CN106947992A - A kind of flexible nano comeplex structure and preparation method thereof - Google Patents

A kind of flexible nano comeplex structure and preparation method thereof Download PDF

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CN106947992A
CN106947992A CN201710004297.2A CN201710004297A CN106947992A CN 106947992 A CN106947992 A CN 106947992A CN 201710004297 A CN201710004297 A CN 201710004297A CN 106947992 A CN106947992 A CN 106947992A
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comeplex
aluminium flake
aluminium
nano
flexible
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CN106947992B (en
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周张凯
韦志强
薛建材
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National Sun Yat Sen University
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    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
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    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
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    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
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    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
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Abstract

The present invention relates to flexible electronics field, more particularly to a kind of flexible nano comeplex structure and preparation method thereof, it is characterised in that：Including flexible substrates, anodic oxidation aluminium formwork is fixed with the flexible substrates；Sputtering has a metal nano comeplex on affiliated anodic oxidation aluminium formwork, and the nanometer comeplex is stacked by many nano wires and formed, and the nanowire diameter is between 20 40nm, to be distributed in clump tufted；The substrate is dimethyl silicone polymer.The beneficial effect of technical solution of the present invention is：(1) prepare simple, low cost, prepare the advantages such as environment-friendly, sample area is big；(2) can be to prepare wearable optical moisture sensors part.

Description

A kind of flexible nano comeplex structure and preparation method thereof
Technical field
The present invention relates to flexible electronics field, more particularly to a kind of flexible nano comeplex structure and its preparation Method.
Background technology
Various flexible sensing detecting function materials are just widely used in preparing various wear due to good integrated performance Equipment is worn, is that the mankind open a kind of convenience, such as comfortable and safe life style, Google's glasses（S.Feng, et al. ACS Nano. 8,3069,2014）With epidermis electronic system（D.H.Kim, et al. Science. 333,838,2011）Deng.But It is that many flexible detection materials are in general very sensitive to sample structure due to the detection sensing capabilities of material, cause sample Performance be difficult to be protected under the deformed state such as be bent or be stretched.Therefore, one kind is developed to protect under deformed state Hold the development that the stable flexible sensing detection material of performance will greatly promote the field, will also expedite the emergence of and more possess excellent performance Wearable device.
The content of the invention
The present invention is to overcome at least one defect described in above-mentioned prior art（It is not enough）There is provided a kind of flexible nano comeplex Structure, further, the present invention also provide a kind of flexible nano comeplex preparation method.
In order to solve the above technical problems, technical scheme is as follows：
Anodic oxidation aluminium formwork is fixed with a kind of flexible nano comeplex structure, including flexible substrates, the flexible substrates；It is affiliated Flexible metal nano comeplex is sputtered on anodic oxidation aluminium formwork, the nanometer comeplex is stacked by many nano wires and formed, described Nanowire diameter be 20-40nm between, in clump tufted be distributed；The substrate is dimethyl silicone polymer.
Further, the nanometer comeplex can change color when running into moisture.
Further, the nanometer comeplex is in canescence in dry air, runs into moisture and then becomes glassy yellow.
