CN105355262B - Transparent conductive film and preparation method thereof - Google Patents
Transparent conductive film and preparation method thereof Download PDFInfo
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- CN105355262B CN105355262B CN201510830331.2A CN201510830331A CN105355262B CN 105355262 B CN105355262 B CN 105355262B CN 201510830331 A CN201510830331 A CN 201510830331A CN 105355262 B CN105355262 B CN 105355262B
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- Prior art keywords
- brushing
- transparent
- nano silver
- silver wire
- silane
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- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 41
- 230000001680 brushing effect Effects 0.000 claims abstract description 38
- 239000000758 substrate Substances 0.000 claims abstract description 38
- 238000012545 processing Methods 0.000 claims abstract description 20
- 239000002042 Silver nanowire Substances 0.000 claims abstract description 18
- 239000004094 surface-active agent Substances 0.000 claims abstract description 16
- 239000000725 suspension Substances 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 12
- 238000002834 transmittance Methods 0.000 claims abstract description 12
- 238000004140 cleaning Methods 0.000 claims abstract description 11
- 230000000640 hydroxylating effect Effects 0.000 claims abstract description 6
- 239000002002 slurry Substances 0.000 claims abstract description 6
- 230000033444 hydroxylation Effects 0.000 claims abstract description 5
- 238000005805 hydroxylation reaction Methods 0.000 claims abstract description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 40
- 229910052710 silicon Inorganic materials 0.000 claims description 28
- 239000010703 silicon Substances 0.000 claims description 28
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 27
- 239000012530 fluid Substances 0.000 claims description 22
- 239000000463 material Substances 0.000 claims description 21
- 239000000377 silicon dioxide Substances 0.000 claims description 19
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 239000012528 membrane Substances 0.000 claims description 12
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 10
- 150000004756 silanes Chemical class 0.000 claims description 9
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 8
- RZJRJXONCZWCBN-UHFFFAOYSA-N octadecane Chemical compound CCCCCCCCCCCCCCCCCC RZJRJXONCZWCBN-UHFFFAOYSA-N 0.000 claims description 8
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 claims description 8
- 239000005052 trichlorosilane Substances 0.000 claims description 8
- 150000003863 ammonium salts Chemical class 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 239000004593 Epoxy Substances 0.000 claims description 6
- 235000019270 ammonium chloride Nutrition 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 150000002367 halogens Chemical class 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- BGHCVCJVXZWKCC-UHFFFAOYSA-N tetradecane Chemical compound CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 claims description 6
- -1 γ-(β-aminoethyl) aminopropyl Chemical group 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 150000008422 chlorobenzenes Chemical class 0.000 claims description 4
- 239000000470 constituent Substances 0.000 claims description 4
- 238000001548 drop coating Methods 0.000 claims description 4
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 238000002604 ultrasonography Methods 0.000 claims description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 4
- 229920002554 vinyl polymer Polymers 0.000 claims description 4
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 3
- 238000010521 absorption reaction Methods 0.000 claims description 3
