WO2013125929A1 - Solution reaction apparatus and solution reaction method using the same - Google Patents

Description

Solution Reactor and Solution Reaction Method Using The Same

The present invention relates to a solution reaction apparatus and a solution reaction method using the same, and more particularly, using a substrate, a sealing member, and a reaction vessel forming member to form a reaction vessel having a bottom portion of the substrate, and adding the reaction solution to the reaction vessel. The present invention relates to a solution reaction apparatus capable of controlling the temperature of the substrate and the temperature of the solution differently by supporting only one surface of the solution in contact with the solution, and a solution reaction method using the same.

Research is currently being conducted to fabricate semiconductor devices, optical devices, and memory devices using the unique electrical, optical, and magnetic properties of nanomaterials. Technology to grow is essential. Conventionally, these device structures have been implemented by a top-down method in which a semiconductor thin film is first grown and then the structure remains at a desired position through etching. However, the etching in this way is inevitable physical and chemical damage of the deposition material by the process, and the fatal problem of the existing process acts as an inhibitory factor for implementing an active optical device such as a laser.

Due to the problems of the top-down method, a bottom-up method for selectively growing nanomaterials has been researched and developed. The basic concept is different from the existing top-down method, and thus a desired material is selected in a selected region without introducing an etching process. There is an advantage to grow to the desired form. As a bottom-up method, a method of forming a microstructure through a chemical reaction in a solution is easy for low temperature and mass production, and the research is being actively conducted. The general method of hydrothermal synthesis of the crystal reaction method using a solution reaction, that is, a chemical reaction occurring in the solution is to mix the reaction solution and the additives necessary for the growth of the crystal together with the metal, the inorganic oxide and the hydrate, and the suspension is a high-pressure reactor as a reactor. It is a method of synthesizing or growing crystals at a temperature of about 300 ° C. or below and a pressure of 100 Mpa or less. It is known that crystals can be grown.

This conventional hydrothermal synthesis method has the advantage that the crystal growth at a relatively low temperature, and mass production is possible than the catalyst and vacuum deposition method. However, since the substrate itself was immersed and reacted in the reaction solution of the high pressure reactor, the temperature of the substrate and the solution had to be the same, and it was impossible to change the type and concentration of the solution as the reaction proceeded. Since there is a need to mix at a time, there was a problem that it is impossible to sequentially inject the reaction solution as the reaction proceeds.

The present invention is to solve the above problems, by improving the conventional technique using the hydrothermal synthesis, by forming a reaction vessel with the substrate to the bottom without immersing the substrate in the solution to separate the temperature of the substrate and the reaction solution It is an object of the present invention to provide a new solution reaction apparatus which can be controlled and can circulate the reaction solution during the reaction to freely control the temperature and concentration of the reaction solution.

Another object of the present invention is to provide a solution reaction method using the solution reaction device according to the present invention.

The present invention to solve the above problems

Board;

A sealing member laminated on one surface of the substrate;

A reaction container forming member laminated on the sealing member and forming a reaction container capable of supporting a reaction solution for solution reaction with the substrate as a bottom portion; And

It provides a solution reaction apparatus comprising a reaction solution circulation unit for circulating the reaction solution into the reaction vessel formed of the substrate, the sealing member and the reaction vessel forming member.

In the solution reaction apparatus of the present invention, the substrate is selected from Si, Al ₂ O ₃ , GaN, GaAs, ZnO, InP, SiC, glass and plastic substrate.

In the solution reaction apparatus of the present invention, the plastic substrate is polyethylene naphthalate (PEN), polyethylene terephthalate (PET), polyethersulfone (PES), polyimide, polycarbonate, cyclic olefin copolymer or mixtures thereof. Characterized in that selected from the group consisting of.

In the solution reaction apparatus of the present invention, the sealing member is characterized in that the O-ring or silicon.

In the solution reaction apparatus of the present invention, the reaction vessel forming member is made of Teflon, epoxy or urethane.

In the solution reaction apparatus of the present invention, the substrate further comprises a buffer layer.

In the solution reaction apparatus of the present invention, the substrate is characterized in that it further comprises a nanostructure layer.

In the solution reaction apparatus of the present invention, the reaction solution circulation portion inlet for injecting the reaction solution for the solution reaction treatment of the substrate into the reaction vessel formed of the substrate and the reaction vessel forming member; An outlet for outflowing the reaction solution from the reaction vessel; And a circulation pump connected to each of the inlet and the outlet to circulate the reaction solution.

In the solution reaction apparatus of the present invention, the inlet is characterized in that a plurality is included.

