CN113046807A - Micro-area electrochemical machining device and method for preparing electro-deposition cuprous oxide by using same - Google Patents

Micro-area electrochemical machining device and method for preparing electro-deposition cuprous oxide by using same Download PDF

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CN113046807A
CN113046807A CN202110243098.3A CN202110243098A CN113046807A CN 113046807 A CN113046807 A CN 113046807A CN 202110243098 A CN202110243098 A CN 202110243098A CN 113046807 A CN113046807 A CN 113046807A
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micro
working electrode
microelectrode
cuprous oxide
electrode
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CN113046807B (en
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郭燕玲
陈罗明
欧阳志诚
马信洲
叶远昌
陈庭超
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Foshan University
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D9/00—Electrolytic coating other than with metals
    • C25D9/04—Electrolytic coating other than with metals with inorganic materials
    • C25D9/08—Electrolytic coating other than with metals with inorganic materials by cathodic processes
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D21/00—Processes for servicing or operating cells for electrolytic coating
    • C25D21/12—Process control or regulation
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/18—Electroplating using modulated, pulsed or reversing current

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  • Electrical Discharge Machining, Electrochemical Machining, And Combined Machining (AREA)

Abstract

The invention discloses a micro-area electrochemical processing device and a method for preparing electro-deposition cuprous oxide by using the same, wherein the processing device comprises an electrolytic cell and a pulse generator, and a working electrode, a microelectrode, an auxiliary electrode and a reference electrode are arranged in the electrolytic cell; nanosecond pulses output by the pulse generator act between the microelectrode and the working electrode to induce the microelectrode and the working electrode to be rapidly polarized, so that the electrochemical reaction is restricted in a submicron region. The preparation method of the electro-deposition cuprous oxide improves the processing precision of the cuprous oxide film by regulating and controlling the time for depositing the cuprous oxide, the distance between the tip surface of the microelectrode and the working electrode, the pulse voltage, the pulse width and other parameters, adopts a four-electrode system, restrains the electro-deposition cuprous oxide reaction in a submicron region in electrolyte through nanosecond long ultrashort pulses, realizes fixed-point modification or processing of the working electrode in the micro region, and prevents the solution from boiling and damaging a workpiece due to heat generated during processing.

Description

Micro-area electrochemical machining device and method for preparing electro-deposition cuprous oxide by using same
Technical Field
The invention relates to the technical field of electrochemical micro-machining, in particular to a micro-area electrochemical machining device and a method for preparing electrodeposited cuprous oxide by using the same.
Background
With the rapid development of high-tech industries such as microelectronics, micro-nano electromechanical systems, modern precise optical systems and the like in recent years, higher requirements are put forward on micro-nano processing technology. The problems of tool abrasion, rigid heat effect and the like often exist in the traditional micro-nano processing technology. In addition, the problem of thermal effect also exists in the non-traditional micro-nano processing technology such as electric spark, laser beam, electron beam and the like. In the same way, the processing modes have the defects of high energy consumption, low precision and environmental pollution and waste.
Among them, the electrochemical micromachining technology is a technology without mechanical force action, and has significant advantages for machining applications of hard metals. At present, the electrochemical micromachining technology is mainly applied to micro-electrolysis removal of metal materials, but electrolyte in gaps is easy to boil under the action of highly concentrated current during machining, generated heat enables a cathode and an anode to expand, electrolysis products are difficult to discharge, silting and adhesion are easy to occur, and therefore short circuit is caused, and normal operation of the machining process is affected.
Disclosure of Invention
In order to solve the technical problems of the existing electrochemical micromachining, the invention provides a micro-area electrochemical machining device and a method for preparing electrodeposited cuprous oxide by using the same.
The technical scheme adopted by the invention for solving the technical problems is as follows: a micro-area electrochemical machining device, comprising:
the electrolytic cell is internally provided with four electrodes which are respectively a working electrode, a microelectrode, an auxiliary electrode and a reference electrode;
the pulse generator is electrically connected with the microelectrode and used for outputting nanosecond pulses and acting between the microelectrode and the working electrode to induce the microelectrode and the working electrode to be rapidly polarized.
