CN103107737A - Piezoelectric friction combined type micro-nano generator and prepared method thereof - Google Patents
Piezoelectric friction combined type micro-nano generator and prepared method thereof Download PDFInfo
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Abstract
The invention relates to the field of micro-electromechanical systems (MEMS) integrated processing and particularly relates to a piezoelectric friction combined type micro-nano generator and a prepared method thereof. A piezoelectric type generator is formed by means of using a piezoelectric film, and a friction-type generator is formed by using a piezoelectric film metal electrode and the difference between other flexible polymer materials and an electric charge binding capacity. Compared with a traditional piezoelectric type generator and a traditional friction-type generator, the piezoelectric friction combined type micro-nano generator combines the piezoelectricity with the friction and uses reasonable external circuit connection modes , so that a capacitance can be charged effectively and voltage output which reaches hectovolt can be provided. The piezoelectric friction combined type micro-nano generator and the prepared method of the piezoelectric friction combined type micro-nano generator is low in cost, high in productivity and simple in process and is provided with high voltage output and strong charging ability. The structure of the generator comprises piezoelectric film, a piezoelectric film electrode, the flexible polymer materials with micro-nano composite structure and a polymer 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-mechanical system, MEMS) is an emerging multi-field cross discipline, and development in recent years is very rapid, has been subject to extensive concern both domestic and external.For various MEMS devices, generally all need the power supply energy supply, yet traditional energy-provision way such as battery, transmission line can't satisfy the demand of miniaturization.In recent years, the MEMS device 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 vibrational energy with the external world changes into electric energy.
For the piezo-electric type nano generator, Wang Zhonglin professor research group utilizes zinc oxide nanowire successfully to prepare piezo-electric type nano generator [Wang, Z.L.et al.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].The piezo-electric type nano generator has transfer charge ability preferably, and is very fast to the charging rate of electric capacity, but its output voltage limited (being about tens volts) has limited its charging ability to a certain extent.
Than the piezo-electric type nano generator, the friction-type nano generator utilizes the difference of different materials receiving and losing electrons ability, make the different materials surface with the xenogenesis electric charge by friction, when different surfaces produces relative motion, variation due to capacitance between two surfaces, have flow of charge in external circuit, thereby reach the effect of generating.Make two surfaces separate rapidly [Wang by domes, S., Lin, L.and Wang, Z.L.Nano Letters, vol.12, pp.6339,2012], can obtain the friction-type nano generator of high voltage output, its output voltage peak value is up to several hectovolts, but the equivalent internal resistance of friction-type nano generator is very large, and the 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 piezoelectricity combined type micro-nano generator and preparation method thereof, adopt piezoelectric membrane to consist of the piezo-electric type generator, utilize piezoelectric membrane metal electrode and other flexible polymeric materials to consist of the friction-type generator to the difference of electric charge constraint ability.Compare with traditional piezo-electric type generator, friction-type generator, piezoelectricity is compound with friction, and by rational external circuit connected mode, can be capacitor charging efficiently, and the Voltage-output up to hectovolt is provided.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 is that metallic aluminium or other have than the metal of the positive power of strong band such as nickel, copper, silver; Described flexible polymeric materials with micro-nano compound structure is the bonding structure of dimethyl silicone polymer (polydimethyl siloxane, PDMS) and PETG (polyethylene terephthalate, PET); Described polymeric material electrode is the semi-conducting material metals like gold that comprises indium tin metal oxide (ITO) or other good conductivity, silver, platinum, copper, aluminium etc.
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 μ m-200 μ m, and spacing is 1 μ m-50 μ m; Nanostructure is nanometer burr or nanometer sieve aperture, and characteristic size is 2nm-1000nm, spacing 2nm-500nm.
The present invention also provides a kind of nano generator manufacture method, comprises the following steps:
1), by the method for spin coating or Self-leveling, PVDF solution is covered on silicon chip or other horizontal surface, heating PVDF solution is made the PVDF film;
2), polarization PVDF film makes it have piezoelectricity under highfield;
3), by evaporation or sputtering technology, at PVDF film both sides making electrode;
4), by photoetching, wet etching or dry etching, make micrometer structure on silicon chip or glass substrate;
5), the deep reaction ion etching technique by optimizing, make on the micrometer structure surface and have 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, will have PDMS film and the PET film bonding of micro-nano compound structure;
8), by evaporation or sputter or chemical vapor deposition method, at PET film surface making electrode;
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 the PVDF powder, and solvent is DMF (N, N-dimethyl formamide, DMF), and the solute mass fraction is 5%-20%, and heating-up temperature is 80-130 ℃, 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 to have than the metal of the positive power of strong band such as aluminium, nickel, copper, silver etc.
