CN104928737B - Two-dimensional space electrochemical deposition receives the improved method of micro- ordered structural material - Google Patents
Two-dimensional space electrochemical deposition receives the improved method of micro- ordered structural material Download PDFInfo
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- CN104928737B CN104928737B CN201510345682.4A CN201510345682A CN104928737B CN 104928737 B CN104928737 B CN 104928737B CN 201510345682 A CN201510345682 A CN 201510345682A CN 104928737 B CN104928737 B CN 104928737B
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Abstract
Receive the improved method of micro- ordered structural material the invention discloses a kind of two-dimensional space electrochemical deposition, belong to electrochemical technology field.Solve prior art experiment repetitive rate not high, the problem of production efficiency is low.The present invention replaces ordinary straight strip foil electrode of the prior art using the foil electrode with cuspidated, regular shape as negative electrode, it can be effectively increased and control number and the position of growing point, and increase and receive the gross area of micro- ordered structural material, reach the purpose for improving experiment repetitive rate and production efficiency.The inventive method is adapted to preparation and receives micro- ordered structural material.
Description
Technical field
Receive the improved method of micro- ordered structural material the present invention relates to a kind of two-dimensional space electrochemical deposition, belong to electrochemistry
Technical field.
Background technology
Electrochemical deposition is that in the presence of extra electric field, occur by the lewis' acid in electrolyte in electrode surface
The process such as electrochemistry or physics, and obtain the process of material product.Electrochemical deposition method can quickly, in large quantities as one kind
Prepare the environment-protective process of functional material and develop by leaps and bounds.In recent years, electrochemical deposition method is widely used in newly
Among the preparation research of material, the preparation from inorganic substances to organic substance, the preparation from common material to nano material, from body
Section bar expects preparation of thin-film material etc..Conventional electrochemical deposition process is deposited in electrolyte, electrolyte using electrolytic cell
Each component keeps good three-dimensional motion pattern in the solution, the three kinds of motions mode such as it spreads, convection current and electromigration not by
To any limitation, the sample being deposited can not fixation in situ, so Conventional electrochemical deposition process set up feature it is orderly
It is limited in one's ability in terms of structural material.
Electrochemical deposition method in two-dimensional space, which is proved to be to prepare, receives one of the effective ways of micro- ordered structure.With biography
Electrochemical method of uniting is different, and this method needs to build two-dimentional electrolytic cell first, electrolyte is uniformly tied by creating low temperature environment
About 300nm thickness, the ultra-thin liquid layer rich in electrolyte, i.e., two-dimentional electro-deposition can be formed after ice, between ice sheet and substrate
Space.In this space, the diffusion and convection current of electrolyte are limited, and can only be moved in a kind of mode of electromigration.Therefore, it is electric
Matter is solved under deposition electric field action, moves about at deposition interface and is deposited, and deposit is limited only by space scale
Deposition position can be rested on, finally realizes that electrochemical in-situ is deposited, realizes the purpose of constructing function ordered structural material.
Electrochemical deposition assemble method in two-dimensional space is using purified water and solute configuration electrolyte, in temperature-controllable
Growth room in, using silicon chip or sheet glass of surface oxidation treatment etc. as substrate, substrate is lain in growth room, then will
The foil electrode of two vertical bar shapes is parallel to be placed on above substrate, then between two electrodes drop on electrolyte, last covered.
Electrolyte is set to freeze in suitable temperature temperature control, so that build two-dimensional ultrathin liquid layer deposition space, i.e., two-dimentional electrolytic cell.
Apply different frequency, the periodicity deposition potential of amplitude on electrode again, make electrolyte periodically deposition.Last deposit attachment
In substrate, sample can be obtained by being cleaned with purified water after substrate.But current two-dimensional space electrochemical deposition method, which still has, to be needed
Want improved place., it is necessary to the condition such as strict temperature control, the icing uniformity, deposition voltage when preparing ordered structural material.Should
Growing point quantity is about 2-3 when method is deposited and position is not fixed, and deposits obtained extensive deposition material most of (outstanding
Its fringe region) it is unordered, only central area is ordered structure, and area is small and repeated undesirable.Micro element is received in preparation
When need to remove substantial amounts of disordered structure part, waste raw material and time.This is used mainly due to prior art
It is a pair of parallel straight strip shaped electric poles, electrode side is equivalent everywhere, so can not fix the growth of primary deposit in electrode side
Point.After deposit starts growth in growing point, it, which grows front end and anode, can constantly form new deposition Electric Field Distribution, and
This electric field is diverging, is unfavorable for the structural material that manufacturing cycle is stable, parallelism structural is controllable, cause to prepare it is uncertain because
It is plain excessive, thus experiment repetitive rate is not high, production efficiency is low.
