CN104916344A - Transparent conductor using silver nanowires to improve haze and electrical conductivity - Google Patents
Transparent conductor using silver nanowires to improve haze and electrical conductivity Download PDFInfo
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- CN104916344A CN104916344A CN201410148094.7A CN201410148094A CN104916344A CN 104916344 A CN104916344 A CN 104916344A CN 201410148094 A CN201410148094 A CN 201410148094A CN 104916344 A CN104916344 A CN 104916344A
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 112
- 239000004020 conductor Substances 0.000 title claims abstract description 72
- 239000002042 Silver nanowire Substances 0.000 title abstract description 4
- 239000000758 substrate Substances 0.000 claims abstract description 54
- 230000001070 adhesive effect Effects 0.000 claims abstract description 26
- 239000000853 adhesive Substances 0.000 claims abstract description 25
- 239000010410 layer Substances 0.000 claims description 49
- 239000003595 mist Substances 0.000 claims description 37
- 239000011241 protective layer Substances 0.000 claims description 23
- 238000002834 transmittance Methods 0.000 claims description 21
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical class OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 16
- 239000004814 polyurethane Substances 0.000 claims description 15
- 229920002635 polyurethane Polymers 0.000 claims description 15
- 229920002678 cellulose Polymers 0.000 claims description 8
- 239000001913 cellulose Substances 0.000 claims description 8
- 239000001856 Ethyl cellulose Substances 0.000 claims description 6
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 claims description 6
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 6
- 229920001249 ethyl cellulose Polymers 0.000 claims description 6
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 claims description 6
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 claims description 6
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 claims description 6
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 claims description 6
- 229920000609 methyl cellulose Polymers 0.000 claims description 6
- 239000001923 methylcellulose Substances 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 3
- 239000003522 acrylic cement Substances 0.000 claims description 3
- 239000012528 membrane Substances 0.000 claims description 3
- -1 polyethylene Polymers 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 239000002070 nanowire Substances 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 description 29
- 238000000576 coating method Methods 0.000 description 29
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- 230000003287 optical effect Effects 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000000470 constituent Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000010276 construction Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 229920005644 polyethylene terephthalate glycol copolymer Polymers 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229920002521 macromolecule Polymers 0.000 description 3
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000004642 Polyimide Substances 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002121 nanofiber Substances 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 208000034189 Sclerosis Diseases 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 229910052946 acanthite Inorganic materials 0.000 description 1
- 229920006397 acrylic thermoplastic Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000001579 optical reflectometry Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- 229940056910 silver sulfide Drugs 0.000 description 1
- XUARKZBEFFVFRG-UHFFFAOYSA-N silver sulfide Chemical compound [S-2].[Ag+].[Ag+] XUARKZBEFFVFRG-UHFFFAOYSA-N 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 229940116411 terpineol Drugs 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 239000003021 water soluble solvent Substances 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/14—Conductive material dispersed in non-conductive inorganic material
- H01B1/16—Conductive material dispersed in non-conductive inorganic material the conductive material comprising metals or alloys
-
- 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
Landscapes
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Non-Insulated Conductors (AREA)
- Laminated Bodies (AREA)
Abstract
The invention relates to a transparent conductor, comprising a conductive layer, wherein on the transparent substrate thereof, a plurality of silver nanowires with the average diameter of 15-22 nm, and average length of 10-20 mu m are combined through an adhesive to form a conductive network; and a protection layer formed on the conductive layer. Accordingly, the transparent conductor has excellent transparency, conductivity and haze.
Description
Technical field
The present invention relates to transparent conductor, relate to the transparent conductor utilizing nano silver wire with outstanding electrical characteristics and optical characteristics.
Background technology
Recently, transparent conductor is widely used in the fields such as contact panel (touch panel), liquid crystal display (liquid crystal display), organic light emitting diode device (organic light emitting diode devices) and thin film photocell (thin film photovoltaic cells).Representative transparent conductivity electric conductor is ito substrate.
But, as ITO metal conductive oxide body because of its reaction engineering complicated, depositing thick oxide skin(coating) to embody higher electrical conductivity, needing the annealing (annealing) of high temperature.Therefore have light transmittance low, not there is flexible shortcoming.