- 238000003851 corona treatment Methods 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- YCOZIPAWZNQLMR-UHFFFAOYSA-N heptane - octane Natural products CCCCCCCCCCCCCCC YCOZIPAWZNQLMR-UHFFFAOYSA-N 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- PZJJKWKADRNWSW-UHFFFAOYSA-N trimethoxysilicon Chemical compound CO[Si](OC)OC PZJJKWKADRNWSW-UHFFFAOYSA-N 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 2
- KSCAZPYHLGGNPZ-UHFFFAOYSA-N 3-chloropropyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)CCCCl KSCAZPYHLGGNPZ-UHFFFAOYSA-N 0.000 claims description 2
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 claims description 2
- GBQYMXVQHATSCC-UHFFFAOYSA-N 3-triethoxysilylpropanenitrile Chemical compound CCO[Si](OCC)(OCC)CCC#N GBQYMXVQHATSCC-UHFFFAOYSA-N 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Natural products CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000005977 Ethylene Substances 0.000 claims description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 2
- NOZAQBYNLKNDRT-UHFFFAOYSA-N [diacetyloxy(ethenyl)silyl] acetate Chemical compound CC(=O)O[Si](OC(C)=O)(OC(C)=O)C=C NOZAQBYNLKNDRT-UHFFFAOYSA-N 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- ZDOBWJOCPDIBRZ-UHFFFAOYSA-N chloromethyl(triethoxy)silane Chemical compound CCO[Si](CCl)(OCC)OCC ZDOBWJOCPDIBRZ-UHFFFAOYSA-N 0.000 claims description 2
- CAXZYJLKQUXPBS-UHFFFAOYSA-N dichloro(3-chloropropyl)silane Chemical compound ClCCC[SiH](Cl)Cl CAXZYJLKQUXPBS-UHFFFAOYSA-N 0.000 claims description 2
- YLJJAVFOBDSYAN-UHFFFAOYSA-N dichloro-ethenyl-methylsilane Chemical compound C[Si](Cl)(Cl)C=C YLJJAVFOBDSYAN-UHFFFAOYSA-N 0.000 claims description 2
- GAURFLBIDLSLQU-UHFFFAOYSA-N diethoxy(methyl)silicon Chemical compound CCO[Si](C)OCC GAURFLBIDLSLQU-UHFFFAOYSA-N 0.000 claims description 2
- 235000019441 ethanol Nutrition 0.000 claims description 2
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 2
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 2
- 125000005909 ethyl alcohol group Chemical group 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- KOVKEDGZABFDPF-UHFFFAOYSA-N n-(triethoxysilylmethyl)aniline Chemical compound CCO[Si](OCC)(OCC)CNC1=CC=CC=C1 KOVKEDGZABFDPF-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 229940038384 octadecane Drugs 0.000 claims description 2
- 229910000077 silane Inorganic materials 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- OOXSLJBUMMHDKW-UHFFFAOYSA-N trichloro(3-chloropropyl)silane Chemical compound ClCCC[Si](Cl)(Cl)Cl OOXSLJBUMMHDKW-UHFFFAOYSA-N 0.000 claims description 2
- GQIUQDDJKHLHTB-UHFFFAOYSA-N trichloro(ethenyl)silane Chemical compound Cl[Si](Cl)(Cl)C=C GQIUQDDJKHLHTB-UHFFFAOYSA-N 0.000 claims description 2
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 claims description 2
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 claims description 2
- 239000005050 vinyl trichlorosilane Substances 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 2
- LMVLVUPTDRWATB-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propan-1-ol Chemical compound CO[Si](C)(OC)CCCO LMVLVUPTDRWATB-UHFFFAOYSA-N 0.000 claims 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 claims 1
- UIFBMBZYGZSWQE-UHFFFAOYSA-N 4-[dichloro(methyl)silyl]butanenitrile Chemical compound C[Si](Cl)(Cl)CCCC#N UIFBMBZYGZSWQE-UHFFFAOYSA-N 0.000 claims 1
- PHCFOBSXZDJTQS-UHFFFAOYSA-N COO[SiH](C)OOC Chemical compound COO[SiH](C)OOC PHCFOBSXZDJTQS-UHFFFAOYSA-N 0.000 claims 1
- NKLOIQIDDWPNFE-UHFFFAOYSA-N [SiH4].C(C)(C)(C)OOC(C)(C)C Chemical compound [SiH4].C(C)(C)(C)OOC(C)(C)C NKLOIQIDDWPNFE-UHFFFAOYSA-N 0.000 claims 1
- GNHQSAUHXKRQMC-UHFFFAOYSA-N benzene;chlorine Chemical compound [Cl].C1=CC=CC=C1 GNHQSAUHXKRQMC-UHFFFAOYSA-N 0.000 claims 1
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 claims 1
- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical compound CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 claims 1
- ZMYXZXUHYAGGKG-UHFFFAOYSA-N propoxysilane Chemical compound CCCO[SiH3] ZMYXZXUHYAGGKG-UHFFFAOYSA-N 0.000 claims 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- 229910052814 silicon oxide Inorganic materials 0.000 claims 1