Furthermore, the micro-area electrochemical machining device also comprises an amplifier, wherein the amplifier is arranged between the pulse generator and the micro-electrode and is used for amplifying the nanosecond pulse output by the pulse generator.
Furthermore, the micro-area electrochemical machining device also comprises a potentiometer which is electrically connected with the four electrodes and is used for controlling and measuring the potentials and currents of the microelectrode and the working electrode.
Further, the micro-area electrochemical machining device further includes:
the image acquisition module is arranged below the working electrode and used for recording the electrochemical reaction process in real time;
the optical positioning instrument is arranged between the image acquisition module and the working electrode and used for monitoring the movement and the electrochemical reaction process of the microelectrode in real time, and the image acquisition module and the optical positioning instrument are both electrically connected with the computer processing terminal.
Furthermore, the micro-area electrochemical machining device further comprises a positioning platform, the microelectrode is fixed on the positioning platform with an adjustable position, and the positioning platform drives the microelectrode to move and focus and position the working electrode.
Further, a heater for heating the electrolyte is arranged at the bottom of the electrolytic cell.
The invention also provides a preparation method of the micro-area electro-deposition cuprous oxide, which adopts the micro-area electrochemical processing device for preparation and comprises the following steps:
s1, adding copper sulfate into a lactic acid solution, and adjusting the pH value through an alkali liquor to prepare an electrolyte;
s2, using a working electrode as a cathode to be arranged at the bottom of an electrolytic cell, assembling the working electrode and the electrolytic cell together, and fixing the microelectrode on a positioning platform to enable a needle point surface at the bottom of the microelectrode to be parallel to the working electrode;
s3, opening and adjusting the optical position finder to enable the needle point to face the central position of a light spot generated by the focal optical position finder, moving the microelectrode through the positioning platform, and adjusting the distance between the needle point and the working electrode;
s4, adding the electrolyte prepared in the step S1 into the electrolytic cell, starting and adjusting the potentiometer, the pulse generator, the amplifier and the heater, and performing micro-area electrodeposition of cuprous oxide on the working electrode.
Further, the electrolyte prepared in the step S1 comprises the following components: 0.3-0.6 mol/L of anhydrous copper sulfate, 2-4 mol/L of lactic acid and the pH value is adjusted to 10-13.
Further, in the step S3, the distance between the needle tip surface and the working electrode is 8-14 μm.
Further, the parameters of the electrodeposition micro-area in the step S4 are: the pulse width acted between the microelectrode and the working electrode is 40-80 ns, the electrodeposition time is 300-600 s, the heating temperature of the electrolyte is 60-70 ℃, and the cathode voltage is-0.15-0.25V.
The technical scheme provided by the embodiment of the application at least has the following technical effects or advantages:
the invention adopts a four-electrode system, a working electrode (a processed workpiece) and a temperature-controllable electrolytic cell are assembled together, and nanosecond ultrashort pulses are input between a microelectrode (a tool electrode) and the working electrode to realize the rapid polarization of the two electrodes, so that an electrochemical reaction is restricted in a submicron region in an electrolyte, the fixed-point modification or processing of the working electrode in a micro region is realized, and the solution is prevented from boiling and damaging the workpiece due to heat generated during processing. Meanwhile, the processing precision of the cuprous oxide film can be improved by regulating and controlling the time for depositing cuprous oxide, the distance between the needle point surface of the microelectrode and the working electrode, the pulse voltage, the pulse width and other parameters, and the method is suitable for processing various materials and dimensions of semiconductors, metals, organic polymers and the like, and is suitable for scientific research in the fields of semiconductor micro-area electrodeposition, micro-area electrochemical dissolution, metal micro-area electrodeposition and the like.