Therefore, developing also volume production recently to have compared with high connductivity degree, outstanding light transmittance and the flexible transparent conductor based on nano silver wire.
The existing transparent conductor based on nano silver wire uses the nano silver wire that diameter is 40nm, length is 30 μm, about sheet resistance (sheet resistance) 90 ~ 100 Ω/m
2, light transmittance 92% and mist degree (haze) 1.8%.Further, the transparent conductor that use average diameter is 30nm, average length is the nano silver wire of 25 μm, presents sheet resistance 80 Ω/m
2, light transmittance 91% and mist degree (haze, mist degree) 0.9 ~ 1.2%.Therefore, based on the transparent conductor of existing nano silver wire, although present outstanding sheet resistance and light transmittance, for mist degree, be respectively 1.8% and 0.9 ~ 1.2%, compare ITO, there is higher mist degree.
Especially, on transparent conductor, implement electrode pattern in order to use for transparency electrode, because of the comparatively haze of nano silver wire, pattern part and non-pattern portion are presented conductive electrode by distinguishing, and become the reason that visibility is bad.
The reason that nano silver wire produces mist degree is as follows.Nano silver wire, as Fig. 1, presents the five corner post shapes with crystal plane 111 and 100.Crystal plane 100 has planar structure, very high to light reflectance.In order to reduce the mist degree of the transparent conductor based on nano silver wire, reduce the content of nano silver wire, but reduce the content of the nano silver wire in transparency electrode, sheet resistance can rise.
As the method for dealing with problems, in order to reduce mist degree and sheet resistance, No. PCT/US2006/031918, International Application Publ discloses transparent conductor conductive layer adding and comprises antireflection layer, antiglare layers etc.
Further, korean patent application publication 10-2011-0113129, reduces in the process of nano silver wire content in order to reduce mist degree, proposes light sintering to reduce the sheet resistance of rising.
Outside the method for described proposition, propose the method reducing mist degree and sheet resistance in a variety of ways, but so far, be not enough to alternative ito substrate.
Therefore, need to provide a kind of technology, the transparent conductor with suitable electrical, optical and mechanical property can be provided, especially can be applicable to multiple substrate, engineering can also be used for lower expense, high handling rate and manufacture transparent conductor.
Summary of the invention
(technical problem that will solve)
The object of the invention is to, a kind of transparent conductor utilizing nano silver wire is provided, be applicable to improving light transmittance, effectively reducing sheet resistance and mist degree.
(means of dealing with problems)
In order to solve the problems of the technologies described above, transparent conductor provided by the invention, comprising: substrate, transparent; Conductive layer, on described substrate, multiple nano silver wires of average diameter 15 ~ 22nm, average length 10 ~ 20 μm are combined by adhesive and form conductive network; And protective layer, described conductive layer is formed.At this moment, described substrate is transparent rigid substrate or flexible base plate.
Preferably, described substrate also comprises hard membrane layer.
Preferably, described nano wire, relative to substrate area, is 10 ~ 25mg/m
2.
Preferably, described adhesive is made up of at least more than one in cellulose-based, polyethylene-based, acrylic acid series, polyurethane series, acrylic acid-polyurethane copolymer.
Preferably, described adhesive is made up of at least more than one in hydroxypropyl methylcellulose (HPMC) or methylcellulose (MC) or ethyl cellulose (EC).At this moment, described adhesive also can comprise at least more than one polyurethane or acrylic adhesive.
Preferably, described protective layer, is mixed by least more than one list amount body in acrylic acid series list amount body, polyurethane series list amount body, acrylic acid-polyurethane list amount body and bridging agent.
Preferably, described transparent conductor has 50 Ω/m
2following sheet resistance, the light transmittance of more than 90% and less than 0.8% mist degree.
Preferably, described substrate bottom also comprises: other conductive layers, and multiple nano silver wires of average diameter 15 ~ 22nm, average length 10 ~ 20 μm are combined by adhesive and form conductive network; And other protective layers, other conductive layer bottoms described are formed.
Preferably, described transparent conductor, surface is pressurized, or illuminated light or heat energy.
(effect of invention)
According to the present invention, the light transmittance do not embodied at present is more than 90%, sheet resistance is 50 Ω/m
2below, mist degree is the transparent conductor of less than 0.8%, embodies by forming network by the nano silver wire of average diameter 15 ~ 22nm, average length 10 ~ 20 μm.