- FRGPKMWIYVTFIQ-UHFFFAOYSA-N triethoxy(3-isocyanatopropyl)silane Chemical class CCO[Si](OCC)(OCC)CCCN=C=O FRGPKMWIYVTFIQ-UHFFFAOYSA-N 0.000 claims 1
- AKZSUEMPWJZYNK-UHFFFAOYSA-N trifluoro(hexadecyl)silane Chemical compound C(CCCCCCCCCCCCCCC)[Si](F)(F)F AKZSUEMPWJZYNK-UHFFFAOYSA-N 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 229910052709 silver Inorganic materials 0.000 description 5
- 239000004332 silver Substances 0.000 description 5
- 239000002238 carbon nanotube film Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910021389 graphene Inorganic materials 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 3
- 238000005452 bending Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002905 metal composite material Substances 0.000 description 2
- 238000013086 organic photovoltaic Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- PXKPPXIGPAIWDZ-UHFFFAOYSA-N 3-[dichloro(methyl)silyl]propanenitrile Chemical compound C[Si](Cl)(Cl)CCC#N PXKPPXIGPAIWDZ-UHFFFAOYSA-N 0.000 description 1
- OLBGECWYBGXCNV-UHFFFAOYSA-N 3-trichlorosilylpropanenitrile Chemical compound Cl[Si](Cl)(Cl)CCC#N OLBGECWYBGXCNV-UHFFFAOYSA-N 0.000 description 1
- KHLRJDNGHBXOSV-UHFFFAOYSA-N 5-trimethoxysilylpentane-1,3-diamine Chemical compound CO[Si](OC)(OC)CCC(N)CCN KHLRJDNGHBXOSV-UHFFFAOYSA-N 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 229910003978 SiClx Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- PKTOVQRKCNPVKY-UHFFFAOYSA-N dimethoxy(methyl)silicon Chemical compound CO[Si](C)OC PKTOVQRKCNPVKY-UHFFFAOYSA-N 0.000 description 1
- YQGOWXYZDLJBFL-UHFFFAOYSA-N dimethoxysilane Chemical compound CO[SiH2]OC YQGOWXYZDLJBFL-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000010406 interfacial reaction Methods 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- VNBLTKHUCJLFSB-UHFFFAOYSA-N n-(trimethoxysilylmethyl)aniline Chemical compound CO[Si](OC)(OC)CNC1=CC=CC=C1 VNBLTKHUCJLFSB-UHFFFAOYSA-N 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 235000012149 noodles Nutrition 0.000 description 1
- NJPPVKZQTLUDBO-UHFFFAOYSA-N novaluron Chemical compound C1=C(Cl)C(OC(F)(F)C(OC(F)(F)F)F)=CC=C1NC(=O)NC(=O)C1=C(F)C=CC=C1F NJPPVKZQTLUDBO-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- KNSVRQSOPKYFJN-UHFFFAOYSA-N tert-butylsilicon Chemical compound CC(C)(C)[Si] KNSVRQSOPKYFJN-UHFFFAOYSA-N 0.000 description 1
- 238000002207 thermal evaporation Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000005406 washing 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
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
-
- 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
-
- 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
Landscapes
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Non-Insulated Conductors (AREA)
- Photovoltaic Devices (AREA)
Abstract
The present invention provides a kind of transparent conductive films, are made after brushing nano silver wire slurry on a transparent substrate using the brushing element of surface hydroxylation processing.Its specific preparation method includes the following steps：Element will be brushed and carry out standardization cleaning；Surfactant hydroxylating processing formation hair brush-like structure is carried out to brushing element surface；Prepare AgNWs suspensions；Transparent substrates are horizontal positioned, then prepared AgNWs suspensions are dripped in transparent substrates, and nano silver wire is brushed on the surface of the process surfactant hydroxylating for brushing element processing on a transparent substrate, be finally dried.Transparent conductive film provided by the invention has higher light transmittance and preferable electric conductivity, 6 15 Ω of sheet resistance/sq, visible wavelength mean transmissivity is more than 70%, can be applied under more occasions, have to existing ITO and FTO conductive films well it is alternative, can be used for various new industrial products.