Goal of the invention
Receive the improved method of micro- ordered structural material it is an object of the invention to provide a kind of two-dimensional space electrochemical deposition,
Many with growing point, experiment uncertain factor is few, the advantages of testing repetitive rate and high production efficiency.
Described two-dimensional space electrochemical deposition receives the improved method of micro- ordered structural material, first using distilled water and molten
Matter configures electrolyte, then using the silicon chip or sheet glass of surface oxidation treatment as substrate and lies in the growth of temperature-controllable
Interior, using two panels foil electrode as two-dimentional cathode of electrolytic tank and anode, parallel is placed on above substrate.Between two electrodes
Electrolyte in drop, covered, and control temperature electrolyte is frozen.Apply deposition potential on electrode again, it is to be deposited complete
Finish, deposit is attached in substrate.Finally substrate is cleaned with distilled water.Described two-dimentional cathode of electrolytic tank be with it is cuspidated,
The foil electrode of regular shape, described deposition potential is one kind in voltage stabilizing potential or periodicity deposition potential.
The foil electrode thickness as two-dimentional cathode of electrolytic tank is 20-50 μm, and a width of 1-3mm, tip length is 1-
At a distance of 0.1-2mm between 2mm, tip.
Described periodicity deposition potential is one in DC voltage or sine voltage, pulse wave voltage, square-wave voltage
Kind.
Described periodicity deposition potential voltage amplitude scope is 0.3V-1.8V, and periodic voltage frequency is 0.1-2Hz.
Specific two-dimensional space electrochemical deposition receives the improved method of micro- ordered structural material, comprises the following steps：
(1) 20mM-100mM electrolyte is configured using distilled water and electrolyte raw material；
(2) it is cloudy using being used as using the silicon chip or sheet glass of surface oxidation treatment as substrate in the growth room of temperature-controllable
The band of pole is cuspidated, regular shape foil electrode and as anode vertical bar shape foil electrode with a distance of 6-8mm away from
It is placed on from parallel above substrate, 20-30 μ L electrolyte, covered, by temperature control in -2--8 is added dropwise between two electrodes
DEG C, place 20-40 minutes；Wherein as Ka band is cuspidated, regular shape foil electrode thickness is 20-50 μm,
A width of 1-3mm, tip length is 1-2mm, at a distance of 0.1-2mm between tip；
(3) and then electrolyte is freezed with the cooling module in growth room and frozen, and it is small to keep temperature constant state to place 0.5-1
When；
(4) applying DC voltage or sine wave, impulse wave, square wave quasi-periodic waveform voltage on electrode makes electrolyte sink
Product, wherein voltage amplitude scope are 0.3V-1.8V, and periodic voltage frequency is 0.1-2Hz；
(5) substrate is taken out after deposition terminates and is cleaned with distilled water, obtains being attached to micro- ordered structure material of receiving in substrate
Material.
Compared with prior art, the beneficial effects of the invention are as follows：
The electrochemical deposition method that the present invention is realized in two-dimensional space controls deposition growing point by point discharge, and
Produce the purpose of the parallel quasistatic uniform electric field of class.By using with cuspidated depositing electrode, before two parallel poles it
Between big and unstable deposition electric field resolve into many small, more stable initial equalization electric fields, and keep deposition growing mistake
Electric field is always that quasistatic is uniformly distributed in journey, and then reduces the uncertain factor in this method preparation process, is greatly improved
Test repetitive rate.Growing point has 3-6 during present invention deposition, and only starts what is deposited at deposition, each growing point at sophisticated place
Structural material area averagely reduces by 1/7th or so, but the gross area increase about 50% of ordered structure than original, and different
The ordered structural material deposited at growing point is discrete each other, can easily be separated and for multiple systems for receiving micro element
It is standby, improve production efficiency.The present invention can be by the change of electrode shape (zigzag, comb shape, arc curve etc.), material etc.