In the solution reaction apparatus of the present invention, the outlet portion is characterized in that a plurality is included.

Solution reaction apparatus of the present invention is characterized in that it further comprises a control unit.

Solution reaction apparatus of the present invention is characterized in that it further comprises a temperature sensor.

Solution reaction apparatus of the present invention is characterized in that it further comprises a heating device for heating the substrate in the lower portion of the substrate.

The present invention also provides a method for preparing a substrate for solution reaction treatment;

Installing a sealing member on an upper surface of the substrate;

Installing a reaction vessel forming member on top of the sealing member;

Introducing a reaction solution into a reaction vessel formed of the substrate, the sealing member and the reaction vessel forming member; And

It provides a solution reaction method consisting of; flowing out the reaction solution from the reaction vessel.

Hereinafter, the present invention will be described in more detail with reference to the drawings.

1 and 3 are perspective views of the solution reaction apparatus according to the present invention, Figures 2 and 4 show an exploded perspective view thereof.

1 to 2, the solution reaction apparatus according to the present invention comprises a substrate (10, 100) for solution reaction treatment; A sealing member (20, 200) laminated on one surface of the substrate and forming a circular closed space along an edge of the substrate; A reaction vessel forming member (30, 300) stacked on the sealing member and forming a reaction vessel capable of supporting a reaction solution for solution reaction with the substrate as a bottom portion; And a reaction solution circulation unit 50, 51, 60, 61; 500, 510, 600, 610 for circulating the reaction solution into the reaction vessel formed of the substrate, the sealing member, and the reaction vessel forming member.

In the solution reaction apparatus according to the present invention, the sealing members 20 and 200 and the reaction vessel forming members 30 and 300 are sequentially stacked on the substrate, so that the substrate may be used as the bottom to support the solution reaction solution. Form the reaction vessel.

The sealing members 20 and 200 are provided between the substrate and the reaction vessel forming member to be made of an elastic material to serve to seal between the reaction vessel forming member and the substrate. If the stackable closed curve shape is not limited to the overall shape, it is possible to form a circle 20 as shown in Figs. 1 and 2, or a quadrangle 200 as shown in Figs.

Specifically, in the present invention, it is preferable that the sealing members 20 and 200 use O-rings or silicon.

The reaction vessel forming members 30 and 300 may be formed to have a predetermined height in the same shape as the sealing member so that the reaction vessel may be formed while pressing the sealing members 20 and 200, and Teflon and epoxy may be used. Or it is preferable to use a urethane material.

In the solution reaction apparatus of the present invention, the substrate 10 is a substrate for solution reaction treatment, the material is not particularly limited, Si, Al ₂ O ₃ , GaN, GaAs, ZnO, InP, SiC, glass and plastic One selected from the substrates can be used.

In the solution reaction apparatus of the present invention, the plastic substrate is polyethylene naphthalate (PEN), polyethylene terephthalate (PET), polyethersulfone (PES), polyimide, polycarbonate, cyclic olefin copolymer or mixtures thereof. Characterized in that selected from the group consisting of.

In the present invention, as the substrate, a buffer layer may be already deposited on the substrate, or a substrate on which the nanostructure is already formed may be used. That is, it is possible to use a substrate on which ITO is deposited on a glass substrate or a substrate on which FTO is deposited on a glass substrate.

In the solution reaction apparatus of the present invention, the nanostructure may be further formed on the substrate on which the nanostructure is already formed by adjusting the temperature, the concentration, the injection rate, and the injection timing of the incoming reaction solution.

In the solution reaction apparatus according to the present invention as shown in Figure 5, the reaction solution circulation portion inlet 50 for injecting the reaction solution for the solution reaction treatment of the substrate into the reaction vessel formed of the substrate and the reaction vessel forming member ); An outlet part 60 for outflowing the reaction solution from the reaction vessel; It is characterized in that it comprises a circulation pump (51, 61) connected to each of the inlet, the outlet and circulating the reaction solution.

As shown in FIG. 6, in the solution reaction apparatus according to the present invention, the inlet 50 introduces the reaction solution from the external reaction solution storage 52 into the reaction vessel, and the outlet 60 is The reaction solution is circulated in the reaction vessel while the reaction solution flows out of the reaction vessel into the external reaction solution reservoir 62.

The inlet portion 50 and the outlet portion 60 are formed independently of the reaction vessel forming member as shown in FIGS. 5 and 6, or the side surfaces of the reaction vessel forming member 30 as shown in FIG. 5. It is possible to form directly connected.

Solution reaction apparatus according to the present invention may further include a control unit 70 as shown in FIG.