And the conductive layer forming nano silver wire network has protective layer, thus improve the tender spots of nano silver wire network layer and internal oxidition and chemically interior, and improve mist degree.
Accompanying drawing explanation
Fig. 1 is the key diagram of the light reflectivity of the diameter presented according to nano silver wire.
Fig. 2 is the key diagram of quality versus's nano silver wire number of the diameter presented according to nano silver wire.
Fig. 3 is in the diameter of nano silver wire of current embodiment 1 and the photo of length.
Fig. 4 is the diameter of the nano silver wire presenting comparative example 1 and the photo of length.
Fig. 5 presents the figure that the transparent conductor stepped construction of protective layer is formed at substrate top.
Fig. 6 presents the figure that substrate upper and lower part forms the transparent conductor stepped construction of protective layer.
Embodiment
Transparent conductor of the present invention, comprises conductive layer, on its electric hybrid board adhesive and average diameter 15 ~ 22nm, average length 10 ~ 20 μm nano silver wire and form the conductive network that nano silver wire intersects.This conductive layer is transparent and soft, comprises at least one surface with conductivity.
Conductive layer comprises rigid substrate and flexible base plate, can coating or be laminated on multiple substrate, can coating and being laminated on transparent or opaque substrate.Conductive layer can form a part for the composite construction comprising matrix material and nano silver wire.Matrix material can be given chemically to typical complex structure body, mechanicalness and optical characteristics.
Nano silver wire is the required inscape that the product manufactured to conductive board or use conductive board gives electrical conductivity.
The concentration of nano silver wire determines the number of the nano silver wire in the single area of regulation substrate.Further, nano silver wire number determines the number of current path.The number of nano silver wire is more, and electrical conductivity is higher, but light transmittance and mist degree reduce.On the contrary, during in order to improve light transmittance and mist degree and reduce nano silver wire number, electrical conductivity can reduce.
Nano silver wire is 1 dimension linear structure, has diameter and the length of regulation.When substrate using the nano silver wire of same concentrations, such as, phase diameter group is the nano silver wire of 40nm, and diameter is that the nano silver wire number of 30nm is more, therefore improves electrical conductivity, realizes the improvement of mist degree because of the minimizing of diameter.
Therefore, when the average diameter of nano silver wire is about 20nm, if on the transparent substrate, form network with the nano silver wire of same concentrations, because of the nano silver wire increased, add current path, reduce sheet resistance, because reflecting surface is narrow and small, the reflection of light is few, light reduces mist degree with multiple angles scattering, improves the visibility of transparent conductor.
In addition, the aspect ratio of nano silver wire act as the key factor of electrical conductivity.Aspect ratio has the mathematical expression of length (the Length)/diameter (Diameter) of nano silver wire.Compare the fixed diameter of nano silver wire, in short-term, because the face that contacts with each other between nano silver wire reduces, contact resistance increases length, thus sheet resistance can increase.Generally, when aspect ratio is more than 500, when forming nano silver wire network, there is low sheet resistance.Therefore, aspect ratio is larger, and because length vs's diameter is elongated, contact resistance can diminish.
But be not that aspect ratio is larger, electrical conductivity, light transmittance and mist degree are just good.Such as, aspect ratio is the length of the nano silver wire of the diameter 40nm of 700 is 28 μm, and aspect ratio is the length of the nano silver wire of the diameter 30nm of 600 is 18 μm.
When taking aspect ratio as the nano silver wire manufacture transparent conductor of the diameter 40nm of 700, can think because length is long, relative contact resistance reduces and sheet resistance can reduce, but contrast nano silver wire quality, the number of line is few, can not guarantee current path and resistance can rise.Further, diameter is larger, and reflecting surface is wider, becomes the reason that mist degree increases.
Aspect ratio is 600, length is shorter comparatively speaking for the nano silver wire of diameter 30nm, but diameter is little, comparatively speaking, quality versus, multiple nano silver wire occupies substrate surface and sheet resistance diminishes, and because diameter is little, reflectivity is low, and light reduces mist degree to multiple directions scattering.