In described step 4), the characteristic size of micrometer structure is 1 μ m-200 μ m, and spacing is 1 μ m-50 μ m.
In described step 5), the characteristic size of nanostructure is 2nm-1000 μ m, 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 dull and stereotyped power is 6W-12W, and etching/passivation time is than being 10s:10s-4s:4s, etching/passivation cycle 60-200 time; The 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 dull and stereotyped 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 ℃, and the time is 30 minutes-2 hours.
In described step 8), electrode is the semi-conducting material metals like gold that comprises indium tin metal oxide (ITO) or other good conductivity, silver, platinum, copper, aluminium etc.
The above preparation process, its process sequence is not to immobilize, according to actual needs capable of regulating process sequence or delete processing step.
Adopt prepared its output voltage of piezoelectricity friction combined type micro-nano generator of above-mentioned steps more than or equal to 10 volts, be preferably greater than and equal 50 volts, more preferably greater than equaling a hectovolt, single transfer electric charge ability is more than or equal to 10 Na Ku, be preferably greater than and equal 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 characteristics of this combined type micro-nano generator high output voltage, high charge transport capability, device that can the present invention is designed is as mutually integrated in mobile phone, MP3 etc. with portable electric appts, in conjunction with the respective handling circuit, is the portable electric appts charging.
2, the device that the present invention is designed is placed in the general occasion of mechanical movement, as sole, road surface, tire, mouse, keyboard etc., can effectively gather 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 the piezoelectricity friction composite structure, can be used as self-driven transducer for detection of the variation 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, compare with simple piezo-electric type generator, friction-type generator, aspect output voltage, charging ability, lifting arranged, and realized the mutual supplement with each other's advantages of piezo-electric type generator and friction-type generator.
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, has improved surface roughness, thereby has improved 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 the casting film transfer printing process, large tracts of land prepares the PDMS film with micro-nano compound structure in enormous quantities
Description of drawings
Fig. 1 is piezoelectricity friction combined type micro-nano electric generator structure schematic diagram 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.
The waveform that Fig. 4 (b) is capacitor charging for micro-nano generator of the present invention.
Embodiment
Further describe the present invention below in conjunction with embodiment.Scope of the present invention is not subjected to the restriction of these embodiment, and scope of the present invention proposes in claims.
Set forth the concrete steps of piezoelectricity friction combined type micro-nano generator provided by the invention and preparation method thereof below in conjunction with accompanying drawing 1-Fig. 4.
With reference to Fig. 1, Fig. 1 is 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.With reference to Fig. 2, Fig. 2 is PVDF piezoelectric membrane stereoscan photograph of the present invention.With reference to Fig. 3, Fig. 3 is the mould stereoscan photograph with micro-nano compound structure of the present invention.With reference to Fig. 4, Fig. 4 (a) is the output voltage waveforms of micro-nano generator of the present invention, the waveform that Fig. 4 (b) is capacitor charging for micro-nano generator of the present invention.The preparation process of structure shown in Figure 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 is made PVDF film 1, and heating-up temperature is 80-130 ℃, and the time is 2 hours-4 hours;
Step 2: polarization PVDF film makes it have piezoelectricity under highfield, and electric field strength is 50kV/cm-1500kV/cm;
Step 3: by evaporation or sputtering technology, at PVDF film both sides making metal electrode 2;
Step 4: by photoetching, wet etching or dry etching, make micrometer structure on silicon chip or glass substrate, micrometer structure comprises pyramid array or groove grid array or hemisphere array, and characteristic size is 1 μ m-200 μ m, spacing 1 μ m-50 μ m;
Step 5: by the deep reaction ion etching technique of optimizing, make on the micrometer structure surface 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 the PDMS film 3 and PET film 4 bondings of micro-nano compound structure, heating-up temperature is 50-100 ℃, and the time is 30 minutes-2 hours;
Step 8: by evaporation or sputter or chemical vapor deposition method, at pet layer surface making electrode 5;
Step 9: will assemble and encapsulate with PVDF piezoelectric membrane and the electroded PDMS-PET bonding structure of electrode.
With reference to Fig. 4 (a), adopt the prepared piezoelectricity friction combined type micro-nano generator of above step the adding under vibration of 5Hz, the output voltage peak-to-peak value is 90.4V.With reference to Fig. 4 (b), this piezoelectricity friction combined type micro-nano generator adds under vibration 10Hz's, can be with the capacitor charging of 1 μ F to 19.4V in 120s.
