CN101656486B - Zinc oxide nano wire/polymer nano composite energy converter and preparation method thereof - Google Patents
Zinc oxide nano wire/polymer nano composite energy converter and preparation method thereof Download PDFInfo
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- CN101656486B CN101656486B CN2009101958873A CN200910195887A CN101656486B CN 101656486 B CN101656486 B CN 101656486B CN 2009101958873 A CN2009101958873 A CN 2009101958873A CN 200910195887 A CN200910195887 A CN 200910195887A CN 101656486 B CN101656486 B CN 101656486B
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 137
- 229920000642 polymer Polymers 0.000 title claims abstract description 58
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 27
- 239000002184 metal Substances 0.000 claims abstract description 27
- 239000000758 substrate Substances 0.000 claims abstract description 20
- 230000008859 change Effects 0.000 claims abstract description 12
- 239000011787 zinc oxide Substances 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 24
- 229960001296 zinc oxide Drugs 0.000 claims description 19
- 239000004800 polyvinyl chloride Substances 0.000 claims description 11
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 10
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- 238000006243 chemical reaction Methods 0.000 claims description 7
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 5
- 238000005229 chemical vapour deposition Methods 0.000 claims description 5
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- 238000001020 plasma etching Methods 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 230000008602 contraction Effects 0.000 claims description 3
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- 238000010894 electron beam technology Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 238000004528 spin coating Methods 0.000 claims description 2
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- 230000000694 effects Effects 0.000 description 16
- 238000010438 heat treatment Methods 0.000 description 6
- 239000010936 titanium Substances 0.000 description 6
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- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a zinc oxide nano wire/polymer nano composite energy converter and a preparation method thereof. The oxide nano wire/polymer nano composite energy converter comprises a zinc oxide nano wire, a polymer, a substrate and two metal electrodes, wherein the polymer senses the change of an environment signal to produce shrinkage or expansion to drive the zinc oxide nano wire covered by the polymer to generate distortion, thereby producing electric signals to convert other energies in the environment into electric energy. The invention skillfully utilizes a zinc oxide nano wire and polymer composite structure to prepare a nano generator element, and enables the zinc oxide nano wire to convert heat energy, chemical energy and the like into electric energy in the environment by means of the action of the polymer.
Description
Technical field:
The present invention relates to miniature power conversion device, be specifically related to a kind of device that utilizes polymer and zinc oxide nanowire acting in conjunction the heat energy in the environment or luminous energy or chemical energy etc. to be converted to electric energy.
Background technology:
Along with the development of nanometer technology, increasing nano electron device has appearred, and these nano electron devices all are widely used in fields such as military affairs, biologies.And all nano electron devices all need the power supply of a micro-scale and come energize, have only power supply also microminiaturized, could realize the real system integration, make really " nanometer " change of nano electron device.Especially the device of under some extreme environment, working, as the electronic device of working in the device transplanted in the human or animal body, the transducer, space under the adverse circumstances etc., conventional electric power system can't provide electric energy, and if the use battery has the restriction in life-span again.Therefore, exploitation can self-powered, also be that device itself can the absorbing environmental power conversion be the device of electric energy, for the application of nano electron device important meaning is arranged.
ZnO nano wire along the growth of c direction of principal axis has the non-centrosymmetry structure, and oxygen atom and zinc atom form tetrahedral structure at crystal face separately, and pile up along the c direction of principal axis.If nano wire is subjected to extraneous stress and produces distortion such as stretching, compression, bending, the charge-site of negative ions will be moved, and produce macroscopical electric charge accumulation, thereby produce voltage.Zinc oxide material has maximum piezoelectric constant in the semiconductor of all tetrahedral structures, can produce big mechanical-electric coupling.And research data shows, the zinc oxide nanowire of low-dimensional has bigger piezoelectric effect than conventional macroscopic material.Simultaneously, the zinc oxide nanowire of preparation attitude is the n N-type semiconductor N, has conductivity.If will have the nano wire two ends of positive and negative charge accumulation to be linked to be a loop, and just can have electric current to flow so in the loop, the results electric energy by the electricity level.The application that the piezoelectric effect of zinc oxide nanowire and semiconductor property make it in the micro cell device becomes possibility.