Fig. 1 (a), (b) are the key diagrams of the reflecting surface of the light of the diameter (20nm and 40nm) presented according to nano silver wire, and Fig. 2 (a), (b) and (c) are the key diagrams of the number of quality versus's line of the diameter (20nm, 30nm and 40nm) presented according to nano silver wire.
Therefore, the aspect ratio of nano silver wire, is the bigger the better in the nano silver wire of same diameter, but does not consider that the aspect ratio of diameter is to electrical, the optical characteristics of improving transparent conductor, without any meaning.
According to the present invention, in order to manufacture low sheet resistance (50 Ω/m
2below), the transparent conductor of high-transmittance (more than 90%) and low haze (less than 0.8%), the average diameter of nano silver wire is preferably 15 ~ 22nm.If average diameter is very little, electrically, optical characteristics can outstanding, but thermal endurance can die down, if too greatly, there will be aforesaid sheet resistance and mist degree becomes large problem.
Further, nano silver wire there is above-mentioned average diameter and its average length 10 ~ 20 μm time, best embody described characteristic.If average length is too short, sheet resistance can increase and produce the problem that will use a large amount of nano silver wire, if oversize, in the synthesis of nano silver wire, can produce the problem of mutual distortion between line.
Further, preferably, the nano silver wire with above-mentioned average diameter and average length is 10 ~ 20mg/m
2amount on substrate, form conductive layer.Very little, mist degree is low and sheet resistance is high for coating weight, otherwise coating is too many, and sheet resistance reduces, and mist degree increases.
In addition, up to the present in the patent of publication and document, unexposed specific embodiment or experiment value and describe that spendable nano silver wire diameter is 1 ~ 100nm, length is 2 ~ 100 μm, but specifically, unexposed mistake is about the diameter of nano silver wire and length and the amount of nano silver wire forming conductive layer.
Below; with reference to accompanying drawing illustrate form transparency carrier of the present invention, nano silver wire synthetic method, for form conductive layer coating constituent after, illustrate in order and the formation method of conductive layer on substrate and conductive layer form the method for protective layer and improve the rear engineering of electrical conductivity.
1, transparency carrier
Nano silver wire is coating on substrate.Substrate is rigid or soft.What belong to rigid substrate is acrylic acid (acrylics), Merlon (polycarbonates), glass (glass) etc.What belong to flexible base plate is PETG (PET), PEN (PEN), polyimides (PI), nanofiber (nano fiber) or film glass (thin glass).
This substrate presents dimensional stability in the coating and drying of conductive layer, requires coating and the adhesiveness with substrate top.In addition, can use to improve coating on substrate and hardness and forming the multilager base plate of hard membrane layer.
In the present invention, in order to improve the hardness of coating and film and PETG (PET) film thickness employing hard conating is the substrate of 100 μm.Light transmittance as the pet substrate of insulator is 92%, and mist degree presented for 0.2 (with reference to table 1).
2, the synthesis of nano silver wire (Silver nanowire)
The ethylene glycol mixing Ag chloride as Ag nucleator, the organic halogen as Ag concentration regulator and the metal halogen of the 1st solution 140 DEG C and the PVP as end-capping reagent, ethylene glycol the 2nd solution dissolving AgNO3 is added to the 1st solution, reacts 6 hours and produce nano silver wire.
The nano silver wire solution manufactured adds the acetone of ormal weight, cohesion nano silver wire also throws away upper liquid.At this moment, upper liquid comprises silver nano-grain, PVP, ethylene glycol, nucleator and concentration regulator etc.Again on nano silver wire agglomerate, add the distilled water of ormal weight and after dispersion, add the acetone of ormal weight and condense nano silver wire, throwing away upper liquid.After described process carries out 3 ~ 4 times repeatedly, be recovered to pure nano silver wire (hereinafter referred to as the nano silver wire of the embodiment 1 ' ').The average diameter of the nano silver wire of embodiment 1 is 20nm, and average length is 15 ~ 18 μm.Fig. 3 measures the nano silver wire diameter of embodiment 1 and the TEM photo of length.
In addition, in order to contrast with the nano silver wire of embodiment 1, according to same procedure, change Ag nucleator AgCl and Ag
+the concentration of the KBr of concentration regulator, obtains the nano silver wire (hereinafter referred to as ' nano silver wire of comparative example 1 ') that average diameter is 30nm, average length is 25 μm.Fig. 4 is the diameter of nano silver wire and the TEM photo of length that measure comparative example 1.The method identical according to the nano silver wire of comparative example 1, obtains average diameter 40nm, average length is the nano silver wire (hereinafter referred to as ' nano silver wire of comparative example 2 ') of 30 μm.
