CN102431954A - Electrochemical micromachining method for ZnO substrate with high-frequency alternating-current (AC) electric heating technology - Google Patents
Electrochemical micromachining method for ZnO substrate with high-frequency alternating-current (AC) electric heating technology Download PDFInfo
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- CN102431954A CN102431954A CN2011102927973A CN201110292797A CN102431954A CN 102431954 A CN102431954 A CN 102431954A CN 2011102927973 A CN2011102927973 A CN 2011102927973A CN 201110292797 A CN201110292797 A CN 201110292797A CN 102431954 A CN102431954 A CN 102431954A
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- 238000005485 electric heating Methods 0.000 title claims abstract description 10
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- 238000005459 micromachining Methods 0.000 title abstract 3
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Abstract
本发明涉及一种高频交流电加热技术应用于ZnO基底电化学微加工方法，其特征在于，包括以下步骤：步骤1：提供含有NaNO2的蚀溶液；步骤2：提供一高频交流电升温装置和一扫描化学显微镜，将所述高频交流电升温装置的加热微电极固定在该扫描化学显微镜上；步骤3：将合成ZnO的纳米线或薄膜作为微加工的基底置于所述蚀溶液中，利用扫描电化学显微镜的逼近装置，使所述加热微电极接近ZnO基底，然后调节加热微电极的温度，从而对ZnO基底进行微加工。本发明不仅能提高电化学微加工效率，而且可以调控加工的分辨率，方法简单，具有较好的实用价值。
The invention relates to a method for applying high-frequency alternating current electric heating technology to ZnO substrate electrochemical micromachining, which is characterized in that it comprises the following steps: step 1: providing an etching solution containing NaNO 2 ; step 2: providing a high-frequency alternating current heating device and A scanning chemical microscope, fixing the heating microelectrode of the high-frequency alternating current heating device on the scanning chemical microscope; Step 3: placing the nanowire or thin film of synthesized ZnO in the etching solution as a microfabricated substrate, using The approaching device of the scanning electrochemical microscope makes the heating microelectrode close to the ZnO substrate, and then adjusts the temperature of the heating microelectrode, so as to perform microprocessing on the ZnO substrate. The invention can not only improve the efficiency of electrochemical micromachining, but also can regulate the resolution of machining, the method is simple, and has good practical value.
Description
Technical field
The present invention relates to the little processing of a kind of electrochemistry, relate in particular to a kind of hot microelectrode that utilizes high-frequency alternating current to heat up and combine the processing method of scan-type electrochemical microscope in zno-based basal surface etching processing micro.
Background technology
Method for electrochemical machining based on little/nano electrode is after electrochemistry scanning probe microscopy (ECSPM) and scan-type electrochemical microscope technical developments such as (SECM); The effective tool that can on micron and nanoscale, process that people propose; This type technology can also be carried out the original position field imaging in the surface micromachined while, thereby in little processing mechanism of electrochemistry and Mechanism Study, occupies extremely important status.This respect research at present comprises the etching processing method based on SECM (scan-type electrochemical microscope) that Bard seminar and Heinze seminar propose; The processing method of the ECSTM (electrochemical scanning tunneling microscopy) that Kolb seminar proposes; The ultrashort potential pulse method that Schuster seminar proposes, and Tian Zhaowu seminar of Xiamen University proposes constraint etch layer technology etc.The common ground of these methods is to utilize the electrode of micron or nanoscale as working electrode, through on working electrode, applying electrode potential, makes that the generation electrochemical process is induced in the part on substrate or the workpiece, thereby is implemented in the electrochemistry processing on the workpiece.Development along with electrochemical techniques; Illumination, heating, mechanical oscillation etc. add parameter and have been applied in the electrochemical process; Wherein temperature is important factor in order in the electrochemical reaction, and it can influence the electrode potential of material in the mass transfer rate of electrode surface, chemical reaction rate, redox reaction to a great extent.Generally, the researcher is the temperature that changes electrolyte through instrument and equipments such as constant temperature water baths, and the process that this method changes temperature slowly and can influence the current potential of reference electrode; In addition when research system is organic solution system or ionic liquid, the aggravation that evaporates, this can damage health and contaminated environment.Freyland etc. have developed the high temperature PSTM, and he has sealed liquid chamber earlier and then molten salt system and probe is carried out integral body and heat up, but such system price is high and and be inconvenient to use.