Change, the different deposition electric field of distribution is built by the combination of different shapes of two electrodes, preparing has different structure, different cycles
Pattern receives micro- ordered structural material.Receive the method for micro- ordered structural material by being prepared to two-dimensional space electrochemical deposition method and enter
Row is improved, and receive micro- ordered structural material gross area, repetitive rate etc. of preparation all have clear improvement, and improve production efficiency.Experiment
After end, electrode can be removed reuse, and deposited samples are retained in substrate, available for next step processing or device
Processing.
Brief description of the drawings
The optics picture of the straight strip shaped electric poles of Fig. 1.Electrode material is copper in figure, and thickness is 25 μm, neat in edge.
The optics picture of the cuspidated zigzag electrode of Fig. 2 bands.Electrode material is copper, and thickness is 25 μm, with another electrode
Opposite side is with zigzag tip.
Fig. 3 is the optics picture of eletrode tip discharge growth in the electrodeposition process of embodiment 1.As can be seen from the figure grow
Point is fixed on tip, and position is effectively controlled.
Fig. 4 is the optics picture of quasistatic uniform electric field structure in the electrodeposition process of embodiment 1.Interstitial growth is shown in figure
The growth front end of point is constantly promoted, and constantly forms new deposition electric field with anode, and this electric field is by both sides growth spot deposition
Material is surrounded, so as to form quasistatic uniform electric field of the direction of an electric field perpendicular to another electrode.
Fig. 5 is the copper nanometer parallel linear array structure that embodiment 1 is deposited.
Fig. 6 is the two-dimentional copper nano thin-film array structure materials with strict periodic structure that embodiment 2 is deposited.
Fig. 7 is the two-dimentional bismuth nano-array composite structural material with strict periodic structure that embodiment 3 is deposited.
Embodiment
With reference to specific embodiment, the present invention will be further described.
Embodiment 1
Two-dimensional space electrochemical deposition receives the improved method of micro- ordered structural material, comprises the following steps：
1st, using distilled water, copper sulphate, 50mM electrolyte is configured.
2nd, in the growth room of temperature-controllable, using the silicon chip of surface oxidation treatment as substrate, using the sawtooth as negative electrode
The copper foil plate electrode of shape is placed in substrate with the vertical bar shape copper foil plate electrode as anode so that the distance of 6mm apart is parallel
Face, is added dropwise 20 μ L electrolyte between two electrodes, and covered, by temperature control at -2 DEG C, is placed 20 minutes；Wherein as the moon
The thickness of the copper foil plate electrode of the zigzag fashion of pole is 20-50 μm, and a width of 1-3mm, tip length is 1-2mm, phase between tip
Away from 0.1-2mm；
3 then with the cooling module in growth room by electrolyte freeze solidify, and keep temperature constant state place 0.5 hour.
4th, applying 1.2V direct current deposition voltages on electrode makes electrolyte deposition.
5th, substrate is taken out after deposition terminates and is cleaned with distilled water, obtains being attached to the copper nanometer parallel linear array in substrate
Material.
Embodiment 2：
Two-dimensional space electrochemical deposition receives the improved method of micro- ordered structural material, comprises the following steps：
1st, using distilled water, copper sulphate, 100mM electrolyte is configured.
2nd, in the growth room of temperature-controllable, using the silicon chip of surface oxidation treatment as substrate, using the comb as negative electrode
The copper foil plate electrode of shape is placed in substrate with the vertical bar shape copper foil plate electrode as anode so that the distance of 8mm apart is parallel
Face, is added dropwise 25 μ L electrolyte between two electrodes, and covered, by temperature control at -6 DEG C, is placed 30 minutes；Wherein as the moon
The thickness of the copper foil plate electrode of the comb form of pole is 20-50 μm, and a width of 1-3mm, tip length is 1-2mm, phase between tip
Away from 0.1-2mm；
3 then with the cooling module in growth room by electrolyte freeze solidify, and keep temperature constant state place 0.8 hour.
4th, 0.1-1Hz is applied on electrode, amplitude range is 0.3-1.2V semisinusoidal periodicity deposition potential, makes electrolysis
Matter is periodically deposited.