Drawings
FIG. 1 is a schematic structural view of a micro-area electrochemical machining apparatus according to an embodiment of the present application;
FIG. 2 is an SEM image of cuprous oxide film at different deposition times for example 1 of the present application;
FIG. 3 is an SEM image of cuprous oxide films of different deposition distances of example 2 of the present application;
FIG. 4 is an SEM image of cuprous oxide film of example 3 of the present application at different pulse voltages;
fig. 5 is SEM images of cuprous oxide films of different pulse widths of example 4 of the present application.
Detailed Description
The present invention is described in detail below by way of examples to facilitate understanding of the present invention by those skilled in the art, and it is to be specifically noted that the examples are provided only for the purpose of further illustrating the present invention and are not to be construed as limiting the scope of the present invention.
The invention relates to a micro-area electrochemical machining device which comprises an electrolytic cell 1, a pulse generator 2, an amplifier 3 and a potentiometer 4.
Four electrodes soaked in electrolyte are arranged in the electrolytic cell 1 to form a four-electrode system, wherein the four electrodes are respectively a working electrode 11, a microelectrode 12, an auxiliary electrode 13 and a reference electrode 14, and the four electrodes are as follows: the working electrode is ITO conductive glass, the microelectrode 12 is easier to control the gap in real time than common micro-electrolysis processing, the auxiliary electrode 13 is mainly used for forming a polarization loop with the working electrode 11, so that current passes through the working electrode 11, and the potential of the reference electrode 14 is kept unchanged and is used for observing and measuring the potential of the working electrode 11. The four-electrode system can accurately control the electric potential between the working electrode 11 and the microelectrode 12 and the processing distance between the working electrode 11 and the microelectrode 12, and the local polarization strength of the working electrode 11 is related to the distance between the working electrode and the microelectrode 12, so the four-electrode system can effectively control the area size of electrochemical reaction.
The pulse generator 2 is electrically connected with the microelectrode 12, the output pulse acts between the microelectrode 12 and the working electrode 11, the microelectrode 12 and the working electrode 11 are induced to be rapidly polarized, the nanosecond long pulse output by the pulse generator 2 acts between the microelectrode 12 and the working electrode 11, the microelectrode 12 and the working electrode 11 are induced to be rapidly polarized, the polarization time is consistent with the nanosecond pulse length output by the pulse generator 2, and the electrochemical reaction is restricted in a submicron region. The pulse generator 2 can process mV, muA and other weak electric signals through the amplifier 3.
The pulse periodic intermittent discharge of the pulse generator 2 replaces the conventional continuous dc discharge, and the working electrode 11 performs anodic dissolution or cathodic deposition of the electrochemical reaction. With the addition of the pulse power supply, the intermittent power-off between pulses can depolarize and dissipate heat of the electrode, so that the electrochemical characteristics, flow field and electric field of the gap are restored to the initial state. Meanwhile, nanosecond ultrashort pulses output by a pulse generator 2(150MHz) induce local rapid polarization of the microelectrode 12 and the working electrode 11 after passing through the amplifier 3, and the reaction area of anodic dissolution or cathodic deposition of electrochemical reaction can be confined in a micro-nano area according to theoretical calculation of an electric double layer polarization time constant tau (tau is rho.d.cdl, rho is solution conductivity, CDL is characteristic electric double layer capacitance, and d is the distance between a tool electrode and a processed workpiece), so that the effect of micro-area electrochemical micromachining is achieved.
On the basis of the original electrochemical micromachining, nanosecond pulses are added, continuous direct current discharge is changed into periodic intermittent discharge, depolarization and heat dissipation can be carried out in the power-off interval, the electrochemical property, the flow field and the electric field of the gap can be recovered to the initial state, and the electrochemical reaction is guaranteed to reach the optimal state.
The potentiometer 4 is a double constant potentiometer, and the potentiometer 4 is electrically connected with the four electrodes and is used for controlling and measuring the potential and the current of the microelectrode 12 and the working electrode 11. The double potentiostats measure the potential of the electrifying point through the reference electrode 14, and compare the potential with a control signal as a sampling signal to realize control and adjust the polarization current output of the microelectrode 12, so that the electrifying potential is kept at a set control potential.
