CN106129134B - A kind of method for improving flexible nano silver wire transparency electrode electric conductivity using solar irradiation - Google Patents
A kind of method for improving flexible nano silver wire transparency electrode electric conductivity using solar irradiation Download PDFInfo
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- CN106129134B CN106129134B CN201610559577.5A CN201610559577A CN106129134B CN 106129134 B CN106129134 B CN 106129134B CN 201610559577 A CN201610559577 A CN 201610559577A CN 106129134 B CN106129134 B CN 106129134B
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 127
- 238000000034 method Methods 0.000 title claims abstract description 38
- 239000000758 substrate Substances 0.000 claims abstract description 47
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims abstract description 34
- 239000004926 polymethyl methacrylate Substances 0.000 claims abstract description 34
- 239000010409 thin film Substances 0.000 claims abstract description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000010408 film Substances 0.000 claims abstract description 16
- 229920002120 photoresistant polymer Polymers 0.000 claims abstract description 16
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000725 suspension Substances 0.000 claims abstract description 14
- 239000010703 silicon Substances 0.000 claims abstract description 8
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims abstract description 5
- 230000009514 concussion Effects 0.000 claims description 4
- 238000004528 spin coating Methods 0.000 claims description 4
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- 150000001875 compounds Chemical class 0.000 claims description 2
- 238000002834 transmittance Methods 0.000 abstract description 7
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 238000001755 magnetron sputter deposition Methods 0.000 abstract description 2
- 239000004698 Polyethylene Substances 0.000 description 11
- 238000005452 bending Methods 0.000 description 11
- 238000012545 processing Methods 0.000 description 9
- 230000005540 biological transmission Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000005286 illumination Methods 0.000 description 5
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910021389 graphene Inorganic materials 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
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- 238000009826 distribution Methods 0.000 description 2
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- 238000010894 electron beam technology Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 239000002070 nanowire Substances 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- -1 tungsten halogen Chemical class 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- 241000580952 Morus capensis Species 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002042 Silver nanowire Substances 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
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- 230000007812 deficiency Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 description 1
- 230000004807 localization Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 235000012149 noodles Nutrition 0.000 description 1
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- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
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- 235000009566 rice Nutrition 0.000 description 1
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- 230000008023 solidification Effects 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
- H01B13/0026—Apparatus for manufacturing conducting or semi-conducting layers, e.g. deposition of metal
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022466—Electrodes made of transparent conductive layers, e.g. TCO, ITO layers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The present invention relates to a kind of method for improving flexible nano silver wire transparency electrode electric conductivity using solar irradiation, including step：1）Separate nano silver wire alcohol suspending liquid；2）Nano silver wire is evenly spread in PMMA photoresists, forms nano silver wire PMMA suspensions；3）Prepare flexible and transparent substrate and silicon chip；4）Nano silver wire PMMA suspensions are uniformly coated in flexible and transparent substrate, form nano silver wire PMMA films；5）Flexible and transparent substrate surface PMMA is removed with acetone；6）Flexible nano silver wire transparency electrode is made；7）It is no less than 15 minutes with sun natural light or simulated solar light irradiation flexibility nano silver wire transparency electrode, light application time.This method can effectively reduce the square resistance of nano silver wire transparency electrode, and the nano silver wire transparency electrode after improvement has good electric conductivity, light transmittance and buckle resistance energy, and this method is not damaged to RF magnetron sputtering, simple and easy, suitable for large-scale production；The thin film heater function admirable prepared using the transparency electrode.
Description
Technical field
The invention belongs to photoelectron technical field, and in particular to one kind utilizes solar irradiation（Or solar simulator light
The artificial light source of source isocandela appropriateness）Improve the method for flexible nano silver wire transparency electrode electric conductivity, and be related to the silver after improving
Application of the nano line electrode in terms of thin film heater.
Background technology
Transparency electrode is a variety of opto-electronic devices such as light emitting diode, touch-screen, thin film heater, solar cell etc.
