CN108091416A - A kind of dual light trapping structure transparent conductive film and its preparation - Google Patents
A kind of dual light trapping structure transparent conductive film and its preparation Download PDFInfo
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- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
- H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
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- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/08—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances oxides
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Abstract
The present invention relates to a kind of glass substrate/dual light trapping structure transparent conductive films of nano silver wire/zinc oxide/zinc-oxide nano column and preparation method thereof.The present invention introduces silver nanowire layer on the glass substrate, and with zinc-oxide film covering thereon, prepares zinc-oxide nano column afterwards.The dual light trapping structure transparent conductive film that the present invention is prepared has the following advantages：1) nano silver wire is supported on glass by simple method, the advantage that can play nano silver wire realizes the transparent conductive film of high conductivity and high transmittance；Raw material sources enrich and easy to operate, are not required the critical conditions such as high temperature, vacuum, and the multi-layer transparent electroconductive film of preparation has many advantages, such as at low cost；2) the surface plasma stimulus effect using nano silver wire and the wide spectrum scattering to light can realize the scattering to light for the first time；Second of effectively scattering to light can be realized using zinc-oxide nano rod structure, can be realized to the multiple of light, the scattering of different directions.
Description
Technical field
The present invention relates to a kind of transparent conductive films and preparation method thereof, and in particular to and a kind of glass substrate/nano silver wire/
The dual light trapping structure method for preparing transparent conductive film of zinc oxide/zinc-oxide nano column, belongs to technical field of material chemistry.
Background technology
In recent years, transparent conductive film material widely uses in fields such as electronic product, semiconductor devices, photoelectric devices.
Transparent conductive film (TCFs, transparent conduction films) refers to (λ in UV, visible light near infrared light region
=380~1000nm) there is higher transmitance, and there is excellent electric conductivity, sheet resistance can reach the film material of 10 Ω/below Sq
Material.Transparent conductive film is the important component of many opto-electronic devices, such as shows (Display), solar cell (Solar
Cells), Organic Light Emitting Diode (OLED), touch-screen (Touch panel) etc..Indium tin oxide films (ITO) are current transparents
The main material of conductive film.Ito thin film during preparation and use there is also some shortcomings, including：(1) metal
Phosphide material causes its price continuous rise since exploitation refinement is difficult and usage amount goes up year by year so that ITO becomes increasingly expensive
Material；(2) ito thin film is not supported resistant to bending, and friable structure does not support the performance requirement of flexible optoelectronic part；(3)ITO
The preparation method of film generally use vacuum coating, equipment is expensive, also causes ito thin film expensive.To obtain low cost
Transparent conductive film material, numerous scientists have carried out the research to nano silver wire material substitution ito thin film, nano silver wire into
For one dazzling research hotspot of material science and industrial circle.Nano silver wire has one-dimensional linear structure, and nano wire is two-dimentional empty
Between contact with each other to form reticulated conductive structure, with excellent conductive structure and transparent characteristic, bending resistance is very excellent
More, show many outstanding material properties, the research of nano silver wire material substitution indium tin oxide transparent conductive material also in
Initial stage, therefore nano silver wire transparent conductive film is a promising research work.Nano silver wire materials synthesis uses
It is chemically synthesized, it is cheap, therefore nano silver wire structure on the glass substrate can substitute traditional ito thin film.
The content of the invention
It is specially a kind of glass present invention aims at a kind of dual light trapping structure transparent conductive film and its preparation is provided
Substrate/dual light trapping structure transparent conductive film of nano silver wire/zinc-oxide film/zinc-oxide nano column and its preparation.
A kind of dual light trapping structure transparent conductive film, including：
Glass substrate, the one layer of nano silver wire film coated on the glass substrate, one coated on nano silver wire film
Layer zinc-oxide film and the one layer of zinc-oxide nano column grown on zinc-oxide film, as shown in Figure 2.
Further, the one kind of the glass substrate in soda-lime glass, ultra-clear glasses, quartz glass, flexible glass,
The thickness range of the glass substrate is between 0.05mm-50mm, and transmitance is between 91%-83%.
Further, the nano silver wire film thickness is 150-1000nm.
Further, the zinc oxide films film thickness is 20-200nm.
