KR100838026B1 - The apparatus for mass production of zno nanostructures and the process for mass production thereof - Google Patents

Abstract

An apparatus and a method for mass-producing zinc oxide nanostructures are provided to synthesize the zinc oxide nanostructures in commercial quantity through gas-phase synthesis without using a substrate. An apparatus for mass-producing zinc oxide nanostructures includes (a) a catalyst sauce supply part(110) which supplies a catalyst source, (b) a reaction source supply part(100) which supplies a reaction source, (c) a reaction furnace(130) which provides a space for synthesizing zinc oxide nanostructures by a pyrolysis of the catalyst source and reaction source and an interaction between the pyrolyzed gas-phase sources; and (c) a gas discharge part which discharges the gas-phase sources that do not take part in the reaction. Further, the reaction furnace is a tube comprised of quartz and contains one or more resistance heating elements.

Description

Mass synthesis apparatus of zinc oxide nanostructures and mass synthesis method of zinc oxide nanostructures {THE APPARATUS FOR MASS PRODUCTION OF ZnO NANOSTRUCTURES AND THE PROCESS FOR MASS PRODUCTION THEREOF}

1 is a schematic diagram of a horizontal reactor having only a first resistance heating element for mass synthesis of zinc oxide nanostructures according to the present invention.

2 is a schematic diagram of a horizontal reactor having a first resistance heating element and a second resistance heating element for mass synthesis of zinc oxide nanostructures according to the present invention.

3 is a schematic view of a vertical reactor having only a first resistance heating element for mass synthesis of zinc oxide nanostructures according to the present invention.

4 is a schematic view of a vertical reactor having a first resistance heating element and a second resistance heating element for mass synthesis of zinc oxide nanostructures according to the present invention.

5 is a schematic view of an injector in the form of a nozzle, multi-nozzle or shower head installed in each reactor tube.

6 is a schematic of a synthesized zinc oxide nanostructure collector employed in a vertical reactor.

Explanation of symbols on the main parts of the drawings

100: horizontally the reaction source supply

110: catalyst source supply horizontally

120: inert carrier gas supply unit

130: reactor and collector

140: gas outlet

200: reaction source supply vertically

210: catalyst source supply vertically

220: inert carrier gas supply unit

230: reactor

240 gas discharge unit

250: Collector

The present invention relates to the synthesis of zinc oxide nanostructures, and more particularly, to a synthesis apparatus for synthesizing zinc oxide nanostructures in large quantities and a synthesis method using the synthesis apparatus.

Zinc oxide is a II-VI compound semiconductor with a hexagonal structure. It has a band gap of 3.37 eV at room temperature, and has an exciton binding energy of 60 mV, which is much larger than 24 mV of thermal energy at room temperature. This is an easy characteristic. The excellent electrical and optical properties of zinc oxide are further enhanced when nanostructured. Due to the excellent optical properties of zinc oxide, research and development of high efficiency light emitting diodes based on zinc oxide nanostructure technology is underway.

Meanwhile, development of flexible display devices and lighting display devices using metal oxide thin film type transparent electrodes and carbon nanotube electrodes has been in progress, but technical limitations and limitations have made it difficult to commercialize these devices. Efforts have been made to implement high efficiency flexible displays through highly flexible and highly efficient transparent electrodes using zinc oxide's one-dimensional nanostructure network, which is a kind of excellent transmission conducting oxide.

Despite the excellent optical properties and applicability of zinc oxide, it is still difficult to commercialize devices using zinc oxide nanostructures due to the difficulty of mass synthesis of zinc oxide nanostructures. Currently, zinc oxide nanostructures are synthesized by various methods such as organometallic chemical vapor deposition, molecular beam deposition, sol-gel deposition, sputtering, reaction evaporation, spray pyrolysis, pulsed laser deposition, electro-discharge, and gas phase synthesis. ought.

However, except for the gas phase synthesis method, a method of depositing and synthesizing a zinc oxide nanostructure on the surface of the substrate, the synthesis method of the zinc oxide nanostructure using the substrate has shown a limitation in synthesizing the zinc oxide nanostructure in large quantities.