3, the manufacture of coating constituent
Form the preparation of the water-soluble coating constituent of conductive layer by mixing water or more than one polymer adhesive and multiple inscape, or the water-soluble solvent such as methyl alcohol, ethanol, propyl alcohol, ethylene glycol or terpineol and completing on a small quantity.Further, surfactant and other coating additives are added to coating solution.
In the actual manufacturing process of transparent conductor, importantly as the polymer adhesive had in the conductivity filling inscape of nano silver wire and solvent.Polymer adhesive is the dispersant of nano silver wire, prevents the effect of the viscosity modifier sharply precipitated of nano silver wire when playing coating on substrate, and plays the adhesive effect making nano silver wire paste substrate.After this polymer adhesive coating to substrate, electrical conductivity, light transmittance and mist degree can not be reduced.
Further, polymer adhesive will have the solubility of applicable solvent.Polymer adhesive can use in cellulose-based, polyethylene-based, acrylic acid series, polyurethane series, acrylic acid-polyurethane copolymer at least more than one.Optimum fiber prime system.Light transmittance, the decentralization of cellulose-based adhesive are outstanding, easily carry out viscosity adjustment according to addition, well soft.This cellulose-based adhesive can use in hydroxypropyl methylcellulose (HPMC) or methylcellulose (MC) or ethyl cellulose (EC) at least more than one.
Polymer adhesive is approximately present in coating solution constituent with 0.01 ~ 10 % by weight.Preferably, exist with 0.05 ~ 0.5 % by weight.
In order to improve the degree of being close between cellulose and substrate, auxiliary polyalcohol adhesive can be added.This auxiliary polyalcohol adhesive can use in polyurethane and acrylic adhesive at least more than one.
Coating solution constituent of the present invention employs distilled water 93 ~ 97wt%, cellulose 0.05 ~ 0.25wt%, auxiliary binder 0.05 ~ 0.15wt%, fluorine system dispersant 0.001 ~ 0.01wt%, ethanol class 2 ~ 8wt%, and the concentration of nano silver wire is 0.05 ~ 0.09wt%.
4, the formation of conductive layer
Utilize above-mentioned coating solution constituent and on substrate, form the method for transparency conducting layer, the multiple methods such as the coating of coating applications, channel mould, dip coated, knife coating, curtain coating, concave surface coating or airblade coating can be used.
At this moment, the amount forming the nano silver wire of conductive layer is 10 ~ 25mg/m
2(per unit substrate sheet resistance 10 ~ 25mg).
According to the thickness of conductive layer, drying time be 1 minute ~ 1 point 30 seconds, temperature can regulate within the scope of 80 ~ 140 DEG C, can be divided into 1 ~ 4 interval, but be not limited thereto between dry section.
Maintain the high-transmittance of conductive layer the dry coating thickness that is applicable to be approximately 0.03 ~ 2.0 μm, preferably, about 0.04 ~ 0.5 μm.
Time dry after coating, as needed for transparent conductor electrically and optical characteristics, 1) sheet resistance is 200 Ω/m
2below, preferred 50 Ω/m
2below, 2) light transmittance more than 80%, preferably more than 90%, 3) mist degree is less than 2.0%, preferably less than 1%, be more preferably less than 0.8%.
5, the formation of protective layer
Nano silver wire is metallics, according to the oxygen in air and sulphur, can be oxidized.Oxidation can make the surface of nano silver wire form the multiple oxide layer such as silver sulfide or silver oxide, causes electrical conductivity sharply to decline.In order to prevent the surface oxidation of nano silver wire, need polymer protection layer.
Further, only use the adhesive of conductive layer and cellulose and auxiliary binder, because the adhesive force of nano silver wire and substrate is weak, can scratch because of the strength of outside, need to form polymer protection layer on the electrically conductive.