According to top analysis, the distortion of ZnO nano wire can produce voltage (piezoelectric effect), and the process of distortion is equivalent to micro cell " charging " process; Positive and negative charge is linked to be a loop can gather in the crops electric energy (semiconductor property), is equivalent to micro cell " discharge " process.The once distortion of ZnO nano wire can produce the signal of telecommunication of a moment, still, the real micro cell device of supplying with as electric energy, must can produce lasting and constant electric current.If the generation deformation that thousands of nano wire does not stop, reduction will constantly be in the cyclic process of charge/discharge so then, obtains the constant DC signal, satisfies the demand that external little electric energy is supplied with.Thousands of nano wire is out of shape simultaneously and produces voltage, and can gather in the crops the electric energy that every nano wire produces simultaneously, is the key of this type of micro cell device.Although external scientist has proposed to drive the concept nature " nano generator " that nano wire shakes with ultrasonic wave as external energy, owing to the problem of device itself, have to the electric current of 0.4nA, be difficult to obtain big current signal.And this type of all at present nano generators all is absorbed in and directly utilizes zinc oxide nanowire to make the mechanical energy in the environment change electric energy into, and this just makes its application that certain limitation is arranged, because environment kinetic energy is not what be available anywhere.
Summary of the invention:
The objective of the invention is to utilize zinc oxide nanowire, a kind of " nano generator " that can directly absorb luminous energy or heat energy or chemical energy etc. from environment and be converted to electric energy is provided, be mainly used in to various nano electron devices energy is provided.
In order to achieve the above object, the invention provides a kind of zinc oxide nano-wire array/polymer nanocomposite multiple device, the zinc oxide nanowire that the contraction of polymer or the drive of expanding are inlayed wherein when utilizing environment change produces distortion, thereby generation piezoelectric effect, and then utilize the piezoelectric effect work of zinc oxide nanowire, realize the light in the environment or heat or chemical energy etc. are converted to electric energy.
The technical solution adopted in the present invention:
A kind of Zinc oxide nano wire/polymer nano composite energy switching device, comprise zinc oxide nanowire, polymer, substrate and two metal electrodes, the wherein variation of polymer induced environment signal and produce contraction or expansion and drive the zinc oxide nanowire coated and produce distortion, thereby the generation signal of telecommunication is an electric energy with other power conversion in the environment.
The variation of described ambient signal is meant the variation of light signal in the environment, thermal signal or chemical signal.
Other energy in the described environment are luminous energy, heat energy or chemical energy.
Described zinc oxide nanowire is the zinc oxide nano-wire array of arranging perpendicular to substrate.
Zinc oxide nano-wire array can be conventional various types of arrays.
In the zinc oxide nano-wire array, the diameter of zinc oxide nanowire is 6-100nm.
Described zinc oxide nanowire is the ZnO nano wire along the growth of c direction of principal axis.
Described polymer can induced environment light for any one or ambient signals such as heat or chemistry change produce deformation or distortion, dielectric, not with zinc oxide generation chemical reaction and polymeric material that can form the continuous solid body film.
Described polymer evenly is filled between the zinc oxide nano-wire array, combines closely with zinc oxide surface.
Described polymer plays the insulating effect between the electrode simultaneously.
Described substrate is monocrystalline Al
2O
3Perhaps monocrystalline MgO.
Also has the zinc oxide films rete between the film that described substrate surface and polymer form.
Described metal electrode is the metal electrode B that contacts with substrate surface zinc oxide films rete, and a metal electrode A who is positioned at polymer substrate terminal far away and links to each other with zinc oxide nanowire.
Being Schottky contacts between described zinc oxide nanowire and the electrode A, is ohmic contact between zinc oxide films rete and the electrode B.
Metal electrode A can be Ti/Pt, Ti/Pd or Ti/Au.Metal electrode B can be conductive silver glue or conducting metal silver or Zr film.
Nano composite energy switching device of the present invention utilizes the piezoelectric effect of zinc oxide nanowire to obtain electric energy, but device is not the mechanical energy of directly changing in the environment.
