nozzle device for discharging the solution supplied from the solution storage device; iii) a voltage applying device for applying a high voltage to the nozzle; iv) a collector for fixing the substrate; v) a robot stage for moving the collector in a horizontal direction; vi) a micro-distance adjuster for moving the collector in a vertical direction; And vii) a collector that supports the collector below the collector.

2 is a schematic diagram of an electric field assisted robotic nozzle printer 100. As shown in FIG. Specifically, the electric field assisted robotic nozzle printer 100 includes a solution storing device 10, a discharge regulator 20, a nozzle 30, a voltage applying device 40, a collector 50, a robot stage 60, A stone quartz plate 61, and a micro distance adjuster 70.

The solution storage device 10 stores a solution of the oxide semiconductor precursor / organic polymer complex 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 the 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 oxide semiconductor wires of the core shell structure may be formed.

The discharge regulator 20 is a part for applying pressure to the solution in the solution storage device 10 to discharge the solution of the oxide semiconductor precursor / organic polymer complex solution in the solution storage device 10 through the nozzle 30 at a constant rate, to be. As the discharge regulator 20, a pump or gas pressure regulator may be used. The discharge regulator 20 can adjust the discharge speed of the solution within a 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 portion through which the solution of the oxide semiconductor precursor / organic polymer complex is supplied from the solution storage device 10, and the solution is discharged from the nozzle 30 at the end of the nozzle 30 . The diameter of the nozzle 30 may range from about 15 [mu] m to about 1.5 mm.

The nozzle 30 may include a single nozzle, a dual-concentric nozzle, and a triple-concentric nozzle. In the case of forming an oxide semiconductor wire having a core shell structure, two or more types of oxide semiconductor precursor / organic polymer composite solution 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. The voltage application device 40 can 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 a wire is continuously formed at the end.

The collector 50 is a portion where wires 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 (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 to 100 cm, for example, within a range of 10 μm 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 planar view within a range of 0.5 μm to 5 μm. The distance between the nozzle 30 and the collector 50 can be controlled to be constant by the plan view of the stone pot 61. The stone stone table 61 can control the precision of the oxide semiconductor precursor / organic polymer composite wire 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 centimeters, and the fine adjuster 72 can be used to adjust a fine distance of at least 10 microns. 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 to 20 mm.

The three-dimensional path of the wire radiating from the nozzle in the electrospinning can be represented by the following equation (DH Reneker, AL Yarin, H. Fong, S. Koombhongse, "Bending instability of polymer solutions in electrospinning" Appl. Phys., 87, 9, 4531-4546 (2000)). As can be seen from the following formulas (1a) and (1b), the greater the distance between the collector and the nozzle, the greater the perturbation of the wire.

‥‥‥‥‥‥‥ 식 (1a)

... (1a)

‥‥‥‥‥‥‥ 식 (1b) 이다.

... (1b).

L is a constant representing the length scale,? Is the perturbation wavelength, z is the collector of the wire (z = 1, 2, ..., 0), and h is the distance between the nozzle and the collector. From the above equations (1a) and (1b), it can be seen that the larger the distance h between the collector and the nozzle is for the same z value, the larger the x and y values indicating disturbance of the wire.

For example, the collector 50 parallel to the xy plane can be moved on the xy plane by the robot stage 60 and can be moved between the nozzle 30 and the collector 50 in the z- Can be adjusted.

The electric field assisted robotic nozzle printer 100 according to an embodiment of the present invention can sufficiently narrow the distance between the nozzle 30 and the collector 50 by a unit of tens to several tens of micrometers so that the collector 50 , Whereby a pattern of elaborate wires can be formed by the movement of the collector 50. [

The formation of the wire pattern by the movement of the collector makes it possible to form a more precise wire pattern by reducing the disturbance parameter of the wire pattern as compared with the movement of the nozzle.

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 injected gas may be nitrogen, dry air or the like, and the oxide semiconductor 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 adjust the vapor pressure in the housing to control the rate of evaporation of the solvent when the wire is formed. 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 oxide semiconductor wire. If the evaporation rate of the solvent is too fast, the solution will dry at the nozzle tip before the oxide semiconductor wire is formed, causing the nozzle to clog. If the evaporation rate of the solvent is too slow, the wires of the solid oxide semiconductor precursor / organic polymer complex are not formed and are placed on the collector in liquid form. The liquid type oxide semiconductor precursor / organic polymer complex solution can not be used for device fabrication because it does not have characteristic electrical characteristics of the wire. As the evaporation rate of the solvent affects the formation of the wire, the ventilator plays an important role in the wire formation.

