CN1325698C

CN1325698C - Preparation method of ordered porous anodic alumina template

Info

Publication number: CN1325698C
Application number: CNB2003101118341A
Authority: CN
Inventors: 程发良
Original assignee: Dongguan University of Technology
Current assignee: Dongguan University of Technology
Priority date: 2003-10-21
Filing date: 2003-10-21
Publication date: 2007-07-11
Anticipated expiration: 2023-10-21
Also published as: CN1609283A

Abstract

The invention discloses a preparation method of an ordered porous anodic alumina membrane. Compared with the prior art, the preparation method has the advantages that: large-area highly ordered nano-templates can be prepared; the success rate of template preparation is improved; the quality of the template is greatly improved, such as the arrangement sequence of nano holes, the uniformity of pore diameter, the consistency of depth and the improvement of void ratio (which can reach 10)¹¹One cm^-2)。

Description

The preparation method of ordered porous anodic alumina template

Technical field

The present invention relates to a kind of preparation method of ordered porous anodic alumina template.

Background technology

Nano material is meant the material that has only nanoscale size in the material structure, and nano material is because its special electronic structure and physicals make it more and more be subjected to people's attention as functional material.In recent years, a large amount of work concentrates in the research of nano materials such as nano thread, nanotube, nanometer rod, nano belt and Nanoalloy, the monodimension nanometer material that wherein with the nanotube is representative becomes the focus in the nano material because it is had outstanding performance in nature in sound, light, electricity, magnetic, power and heat etc.The preparation nanotube generally adopts the template synthesis method, and the template of nano materials commonly used has porous silicon, polycarbonate, anodised aluminium templates such as (AAO).

Existing press mold technology, photoetching and electron beam lithography technology can obtain large-area nano sequential holes template, but can not obtain the long uniform nano aperture of diameter, and directly anonizing can only obtain small area ordered nano hole template.

Summary of the invention

The object of the present invention is to provide a kind of preparation method of ordered porous anodic alumina template, that the relative other materials of anodised aluminium (AAO) template for preparing with this method has is high temperature resistant, stable in properties, pore distribution are uniform sequential, and since between the hole size and the thickness in density, hole adjustable within the specific limits.

Technical scheme of the present invention is as follows:

A kind of preparation method of ordered porous anodic alumina template may further comprise the steps:

(1) aluminium flake was polished 5～10 minutes down at 0～5 ℃ with 70% perchloric acid and dehydrated alcohol mixed solution (volume ratio 1: 4) earlier, voltage is 15～22V;

(2) (sulfuric acid 18～22V, oxalic acid 30～50V, phosphatase 11 00～130V) oxidation first 1～2 hour were done counter electrode with stainless steel plate with each self-corresponding voltage at polyprotonic acid (0.5～1.5mol/L sulfuric acid, 0.1～0.5mol/L oxalic acid or 0.3～1.0mol/L phosphoric acid) after aluminium flake cleaned with secondary water;

(3) under 60 ℃, mix washing lotion again and clean aluminium flake half an hour, remove oxide film with the chromic acid of 6% phosphoric acid and 1.8%;

(4) after aluminium flake cleans with secondary water, use with step (2) in same voltage carried out anodic oxidation 5～10 hours;

(5) peel off aluminum matrix with the muriate saturated aqueous solution, the phosphoric acid reaming with 5% 5～20 minutes is kept in the secondary water at last.

If the template that all open on the aluminium flake two sides need increase about 30 minutes reaming time.

As improvement of the technical scheme, used muriate is the tin protochloride saturated aqueous solution in the step 5 among the above-mentioned preparation method.

Beneficial effect of the present invention is: method of the present invention has improved the area scale and the success ratio of template preparation, has improved the quality of template greatly, as the nanoporous order of arranging, and the aperture homogeneity, the consistence of the degree of depth and the raising of voidage (can reach 10 ¹¹Individual cm ^-2).

In addition, the anodised aluminium that method of the present invention makes (AAO) template with respect to other template have high temperature resistant, stable in properties, pore distribution is uniform sequential, and because the size in density, hole and thickness are adjustable in the certain limit again between the hole, this just makes with AAO to be that the nano material that template prepares has more use value.Utilize the AAO template can prepare a series of nano materials such as metal nano material (nano magnetic material, ultra micro pencil electrode materials, nanocomposite optical material and nanometer optical-thermal conversion material), semiconductor nano material, carbon nanomaterial and carbon nano-composite material with strange characteristic and function.

Description of drawings

Fig. 1 observes for the sample that adopts SEM (HITACHI S-5200) that embodiment 1 is made and obtains figure;

Fig. 2 observes for the sample that adopts SEM (HITACHI S-5200) that embodiment 1 is made and obtains figure;

Fig. 3 carries out the figure of surface observation gained for the sample that adopts AFM (DI-D3000) that embodiment 1 is made;

Fig. 4 carries out the rotation diagram of the figure that surface observation gets for the sample that adopts AFM (DI-D3000) that embodiment 1 is made;

Fig. 5 utilizes TME that the sample that embodiment 1 makes is carried out observable figure;

Fig. 6 utilizes SEM that the sample that embodiment 2 makes is carried out observable figure.