In a preferred embodiment, the micro-area electrochemical machining device further comprises an image acquisition module 5 and an optical locator 6.
The image acquisition module 5 is a CCD camera and is arranged below the working electrode 11, and the image acquisition module 5 observes and records the whole micro-area electrochemical reaction process in real time. The optical locator 6 is a bright/dark field inverted optical microscope, is arranged between the image acquisition module 5 and the working electrode 11, and is used for monitoring the moving of the microelectrode 12 and the electrodeposition or dissolution process in real time. The image acquisition module 5 and the optical locator 6 are both electrically connected with a computer processing terminal, and data such as the temperature of an electrochemical reaction system, the current flowing through the microelectrode 12 and the working electrode 11, the position of the needle point surface 121 at the bottom of the microelectrode 12 and the like are collected in real time through an NI USB-6289 multifunctional data acquisition card, and the data are accurately controlled and measured by software developed by IgorPro.
As a preferable embodiment, the micro-area electrochemical machining device further comprises a positioning platform 7 with an adjustable position, wherein the micro-electrode 12 is fixed on the positioning platform 7, and the positioning platform 7 drives the micro-electrode 12 to move and focus and position the working electrode 11.
The bottom of the electrolytic cell 1 is provided with a heater 8 for heating the electrolyte, and the heater 8 heats the electrolyte to the optimal reaction temperature and maintains the optimal reaction temperature, so as to facilitate the electrochemical reaction.
The invention also provides a preparation method of the micro-area electro-deposition cuprous oxide, which adopts the micro-area electrochemical processing device for preparation and comprises the following steps:
s1, adding copper sulfate into a lactic acid solution, and adjusting the pH value through an alkali liquor to prepare an electrolyte, wherein the electrolyte comprises the following components: 0.3-0.6 mol/L of anhydrous copper sulfate, 2-4 mol/L of lactic acid, 10-13 of PH value and NaOH solution as alkali solution.
S2, a working electrode 11 is taken as a cathode and arranged at the bottom of the electrolytic cell 1, the working electrode and the electrolytic cell 1 are assembled together, and a microelectrode 12 is fixed on a positioning platform 7, so that a needle point surface 121 of the microelectrode 12 is parallel to the working electrode 11;
s3, opening and adjusting the optical position finder to enable the needle point surface 121 of the microelectrode 12 to focus the central position of a light spot generated by the optical position finder 6, and moving the microelectrode 12 through the positioning platform 7, wherein the distance between the needle point surface 121 and the working electrode 11 is 8-14 mu m.
S4, adding the electrolyte prepared in the step S1 into the electrolytic cell 1, starting and adjusting a potentiometer 4, a pulse generator 2, an amplifier 3 and a heater 8, performing micro-area electro-deposition of cuprous oxide on the working electrode 11, wherein the pulse width of the pulse output by the pulse generator 2, which is applied between the microelectrode 12 and the working electrode 11 after passing through the amplifier 3, is 40-80 ns, and the parameters of the micro-area of electro-deposition are as follows: the electrodeposition time is 300-600 s, the heating temperature of the electrolyte is 60-70 ℃, and the cathode voltage is-0.15-0.25V.
The cuprous oxide electrodeposition reaction comprises the following steps: 2Cu2++2e-+2OH-(aq)→Cu2O(s)+H2O(l)
Example 1
The preparation method of the micro-area electro-deposition cuprous oxide comprises the following steps:
preparing an electrolyte, wherein the electrolyte comprises the following components: 0.4mol/L of anhydrous copper sulfate, 3mol/L of lactic acid and pH 11 of sodium hydroxide adjusting solution.
A working electrode 11 is taken as a cathode and arranged at the bottom of an electrolytic cell 1, the working electrode and the electrolytic cell 1 are assembled together, and a microelectrode 12 is fixed on a positioning platform 7, so that a needle point surface 121 is parallel to ITO conductive glass;
opening and adjusting the optical position finder 6 to enable the needle point surface 121 of the microelectrode 12 to focus the central position of a light spot generated by the optical position finder 6, moving the microelectrode 12 through the positioning platform 7, and adjusting the distance between the needle point surface 121 and the ITO conductive glass, wherein the distance between the needle point surface 121 and the ITO conductive glass is 10 micrometers.