Specifically, the step of aligning the ordered oxide semiconductor precursor / organic polymer composite wire using the electric field assisted robotic nozzle printer 100 includes the steps of: i) depositing the oxide semiconductor precursor / organic polymer composite Supplying a solution; ii) discharging the oxide semiconductor precursor / organic polymer complex solution from the nozzle while applying a high voltage to the nozzle through the voltage application device of the electric field assisted robotic nozzle printer, And moving the collector on which the substrate is placed in a horizontal direction when the precursor / organic polymer composite solution is ejected.

The solution containing the oxide semiconductor precursor and the organic polymer is injected into the syringe 10 and then discharged from the nozzle 30 by the syringe pump 20, . 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 in the droplet and the collector 50 And adheres to the substrate on the collector 50 while extending in the direction of the electric field.

At this time, as the droplet increases, the oxide semiconductor precursor / organic polymer composite wire having a longer length in one direction than the other direction from the droplet can be formed. The diameter of the oxide semiconductor precursor / organic polymer composite wire can be adjusted to a micrometer level or a sub micrometer level by adjusting an applied voltage and a nozzle size.

The oxide semiconductor precursor / organic polymer composite wire formed from the charged discharge of the nozzle 30 can be aligned on the substrate on the collector 50. [ At this time, by adjusting the distance between the nozzle 30 and the collector 50 to be within the range of 10 μm to 20 mm, the oxide semiconductor precursor / organic polymer composite wire is not a tangled form, . At this time, the distance between the nozzle 30 and the collector 50 can be adjusted using the micro distance adjuster 70.

Thus, by moving the collector 50 very finely as the micro distance adjuster 70 and the fine adjuster 72, the oxide semiconductor precursor / organic polymer composite wire can be arranged at a desired position on the substrate in a desired direction, .

The ordered oxide semiconductor wire pattern can be formed by heating the oxide semiconductor precursor / organic polymer composite wire aligned at the desired position, direction and number of times at a temperature of 100 ° C to 900 ° C for 10 minutes to 24 hours. More specifically, it is heated at a temperature in the range of 400 ° C to 800 ° C for 3 hours to 10 hours. In this case, oxide semiconductor crystals having the most uniform size are formed and the charge mobility is improved. Heating utilizes equipment that can be heated uniformly globally, such as a furnace or a vacuum hot-plate.

As the oxide semiconductor precursor / organic polymer composite wire is heated, the organic polymer is decomposed and the oxide semiconductor precursor is converted into an oxide semiconductor, so that an aligned wire-type oxide semiconductor can be obtained. The oxide semiconductor wire produced may have a diameter in the range of 10 nm to 1000 μm, more specifically 50 nm to 5 μm. This diameter can be controlled by the ratio and concentration of the oxide semiconductor precursor and the organic polymer. The length of the oxide semiconductor wire can be formed to be as long as desired by as much as 10 nm or more, or as long as several thousand km or more, and more specifically, as long as 1 μm to 1 km have. One feature of the oxide semiconductor wire produced above is a small diameter and hence a large surface area. A diameter much smaller than that of visible light or visible light can be easily produced, and a very large surface area can be formed.

Since the oxide semiconductor wires manufactured according to the present invention are horizontally aligned, they can be used in various electronic devices such as a pressure sensor, an optical sensor, a CMOS sensor, a solar cell, a light emitting transistor, a laser device, a memory, , A ring oscillator, and the like.

Hereinafter, specific embodiments of the present invention will be described. However, the embodiments described below are only intended to illustrate or explain the present invention, and thus the present invention should not be limited thereto.

Example

Example  One

A horizontally aligned zinc oxide nanowire pattern was produced according to the method described below.

First, a zinc acetate precursor / PVA solution was prepared by dissolving a zinc acetate dihydrate (Zn (CH ₃ (COO) ₂ .2H ₂ O) (80 wt%) and polyvinyl alcohol (PVA) The prepared zinc oxide precursor / PVA solution was placed in a syringe of an electric field assisted robotic nozzle printer, and a voltage of about 2.0 kV was applied to the nozzle to form a zinc oxide precursor / PVA Solution was ejected from the nozzle. A zinc oxide precursor / PVA composite 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 and the applied voltage was 2.1 kV. The distance between the nozzle and the collector was kept constant at 5 mm. The moving distance in the Y axis direction of the robot stage was 50 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 type of the substrate was a silicon (Si) wafer in which a silicon oxide film (SiO ₂ ) was coated to a thickness of 100 nm.