Embodiment

Following embodiment will help those of ordinary skill in the art further to understand the present invention, but not limit the present invention in any form.

Embodiment 1

1, aluminium flake was polished 10 minutes down at 5 ℃ with 70% perchloric acid and dehydrated alcohol mixed solution (volume ratio 1: 4) earlier, voltage is 20V;

2, aluminium flake with secondary water clean the back in the sulfuric acid of 1.0mol/L with the voltage oxidation first of 20V 2 hours, do counter electrode with stainless steel plate;

3, under 60 ℃, mix washing lotion again and clean aluminium flake half an hour, remove oxide film with the chromic acid of 6% phosphoric acid and 1.8%;

4, after aluminium flake cleans with secondary water, use with step 2 in identical voltage carried out anodic oxidation 5 hours;

5, peel off aluminum matrix with saturated tin protoxide, the phosphoric acid reaming with 5% 15 minutes is kept in the secondary water at last.

Embodiment 2

1, aluminium flake was polished 10 minutes down at 0 ℃ with 70% perchloric acid and dehydrated alcohol mixed solution (volume ratio 1: 4) earlier, voltage is 20V;

2, aluminium flake with secondary water clean the back in the oxalic acid of 0.3mol/L with the voltage oxidation first of 40V 2 hours, do counter electrode with stainless steel plate;

4, after aluminium flake cleans with secondary water, use with step 2 in identical voltage carried out anodic oxidation 8 hours;

5, peel off aluminum matrix with saturated tin protoxide, the phosphoric acid reaming with 5% 20 minutes is kept in the secondary water at last.

Embodiment 3

1, aluminium flake was polished 10 minutes down at 3 ℃ with 70% perchloric acid and dehydrated alcohol mixed solution (volume ratio 1: 4) earlier, voltage is 20V;

2, aluminium flake with secondary water clean the back in the phosphoric acid of 0.6mol/L with the voltage oxidation first of 110V 1.5 hours, do counter electrode with stainless steel plate;

4, after aluminium flake cleans with secondary water, use with step 2 in same voltage carry out anodic oxidation 8 hours;

5, peel off aluminum matrix with saturated tin protoxide, the sulfuric acid reaming with 5% 10 minutes is kept in the secondary water at last.

Embodiment 4 effect Experimental Characterization

The sample that adopts SEM (HITACHI S-5200) that embodiment 1 is made is observed and is obtained Fig. 1 and Fig. 2, and hole integral body is arranged uniform sequential as seen from Figure 1; Fig. 2 illustrates the big or small almost equal of hole; The aperture is between 25～35nm, and hole density is about 4.8 * 10 ¹⁰Cm ^-2

The sample that adopts AFM (DI-D3000) that embodiment 1 is made carries out surface observation and gets Fig. 3 and Fig. 4, and Fig. 4 is the rotation diagram on surface, can be clearly seen that the surface appearance of template from Fig. 4.

Utilize TEM (JEM-100SX) that the sample that embodiment 1 makes is observed, obtain Fig. 5, from the cut-plane slices of Fig. 5 sample as can be seen the aperture be parallel to each other and with the plane be strict vertical straight hole.

Utilize SEM that the sample that embodiment 2 makes is observed, obtain Fig. 6, hole integral body is arranged uniform sequential as seen from Figure 6; Fig. 6 illustrates the big or small almost equal of hole; The aperture is between 60～75nm, and hole density is about 1.0 * 10 ¹⁰Cm ^-2

Claims

1. A method for preparing an ordered porous anodized aluminum template, comprising the following steps:

(1) Polish the aluminum sheet with a mixture of 70% perchloric acid and absolute ethanol with a volume ratio of 1:4 at 0-5°C for 5-10 minutes, and the voltage is 15-22V;

(2) After the aluminum sheet is washed with secondary water, it is oxidized for the first time in a polybasic acid with a corresponding voltage for 1 to 2 hours, and a stainless steel plate is used as a counter electrode;

(3) Clean the aluminum sheet with 6% phosphoric acid and 1.8% chromic acid mixed lotion at 60°C for half an hour to remove the oxide film;

(4) After the aluminum sheet is cleaned with secondary water, carry out anodic oxidation with the same voltage as in step (2) for 5 to 10 hours;

(5) Peel off the aluminum matrix with a chloride saturated aqueous solution, expand the pores with 5% phosphoric acid for 5-20 minutes, and finally store in secondary water.

2. The method for preparing an ordered porous anodic alumina template according to claim 1, characterized in that the polybasic acid used in step (2) is 0.5-1.5 mol/L sulfuric acid, 0.1-0.5 mol/L oxalic acid or 0.3 ～1.0mol/L phosphoric acid, the corresponding voltage is 18～22V for sulfuric acid, 30～50V for oxalic acid, and 100～130V for phosphoric acid.

3. The method for preparing an ordered porous anodic alumina template according to claim 1, characterized in that the chloride used in step (5) is a saturated aqueous solution of stannous chloride.