Macromolecule layer is by being mixed with at least more than one list amount body in acrylic acid series list amount body, polyurethane series list amount body, acrylic acid-polyurethane list amount body and bridging agent and using.Present invention uses acrylic acid series macromolecule layer, namely dry by preparation after metering bar coater or channel mould mode coating acrylic acid series list amount body and bridging agent mixed liquor, then carry out the macromolecule layer of UV sclerosis polymerization.Accordingly, there is because of the refringence of conductive layer and protective layer the Li Chu improving mist degree.Fig. 5 presents the figure that the transparent conductor stepped construction of protective layer is formed at substrate top.
In addition, above-mentioned transparent conductor only defines protective layer after conductive layer is formed at the top of substrate, but according to other embodiments of the invention, the top of substrate and bottom also can form conductive layer and protective layer respectively.Fig. 6 presents the figure that substrate upper and lower part forms the transparent conductor stepped construction of protective layer.
6, the rear engineering of electrical conductivity is improved
Nano silver wire is also dry in coating to substrate on atmospheric pressure, and when forming nano silver wire network, the contact between line becomes easy.Therefore, contact-making surface is little, and contact resistance can be high.
Therefore, in order to increase the contact area between line-line, by roll-type compacting (roll-press) pressured conductive body or irradiate heat energy or luminous energy, thus molten silver nano wire and improve electrical conductivity.But, add diameter because of pressurization nano silver wire, add mist degree.
The nano silver wire used in the present invention is average diameter 15 ~ 22nm, and average length 10 ~ 20 μm, compares the nano silver wire of average diameter 30nm and 40nm, the non-constant width of whole surface area, network is formed very smooth and easy, without the need to other roll-type pressing process, also embodies low sheet resistance.Further, when coating and dry transparent conductor, in baking temperature 80 ~ 140 DEG C, also there is melting effect, without the need to other heat energy or optical energy irradiation, also embody low sheet resistance in fusion point step-down.Therefore, according to the present invention, rear engineering phase can be omitted, manufacturing expense has advantage.
Below, relatively and arranged electrical, the optical characteristics of transparent conductor according to multiple embodiment of the present invention and the transparent conductor according to comparative example, as table 1.
Table 1
-embodiment 1: as above-mentioned, utilizes the nano silver wire of the average diameter 20nm manufactured, pet substrate (light transmittance 92%, mist degree 0.2%) only forms conductive layer, does not form the transparent conductor of protective layer
-embodiment 2: the transparent conductor conductive layer of embodiment 1 being formed above-mentioned protective layer
-comparative example 1: the nano silver wire utilizing average diameter 30nm, after substrate forms conductive layer, is identically formed the transparent conductor of protective layer with embodiment 2
-comparative example 2: the nano silver wire utilizing average diameter 40nm, after substrate forms conductive layer, is identically formed the transparent conductor of protective layer with embodiment 2
-embodiment 3: with 340psi, carries out the transparent conductor of a roll-type compacting to the transparent conductor of embodiment 2
-embodiment 4: with xenon lamp 20J/ ㎝
2energy, the transparent conductor of embodiment 2 is irradiated to the transparent conductor of 2 times
-embodiment 5: the upper and lower part of substrate forms the transparent conductor of conductive layer and protective layer respectively
-embodiment 6: with 340psi, carries out the transparent conductor of a roll-type compacting to the transparent conductor of embodiment 5
-embodiment 7: with xenon lamp 20J/ ㎝
2energy, the transparent conductor of embodiment 5 is irradiated to the transparent conductor of 2 times
According to above-mentioned table 1, compare the nano silver wire according to use 20nm of the present invention, only have a transparent conductor (embodiment 1) of conductive layer, the transparent conductor (embodiment 2) forming protective layer is outstanding in sheet resistance and mist degree.Further, embodiment 2 compares the comparative example 1,2 of the relatively large nano silver wire of use diameter, outstanding in sheet resistance and mist degree.
Pressurization transparent conductor (embodiment 3) compare embodiment 2, sheet resistance decreases, but light transmittance and mist degree bad, this be because of pressurization nano silver wire intersect part in contact area increase and cause.
Further, the transparent conductor (embodiment 4) irradiating heat or luminous energy compares embodiment 2, and almost identical with embodiment 3, sheet resistance decreases, but light transmittance is almost identical with embodiment 2 with mist degree.The cross section of nano silver wire welds, and this represents that contact area does not increase because of welding.Therefore, according to the sheet resistance of transparent conductor of the present invention, adjusted by heat or optical energy irradiation.
