CN102887478A - Micro-nano machining method based on electrochemical micro-nano system for functional material and device thereof - Google Patents
Micro-nano machining method based on electrochemical micro-nano system for functional material and device thereof Download PDFInfo
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Abstract
The invention provides a micro-nano machining method based on an electrochemical micro-nano system for a functional material and a device thereof. According to the method and the device, a functional material of a micro-nano scale can be synthesized in situ on a specific substrate or a micro-nano chip for constructing an all-solid-state micro-nano device. The method comprises the following steps of: constructing an electrochemical reactor of a micro-nano scale to limit a physical-chemical process for synthesizing the functional material in a space of a micro-nano scale; and regulating and controlling a micro-area physical-chemical environment on a conducting substrate or a chip to be processed to synthesize the functional material of the micro-nano scale in situ on the conducting substrate or the micro-nano chip. The device comprises an electrochemical reactor of a micro-nano scale, an electrochemical workstation, a three-dimensional inching system of micro-nano accuracy, a video monitor and an information processing computer.
Description
Technical field
The present invention relates to a kind of micro-nano processing method and device thereof of the functional material based on electrochemistry micro-nano system, more specifically, relate to a kind of can be on particular substrate or micro-nano chip processing method and the device of the functional material of original position synthetizing micro-nano yardstick, can be used for constructing all solid state micro-nano device.
Background technology
Under the promotion of super large-scale integration, micro electronmechanical, precision optics industry, the function components and parts are towards microminiaturized, integrated direction development, even reach the molecular device of unimolecule aspect.Owing to must rely on scanning probe microscopy (SPM) at molecular level assembling molecular device, such as PSTM (STM) and AFM (AFM), complicated operation, inefficiency, also depend on to a great extent the experiment skill of actual operator, the technique of the mass manufacturing function components and parts of at present practical application can only reach micron order and submicron order.Electrochemical method is not only having great importance aspect the micro-nano chip manufacture making, and aspect the constructing of micro-nano function components and parts original application is arranged also.For example, by the method for electrochemical regulating and controlling, can design the micro-nano electrochemistry components and parts such as switch, motor, molecular transistors.Traditional electrochemistry components and parts all are that the redox reaction by Cathode/Solution Interface realizes its specific function, namely work under specific solution environmental.Yet when the yardstick of electrochemistry components and parts reached micro/nano level, because the long-pending high-vapor-pressure that causes of microbody, solution environmental had been difficult to keep.In addition, bring great difficulty also for the integrated and encapsulation of micro-nano device.In order to adapt to microminiaturization, integrated requirement, must all solid state electrochemical function components and parts of development.
The existing history for many years of electrochemistry of solids development has significant progress at aspects such as electrochemistry basis theory, electrochemical sensor, electrochromic devices, photoelectrocatalysis, energy conversion.But solid electrolyte is difficult to machine-shaping; Even machine-shaping also is difficult to effectively be assembled in the micro element go, be difficult to guarantee contact well between solid electrolyte and the electrode.For example, Prussian blue is a kind of good electron-ion mixed conductor, and has good electro-chemical activity.The Prussian blue material of cultivating various yardsticks is not difficult matter, yet because its bad mechanical strength will be assembled into cultured Prussian blue material in the micro-nano device, and guarantee that the contact between Prussian blue and the electrode is good, namely having lower contact resistance, almost is unlikely.Up to now, has the functional material of original position synthetizing micro-nano yardstick on micro-nano device of practical value, also rarely seen report.The invention provides a kind of micro-nano processing method and device thereof of the functional material based on electrochemistry micro-nano system, can be on particular substrate or micro-nano chip the functional material of original position synthetizing micro-nano yardstick, thereby realize efficient, the batch machining of all solid state micro-nano device.
Summary of the invention
The object of the present invention is to provide a kind of micro-nano processing method of the functional material based on electrochemistry micro-nano system, described method comprises: construct the electrochemical reactor of micro-nano-scale, be limited in the physical and chemical process with the complex functionality material in the space of micro-nano-scale; And microcell physicochemical environment on regulation and control conductive substrates or the chip is with the functional material of original position synthetizing micro-nano yardstick on conductive substrates or micro-nano chip.
