CN102431954B - 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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- CN102431954B CN102431954B CN201110292797.3A CN201110292797A CN102431954B CN 102431954 B CN102431954 B CN 102431954B CN 201110292797 A CN201110292797 A CN 201110292797A CN 102431954 B CN102431954 B CN 102431954B
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Abstract
The invention relates to an electrochemical micromachining method for a ZnO substrate with a high-frequency AC electric heating technology. The method is characterized in that the method comprises the following steps: 1, preparing a corrosion solution containing NaNO2; 2, providing a high-frequency AC electric heater and a scanning electrochemical microscope (SECM), and fixing the heating microelectrode of the high-frequency AC electric heater on the SECM; and 3, putting a nano-wire or a film for synthesizing ZnO in the corrosion solution as a micromachining substrate, allowing the heating microelectrode to approach the ZnO substrate through the approximation device of the SECM, and adjusting the temperature of the heating microelectrode to carry out micromachining on the ZnO substrate. The method of the invention, which has the advantages of electrochemical micromachining efficiency improvement, controllable machining resolution and simplicity, has a good practicable value.
Description
Technical field
The present invention relates to the micro-processing of a kind of galvanochemistry, relate in particular to a kind of utilize hot microelectrode that high-frequency alternating current heats up in conjunction with scan-type electrochemical microscope the job operation in zno-based basal surface lithography micro/nano structure.
Background technology
Method for electrochemical machining based on micro-/nano electrode is after the technical developments such as Electrochemical Scanning probe microscope (ECSPM) and scan-type electrochemical microscope (SECM), the effective tool that can process on micron and nanoscale that people propose, this class technology can also be carried out original position field imaging in the surface micromachined while, thereby occupies extremely important status in the micro-processing mechanism of galvanochemistry and Mechanism Study.At present this respect research comprise that Bard seminar and Heinze seminar propose based on SECM(scan-type electrochemical microscope) lithography method, the ECSTM(electrochemical scanning tunneling microscopy that Kolb seminar proposes) job operation, 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, by apply electrode potential on working electrode, makes local induction on substrate or workpiece that electrochemical process occur, thereby realizes the galvanochemistry processing on workpiece.Development along with electrochemical techniques, the additional parameters such as illumination, heating, mechanical vibration have been applied in electrochemical process, wherein temperature is an important factor in order in electrochemical reaction, and it can affect material to a great extent at the electrode potential of the mass transfer rate of electrode surface, chemical reaction rate, redox reaction.Generally, researchist changes the temperature of electrolytic solution by the instrument and equipment such as constant temperature water bath, and the process that this method changes temperature slowly and can affect the current potential of contrast 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 high temperature scanning tunnel microscope, and he has first sealed liquid chamber and then molten salt system and probe has been carried out to integral body intensification, but such system price is high and not easy 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 method, 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 energy quick adjustment electrode.Grundler has designed the working electrode of symmetrical structure in nineteen ninety-five, the input end that working electrode is connected to electrochemical workstation is received the mid point of electrode, adopt high-frequency alternating current directly to heat thread microelectrode, this design has been eliminated the heating current of high-frequency alternating current to detecting the interference of electrochemical signals.Within 2002, Baranski substitutes the alternating current of 100kHz in the past up to the electric current of 100kHz-2MHz by frequency, and heated filament electrode technology is applied to common microdisk electrode, has developed the heating new method that can be applicable to microdisk electrode.Because electrode solution around has higher resistance than electrode self material, heating current has produced Joule heat on microcell solution around at electrode.The microcell solution rather than the electrode itself that to liking electrode, close on of this method heating, so electrode is just passable with microelectrode.Baranski side's ratio juris is that near microcell solution microelectrode is heated in addition, the high-frequency ac voltage applying is at very large solution resistance and very on small electrode/interface resistance, carries out pro rata distribution, the electric frequency of increasing exchanges can make the magnitude of voltage distributing on solution resistance increase, thereby reduces the electrochemical process impact of alternating current on Cathode/Solution Interface.
Summary of the invention
The object of this invention is to provide a kind of high-frequency ac electric-heating technology and be applied to galvanochemistry micro-processing method at the bottom of zno-based,
The present invention adopts following scheme to realize: a kind of high-frequency ac electric-heating technology is applied to galvanochemistry micro-processing method at the bottom of zno-based, it is characterized in that, comprises the following 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 described high-frequency alternating current heat riser is fixed on this scanning chemical microscope;
Step 3: nano wire or the film of synthetic ZnO are placed in to described erosion solution as micro-machined substrate, utilize the device that approaches of scan-type electrochemical microscope, at the bottom of making described heating microelectrode approach zno-based, then regulate the temperature of heating microelectrode, thereby to carrying out micro-processing at the bottom of 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 high frequency signal generator, the temperature by this high frequency signal generator regulation output frequency with control heating microelectrode.
In one embodiment of this invention, described reference frequency output is: 10 ~ 2000MHz.
The present invention heats by change the temperature that frequency or effective voltage are controlled the microcell solution that microelectrode closes on, thereby reaches the different etching effect of ZnO.The method has realized heating, detection, micro-machined integrated, compare traditional micro fabrication simple to operate, without the concentration that changes etching liquid, can reach different micro-processing effects, for micro-processing of ZnO provide a kind of accurately, novel, cheap processing approach.
Accompanying drawing explanation
Fig. 1 high-frequency ac electrical heating microelectrode is applied to the micro-machined schematic diagram of galvanochemistry.
Fig. 2 is the cyclic voltammogram of the electrode under the embodiment of the present invention 1 medium-high frequency AC electric-heating.