Adding prepared electrolyte into an electrolytic cell 1, starting and adjusting a potentiometer 4, a pulse generator 2, an amplifier 3 and a heater 8, carrying out micro-area electrodeposition of cuprous oxide on the ITO conductive glass, wherein the pulse voltage output by the pulse generator 2 is 1.45V, the pulse width applied between a microelectrode 12 and a working electrode 11 after passing through the amplifier 3 is 50ns, the heating temperature of the electrolyte is 65 ℃, and the cathode voltage is-0.2V. The electrodeposition time was 300s, 400s, 500s and 600s, respectively.
The ITO conductive glass was removed, washed several times with deionized water, dried, and the surface topography of the cuprous oxide deposit was analyzed, as shown in fig. 2, it can be seen from the figure that the thickness of the cuprous oxide became thicker as the electrodeposition time varied, and in addition, the cuprous oxide deposited in the micro-domains diffused outward as the actual deposition was prolonged.
Example 2
The preparation method of the micro-area electro-deposition cuprous oxide comprises the following steps:
preparing an electrolyte, wherein the electrolyte comprises the following components: 0.4mol/L of anhydrous copper sulfate, 3mol/L of lactic acid and pH 11 of sodium hydroxide adjusting solution.
A working electrode 11 is taken as a cathode and arranged at the bottom of an electrolytic cell 1, the working electrode and the electrolytic cell 1 are assembled together, and a microelectrode 12 is fixed on a positioning platform 7, so that a needle point surface 121 is parallel to ITO conductive glass;
opening and adjusting the optical position finder 6 to enable the needle point surface 121 to focus the central position of the light spot generated by the optical position finder 6, moving the microelectrode 12 through the positioning platform 7, and adjusting the distance between the needle point surface 121 and the ITO conductive glass, wherein the distances between the needle point surface 121 and the ITO conductive glass are respectively 8 micrometers, 10 micrometers, 12 micrometers and 14 micrometers.
Adding prepared electrolyte into an electrolytic cell 1, starting and adjusting a potentiometer 4, a pulse generator 2, an amplifier 3 and a heater 8, carrying out micro-area electro-deposition of cuprous oxide on the ITO conductive glass, wherein the pulse voltage output by the pulse generator 2 is 1.45V, the pulse width applied between a microelectrode 12 and a working electrode 11 after passing through the amplifier 3 is 50ns, the heating temperature of the electrolyte is 65 ℃, the cathode voltage is-0.2V, and the electro-deposition time is 300 s.
The ITO conductive glass is taken down, washed with deionized water for several times, and dried, and then the surface morphology of the cuprous oxide deposit is analyzed, as shown in fig. 3, it can be seen from the figure that when the distance between the needle point surface 121 and the ITO conductive glass is 8-10 μm, the microscopic morphology of cuprous oxide is not changed much, but when the distance between the needle point surface 121 and the ITO conductive glass is 14 μm, the crystal grains of cuprous oxide become smaller.
Example 3
The preparation method of the micro-area electro-deposition cuprous oxide comprises the following steps:
preparing an electrolyte, wherein the electrolyte comprises the following components: 0.4mol/L of anhydrous copper sulfate, 3mol/L of lactic acid and pH 11 of sodium hydroxide adjusting solution.
A working electrode 11 is taken as a cathode and arranged at the bottom of an electrolytic cell 1, the working electrode and the electrolytic cell 1 are assembled together, and a microelectrode 12 is fixed on a positioning platform 7, so that a needle point surface 121 is parallel to ITO conductive glass;
opening and adjusting the optical position finder 6 to enable the needle point surface 121 to focus the central position of the light spot generated by the optical position finder 6, moving the microelectrode 12 through the positioning platform 7, and adjusting the distance between the needle point surface 121 and the ITO conductive glass, wherein the distance between the needle point surface 121 and the ITO conductive glass is respectively 10 micrometers.
