CN103590084A - Apparatus and method used for quick preparation of nanostructured arrays - Google Patents

Abstract

The invention discloses a device and a method for rapidly preparing a nanostructure array. The device includes: a clamp, clamping a metal sheet; a nozzle, arranged opposite to the metal sheet, so as to be suitable for spraying electrolyte solution on the surface of the metal sheet; a motor, connected with the clamp to drive the clamp to rotate relative to the nozzle, move vertically or Horizontal movement; variable DC power supply, the anode of the variable DC power supply is electrically connected to the metal sheet, and the cathode of the variable DC power supply is electrically connected to the nozzle; the cavity is suitable for recovering the electrolyte sprayed on the surface of the metal sheet; and the refrigeration device is connected with the metal sheet. The cavity is connected with the nozzle, and the cooling device can cool the electrolyte in the cavity and supply the cooled electrolyte to the nozzle. In the present invention, the electrolyte is recovered and cooled and supplied to the nozzle again, and sprayed onto the surface of the metal sheet by the nozzle for electrochemical anodization, thereby eliminating the heat generated by increasing the electrochemical anodization voltage, so that the electrolytic anodization can be improved by increasing the electrolytic anodic oxidation voltage. The chemical anodizing voltage is used to increase the preparation rate of the nanostructure array, and in addition, the device is also suitable for preparing a large-area nanostructure array.

Description

A device and method for rapidly preparing nanostructure arrays

technical field

The invention relates to the technical field of preparation of nanostructure arrays, in particular to a device and method for rapidly preparing nanostructure arrays.

Background technique

In recent years, nanotechnology has developed vigorously and has shown broad application prospects in different fields. Among them, regular and periodic nanostructure array materials are widely used in the fields of photonic crystals, memory and optoelectronic devices. Periodic nanostructure arrays can usually be prepared by focused ion beam, template method, and electrochemical anodization. Among them, electrochemical anodization is a simple and low-cost method for preparing self-assembled nanostructure arrays.

Nanostructure arrays prepared by electrochemical anodization include porous nanoarrays and nanotube arrays. Porous nano-arrays prepared electrochemically are more commonly porous anodized alumina. The preparation methods of anodized alumina include constant voltage, constant current or pulse oxidation, etc., and are prepared in electrolytes such as oxalic acid, sulfuric acid or phosphoric acid. The typical preparation process of anodized aluminum is to electrochemically oxidize metal aluminum flakes in 0.3M oxalic acid solution at a voltage of 40V at room temperature. Although this preparation method can obtain alumina nano-arrays with very good regularity, its further application is limited due to the low reaction rate and slow film growth.

In order to increase the growth rate of the film, in the process of electrochemical anodic oxidation, the growth rate of the film can be increased by increasing the voltage across the electrodes or changing the concentration of the electrolyte. However, due to the increased oxidation rate, the reaction generates a large amount of reaction heat, which will cause the temperature of the local electrolyte in the electrolytic cell to rise rapidly. If the heat is not removed in time, the formed film may be broken down. At the same time, the temperature rise of the electrolyte will also cause the dissolution of the formed film. In addition, under higher voltage conditions, the current density is higher (greater than 20mAcm ^-2 ), and more reaction heat is generated. When the size of the metal sheet is too large, it is not appropriate to remove too much by stirring in the electrolytic cell. The reaction is hot, so in the electrolytic cell, it cannot be anodized to prepare large-area nanostructure arrays. Therefore, the method of preparing nanostructure arrays by electrochemical anodization in an electrolytic bath is increasingly unable to meet the needs of the development of nanotechnology because of its low preparation rate and the inability to prepare large-area nanostructure arrays.

Contents of the invention

The purpose of the present invention is to provide a device capable of rapidly preparing large-area nanostructure arrays for the defects of the above-mentioned background technology.

In order to achieve the above object, the present invention provides a device for rapidly preparing nanostructure arrays, including: a clamp, clamping a metal sheet; a nozzle, arranged to be opposite to the metal sheet, so as to be suitable for spray electrolyte on the surface of the nozzle; a motor connected with the fixture to drive the fixture to rotate, move vertically or horizontally relative to the nozzle; a variable DC power supply, the anode of the variable DC power supply is electrically connected to the The metal sheet, the cathode of the variable DC power supply is electrically connected to the nozzle; a cavity is suitable for recovering the electrolyte sprayed on the surface of the metal sheet; and a refrigeration device is connected with the cavity and the nozzle connected, the cooling device can cool the electrolyte in the cavity and supply the cooled electrolyte to the nozzle.