It is basic to form part.In decades, tin indium oxide（ITO）Occupied always in the field by its excellent translucency and electric conductivity
Ascendancy.However, the scarcity of indium resource causes ITO price increasingly plus the preparation technology of vacuum coating high annealing
Height, the intrinsic fragility of material also counteracts that its application on flexible device.In order to overcome ITO these deficiencies, researcher
The alternative solutions such as conductive organic matter, CNT, graphene, metalolic network are proposed, wherein, the unstable spy of conductive organic matter
Property and weaker electric conductivity it is also had with a distance from quite remote from practical application；Contact resistance and characteristic of semiconductor between high pipe
Also reduce the competitiveness of CNT；Although electron mobility is very high, because electron density is too low, graphene is in electric conductivity side
Face is also difficult to be equal to ITO, and it is also urgently to be resolved hurrily how inexpensively to prepare graphene in large area.And metalolic network, especially
Random nano silver wire network with excellent light transmission and electric conductivity, as the most promising substitutes of ITO gradually to be more next
Known to more people；Also, there is spy compared to what electron beam exposure to be used, vacuum evaporation or the contour cost process of sputtering made
Determine the metal grill of pattern, nano silver wire can be prepared on a large scale by cheap solution methods, and this causes it especially has to inhale
Gravitation.（Refer to survey article K. Ellmer, Nature Photonics 2012,6,809；G. U Kulkarni, S.
Kiruthika, R. Gupta1, K. Rao, Curr. Opin. Chem. Engi. 2015, 8, 60；D. S.
Hecht, L. Hu, G. Irvin, Adv. Mater. 2011, 23, 1482；J. Song, H. Zeng, Angew.
Chem. Int. Ed. 2015, 54, 9760.）
During nano silver wire is prepared, in order to prevent nano silver wire cluster, them are made to be uniformly distributed in solution, one
As need add PVP（Polyvinylpyrrolidone）As stabilizer, so as in the very thin medium of nano silver wire Surface coating last layer
Layer；In this way, when forming random nano silver wire network on substrate using as transparency electrode, between nano silver wire and nano silver wire
Contact resistance will be very big, and then limits the overall performance of nano silver wire network, and when substrate is flexible, this problem is more prominent
Go out.
The traditionally general electric conductivity for improving random nano silver wire network using the method for being heated to 200 DEG C（J.-Y.
Lee, S. T. Connor, Y. Cui , P. Peumans, Nano Lett. 2008, 8, 689；J. - Y. Lee,
S. T. Connor, Y. Cui , P. Peumans, Nano Lett. 2010, 10, 1276；P. Lee, J. Lee,
H. Lee, J. Yeo, S. Hong, K. H. Nam, D. Lee, S. S. Lee, S. H. Ko, Adv. Mater.
2012, 24, 3326；A. R. Madaria, A. Kumar, F. N. Ishikawa, C. Zhou, Nano Res.
2010, 3, 564；S. Coskun, E. Selen Ates, H. E. Unalan, Nanotechnology 2013, 24,
125202；C. Sachse, L. Muller-Meskamp, L. Bormann, Y. H. Kim, F. Lehnert, A.
Philipp, B. Beyer, K. Leo, Org. Electron. 2013, 14, 143.）；If with reference to mechanical pressure, temperature
Degree can be reduced to 100-150 DEG C（S. De, T. M. Higgins, P. E. Lyons, E. M. Doherty,P. N.
Nirmalraj, W. J. Blau, J. J. Boland, J. N. Coleman, ACS Nano 2009, 3, 1767；
S.-E. Park, S. Kim, D.-Y. Lee, E. Kim, J. Hwang, J. Mater. Chem. A 2013, 1,
14286；T. L. Chen, D. S. Ghosh, V. Mkhitaryan, V. Pruneri, ACS Appl. Mater.
Interfaces 2013, 5, 11756.）；If controlling humidity again, temperature can be reduced further（N. Weiß, L.