Nano composite energy switching device of the present invention is taked following method preparation:
1) growth of zinc oxide nano line orthogonal array on substrate.
The zinc oxide nanowire deposition process is gas phase-liquid phase-solid phase (VLS) method.
In the zinc oxide nanowire growth course, at first form zinc-oxide film at substrate surface.
2) the polymer uniform deposition is formed continuous film in zinc oxide nano-wire array.
The polymer deposition method can be used chemical vapour deposition technique, drip or spin-coating method etc.
Described chemical vapour deposition technique is: reactive material issues biochemical reaction in the gaseous state condition, generates solid matter and is deposited on the solid matrix surface of heating, and then make the technology of solid material.
The polymer deposition process can not change the vertical orientated of zinc oxide nanowire.
3) use the plasma etching excess polymer, expose the zinc oxide nanowire top;
4) scrape one jiao of device off, expose ZnO film.
5) deposit metal electrodes A and B.
Can adopt electron-beam vapor deposition method or magnetron sputtering method.
According to above-mentioned device preparation method, polymer can not destroy the arrangement and the structure thereof of original zinc oxide nano-wire array in deposition process.In electrode A and B deposition process, should take suitable mask, avoid the short circuit between electrode A and the B.
The present invention has widened the intension of zinc-oxide nano generator in the past greatly.Polymer is a huge family, wherein has a lot of polymer to have photo-deformable or heat deformation or soda acid and causes deformation character, such as thermoplastic polymers such as polyvinyl chloride, when ambient temperature raises, volume will expand, and when ambient temperature reduces, volume will shrink.According to environmental condition, can choose corresponding polymer and zinc oxide nanowire is compound, can be prepared into various dissimilar nano generator devices.By means of the effect of polymer, but the luminous energy in the device absorbing environmental, heat energy, chemical energy etc. change mechanical energy earlier into, change mechanical energy into electric energy by zinc oxide nanowire then.Can avoid the shortcoming that zinc oxide nanowire nano generator device in the past can only single absorption mechanical energy like this.In addition,, can easily separate upper and lower electrode, avoid complex devices synthesis technique in the past because most of polymer all insulate.After this type of Zinc oxide nano wire/polymer device is synthetic, also can thinks and regulate ambient signal, to produce electric energy according to device property.Equally, device itself also can be used as the temperature sensor that need not power supply, chemical sensor etc.
Beneficial effect of the present invention is: 1) the present invention has utilized zinc oxide nanowire and polymer complex structure to prepare the nano generator device dexterously, makes zinc oxide nanowire the heat energy in the environment, chemical energy etc. can be converted to electric energy by means of the effect of polymer.And zinc oxide nanowire nano generator in the past can only be changed the mechanical energy in the environment.2) the present invention utilizes the stretching of zinc oxide nanowire or compression to realize piezoelectric effect, this with realized by means of zinc oxide nanowire flexural deformation that piezoelectric effect had a great difference in the past, not only piezoelectric effect is bigger, and has avoided complicated electrode processing technology (electrode can only catalytic oxidation zinc side).Because the polymer interaction energy makes zinc oxide nanowire deform along the c direction of principal axis, can obtain maximum piezoelectric effect, because zinc oxide has maximum piezoelectric constant at the c direction of principal axis.3) polymer can play the insulating effect of electrode A and B simultaneously, has avoided separation A, the additional technique that the B electrode is required.
Description of drawings:
Fig. 1 basic device structure schematic diagram.
Fig. 2 zinc oxide nanowire stereoscan photograph (from the top).
Fig. 3 polymer deposition falls the stereoscan photograph of partial polymer rear oxidation zinc nano-wire array then with plasma etching in zinc oxide nano-wire array.
Fig. 4 zinc oxide nanowire/the voltage signal of PVC multiple device under different heating condition.
The operation principle schematic diagram of Fig. 5 zinc oxide nanowire/PVC multiple device.(a) distortion of initial condition (b) device heats rear oxidation zinc nano wire and the expansion of polymer.
Fig. 6 zinc oxide nanowire is stretched and the piezoelectric effect schematic diagram when compressing.
Embodiment:
Below enumerate instantiation with further elaboration the present invention, should be understood that example is not to be used to limit protection scope of the present invention.