Another object of the present invention is to provide a method for rapidly preparing a large-area nanostructure array using the above-mentioned device, comprising the following steps:

Clamp the metal sheet on the fixture;

Spraying an electrolyte solution onto the surface of the metal sheet through a nozzle to wet the surface of the metal sheet;

recovering the electrolyte sprayed onto the surface of the metal sheet in the cavity; and

The electrolyte in the cavity is cooled by a cooling device and the cooled electrolyte is re-supplied to the nozzle.

To sum up, the present invention provides a device and method for rapidly preparing nanostructure arrays by recovering and cooling the electrolyte solution and then supplying it to the nozzle again, and spraying it onto the surface of the metal sheet for electrochemical anode Oxidation, due to the circulating flow of the electrolyte and being cooled, the heat generated by increasing the electrochemical anodizing voltage can be eliminated, so that the preparation rate of the nanostructure array can be increased by increasing the electrochemical anodizing voltage. In addition, the device is also It is suitable for preparing large-area nanostructure arrays.

Description of drawings

FIG. 1 is a schematic cross-sectional structure diagram of a device for rapidly preparing nanostructure arrays according to the present invention.

Fig. 2 is a schematic cross-sectional structure diagram of the electrochemical anodizing device of the present invention.

Fig. 3 is a schematic diagram after coating the insulating polymer on the edge of the surface of the metal sheet and its sidewall.

Fig. 4 is a sectional view along line A-A' of Fig. 3 .

Figures 5(a) to 5(c) illustrate the process of preparing nanostructure arrays.

Fig. 6 is a flowchart of a method for rapidly preparing nanostructure arrays in the present invention.

Detailed ways

In order to describe the technical content, structural features, achieved goals and effects of the present invention in detail, the following will be described in detail in conjunction with the embodiments and accompanying drawings.

Please refer to FIG. 1 to FIG. 4 , a device for rapidly preparing nanostructure arrays in the present invention includes an electrochemical anodizing device and an electrolyte supply device.

The electrochemical anodizing device includes a fixture 101 , a nozzle 102 , a motor 103 , a variable DC power supply 109 and a voltage controller (not shown in the figure). The fixture 101 clamps a metal sheet 200 with a large size. The metal sheet 200 can be made of metals such as aluminum, titanium and tin, and different metals can be selected according to different requirements. The nozzle 102 is disposed opposite to the metal sheet 200 to be suitable for spraying the electrolytic solution 104 to the metal sheet 200 . The motor 103 is connected with the clamp 101 to drive the clamp 101 to rotate relative to the nozzle 102 , to move vertically or horizontally. The anode of the variable DC power supply 109 is electrically connected to the back of the metal sheet 200 through the clamp 101, and the cathode of the variable DC power supply 109 is electrically connected to the nozzle 102. In this embodiment, a programmable DC power supply is selected to provide power for electrochemical anodization. The voltage controller is connected with the variable DC power supply 109 and controls the voltage output of the variable DC power supply 109. The voltage controller controls the output voltage of the variable DC power supply 109 to be 10V to 300V. When the variable DC power supply 109 is turned on and the electrolyte 104 is sprayed to the metal sheet 200 , the nozzle 102 , the electrolyte 104 , the metal sheet 200 and the variable DC power supply 109 form a current loop to oxidize the metal sheet 200 .

The electrolyte supply device includes a cavity 105 , an electrolyte tank 106 , a cooling device 107 and a flow controller 108 . The cavity 105 is adapted to recover the electrolyte 104 sprayed onto the metal sheet 200. Specifically, during the electrochemical anodizing process of the metal sheet 200, the electrolyte 104 on the metal sheet 200 is thrown away due to the rotation of the clamp 101 driven by the motor 103. The metal sheet 200 falls into the cavity 105 . The electrolyte tank 106 communicates with the cavity 105 and the nozzle 102 respectively, the electrolyte 104 in the cavity 105 is introduced into the electrolyte tank 106, and flows into the cooling device 107 through the electrolyte tank 106, and the cooling device 107 cools the electrolyte 104 to The target temperature is set, and then the cooled electrolyte 104 is led back to the electrolyte tank 106 , and finally re-supplied from the electrolyte tank 106 to the nozzle 102 . A flow controller 108 is arranged between the electrolyte tank 106 and the nozzle 102, which is used to adjust the pressure and flow of the electrolyte 104, so as to supply the electrolyte 104 with a certain pressure and flow to the nozzle 102, and the nozzle 102 will cool the The electrolytic solution 104 is sprayed onto the surface of the metal sheet 200 to oxidize the metal sheet 200 .