Another object of the present invention is to provide a kind of micro-nano processing unit (plant) of the functional material based on electrochemistry micro-nano system, described device comprises three-dimensional fine motion system, video-frequency monitor and the information processing computer of electrochemical reactor, electrochemical workstation, the micro-nano precision of micro-nano-scale
Described electrochemical reactor is provided with: the container with open pointed tip of micro-nano-scale; Be contained in the auxiliary and reference electrode in the described container, and as processed substrate or the chip of working electrode, between wherein said container and described processed substrate or the chip by ascend to heaven (～fL) to the skin liter (～pL) electrolyte solution of level is in contact with one another, and forms an electrochemistry micro-nano reactor;
Described electrochemical workstation is used for control by voltage, electric current and the frequency thereof of electrochemistry micro-nano reactor, thereby the microcell physicochemical environment on regulation and control conductive substrates or the micro-nano chip, with the modes such as crystallization, precipitation, electro-deposition, electrochemical polymerization, electrochemistry induced polymerization, the functional material of original position synthetizing micro-nano yardstick on conductive substrates or micro-nano chip;
The three-dimensional fine motion system of described micro-nano precision is used for accurate mobile electrochemistry micro-nano reactor to the ad-hoc location of conductive substrates or micro-nano chip;
Described video-frequency monitor is used for the process Real Time Monitoring, enters the ad-hoc location of conductive substrates or micro-nano chip and with it contact to guarantee electrochemistry micro-nano reactor; And
Described information processing computer is used for instruction transmission and the feedback information to electrochemical workstation, three-dimensional fine motion system, video-frequency monitor, and that guarantees to process carries out smoothly.
In addition, a further object of the present invention provides a kind of using method of micro-nano processing unit (plant) of the functional material based on electrochemistry micro-nano system of the present invention, said method comprising the steps of:
1) container of preparation with micro-nano-scale open pointed tip is with as electrochemistry micro-nano electrolytic cell;
2) conductive substrates or micro-nano chip are fixed on the base as electrochemical working electrode;
3) the electrolyte solution injection is had in the container of micro-nano-scale open pointed tip, insert reference electrode and auxiliary electrode;
The container that 4) electrolyte solution, reference electrode and auxiliary electrode will be housed is fixed on the fixed mount of three-dimensional fine motion system;
5) LED lamp and high magnification amplification CCD camera lens are fixed on the video fixture, regulate light path, focus on the position that will process on conductive substrates or the micro-nano chip;
6) start three-dimensional fine motion system, the Working position of mobile container as electrochemistry micro-nano electrolytic cell to conductive substrates or the micro-nano chip; Regulate three-dimensional fine motion system, the solution at container tip is contacted with the Working position of conductive substrates or micro-nano chip, consist of electrochemistry micro-nano reactor; And
7) start electrochemical workstation, regulation and control microcell electrochemical reaction, the original position of carrying out functional material at conductive substrates or micro-nano chip is synthetic.
Micro-nano processing method and the device based on the functional material of electrochemistry micro-nano system of the application of the invention, can be on particular substrate or micro-nano chip the functional material of original position synthetizing micro-nano yardstick, thereby realize efficient, the batch machining of all solid state micro-nano device.
Description of drawings
Fig. 1 is the composition schematic diagram of the micro-nano processing unit (plant) of the functional material based on electrochemistry micro-nano system of the present invention.
Fig. 2 (a) is the scanning electron microscope diagram of the present invention at the on glass synthetic silico-tungstic acid crystal of platinum plating.Fig. 2 (b) is the cyclic voltammetry curve of silico-tungstic acid individual particle material.
Fig. 3 (a) for the present invention at the synthetic scanning electron microscope diagram that is doped with potassium ferrocyanide, the potassium ferricyanide and Prussian blue sodium chloride crystal of micro-nano chip.Fig. 3 (b) is the cyclic voltammetry curve of this crystal.Fig. 3 (c) is the electrochemical impedance of this crystal.Fig. 3 (d) is the Raman spectrogram of this crystal.
Fig. 3 (e) is the present invention's scanning electron microscope diagram of being doped with potassium ferrocyanide, the potassium ferricyanide and Prussian blue sodium chloride crystal array synthetic on the platinum surface.Fig. 3 (f) is the electron energy scattering spectra (EDS) of this crystal.
Fig. 4 is that the present invention is at the scanning electron tunnel microscope figure of the synthetic layer/polyaniline conductive material of electro-conductive glass.
Fig. 5 (a) is the PSTM figure of the present invention at the synthetic zinc oxide nano film material of electro-conductive glass, and Fig. 5 (b) is that micrograph is amplified in the part of this material among Fig. 5 (a).Fig. 5 (c) is the electron energy scattering spectra (EDS) of this this material.
The specific embodiment
Definition
Term used herein " micro-nano " refers to the size range from some nanometers to tens micron.
The micro-nano processing method of the functional material based on electrochemistry micro-nano system of the present invention, by microcell physicochemical environment on regulation and control conductive substrates or the chip, with the modes such as crystallization, precipitation, electro-deposition, electrochemical polymerization, electrochemistry induced polymerization, the functional material of original position synthetizing micro-nano yardstick on conductive substrates or micro-nano chip.