Description
Technical field
The invention belongs to electrically conducting transparent technical field of membrane more particularly to a kind of transparent conductive film for being loaded with nano silver wire and
Preparation method.
Background technology
Transparent conductive film (TCF) refer to wave-length coverage 380 to the visible ray between 780nm transmitance 70~
90%th, 4~1000 Ω of sheet resistivity/sq.
Transparent conductive film is widely used in touch control liquid crystal panel, Organic Light Emitting Diode (OLED), organic photovoltaic devices
(OPV) and electromagnetic shielding etc. fields.At present, transparent TCF can be broadly divided into according to the difference of conductive material:Oxide is partly led
Body film (TCO), metal film, metal composite film, polymeric membrane and carbon nanotube film (CNT), graphene film (Graphene), metal
Line film etc..
Metallic transparent conductive film good conductivity, but transmitance is relatively low, and the intensity of simple metal and hardness is not high, valency
Lattice are expensive, are mainly used as transparency electromagnetic wave shield material.
Although oxide TCF photoelectric properties are outstanding, heat-resisting and corrosion resistant candle property is preferable, its bending property, soft just property are poor.
Although ITO is the oxide TCF for studying and being most widely used at present, its raw material resources is increasingly rare, and film matter is crisp
Characteristic limits its application in flexible electronic device.
Metal composite film has very big advantage in terms of low resistance is realized, compound high refractive index dielectric and TCO can also
Obtain excellent visible light transmittance.But due to the material Presence of an interface problem of multilayered structure, interfacial reaction products influence its light
Electrical property makes its thermal stability, carves candle property and prepares complicated.
Macromolecule TCF it is soft just property it is fine, it is flexible, but electric conductivity compare it is poor.
In contrast, CNT films, Graphene and metal wire not only excellent conductivity, and since its material itself is special
Pattern and with well it is soft just property.Because it is to pass through object with CNT, Graphene and AgNWs electrically conducting transparent network prepared
Van der Waals between matter and build, electronics is moved by tunnel-effect at the node that is in contact with each other, when external force applies, he
The node relative movement that contacts each other, but the transmission of electronics can't be influenced, so bending or after stretching, film is led
It can't electrically be much affected.
But present widely applied oxidic transparent conductive film example, need large scale equipment, magnetron sputtering or high vacuum
Environment, complex process, buying equipment cost is high, and on the other hand, high energy consumption is also very unfavorable from environmental protection.
Since silver is the good conductor of electricity, resistivity is low, and conductivity is high, thus nano-silver thread is applied to conductive layer by receipts
The electric current export of collection, can reduce energy loss compared with TCO semiconductors.Simultaneously when the grain size of nano-silver thread is less than the incidence of visible ray
During wavelength, it can arrange silver wire very intensive, the catchment area of the silver electrode of solar cell can not only be increased, and do not hinder
The transmission being in the light is conducive to improve the efficiency of solar cell.
Silver nano material is due to its high heat transfer electric conductivity, antibiotic property and catalysis characteristics, and its surface plasma resonance
Effect (SPR) has become the hot spot of Recent study.At present, one-dimensional nano silver wire (AgNWs) material is in addition to possessing conventional silver
Possessed by material outside outstanding electric conductivity, ductility and tensile property, due to its unique nanoscale shape characteristic, thus
With series of features such as the electricity different from massive material, optics.Currently, which can pass through the chemistry such as hydro-thermal
Method is largely prepared, and is used as in transparent conductive electrode and meterial additive applied to solar cell display etc. and is reached material
Expect modified purpose.