Further, the zinc-oxide nano column thickness is 200-5000nm.
Substrate of glass of the present invention/dual light trapping structure the electrically conducting transparent of nano silver wire/zinc oxide/zinc-oxide nano column
Method for manufacturing thin film introduces silver nanowire layer, and with zinc-oxide film covering thereon, prepares oxidation afterwards on the glass substrate
Zinc nano-pillar, process flow chart are as shown in Figure 1.
A kind of preparation of dual light trapping structure transparent conductive film, comprises the following steps：
1) nano silver wire suspension is prepared：Using the hot method reduction silver nitrate of polyalcohol, the solution containing nano silver wire is prepared, it will
Nano silver wire solution dilutes the nano silver wire alcohol dispersion liquid for being configured to 0.01-10mg/ml, was ultrasonically treated, obtains by 1-30 minutes
To the nano silver wire solution of stable dispersion；
2) zinc oxide precursor liquid is prepared：By zinc source, ethanolamine and ethyl alcohol are mixed and reacted at 20-80 DEG C, ageing
The amount ratio of the substance of formation zinc oxide colloidal sol after 20-28h, zinc concentration 0.01-1mol/L, ethanolamine and zinc is 1:2；
3) glass substrate is handled：After cleaning glass substrate drying, by glass immersion in the concentrated sulfuric acid that mass concentration is 98%
With reach in hydrogen peroxide solution that mass concentration is 30% 24 it is small when more than, the volume ratio of the solution is the concentrated sulfuric acid:Hydrogen peroxide
=7:3, glass is cleaned multiple times and is dried up using deionized water after the completion of immersion, is subsequently placed in 0.001~0.1mol/L
PEDOT:It when the alcohol solution dipping 2-4 of PSS is small, is cleaned and is dried up with deionized water after taking-up, glass exists by treated
The 80-110 DEG C of drying of below 100Pa vacuum, by treated, glass is maintained in nitrogen environment, and 30 degrees Celsius of constant temperature is maintained to protect
It deposits；
4) preparation of glass substrate/nano silver wire film：Glass is placed on whirler, nano silver wire solution
It drops on glass, solution uses 300-3000rpm/min speed to rotate 5-30s after being uniformly distributed, and is adjusted and revolved according to solution concentration
Transfer film number obtains nano silver wire film, above-mentioned film forms glass substrate/silver using 100-200 DEG C of drying 5-30min
Nano wire film, the nano silver wire film thickness is 150-1000nm；
5) zinc-oxide film is prepared：Zinc-oxide film is obtained by solution rotating film mode, glass nano silver wire is thin
Film is placed on whirler, by step 2) the zinc oxide precursor drop on sample, using 1000-3000rpm/
Min speed rotates 10-50s, by above-mentioned film using 80-150 DEG C of scope drying 10-120min of below 100Pa vacuum, that is, is formed
Glass substrate/nano silver wire/zinc-oxide film, the zinc oxide films film thickness is 20-200nm；
6) zinc-oxide nano column is prepared:Above-mentioned film is placed in Teflon liner water heating kettle, film is face-down, in water heating kettle
Place zinc nitrate:Hexa-methylene time amine (HMT)=1:1 aqueous solution, wherein nitric acid zinc concentration be 0.05-0.5mol/L, hydro-thermal
Kettle is put into air dry oven, 90-100 DEG C of heating 1-6h, and sample is taken out after natural cooling, that is, obtain glass substrate/nano silver wire/
Zinc-oxide film/zinc-oxide nano column, zinc-oxide nano column altitude range is in 200nm-5000nm.
Preferably, the alcohol in nano silver wire alcohol dispersion liquid in the step 1) includes methanol, ethyl alcohol, isopropanol and
The arbitrary proportion mixed solution of above-mentioned solution.
Preferably, polyalcohol in the step 1) is ethylene glycol, glycerine, one kind in propylene glycol or butanediol.
Preferably, zinc source described in the step 2) is zinc acetate, one kind in zinc nitrate or zinc acetylacetonate.
Preferably, the preparation of glass substrate/nano silver wire film can also use dip-coating method in the step 4)
Mode prepare nano silver wire film, when nano silver wire Best-Effort request is film-made, film pull rate 10-1000 μm/min it
Between, the stand-by period is 1-10min after lifting, and lifting number is between 1-20 times.