Muller-Meskamp, F. Selzer, L. Bormann, A. Eychmuller, K. Leob, N. Gaponik,
RSC Adv. 2015, 5, 19659.）.But these conditions may damage some Sensitive Apparatuses such as organic electronic element.
Also contact resistance between method improvement line that can be by depositing gold grain in nano silver wire surface chemistry, but roughness can be increased, lead
Transmittance declines（L. Hu, H. S. Kim, J.-Y. Lee, P. Peumans, Y. Cui, ACS Nano 2010,
4, 2955.）.
In recent years, the method for local welding has obtained the concern of researcher.Nano silver wire network galvanization is given, online-line
Contact point produces Joule heat and electromigration（T.-B. Song, Y. Chen, C.-H. Chung, Y. Yang, B. Bob,
H.-S. Duan, G. Li, K.-N. Tu, Y. Huang, Y. Yang, ACS Nano 2014, 8, 2804.）；Using
The chemical reaction of plasma guiding（H. Lu, D. Zhang, X. Ren, J. Liu, W. C. H. Choy, ACS
Nano 2014, 8, 10980.）Or the solution methods based on alcohol（H. Lu , D. Zhang , J. Cheng , J.
Liu , J. Mao , W. C. H. Choy, Adv. Funct. Mater. 2015, 25, 4211.）, optionally exist
Line-linear contact lay spot deposition Argent grain；Make contact point welding using capillary condensation（S.-S. Yoon, D.-Y. Khang, Nano
Lett. 2016, DOI: 10.1021/acs.nanolett.6b00621.）It is reported etc. a variety of methods.But the former is operating
In first need to do electrode to network, it is very inconvenient；Middle person reduces obvious due to shadow effect, light transmittance；The latter can be to nano wire
There is corrosiveness.E. C. Gannet etc. are in the localization proposed in 2012, the photo plasma nanometer fusion techniques from limit
（E. C. Garnett, W. Cai, J. J. Cha, F. Mahmood, S. T. Connor, M. Greyson
Christoforo, Y. Cui, M. D. McGehee, M. L. Brongersma, Nat. Mater. 2012, 11,
241）Obtain extensive concern and application, but, this method often to use tungsten halogen lamp with very high power density or
Xenon flash lamp（J. Jiu, M. Nogi, T. Sugahara, T. Tokuno, T. Araki, N. Komoda, K.
Suganuma, H. Uchidab, K. Shinozaki, J. Mater. Chem., 2012, 22, 23561.）, Huo Zhezi
Outer laser（J. A. Spechler, C. B. Arnold, Appl. Phys. A 2012,108, 25；Q. Nian,
M. Saei, Y. Xu, G. Sabyasachi, B. Deng, Y. P. Chen, G. J. Cheng, ACS Nano
2015, 9, 10018.）, it is not only dangerous, and Ultra-Violet Laser due to hot spot it is small, treatment effeciency is very low.If light source is replaced
For electron beam（C.-H. Hong, S. K. Oh, T. K. Kim, Y.-J. Cha, J. S. Kwak, J.-H. Shin,
B.-K. Ju, W.-S. Cheong, Sci. Repo. 2015, 5, 17716.）Or plasma（S. Zhu, Y.
Gao, B. Hu, J. Li, J. Su, Z. Fan, J. Zhou, Nanotechnology 2013, 24, 335202.）,
Expensive high-vacuum chamber is needed again.
Patent application 201510013871.1 discloses the method and silver that a kind of large area prepares nano silver wire transparency electrode
Nano wire transparency electrode, this method are that nano silver wire transparency electrode is prepared in transparency silica glass substrate.And the present invention is at this
One kind is developed on the basis of patent work first in flexible and transparent substrate and utilizes solar irradiation（Or solar simulator
The artificial light source of light source isocandela appropriateness）Improve the method for flexible nano silver wire transparency electrode electric conductivity, obtained silver nanoparticle
Line transparency electrode is applied to thin film heater.
