CN103107737B - Piezoelectricity friction combined type micro-nano generator and preparation method thereof - Google Patents
Piezoelectricity friction combined type micro-nano generator and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to the integrated manufacture field of MEMS, be specifically related to a kind of based on piezoelectricity friction combined type micro-nano generator and preparation method thereof, adopt piezoelectric membrane to form piezo-electric type generator, utilize piezoelectric membrane metal electrode and other flexible polymeric materials to form friction-type generator to the difference of charge confinement ability.Compare with traditional piezo-electric type generator, friction-type generator, by piezoelectricity and friction compound, and by rational external circuit connected mode, can be capacitor charging efficiently, and provide the voltage up to hectovolt to export.In sum, piezoelectricity friction combined type micro-nano generator that the present invention proposes and preparation method thereof cost is low, productive rate is high, technique is simple, and has high voltage output and very strong charging ability.Electric generator structure comprises: piezoelectric membrane, piezoelectric membrane electrode, the flexible polymeric materials with micro-nano compound structure, polymeric material electrode.
Description
Technical field
The present invention relates to the integrated manufacture field of MEMS, be specifically related to a kind of based on piezoelectricity friction combined type micro-nano generator and preparation method thereof.
Background technology
MEMS (micro electro mechanical system) (Micro-electro-mechanicalsystem, MEMS) is an emerging multi-field cross discipline, and development in recent years is very rapid, receives extensive concern both domestic and external.For various MEMS, generally all need power supply energy supply, but traditional energy-provision way such as battery, transmission line cannot meet miniaturized demand.In recent years, the MEMS that develops into of nano generator provides a kind of new energy-provision way.According to different operation principles, nano generator can be divided into several classes such as piezo-electric type, thermoelectric type, friction-type.Wherein piezo-electric type and friction-type are all that the vibrational energy in the external world is changed into electric energy.
For piezo-electric type nano generator, Wang Zhonglin teaches research group and utilizes zinc oxide nanowire successfully to prepare piezo-electric type nano generator [Wang, Z.L.etal.Science, vol.312, pp.5771,2006; Zhu Guang etc., nano generator and manufacture method thereof, Chinese invention patent, application number: 201210116881.4; Li Mengke etc., a kind of nano generator, Chinese invention patent, application number: 200910188057.8; Wang Zhonglin etc., nano generator, nanometer generating assembly and self-contained electric system thereof, Chinese invention patent, application number: 201210142387].Piezo-electric type nano generator has good transfer charge ability, very fast to the charging rate of electric capacity, but its output voltage limited (being about tens volts), limit its charging ability to a certain extent.
Compared to piezo-electric type nano generator, friction-type nano generator utilizes the difference of different materials receiving and losing electrons ability, make different materials surface with xenogenesis electric charge by friction, when different surfaces produces relative motion, due to the change of capacitance between two surfaces, have flow of charge in external circuit, thus reach the effect of generating.Two surfaces are made to be separated [Wang rapidly by domes, S., Lin, L.andWang, Z.L.NanoLetters, vol.12, pp.6339,2012], the friction-type nano generator that high voltage exports can be obtained, its output voltage peak value is up to a few hectovolt, but the equivalent internal resistance of friction-type nano generator is very large, and individual layer friction structure is not strong to the charging ability of electric capacity.
Summary of the invention
The object of the present invention is to provide a kind of friction Piezoelectric anisotropy formula micro-nano generator and preparation method thereof, adopt piezoelectric membrane to form piezo-electric type generator, utilize piezoelectric membrane metal electrode and other flexible polymeric materials to form friction-type generator to the difference of charge confinement ability.Compare with traditional piezo-electric type generator, friction-type generator, by piezoelectricity and friction compound, and by rational external circuit connected mode, can be capacitor charging efficiently, and provide the voltage up to hectovolt to export.In sum, piezoelectricity friction combined type micro-nano generator that the present invention proposes and preparation method thereof cost is low, productive rate is high, technique is simple, and has high voltage output and very strong charging ability.
For achieving the above object, the invention provides a kind of piezoelectricity friction combined type micro-nano generator, this structure comprises: piezoelectric membrane, piezoelectric membrane electrode, the flexible polymeric materials with micro-nano compound structure, polymeric material electrode.Described piezoelectric membrane is Kynoar (polyvinylidenefluoride, PVDF); Described piezoelectric membrane electrode be metallic aluminium or other there is metal compared with the positive power of strong band as nickel, copper, silver; The described flexible polymeric materials with micro-nano compound structure is the bonding structure of dimethyl silicone polymer (polydimethylsiloxane, PDMS) and PETG (polyethyleneterephthalate, PET); Described polymeric material electrode is the metals like gold, silver, platinum, copper, aluminium etc. that semi-conducting material comprises indium tin metal oxide (ITO) or other good conductivity.