The present invention also provides a kind of preparation method of flexible nano comeplex, comprises the following steps：
（1）Aluminium flake is cleaned：It is then molten with the NaOH that concentration is 0.5-1.5mol/L using acetone soak aluminium flake 5-15min Immersion steeps aluminium flake 5-15min, finally with alcohol-pickled aluminium flake 5-15min；
（2）Aluminium flake is polished：It is molten between 0.15-0.35 that aluminium flake after will be alcohol-pickled, which is put into perchloric acid and alcohol by volume ratio, Liquid, using 10-30V voltage, electrochemical polish 2-6min, aluminium flake connects anode, and platinized platinum is cooked negative electrode, and polish temperature is 0-4 DEG C；
（3）Aluminium flake is aoxidized for the first time：Aluminium flake after polishing is put into electrolytic cell, electrolyte uses 0.1-0.3 mol/L grass Acid solution, growth voltage is 30-50V, and aluminium flake jointed anode, platinized platinum is cooked negative electrode, oxidization time 2-8 hours, and reaction temperature is 4-8 ℃；
（4）Aluminium flake is etched：Aluminium flake after first time is aoxidized is put into the mixed solution of chromic acid, phosphoric acid and distilled water, is maintained at 45-75 DEG C of temperature, keeps 60-90min；
（5）Second of oxidation of aluminium flake：Aluminium flake after etching is put into electrolytic cell, electrolyte use mass fraction for 10% phosphoric acid Solution, growth voltage is 40V, and voltage is tuned up to 80V rapidly after continuing 3min, then is kept for about 2.5 hours；Aluminium flake connection sun Pole, platinized platinum is cooked negative electrode, and oxidizing temperature is 20 DEG C or so, obtains a kind of irregular anodic oxidation aluminium formwork；
（6）Sputtered metal film：Using sputter, from metal targets, anodic oxidation aluminium formwork is placed on generated beneath, utilized 5-100mA sputtering current, sputtering time is 50-100s, and metal nano comeplex is formed on anodic oxidation aluminium formwork；
（7）Change flexible substrates：With 0.5-1mol/L CuCl2Solution corrodes the original aluminium substrate of anodic oxidation aluminium formwork Fall, the dimethyl silicone polymer prepared is dropped in the back side of anodic oxidation aluminium formwork, form " the sun of metal nanometer line-irregular The sample, is put into vacuum and filled, 40- is evacuated with mechanical pump by the sample of pole aluminum oxide-dimethyl silicone polymer " three-decker 60min, is then transferred into baking box by sample, and 200-300min is dried in the environment of 60-80 DEG C.
Further, step（1）Aluminium flake used, thickness is more than 1mm.
Further, step（4）In mixed solution used, chromic acid mass fraction is 1-3%, and phosphoric acid quality fraction is 4- 8%。
Further, step（5）During aluminium flake secondary oxidation, the hole wall of anodised aluminium is etched to and will crushed, and obtains To the hole wall of porous alumina formwork have incompleteness.
Further, step（6）Selected metal can be silver or gold.
Compared with prior art, the beneficial effect of technical solution of the present invention is：
(1) the nano wire plex structure of splash-proofing sputtering metal can be obtained by anodic oxidation aluminium formwork uniform diameter, the party are passed through Method, which has, to be prepared simple, low cost, prepares the advantages such as environment-friendly, sample area is big；
(2) gained flexible metal nano wire plex structure can easily be prepared into wearable device, simultaneously because its property, When surface dielectric changes, nano wire has different response characteristics to light, therefore can be wet to prepare wearable optics Spend senser element.
Brief description of the drawings
Fig. 1 is the growth schematic diagram and corresponding scanning electron microscope (SEM) photograph of each stage of special irregular AAO templates, is general first Logical AAO templates, transition oxidation is allowed to occur irregular corrosion, nano wire occurs after becoming special AAO templates, sputtering silver Clump.
Fig. 2 is the diameter and length statistical Butut of nano silver wire, and the direct of nano wire is concentrated mainly on 20-40nm, long Degree is then dispersed in 200-2000nm.
Fig. 3 is the cross-sectional scans electron microscope of one nanometer of comeplex, and the thickness of irregular AAO templates is about 9 μm, silver nanoparticle comeplex Thickness be about 400nm.
Fig. 4 is the preparation flow schematic diagram and sample photo of flexible silver nanoparticle comeplex.Mainly use CuCl2Solution receives silver The aluminium substrate of rice noodles clump is eroded, and flexible good PDMS is used as substrate in replacement.
Fig. 5 is the displaying that flexible silver nanoparticle comeplex prepares humidity sensor bracelet.Fig. 5 a are to put on before bracelet is run and Fig. 5 b The photo run after perspiring, before running, bracelet sample area is silvery white, is glassy yellow after perspiration.
