CN102646788A - Nano generator and manufacturing method thereof - Google Patents
Nano generator and manufacturing method thereof Download PDFInfo
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- CN102646788A CN102646788A CN2012101168814A CN201210116881A CN102646788A CN 102646788 A CN102646788 A CN 102646788A CN 2012101168814 A CN2012101168814 A CN 2012101168814A CN 201210116881 A CN201210116881 A CN 201210116881A CN 102646788 A CN102646788 A CN 102646788A
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N30/00—Piezoelectric or electrostrictive devices
- H10N30/30—Piezoelectric or electrostrictive devices with mechanical input and electrical output, e.g. functioning as generators or sensors
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N30/00—Piezoelectric or electrostrictive devices
- H10N30/01—Manufacture or treatment
- H10N30/07—Forming of piezoelectric or electrostrictive parts or bodies on an electrical element or another base
- H10N30/074—Forming of piezoelectric or electrostrictive parts or bodies on an electrical element or another base by depositing piezoelectric or electrostrictive layers, e.g. aerosol or screen printing
Abstract
The invention provides a nano generator and a manufacturing method thereof. The nano generator comprises a base, a first electrode, a zinc oxide nano wire array, a macromolecule insulating layer and a second electrode, wherein the first electrode is arranged on the base; the zinc oxide nano wire array vertically grows on a first electrode layer; the macromolecule insulating layer is coated on a zinc oxide nano wire array layer; the zinc oxide nano wire array layer covers the zinc oxide nano wire array, and the second electrode is arranged on the macromolecule insulating layer; and the first electrode and the second electrode are used as a voltage output pole and a current output pole of the nano generator. The nano generator disclosed by the invention adopts a unique structure so that the electric performance output and the stability are effectively improved.
Description
Technical field
The present invention relates to a kind of nano generator and manufacturing approach thereof, especially relate to a kind of TRT that utilizes the nanometer piezoelectric to process.
Background technology
The collection of energy and the conversion equipment that adopt nanometer technology to make up; In manufacturing and driving self-powered nano-device and nanosystems device, play critical effect probably; Because its unique self power generation and drive character has certainly received the increasing concern of various countries researcher recently.2006, the Wang Zhonglin of georgia ,u.s.a Institute of Technology professor seminar successfully realized utilizing zinc oxide nanowire mechanical energy to be changed into the piezoelectric type nano generator of electric energy first.Subsequently, be the basis with the piezoelectric effect, developed in succession based on the various nano generators of different materials and structure.At present, the power output of nano generator is enough to drive commercial light-emitting diode (LED), small-sized LCD even self-power wireless data transfer equipment.But the power output of nano generator is still its development key factor of restriction.
One Chinese patent application CN200710097875.8 discloses a kind of AC nano generator; This disclosure of the Invention nanometic zinc oxide rod array is combined with microelectromechanical structure; Utilize zinc oxide nano rod piezoelectric effect that stressed flexural deformation produces; Convert the mechanical vibrational energy that acts on the microelectromechanical structure to electric energy, constitute AC nano generator.Utilize a plurality of this generators of series connection or diode-capacitance boost device again, small voltage is increased to certain voltage.This patent application attempts to adopt device such as diode-electric capacity that the electricity that nano generator sends is boosted, and the voltage when just having improved voltage transmission does not improve generating capacity of generator itself.
One Chinese patent application CN201110253998.2 discloses a kind of heterojunction piezoelectric type nano generator and manufacturing approach thereof; This heterojunction piezoelectric type nano generator comprises semiconductor nanorods array, semiconductor nano groove array, conductive substrates, encapsulated layer and lead-in wire; Said semiconductor nanorods array is vertical on the conductive substrates as the generator bottom electrode; Semiconductor nano groove array and semiconductor nanorods array form nested structure; The semiconductor nano groove array is the top electrode of generator, and the generator upper/lower electrode is picked out by different lead-in wires respectively; Semiconductor nano groove array and semiconductor nanorods array periphery are provided with encapsulated layer.This patent application adopts the p-n heterojunction to replace the schottky junction in the piezoelectric type nano generator, realizes circuit individual event conducting, is a kind of change that utilizes characteristic of semiconductor.This nano generator structure also has open in U.S. Pat 8003982.There are problems such as the stable of generating output variable, generator and manufacturing difficulty in the disclosed scheme of this patent application.
Summary of the invention
The present invention provides for solving the problems of the prior art that a kind of delivery efficiency is higher, performance more stabilized nano generator and manufacturing approach thereof.