The flexible polymeric materials of described micro-nano compound structure comprises micrometer structure and nanostructure, and wherein micrometer structure is pyramid array or groove grid array or hemisphere array, and characteristic size is 1 μm-200 μm, and spacing is 1 μm-50 μm; Nanostructure is nanometer burr or nanometer sieve aperture, and characteristic size is 2nm-1000nm, spacing 2nm-500nm.
Present invention also offers a kind of nano generator manufacture method, comprise the following steps:
1), by the method for spin coating or Self-leveling, be covered in by PVDF solution on silicon chip or other horizontal surface, heating PVDF solution, makes PVDF thin film;
2) PVDF thin film that, polarizes under strong electric field makes it have piezoelectricity;
3), by evaporation or sputtering technology, electrode is made in PVDF thin film both sides;
4), by photoetching, wet etching or dry etching, silicon chip or glass substrate make micrometer structure;
5) the deep reaction ion etching technique, by optimizing, makes on the surface at micrometer structure and has high-aspect-ratio and highdensity nanostructure, and reduces the surface energy of body structure surface by aftertreatment technology;
6), by PDMS casting film transfer printing process, preparation has the PDMS fexible film of micro-nano compound structure;
7), by heating, PDMS film and the PET film bonding of micro-nano compound structure will be had;
8), by evaporating or sputtering or chemical vapor deposition method, electrode is made on PET film surface;
9), electroded PVDF piezoelectric membrane and electroded PDMS-PET bonding structure are assembled and encapsulated.
In described step 1), the solute of PVDF solution is PVDF powder, and solvent is DMF (N, N-dimethylformamide, DMF), and Solute mass fraction is 5%-20%, and heating-up temperature is 80-130 DEG C, and the time is 2 hours-4 hours.
Described step 2) in, polarized electric field intensity is 50kV/cm-1500kV/cm.
In described step 3), electrode is have metal compared with the positive power of strong band as aluminium, nickel, copper, silver etc.
In described step 4), the characteristic size of micrometer structure is 1 μm-200 μm, and spacing is 1 μm-50 μm.
In described step 5), the characteristic size of nanostructure is 2nm-1000 μm, and spacing is 2nm-500nm; The technological parameter of preparation nanostructure is: coil power is 800W – 900W, and pressure is 20mTorr-30mTorr, etching gas SF
6flow is 20sccm – 45sccm, passivation gas C
4f
8or O
2flow is 30sccm-50sccm, wherein SF
6and C
4f
8gas flow ratio is 1:1-1:2, and platen power is 6W-12W, and etching/passivation time is than being 10s:10s-4s:4s, etching/passivation cycle 60-200 time; Aftertreatment technology parameter is: coil power is 800W-900W, and pressure is 20mTorr-30mTorr, etching gas SF
6flow is 0sccm, passivation gas C
4f
8or O
2flow is 30sccm-50sccm, and platen power is 6W-12W, and etching/passivation time is than being 0s:10s-0s:4s, etching/passivation cycle 1-20 time.
In described step 7), heating-up temperature is 50-100 DEG C, and the time is 30 minutes-2 hours.
In described step 8), electrode is the metals like gold, silver, platinum, copper, aluminium etc. that semi-conducting material comprises indium tin metal oxide (ITO) or other good conductivity.
The above preparation process, its process sequence not immobilizes, according to actual needs adjustable process sequence or delete processing step.
Its output voltage of piezoelectricity friction combined type micro-nano generator prepared by above-mentioned steps is adopted to be more than or equal to 10 volts, be preferably greater than or equal to 50 volts, more preferably greater than equaling a hectovolt, single transfer charge capability is more than or equal to 10 Na Ku, be preferably greater than or equal to 50 Na Ku, more preferably greater than equaling 100 Na Ku.
Piezoelectricity friction combined type micro-nano generator provided by the present invention can be applied to following field:
1, in conjunction with the feature of this combined type micro-nano generator high output voltage, high charge transport capability, can, by as mutually integrated in mobile phone, MP3 etc. to the device designed by the present invention and portable electric appts, in conjunction with respective handling circuit, be portable electric appts charging.
2, the device designed by the present invention is placed in the general occasion of mechanical movement, as sole, road surface, tire, mouse, keyboard etc., effectively can gathers the mechanical energy in environment, and convert thereof into electric energy for utilization.
3, that this micro-nano generator is vibrated to external world is very responsive for piezoelectricity friction composite structure, can as self-driven transducer for detecting the change of external environment, as leak of liquid, structural mutation etc.