The following briefly introduces the process of preparing nanostructure arrays using the above-mentioned device. First, before electrochemical anodization, move the clamp 101 so that the nozzle 102 is facing the center of the metal sheet 200, the nozzle 102 sprays the electrolyte 104 to the surface of the metal sheet 200, and the motor 103 drives the clamp 101 to rotate at a constant angular velocity, because Under the effect of centrifugal force, the electrolytic solution 104 sprayed onto the surface of the metal sheet 200 is scattered around the surface of the metal sheet 200, thereby fully wetting the surface of the metal sheet 200, and the surface of the metal sheet 200 is covered with a thin layer of electrolyte solution to avoid the The metal-air-electrolyte triple point appears on the surface of the metal sheet 200, because once the metal-air-electrolyte triple point occurs, the electric field distribution on the surface of the metal sheet 200 will be uneven and unable to Generate arrays of nanostructures.

After the step of wetting the surface of the metal sheet 200 and before the subsequent step of reclaiming the electrolyte sprayed onto the surface of the metal sheet in the cavity, the variable DC power supply 109 is switched on at a lower constant voltage The surface of the metal sheet 200 is oxidized and an oxide layer 400 is formed on the surface of the metal sheet 200 , as shown in FIG. 5( b ). In the process of forming the oxide layer 400, the electrochemical anodic oxidation voltage is relatively low. Taking the preparation of porous anodized aluminum as an example, in 0.3M oxalic acid solution at a temperature ^of 0°C, the oxidation voltage is less than 40V or the current density is less than 5mAcm- ² and under the condition that the oxidation time is 1 to 2 minutes, an aluminum oxide layer with a thickness of several hundred nanometers can be formed on the surface of the aluminum sheet.

The nozzle 102 continues to spray the electrolyte 104 on the surface of the metal sheet 200, while increasing the voltage of electrochemical anodization, the surface of the metal sheet 200 is further rapidly oxidized to form a nanostructure array 500, as shown in FIG. 5(c). Taking the preparation of porous anodic alumina in oxalic acid solution as an example, the oxidation voltage is increased to 70V to 130V, and the current density is 20mAcm ^-2 to 200mAcm ^-2 at this time, and the surface of metal aluminum is rapidly oxidized to form an alumina nanostructure array. Although increasing the voltage of electrochemical anodization can generate a large amount of heat in the process of forming the nanostructure array 500, yet, because the electrolyte 104 in this device is circulated and cooled, so the generated heat can be eliminated quickly, avoiding The generated heat damages the formed nanostructure array 500 . Due to factors such as ion diffusion, the oxidation reaction on the surface of the metal sheet 200 mainly occurs in the area facing the nozzle 102. Therefore, the central area of the surface of the metal sheet 200 is first oxidized, and then the horizontal movement of the clamp 101 and the rotation of the clamp 101 make the metal Other areas on the surface of the sheet 200 are oxidized, and then the nanostructure array 500 is formed on the entire surface of the metal sheet 200, so that a large-area nanostructure array 500 can be prepared. In addition, the angular velocity or linear velocity and rotation speed of the fixture 101 can be set according to the required thickness of the oxide.

Preferably, please refer to FIG. 3 and FIG. 4 , the edge of the surface of the metal sheet 200 and its sidewall are coated with a layer of insulating polymer 300 . In the electrochemical anodizing process, due to the existence of the edge section of the metal sheet 200, when the oxidation proceeds to the edge of the metal sheet 200, the current distribution on the metal sheet 200 will be uneven, and the edge of the metal sheet 200 surface and its Coating a layer of the insulating polymer 300 on the side wall can solve this problem well.

Please refer to Figures 5(a) to 5(c) and Figure 6, the present invention also provides a method for rapidly preparing nanostructure arrays using the above device, including the following steps:

S11: Clamp the metal sheet 200 on the fixture 101;

S12: using the nozzle 102 to spray the electrolyte 104 on the surface of the metal sheet 200 to wet the surface of the metal sheet 200;

S13: Recover the electrolyte 104 sprayed onto the surface of the metal sheet 200 in the cavity 105;

S14 : cooling the electrolyte 104 in the cavity 105 by the cooling device 107 and supplying the cooled electrolyte 104 to the nozzle 102 again.