The invention provides a kind of nano generator; Comprise substrate, first electrode, zinc oxide nano-wire array, polymeric dielectric layer and second electrode; Said first electrode is arranged in the substrate, and said zinc oxide nano-wire array vertical-growth is coated with said polymeric dielectric layer on the said zinc oxide nano-wire array layer on first electrode layer; Said polymeric dielectric layer coats said zinc oxide nano-wire array, and second electrode is arranged on the polymeric dielectric layer; First electrode and second electrode are the voltage and current output stage of nano generator.
Further preferred; Said zinc oxide nano-wire array is grown in a plurality of zones; Have the gap between zone and the zone, said polymeric dielectric layer is coated on the zinc oxide nano-wire array, and is filled in the regional gap and zinc oxide nano-wire array is cut apart, coated.
Said substrate is to be selected from silicon base, the gallium nitrate based end, conductive metal sheet substrate, conductivity ceramics substrate or to be coated with a kind of in the macromolecule polymer material substrate of metal electrode.Said polymeric dielectric layer is for being selected from a kind of in polymethyl methacrylate (PMMA), dimethyl silicone polymer (PDMS) or the p type macromolecular material.Said first electrode is for being selected from a kind of in indium tin metal oxide (ITO), Graphene or the nano silver wire membrane coat, perhaps its material be selected from gold, silver, platinum, aluminium, nickel, copper, titanium, iron, a kind of in selenium or its alloy.The material of said second electrode be selected from gold, silver, platinum, aluminium, nickel, copper, titanium, iron, a kind of in selenium or its alloy, and be plated on the polymeric dielectric layer through vacuum sputtering or vapour deposition method.
Said nano generator also comprises a package casing, and said shell adopts macromolecule insulation material.
Nano generator provided by the invention can or be composed in series generating set by described monomer nano generator parallel connection, and the output voltage or the electric current of generator is provided.
The present invention also provides a kind of nano generator manufacturing approach, comprising:
A. through the radio frequency sputter first electrode layer and zinc oxide seed are placed in the substrate of cleaning in advance;
B. adopt wet chemistry method growth of zinc oxide nano linear array, make the zinc oxide nanowire vertical-growth on the zinc oxide seed surface;
C. through spin-coating method polymeric dielectric layer is covered on the zinc oxide nano-wire array layer;
D. apply second electrode.
Said step b preferably also comprises:
E. a plurality of growth districts of photoetching zinc oxide nanowire are provided with the photoresist layer on first electrode layer and zinc oxide seed layer, and form the zinc oxide nanowire growth district through wet mechanical method;
F. photoresist form a plurality of growth districts in, adopt wet chemistry method growth of zinc oxide nano linear array, zinc oxide nanowire only is grown on the surface of the seed of exposure;
G. peel off all residue photoresists.
Step e, f, g are preferably to process the method that comprises a plurality of regions perpendicular developing zinc oxide arrays.
Said nano generator manufacturing approach; Wherein, Said step g also comprises the zinc oxide nanowire heating anneal, through possibly reduce the concentration of zinc oxide nanowire band free charge itself in heating anneal heat treatment, reduces between the nano wire mutually charge migration and reduces energy output.
Substrate among the said step a is to be selected from silicon base, the gallium nitrate based end, conductive metal sheet, conductivity ceramics or to be coated with a kind of in the macromolecule polymer material of metal electrode.The material of first electrode among the said step a is for being selected from a kind of in indium tin metal oxide (ITO), Graphene or the nano silver wire membrane coat.The material of the polymeric dielectric layer among the said step e is for being selected from a kind of in polymethyl methacrylate (PMMA) or the dimethyl silicone polymer (PDMS).In said step f, the material of second electrode be selected from gold, silver, platinum, aluminium, nickel, copper, titanium, iron, a kind of in selenium or its alloy.
Nano generator advantage provided by the invention is; Owing on the zinc oxide nano-wire array layer, adopted polymeric dielectric layer; The existence of insulating barrier provides the potential barrier of an infinite height; Stop the piezoelectron on the zinc oxide nanowire to be derived, and form piezoelectric field through zinc oxide/Metal Contact face is inner; Piezoelectric field further forms charge inducing at first electrode and second electrode, and charge inducing forms current circuit under the situation that external circuits is connected.In addition; Polymeric dielectric layer is filled in the space of nano wire dispersedly and forms cover layer at top layer; When vertically applying external force, stress can be sent to the nano wire under all application of force zones through cover layer, has promoted the efficient of nano generator greatly; Simultaneously cover layer also is coated on nano-wire array top and on every side, bears external force at nano wire and plays cushioning effect to a certain degree as the time spent, and strengthened contacting of nano-wire array and first electrode layer, thereby improved the stability of nano generator.