On the other hand, the gas phase synthesis method is a method of synthesizing zinc oxide nanostructures by oxidizing a gaseous reaction source by pyrolyzing a reaction source containing solid, gaseous or liquid zinc in a reactor of artificial or natural oxygen atmosphere without using a substrate. The continuous supply of catalyst and reaction sources allows the synthesis of zinc oxide nanostructures, which is advantageous for mass synthesis.

Accordingly, an object of the present invention is to provide a device capable of synthesizing a large amount of zinc oxide nanostructures through vapor phase synthesis without using a substrate and a synthesis method using the same.

The mass synthesis of the zinc oxide nanostructures of the present invention uses a gas phase synthesis method, the principle of which is a liquid or gaseous reaction source containing zinc in combination with a transition metal or a catalyst source containing a transition metal of a high temperature of atmospheric pressure or low pressure It is made by injecting into the reactor to pyrolyze the catalyst source and oxidize the reaction source.

As a reaction source used in the synthesis of the zinc oxide nanostructures of the present invention, zinc oxide powder (ZnO powder), zinc powder (Zn powder), zinc pellet (Zn pellet), zinc metal (Zn metal), zinc nitrate powder ( Zn nitrate powder), DEZn (diethyl zinc), DMZn (dimethyl zinc) and zinc nitrate solution (Zn nitrate solution) with and the like, the catalyst source is _{Fe (CO) 5, Mo (} CO) 6, Co ₂ (CO) ₈ , (C ₅ H ₅ ) ₂ Fe, Ni (CO) ₅ , an organometallic compound selected from the group consisting of zinc acetate powder, metal nanoparticles or zinc acetate powder, and the like.

Mass production apparatus of the zinc oxide nanostructures of the present invention, which can be used for mass synthesis of such zinc oxide nanostructures,

(a) a catalyst source supply for supplying a catalyst source;

(b) a reaction source supply for supplying a reaction source;

(c) a reactor that provides a synthesis space for the zinc oxide nanostructures by the interaction between the pyrolysis and pyrolyzed gaseous sources of the catalyst source and the reaction source; And

and (d) a gas outlet for discharging a gaseous source not participating in the reaction.

In order to facilitate understanding of the apparatus for synthesizing the zinc oxide nanostructures of the present invention, the apparatus for synthesizing the zinc oxide nanostructures of the present invention will now be described with reference to the accompanying drawings.

In the apparatus for synthesizing the zinc oxide nanostructures of the present invention, the reaction source supply units 100 and 200 and the catalyst source supply units 110 and 210 may be formed in the outer (FIG. 1 to FIG. 4) or the inner ( It may be installed in (not shown). In the case where the reaction source and the catalyst source are organometallic compounds, it is preferable to provide the reaction source supply parts 100 and 200 and the catalyst source supply parts 110 and 210 outside the reactor.

If the reaction source supply unit 100, 200 and the catalyst source supply unit 110, 210 are installed outside the reactor, the apparatus for synthesizing the zinc oxide nanostructures may include a carrier gas supplier 121, 122, or 221, 222. Further comprising a carrier gas supply unit (120, 220) comprising a, so that the reaction source supply unit (100, 200) and catalyst source supply unit (110, 210) includes a vaporizer (102, 111, 201, 211), It is preferred that the catalyst source and the reaction source be fed into the reactor by the inert carrier gas from the vaporizer.

In the vaporizers 102, 111, 201, and 211, an organometallic compound is provided as a reaction source and a catalyst source, and the reaction source or catalyst source in the vaporizer is provided by an inert carrier gas supplied from the carrier gas supply units 120 and 220. After the vaporization is supplied to the reactor (130, 230). The carrier gas used in the above carrier gas supplier is preferably an inert gas such as argon gas. This carrier gas is responsible for the supply and delivery function of the reaction source or catalyst source, the flow of the carrier gas is used that is 10 to 5000 sccm.

On the other hand, when the reaction source supply unit 100 and 200 and the catalyst source supply unit 110 and 210 are installed inside the reactor, the reaction source and the catalyst source are transported to the site where the nanostructures are to be synthesized by the inert carrier gas. do.