Adding prepared electrolyte into an electrolytic cell 1, starting and adjusting a potentiometer 4, a pulse generator 2, an amplifier 3 and a heater 8, performing micro-area electro-deposition of cuprous oxide on ITO conductive glass, wherein pulse voltages output by the pulse generator 2 are 1.3V, 1.4V, 1.5V and 1.6V respectively, the pulse width applied between a microelectrode 12 and a working electrode 11 after passing through the amplifier 3 is 50ns, the heating temperature of the electrolyte is 65 ℃, the cathode voltage is-0.2V, and the electro-deposition time is 300s respectively.
The ITO conductive glass was removed, washed several times with deionized water, and dried, and the surface morphology of the cuprous oxide deposit was analyzed, as shown in fig. 4, it can be seen that the pulse voltage had little effect on the diameter and microscopic morphology of the cuprous oxide disk deposited in the micro-zone.
Example 4
The preparation method of the micro-area electro-deposition cuprous oxide comprises the following steps:
preparing an electrolyte, wherein the electrolyte comprises the following components: 0.4mol/L of anhydrous copper sulfate, 3mol/L of lactic acid and pH 11 of sodium hydroxide adjusting solution.
A working electrode 11 is taken as a cathode and arranged at the bottom of an electrolytic cell 1, the working electrode and the electrolytic cell 1 are assembled together, and a microelectrode 12 is fixed on a positioning platform 7, so that a needle point surface 121 is parallel to ITO conductive glass;
opening and adjusting the optical position finder 6 to enable the needle point surface 121 of the microelectrode 12 to focus the central position of a light spot generated by the optical position finder 6, moving the microelectrode 12 through the positioning platform 7, and adjusting the distance between the needle point surface 121 and the ITO conductive glass, wherein the distance between the needle point surface 121 of the microelectrode 12 and the ITO conductive glass is respectively 10 micrometers.
Adding prepared electrolyte into an electrolytic cell 1, starting and adjusting a potentiometer 4, a pulse generator 2, an amplifier 3 and a heater 8, performing micro-area electro-deposition of cuprous oxide on the ITO conductive glass, wherein the pulse voltage output by the pulse generator 2 is 1.45V, the pulse widths applied between a microelectrode 12 and a working electrode 11 after passing through the amplifier 3 are respectively 40ns, 50ns, 60ns and 70ns, the heating temperature of the electrolyte is 65 ℃, the cathode voltage is-0.2V, and the electro-deposition time is respectively 300 s.
The ITO conductive glass was removed, washed several times with deionized water, dried, and the surface topography of the cuprous oxide deposit was analyzed, as shown in fig. 5, it can be seen from the figure that the pulse time length had a significant effect on the diameter of the cuprous oxide disk, and as the pulse length increased from 40ns to 70n, the grain size became relatively uniform as the pulse length increased.
The method for preparing the electro-deposition cuprous oxide by using the micro-area electrochemical processing device comprises the following operation and use steps in actual use:
(1) preparing an electrolyte;
(2) after being assembled with the temperature-controlled micro electrolytic cell 1 as a cathode, the ITO conductive glass is fixed on a processing platform 9;
(3) vertically fixing a microelectrode 12 on a needle point clamp 71 of a positioning platform 7, and enabling a needle point surface 121 of the microelectrode 12 to be parallel to the surface of the ITO conductive glass;
(4) turning on a switch of a main power supply and a switch of an optical microscope, finding a bright light spot on the ITO conductive glass by the optical microscope, and adjusting the position of the light spot to the midpoint of the ITO conductive glass;
(5) opening the computer terminal, opening Live video in the CCD, wherein the interface is an IDS interface, then opening an Open camera, adjusting the positioning platform 7, and approaching the pinpoint surface 121 to the ITO conductive glass at the center so as to shorten the vertical distance between the pinpoint surface 121 and the ITO conductive glass until clear light spots appear on the CCD;
(6) in the step (5), if the adjustment is proper, the microscopic condition of the tip surface 121 can be seen on the CCD, if the image of the surface of the tip surface 121 cannot be observed on the CCD, the objective lens magnification under the optical microscope can be adjusted to find the microscopic image of the tip surface 121, and then the surface of the tip surface 121 is observed with a better high magnification;
(7) and (3) turning on the pulse generator 2, the amplifier 3, the potentiometer 7 and the data acquisition card, pressing an OUPUT key of the power supply when the just-turned-on power supply device does not have any output voltage, and starting the power supply until the power supply device displays an out mark, wherein the voltage is mainly used for supplying power to the operational amplifier.