The ordered zinc oxide precursor / PVA nanowire pattern was heated in a furnace to 500 < 0 > C for 4 hours each to form an ordered zinc oxide nanowire pattern.

Example  2

Aligned copper oxide nanowire patterns were fabricated according to the method described below.

First, copper trifloro acetate hydrate (Cu (CO ₂ CF ₃ ) ₂ .nH ₂ O) (25 wt%) and polyvinylpyrrolidone (PVP) (10 wt%) were dissolved in dimethylformamide and tetrahydrofuran To prepare a copper oxide precursor / PVP solution. The concentration of the precursor / PVP solution was 31 wt%. The prepared copper oxide precursor / PVP solution was placed in a syringe of an electric field assisted robotic nozzle printer, and a copper oxide precursor / PVP solution was discharged from the nozzle while applying a voltage of about 0.5 kV to the nozzle. A copper oxide precursor / PVP composite 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 and the applied voltage was 0.5 kV. The distance between the nozzle and the collector was kept constant at 7 mm. 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 copper oxide precursor / PVP nanowire pattern was heated from the furnace to 450 < 0 > C each for 1 hour to form aligned copper oxide nanowire patterns.

Example  3

Oxide semiconductor nanowire inverters were fabricated using the aligned zinc oxide nanowire patterns and copper oxide nanowire patterns prepared in Examples 1 and 2 above.

A zinc oxide nanowire pattern and a copper oxide nanowire pattern were fabricated according to the above Examples 1 and 2 using a silicon (Si) wafer having a thickness of 300 nm as a silicon oxide film (SiO ₂ ). At this time, the size of the substrate was 2.5 cm x 2.5 cm, and silicon (Si) and silicon oxide (SiO ₂ ) were used as gate and gate insulating films, respectively. A 100 nm thick gold was deposited on the nanowire pattern by thermal evaporation to form a source / drain / output electrode.

The oxide semiconductor nanowire inverter exhibited gain values of 7.5, 12.7, and 16.5 for drain voltages of 30, 40, and 50 V, respectively.

It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the present invention as defined by the following claims. As will be understood by those skilled in the art. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive.

Claims (36)