Above a kind of piezoelectricity friction combined type micro-nano generator provided by the present invention and preparation method thereof is described in detail, abovely is described with reference to the exemplary embodiment of accompanying drawing to the application.Those skilled in the art should understand that; above-mentioned embodiment is only the example of lifting for illustrative purposes; rather than be used for limiting; all in the application instruction and the claim protection range under do any modification, be equal to replacement etc., all should be included in the claimed scope of the application.
Claims (10)
1. piezoelectricity friction combined type micro-nano generator, its structure comprises: piezoelectric membrane, piezoelectric membrane electrode, the flexible polymeric materials with micro-nano compound structure, polymeric material electrode.
2. a kind of piezoelectricity friction combined type micro-nano generator according to claim 1, described piezoelectric membrane is Kynoar; Described piezoelectric membrane electrode is metallic aluminium, nickel, copper and/or silver; Described flexible polymeric materials with micro-nano compound structure is the bonding structure of dimethyl silicone polymer and PETG; Described polymeric material electrode is the metal of semi-conducting material or other good conductivity.
3. a kind of piezoelectricity friction combined type micro-nano generator according to claim 2, described piezoelectric membrane electrode is in the polyvinylidene difluoride film both sides, described semi-conducting material is indium tin metal oxide (ITO), and the metal of described good conductivity is gold, silver, platinum, copper and/or aluminium; The flexible polymeric materials of described micro-nano compound structure is micrometer structure and nanostructure and deposits.
4. a kind of piezoelectricity friction combined type micro-nano generator according to claim 3, described micrometer structure is pyramid array or groove grid array or hemisphere array, and characteristic size is 1 μ m-200 μ m, and spacing is 1 μ m-50 μ m; Described nanostructure is nanometer burr or nanometer sieve aperture, and characteristic size is 2nm-1000nm, spacing 2nm-500nm.
5. one of according to claim 1-4 described a kind of piezoelectricity friction combined type micro-nano generators, output voltage is more than or equal to 10 volts, be preferably greater than and equal 50 volts, more preferably greater than equaling a hectovolt, single transfer electric charge ability is more than or equal to 10 Na Ku, be preferably greater than and equal 50 Na Ku, more preferably greater than equaling 100 Na Ku.
6. the preparation method of a piezoelectricity friction combined type micro-nano generator as described in one of claim 1-5 comprises the following steps:
1), by the method for spin coating or Self-leveling, PVDF solution is covered on silicon chip or other horizontal surface, heating PVDF solution is made the PVDF film;
2), polarization PVDF film makes it have piezoelectricity under highfield;
3), by evaporation or sputtering technology, at PVDF film both sides making electrode;
4), by photoetching, wet etching or dry etching, make micrometer structure on silicon chip or glass substrate;
5), by deep reaction ion etching technique, make on the micrometer structure surface and have 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, will have PDMS film and the PET film bonding of micro-nano compound structure;
8), by evaporation or sputter or chemical vapor deposition method, at PET film surface making electrode;
9), electroded PVDF piezoelectric membrane and electroded PDMS-PET bonding structure are assembled and encapsulated.
7. the preparation method of piezoelectricity friction combined type micro-nano generator as claimed in claim 6, in described step 1), the solute of PVDF solution is the PVDF powder, solvent is DMF, and the solute mass fraction is 5%-20%, heating-up temperature is 80-130 ℃, 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 metallic aluminium, nickel, copper and/or silver.
8. the preparation method of piezoelectricity friction combined type micro-nano generator as claimed in claim 6, in described step 4), the characteristic size of micrometer structure is 1 μ m-200 μ m, spacing is 1 μ m-50 μ m; In described step 5), the characteristic size of nanostructure is 2nm-1000 μ m, 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 dull and stereotyped power is 6W-12W, and etching/passivation time is than being 10s:10s-4s:4s, etching/passivation cycle 60-200 time; The 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 dull and stereotyped power is 6W-12W, and etching/passivation time is than being 0s:10s-0s:4s, etching/passivation cycle 1-20 time.
9. the preparation method of piezoelectricity friction combined type micro-nano generator as claimed in claim 6, in described step 7), heating-up temperature is 50-100 ℃, the time is 30 minutes-2 hours; In described step 8), electrode is the metal of semi-conducting material or other good conductivity.
10. the purposes of described a kind of piezoelectricity friction combined type micro-nano generator of one of claim 1-5, comprising: be the portable electric appts charging, preferred mobile phone, MP3; Be placed in the environment collecting mechanical energy, preferred sole, road surface, tire, mouse, keyboard; Self-driven environmental monitoring, preferred liquid is leaked, structural mutation.
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