Preferably, the preparation of the zinc-oxide film in the step 5) can also obtain mode using dip-coating method and prepare
Zinc-oxide film, when being film-made using Best-Effort request, film pull rate is between 100-2000 μm/min, the stand-by period after lifting
For 1-10min, lifting number is between 1-3 times.
Compared with prior art, glass substrate/nano silver wire/zinc oxide/zinc-oxide nano column that the present invention is prepared
Dual light trapping structure transparent conductive film has the following advantages with respect to other transparent conductive films：
1) nano silver wire is supported on glass by simple method, the advantage that can play nano silver wire realizes height
The transparent conductive film of electrical conductivity and high transmittance；Zinc-oxide film and zinc-oxide nano column, raw material are prepared using sol gel process
Abundance and easy to operate, is not required the critical conditions such as high temperature, vacuum, and the multi-layer transparent electroconductive film of preparation has at low cost
The advantages that.
2) the surface plasma stimulus effect using nano silver wire and the wide spectrum scattering to light can be realized for the first time
Scattering to light；It can be realized using zinc-oxide nano rod structure and second of light is effectively scattered, in this transparent conductive film
Nano silver wire is kept apart with zinc oxide transparent conductive film by zinc-oxide film, nano silver wire plane distribution in glass surface,
For zinc-oxide nano column vertical distribution in glass surface, the two characteristic size is different, therefore can realize to the multiple of light, not Tongfang
To scattering.
Description of the drawings
Fig. 1 is the preparation flow schematic diagram of the dual light trapping structure transparent conductive film of the present invention.
Fig. 2 is the schematic diagram of the dual light trapping structure structure of transparent conductive film of the present invention.
Fig. 3 is the scanning electron microscope diagram of glass substrate/nano silver wire in embodiment 1.
Fig. 4 is the scanning electron microscope diagram of glass substrate/nano silver wire/zinc-oxide film in embodiment 1.
Fig. 5 is the scanning electron microscopy of glass substrate/nano silver wire/zinc-oxide film/zinc-oxide nano column in embodiment 1
Mirror figure.
Wherein, in figure 1 be glass substrate, 2 be nano silver wire film, 3 be zinc-oxide film, and 4 be zinc-oxide nano column.
Specific embodiment
Embodiment 1
(1) nano silver wire suspension is prepared
The hot method reduction silver nitrate of polyalcohol by the use of ethylene glycol as solvent, obtains nano silver wire solution 30ml, centrifuge
Nano silver wire (0.2g) and solvent are isolated, after removing solvent, nano silver wire (0.2g) is dissolved in ethanol solution, is configured to 5mg/
The nano silver wire alcohol dispersion liquid (40ml) of ml was ultrasonically treated by five minutes, obtains the nano silver wire solution (concentration of stable dispersion
5mg/ml, volume 40ml).
(2) zinc oxide precursor liquid is prepared
By zinc acetate (0.01mol), ethanolamine (0.005mol) and ethyl alcohol (100ml) are mixed at 50 DEG C and carried out anti-
Should, form zinc oxide colloidal sol (100ml), zinc concentration 0.1mol/L after being aged 20h.
(3) glass substrate is handled
Diameter 3cm glass is selected as substrate, is respectively adopted acetone, methanol, ethyl alcohol, deionized water ultrasound 20 minutes, after
It is cleaned with deionized water；Then substrate is dried up using nitrogen, 120 degrees Celsius of drying of air dry oven；
It impregnates and preserves：Glass immersion is water-soluble in the mass concentration concentrated sulfuric acid for being 98% and dioxygen that mass concentration is 30%
Reach in liquid 24 it is small when more than, the volume ratio of the solution is the concentrated sulfuric acid：Hydrogen peroxide=7:3, use deionization after the completion of impregnating
Water is cleaned multiple times and is dried up to glass, is subsequently placed in the PEDOT of 0.001mol/L:When the alcohol solution dipping 3 of PSS is small,
Cleaned and dried up with deionized water after taking-up, will treated glass in the 80 DEG C of dryings of below 100Pa vacuum, will treated glass
Glass is maintained in nitrogen environment, and 30 degrees Celsius of constant temperature is maintained to preserve；
(4) nano silver wire film is prepared
Glass substrate Jing Guo above-mentioned processing is placed on whirler, nano silver wire solution (5mg/ml) drops to
Glass (9cm handled by step (3)2) on, solution uses 2000rpm/min speed to rotate 10s after being uniformly distributed, using 150
DEG C drying 5-30min, that is, form glass substrate/nano silver wire film, and nano silver wire film thickness is 200nm, scanning electron
Microscope figure is shown in Fig. 3.