Dissolving an oxide semiconductor precursor and an organic polymer in distilled water or an organic solvent to provide an oxide semiconductor precursor / organic polymer composite solution;
Dropping the oxide semiconductor precursor / organic polymer composite solution vertically from the substrate and aligning the oxide semiconductor precursor / organic polymer composite wire on the substrate;
And heating the aligned oxide semiconductor precursor / organic polymer composite wire to form a pattern of aligned oxide semiconductor wires. The method according to claim 1,
The step of dropping the oxide semiconductor precursor / organic polymer composite solution may include dropping the solution from a position vertically 10 to 20 mm away from the substrate The method according to claim 1,
The step of forming the aligned oxide semiconductor wire pattern may include heating the oxide semiconductor precursor / organic polymer composite wire for 10 minutes to 24 hours at a temperature of 100 ° C to 900 ° C. . The method according to claim 1,
The step of aligning the ordered oxide semiconductor precursor / organic polymer composite wire is performed by an electric field assisted robotic nozzle printer, the electric field assisted robotic nozzle printer
i) a solution storage device for containing an oxide semiconductor precursor / organic polymer complex solution;
ii) a nozzle device for discharging the solution supplied from the solution storage device;
iii) a voltage applying device for applying a high voltage to the nozzle;
iv) a collector for fixing the substrate;
v) a robot stage for moving the collector in a horizontal direction;
vi) a micro-distance adjuster for moving the collector in a vertical direction; And
vii) a stone quartz support for supporting the collector. 5. The method of claim 4,
The step of aligning the ordered oxide semiconductor precursor / organic polymer composite wire
i) supplying the oxide semiconductor precursor / organic polymer complex solution to the solution storage device;
ii) discharging the oxide semiconductor precursor / organic polymer complex solution from the nozzle while applying a high voltage to the nozzle through the voltage application device of the electric field assisted robotic nozzle printer,
Wherein when the oxide semiconductor precursor / organic polymer composite solution is discharged from the nozzle, the collector on which the substrate is placed is moved in the horizontal direction. The method according to claim 1,
Wherein the substrate is selected from the group consisting of an insulating material, a metal material, a carbon material, and a composite material of a conductor and an insulating film. The method according to claim 1,
The oxide semiconductor precursor may be a zinc oxide precursor, an indium oxide precursor, a tin oxide precursor, a gallium oxide precursor, a tungsten oxide precursor, an aluminum oxide precursor, a titanium oxide precursor, a vanadium oxide precursor, a molybdenum oxide precursor, a copper oxide precursor, A precursor, an iron oxide precursor, a chromium oxide precursor, a bismuth oxide precursor, and combinations thereof. 8. The method of claim 7,
The zinc oxide precursor may be at least one 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) (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 ) (Zn (CH ₃ COCHCOCH ₃ ) ₂ ), zinc acetylacetonate hydrate (Zn (CH ₃ COCHCOCH ₃ ) ₂ .nH ₂ O), and combinations thereof. 8. The method of claim 7,
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. 8. The method of claim 7,
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 Of the oxide semiconductor wire pattern. 8. The method of claim 7,
The gallium oxide precursor is gallium nitrate _{(Ga (NO 3) 3)} , gallium nitrate hydrate _{(Ga (NO 3) 3 ·} nH 2 O), gallium acetylacetonate _{(Ga (CH 3 COCHCOCH 3)} 3), gallium acetylacetonate carbonate hydrate _{(Ga (CH 3 COCHCOCH 3)} 3 · nH 2 O), gallium chloride _{(Ga 2 Cl 4, GaCl 3} ) and a method for manufacturing the oxide semiconductor wire pattern is selected from the group consisting of. 8. The method of claim 7,
The tungsten oxide precursor is tungsten carbide (WC), tungsten acid powder (H ₂ WO _4), chloride, tungsten (WCl _4, WCl _6), tungsten isopropoxide _{(W (OCH (CH 3)} 2) 6), tungsten Sodium nitrate (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. 8. The method of claim 7,
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 (CH ₃ ) O)), and combinations thereof. 8. The method of claim 7,
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. 8. The method of claim 7,
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 _{(V (CH 3 COCHCOCH 3)} 3 · nH 2 O and the method for manufacturing the oxide semiconductor wire pattern is selected from the group consisting of. 8. The method of claim 7,
Denyum the oxidized molybdenum denyum precursors include molybdenum isopropoxide _{(Mo (OC 3 H 7)} 5), chloride molybdate denyum isopropoxide _{(MoCl 3 (OC 3 H 7} ) 2), molybdenum having nyumsan ammonium ((NH ₄ ) ₂ MoO ₄ ), ammonium molybdodeniate hydrate ((NH ₄ ) ₂ MoO ₄ .nH ₂ O), and combinations thereof. 8. The method of claim 7,
