Solution reaction apparatus and solution reaction method using the same

Abstract

The present invention relates to a solution reaction apparatus and solution reaction method using the same, and more particularly a solution reaction apparatus and a solution reaction method using the same, wherein a reaction vessel is made by using a sealing member, a reaction vessel forming member, and a substrate serving as the bottom part of the reaction vessel so as to cause one side of a reaction solution only to contact the solution, thereby adjusting the temperature of the substrate differently from the temperature of the solution. The solution reaction apparatus of the present invention can control temperature of the substrate and temperature of the reaction solution separately, thereby it can control the temperature of the solution above the boiling point of the solution, and can react the solution while constantly maintaining the concentration of the solution by the solution circulatory device. Accordingly, it has an effect of freely forming various nanostructures on the substrate.

Claims

1. A solution reaction apparatus, which comprises: a substrate; a sealing member laminated on one side of the substrate; a reaction vessel forming member being laminated on the sealing member and forming a reaction vessel, which can contain reaction solution for solution reaction, using the substrate as a bottom part; and a reaction solution circulatory part circulating the reaction solution into the reaction vessel, which is formed from the substrate, the sealing member and the reaction vessel forming member, wherein the substrate comprises a nanostructure layer.

2. The solution reaction apparatus according to claim 1, wherein the substrate is selected from the group consisting of Si, Al.sub.2O.sub.3, GaN, GaAs, ZnO, InP, SiC, glass and plastic substrates.

3. The solution reaction apparatus according to claim 2, wherein the plastic substrate is selected from the group consisting of polyethylene naphthalate (PEN), polyethylene terephthalate (PET), polyether sulfone (PES), polyimide, polycarbonate, cyclic olefin copolymer and a mixture thereof.

4. The solution reaction apparatus according to claim 1, wherein the sealing member is O-ring or silicon rubber.

5. The solution reaction apparatus according to claim 1, wherein the reaction vessel forming member is made of Teflon, epoxy or urethane.

6. The solution reaction apparatus according to claim 1, wherein the substrate further comprises a buffer layer.

7. The solution reaction apparatus according to claim 1, wherein the reaction solution circulatory part comprises: an inlet, which inpours the reaction solution for solution reaction treatment of the substrate into the reaction vessel formed from the substrate and the reaction vessel forming member; an outlet, which outpours the reaction solution from the reaction vessel; and a circulation pump, which is connected to the inlet and the outlet, respectively, and circulates the reaction solution.

8. The solution reaction apparatus according to claim 7, which comprises a plurality of the inlets.

9. The solution reaction apparatus according to claim 7, which comprises a plurality of the outlets.

10. The solution reaction apparatus according to claim 1, wherein the solution reaction apparatus further comprises a control part.

11. The solution reaction apparatus according to claim 1, wherein the solution reaction apparatus further comprises a temperature sensor.

12. The solution reaction apparatus according to claim 1, which further comprises a heating part for heating the substrate at the bottom of the substrate.

Description

BRIEF DESCRIPTION OF DRAWINGS

(1) The above and other objects and features of the present invention will become apparent from the following description of the invention taken in conjunction with the following accompanying drawings, which respectively show:

(2) FIG. 1 to FIG. 4: perspective views and exploded perspective views of the solution reaction apparatus according to the present invention;

(3) FIG. 5 to FIG. 11: schematic diagrams of the solution reaction apparatus according to the present invention;

(4) FIG. 12: results of manufacturing zinc oxide nanostructures by the solution reaction apparatus and the solution reaction method according to one Example of the present invention;

(5) FIG. 13: results of manufacturing zinc oxide nanostructures by the solution reaction apparatus and the solution reaction method according to one Example of the present invention;

(6) FIG. 14: results of manufacturing zinc oxide nanostructures by the solution reaction apparatus and the solution reaction method according to one Example of the present invention;

(7) FIG. 15: SEM images of the zinc oxide nanostructures, which are manufactured by changing the growth time to (a) 1 min, (b) 5 min, (c) 10 min, (d) 20 min, (e) 40 min, (f) 60 min and (g) 100 min at the growth temperature of 120 C.;