(5) zinc-oxide film is prepared
The glass substrate being prepared in step 4)/nano silver wire film is placed on whirler, by step (2)
Prepared zinc oxide precursor sol liquid 100ul drops are revolved on glass substrate/nano silver wire film using 2000rpm/min speed
Turn 30s, using 120 DEG C of scope drying 10min of below 100Pa vacuum, that is, form glass substrate/nano silver wire/zinc-oxide film,
Zinc oxide films film thickness is 40nm, and scanning electron microscope diagram is shown in Fig. 4.
(6) zinc-oxide nano column is prepared
Glass substrate/nano silver wire/the zinc-oxide film being prepared in step 5) is placed in Teflon liner water heating kettle,
Film is face-down, and zinc nitrate is placed in water heating kettle:Hexa-methylene time amine (HMT)=1:1 aqueous solution, wherein nitric acid zinc concentration are
0.1mol/L, water heating kettle are put into air dry oven, and 90 DEG C are heated 5h, are taken out sample after natural cooling, that is, are obtained glass substrate/silver
Nano wire/zinc-oxide film/zinc-oxide nano column, gained zinc-oxide nano column thickness be 3000nm, scanning electron microscope
Figure is shown in Fig. 5.
Embodiment 2
(1) nano silver wire suspension is prepared
The hot method reduction silver nitrate of polyalcohol by the use of ethylene glycol as solvent, obtains nano silver wire solution 100ml, centrifuge
Nano silver wire (900mg) and solvent are isolated, after removing solvent, nano silver wire (900mg) is dissolved in ethanol solution, is configured to
The nano silver wire alcohol dispersion liquid (450ml) of 2mg/ml was ultrasonically treated by five minutes, obtains the nano silver wire solution of stable dispersion
(concentration 2mg/ml, volume 450ml).
(2) zinc oxide precursor liquid is prepared
By zinc acetate (0.06mol), ethanolamine (0.03mol) and ethyl alcohol (1000ml) are mixed at 50 DEG C and carried out anti-
Should, form zinc oxide colloidal sol (1000ml), zinc concentration 0.06mol/L after being aged 20h.
(3) glass substrate is handled
Diameter 4cm glass is selected as substrate, is respectively adopted acetone, methanol, ethyl alcohol, deionized water ultrasound 20 minutes, after
It is cleaned with deionized water；Then substrate is dried up using nitrogen, 120 degrees Celsius of drying of air dry oven；
It impregnates and preserves：Glass immersion is water-soluble in the mass concentration concentrated sulfuric acid for being 98% and dioxygen that mass concentration is 30%
Reach in liquid 24 it is small when more than, the volume ratio of the solution is the concentrated sulfuric acid:Hydrogen peroxide=7:3, use deionization after the completion of impregnating
Water is cleaned multiple times and is dried up to glass, is subsequently placed in the PEDOT of 0.1mol/L:When the alcohol solution dipping 3 of PSS is small, take
Cleaned and dried up with deionized water after going out, will treated glass in the 100 DEG C of dryings of below 100Pa vacuum, will treated glass
Glass is maintained in nitrogen environment, and 30 degrees Celsius of constant temperature is maintained to preserve；
(4) nano silver wire film is prepared
Glass substrate Jing Guo above-mentioned processing is placed on whirler, nano silver wire solution (2mg/ml) drops to
Glass (area 16cm handled by step (3)2) on, glass is placed under lifting coating machine, glass one side uses glue
Band protection, nano silver wire film is formed using dip-coating method, is lifted glass using 300 μm/min speed, is waited 5 minutes nanometers
Line film drying repeats lifting 10 times, that is, forms glass substrate/nano silver wire film, nano silver wire film 500nm.