In recent years, people have been developed a series of only to microelectrode or close on the method that the solution thin layer of microelectrode heats, and this has comprised light beam heating, radio frequency heating, microwave heating method, high-frequency ac electrical heating method.Compare other heating means, the system of high-frequency ac electrical method is simple, the temperature of ability quick adjustment electrode.Grundler has designed the working electrode of symmetrical structure in nineteen ninety-five; The input that working electrode is connected electrochemical workstation is received the mid point of electrode; Adopt high-frequency alternating current that thread microelectrode is directly heated, this design has been eliminated the heating current of high-frequency alternating current to detecting the interference of electrochemical signals.Baranski in 2002 substitutes the alternating current of 100kHz in the past with frequency up to the electric current of 100kHz-2MHz, and the heated filament electrode technology is applied to common microdisk electrode, develops the heating new method that can be applicable to microdisk electrode.Because the solution around the electrode has higher resistance than electrode self material, heating current has produced Joule heat on the microcell solution around electrode.The heating of this method to as if electrode the microcell solution rather than the electrode itself that close on, so electrode is just passable with microelectrode.The principle of Baranski method is that near the microcell solution the microelectrode is heated in addition; The high-frequency ac voltage that applies is at very big solution resistance and carries out pro rata distribution on small electrode/interface resistance very much; The electric frequency of increasing exchanges can make the magnitude of voltage that on solution resistance, distributes increase, thereby reduces the electrochemical process influence of alternating current to electrode/solution interface.
Summary of the invention
The purpose of this invention is to provide a kind of high-frequency ac electric-heating technology and be applied to electrochemistry micro-processing method at the bottom of the zno-based,
The present invention adopts following scheme to realize: a kind of high-frequency ac electric-heating technology is applied to electrochemistry micro-processing method at the bottom of the zno-based, it is characterized in that, may further comprise the steps:
Step 1: provide and contain NaNO
2Erosion solution;
Step 2: a high-frequency alternating current heat riser and one scan chemical microscope are provided, the heating microelectrode of said high-frequency alternating current heat riser is fixed on this scanning chemical microscope;
Step 3: the nano wire or the film that will synthesize ZnO place said erosion solution as micro-machined substrate; Utilize the device that approaches of scan-type electrochemical microscope; At the bottom of making said heating microelectrode near zno-based, regulate the temperature of heating microelectrode then, thereby to carrying out little processing at the bottom of the zno-based.
In one embodiment of this invention, the NaNO of described erosion solution
2Concentration is 0.04mol/L ~ 1 mol/L.
In one embodiment of this invention, described high-frequency alternating current heat riser comprises a HF signal generator, regulates the temperature of output frequency with control heating microelectrode through this HF signal generator.
In one embodiment of this invention, described reference frequency output is: 10 ~ 2000MHz.
The present invention controls the temperature of the microcell solution that microelectrode closes on through changing heating frequency or effective voltage, thereby reaches the different etching effect of ZnO.This method has realized heating, detection, micro-machined integrated; It is simple to operate to compare traditional micro fabrication; The concentration that need not to change etching liquid can reach different little processing effects, for little processing of ZnO provide a kind of accurately, novel, cheap processing approach.
Description of drawings
Fig. 1 high-frequency ac electrical heating microelectrode is applied to the micro-machined schematic diagram of electrochemistry.
Fig. 2 is the cyclic voltammogram of the electrode under the heating of the embodiment of the invention 1 medium-high frequency alternating current.