Current research finds that the arrangement mode of monodimension nanometer material has its optics and electrical effects macroscopically aobvious
The influence of work, so becoming one of current research hotspot in the field to the arrangement of nanometer filamentary material.At present, the method for orientation
Mainly one-dimensional nano line is carried out using the methods of LB molecules embrane method, thermal evaporation and extra electric field, magnetic field and fluid impact
Oriented alignment.However, these methods are more demanding to equipment etc., it is expensive, and orientation on a large scale difficult to realize.
Invention content
One of present invention aims to overcome that the deficiency in existing electrically conducting transparent membrane technology, provide a kind of light transmittance it is high and
The transparent conductive film of good conductivity.
Transparent conductive film provided by the invention, the brushing element handled using surface hydroxylation brush silver on a transparent substrate
It is made after nano wire slurry, the element of brushing includes the base material that an at least surface is silica surface, the dioxy of the base material
SiClx surface is handled using surfactant hydroxylating, and light transmittance is more than 85%；Described brushes point of the element by solute
Sub- polar forces, the hydroxyl absorption connection that major part halogen constituent element element side has the one side of silica exposed with base material are formed, and make silicon
There is piece the one side of silica to form similar " hairbrush " shape structure, and the molecular structure of the solute includes backbone, one
3 identical halogens of a methyl and a silicon Si connection.
Transparent conductive film provided by the invention, have higher light transmittance and preferable electric conductivity, sheet resistance 6-15 Ω/
Sq, it is seen that wavelength mean transmissivity is more than 70%；It can apply under more occasions, have well to existing ITO and FTO conductive films
It is alternative, it can be used for various new industrial products, for example, touch screen transparent electrode, Organic Light Emitting Diode transparent electrode, have
Machine photovoltaic device transparent electrode etc..
Another object of the present invention includes the following steps there is provided the preparation method of above-mentioned transparent conductive film：
The brushing element is subjected to standardization cleaning；
Surfactant carboxylated processing is carried out to the brushing element surface；
Prepare AgNWs suspensions；
The transparent substrates are horizontal positioned, then prepared AgNWs suspensions are dripped in the transparent substrates, and
Nano silver wire is brushed into the surface that the process surfactant carboxylated for brushing element is handled in the transparent substrates；
Processing is dried in the transparent substrates that brushing has nano silver wire, that is, forms transparent conductive film.
The production method of above-mentioned nano silver wire transparent conductive film provided by the invention passes through surface-active by using a kind of
The brushing element of agent carboxylated processing, by nano silver wire slurry brush in transparent substrates, can ensure nano silver wire uniformly, it is fixed
To being arranged in transparent substrates, and be firmly combined with transparent substrates, obtain that a kind of light transmittance is high after drying and good conductivity
Transparent conductive film, alternative existing ITO and FTO conductive films have well it is alternative.Using preparation method of the present invention, have
Equipment is not depended on, does not need to vacuum condition, does not need to high temperature, low energy consumption is easy to operate, and favorable repeatability, cost is extremely low, takes
The advantages that extremely short.
Description of the drawings
Fig. 1 is preparation method flow diagram of the embodiment of the present invention；
Fig. 2 is the surface treatment liquid structure of solute figure that the present invention brushes device embodiments silicon chip；
Fig. 3 is the surface treatment effect figure that the present invention brushes device embodiments silicon chip；
Fig. 4 is the electrically conducting transparent film production schematic diagram of the embodiment of the present invention；
Fig. 5 is the scanning electron microscope diagram of nano silver wire raw material used in the embodiment of the present invention.
In order to illustrate more clearly of technical scheme of the present invention, will simply be situated between to required attached drawing below
It continues, it should be apparent that, the accompanying drawings in the following description is only some embodiments of the present invention, for those of ordinary skill in the art
For, without creative efforts, other attached drawings can also be obtained by attached drawing according to these embodiments.
Specific embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, with reference to the accompanying drawings and embodiments, it is right
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.
The present invention provides a kind of transparent conductive films, are transparent by using the processed element of brushing of surface hydroxylation
It is made after brushing nano silver wire slurry in substrate.