Accompanying drawing being given for example only property explanation, it is impossible to be interpreted as the limitation to this patent；It is attached in order to more preferably illustrate the present embodiment Scheme some parts to have omission, zoom in or out, do not represent the size of actual product；To those skilled in the art, Some known features and its explanation may be omitted and will be understood by accompanying drawing；Same or analogous label correspondence is same or similar Part；Term the being given for example only property explanation of position relationship described in accompanying drawing, it is impossible to be interpreted as the limitation to this patent.
Embodiment
Technical scheme is described further with reference to the accompanying drawings and examples.
Embodiment 1
A kind of flexible nano comeplex structure, it is characterised in that：Including flexible substrates, anodic oxidation is fixed with the flexible substrates Aluminum alloy pattern plate；Affiliated anodic oxidation aluminium formwork（AAO）The upper flexible metal nano comeplex of sputtering, the nanometer comeplex is by many nanometers Line stack form, the nanowire diameter be 20-40nm between, in clump tufted be distributed；The substrate is dimethyl silicone polymer (PDMS)；The nanometer comeplex is in canescence in dry air, runs into moisture and then becomes glassy yellow.
Embodiment 2
Thickness successively is put into acetone, 1.5mol/L sodium hydroxide solution and alcoholic solution for 0.2cm aluminium foil respectively to soak Clean 15min；It is 0.3 solution that aluminium flake after will be alcohol-pickled, which is put into perchloric acid and alcohol by volume ratio, using 20V voltage, Electrochemical polish 6min, aluminium flake connects anode, and platinized platinum is cooked negative electrode, and polish temperature is 0 DEG C.
Aluminium flake after polishing carries out first time anodic oxidation, and electrolyte uses 0.3 mol/L oxalic acid solution, growth electricity Press as 45V, aluminium flake jointed anode, platinized platinum is cooked negative electrode, oxidization time 4-8 hours, reaction temperature is 4 DEG C.After aoxidizing for the first time Aluminium flake is put into the mixed solution of chromic acid, phosphoric acid and distilled water（Chromic acid mass fraction is 1.8%, and phosphoric acid quality fraction is 6%）, keep In 60 DEG C of temperature 60min, the aluminum oxide of oxidation production for the first time is removed.Then aluminium flake after etching is put into electrolytic cell, be electrolysed Liquid uses mass fraction for 10% phosphoric acid solution, and growth voltage is 40V, and voltage is tuned up to 80V rapidly after continuing 3min, then Kept for about 2.5 hours.Aluminium flake jointed anode, platinized platinum is cooked negative electrode, and oxidizing temperature is 15 DEG C or so.Generate surface and occur irregular corruption Erosion, remains some sophisticated special anodic oxidation aluminum alloy pattern plates.
Reacted alumina formwork is put into sputter, from Ag as sputtering target material, using 60mA sputtering current, 60s is sputtered, so that nano silver wire plex structure just can be formed.Fig. 1 be the special anodic oxidation aluminum alloy pattern plate growth course schematic diagram and Each stage sample scanning electron microscope (SEM) photograph, Fig. 2 is the diameter and length statistical Butut of nano silver wire, and Fig. 3 is that sample in cross section scans electricity Mirror figure.It can be seen that, the length of nano silver wire is dispersed in 200-2000nm, and diameter is concentrated mainly on 20-40nm, comparatively Than more uniform.The thickness of AAO templates is about 9 μm, and the thickness of silver nanoparticle comeplex is about 400nm.
Embodiment 3
Thickness successively is put into acetone, 1.5mol/L sodium hydroxide solution and alcoholic solution for 0.2cm aluminium foil respectively to soak Clean 15min；It is 0.3 solution that aluminium flake after will be alcohol-pickled, which is put into perchloric acid and alcohol by volume ratio, using 20V voltage, Electrochemical polish 6min, aluminium flake connects anode, and platinized platinum is cooked negative electrode, and polish temperature is 0 DEG C.