Fig. 3 be in the embodiment of the present invention 2, utilize can refining temperature microelectrode ZnO is carried out to the micro-machined metaloscope figure of galvanochemistry.
Embodiment
Below in conjunction with drawings and Examples, the present invention will be further described.
The invention provides a kind of high-frequency ac electric-heating technology and be applied to galvanochemistry micro-processing method at the bottom of zno-based, it is characterized in that, comprise the following 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 described high-frequency alternating current heat riser is fixed on this scanning chemical microscope;
Step 3: nano wire or the film of synthetic ZnO are placed in to described erosion solution as micro-machined substrate, utilize the device that approaches of scan-type electrochemical microscope, at the bottom of making described heating microelectrode approach zno-based, then regulate the temperature of heating microelectrode, thereby to carrying out micro-processing at the bottom of zno-based.
Please refer 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 galvanochemistry, the present invention applies certain current potential by SECM to microelectrode, and the etching agent that utilizes microelectrode constantly to produce by electrochemical process carries out etching to ZnO.When adopting intensification electrode can directly pass through the numerical value of the rate constant of temperature control effect chemical reaction and the rate of propagation of etching agent, thereby directly change the resolution of lithography.If etching reaction is brought up to 80 ℃ from room temperature, its reaction velocity can improve tens to hundred times, improves so the micro-working (machining) efficiency of galvanochemistry and also can regulate and control the resolution of processing.
Please refer to Fig. 2, Fig. 2 utilizes heater circuit to apply the stable state cyclic voltammetry curve of the Pt microdisk electrode after different voltage.
Here we with needs, accurately control pH value of solution numerical value ZnO nanowire array be processed as example, utilize the electrochemical reaction occurring on microelectrode, make NO in solution
2 -on microelectrode, oxidation generates HNO
3, then ZnO is corroded.Its principle of work is: at electrode surface, pass through
electrochemical reaction produce a large amount of etching agent HNO
3, then utilize
chemical reaction the ZnO on ITO surface is carried out to etching.
Fig. 3 be diameter be about 100 m Pt microdisk electrode at 0.06 M NaNO
2in solution, apply the metaloscope figure of the ZnO of etching after the 100MHz high-frequency alternating current of different current effective values, electrode potential steps to 1.5 V from 0.5V, the distance of microelectrode and ZnO nano-wire is that this distance of metal electrode that 3 m(are 1 ~ 3 μ m for diameter should be less than 3 μ m), etching time 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.From figure, can tentatively find out, along with the increase of voltage effective value, the figure radius that etching obtains first increases, after reduce, etching resolution reduces increasing successively.
Embodiment 3 ~ 40 its experimental procedures are similar to the above embodiments, its difference is the frequency of applied high-frequency alternating current, the concentration of etching liquid and etching time, actual conditions and etching effect refer to table 1(wherein "+" represent that etching effect is good, "-" represents that etching effect is poor).
Table 1
The intensification electrode that the present invention is based on microelectrode can be applicable to galvanochemistry micro-/ nano process technology, and its main advantage is: the method that (1) compares other heated by electrodes is simpler, more convenient, quicker; (2) can obtain and within the relatively long time, keep a very high surface temperature.Therefore, it all will be expected to be significantly improved to the machining resolution of the system of diffusion control and dynamics Controlling; (3) in principle, this method can obtain the heating region less than laser facula heating, in medical science with biologically have a potential application.
The foregoing is only preferred embodiment of the present invention, all equalizations of doing according to the present patent application the scope of the claims change and modify, and all should belong to covering scope of the present invention.
Claims (1)
1. high-frequency ac electric-heating technology is applied to a galvanochemistry micro-processing method at the bottom of zno-based, it is characterized in that, comprises the following 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 described high-frequency alternating current heat riser is fixed on this scanning chemical microscope;
Step 3: nano wire or the film of synthetic ZnO are placed in to described erosion solution as micro-machined substrate, utilize the device that approaches of scan-type electrochemical microscope, at the bottom of making described heating microelectrode approach zno-based, then regulate the temperature of heating microelectrode, thereby to carrying out micro-processing at the bottom of zno-based; The NaNO of described erosion solution
2concentration is 0.04mol/L ~ 1 mol/L; Described high-frequency alternating current heat riser comprises a high frequency signal generator, the temperature by this high frequency signal generator regulation output frequency with control heating microelectrode; Described reference frequency output is: 10 ~ 2000MHz.
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| 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 |
| CN109030337B (en) * | 2018-07-03 | 2021-05-07 | 北京工业大学 | Buried metal pipeline corrosion and anticorrosive coating peeling test system based on SECM |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| WO2008066779A3 (en) * | 2006-11-27 | 2008-07-24 | Georgia Tech Res Inst | Near field scanning measurement-alternating current-scanning electrochemical microscopy devices and methods of use thereof |
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| JPH0778806A (en) * | 1993-09-08 | 1995-03-20 | Fuji Electric Co Ltd | Dry etching method |
| JP3234187B2 (en) * | 1998-03-05 | 2001-12-04 | セイコーインスツルメンツ株式会社 | Manufacturing method of electrochemical STM tip |
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| WO2008066779A3 (en) * | 2006-11-27 | 2008-07-24 | Georgia Tech Res Inst | 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 (4)
| 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》.ELSEVIER,2004,第378卷(第1-2期), |
| Imaging localised corrosion of NiTi shape memory alloys by means of alternating current scanning electrochemical microscopy (AC-SECM);A.Schulte, et al.;《Materials Science and Engineering: A》;ELSEVIER;20040725;第378卷(第1-2期);第524页2.Experimental procedure、图1-3 * |
| JP特开平11-248720A 1999.09.17 |
| JP特开平7-78806A 1995.03.20 |
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