(8) FIG. 16: results of measuring length, diameter, aspect ratio and growth rate of the nanostructure grown at each time;

(9) FIG. 17: SEM images of the zinc oxide nanostructures, which are manufactured by changing the growth temperature to (a) 100 C., (b) 110 C., (c) 120 C., (d) 130 C., (e) 140 C., (f) 150 C., (g) 160 C., (h) 170 C., (i) 180 C., (j) 190 C., (k) 200 C. and (l) 210 C. for the growth time of 20 min;

(10) FIG. 18: results of measuring length, diameter, aspect ratio and growth rate of the nanostructure grown at each temperature;

(11) FIG. 19: results of comparing the growth rate of the zinc oxide in Example of the present invention and Comparative Examples;

(12) FIG. 20: SEM images of the copper oxide nanostructure of Example 5 of the present invention; and

(13) FIG. 21: SEM images of the copper oxide nanostructure disclosed in [Journal of Alloys and Compounds 511 (2012) 195. 197] as Comparative Example.

DETAILED DESCRIPTION OF THE INVENTION

(14) Hereinafter, the present invention will be described in further detail with reference to examples, and the scope of the present invention cannot be limited thereby in any way.

Example 1

Manufacturing of Zinc Oxide Nanostructure Using Glass Substrate

(15) Zinc oxide nanostructures were manufactured on a glass substrate by the solution reaction method as follows.

(16) First of all, a solution reaction apparatus was manufactured as illustrated in FIG. 1. As a substrate, a glass substrate on which ITO was deposited to a thickness of 50 nm, as a sealing member on the substrate, an O-ring was used, and as a reaction vessel forming member, Teflon was used.

(17) Zinc acetate and ammonia aqueous solution were used as a reaction solution for growing zinc oxide. The substrate was installed on a heating plate, and zinc oxide nanoparticles were formed by controlling the temperature of the substrate to (a) 150 C., (b) 160 C. and (c) 180 C., respectively. SEM images are shown in FIG. 12.

Example 2

Manufacturing of Zinc Oxide Nanostructure Using Silicon Substrate

(18) The procedure of Example 1 was repeated except for using a silicon substrate on which a 50 nm zinc oxide buffer layer was already formed as a substrate to manufacture zinc oxide nanostructures.

(19) Zinc acetate and ammonia aqueous solution were used as a reaction solution for growing zinc oxide. The substrate was installed on a heating plate, and zinc oxide nanoparticles were formed by controlling the temperature of the substrate to 150 C. and the reaction time to (a) 10 min, (b) 30 min and (c) 60 min, respectively. SEM images are shown in FIG. 13.

Example 3

Manufacturing Zinc Oxide Nanostructure

(20) A silicon substrate on which a 50 nm zinc oxide buffer layer was already formed was used as a substrate, and zinc oxide nanostructures were manufactured by using two kinds of reaction solution but changing the type, concentration, inpouring rate, substrate temperature and growth time of each kind of reaction solution as shown in the following Table 1. SEM images of the manufactured zinc oxide nanostructures are shown in FIG. 14.

(21) TABLE-US-00001 TABLE 1 Reaction Solution Substrate Reaction Reaction Inpouring Temperature Reaction Solution 1 Solution 2 Rate ( C.) Time a Zinc Ammonia 5 95 10 min Acetate 40:1 0.005M b Zinc Ammonia 7 160 30 min Acetate 40:1 0.005M c Zinc Ammonia 5 95 10 min Acetate 40:1 0.005M d Zinc Hexamethylene 5 100 2 hr Acetate Tetramine 0.005M 0.01M

Example 4

Manufacturing Zinc Oxide Nanostructure

Example 4-1

Manufacturing Zinc Oxide Nanostructure Depending on Growth Time

(22) A silicon substrate on which a 50 nm zinc oxide buffer layer was already formed was used as a substrate, a mixture of zinc acetate 0.01 M and ammonia at the ratio of 10:1 was used as a reaction solution, and zinc oxide nanostructures were manufactured by changing the inpouring rate from 2.5 to 5 rpm and the growth time to (a) 1 min, (b) 5 min, (c) 10 min, (d) 20 min, (e) 40 min, (f) 60 min and (g) 100 min at the growth temperature 120 C. SEM images of the manufactured zinc oxide nanostructures are shown in FIG. 15.