In addition; Zinc oxide nanowire is a semiconductor, has conductivity to a certain degree, when zinc oxide nanowire contacts with each other; Himself with electric charge in the deformation power generation process, can produce and influence each other; Thereby can offset the part piezoelectric charge, the output electric weight that causes generating electricity reduces, and has reduced the power generation performance of nano generator.And in the present invention, zinc oxide nano-wire array is only grown in the zone of appointment or regular domain, influences less each other.Owing to adopt the method for zinc oxide nano-wire array subregion growth; And it is cut apart, coats with polymeric dielectric layer; Do the time spent receiving external force; Produce the nano wire of piezoelectric charge and direct pressurized and do not produce and form shielding between the nano wire of piezoelectric charge and cut apart, thereby stoped the reduction of piezoelectricity electromotive force, and then the energy output of raising.
Description of drawings
Fig. 1 is the structural representation of a nano generator embodiment of the present invention.
Fig. 2 is the structural representation of another nano generator embodiment of the present invention.
Fig. 3 is zinc oxide nanowire of the present invention subregion growth sketch map.
Fig. 4 is the schematic perspective view of nano generator involved in the present invention.
Fig. 5 is the microstructure enlarged diagram of nano generator involved in the present invention.
Fig. 6 is the electric performance test figure of a specific embodiment of nano generator involved in the present invention.
Among the figure: 1, second electrode, 2, polymeric dielectric layer, 3, zinc oxide nano-wire array, 4, first electrode, 5, substrate, 6, polymeric dielectric layer gap filling part, 7, the zinc oxide nanowire subregion.
Embodiment
Below, further specify in conjunction with the accompanying drawing specific embodiments of the invention.
The accompanying drawing 1 of specification provides the embodiment of nano generator of the present invention; As shown in the figure; With first electrode, 4 indium tin metal oxide (ITO) coating and zinc oxide seed layer; On the silicon base of cleaning in advance 5, the ITO coating is not only as a conductive electrode through the radio frequency sputter, and can improve the adhesive force between zinc oxide seed and silicon base.On zinc oxide seed layer, adopt wet chemistry method growth of zinc oxide nano linear array 3.Wet chemistry method growth of zinc oxide nano linear array adopts known technology can realize that the method that discloses a kind of hydro thermal method synthesizing zinc oxide nanometer stick array in the patent application 201110253998.2 can adopt.After accomplishing the zinc oxide nano-wire array growth, and it is carried out heating anneal.Then through spin coating with polymeric dielectric layer 2 polymethyl methacrylate layers capping oxidation zinc nano-wire arrays 3, coating top layer is as the aluminum metal electrode of second electrode 1 subsequently.At last, adopt another polymethyl methacrylate coating to carry out the package casing encapsulation.First electrode 4 and second electrode 1 are as the voltage and current output electrode of nano generator.
Accompanying drawing 2 provides the another kind of specific embodiment of nano generator of the present invention, and first electrode, 4 indium tin metal oxide (ITO) coatings and zinc oxide seed layer are passed through the radio frequency sputter on a silicon base 5 that cleans in advance.On first electrode 4, cover photoresist then; On photoresist, offer the square window array of a rule with little processing offset printing method; Shown in Figure of description 3, the square window inner region, exposing has zinc oxide seed; As the zone 7 of zinc oxide nano-wire array growth, there is photoresist in the square window gap and zinc oxide nanowire can't be grown.Photoresist is equivalent to a subregion mould in zinc oxide nanowire growth course subsequently, zinc oxide nanowire only is grown in makes on the zinc oxide seed area exposed, thereby grow in the subregion of realizing zinc oxide nano-wire array.Next peel off all residue photoresists, and to the nano-wire array heating anneal.Be covered on the zinc oxide nano-wire array as the polymethyl methacrylate layers with polymeric dielectric layer 2 through spin coating then, and form zinc oxide nanowire zone filling part 6, it is divided into predefined zone with zinc oxide nanowire.At last, adopt another polymethyl methacrylate coating to carry out the package casing encapsulation.First electrode 4 and second electrode 1 are as the voltage and current output electrode of nano generator.The nano generator of present embodiment can be referring to Figure of description 4, and the electron scanning micrograph of local high-amplification-factor is referring to Figure of description 5.