But Fig. 3 carries out the micro-machined metallographic microscope figure of electrochemistry for utilizing the microelectrode of refining temperature in the embodiment of the invention 2 to ZnO.
The specific embodiment
Below in conjunction with accompanying drawing and embodiment the present invention is further specified.
The present invention provides a kind of high-frequency ac electric-heating technology to be applied to electrochemistry micro-processing method at the bottom of the zno-based, it is characterized in that, may further comprise the steps:
Step 1: provide and contain NaNO
2Erosion solution;
Step 2: a high-frequency alternating current heat riser and one scan chemical microscope are provided, the heating microelectrode of said high-frequency alternating current heat riser is fixed on this scanning chemical microscope;
Step 3: the nano wire or the film that will synthesize ZnO place said erosion solution as micro-machined substrate; Utilize the device that approaches of scan-type electrochemical microscope; At the bottom of making said heating microelectrode near zno-based, regulate the temperature of heating microelectrode then, thereby to carrying out little processing at the bottom of the zno-based.
Please with reference to Fig. 1; Fig. 1 is that high-frequency ac electrical heating microelectrode of the present invention is applied to the micro-machined schematic diagram of electrochemistry; The present invention applies certain current potential through SECM to microelectrode, utilizes microelectrode through the etching agent that electrochemical process constantly produces ZnO to be carried out etching.When adopting the intensification electrode can be directly influence the numerical value of diffusion velocity of speed constant and the etching agent of chemical reaction, thereby directly change the resolution ratio that etching is processed through temperature control.If bring up to 80 ℃ to etching reaction from room temperature, its reaction speed can improve tens to hundred times, improves the resolution ratio that the little working (machining) efficiency of electrochemistry also can be regulated and control processing like this.
Please with reference to Fig. 2, Fig. 2 utilizes heater circuit to apply the stable state cyclic voltammetry curve of the Pt microdisk electrode behind the different voltages.
Here we accurately control with needs pH value of solution numerical value the ZnO nano-wire array be processed as example, utilize the electrochemical reaction that takes place on the microelectrode, make NO in the solution
2 -Oxidation generates HNO on microelectrode
3, then ZnO is corroded.Its operation principle is: pass through at electrode surface
Electrochemical reaction produce a large amount of etching agent HNO
3, then utilize
Chemical reaction the ZnO on ITO surface is carried out etching.
Fig. 3 is about the microdisk electrode of 100 m Pt at 0.06 M NaNO for diameter
2Apply the metallographic microscope figure of the ZnO of etching behind the 100MHz high-frequency alternating current of different current effective values in the solution; Electrode potential steps to 1.5 V from 0.5V; The distance of microelectrode and ZnO nano wire is 3 m (are that this distance of metal electrode of 1 ~ 3 μ m should be less than 3 μ m for diameter), and etch period is 500s.Fig. 3 is that the voltage effective value of the high-frequency alternating current of 100 MHz that apply is 0,200,400,600,800,1000mVrms.The radius of its etching figure is followed successively by 98.76 μ m, 105.95 μ m, 109.28 μ m, 107.41 μ m, 104.05 μ m, 98.99 μ m.Can find out tentatively that from figure along with the increase of voltage effective value, figure radius that etching obtains increases earlier, after reduce, etching resolution ratio reduces increasing successively.
Table 1
The intensification electrode that the present invention is based on microelectrode can be applicable to electrochemistry micro-/ nano process technology, and its main advantage is: the method that other heated by electrodes are compared in (1) is simpler, more convenient, quicker; (2) can obtain and in the long relatively time, keep a very high surface temperature.Therefore, it all will be expected significant improvement to the machining resolution of the system of DIFFUSION CONTROLLED and dynamics Controlling; (3) on principle, this method can obtain the heating region littler than laser facula heating, in medical science with biologically have a potential application.
The above is merely preferred embodiment of the present invention, and all equalizations of doing according to claim of the present invention change and modify, and all should belong to covering scope of the present invention.