Described microcell physicochemical environment comprises herein: hydrophily or the hydrophobicity of the open pointed tip of micro-nano-scale, processed conductive substrates or micro-nano chip surface; Connect ascending to heaven to shape, surface tension or the vapour pressure etc. of the electrolyte solution of skin upgrading volume of the open pointed tip of micro-nano-scale and processed conductive substrates or micro-nano chip surface; Processed conductive substrates or micro-nano chip surface and ascend to heaven to the pH value of the electric double layer character of the electrochemical interface of the electrolyte solution compositions of skin upgrading volume, electrode potential, interface zone etc.
The micro-nano processing unit (plant) of the functional material based on electrochemistry micro-nano system of the present invention, this device by the electrochemical reactor of micro-nano-scale (be called for short: electrochemistry micro-nano reactor), the three-dimensional fine motion system of electrochemical workstation, micro-nano precision (be called for short: three-dimensional fine motion system), video-frequency monitor and information processing computer form, can realize all solid state function element of micro/nano level efficiently, batch making.
Electrochemical reactor is provided with the capillary vessel at micro-or nano size tip, auxiliary and reference electrode, working electrode.Container with micro-nano-scale opening for example by the capillary glass tube with micro-nano most advanced and sophisticated opening or the quartz capillary of laser pulling method preparation, is used for holding electrolyte solution, reference electrode and to electrode; Generally speaking, processed substrate or micro-nano chip serve as working electrode; Between the two by ascend to heaven (～fL) to the skin liter (～pL) level volume electrolyte solution be in contact with one another, consist of an electrochemistry micro-nano reactor.
Electrochemical workstation is used for control by voltage, electric current and the frequency thereof of electrochemistry micro-nano reactor, thereby microcell physics, chemical environment on regulation and control conductive substrates or the micro-nano chip, with the modes such as crystallization, precipitation, electro-deposition, electrochemical polymerization, electrochemistry induced polymerization, the functional material of original position synthetizing micro-nano yardstick on substrate or micro-nano chip.
The three-dimensional fine motion system of micro-nano precision can be provided with the control device of top fixed mount, bottom fixed mount, the three-dimensional microdrive of X-Y-Z and three-dimensional fine motion system.Three-dimensional fine motion system is used for accurate mobile electrochemistry micro-nano reactor to the ad-hoc location of substrate or micro-nano chip, carries out efficient, the batch making of all solid state function components and parts of micro/nano level.
Video-frequency monitor can be provided with light emitting diode (being called for short LED) lamp, high magnification amplifies the CCD camera (namely with the remote sensing camera of charge-coupled image sensor (CCD) as light sensor and optical-electrical converter.) camera lens and display, be used for the process Real Time Monitoring, guarantee that electrochemistry micro-nano reactor enters the ad-hoc location of substrate or micro-nano chip and good contact with it.
The information processing computer is used for electrochemical workstation, three-dimensional fine motion system, video-frequency monitor are sent instruction and feedback information, and that guarantees to process carries out smoothly.
The material capillaceous that is used for formation electrochemistry micro-nano reactor for example is glass and quartz, and the laser tensilometer of employing sequencing (PS2000 is made by Sutter Co.) heats middle part capillaceous and stretches.When capillary disconnects, can form the smooth circular open with micro-or nano size, its diameter can be by changing the laser tensilometer parameter (for example, laser output power, laser conduction speed, the flow velocity of melten glass, heating time-delay and/or the strength that stretches) to regulate, scope is 20nm～200 μ m.In order further to improve the quality of the micro-nano opening of capillary, can adopt accurate polishing instrument that it is polished.Can also adopt silane coupler that its surfaces externally and internally is carried out modification by capillarity and substrate or micro-nano chip good contact in order to ensure the electrolyte solution in the capillary, improve the affinity of capillary wall and electrolyte solution.
Being fixed on the capillary with micro/nano level open pointed tip in the three-dimensional fine motion system, also is the probe of a movement simultaneously.Under the synergy of video-frequency monitor, when it contacts by little drop with the ad-hoc location of substrate or micro-nano chip, just consisted of electrochemistry micro-nano reactor.The physical and chemical process of electrochemical regulating and controlling just occurs in this little drop, thereby has guaranteed the micro-nano precision of processing.
The electrochemistry microreactor is take the conductive substrates of processing or the ad-hoc location of micro-nano chip as working electrode, to have the capillary micro cell of micro-nano opening, wherein holds electrolyte solution, reference electrode and to electrode.Since working electrode only with one ascend to heaven (～fL) to the skin liter (～pL) level volume the electrolyte drop contact with micro cell, its yardstick is also at micro/nano level, operating current is very little, experimentally reference electrode and can unite two into one to electrode is only implanted in the capillary with a silver/silver chloride electrode.