(8) Opening the IGOR Pro, clicking Start on the IGOR Pro to Start working, adjusting the needle point surface 121 to move towards the ITO conductive glass on software, setting a preset value (the preset value is a little larger than the Current value contacting the ITO conductive glass and ranges from 4 to 7 muA to the right) at the Current set point [ mu A ], clicking Tip Aproach to enable the needle point surface 121 and the ITO conductive glass to Approach, automatically returning to the position when the needle point surface 121 and the ITO conductive glass contact, wherein the returning position can be set at Jump step after [ mu m ];
(9) when the tip face 121 is in contact with the ITO conductive glass, the current of the window Graph2, temperturewave vs Timewave, becomes larger instantaneously (the phenomenon of short circuit occurs at the moment of contact, thus causing the current to become larger instantaneously). When the magnitude of the current exceeds the threshold, as the tip face 121 immediately returns to the predetermined position, the return of the tip face 121 occurs and returns to the predetermined position from the ITO conductive glass on the image of the tip in window Graph0: tipposioniwave vs Timewave;
(10) after the position and the current are determined, the needle point surface 121 is adjusted back to the highest position, the position of the tipposinwave vs. Timewave needle point is 0 position in the window Graph0, and when electrolyte is added, the current value needs to be adjusted to be large first, so that the needle point surface 121 is prevented from rebounding;
(11) adding electrolyte into a temperature-controlled electrolytic cell 1, starting a heater 8, maintaining according to the optimal reaction temperature of the electrolyte, and observing obvious temperature rise in a window Graph2 of software, namely tempertewave vs Timewave;
(12) adjusting the microelectrodes 12 to a specific processing position in preparation for an electrochemical reaction, the electrodeposition time being set according to the reaction time;
(13) if the Current (WECURRENT [ uA ]) is changed in the process of adjusting the potential, the potential of the commonly used working electrode 11 is smaller than the electrode potential (WEpotential vs RE [ V ]) of the electrode reaction, if the Current becomes larger, the potential of the working electrode 11 can be adjusted to be larger, so that the Current is smaller, and if the Current is larger, the corresponding Current threshold [ uA ] is also correspondingly adjusted to be larger;
(14) after the potential adjustment is finished, carrying out progressive operation, clicking Hold and then clicking Tip Approach to start, releasing pulses at a certain time, firstly adjusting a Current threshold set point to be 100 times of the original Current threshold set point, then placing a pulse cursor On a switch On a device of a pulse instrument, clicking output pulses On software to start outputting pulses, and simultaneously displaying obvious pulses On an oscilloscope of a pulse generator, wherein one straight line On the oscilloscope is the pulse applied to the needle point surface 121 and the other straight line below the oscilloscope is two electrodes through which Current flows;
(15) preparation and judgment of the second experiment: judging whether the reaction is finished or not can be judged by time, setting time at pulse out time [ s ], stopping the image of a window Graph0, or judging the image of the pulse, wherein the pulse image is a straight line when the reaction is finished;
(16) after the experiment is judged to be finished, clicking Hold, resetting the needle point surface 121, clicking Go Home to reset, seeing the position change on a position display, adjusting the processing position after resetting is finished, adjusting Jump post after contact [ mu m ] to set a preset value, adjusting the Current threshold set point to the preset value, pressing Tip Aproach to Approach an ITO conductive glass plate by the needle point, wherein in the approaching process, the position and an optical microscopic image have obvious changes, adjusting the Current threshold set point to 100 times of the original value after the needle point surface 121 is adjusted back, and then clicking Output pulses to apply pulses;
(17) and repeating the steps, and obtaining the cuprous oxide films with different shapes according to different actual requirements by regulating and controlling the deposition time of the micro-area electro-deposition cuprous oxide, the distance between the microelectrode 12 and the surface of the ITO conductive glass, the pulse voltage, the pulse width and other parameters.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are intended to be within the scope of the invention.