5th, substrate is taken out after deposition terminates and is cleaned with distilled water, obtaining being attached in substrate has strict periodic structure
Two-dimentional copper nano thin-film array structure materials.
Embodiment 3：
Two-dimensional space electrochemical deposition receives the improved method of micro- ordered structural material, comprises the following steps：
1st, using distilled water, nitric acid, bismuth nitrate, the electrolyte that configuration 20mM, pH are 1-1.8.
2nd, in the growth room of temperature-controllable, using sheet glass as substrate, using the jagged silver foil piece electricity as negative electrode
Pole is placed on above substrate with the vertical bar shape silver foil plate electrode as anode so that the distance of 7mm apart is parallel, is dripped between two electrodes
Plus 30 μ L electrolyte, covered, by temperature control at -8 DEG C, place 40 minutes；Wherein as the jagged silver of negative electrode
The thickness of foil electrode is 20-50 μm, and a width of 1-3mm, tip length is 1-2mm, at a distance of 0.1-2mm between tip；
3 then with the cooling module in growth room by electrolyte freeze solidify, and keep temperature constant state place 1 hour.
4th, apply the semisinusoidal periodicity deposition potential that 1-2Hz, amplitude range are 1.0-1.8V on electrode, make electrolyte
Periodically deposit.
5th, substrate is taken out after deposition terminates and is cleaned with distilled water, obtaining being attached in substrate has strict periodic structure
Two-dimentional bismuth nano-array composite structural material.
Claims (4)
1. a kind of two-dimensional space electrochemical deposition receives the improved method of micro- ordered structural material, matched somebody with somebody first using distilled water and solute
Electrolyte is put, then the silicon chip or sheet glass using surface oxidation treatment are lain in the growth room of temperature-controllable as substrate, will
Two panels foil electrode is respectively as the negative electrode and anode of two-dimentional electrolytic cell, and parallel is placed on above substrate, between two electrodes in drop
Electrolyte, covered, and control temperature electrolyte is frozen, then apply deposition potential on electrode, and it is to be deposited to finish, sink
Product thing is attached in substrate, finally cleans substrate with distilled water, it is characterised in that：Described two-dimentional cathode of electrolytic tank is with point
End, regular shape foil electrode, described deposition potential is one kind in voltage stabilizing potential or periodicity deposition potential.
2. two-dimensional space electrochemical deposition according to claim 1 receives the improved method of micro- ordered structural material, its feature
It is：The foil electrode thickness as two-dimentional cathode of electrolytic tank is 20-50 μm, and a width of 1-3mm, tip length is 1-2mm,
At a distance of 0.1-2mm between tip.
3. two-dimensional space electrochemical deposition according to claim 2 receives the improved method of micro- ordered structural material, its feature
It is：Described periodicity deposition potential is one kind in sine voltage, pulse wave voltage.
4. two-dimensional space electrochemical deposition according to claim 3 receives the improved method of micro- ordered structural material, its feature
It is：Described periodicity deposition potential voltage amplitude scope is 0.3V-1.8V, and periodic voltage frequency is 0.1-2Hz.
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| CN109355685A (en) * | 2018-12-06 | 2019-02-19 | 陕西理工大学 | A kind of preparation method of the micro-nano periodic structure material of the copper of ring-segment-like |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101486442A (en) * | 2009-02-24 | 2009-07-22 | 吉林大学 | Preparation of semiconductor and metal quasi-one-dimensional nano heterogeneous cycle structure array |
| CN101845651A (en) * | 2009-12-28 | 2010-09-29 | 吉林大学 | Preparation method of cadmium oxide micro-nanometer ordered structural material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101486442A (en) * | 2009-02-24 | 2009-07-22 | 吉林大学 | Preparation of semiconductor and metal quasi-one-dimensional nano heterogeneous cycle structure array |
| CN101845651A (en) * | 2009-12-28 | 2010-09-29 | 吉林大学 | Preparation method of cadmium oxide micro-nanometer ordered structural material |
Non-Patent Citations (1)
| Title |
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| 准二维铜周期薄膜电化学沉积及其线阵列湿刻制备;姚彬彬;《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》;20081015(第10期);第B020-79页 * |
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