It is consistent that the present invention makes the process flow and the mass production technique of nano generator, allow a plurality of silicon base parallel processings then dice form the monomer generator.Therefore, it has superiority aspect expanding the scale of production and reducing cost.
In second specific embodiment, zinc oxide nanowire can only be grown in controlled zone, and the controlled zone of rule can be made through little processing offset printing method.This design is not only promoted the effect that nano wire obtains energy because each unit can both work alone, and improves the stability of tolerance defective.The high-amplification-factor electron scanning micrograph shows the nano-wire array vertical alignment that growth obtains, shown in Figure of description 5, and the intensive growth of nano wire, most of nano wire is interconnected or even mixing in the wherein single zone.Accompanying drawing 5 shows that further polymethyl methacrylate closely is filled in the gap of nano wire and the directly mutual subregion of nano-wire array.
The nano generator that makes with this method be under pressure, mechanical presses or flexural deformation can take place in the dynamic impulsion of linear electric machine that speed and frequency are controlled.A commercial bridge rectifier is connected to the nano generator output electrode can just be exchanged output and change direct current output into.Test the nano generator of the effective dimensions of the 1cm * 1cm that occupies by zinc oxide nanowire * 10 μ m, open circuit voltage (V
Oc) and short circuit current (I
Sc) under 1MPa pressure respectively up to 37V (Fig. 6 a) with 12 μ A (Fig. 6 b).
According to the Theoretical Calculation of piezoelectricity electromotive force, the induced electricity potential difference of result of calculation two electrodes under the applied stress of 1MPa should be 45V.The reason that experimental result is littler than the analogue value is likely owing to there is screen effect mutually in free charge in the nano wire.
The superior function of nano generator and stability in the present embodiment are owing to the polymeric dielectric layer polymethyl methacrylate layers between nano-wire array and metal electrode.This skim has many advantages.At first, it is an insulating barrier that unlimited height barrier is provided, and stops the induction electronics in the electrode to pass through zinc oxide/Metal Contact face inner " leakage ".It substitutes Schottky contacts of the prior art and contacts with the P/N knot.In addition, polymethyl methacrylate is filled in the space between nano wire dispersedly, and forms cover layer at top layer.Therefore when the application of force vertically, stress can be sent to the nano wire under all application of force zones through cover layer, strengthens the efficient of nano generator greatly.This also can make, and only a part of nano wire that is fit to length is effectively improved because of the situation of contact deformation in the prior art, and it does not intimately interact with electrode as resilient coating protection nano wire, has improved the stability of nano generator.
It should be noted that equally nano wire is in the selectively growth of the zone of photoetching process appointment.This subregion property design is in order to make the output optimization of nano generator.Possibly help to reduce the concentration of free charge carrier through heat treatment during manufacture, still limited conductivity in the zinc oxide nanowire.Therefore, the free charge carrier in the nano wire is with partly shielding effect piezoelectricity electromotive force, and the electric weight level that causes generating electricity reduces, thereby reduces the performance of nano generator.Shown in Figure 2 is the cutaway view of this device, and the intensive filling of nano wire is arranged parallel to each other.If when applying external force or externally applied forces skewness in the little zone of ratio device size, the nano wire that then is located immediately at stress area below produces the piezoelectricity electromotive force, thereby they are called as and enliven nano wire.Because subregional existence, the original free charge carrier under stress area in the directly not compacted nano wire (being called as inactive nano wire) with enliven nano wire and separate, therefore, they can not influence each other, and have stoped the piezoelectricity electromotive force further to reduce.If but there is not the subregion in the nano wire, the free charge in the inactive nano wire tends to towards the high-tension electricity electromotive force one side migration that enlivens nano wire, thus this will reduce local piezoelectricity electromotive force reduction output.
Electrical property output can obtain effectively to increase in proportion through linear superposition.A nanometer generating unit is made in 9 monomer nano generator parallel connections.The operator fiercelys attack with palm, V
OcAnd I
ScPeak value surpass 58V and 134 μ A respectively.Use this nanometer generating unit, buffeting is no more than 20 times, also can charge to more than the 3V for the capacitor of one 2 μ F.
In a word, adopt nano generator provided by the invention, or nanometer generating unit provided by the invention can realize that electrical property output reaches the high record of 58V and 134 μ A, and maximum power density 0.78W/cm
3, be the maximum power output that does not reach through nano generator in the prior art.
The present invention is not limited to above-mentioned execution mode, and under the situation that does not deviate from flesh and blood of the present invention, any distortion that it may occur to persons skilled in the art that, improvement, replacement all fall into scope of the present invention.