As currently preferred mode, the element of brushing includes the base material that an at least surface is silica surface,
The silica surface of the base material is handled using surfactant carboxylated, and light transmittance is more than 85%.In specific embodiment,
The brushing device substrate can be flat member, such as silicon chip, glass slide, quartz plate, it is possible to understand that ground, the brushing element
Base material be not limited only to flat member, be also not necessarily limited to silicon chip, can be arbitrary material, as long as the base material have silicon dioxide meter
Face, convenient for the exposed processing of hydroxylating.
As currently preferred mode, the nano silver wire diameter may be selected in the range of 50-100nm, length selection
In 30 μm of -80 μ m.It is demonstrated experimentally that the nano silver wire in the range of being somebody's turn to do is preferable in the arrangement and distribution of transparent substrates, and have
It mutually overlaps to form conductive channel conducive to nano silver wire.
Above-mentioned transparent conductive film provided by the invention, by using the processed element of brushing of surface hydroxylation in transparent base
The mode of nano silver wire slurry is brushed on bottom, can ensure that nano silver wire is evenly distributed in transparent substrates, and with stronger
Adhesive force is firmly combined with transparent substrates, and manufactured transparent conductive film product has higher light transmittance and preferable electric conductivity
Can, sheet resistance 6-15 Ω/sq, it is seen that wavelength mean transmissivity is more than 70%；Can be applied under more occasions, to existing ITO and
FTO conductive films have well it is alternative, can be used for various new industrial products, for example, touch screen transparent electrode, organic light emission
Diode transparent electrode, organic photovoltaic devices transparent electrode etc..
Referring to Fig. 1, the present invention also provides the preparation method embodiments of above-mentioned transparent conductive film, include the following steps：
The brushing element is subjected to standardization cleaning；
Surfactant carboxylated processing is carried out to the brushing element surface；
Prepare AgNWs suspensions；
The transparent substrates are horizontal positioned, then prepared AgNWs suspensions are dripped in the transparent substrates, and
Nano silver wire is brushed in the transparent substrates using the brushing element by the processing of surfactant carboxylated；
Processing is dried in the transparent substrates that brushing has nano silver wire, that is, forms transparent conductive film.
As preparation method specific embodiment of the present invention, silicon chip can be selected in the base material for brushing element, and the standardization is clear
It is that the side that silicon chip contains silica is used deionized water, acetone, isopropanol difference ultrasound 20-30min to wash step.According to
Above-mentioned cleaning solution is transmitted by means of ultrasonic wave acoustic energy, by cavitation effect, silicon chip surface pollution impurity can be removed, ensure that subsequent technique obtains
To the product of high-quality.It is to be appreciated that the step cleaning solution is not limited to the deionized water, acetone, isopropanol, other party
As long as formula and selected cleaning solution can guarantee that effectively removing impurity all may be used.
As preparation method specific embodiment of the present invention, the silicon chip uses surfactant carboxylated processing step
It is：The side that silicon chip after cleaning contains silica is handled into 20- with corona treatment 2-10min or UV ozone
Then 30min is impregnated with silanes treatment fluid or ammonium class treatment fluid.