Preferably, after wetting the surface of the metal sheet 200, first oxidize the surface of the metal sheet 200 at a low voltage to form an oxide layer 400, then increase the electrochemical anodic oxidation voltage and continue to oxidize the surface of the metal sheet 200 to quickly form nano structure array 500 .

As can be seen from the above, a device and method for rapidly preparing nanostructure arrays in the present invention recovers and cools the electrolyte 104 and then supplies it to the nozzle 102 again, and sprays the nozzle 102 onto the surface of the metal sheet 200 for electrochemical anodic oxidation. The circulation of the electrolyte 104 flows and is cooled, thereby eliminating the heat generated by increasing the electrochemical anodizing voltage, so that the preparation rate of the nanostructure array 500 can be increased by increasing the electrochemical anodizing voltage. In addition, the device is also suitable for To prepare a large-area nanostructure array 500 .

In summary, a device and method for rapidly preparing nanostructure arrays according to the present invention has disclosed related technologies in detail and in detail through the above-mentioned embodiments and related drawings, so that those skilled in the art can implement them accordingly. The above-mentioned embodiments are only used to illustrate the present invention, rather than to limit the present invention, and the scope of rights of the present invention should be defined by the claims of the present invention. Changes in the number of elements described herein or substitution of equivalent elements should still fall within the scope of the present invention.

Claims (9)

1. prepare fast a device for nano-structure array, comprising:

One fixture, clamps a tinsel;

One nozzle, be arranged to relative with described tinsel, to be suitable for the jet surface electrolytic solution to described tinsel;

One motor, is connected to drive described fixture to rotate, vertically move or move horizontally relative to described nozzle with described fixture;

One variable direct supply, the anode of described variable direct supply is electrically connected to described tinsel, and the cathodic electricity of described variable direct supply connects described nozzle;

One cavity, is suitable for reclaiming the electrolytic solution that is ejected into described tinsel surface; And

One refrigeration plant, is connected with described nozzle with described cavity, and the electrolytic solution of described refrigeration plant in can cooling described cavity is also supplied to described nozzle by cooled electrolytic solution.

2. a kind of device of preparing fast nano-structure array according to claim 1, is characterized in that: between described cavity and described refrigeration plant, be provided with an electrolytic bath, described electrolytic bath is communicated with described cavity and described nozzle respectively,

Wherein, the electrolytic solution in described cavity is introduced into described electrolytic bath, and flows into and in described refrigeration plant, carry out coolingly via described electrolytic bath, and cooled electrolytic solution is drawn gets back to described electrolytic bath, by described electrolytic bath, is supplied to described nozzle.

3. a kind of device of preparing fast nano-structure array according to claim 2, it is characterized in that: between described electrolytic bath and described nozzle, be provided with a flow director, this flow director is suitable for regulating the pressure of electrolytic solution and flow so that the electrolytic solution with certain pressure and flow is supplied to described nozzle.

4. a kind of device of preparing fast nano-structure array according to claim 1, is characterized in that: edge and the sidewall thereof on described tinsel surface scribble one deck insulating polymer.

5. a kind of device of preparing fast nano-structure array according to claim 1, it is characterized in that: also further comprise a voltage controller, described voltage controller is connected with described variable direct supply and controls the Voltage-output of described variable direct supply.

6. a kind of device of preparing fast nano-structure array according to claim 5, is characterized in that: the voltage that described voltage controller is controlled described variable direct supply output is 10V to 300V.

7. a kind of device of preparing fast nano-structure array according to claim 1, is characterized in that: described variable direct supply is programmable DC power supply.

8. the device described in right to use requirement 1 is prepared a method for nano-structure array fast, comprises the steps:

Tinsel is held on fixture;

Utilize nozzle to the jet surface electrolytic solution of described tinsel, the surface of wetting described tinsel;

The electrolytic solution that is ejected into described tinsel surface is recovered in cavity; And

Electrolytic solution in the cooling described cavity of refrigeration plant is also supplied to described nozzle again by cooled electrolytic solution.

9. a kind of method of preparing fast nano-structure array according to claim 8, it is characterized in that: after the surperficial step of wetting described tinsel and before the electrolytic solution that is ejected into described tinsel surface is recovered in to the step in cavity, further comprise: first under low voltage, be oxidized the surface of described tinsel, form a zone of oxidation, the surface of then improving electrochemical anodic oxidation voltage and continuing the described tinsel of oxidation, forms nano-structure array fast.

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