The content of the invention
Improve flexible nano silver wire transparency electrode electric conductivity using solar irradiation it is an object of the invention to provide a kind of
Method, and the nano silver wire transparency electrode after performance improvement is applied to thin film heater.
The present invention technical principle be：Appropriate nano silver wire solution is taken first, and nano silver wire and molten is isolated with centrifuge
Agent, after removing solvent, bottom nano silver wire is mixed in certain photoresist（Such as polymethyl methacrylate）In, concussion is until silver is received
Rice noodles are evenly spread in photoresist, form nano silver wire-photoresist suspension；In the transparent substrates cleaned up, in drop
Nano silver wire-photoresist suspension, and with certain rotation speed rotating transparent substrate so that nano silver wire-photoresist suspension
Uniformly it is coated in transparent substrates, forms nano silver wire-photoresist film；Spin coating there is into the saturating of nano silver wire-photoresist film
Bright substrate immerses organic solution（Such as acetone）Middle removal photomask surface glue；Transparent substrates are taken out, after the volatilization of its surface solution, silver
Nano wire stays naturally forms uniform nano silver wire network, i.e. nano silver wire transparency electrode on a transparent substrate；Use sunshine（Or
The artificial light source of person's solar simulator light source isocandela appropriateness）Irradiate the nano silver wire transparency electrode regular hour.
Technical scheme is used by realizing the object of the invention：One kind is transparent using the flexible nano silver wire of solar irradiation improvement
The method of electrode conductivuty, comprises the following steps：
（1）Appropriate nano silver wire alcohol suspending liquid is taken, nano silver wire and ethanol are isolated with centrifuge；
（2）After removing ethanol, bottom nano silver wire is mixed in PMMA photoresists, concussion is until nano silver wire is dispersed
Into PMMA photoresists, nano silver wire-PMMA suspensions are formed；
（3）Clean and dry flexible and transparent substrate and silicon chip, flexible and transparent substrate is fixed on silicon chip by blend compounds band；
（4）By step 2）Obtained nano silver wire-PMMA suspensions are dripped in flexible and transparent substrate, rotating transparent substrate,
So that nano silver wire-PMMA suspensions are uniformly coated in flexible and transparent substrate, nano silver wire-PMMA films are formed；
（5）The flexible and transparent substrate that spin coating there are nano silver wire-PMMA films is immersed in organic solvent-acetone, removes surface
PMMA films；
（6）Flexible and transparent substrate is taken out, after organic solvent-acetone volatilization, nano silver wire stays in shape in flexible and transparent substrate
Into uniform nano silver wire network, i.e., flexible nano silver wire transparency electrode；
（7）With sun natural light or simulated solar light irradiation flexibility nano silver wire transparency electrode, light application time is no less than 15
Minute.
Preferably, step 1）Described in the concentration of nano silver wire alcohol suspending liquid be 5 mg/mL, described nano silver wire
A diameter of 60 nm, length are 15 μm.
Step 2）Described in the mass volume ratio of nano silver wire and PMMA photoresists be 1mg：1mL.
Step 3）Described in transparent substrates be polythene material.
Step 4）Described in nano silver wire-PMMA film thicknesses be 270 nm.
Step 7）Described in simulated solar irradiation the W/m of energy density 10002。
It is furthermore preferred that step 4）Middle rotating transparent substrate, rotated using two sections, the 1st section of rpm of rotating speed 2000, the s of time 3,
The 2nd section of rpm of rotating speed 4000, the s of time 59.
Particularly, the nano silver wire transparency electrode obtained by the present invention can be applied to thin film heater.