As shown in FIG. 8, the control unit 70 is connected to an inlet circulation pump or an outlet circulation pump 51, 61 to change the speed of the reaction solution flowing into the reaction vessel, or flow out of the reaction vessel. It is possible to change the speed of the reaction solution to be produced. In addition, as shown in FIG. 8, it may be separately connected to each circulation pump, or as shown in the controller 70 ′ of FIG. 9, the inlet circulation pump and the outlet circulation pump may be simultaneously connected and integratedly controlled.

In addition, although not separately shown, in the solution reaction apparatus according to the present invention, the controller may be connected to the heating device 40 of the substrate to control the temperature of the substrate.

In the solution reaction apparatus according to the present invention, as shown in FIG. 10, the inlet or the outlet may be provided in plural as necessary. That is, in this case, by connecting each circulation pump to the controller 70 ″, it is possible to inject a plurality of reaction solutions at different temperatures, or to react at a time difference.

The solution reaction apparatus according to the present invention may further include heating devices 40 and 400 for heating the substrate under the substrate as shown in FIGS. 1 to 11. Heating devices 40 and 400 for heating the substrate may be used, such as a heating plate, but is not particularly limited, it is possible to use a device used to heat the substrate in a general chemical vapor deposition or the like. As described above, the temperature of the substrate can be adjusted independently of the temperature of the solution supplied into the upper reaction vessel of the substrate by the substrate heating apparatus 40.

As shown in FIG. 11, in the solution reaction apparatus according to the present invention, it is possible to further include a temperature sensor 80 in the reaction vessel. As shown in FIG. 11, the temperature sensor 80 may be connected to the control unit 70 to operate a heater according to the temperature in the reaction vessel, or to change the injection rate of the reaction solution into the solution reactor.

Method for the solution reaction using the solution reaction apparatus as described above of the present invention comprises the steps of preparing a substrate for solution reaction treatment;

Installing a sealing member on an upper surface of the substrate;

Installing a reaction vessel forming member on top of the sealing member;

Introducing a reaction solution into a reaction vessel formed of the substrate, the sealing member and the reaction vessel forming member; And

Condensing the reaction solution from the reaction vessel.

In the solution reaction apparatus of the present invention, the temperature of the substrate and the temperature of the reaction solution can be adjusted separately. Accordingly, it is possible to adjust the temperature of the solution to above the boiling point of the solution, and keep the concentration of the solution constant by the solution circulation device. Since it is possible to react while being able to freely generate various nanostructures on the substrate.

1 to 4 show a perspective view and an exploded perspective view of the solution reaction apparatus according to the present invention.

5-11 shows the schematic diagram of the solution reaction apparatus by this invention.

12 shows the results of manufacturing the zinc oxide nanostructures prepared by the solution reaction apparatus and the solution reaction method according to an embodiment of the present invention.

Figure 13 shows the results of manufacturing the zinc oxide nanostructures prepared by the solution reaction apparatus and the solution reaction method according to an embodiment of the present invention.

Figure 14 shows the results of manufacturing the zinc oxide nanostructures prepared by the solution reaction apparatus and the solution reaction method according to an embodiment of the present invention.

FIG. 15 shows an SEM image of the zinc oxide nanostructures prepared while changing the type, concentration and inflow rate of the reaction solution, substrate temperature, and growth time.

Figure 16 shows the growth time at (a) 1 minute, (b) 5 minutes, (c) 10 minutes, (d) 20 minutes, (e) 40 minutes, (f) 60 minutes and (g) at a growth temperature of 120 ° C. SEM images of the zinc oxide nanostructures prepared while changing to 100 minutes are shown, and FIG. 14 shows the results of measuring the length, diameter, aspect ratio, and growth rate of the nanostructures grown at each time.

17 shows a growth time of 20 minutes, a growth temperature of (a) 100 ° C, (b) 110 ° C, (c) 120 ° C, (d) 130 ° C, (e) 140 ° C, (f) 150 ° C, SEM images of the zinc oxide nanostructures prepared while changing to (g) 160 ° C, (h) 170 ° C, (i) 180 ° C, (j) 190 ° C, (k) 200 ° C, and (l) 210 ° C are shown. 18 shows the results of measuring the length, diameter, aspect ratio and growth rate of the nanostructures grown at each temperature.

19 shows the result of comparing the zinc oxide growth rate in the Example of this invention and a comparative example.

FIG. 20 is a SEM photograph of the copper oxide nanostructure of Example 5 of the present invention, and a SEM photograph of the copper oxide nanostructures published in Journal of Alloys and Compounds 511 (2012) 195. 197 as a comparative example. It was.