Electrolyte solution in the electrochemistry microreactor, different according to synthetic object, its solvent can for water, organic solvent (such as acetonitrile, methyl-sulfoxide, N, N '-dimethyl formamide, dichloroethanes, ortho-nitrophenyl octyl ether etc.), ionic liquid (take quaternary ammonium salt ion, quaternary alkylphosphonium salt ion, imidazole salts ion and pyrroles's salt ion etc. as cation) or the mixed solvent that formed by them.
Described functional material comprises inorganic functional material and organic functional material
Inorganic functional material can be by electrochemistry micro-nano reactor the variation of microcell physical parameter, vapour pressure for example generates with the method for physical crystal, in the process of crystallization, can also mix by electrochemical method.Isopolyacid and the heteropoly acid thereof that can synthesize in this way, the elements such as vanadium with good optics, electricity and catalytic property, niobium, molybdenum, tungsten, tantalum, chromium, silicon, phosphorus, boron; Can also synthesize the functional inorganic materials with special light, electricity, magnetic property, comprising the formed solid solution of cyanogen root complex of the transition metal such as doping iron, cobalt, rhodium, iridium, nickel, palladium, platinum, copper, silver, gold, zinc in sodium chloride, potassium chloride or silver chlorate material.
Organic functional material (material) comprises the conducting polymer take aniline, pyrroles, thiophene, benzene and its derivative as monomer, can directly generate by the mode of electrochemical polymerization; For non-conductive polymer, then can produce free radical by electrochemical reaction, come original position synthetic in the mode of induced polymerization, for example, produce sulfate radical free radical (SO by electrochemical method
4 2-) induce the polymerization of ethene and derivative thereof.
Semiconductor function nano material, comprise titanium dioxide with good light electro catalytic activity, zinc oxide, manganese dioxide, cadmium selenide etc., not only can be by electrochemical method preparation, and, by regulating the physical-chemical parameters of electrochemistry micro-nano reactor microcell, can control the pattern of these function nano materials.
Preparation or the using method of the micro-nano processing unit (plant) of the functional material based on electrochemistry micro-nano system of the present invention may further comprise the steps:
1) prepare the container with micro-nano-scale open pointed tip, the capillary glass tube or the quartz capillary that for example have the micro-nano-scale open pointed tip are as electrochemistry micro-nano electrolytic cell;
2) processed conductive substrates or micro-nano chip are fixed on the base as electrochemical working electrode;
3) electrolytical solution is injected the electrochemistry micro-nano electrolytic cell with micro-nano-scale opening, insert reference electrode and auxiliary electrode;
The electrochemistry micro-nano electrolytic cell that 4) electrolyte solution, reference electrode and auxiliary electrode will be housed is fixed on the fixed mount of three-dimensional fine motion system;
5) LED lamp and high magnification amplification CCD camera lens are fixed on the video fixture, regulate light path, focus on the position that will process on substrate or the micro-nano chip;
6) start three-dimensional fine motion system, the Working position of mobile electrochemistry micro-nano electrolytic cell to substrate or the micro-nano chip; Regulate three-dimensional fine motion system, the solution of capillary tip is contacted with the Working position of substrate or micro-nano chip, consist of electrochemistry micro-nano reactor;
7) start electrochemical workstation, regulation and control microcell electrochemical reaction, the original position of carrying out functional material at substrate or micro-nano chip is synthetic.
With the technology based on SPM, compare with the AFM technology such as STM, the present invention has following outstanding advantages:
1) electrochemistry micro-nano electrolytic cell contacts by the electrolyte drop with substrate or micro-nano chip surface, does not have actual Mechanical Contact, thereby can not produce mechanical damage to substrate or micro-nano chip;
2) substrate or micro-nano chip place atmospheric environment, and only the specific site in processing contacts with electrolyte solution, can not pollute and destroy substrate or micro-nano chip.
3) adopt the integrated electrochemistry micro-nano electrolytic cell of array, also can realize efficient, batch machining.
4) guaranteeing that processing unit (plant) is simple to operate, cheap under the prerequisite of micro-nano precision, less demanding to processing environment has significant cost advantage.