(5) zinc-oxide film is prepared
Glass substrate/nano silver wire film in step (4) is placed under lifting coating machine, by 50ml steps (2) institute
It prepares zinc oxide precursor sol liquid to be placed under above-mentioned glass film, glass one side is protected using adhesive tape, using 100 μm/min speed
Degree lifting glass 1 time, that is, form glass substrate/nano silver wire/zinc-oxide film, and zinc oxide films film thickness is 30nm.
(6) zinc-oxide nano column is prepared
Above-mentioned film is placed in Teflon liner water heating kettle, film is face-down, and zinc nitrate is placed in water heating kettle:Hexa-methylene
Secondary amine (HMT)=1:1 aqueous solution, wherein nitric acid zinc concentration are 0.15mol/L, and water heating kettle is put into air dry oven, and 95 DEG C add
Hot 2h takes out sample after natural cooling, that is, obtains glass substrate/nano silver wire/zinc-oxide film/zinc-oxide nano column, oxidation
Zinc nano-pillar thickness is 1500nm.
This place embodiment is in place of the claimed non-limit of technical scope midrange and in embodiment technology
The new technical solution formed is replaced on an equal basis to single or multiple technical characteristics in scheme, equally all the present invention claims
In the range of protection；Simultaneously the present invention program it is all enumerate or unrequited embodiment in, in the same embodiment each
Parameter is merely representative of an example (i.e. a kind of feasible scheme) for its technical solution, and between parameters and is not present stringent
Cooperation and qualified relation, wherein each parameter can be replaced mutually when stating and asking without prejudice to axiom and the present invention, special declaration
Except.
The technical means disclosed in the embodiments of the present invention is not limited to the technical means disclosed in the above technical means, and is further included
Formed technical solution is combined by more than technical characteristic.The above is the specific embodiment of the present invention, should be referred to
Go out, for those skilled in the art, without departing from the principle of the present invention, can also make several
Improvements and modifications, these improvements and modifications are also considered as protection scope of the present invention.
Claims (10)
1. a kind of dual light trapping structure transparent conductive film, it is characterised in that including：
Glass substrate, the one layer of nano silver wire film coated on the glass substrate, the one layer of oxygen coated on nano silver wire film
Change zinc film and the one layer of zinc-oxide nano column grown on zinc-oxide film.
A kind of 2. dual light trapping structure transparent conductive film according to claim 1, it is characterised in that the glass substrate choosing
One kind from soda-lime glass, ultra-clear glasses, quartz glass, flexible glass, the thickness range of the glass substrate is in 0.05mm-
Between 50mm, transmitance is between 91%-83%.
A kind of 3. dual light trapping structure transparent conductive film according to claim 1, it is characterised in that the nano silver wire
Film thickness is 150-1000nm.
A kind of 4. dual light trapping structure transparent conductive film according to claim 1, it is characterised in that the zinc oxide films
Film thickness is 20-200nm.
A kind of 5. dual light trapping structure transparent conductive film according to claim 1, it is characterised in that the zinc oxide nano
Rice column thickness is 200-5000nm.