The present invention advantageous effects be：
（1）The electric conductivity of the nano silver wire transparency electrode improved by the inventive method substantially quickly improves, and light transmission
（The nm of wavelength 550）It is held essentially constant；The average square resistance of the primary sample of solar irradiation before processing is 67.5 Ω/sq,
550 nm light transmission rates are 88.1%；Solar simulator（AM 1.5）After irradiating 15 min, square resistance rapidly goes to 20.1
Ω/sq；After irradiation 1 hour, square resistance is changed into 17.1 Ω/sq, is 86.6% in 550 nm light transmissions；After irradiation 4 hours,
Square resistance is changed into 15.9 Ω/sq, light transmission 86.6%.
（2）After up to 500 times bendings, its resistance has no bright nano silver wire transparency electrode after being improved by the inventive method
Aobvious change, buckle resistance can be significantly better than ito thin film；And after identical bending number, the resistance of ito thin film increased dramatically, about
Originally 40 times.
（3）The inventive method is to organic flexible substrate not damaged, better than traditional hot plate heating means, 200 DEG C of hot plate heating 1
PE substrates deformation after hour is serious, and the PE substrates after illumination 1 hour are without significant change.
（4）When nano silver wire transparency electrode after being improved by the inventive method is applied to thin film heater, thin film heater
The maximum temperature that can reach（Irradiation 1 hour, 60 DEG C after being powered 120 seconds；After irradiation 4 hours, 84 DEG C after being powered 120 seconds）And temperature
The uniformity coefficient of distribution is significantly better than that the nano silver wire transparency electrode improved without solar irradiation（43 DEG C after being powered 120 seconds）.
Brief description of the drawings
Fig. 1 is with the method processing time increase by the present invention, the change feelings of nano silver wire transparency electrode square resistance
Condition.
Fig. 2 is with the method processing time increase by the present invention, nano silver wire transparency electrode printing opacity at wavelength 550nm
The situation of change of rate.
Fig. 3 be by the present invention method handle 1 hour and 4 hours after nano silver wire transparency electrode and 571nm thickness ITO it is thin
The result of film bending test.
Fig. 4 is not carry out the inventive method processing（A）Nano silver wire transparency electrode when being applied to thin film heater, film
The temperature profile of heater.
Fig. 5 is handled 1 hour by the inventive method（B）When nano silver wire transparency electrode afterwards is applied to thin film heater,
The temperature profile of thin film heater.
Fig. 6 is handled 4 hours by the inventive method（C）When nano silver wire transparency electrode afterwards is applied to thin film heater,
The temperature profile of thin film heater.
Fig. 7 is untreated（A）Handled 1 hour with by the inventive method（B）And 4 hours（C）The transparent electricity of nano silver wire afterwards
When pole is respectively applied to thin film heater, the temperature of thin film heater changes over time situation.
Wherein, abscissa is bending number in Fig. 3（Bending-restore to the original state as bending 1 time）, ordinate normalized resistance
（The ratio of resistance and corresponding initial resistance after bending）, Fig. 4, Fig. 5, Fig. 6 sets forth the square resistance of each sample.
Embodiment
With reference to embodiment and accompanying drawing, the invention will be further described.Those skilled in the art can be in institute of the present invention
Modification and improvement are made in the range of being related to.