Claims (4)
1. a high-frequency ac electric-heating technology is applied to electrochemistry micro-processing method at the bottom of the zno-based, it is characterized in that, may further comprise the steps:
Step 1: provide and contain NaNO
2Erosion solution;
Step 2: a high-frequency alternating current heat riser and one scan chemical microscope are provided, the heating microelectrode of said high-frequency alternating current heat riser is fixed on this scanning chemical microscope;
Step 3: the nano wire or the film that will synthesize ZnO place said erosion solution as micro-machined substrate; Utilize the device that approaches of scan-type electrochemical microscope; At the bottom of making said heating microelectrode near zno-based, regulate the temperature of heating microelectrode then, thereby to carrying out little processing at the bottom of the zno-based.
2. high-frequency ac electric-heating technology according to claim 1 is applied to electrochemistry micro-processing method at the bottom of the zno-based, it is characterized in that: the NaNO of described erosion solution
2Concentration is 0.04mol/L ~ 1 mol/L.
3. high-frequency ac electric-heating technology according to claim 1 is applied to electrochemistry micro-processing method at the bottom of the zno-based; It is characterized in that: described high-frequency alternating current heat riser comprises a HF signal generator, regulates the temperature of output frequency with control heating microelectrode through this HF signal generator.
4. high-frequency ac electric-heating technology according to claim 3 is applied to electrochemistry micro-processing method at the bottom of the zno-based, and it is characterized in that: described reference frequency output is: 10 ~ 2000MHz.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108132238A (en) * | 2018-02-14 | 2018-06-08 | 福州大学 | A kind of high frequency heating electrochemistry-Surface enhanced Raman spectroscopy detecting system |
| CN109030337A (en) * | 2018-07-03 | 2018-12-18 | 北京工业大学 | A kind of buried metal pipeline corrosion and corrosion protection layer peel test system based on SECM |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0778806A (en) * | 1993-09-08 | 1995-03-20 | Fuji Electric Co Ltd | Dry etching method |
| JPH11248720A (en) * | 1998-03-05 | 1999-09-17 | Seiko Instruments Inc | Method for manufacturing electrochemical stm probe |
| CN101026023A (en) * | 2007-03-02 | 2007-08-29 | 上海集成电路研发中心有限公司 | Process for assembling zinc oxide nano wire on atomic force microscope tip |
| WO2008066779A2 (en) * | 2006-11-27 | 2008-06-05 | Georgia Tech Research Corporation | Near field scanning measurement-alternating current-scanning electrochemical microscopy devices and methods of use thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0778806A (en) * | 1993-09-08 | 1995-03-20 | Fuji Electric Co Ltd | Dry etching method |
| JPH11248720A (en) * | 1998-03-05 | 1999-09-17 | Seiko Instruments Inc | Method for manufacturing electrochemical stm probe |
| WO2008066779A2 (en) * | 2006-11-27 | 2008-06-05 | Georgia Tech Research Corporation | Near field scanning measurement-alternating current-scanning electrochemical microscopy devices and methods of use thereof |
| CN101026023A (en) * | 2007-03-02 | 2007-08-29 | 上海集成电路研发中心有限公司 | Process for assembling zinc oxide nano wire on atomic force microscope tip |
Non-Patent Citations (1)
| Title |
|---|
| A.SCHULTE, ET AL.: "Imaging localised corrosion of NiTi shape memory alloys by means of alternating current scanning electrochemical microscopy (AC-SECM)", 《MATERIALS SCIENCE AND ENGINEERING: A》, vol. 378, no. 12, 25 July 2004 (2004-07-25) * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108132238A (en) * | 2018-02-14 | 2018-06-08 | 福州大学 | A kind of high frequency heating electrochemistry-Surface enhanced Raman spectroscopy detecting system |
| CN109030337A (en) * | 2018-07-03 | 2018-12-18 | 北京工业大学 | A kind of buried metal pipeline corrosion and corrosion protection layer peel test system based on SECM |
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