Hereinafter, the present invention will be described in more detail with reference to Examples. However, the present invention is not limited by the following examples.

Example 1 Preparation of Zinc Oxide Nanostructure Using Glass Substrate

Zinc oxide nanostructures were prepared by a solution reaction method on a glass substrate using the solution reaction apparatus prepared in Example 1 above.

First, a solution reaction apparatus as in FIG. 1 was prepared. A glass substrate having 50 nm of ITO deposited was used as a substrate, an O-ring was used as a sealing member, and Teflon was used as a reaction vessel forming member.

Zinc acetate and an aqueous ammonia solution were used as a reaction solution for growing zinc oxide, and the substrate was placed on a heating plate and the temperature of the substrate was adjusted to (a) 150 ° C, (b) 160 ° C and (c) 180 ° C, respectively. Zinc oxide nanoparticles were formed and the SEM photograph is shown in FIG. 12.

Example 2 Fabrication of Zinc Oxide Nanostructure Using Silicon Substrate

Zinc oxide nanostructures were prepared in the same manner as in Example 1, except that a silicon substrate having a 50 nm zinc oxide buffer layer was already used as the substrate.

Zinc acetate and an aqueous ammonia solution were used as a reaction solution for growing zinc oxide. The substrate was placed on a heating plate, the temperature of the substrate was adjusted to 150 ° C., and the reaction time was (a) 10 minutes, (b) 30 minutes, (c) Zinc oxide nanoparticles were formed while adjusting to 60 minutes, and the SEM photograph is shown in FIG.

Example 3 Preparation of Zinc Oxide Nanostructures

As a substrate, a silicon substrate having a 50 nm zinc oxide buffer layer was already used, and two reaction solutions were used, and zinc oxide was changed while changing the type, concentration and inflow rate, substrate temperature, and growth time as shown in Table 1 below. Nanostructures were prepared, and SEM photographs of the prepared zinc oxide nanostructures are shown in FIG. 14.

Table 1 Reaction solution 1 Reaction solution 2 Reaction solution inlet rate Substrate temperature ℃ Reaction time a Zinc Acetate0.005M Ammonia 40: 1 5 95 10 minutes b Zinc Acetate 0.005M Ammonia 40: 1 7 160 30 minutes c Zinc Acetate 0.005M Ammonia 40: 1 5 95 10 minutes d Zinc Acetate 0.005M Hexamethylenetetramine 0.01M 5 100 2 hours

Example 4 Preparation of Zinc Oxide Nanostructures

Example 4-1 Zinc Oxide Nanostructures According to Growth Time

As a substrate, a silicon substrate having a 50 nm zinc oxide buffer layer was already used, and a reaction solution was prepared by mixing zinc acetate 0.01M and ammonia at a ratio of 10: 1, and having an inflow rate of 2.5-5 rpm at a growth temperature of 120 ° C. Zinc oxide was changed to (a) 1 minute, (b) 5 minutes, (c) 10 minutes, (d) 20 minutes, (e) 40 minutes, (f) 60 minutes and (g) 100 minutes at The nanostructures were prepared, and SEM photographs of the prepared zinc oxide nanostructures are shown in FIG. 15.

The length, diameter, aspect ratio and growth rate of the grown nanostructures were measured and shown in FIG. 16. 16, it can be seen that as the growth time increases, the diameter, aspect ratio, and growth rate increase.

Example 4-2 Fabrication of Zinc Oxide Nanostructures According to Growth Temperature

As a substrate, a silicon substrate having a 50 nm zinc oxide buffer layer was already used, and a reaction solution was prepared by mixing zinc acetate 0.01M and ammonia at a ratio of 10: 1, and introducing a growth rate of 2.5 to 5 rpm to achieve a growth time of 20 The growth temperature is (a) 100 ° C, (b) 110 ° C, (c) 120 ° C, (d) 130 ° C, (e) 140 ° C, (f) 150 ° C, (g) 160 ° C, ( h) Zinc oxide nanostructures were prepared while changing to 170 ° C, (i) 180 ° C, (j) 190 ° C, (k) 200 ° C, and (l) 210 ° C, and SEM images of the prepared zinc oxide nanostructures were obtained. It is shown in FIG. The length, diameter, aspect ratio and growth rate of the grown nanostructures were measured and shown in FIG. 18.

As a comparative example, the zinc growth rate when zinc oxide was prepared by electrochemical method, CBD method and MOCVD method using data in the literature is shown in FIG. 19. In Figure 19, the production method of the embodiment of the present invention showed the highest growth rate.