(23) The length, diameter, aspect ratio and growth rate of the grown nanostructure were measured, and the results were shown in FIG. 16. In FIG. 16, it can be found that the length, diameter, aspect ratio and growth rate are increased as the growth time is increased.

Example 4-2

Manufacturing Zinc Oxide Nanostructure Depending on Growth Temperature

(24) A silicon substrate on which a 50 nm zinc oxide buffer layer was already formed was used as a substrate, a mixture of zinc acetate 0.01 M and ammonia at the ratio of 10:1 was used as a reaction solution, and zinc oxide nanostructures were manufactured by changing the inpouring rate from 2.5 to 5 rpm and the growth temperature to (a) 100 C., (b) 110 C., (c) 120 C., (d) 130 C., (e) 140 C., (f) 150 C., (g) 160 C., (h) 170 C., (i) 180 C., (j) 190 C., (k) 200 C. and (l) 210 C. for the growth time of 20 min. SEM images of the manufactured zinc oxide nanostructures are shown in FIG. 17. The length, diameter, aspect ratio and growth rate of the grown nanostructure were measured, and the results were shown in FIG. 18.

(25) As Comparative Examples, using data in literature, the zinc growth rates when manufacturing the zinc oxide by electrochemical method, CBD method and MOCVD method were shown in FIG. 19. In FIG. 19, the manufacturing method of Example according to the present invention shows the fastest growth rate.

Example 5

Manufacturing Copper Oxide Nanostructure

(26) A washed FTO substrate was used as a substrate, and a solution was prepared by using Cu(OAc).sub.2H.sub.2O, 2-Methoxyethanol (2-ME) and monoethanolamine (MEA). The prepared solution was spin-coated on the substrate at 4000 rpm for 30 sec followed by drying in the air for 10 min. This procedure was repeated three times, and the nanostructure was grown with Cu(OAc).sub.2.H.sub.2O solution and ammonia aqueous solution at 175 C. for 20 min by using the solution reaction apparatus manufactured in Example 1, followed by washing with ultra-pure water and dried.

(27) As Comparative Example, copper oxide nanostructures were manufactured by the method of L. Liu disclosed in Journal of Alloys and Compounds 511 (2012) 195. 197. Specifically, a FTO substrate was used, and it was soaked in Cu(OAc).sub.2.H.sub.2O ethanol solution as a reaction solution for 10 sec, dried in the air, heated at 100 C. for 1 min, and then, further heated at 250 C. for 150 min. Nanostructures were grown with Cu(OAc).sub.2.H.sub.2O solution and HMTA aqueous solution at 75 C. for 240 min, washed with ultra-pure water and then dried. SEM images of the copper oxide nanostructures of Example 5 were shown in FIG. 20, and SEM images of the cooper oxide nanostructures disclosed in Journal of Alloys and Compounds 511 (2012) 195. 197 as Comparative Example were shown in FIG. 21. In FIG. 21, (a), (b) and (c) are the SEM images of the nanostructures grown at 85 C., 80 C. and 75 C., respectively.

(28) Characteristics of the nanostructure manufactured in Example 5 and the nanostructure manufactured at 75 C. as Comparative Example were measured, and the results were shown in the following Table 2.

(29) TABLE-US-00002 TABLE 2 Example 4 Comparative Example Processing Time 240 min 20 min 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

(30) As shown in Table 2, it can be found that the copper oxide manufactured by Example of the present invention shows increased length, diameter and aspect ratio of the nanostructure, and its growth rate is 20 times or more higher than Comparative Example.

(31) While the invention has been described with respect to the above specific embodiments, it should be recognized that various modifications and changes may be made and also fall within the scope of the invention as defined by the claims that follow.