The advantage of piezoelectricity friction combined type micro-nano generator provided by the invention is:
1, the piezoelectricity friction combined generator of the present invention's proposition, compared with simple piezo-electric type generator, friction-type generator, has had lifting, has achieved the mutual supplement with each other's advantages of piezo-electric type generator and friction-type generator in output voltage, charging ability.
2, the piezoelectricity friction combined generator of the present invention's proposition, its friction surface adopts the flexible polymeric materials with micro-nano compound structure, improves surface roughness, thus improves the output performance of device.
3, the manufacturing approach craft that proposes of the present invention is simple, cost is low, with short production cycle, in conjunction with casting film transfer printing process, can large area prepare and have the PDMS film of micro-nano compound structure in enormous quantities
Accompanying drawing explanation
Fig. 1 is piezoelectricity friction combined type micro-nano generator structural representation of the present invention.
Fig. 2 is PVDF piezoelectric membrane stereoscan photograph of the present invention.
Fig. 3 is the mould stereoscan photograph with micro-nano compound structure of the present invention.
Fig. 4 (a) is the output voltage waveforms of micro-nano generator of the present invention.
Fig. 4 (b) for micro-nano generator of the present invention be the waveform of capacitor charging.
Embodiment
The present invention is further described below in conjunction with embodiment.Scope of the present invention is not by the restriction of these embodiments, and scope of the present invention proposes in detail in the claims.
The concrete steps of piezoelectricity friction combined type micro-nano generator provided by the invention and preparation method thereof are set forth below in conjunction with accompanying drawing 1-Fig. 4.
Reference Fig. 1, Fig. 1 are piezoelectricity friction combined generator structural representation of the present invention, and its structure comprises: PVDF piezoelectric membrane 1, piezoelectric membrane electrode 2, has the PDMS film 3 of micro-nano compound structure, PET film 4, polymeric material electrode 5.Reference Fig. 2, Fig. 2 are PVDF piezoelectric membrane stereoscan photograph of the present invention.Reference Fig. 3, Fig. 3 are the mould stereoscan photograph with micro-nano compound structure of the present invention.With reference to Fig. 4, Fig. 4 (a) output voltage waveforms that is micro-nano generator of the present invention, Fig. 4 (b) for micro-nano generator of the present invention be the waveform of capacitor charging.Then the preparation process of structure shown in Fig. 1 is as follows:
Step 1: by the method for spin coating or Self-leveling, PVDF solution is covered on silicon chip or other horizontal surface, heating PVDF solution, make PVDF thin film 1, heating-up temperature is 80-130 DEG C, and the time is 2 hours-4 hours;
Step 2: the PVDF thin film that polarizes under strong electric field makes it have piezoelectricity, and electric field strength is 50kV/cm-1500kV/cm;
Step 3: by evaporation or sputtering technology, makes metal electrode 2 in PVDF thin film both sides;
Step 4: by photoetching, wet etching or dry etching, silicon chip or glass substrate make micrometer structure, and micrometer structure comprises pyramid array or groove grid array or hemisphere array, and characteristic size is 1 μm-200 μm, spacing 1 μm-50 μm;
Step 5: by the deep reaction ion etching technique optimized, make on the surface at micrometer structure and have high-aspect-ratio and highdensity nanostructure, nanostructure comprises nanometer burr or nanometer sieve aperture, and characteristic size is 2nm-1000nm, spacing 2nm-500nm;
Step: 6: by PDMS casting film transfer printing process, preparation has the PDMS fexible film 3 of micro-nano compound structure;
Step 7: by heating, will have PDMS film 3 and PET film 4 bonding of micro-nano compound structure, heating-up temperature is 50-100 DEG C, and the time is 30 minutes-2 hours;
Step 8: by evaporating or sputtering or chemical vapor deposition method, makes electrode 5 on pet layer surface;
Step 9: assemble with the PVDF piezoelectric membrane of electrode and electroded PDMS-PET bonding structure and encapsulate.
With reference to Fig. 4 (a), adopt piezoelectricity friction combined type micro-nano generator prepared by above step under the applied vibration of 5Hz, output voltage peak-to-peak value is 90.4V.With reference to Fig. 4 (b), this piezoelectricity friction combined type micro-nano generator, can by the capacitor charging of 1 μ F to 19.4V in 120s under the applied vibration of 10Hz.
Be described in detail a kind of piezoelectricity friction combined type micro-nano generator provided by the present invention and preparation method thereof above, the exemplary embodiment of above reference accompanying drawing to the application is described.Those skilled in the art should understand that; above-mentioned embodiment is only used to the object that illustrates and the example of lifting; instead of be used for limiting; the any amendment done under all instructions in the application and claims, equivalently to replace, the scope that this application claims protection all should be included in.