The reactors 130 and 230 are tubes made of quartz or quartz, and include one or more resistive heating elements that can make the reactor high temperature, thereby allowing the reaction between the pyrolysis of the reaction source and the catalyst source and the interaction of pyrolyzed gaseous sources. It serves to provide a space for the synthesis of zinc oxide nanostructures. The resistance heating element of the reactor preferably has a temperature range of 50 ° C to 1600 ° C. When the catalyst source is zinc acetate powder, the catalyst source supply is preferably installed at the reactor internal resistance heating element position.

The reactor may take both types of horizontal reactor 130 or vertical reactor 230, but in the case of vertical reactor 230, a collector 250 for collecting the synthesized zinc oxide nanostructures. The collector 250 is preferably made of various types of boats 251 made of quartz or quartz, and the shape of the boat is not limited as long as the shape of the tube allows.

In a horizontal reactor, the reaction source supply unit may pyrolyze zinc oxide powder, zinc powder, zinc pellet, zinc metal, and zinc nitrate powder at a first resistance heating element or a second resistance heating element in a reactor tube to supply a gaseous source. In addition, a metal compound raw material supply unit such as DEZn (diethyl zinc), DMZn (dimethyl zinc), and zinc nitrate solution (Zn nitrate solution) may be installed outside the reactor and injected into the reactor to thermally decompose to supply a gaseous reaction source. Can be.

In addition, in the vertical reactor, the reaction source supply part is installed in the outside of the reactor by supplying a metal compound raw material supply unit such as DEZn (diethyl zinc), DMZn (dimethyl zinc) and zinc nitrate solution (Zn nitrate solution) It is preferable to supply a gaseous reaction source by thermal decomposition.

In the reactor tube, injectors 131a to e and 231a to e may be further installed to inject the organometallic raw material source supplied from the reaction source supply unit or the catalyst source supply unit into the reactor tube. It can include a single nozzle, a multi-nozzle form or a shower head form.

Gas outlets 140 and 240 are devices for discharging gaseous sources and carrier gases that do not participate in the reaction. If the release of toxic gas is concerned, the discharge device including the toxic gas purifier (141, 241) can be further installed.

It is obvious that the mass synthesis apparatus of the zinc oxide nanostructures of the present invention may include the extra devices that may be advantageous or necessary to the present invention in addition to the above-described configuration.

The method for synthesizing the zinc oxide nanostructures using the mass synthesis apparatus of the zinc oxide nanostructures of the present invention described above,

(Iii) an organometallic compound catalyst source selected from the group consisting of Fe (CO) ₅ , Mo (CO) ₆ , Co ₂ (CO) ₈ , (C ₅ H ₅ ) ₂ Fe, Ni (CO) ₅ , and zinc acetate powder Injecting a metal nanoparticle catalyst source or a zinc acetate powder catalyst source into a high temperature reactor to pyrolyze to provide a nucleation site of the reaction source;

(Ii) ZnO powder, Zn powder, Zn pellet, Zn metal, Zn metal, Zn nitrate powder, DEZn (diethyl zinc), DMZn Pyrolysis in a high temperature reactor by injecting a gaseous or liquid reaction source selected from the group consisting of (dimethyl zinc) and a zinc nitrate solution into the reactor;

(Iii) initiating the synthesis of the nanostructure by the pyrolysed gaseous reaction source generating nuclei at nucleation sites provided by the gaseous catalyst source; And

(Iii) the synthesis of the zinc oxide nanostructures is completed.

In injecting the catalyst source and the reaction source into the reactor, if the catalyst source and the reaction source is an organometallic compound is supplied to the reactor by an inert carrier gas, such as argon, the catalyst source and the reaction source in the reactor also inert carrier gas Is transported to the site where the synthesis takes place.

Here, the supply of the catalyst source and the reaction source into the reaction furnace may be made by spraying, and the position and the injection shape supplied in the reactor may be variously modified.