Claims (10)

1. A micro-area electrochemical machining device, comprising:
the electrolytic cell is internally provided with four electrodes which are respectively a working electrode, a microelectrode, an auxiliary electrode and a reference electrode;
the pulse generator is electrically connected with the microelectrode and used for outputting nanosecond pulses and acting between the microelectrode and the working electrode.
2. The micro-area electrochemical machining apparatus according to claim 1, further comprising an amplifier provided between the pulse generator and the micro-electrode for amplifying the nanosecond pulse outputted from the pulse generator.
3. The micro-area electrochemical machining device according to claim 1, further comprising a potentiometer electrically connected to each of the four electrodes for controlling and measuring the potential and current of the micro-electrode and the working electrode.
4. The micro-area electrochemical machining device according to claim 1, further comprising:
the image acquisition module is arranged below the working electrode and used for recording the electrochemical reaction process in real time;
the optical positioning instrument is arranged between the image acquisition module and the working electrode and used for monitoring the movement and the electrochemical reaction process of the microelectrode in real time, and the image acquisition module and the optical positioning instrument are both electrically connected with the computer processing terminal.
5. The micro-area electrochemical machining device of claim 1, further comprising a positioning platform, wherein the micro-electrode is fixed on the positioning platform with an adjustable position, and the positioning platform drives the micro-electrode to move and focus the working electrode.
6. The micro-area electrochemical machining device according to claim 1, wherein a heater for heating the electrolyte is provided at a bottom of the electrolytic cell.
7. A preparation method of micro-area electro-deposition cuprous oxide, which is characterized by being prepared by using the micro-area electrochemical processing device as claimed in any one of claims 1-6, and comprises the following steps:
s1, adding copper sulfate into a lactic acid solution, and adjusting the pH value through an alkali liquor to prepare an electrolyte;
s2, using a working electrode as a cathode to be arranged at the bottom of an electrolytic cell, assembling the working electrode and the electrolytic cell together, and fixing the microelectrode on a positioning platform to enable a needle point surface at the bottom of the microelectrode to be parallel to the working electrode;
s3, opening and adjusting the optical position finder to enable the needle point to face the central position of a light spot generated by the focal optical position finder, moving the microelectrode through the positioning platform, and adjusting the distance between the needle point and the working electrode;
s4, adding the electrolyte prepared in the step S1 into the electrolytic cell, starting and adjusting the potentiometer, the pulse generator, the amplifier and the heater, and performing micro-area electrodeposition of cuprous oxide on the working electrode.
8. The method for preparing micro-area electro-deposited cuprous oxide according to claim 7, wherein the components of said electrolyte prepared in step S1 are: 0.3-0.6 mol/L of anhydrous copper sulfate, 2-4 mol/L of lactic acid and the pH value is adjusted to 10-13.
9. The method for preparing micro-area electrodeposited cuprous oxide according to claim 7, wherein the distance between the needle tip surface and the working electrode in said step S3 is 8-14 μm.
10. The method for preparing micro-domain electrodeposited cuprous oxide as claimed in claim 7, wherein the parameters of micro-domain electrodeposition in said step of S4 are: the pulse width acted between the microelectrode and the working electrode is 40-80 ns, the electrodeposition time is 300-600 s, the heating temperature of the electrolyte is 60-70 ℃, and the cathode voltage is-0.15-0.25V.
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