Embodiment 1
In conjunction with the accompanying drawings the present invention is explained in further detail.
A kind of Zinc oxide nano wire/polymer composite Nano power conversion device, as shown in Figure 1, device is made up of substrate, zinc oxide nanowire, thermoplastic polymer polyvinyl chloride (PVC), metal electrode A, metal electrode B.Wherein zinc oxide nanowire is arranged perpendicular to substrate, and polyvinyl chloride is deposited on equably and forms one deck wrap film between the nano-wire array.Metal electrode A is positioned at the device top, be exposed to PVC on terminal linking to each other of zinc oxide nanowire; And metal electrode B contacts with the zinc-oxide film of substrate surface.Zinc-oxide film at first forms at substrate surface in the zinc oxide nanowire growth course, and it contacts with all zinc oxide nanowire.
Preparation of devices specifically comprises the following steps:
1) zinc oxide nanowire adopts the chemical vapour deposition technique preparation:
With a-plane Al
2O
3Be substrate, 99.99% Zinc oxide powder is a presoma.Concrete chemical vapor deposition method condition is: 915 ℃ of growth temperatures, and growth time is: 10 minutes, 50 ℃/minute of heating rates, the Ar throughput is 12sccm.Zinc-oxide film at first forms at substrate surface in the zinc oxide nanowire growth course, and it contacts with all zinc oxide nanowire.
Fig. 2 is the SEM photo (top view) of the zinc oxide nano-wire array of vertical arrangement.
3) the polymer uniform deposition is formed continuous film in zinc oxide nano-wire array.
Polymer deposition method: PVC at first is dissolved in 5% 1,4 para-dioxane, joins in the zinc oxide nano-wire array with drip-injection method then, and room temperature evaporation back forms uniform PVC film.
The polymer deposition process can not change the vertical orientated of zinc oxide nanowire.
3) use the plasma etching excess polymer, expose the zinc oxide nanowire top;
The PVC that removes part with plasma decorations method at quarter exposes the zinc oxide nanowire head portion, as shown in Figure 3.O
2The plasma etch process condition is: power 300W, 5 minutes time.
4) scrape one jiao of device off, expose ZnO film.
5) deposit metal electrodes A and B.
Metal electrode A is the Ti/Au metallic film, and deposited by electron beam evaporation method deposition: pure titanium with 99.99% and 99.99% proof gold target are evaporation source.Ti thickness is 4nm, and Au thickness is 100nm.
Metal electrode B directly contacts the substrate surface zinc-oxide film with conductive silver glue and forms.
Be of the influence of research environment variations in temperature, device heated with a hot platform to device performance.The temperature of sample can be controlled by the input voltage of controlling hot platform.Measurement shows that device temperature is linear the rising with the increase of hot platform input voltage.Measured voltage between metal electrode A and metal electrode B when Fig. 4 is different heating voltage.As seen, along with hot platform input voltage raises, also be the rising of temperature, the voltage between A, the B also increases.This explanation device can change the change of ambient temperature signal into the signal of telecommunication.
Fig. 5 has provided the basic functional principle figure of device.Fig. 5 (a) is the state of zinc oxide nanowire and polymer in the preceding device of heating.Fig. 5 (b) is the state of heating rear oxidation zinc nano wire and polymer.Because PVC is a thermoplastic polymer, when ambient temperature raise, thermal expansion promptly took place, the zinc oxide nanowire that is embedded in is wherein extended or bending.Because the piezoelectric effect (Fig. 6) of zinc oxide nanowire, the accumulation that has just produced electric charge at its two ends forms electrical potential difference.
Claims (6)
1. Zinc oxide nano wire/polymer nano composite energy switching device, comprise zinc oxide nanowire, polymer, substrate and two metal electrodes, described metal electrode is the metal electrode B that contacts with substrate surface zinc oxide films rete, and the metal electrode A that is positioned at the zinc oxide nanowire top and is attached thereto, the wherein variation of polymer induced environment signal and produce contraction or expansion and drive the zinc oxide nanowire coated and produce distortion, thereby the generation signal of telecommunication, with other power conversion in the environment is electric energy, described polymer can induced environment light signal for any one or thermal signal change and to produce deformation or distortion, dielectric, not with zinc oxide generation chemical reaction and polymeric material that can form the continuous solid body film, and described polymer evenly is filled between the zinc oxide nano-wire array, combine closely with zinc oxide surface, described zinc oxide nanowire is the zinc oxide nano-wire array of arranging perpendicular to substrate.