Embodiment 1
A kind of method for improving flexible nano silver wire transparency electrode electric conductivity using solar irradiation of the present embodiment, including such as
Lower step：
（1）Take the mL of nano silver wire ethanol solution 0.8 that concentration is 5 mg/mL, wherein a diameter of 60 nm of nano silver wire, length
Spend for 15 μm or so；
（2）Isolate nano silver wire and alcohol solvent with centrifuge, after removing alcohol solvent, by bottom nano silver wire mix in
In 0.4 mL PMMA photoresists, concussion is evenly spread in PMMA photoresists up to nano silver wire, forms nano silver wire-PMMA
Suspension；
（3）Take the cm of 1.8 cm × 1.8 PE（Polyethylene）The cm silicon chips of transparent substrates and 2 cm × 2, it is acetone, methanol, different
Each normal temperature of propyl alcohol is cleaned by ultrasonic 5 min, and is dried up with drying nitrogen, 90 DEG C of 10 min of drying of baking oven, PE is flattened, consolidated with adhesive tape
Determine onto silicon chip；
（4）Nano silver wire-PMMA suspensions are dripped in PE substrates, with two sections of rotary speeies（1st section：Rotating speed 2000
Rpm, the s of time 3；2nd section：The rpm of rotating speed 4000, the s of time 59）Rotating transparent substrate so that nano silver wire-PMMA suspensions
Uniformly it is coated in the PE substrates, forms nano silver wire-PMMA films, thickness is about 270 nm；
（5）The PE- silicon chips substrate that spin coating there are nano silver wire-PMMA films is immersed in acetone, time 2 h, removes table
Face PMMA；
（6）PE- silicon chip substrates are taken out, after its surface acetone soln volatilization, nano silver wire stays in clear PE substrate naturally
It is upper to form uniform nano silver wire network, i.e. nano silver wire transparency electrode；
（7）Use solar simulator（AM 1.5, i.e. air mass 1.5, the W/m of energy density 10002）In air ambient
Middle irradiation nano silver wire transparency electrode（PE- silicon chip substrates）At least 15min.Illumination in the present invention can also select solar irradiation
And the artificial light source of other light intensity appropriateness.
Fig. 1 and Fig. 2 give nano silver wire transparency electrode square resistance of the present invention and at wavelength 550nm light transmittance with photograph
Time increased situation of change is penetrated, meanwhile, Fig. 1 and Fig. 2 also sets forth the corresponding result of 200 DEG C of hot plate heating as a comparison
And 571nm thickness ITO electric conductivity and light transmittance is as reference.It will be seen from figure 1 that nano silver wire of the present invention after the min of illumination 15
The square resistance of transparency electrode just drops sharply to 20.1 Ω/sq from 67.5 Ω/sq, this result ten heated with 200 DEG C of hot plates
Tap is near（17.6 Ω/sq is reduced to from 76 Ω/sq）, but the PE substrates deformation after 200 DEG C of hot plates heat 1 hour is serious, and
PE substrates after illumination 1 hour are without significant change.It is interesting that the nano silver wire of 200 DEG C of hot plate heating is transparent after processing 15min
The square resistance of electrode remains unchanged substantially（15min, 17.6 Ω/sq；30 min, 17.3 Ω/sq；45 min, 17.4 Ω/
sq；1 h, 17.3 Ω/sq；2 h, 17.3 Ω/sq；3 h, 17.2 Ω/sq；4 h, 17.3 Ω/sq）, and photo-irradiation treatment
The square resistance of nano silver wire transparency electrode can continue slowly to reduce with irradiation time increase（15min, 20.1 Ω/sq；30
Min, 18.2 Ω/sq；45 min, 17.5 Ω/sq；1 h, 17.1 Ω/sq；2 h, 16.4 Ω/sq；3 h, 16.1 Ω/
sq；4 h, 15.9 Ω/sq）, and the nano silver wire transparency electrode that less than 200 DEG C hot plates heat after irradiating 1 hour.Can from Fig. 2
To find out, solar irradiation and 200 DEG C of hot plate heating do not have much affect to the light transmittance of nano silver wire transparency electrode, true
On, both of which can keep 87% high-transmission rate in whole processing procedure.In addition, it is transparent to can be seen that nano silver wire with reference to Fig. 1
Electrode can realize that transmissivity is far above ito thin film after performance improvement while square resistance is much smaller than ito thin film.
Nano silver wire transparency electrode after photo-irradiation treatment 1 hour and 4 hours and 571nm thickness ito thin film are carried out curved
Folding test, transparent substrates are identical PE, and first strip shaped electric poles are done at sample both ends with elargol before bending is tested, and are tested
In, sample that effective length is 1.3 cm using have the one side of nano silver wire or ITO as convex bending to diameter be about 0.6 cm.Figure
3 be the nano silver wire transparency electrode and the bending test of 571nm thickness ito thin film after being handled 1 hour and 4 hours by the method for the present invention
Result.Experiment is found：For nano silver wire transparency electrode of the present invention after photo-irradiation treatment 1 hour and 4 hours, buckle resistance can be very
Good, its resistance has no significant change after up to 500 times bendings；And after identical bending number, the resistance of ito thin film drastically increases
Greatly, about original 40 times.