Fig. 1 has provided the composition schematic diagram of device for carrying out said example of the micro-nano processing method of the functional material based on electrochemistry micro-nano system of the present invention.Adopt the capillary glass tube 1 of micro-or nano size open pointed tip as the electrochemistry micro cell, the Ag silk of 0.3mm or Pt silk insert the solution 9 in the capillary glass tube 1 as auxiliary and reference electrode 2.Capillary glass tube 1 is fixed on the top fixed mount 3 of three-dimensional fine motion system, top fixed mount 3 links to each other with the three-dimensional microdrive 4 of the X-Y-Z of three-dimensional fine motion system, the three-dimensional microdrive 4 of X-Y-Z connects the control device 5 of three-dimensional fine motion system, the control device 5 link information process computers 6 of three-dimensional fine motion system.Base material or micro-nano chip are linked electrochemical workstation 7 as working electrode 8, and working electrode 8 is fixed on the bottom fixed mount 10 of three-dimensional fine motion system, electrochemical workstation 7 link information process computers 6.High magnification is amplified the both sides that CCD camera lens 11 and LED lamp 13 place working electrode 8, connect screen 12, the situation that contacts of sight glass capillary and working electrode, and contact formation electrochemistry micro-nano reactor with the ad-hoc location of working electrode 8 with the three-dimensional microdrive 4 movable glass capillaries 1 of X-Y-Z.Utilize electrochemical workstation 7 controls by voltage, electric current and the frequency thereof of electrochemistry micro-nano reactor, thereby microcell physics, chemical environment on regulation and control substrate or the micro-nano chip, with the modes such as crystallization, precipitation, electro-deposition, the functional material of original position synthetizing micro-nano yardstick on substrate and micro-nano chip.
The micro-nano processing method of the functional material based on electrochemistry micro-nano system of the present invention, the solution contact by capillary tip between its capillary glass tube 1 and the working electrode 8, machinery-free contact.
Below the present invention is further illustrated for general embodiment in conjunction with the drawings.These embodiment only are illustrative, limit the scope of the invention and be not intended to.
Embodiment
Embodiment 1:
The present embodiment uses processing unit (plant) shown in Figure 1 to carry out.Processing conditions: adopting most advanced and sophisticated opening diameter is the container as electrochemical reactor of 5 microns capillary glass tube, and the solution in the capillary contains 0.001mol/dm
3Silico-tungstic acid (H
4SiW
12O
40), solvent is water; Be in the indoor environment; 0.3mm the Ag silk of diameter is as reference electrode with to electrode, the sheet glass of platinum plating is as working electrode.Start three-dimensional fine motion system, according to the screen viewing of video monitoring system, the movable glass capillary approaches until the solution of capillary tip just in time is in contact with it the capillary glass tube tip gradually with the platinum surface.Begin to start electrochemical workstation, adopt cyclic voltammetry, the cyclic voltammetry parameter is as follows: sweep fast 0.1V/s, maximum potential 0.2V, potential minimum-0.3V, the circulation number of turns 1 circle.After time finishes, start in the three-dimensional fine motion system and carry capillary glass tube at once.Repeat above step, obtain silico-tungstic acid material array on the platinum surface.Experimental result is referring to Fig. 2 (a), and it is SEM (FESEM LEO 1530 is made by the LEO Co.) photo of the silico-tungstic acid material array that obtains.Fig. 2 (b) is the cyclic voltammetry curve (CHI960c is made by CHI Instrument Co.) of silico-tungstic acid individual particle material.Resulting silico-tungstic acid individual particle material has several continuous redox peaks when activation polarization, what each peak represented is a kind of state, and such character can be used for making on-off circuit or memory device.
Embodiment 2:
The present embodiment uses processing unit (plant) shown in Figure 1 to carry out.The present embodiment is synthesizing blender potassium ferrocyanide, the potassium ferricyanide and Prussian blue sodium chloride crystal on microchip, processing conditions: microchip cleans up after 12 hours with the acetone immersion; Used container is that tip diameter is 5 microns capillary glass tube, and the solution in the capillary contains 0.05mol/dm
3Sodium chloride (NaCl), 0.001mol/dm
3Potassium ferrocyanide (K
4Fe (CN)
6), solvent is water; Be in the indoor environment; 0.3mm the Ag silk of diameter is as reference electrode with to electrode, the microchip that has cleaned is as working electrode.Start three-dimensional fine motion system, according to the screen viewing of video monitoring system, the movable glass capillary approaches until the solution of capillary tip just in time is in contact with it the capillary glass tube tip gradually with the characteristics position of microchip.Begin to start electrochemical workstation, adopt cyclic voltammetry, the cyclic voltammetry parameter is as follows: sweep fast 0.1V/s, maximum potential 0.5V, potential minimum 0V, the circulation number of turns 1 circle.After time finishes, start in the three-dimensional fine motion system and carry capillary glass tube, obtain doping potassium ferrocyanide, the potassium ferricyanide and Prussian blue sodium chloride crystal at microchip at once.