Example 5 Fabrication of Copper Oxide Nanostructures

A washed FTO substrate was used as a substrate, and a solution was prepared using Cu (OAc) ₂ H ₂ O, 2-Methoxyethanol (2-ME), and Monoethanolamine (MEA). The coating was spun for 30 seconds and then dried in air for 10 minutes. This process was repeated three times, and the nanostructure was grown for 20 minutes at 175 ° C. with a Cu (OAc) ₂ H ₂ O solution and an aqueous ammonia solution using the solution reaction apparatus prepared in Example 1, and then using ultrapure water. After washing it was dried.

As a comparative example, L. Liu prepared a copper oxide nanostructure by the method described in Journal of Alloys and Compounds 511 (2012) 195. 197. Specifically, an FTO substrate was used, soaked in a Cu (OAc) ₂ H ₂ O ethanol solution for 10 seconds as a reaction solution, dried in air and heat-treated at 100 ° C. for 1 minute. Thereafter, heat treatment was further performed at 250 ° C. for 150 minutes _{, the} nanostructures were grown at 75 ° C. for 240 minutes with a u (OAc) ₂ H ₂ O solution and HMTA aqueous solution, and then washed with ultrapure water and dried.

SEM pictures of the copper oxide nanostructures of Example 5 are shown in FIG. 20 and SEM pictures of the copper oxide nanostructures published in the Journal of Alloys and Compounds 511 (2012) 195. 197 as comparative examples. In Figure 21 (a) is 85 ℃, (b) is 80 ℃, (c) shows a SEM image of the structure grown at 75 ℃.

The characteristics of each of the nanostructures prepared in Example 5 and the nanostructures prepared at 75 ° C. as the comparative examples were measured and shown in Table 2 below.

TABLE 2 Example 4 Comparative example Process time 240 minutes 20 minutes Nanorod length About 900 nm About 1600 nm Nanorod diameter About 60 nm About 70 nm Aspect ratio About 15 About 23 Growth rate About 3.8 nm / min About 80 nm / min

As shown in Table 2, the copper oxide prepared according to the embodiment of the present invention increases the length, diameter and aspect ratio of the nanostructure, and it can be seen that the present invention exhibits an effect of 20 times or more compared to the comparative example in the case of growth rate. have.

Claims (14)

Board; A sealing member laminated on one surface of the substrate; A reaction container forming member laminated on the sealing member and forming a reaction container capable of supporting a reaction solution for solution reaction with the substrate as a bottom portion; And And a reaction solution circulation unit configured to circulate the reaction solution into the reaction container formed of the substrate, the sealing member, and the reaction vessel forming member. The method of claim 1, Wherein said substrate is selected from Si, Al ₂ O ₃ , GaN, GaAs, ZnO, InP, SiC, glass and plastic substrates. The method of claim 2, The plastic substrate is selected from the group consisting of polyethylene naphthalate (PEN), polyethylene terephthalate (PET), polyethersulfone (PES), polyimide, polycarbonate, cyclic olefin copolymer or mixtures thereof. Solution reaction apparatus. The method of claim 1, The sealing member is a solution reaction device, characterized in that the O-ring or silicone rubber. The method of claim 1, The reaction vessel forming member is a solution reaction apparatus, characterized in that the Teflon, epoxy or urethane material. The method of claim 1, The substrate is a solution reaction device, characterized in that it further comprises a buffer layer. The method of claim 1, The substrate further comprises a nanostructure layer solution solution device. The method of claim 1, The reaction solution circulation unit An inlet for injecting a reaction solution for solution reaction treatment of the substrate into a reaction vessel formed of the substrate and the reaction vessel forming member; An outlet for outflowing the reaction solution from the reaction vessel; And And a circulation pump connected to the inlet and the outlet, respectively, to circulate the reaction solution. The method of claim 8, Solution inlet unit, characterized in that a plurality of inlets are included. The method of claim 8, Solution reaction apparatus characterized in that the outlet portion is included a plurality. The method of claim 1, The solution reaction device further comprises a control unit. The method of claim 1, The solution reaction device further comprises a temperature sensor. The method of claim 1, Solution heating apparatus further comprises a heating device for heating the substrate under the substrate. Preparing a substrate for solution reaction treatment; Installing a sealing member on an upper surface of the substrate; Installing a reaction vessel forming member on top of the sealing member; Introducing a reaction solution into a reaction vessel formed of the substrate, the sealing member and the reaction vessel forming member; And Outflowing the reaction solution from the reaction vessel; Solution reaction method consisting of.

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