Aluminium flake after polishing carries out first time anodic oxidation, and electrolyte uses 0.3 mol/L oxalic acid solution, growth electricity Press as 45V, aluminium flake jointed anode, platinized platinum is cooked negative electrode, oxidization time 4-8 hours, reaction temperature is 4 DEG C.After aoxidizing for the first time Aluminium flake is put into the mixed solution of chromic acid, phosphoric acid and distilled water（Chromic acid mass fraction is 1.8%, and phosphoric acid quality fraction is 6%）, keep In 60 DEG C of temperature 60min, the aluminum oxide of oxidation production for the first time is removed.Then aluminium flake after etching is put into electrolytic cell, be electrolysed Liquid uses mass fraction for 10% phosphoric acid solution, and growth voltage is 40V, and voltage is tuned up to 80V rapidly after continuing 3min, then Kept for about 2.5 hours.Aluminium flake jointed anode, platinized platinum is cooked negative electrode, and oxidizing temperature is 15 DEG C or so.Generate surface and occur irregular corruption Erosion, remains some sophisticated special anodic oxidation aluminum alloy pattern plates.
Reacted alumina formwork is put into sputter, from Ag as sputtering target material, using 60mA sputtering current, 60s is sputtered, so that nano silver wire plex structure just can be formed.Then 0.5-1mol/L CuCl is used2Solution is by AAO templates original Aluminium substrate is eroded, and the PDMS prepared is dropped in the back side of AAO templates, and sample, which is put into vacuum, to be filled, and 40- is evacuated with mechanical pump 60min, then put sample into baking box, 200-300min is dried in the environment of 60-80 DEG C.Flexibility is just can obtain by above-mentioned steps Nano silver wire plex structure.Fig. 4 is the preparation flow schematic diagram and sample photo of flexible silver nanoparticle comeplex.Fig. 5 is to receive flexible silver Rice noodles plex structure can supervise sample surfaces wet using the displaying with humidity sensor bracelet by direct visual perception color change Degree.
Embodiment 4
Thickness successively is put into acetone, 1.5mol/L sodium hydroxide solution and alcoholic solution for 0.2cm aluminium foil respectively to soak Clean 15min；It is 0.3 solution that aluminium flake after will be alcohol-pickled, which is put into perchloric acid and alcohol by volume ratio, using 20V voltage, Electrochemical polish 6min, aluminium flake connects anode, and platinized platinum is cooked negative electrode, and polish temperature is 0 DEG C.
Aluminium flake after polishing carries out first time anodic oxidation, and electrolyte uses 0.3 mol/L oxalic acid solution, growth electricity Press as 45V, aluminium flake jointed anode, platinized platinum is cooked negative electrode, oxidization time 4-8 hours, reaction temperature is 4 DEG C.After aoxidizing for the first time Aluminium flake is put into the mixed solution of chromic acid, phosphoric acid and distilled water（Chromic acid mass fraction is 1.8%, and phosphoric acid quality fraction is 6%）, keep In 60 DEG C of temperature 60min, the aluminum oxide of oxidation production for the first time is removed.Then aluminium flake after etching is put into electrolytic cell, be electrolysed Liquid uses mass fraction for 10% phosphoric acid solution, and growth voltage is 40V, and voltage is tuned up to 80V rapidly after continuing 3min, then Kept for about 2.5 hours.Aluminium flake jointed anode, platinized platinum is cooked negative electrode, and oxidizing temperature is 15 DEG C or so.Generate surface and occur irregular corruption Erosion, remains some sophisticated special anodic oxidation aluminum alloy pattern plates.Reacted alumina formwork is put into sputter, from different Metal targets, using 60mA sputtering current, sputter 60s, can obtain different metal nano wire plex structure.
Obviously, the above embodiment of the present invention is only intended to clearly illustrate example of the present invention, and is not pair The restriction of embodiments of the present invention.For those of ordinary skill in the field, may be used also on the basis of the above description To make other changes in different forms.There is no necessity and possibility to exhaust all the enbodiments.It is all this Any modification, equivalent and improvement made within the spirit and principle of invention etc., should be included in the claims in the present invention Protection domain within.