In addition, beyond the top of substrate, the transparent conductor (embodiment 5) of conductive layer and protective layer is also formed at bottom; compare embodiment 2; mist degree increases to some extent, with pressurization or irradiates hot or luminous energy transparent conductor (embodiment 6,7) compared with, to above-described embodiment 3,4 similar.
Above explanation is based on embodiments of the invention, but the effect of interest field of the present invention relates to the technological thought recorded within the scope of Patent right requirement and the equipollent being equivalent to impartial field therewith to deformations.
Claims (12)
1. a transparent conductor, comprising:
Substrate is transparent;
Conductive layer, on described substrate, multiple nano silver wires of average diameter 15 ~ 22nm, average length 10 ~ 20 μm are combined by adhesive and form conductive network; And
Protective layer, described conductive layer is formed.
2. transparent conductor according to claim 1, is characterized in that:
Described substrate is transparent rigid substrate or flexible base plate.
3. transparent conductor according to claim 1, is characterized in that:
Described substrate also comprises hard membrane layer.
4. transparent conductor according to claim 1, is characterized in that:
Described nano wire, relative to substrate area, is 10 ~ 25mg/m
2.
5. transparent conductor according to claim 1, is characterized in that:
Described adhesive is made up of at least more than one in cellulose-based, polyethylene-based, acrylic acid series, polyurethane series, acrylic acid-polyurethane copolymer.
6. transparent conductor according to claim 1, is characterized in that:
Described adhesive, is made up of at least more than one in hydroxypropyl methylcellulose (HPMC) or methylcellulose (MC) or ethyl cellulose (EC).
7. transparent conductor according to claim 6, is characterized in that:
Described adhesive can comprise at least more than one polyurethane or acrylic adhesive.
8. transparent conductor according to claim 1, is characterized in that:
Described protective layer is mixed by least more than one list amount body in acrylic acid series list amount body, polyurethane series list amount body, acrylic acid-polyurethane list amount body and bridging agent.
9. transparent conductor according to claim 1, is characterized in that:
Described transparent conductor has 50 Ω/m
2following sheet resistance, the light transmittance of more than 90% and less than 0.8% mist degree.
10. transparent conductor according to claim 1, is characterized in that:
Described substrate bottom also comprises:
Other conductive layers, multiple nano silver wires of average diameter 15 ~ 22nm, average length 10 ~ 20 μm are combined by adhesive and form conductive network;
And other protective layers, other conductive layer bottoms described are formed.
11. transparent conductors according to claim 1 or 10, is characterized in that:
Described transparent conductor, surface is pressurized.
12. transparent conductors according to claim 1 or 10, is characterized in that:
Described transparent conductor, illuminated light or heat energy.
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| KR10-2014-0029468 | 2014-03-13 | ||
| KR1020140029468A KR20150107091A (en) | 2014-03-13 | 2014-03-13 | Transparent conductors using silver nanowires |
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| WO2019000215A1 (en) * | 2017-06-27 | 2019-01-03 | 深圳大学 | Silver nanowire-based transparent conductive film, and manufacturing method thereof |
| CN109206965A (en) * | 2015-12-07 | 2019-01-15 | 叶旭东 | Conductive coating for electronic product |
| CN109493994A (en) * | 2018-12-28 | 2019-03-19 | 广东银研高新材料股份有限公司 | Critical superconduction silver paste based on linear silver nano-grain and preparation method thereof |
| CN109683215A (en) * | 2018-12-12 | 2019-04-26 | 深圳市赛菲鹿鸣科技有限公司 | A kind of optical film and its production technology |
| CN113365762A (en) * | 2019-04-03 | 2021-09-07 | 英属维京群岛商天材创新材料科技股份有限公司 | Purification of metal nanostructures |
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| US10714230B2 (en) | 2017-12-06 | 2020-07-14 | C3Nano Inc. | Thin and uniform silver nanowires, method of synthesis and transparent conductive films formed from the nanowires |
| KR102357733B1 (en) * | 2019-12-18 | 2022-02-04 | 덕산하이메탈(주) | Conductive layer and manufacturing method thereof |
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| KR20150107091A (en) | 2015-09-23 |
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