In the present embodiment, change the substrate/solution phase boundary potential by cyclic voltammetry, thereby can change surface tension and the vapour pressure of little drop, accelerate evaporation of water, the microcell sodium chloride concentration is reached capacity and crystallization rapidly.Simultaneously, in the process of Electrochemical Scanning, the ratio that is doped to the potassium ferricyanide on the crystal lattices and potassium ferrocyanide also can be adjusted.Experimental result is referring to Fig. 3 (a), and it is optical microphotograph (Olympus BX-51 is made by the Olympus Co.) figure behind synthesizing blender potassium ferrocyanide on the microchip that obtains, the potassium ferricyanide and the Prussian blue sodium chloride crystal.Fig. 3 (b) has provided the cyclic voltammetry curve of this crystal, adopts the CHI960c that is made by CHI Instrument Co. to carry out.Fig. 3 (c) is the electrochemical impedance of this crystal, adopts by Advanced MeasurementTechnolgy, and the Parstat 2273 that Inc. makes carries out.Fig. 3 (d) is the Raman spectrogram of this crystal, adopts the Renishaw inVia Raman microscope that is made by Renishaw Plc. to carry out.As seen, the doping potassium ferrocyanide that obtains, the potassium ferricyanide and Prussian blue sodium chloride crystal have good redox property and Raman spectrum character under all solid state environment, can be used for making all solid state electrochemistry micro element or electric look micro element.
Embodiment 3
The present embodiment uses processing unit (plant) shown in Figure 1 to carry out.The present embodiment is synthesizing blender potassium ferrocyanide, the potassium ferricyanide and Prussian blue sodium chloride crystal on the sheet glass of platinum plating, its processing conditions: adopt the open pointed tip diameter be 5 microns capillary glass tube as described container, the solution in the capillary contains 0.05mol/dm
3Sodium chloride (NaCl), 0.00001mol/dm
3Potassium ferrocyanide (K
4Fe (CN)
6), solvent is water; Be in the indoor environment; 0.3mm the Ag silk of diameter is as reference electrode with to electrode, the sheet glass of platinum plating is as working electrode.Start three-dimensional fine motion system, according to the screen viewing of video monitoring system, the movable glass capillary approaches until the solution of capillary tip just in time is in contact with it the capillary glass tube tip gradually with the glass sheet surface of platinum plating.Begin to start electrochemical workstation, adopt cyclic voltammetry, the cyclic voltammetry parameter is as follows: sweep fast 0.1V/s, maximum potential 0.5V, potential minimum 0V, the circulation number of turns 1 circle.After time finishes, start in the three-dimensional fine motion system and carry capillary glass tube at once.Repeat above step, obtain the array of figure of sodium chloride material.
In the present embodiment, change the substrate/solution phase boundary potential by cyclic voltammetry, thereby can change surface tension and the vapour pressure of little drop, accelerate evaporation of water, the microcell sodium chloride concentration is reached capacity and crystallization rapidly.Simultaneously, in the process of Electrochemical Scanning, the ratio that is doped to the potassium ferricyanide on the crystal lattices and potassium ferrocyanide also can be adjusted.Experimental result is referring to Fig. 3 (e), and it is the doping potassium ferrocyanide, the potassium ferricyanide on platinum surface and SEM (FESEM LEO 1530 is made by the LEO Co.) figure of Prussian blue sodium chloride crystal array.Fig. 3 (f) is the electron energy scattering spectra of this crystal, uses the FESEM LEO 1530 that is made by LEO Co. to carry out.In the same manner as in Example 2, the doping potassium ferrocyanide that obtains, the potassium ferricyanide and Prussian blue sodium chloride material also have good redox property and Raman spectrum character under all solid state environment, can be used for making all solid state little electrochemical device or little electrochromic devices.
Embodiment 4:
The present embodiment uses processing unit (plant) shown in Figure 1 to carry out.The present embodiment carries out at conductive glass surface.Processing conditions: adopt the open pointed tip diameter be 25 microns capillary glass tube as described container, the solution in the capillary contains 0.2mol/dm
3Aniline (C
6H
5NH
2), 0.5mol/dm
3Sulfuric acid (H
2SO
4), 0.2mol/dm
3Hydrochloric acid (HCl), solvent are water; Be in the indoor environment; 0.3mm the Ag silk of diameter is as reference electrode with to electrode, the electro-conductive glass sheet is as working electrode.Start three-dimensional fine motion system, according to the screen viewing of video monitoring system, the movable glass capillary approaches until the solution of capillary tip just in time is in contact with it the capillary glass tube tip gradually with conductive glass surface.Begin to start electrochemical workstation, adopt cyclic voltammetry, the cyclic voltammetry parameter is as follows: sweep fast 0.1V/s, maximum potential 0.75V, potential minimum 0.15V, the circulation number of turns 1 circle.After time finishes, start in the three-dimensional fine motion system and carry capillary glass tube, obtain polyaniline material at conductive glass surface at once.Experimental result is referring to Fig. 4, and it is scanning electron tunnel microscope (FESEM LEO 1530 is made by the LEO Co.) figure of the polyaniline material that obtains.In the embodiment of this electrochemical polymerization, the purpose of electrochemical regulating and controlling is to make aniline under the condition of anode polarization electric polymerization reaction to occur, and the polyaniline of generation is the solid polymer that is insoluble to electrolyte solution.The material of gained has good electric conductivity, has good environmental stability.Can be used for preparing all solid state electrochemical devices such as microsensor, micro cell and microcapacitor.