Claims (8)
1. a piezoelectricity friction combined type micro-nano generator, is characterized in that, structure comprises: piezoelectric membrane, piezoelectric membrane electrode, the flexible polymeric materials with micro-nano compound structure and polymeric material electrode; Wherein:
The described flexible polymeric materials with micro-nano compound structure is micrometer structure and nanostructure and the bonding structure of the dimethyl silicone polymer deposited and PETG; Wherein:
Described micrometer structure is pyramid array or groove grid array or hemisphere array, and characteristic size is 1 μm-200 μm, and spacing is 1 μm-50 μm; Described nanostructure is nanometer burr or nanometer sieve aperture, and characteristic size is 2nm-1000nm, spacing 2nm-500nm.
2. a kind of piezoelectricity friction combined type micro-nano generator according to claim 1, it is characterized in that, described piezoelectric membrane is Kynoar; Described piezoelectric membrane electrode is metallic aluminium, nickel, copper and/or silver; Described polymeric material electrode is semi-conducting material or the metal comprising gold, silver, platinum, copper and/or aluminium.
3. a kind of piezoelectricity friction combined type micro-nano generator according to claim 2, is characterized in that, described piezoelectric membrane electrode is in polyvinylidene difluoride film both sides, and described semi-conducting material is indium tin metal oxide (ITO).
4. a preparation method for the piezoelectricity friction combined type micro-nano generator as described in one of claim 1-3, is characterized in that, comprise the following steps:
1), by the method for spin coating or Self-leveling, be covered in by PVDF solution on silicon chip or other horizontal surface, heating PVDF solution, makes PVDF thin film;
2) PVDF thin film that, polarizes under strong electric field makes it have piezoelectricity;
3), by evaporation or sputtering technology, electrode is made in PVDF thin film both sides;
4), by photoetching, wet etching or dry etching, silicon chip or glass substrate make micrometer structure;
5), by deep reaction ion etching technique, make on the surface at micrometer structure and there is high-aspect-ratio and highdensity nanostructure, and reduce the surface energy of body structure surface by aftertreatment technology;
6), by PDMS casting film transfer printing process, preparation has the PDMS fexible film of micro-nano compound structure;
7), by heating, PDMS film and the PET film bonding of micro-nano compound structure will be had;
8), by evaporating or sputtering or chemical vapor deposition method, electrode is made on PET film surface;
9), electroded PVDF piezoelectric membrane and electroded PDMS-PET bonding structure are assembled and encapsulated.
5. the preparation method of piezoelectricity friction combined type micro-nano generator as claimed in claim 4, is characterized in that:
In described step 1), the solute of PVDF solution is PVDF powder, and solvent is DMF, and Solute mass fraction is 5%-20%, and heating-up temperature is 80 DEG C-130 DEG C, and the time is 2h-4h;
Described step 2) in, polarized electric field intensity is 50kV/cm-1500kV/cm;
In described step 3), electrode is metallic aluminium, nickel, copper and/or silver.
6. the preparation method of piezoelectricity friction combined type micro-nano generator as claimed in claim 4, is characterized in that:
In described step 4), the characteristic size of micrometer structure is 1 μm-200 μm, and spacing is 1 μm-50 μm;
In described step 5), the characteristic size of nanostructure is 2nm-1000 μm, and spacing is 2nm-500nm; The technological parameter of preparation nanostructure is: coil power is 800W-900W, and pressure is 20mTorr-30mTorr, etching gas SF
6flow is 20sccm-45sccm, passivation gas C
4f
8or O
2flow is 30sccm-50sccm, wherein SF
6and C
4f
8gas flow ratio is 1:1-1:2, and platen power is 6W-12W, and etching/passivation time is than being 10s:10s-4s:4s, etching/passivation cycle 60-200 time; Aftertreatment technology parameter is: coil power is 800W-900W, and pressure is 20mTorr-30mTorr, etching gas SF
6flow is 0sccm, passivation gas C
4f
8or O
2flow is 30sccm-50sccm, and platen power is 6W-12W, and etching/passivation time is than being 0s:10s-0s:4s, etching/passivation cycle 1-20 time.
7. the preparation method of piezoelectricity friction combined type micro-nano generator as claimed in claim 4, is characterized in that:
In described step 7), heating-up temperature is 50 DEG C-100 DEG C, and the time is 30min-2h;
In described step 8), electrode is semi-conducting material or the metal comprising gold, silver, platinum, copper and/or aluminium.
8. comprise an equipment for the described piezoelectricity friction combined type micro-nano generator of one of claim 1-3, it is characterized in that, equipment comprises:
(1) portable electronic charging device, described charging device is mobile phone or MP3;
(2) be placed in the energy absorption device of environment collecting mechanical energy, described energy absorption device is sole, road surface, tire, mouse or keyboard;
(3) self-driven environment monitoring device, described monitoring device is leak of liquid monitoring device or structural mutation monitoring device.
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