2. Zinc oxide nano wire/polymer nano composite energy switching device according to claim 1 is characterized in that described polymer is a polyvinyl chloride.
3. Zinc oxide nano wire/polymer nano composite energy switching device according to claim 1 is characterized in that described metal electrode A is Ti/Pt, and Ti/Pd or Ti/Au, metal electrode B are selected from conductive silver glue or conducting metal silver or Zr film.
4. as the preparation method of Zinc oxide nano wire/polymer nano composite energy switching device as described in arbitrary claim among the claim 1-3, comprise the following steps:
1) growth of zinc oxide nano line orthogonal array on substrate;
2) the polymer uniform deposition is formed continuous film in zinc oxide nano-wire array;
3) use the plasma etching excess polymer, expose the zinc oxide nanowire top;
4) scrape one jiao of device off, expose ZnO film;
5) deposit metal electrodes A and B.
5. as the preparation method of Zinc oxide nano wire/polymer nano composite energy switching device as described in the claim 4, it is characterized in that in the described step 1), the zinc oxide nanowire deposition process is gas phase-liquid phase-solid phase method; Described step 2) in, the polymer deposition method is chemical vapour deposition technique, drip or spin-coating method; In the described step 5), the method for deposit metal electrodes A and B is electron-beam vapor deposition method or magnetron sputtering method.
6. as the preparation method of Zinc oxide nano wire/polymer nano composite energy switching device as described in the claim 4, it is characterized in that, in the described step 1), in the zinc oxide nanowire growth course, at first form zinc-oxide film at substrate surface.
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| CN102437791B (en) * | 2011-08-30 | 2014-06-18 | 东北师范大学 | Preparation method of photoinduction nano alternative-current power generator |
| CN102445992A (en) * | 2012-01-09 | 2012-05-09 | 上海理工大学 | Keyboard with power generation function |
| CN102593347A (en) * | 2012-03-12 | 2012-07-18 | 北京大学 | Zinc oxide nanowire electric generator based on myocardial cells and preparing method thereof |
| CN102749158B (en) * | 2012-04-13 | 2014-04-09 | 纳米新能源（唐山）有限责任公司 | Self-powered pressure sensor |
| CN102647110B (en) * | 2012-04-23 | 2015-04-08 | 兰州大学 | Magnetically-driven nanogenerator |
| CN102683573A (en) * | 2012-05-09 | 2012-09-19 | 纳米新能源（唐山）有限责任公司 | Nano generator, nano generator set and self-powered system comprising nano generator or nano generator set |
| CN102709464A (en) * | 2012-05-23 | 2012-10-03 | 国家纳米科学中心 | Zinc oxide nanometer power generator and manufacturing method thereof |
| CN103516255B (en) * | 2012-06-15 | 2016-01-06 | 纳米新能源（唐山）有限责任公司 | Integrated nanometer generator and preparation method thereof |
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| CN103332649B (en) * | 2013-06-20 | 2015-08-26 | 西安理工大学 | A kind of preparation method of polyvinylidene fluoride with one-dimensional nanowire array structure |
| CN103499273B (en) * | 2013-09-27 | 2016-06-22 | 三星半导体(中国)研究开发有限公司 | For measuring method and the electronic packing piece of the warpage of electronic packing piece |
| CN105895798A (en) * | 2016-06-03 | 2016-08-24 | 南京工业大学 | ZnO micro-nano wire preparation method and ZnO micro-nano wire piezoelectric transducer element preparation method |
| CN109813760A (en) * | 2019-02-28 | 2019-05-28 | 江苏理工学院 | A kind of zinc oxide nanowire gas sensor and preparation method thereof |
| CN110231064A (en) * | 2019-05-08 | 2019-09-13 | 西安交通大学 | A kind of microflow sensor and its manufacturing system and method |
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