Embodiment 5:
The present embodiment uses processing unit (plant) shown in Figure 1 to carry out processing conditions: adopt tip diameter be 80 microns capillary glass tube as described container, the solution in the capillary contains 0.1mol/dm
3Zinc nitrate (Zn (NO
3)
2), 0.01mol/dm
3Six methines, four ammonium (C
6H
12N
4), solvent is water; Be in the indoor environment; 0.3mm the Ag silk of diameter is as reference electrode with to electrode, the electro-conductive glass sheet is as working electrode.Start three-dimensional fine motion system, according to the screen viewing of video monitoring system, the movable glass capillary approaches until the solution of capillary tip just in time is in contact with it the capillary glass tube tip gradually with conductive glass surface.Begin to start electrochemical workstation, adopt potentiostatic method, the current potential E of working electrode is constant in-1.4V, keep 1800s.After time finishes, start in the three-dimensional fine motion system and carry capillary glass tube, obtain the zinc oxide nano film material at conductive glass surface at once.Fig. 5 (a) is scanning tunneling microscope (the FESEM LEO1530 of the zinc oxide nano film material of acquisition, made by LEO Co.) figure, Fig. 5 (b) is the PSTM figure that amplify the part of nano film material among Fig. 5 (a), Fig. 5 (c) is the electron energy scattering spectra of zinc oxide nano film material, uses the FESEM LEO 1530 that is made by LEO Co. to carry out.
The purpose of electrochemical regulating and controlling is to change the pH value of substrate/solution interface microcell in the present embodiment, so that the zinc ion precipitation forms zinc oxide nano film under alkali condition.The material of gained has many special character, such as non-migrating, fluorescence, piezoelectricity, absorption and scatters ultraviolet ability etc., utilize it in the performance of the aspects such as light, electricity, magnetic, can make gas sensor, fluorophor, rheostat, UV-preventing material, image recording material, piezoelectric, piezo-resistance, effective catalyst, magnetic material and plastic sheeting etc.
Industrial applicability
Micro-nano processing method and the device of the functional material based on electrochemistry micro-nano system of the present invention are particularly suitable for all solid state micro-nano devices field.
Claims (10)
1. micro-nano processing method based on the functional material of electrochemistry micro-nano system, described method comprises:
Construct the electrochemical reactor of micro-nano-scale, be limited in the physical and chemical process with the complex functionality material in the space of micro-nano-scale; And
Regulate and control conductive substrates to be processed or the microcell physicochemical environment on the chip, with the functional material of original position synthetizing micro-nano yardstick on conductive substrates or micro-nano chip.
2. the micro-nano processing method of the functional material based on electrochemistry micro-nano system according to claim 1, the electrochemical reactor of described micro-nano-scale comprises:
Container with open pointed tip of micro-nano-scale;
Place the auxiliary and reference electrode in the described container;
Processed conductive substrates or micro-nano chip, it is as working electrode; And
Be positioned at ascending to heaven to the electrolyte solution of skin upgrading volume of described vessel port tip;
Wherein said micro-nano-scale open pointed tip and processed conductive substrates or micro-nano chip contact by described ascending to heaven to the electrolyte solution of skin upgrading volume.
3. the micro-nano processing method of the functional material based on electrochemistry micro-nano system according to claim 2, described electrolyte solution is definite by required synthetic functional material, and its solvent is at least one that is selected from the following: water, organic solvent, ionic liquid and the mixed solvent that is comprised of them.
4. the micro-nano processing method of the functional material based on electrochemistry micro-nano system according to claim 1, described functional material comprises: by regulation and control microcell physicochemical environment, mix in the inorganic salts crystallization process and the synthetic functional inorganic materials with special light, electricity, magnetic property; Prepare function isopolyacid or the heteropolyacid material with nanoscale and specific micro nano structure by regulation and control microcell physicochemical environment; By regulation and control microcell physicochemical environment, by the direct organic conductive material with micro-nano-scale that generates of the mode of electrochemical polymerization; By regulation and control microcell physicochemical environment, produce free radical by electrochemical reaction, with the synthetic non-conductive polymer with micro-nano-scale of the mode original position of induced polymerization; With, the function nano material with specific morphology of the physical-chemical parameters preparation by regulating electrochemistry micro-nano reactor microcell.