Fig. 4, Fig. 5 and Fig. 6 are not carry out the inventive method processing respectively（A）, processing 1 hour（B）And handle 4 hours（C）
When nano silver wire transparency electrode afterwards is applied to thin film heater, the temperature profile of thin film heater.In experiment, first handling
Sample both ends afterwards prepare strip shaped electric poles with elargol, apply 5V DC voltages at the two poles of the earth respectively after solidification, are remembered with infrared thermoviewer
Record its temperature variations, the temperature profile of thin film heater when Fig. 4, Fig. 5 and Fig. 6 are making alive 120 seconds.Fig. 7 is thin
The temperature of film heater with light application time situation of change, from Fig. 4~Fig. 7 as can be seen that illumination after nano silver wire it is transparent
Thin film heater made of electrode is after the 5V voltage identical times are added, and the temperature that can not only reach is higher, and Temperature Distribution
Also relatively evenly, and processing time is longer, and the temperature that can reach is higher.
The inventive method can effectively reduce the square resistance of nano silver wire transparency electrode, the transparent electricity of nano silver wire after improvement
Have good electric conductivity, light transmittance and buckle resistance energy, and this method is not damaged to RF magnetron sputtering, it is simple and easy,
Cost is cheap, suitable for large-scale production；Meanwhile the thin film heater function admirable prepared using the transparency electrode after improvement.
Claims (2)
- A kind of 1. method for improving flexible nano silver wire transparency electrode electric conductivity using solar irradiation, it is characterised in that：Including with Lower step：（1）Appropriate nano silver wire alcohol suspending liquid is taken, nano silver wire and ethanol are isolated with centrifuge；（2）After removing ethanol, bottom nano silver wire is mixed in PMMA photoresists, concussion is until nano silver wire is evenly spread to In PMMA photoresists, nano silver wire-PMMA suspensions are formed；（3）Clean and dry flexible and transparent substrate and silicon chip, flexible and transparent substrate is fixed on silicon chip by blend compounds band；（4）By step 2）Obtained nano silver wire-PMMA suspensions are dripped in flexible and transparent substrate, rotating transparent substrate so that Nano silver wire-PMMA suspensions are uniformly coated in flexible and transparent substrate, form nano silver wire-PMMA films；（5）The flexible and transparent substrate that spin coating there are nano silver wire-PMMA films is immersed in organic solvent-acetone, removes surface PMMA Film；（6）Flexible and transparent substrate is taken out, after organic solvent-acetone volatilization, nano silver wire is stayed in flexible and transparent substrate and formed Even nano silver wire network, i.e., flexible nano silver wire transparency electrode；（7）With sun natural light or simulated solar light irradiation flexibility nano silver wire transparency electrode, light application time is no less than 15 minutes, The energy density of described simulated solar irradiation is 1000 W/m2；Wherein, step 1）Described in the concentration of nano silver wire alcohol suspending liquid be 5 mg/mL, described nano silver wire is a diameter of 60 nm, length are 15 μm；Step 2）Described in the mass volume ratio of nano silver wire and PMMA photoresists be 1mg：1mL；Step 3）Described transparent substrates are polythene material；Step 4）Described in nano silver wire-PMMA film thicknesses be 270 nm；Step 4）Middle rotating transparent substrate, using two sections of rotations, the 1st section of rpm of rotating speed 2000, the s of time 3, the 2nd section of rotating speed 4000 Rpm, the s of time 59.
- 2. the method according to claim 1 for improving flexible nano silver wire transparency electrode electric conductivity using solar irradiation, its It is characterised by：Obtained nano silver wire transparency electrode is applied to thin film heater.
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