Claims (16)
1. a nano generator comprises substrate, first electrode, zinc oxide nano-wire array, polymeric dielectric layer and second electrode, it is characterized in that,
Said first electrode is arranged in the substrate; Said zinc oxide nano-wire array vertical-growth is on first electrode layer; Be coated with said polymeric dielectric layer on the said zinc oxide nano-wire array layer; Said polymeric dielectric layer coats said zinc oxide nano-wire array, and second electrode is arranged on the polymeric dielectric layer;
Said first electrode and second electrode are the voltage and current output stage of nano generator.
2. nano generator according to claim 1; Wherein, Said zinc oxide nano-wire array is grown in respectively in a plurality of zones, has the gap between zone and the zone, and said polymeric dielectric layer is coated on the zinc oxide nano-wire array; Be filled in the regional gap, and zinc oxide nano-wire array is cut apart, coated.
3. nano generator according to claim 1 and 2, wherein, said substrate is to be selected from silicon base, the gallium nitrate based end, conductive metal sheet substrate, conductivity ceramics substrate or to be coated with a kind of in the macromolecule polymer material substrate of metal electrode.
4. nano generator according to claim 1 and 2, wherein, said polymeric dielectric layer is to be selected from a kind of in polymethyl methacrylate, dimethyl silicone polymer or the p type macromolecular material.
5. nano generator according to claim 1 and 2; Wherein, The material of said first electrode is to be selected from a kind of in indium tin metal oxide, Graphene or the nano silver wire membrane coat, perhaps is selected from gold, silver, platinum, aluminium, nickel, copper, titanium, irons, a kind of in selenium or its alloy.
6. nano generator according to claim 1 and 2, wherein, the material of said second electrode be selected from gold, silver, platinum, aluminium, nickel, copper, titanium, iron, a kind of in selenium or its alloy.
7. nano generator according to claim 1 and 2, wherein, said nano generator also comprises a package casing, said shell adopts macromolecule insulation material.
8. a nanometer generating unit is characterized in that, by the parallel connection of the described monomer nano generator of claim 1-7 or be composed in series.
9. a nano generator manufacturing approach is characterized in that, comprises the steps:
A. through the radio frequency sputter first electrode layer and zinc oxide seed are placed in the substrate of cleaning in advance;
B. adopt wet chemistry method growth of zinc oxide nano linear array, make the zinc oxide nanowire vertical-growth on the zinc oxide seed surface;
C. through spin-coating method polymeric dielectric layer is covered on the zinc oxide nano-wire array layer;
D. apply second electrode.
10. nano generator manufacturing approach according to claim 9, wherein, said step b comprises:
E. a plurality of growth districts of photoetching zinc oxide nanowire are provided with the photoresist layer on first electrode layer and zinc oxide seed layer, and form a plurality of growth districts of zinc oxide nanowire through wet mechanical method;
F. photoresist form a plurality of growth districts in, adopt wet chemistry method vertical-growth zinc oxide nano-wire array, zinc oxide nanowire only is grown on the surface of the seed of exposure;
G. peel off all residue photoresists.
11. nano generator manufacturing approach according to claim 10, wherein, said step g also comprises the zinc oxide nanowire heating anneal.
12. according to claim 9 or 10 described nano generator manufacturing approaches, wherein, the substrate among the said step a is to be selected from silicon base, the gallium nitrate based end, conductive metal sheet, conductivity ceramics or to be coated with a kind of in the macromolecule polymer material of metal electrode.
13. according to claim 9 or 10 described nano generator manufacturing approaches, wherein, first electrode among the said step a is to be selected from a kind of in indium tin metal oxide, Graphene, nano silver wire film or the metal coating.
14. according to claim 9 or 10 described nano generator manufacturing approaches, wherein, the material of the polymeric dielectric layer among the said step e is to be selected from a kind of in polymethyl methacrylate or the dimethyl silicone polymer.
15. according to claim 9 or 10 described nano generator manufacturing approaches, wherein, the material of second electrode among the said step f be selected from gold, silver, platinum, aluminium, nickel, copper, titanium, iron, a kind of in selenium or its alloy.
16. according to claim 9 or 10 described nano generator manufacturing approaches, wherein, said nano generator also comprises a package casing, said shell adopts macromolecule insulation material.
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| CN201210116881.4A CN102646788B (en) | 2012-04-19 | 2012-04-19 | Nano generator and manufacturing method thereof |
| PCT/CN2013/073258 WO2013155924A1 (en) | 2012-04-19 | 2013-03-27 | Nano-generator and manufacturing method thereof |
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