5. the micro-nano processing method of the functional material based on electrochemistry micro-nano system according to claim 1, the microcell physicochemical environment comprises on described conductive substrates or the chip: micro-nano-scale open pointed tip, processed conductive substrates or hydrophily or the hydrophobicity of micro-nano chip surface; Connect ascending to heaven to shape, surface tension or the vapour pressure of the electrolyte solution of skin upgrading volume of the open pointed tip of micro-nano-scale and processed conductive substrates or micro-nano chip surface; And, processed conductive substrates or micro-nano chip surface and ascend to heaven to the pH value of the electric double layer character of the electrochemical interface of the electrolyte solution compositions of skin upgrading volume, electrode potential, interface zone.
6. micro-nano processing unit (plant) based on the functional material of electrochemistry micro-nano system, described device comprise three-dimensional fine motion system, video-frequency monitor and the information processing computer of electrochemical reactor, electrochemical workstation, the micro-nano precision of micro-nano-scale,
Described electrochemical reactor is provided with: the container with micro-nano-scale open pointed tip; Be contained in the auxiliary and reference electrode in the described container, and as processed conductive substrates or the micro-nano chip of working electrode, be in contact with one another by the electrolyte solution of upgrading to skin of ascending to heaven between wherein said container and described processed conductive substrates or the micro-nano chip, form an electrochemistry micro-nano reactor;
Described electrochemical workstation is used for control by voltage, electric current and the frequency thereof of electrochemistry micro-nano reactor, thereby microcell physicochemical environment on regulation and control conductive substrates or the chip, in the mode of crystallization, precipitation, electro-deposition, electrochemical polymerization, electrochemistry induced polymerization, the functional material of original position synthetizing micro-nano yardstick on conductive substrates or micro-nano chip;
The three-dimensional fine motion system of described micro-nano precision is used for accurate mobile electrochemistry micro-nano reactor to the ad-hoc location of conductive substrates or micro-nano chip;
Described video-frequency monitor is used for the process Real Time Monitoring, enters the ad-hoc location of conductive substrates or micro-nano chip and with it contact to guarantee electrochemistry micro-nano reactor; And
Described information processing computer is used for instruction transmission and the information feedback to electrochemical workstation, three-dimensional fine motion system, video-frequency monitor, and that guarantees to process carries out smoothly.
7. the micro-nano processing unit (plant) of the functional material based on electrochemistry micro-nano system according to claim 6, described container with open pointed tip of micro-nano-scale be by with the laser tensilometer of sequencing with middle part capillaceous heating and stretch and form.
8. the micro-nano processing unit (plant) of the functional material based on electrochemistry micro-nano system according to claim 7, described container adopts silane coupler that its surfaces externally and internally is carried out modification.
9. the micro-nano processing unit (plant) of the functional material based on electrochemistry micro-nano system according to claim 6, the microcell physicochemical environment comprises on described conductive substrates or the chip: micro-nano-scale open pointed tip, processed conductive substrates or hydrophily or the hydrophobicity of micro-nano chip surface; Connect ascending to heaven to shape, surface tension or the vapour pressure of the electrolyte solution of skin upgrading volume of the open pointed tip of micro-nano-scale and processed conductive substrates or micro-nano chip surface; And, processed conductive substrates or micro-nano chip surface and ascend to heaven to the pH value of the electric double layer character of the electrochemical interface of the electrolyte solution compositions of skin upgrading volume, electrode potential, interface zone.
10. using method that is used for the micro-nano processing unit (plant) of the functional material based on electrochemistry micro-nano system claimed in claim 6, described method comprises following implementation step:
1) preparation has the container of open pointed tip of micro-nano-scale, with as electrochemistry micro-nano electrolytic cell;
2) conductive substrates or micro-nano chip are fixed on the base as electrochemical working electrode;
3) electrolyte solution is injected in the container of the open pointed tip with micro-nano-scale, insert reference electrode and auxiliary electrode;
The container that 4) electrolyte solution, reference electrode and auxiliary electrode will be housed is fixed on the fixed mount of three-dimensional fine motion system;
5) the LED lamp in the video-frequency monitor and high magnification amplification CCD camera lens are fixed on the video fixture, regulate light path, focus on the position that will process on conductive substrates or the micro-nano chip;
6) start three-dimensional fine motion system, the Working position of mobile container as electrochemistry micro-nano electrolytic cell to conductive substrates or the micro-nano chip; Regulate three-dimensional fine motion system, the solution at container tip is contacted with the Working position of conductive substrates or micro-nano chip, consist of electrochemistry micro-nano reactor; And
7) start electrochemical workstation, regulation and control microcell electrochemical reaction, the original position of carrying out functional material at conductive substrates or micro-nano chip is synthetic.
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