Claims (8)

1. a kind of flexible nano comeplex structure, it is characterised in that：Including flexible substrates, anodic oxygen is fixed with the flexible substrates Change aluminum alloy pattern plate；Sputtering has metal nano comeplex on affiliated anodic oxidation aluminium formwork, and the nanometer comeplex is stacked by many nano wires Form, the nanowire diameter be 20-40nm between, in clump tufted be distributed；The substrate is dimethyl silicone polymer.
2. flexible nano comeplex structure according to claim 1, it is characterised in that：The nanometer comeplex is when running into moisture Color can be changed.
3. flexible nano comeplex structure according to claim 2, it is characterised in that：The nanometer comeplex is in dry air In be in canescence, run into moisture and then become glassy yellow.
4. a kind of preparation method of flexible nano comeplex, it is characterised in that comprise the following steps：
（1）Aluminium flake is cleaned：It is then molten with the NaOH that concentration is 0.5-1.5mol/L using acetone soak aluminium flake 5-15min Immersion steeps aluminium flake 5-15min, finally with alcohol-pickled aluminium flake 5-15min；
（2）Aluminium flake is polished：It is molten between 0.15-0.35 that aluminium flake after will be alcohol-pickled, which is put into perchloric acid and alcohol by volume ratio, Liquid, using 10-30V voltage, electrochemical polish 2-6min, aluminium flake connects anode, and platinized platinum is cooked negative electrode, and polish temperature is 0-4 DEG C；
（3）Aluminium flake is aoxidized for the first time：Aluminium flake after polishing is put into electrolytic cell, electrolyte uses 0.1-0.3 mol/L grass Acid solution, growth voltage is 30-50V, and aluminium flake jointed anode, platinized platinum is cooked negative electrode, oxidization time 2-8 hours, and reaction temperature is 4-8 ℃；
（4）Aluminium flake is etched：Aluminium flake after first time is aoxidized is put into the mixed solution of chromic acid, phosphoric acid and distilled water, is maintained at 45-75 DEG C of temperature, keeps 60-90min；
（5）Second of oxidation of aluminium flake：Aluminium flake after etching is put into electrolytic cell, electrolyte use mass fraction for 10% phosphoric acid Solution, growth voltage is 40V, and voltage is tuned up to 80V rapidly after continuing 3min, then is kept for about 2.5 hours；Aluminium flake connection sun Pole, platinized platinum is cooked negative electrode, and oxidizing temperature is 20 DEG C or so, obtains a kind of irregular anodic oxidation aluminium formwork；
（6）Sputtered metal film：Using sputter, from metal targets, anodic oxidation aluminium formwork is placed on generated beneath, utilized 5-100mA sputtering current, sputtering time is 50-100s, and metal nano comeplex is formed on anodic oxidation aluminium formwork；
（7）Change flexible substrates：With 0.5-1mol/L CuCl2Solution erodes the original aluminium substrate of anodic oxidation aluminium formwork, The dimethyl silicone polymer prepared is dropped in the back side of anodic oxidation aluminium formwork, form " the anodic oxygen of metal nanometer line-irregular The sample, is put into vacuum and filled, 40-60min is evacuated with mechanical pump by the sample of change aluminium-dimethyl silicone polymer " three-decker, Then sample is transferred into baking box, 200-300min is dried in the environment of 60-80 DEG C.
5. the preparation method of flexible nano comeplex according to claim 4, it is characterised in that：Step（1）Aluminium flake used, Thickness is more than 1mm.
6. the preparation method of flexible nano comeplex according to claim 4, it is characterised in that：Step（4）Mixing used In solution, chromic acid mass fraction is 1-3%, and phosphoric acid quality fraction is 4-8%.
7. the preparation method of flexible nano comeplex according to claim 4, it is characterised in that：Step（5）The secondary oxygen of aluminium flake During change, the hole wall of anodised aluminium is etched to and will crushed, and the hole wall of obtained porous alumina formwork has incompleteness.
8. the preparation method of flexible nano comeplex according to claim 4, it is characterised in that：Step（6）Selected gold Category can be silver or gold.
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