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 _{(Cu (NO 3) 2)} , copper nitrate hydrate (Cu (NO _{3) 2 · nH 2 O)} , copper bromide (CuBr, CuBr _2), copper carbonate _{(CuCO 3 · Cu (OH)} 2), copper sulfide (Cu ₂ S, CuS), copper phthalocyanine (C ₃₂ H ₁₆ N ₈ (Cu (CO ₂ CF ₃ ) ₂ ), copper isobutyrate (C ₈ H ₁₄ CuO ₄ ), copper ethyl acetoacetate (C ₁₂ H ₁₈ CuO ₆ ), copper 2-ethylhexano ([CH ₃ (CH ₂ ) ₃ CH (C ₂ H ₅ ) CO ₂ ] ₂ Cu), copper fluoride (CuF ₂ ), formic acid copper hydrate ((HCO ₂ ) ₂ Cu? H ₂ O), copper gluconate _{(C 12 H 22 CuO 14)} , a copper-hexahydro flow acetylacetonate _{(Cu (C 5 HF 6 O} 2) 2), copper-hexahydro Floro acetylacetonate monohydrate _{(Cu (C 5 HF 6 O} 2) 2? H ₂ O), Lee methoxide _{(Cu (OCH 3) 2)} , copper neodecanoate _{(C 10 H 19 O 2 Cu} ), perchlorate, copper hydrate (Cu (ClO _{4) 2 and} 6H ₂ O), copper sulfate (CuSO _4), copper sulfate hydrate _{(CuSO 4 H 2 O?)} , tartaric acid copper hydrate ^{(? [- CH (OH)} CO 2] 2 Cu H 2 O), with a copper triple acetylacetonate _{(Cu (C 5 H 4 F} 3 O 2) ₂ ), copper trifluoromethanesulfonate ((CF ₃ SO ₃ ) ₂ Cu), tetraamine copper sulfate hydrate (Cu (NH ₃ ) ₄ SO _{4 -2} O), and combinations thereof Wherein the method comprises the steps of: 8. The method of claim 7,
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. 8. The method of claim 7,
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. 8. The method of claim 7,
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. 8. The method of claim 7,
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 a combination thereof. ≪ RTI ID = 0.0 > 11. < / RTI > The method according to claim 1,
The organic polymer may be at least one selected from the group consisting of polyvinyl alcohol (PVA), polyethylene oxide (PEO), polystyrene (PS), polycaprolactone (PCL), polyacrylonitrile (PAN), poly (methyl methacrylate) Polyvinylidene fluoride (PVDF), polyaniline (PANI), polyvinyl chloride (PVC), nylon, poly (acrylic acid), poly (chlorostyrene), poly (dimethylsiloxane) Poly (ethyl acrylate), poly (ethyl vinyl acetate), poly (ethyl-co-vinyl acetate), poly (ethylene terephthalate), poly (lactic acid- Poly (styrene sulfonate), poly (styrene-co-acrylonitrile), poly (styrene-co (meth) acrylate) -Butadiene), poly (styrene-co-divinylbenzene), poly (vinyl acetate), poly Poly (vinyl alcohol), polyacrylamide, polybenzimidazole, polycarbonate, poly (dimethylsiloxane-co-polyethylene oxide), poly (etheretherketone), polyethylene, polyethyleneimine, polyisoprene, polylactide , A method of manufacturing an oxide semiconductor wire pattern, wherein the method is selected from the group consisting of polypropylene, polysulfone, polyurethane, poly (vinylpyrrolidone), poly (phenylenevinylene), poly (vinylcarbazole) . The method according to claim 1,
The organic solvent is selected from the group consisting of dichloroethylene, trichlorethylene, chloroform, chlorobenzene, dichlorobenzene, dichloromethane, styrene, dimethylformamide, dimethylsulfoxide, tetrahydrofuran, xylene, toluene, cyclohexene, 2 Wherein the solvent is selected from the group consisting of methoxyethanol, ethanolamine, acetonitrile, butyl alcohol, isopropyl alcohol, ethanol, methanol, and acetone, and combinations thereof. The method according to claim 1,
The step of providing the oxide semiconductor precursor / organic polymer complex solution may include dissolving the oxide semiconductor precursor and the organic polymer at a weight ratio of 10:90 to 97: 3 in distilled water or organic solvent to a concentration of 1 to 30% by weight Wherein the oxide semiconductor wire pattern is formed on the substrate. The method according to claim 1,
Wherein the diameter of the oxide semiconductor wire is 10 nm to 1000 占 퐉. 25. A pressure sensor comprising an aligned oxide semiconductor wire produced by the method of any one of claims 1 to 25. An optical sensor comprising an arrayed oxide semiconductor wire fabricated by the method of any one of claims 1 to 25. 25. A CMOS sensor comprising an aligned oxide semiconductor wire fabricated by the method of any one of claims 1 to 25. 25. A solar cell comprising an aligned oxide semiconductor wire fabricated by the method of any one of claims 1 to 25. 25. A light-emitting transistor comprising an aligned oxide semiconductor wire produced by the method of any one of claims 1 to 25. 25. A laser device comprising an aligned oxide semiconductor wire fabricated by the method of any one of claims 1 to 25. 25. A memory comprising an ordered oxide semiconductor wire fabricated by the method of any one of claims 1 to 25. 25. A piezoelectric device comprising an aligned oxide semiconductor wire produced by the method of any one of claims 1 to 25. 25. A battery comprising an aligned oxide semiconductor wire produced by the method of any one of claims 1 to 25. 25. A logic circuit comprising an aligned oxide semiconductor wire fabricated by the method of any one of claims 1 to 25. 25. A ring oscillator comprising an aligned oxide semiconductor wire produced by the method of any one of claims 1 to 25.

Images