The present invention has been described above with reference to the accompanying drawings, but the accompanying drawings are provided to aid the understanding of the present invention and should not be construed as limiting the scope of the present invention. Those skilled in the art will appreciate that a variety of applications and modifications can be made to those described in the accompanying drawings.

According to the synthesizing apparatus and method of synthesizing the zinc oxide nanostructures of the present invention, mass synthesis of the zinc oxide nanostructures can be performed in a reactor tube. Accordingly, by increasing the synthesis yield of zinc oxide nanostructures having a diameter of several nm to hundreds of nm, it provides benefits for industrial applications of zinc oxide nanostructures that can maximize the efficiency of the optical and electrical properties proven in many studies You can do it.

Claims (12)

(a) a catalyst source supply for supplying a catalyst source; (b) a reaction source supply for supplying a reaction source; (c) a reactor that provides a synthesis space for the zinc oxide nanostructures by the interaction between the pyrolysis and pyrolyzed gaseous sources of the catalyst source and the reaction source; And (d) Apparatus for mass synthesis of zinc oxide nanostructures comprising a gas outlet for discharging a gaseous source not involved in the reaction. The method of claim 1, The reactor is a large-scale synthesis apparatus of zinc oxide nanostructures, characterized in that the tube made of quartz or quartz comprising at least one resistance heating element. The method of claim 2, The resistance heating element is a mass synthesis apparatus of zinc oxide nanostructures, characterized in that having a temperature range of 50 ℃ ~ 1600 ℃. The method of claim 1, Apparatus for mass synthesis of zinc oxide nanostructures further comprising an inert carrier gas supply for supply and delivery of reaction sources and catalyst sources. The method of claim 4, wherein Mass production apparatus of the zinc oxide nanostructures, characterized in that the flow of the carrier gas supplied by the inert carrier gas supply is 10 ~ 5000 sccm. The method according to claim 4 or 5, The catalyst source supply part and the reaction source supply part are installed outside the reactor, and further include a vaporizer, so that the catalyst source and the reaction source is supplied into the reactor by the inert carrier gas from the vaporizer, characterized in that the zinc oxide nano Mass synthesizer of structures. The method according to claim 4 or 5, A catalyst source supplying unit and a reaction source supplying unit are installed inside the reactor, and the catalyst source and the reaction source is a mass synthesis apparatus of the zinc oxide nanostructures, characterized in that for transporting to the place where the synthesis of the nanostructures by the inert carrier gas. The method of claim 4, wherein The gas discharge unit is a mass synthesis device of zinc oxide nanostructures, characterized in that also discharged with an inert carrier gas. The method of claim 1, The reactor is a mass synthesis apparatus of zinc oxide nanostructures, characterized in that the vertical reactor or horizontal reactor. The method of claim 8, The reactor is a vertical reactor, the mass synthesis apparatus of the zinc oxide nanostructures further comprises a collector for collecting the synthesized zinc oxide nanostructures. The method of claim 1, The reactor is a mass synthesis apparatus of zinc oxide nanostructures further comprises an injector capable of injecting a source supplied from the reaction source supply or the catalyst source supply. (Iii) an organometallic compound catalyst source selected from the group consisting of Fe (CO) ₅ , Mo (CO) ₆ , Co ₂ (CO) ₈ , (C ₅ H ₅ ) ₂ Fe, Ni (CO) ₅ , and zinc acetate powder Injecting a metal nanoparticle catalyst source or a zinc acetate powder catalyst source into a high temperature reactor to pyrolyze to provide a nucleation site of the reaction source; (Ii) ZnO powder, Zn powder, Zn pellet, Zn metal, Zn metal, Zn nitrate powder, DEZn (diethyl zinc), DMZn Pyrolysis in a high temperature reactor by injecting a gaseous or liquid reaction source selected from the group consisting of (dimethyl zinc) and a zinc nitrate solution into the reactor; (Iii) initiating the synthesis of the nanostructure by the pyrolysed gaseous reaction source generating nuclei at nucleation sites provided by the gaseous catalyst source; And (Iii) A method of mass synthesis of zinc oxide nanostructures comprising the step of completing the synthesis of zinc oxide nanostructures.

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