6. a kind of preparation of dual light trapping structure transparent conductive film, it is characterised in that comprise the following steps：
1) nano silver wire suspension is prepared：Using the hot method reduction silver nitrate of polyalcohol, the alcoholic solution containing nano silver wire is prepared, by silver
Nanowire solution dilutes the nano silver wire alcohol dispersion liquid for being configured to 0.01-10mg/ml, was ultrasonically treated, obtains by 1-30 minutes
The nano silver wire solution of stable dispersion；
2) zinc oxide precursor liquid is prepared：By zinc source, ethanolamine and ethyl alcohol are mixed and reacted at 20-80 DEG C, are aged 20-
The amount ratio of the substance of formation zinc oxide colloidal sol after 28h, zinc concentration 0.01-1mol/L, ethanolamine and zinc is 1:2；
3) glass substrate is handled：After cleaning glass substrate drying, by glass immersion in the concentrated sulfuric acid and matter that mass concentration is 98%
Amount concentration be reach in 30% hydrogen peroxide solution 24 it is small when more than, the volume ratio of the solution is the concentrated sulfuric acid:Hydrogen peroxide=7:
3, glass is cleaned multiple times and is dried up using deionized water after the completion of immersion, is subsequently placed in 0.001~0.1mol/L's
PEDOT:It when the alcohol solution dipping 2-4 of PSS is small, is cleaned and is dried up with deionized water after taking-up, glass exists by treated
The 80-110 DEG C of drying of below 100Pa vacuum, by treated, glass is maintained in nitrogen environment, and 30 degrees Celsius of constant temperature is maintained to protect
It deposits；
4) preparation of glass substrate/nano silver wire film：Glass is placed on whirler, nano silver wire solution drops to
On glass, solution uses 300-3000rpm/min speed to rotate 5-30s after being uniformly distributed, and adjusting rotation according to solution concentration applies
Film number obtains nano silver wire film, above-mentioned film forms glass substrate/silver nanoparticle using 100-200 DEG C of drying 5-30min
Line film, the nano silver wire film thickness is 150-1000nm；
5) zinc-oxide film is prepared：Zinc-oxide film is obtained by solution rotating film mode, glass nano silver wire film is put
It puts on whirler, by step 2) the zinc oxide precursor drop on sample, using 1000-3000rpm/min speed
Degree rotation 10-50s by above-mentioned film using 80-150 DEG C of scope drying 10-120min of below 100Pa vacuum, that is, forms glass
Substrate/nano silver wire/zinc-oxide film, the zinc oxide films film thickness is 20-200nm；
6) zinc-oxide nano column is prepared:Above-mentioned film is placed in Teflon liner water heating kettle, film is face-down, is placed in water heating kettle
Zinc nitrate：Hexa-methylene time amine (HMT)=1：1 aqueous solution, wherein nitric acid zinc concentration are 0.05-0.5mol/L, and water heating kettle is put
Enter air dry oven, 90-100 DEG C is heated 1-6h, is taken out sample after natural cooling, that is, is obtained glass/nano silver wire/zinc oxide films
Film/zinc-oxide nano column, zinc-oxide nano column altitude range is in 200nm-5000nm.
A kind of 7. preparation of dual light trapping structure transparent conductive film, it is characterised in that the nano silver wire alcohol point in the step 1)
Alcohol in dispersion liquid includes methanol, ethyl alcohol, the arbitrary proportion mixed solution of isopropanol and above-mentioned solution；It is more in the step 1)
First alcohol is ethylene glycol, glycerine, one kind in propylene glycol or butanediol.
8. a kind of preparation of dual light trapping structure transparent conductive film, it is characterised in that zinc source described in the step 2) is acetic acid
One kind in zinc, zinc nitrate or zinc acetylacetonate.
A kind of 9. preparation of dual light trapping structure transparent conductive film, it is characterised in that glass/nano silver wire in the step 4)
The preparation of film can also prepare nano silver wire film by the way of dip-coating method, when nano silver wire Best-Effort request is film-made,
Film pull rate is between 10-1000 μm/min, and the stand-by period is 1-10min after lifting, and lifting number is between 1-20 times.
A kind of 10. preparation of dual light trapping structure transparent conductive film, it is characterised in that the zinc-oxide film in the step 5)
Preparation can also mode be obtained using dip-coating method and prepare zinc-oxide film, when being film-made using Best-Effort request, film lifting speed
Degree is between 100-2000 μm/min, and the stand-by period is 1-10min after lifting, and lifting number is between 1-3 times.
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| CN109585641A (en) * | 2018-11-06 | 2019-04-05 | 浙江海洋大学 | It is a kind of based on PET/ silver nanowires/zinc oxide composite film/zinc oxide nano array nano generator and preparation method |
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| CN104934109A (en) * | 2015-06-03 | 2015-09-23 | 林州市清华·红旗渠新材料产业化发展中心 | Preparation method of glass substrate graphene/silver nano wire transparent conductive film |
| CN106782891A (en) * | 2016-12-31 | 2017-05-31 | 浙江大学 | The preparation method of metal oxide compound silver nanometer line transparent conductive film |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109585641A (en) * | 2018-11-06 | 2019-04-05 | 浙江海洋大学 | It is a kind of based on PET/ silver nanowires/zinc oxide composite film/zinc oxide nano array nano generator and preparation method |
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