Specifically：Solute in the silanes treatment fluid can be at least one of following compounds：N-octadecane base
Trichlorosilane either hexadecane base trichlorosilane either n-tetradecane base trichlorosilane or n-octadecane base trichlorine silicon
Alkane either n-octadecane base silicofluoroform either n-hexadecyl silicofluoroform or n-tetradecane base silicofluoroform.Or
γ-chloropropyl trichloro-silane either γ-chloropropyl dichlorosilane either γ-r-chloropropyl trimethoxyl silane or γ-
Chloropropyl triethoxysilane either chloromethyl triethoxysilane either gamma-aminopropyl-triethoxy-silane or γ-ammonia
Propyl trimethoxy silicane either γ-(β-aminoethyl) aminopropyl trimethoxysilane or γ-urea propyl-triethoxysilicane
Alkane either anilinomethyl triethoxysilane either anilinomethyl trimethoxy silane or γ-(2,3- the third oxygen of epoxy) third
Base trimethoxy silane or γ-(2,3- the third oxygen of epoxy) propyl-triethoxysilicane or γ-(2,3- the third oxygen of epoxy) third
Ylmethyl dimethoxysilane or β-(3,4- epoxycyclohexyl) ethyl trimethoxy silane or γ-methacryloxypropyl
Propyltrichlorosilan either gamma-methyl allyl acyloxypropyl trimethoxysilane or gamma-methyl allyl acyloxypropyl methyl
Diethoxy silane either gamma-methyl allyl acyloxypropyl methyl dimethoxysilane or γ-mercapto propyl trimethoxy silicon
Alkane either gamma-mercaptopropyltriethoxysilane it is either double-(tri- ethoxy silicon propyl of 3-) tetrasulfide or double-(tri- ethoxies of 3-
Silicon propyl) disulphide either vinyl trichlorosilane either vinyltriethoxysilane or vinyl trimethoxy
Silane either vinyl three (2- methoxyethoxies) silane either three peroxide of vinyltriacetoxy silane or vinyl
Change t-butylsilane either vinyl methyl dichlorosilane either β-cyanoethyltrichlorosilane or β-cyanoethyl methyl dichloro
Silane either β-cyanoethyl triethoxysilane either three second of γ-cyanoethyl trimethoxy silane or 3- isocyanatopropyls
Oxysilane；
Solute in the ammonium class treatment fluid is at least one of following compounds：Or octadecyl-dimethyl-
(3- trimethoxy silicon propyl) ammonium chloride or 2- methylacryoyloxyethyls dimethyl-(3- trimethoxy silicon propyl) ammonium chloride or
Person's 4- ethylene benzyls dimethyl-(3- trimethoxy silicon propyl) ammonium chloride.
Referring to Fig. 2, in above-mentioned treatment fluid used in the present invention, the molecular structure of solute 100, including backbone and one
Silicon Si connects 3 identical halogen constituent element elements with carbon C atoms, has the polarity of highly significant, is conducive to silicon or carbon connection halogen group
Element side in the UV processing exposed one sides of transparent substrates hydroxyl because polarity generate molecular force and part key and, can be formed as schemed
Tadpole shape shown in 1.
Solution in the silanes treatment fluid or the ammonium class treatment fluid is dry toluene, dimethylbenzene, chlorobenzene or one
Two chlorobenzenes, a concentration of 0.05-0.5mol/L.
After the silicon chip is contained the side plasma of silica or UV ozone processing 20-30min, silicon
Piece is positioned on film hanger, after be positioned among container, add in above-mentioned silanes treatment fluid or ammonium class treatment fluid and impregnate, then
Be positioned over again on heated at constant temperature platform, treatment fluid be heated to 50 DEG C of -70 DEG C of holding 15-20min, later with dry toluene or
Either chlorobenzene or one or two chlorobenzenes rinse, and dried up with nitrogen (purity 99.99%) dimethylbenzene, are finally positioned over silicon chip
50 DEG C of -70 DEG C of heating 10-20min of warm table (being covered by clean masking foil).
Fig. 3 illustrates silicon chip surface of embodiment of the present invention processing schematic diagram, as shown in Figure 3A, silicon chip upper and lower surface packet used
Include silicon 101 and with silica while 102, it should be noted that brushing face used be with silica
On one side 102, which is impregnated with silanes treatment fluid or ammonium class treatment fluid 104, is just formed after over cleaning and corona treatment
There is the one side 102 of silica to form similar " hairbrush " shape structure 103 for structure shown in Fig. 3 B, i.e. silicon chip.By more than work
Skill, for the solute 100 in treatment fluid because of molecular polarity power, major part halogen constituent element element side has the one side of silica with silicon chip
102 exposed hydroxyl absorption connections, form metastable structure, as shown in Figure 3B, silicon chip are made to have the one side of silica
102 form similar " hairbrush " shape structure 103, that is, complete silicon chip (brushing element) surfactant hydroxylating processing procedure, formed
Brush element 107.Above-mentioned technical process is of the invention crucial, nano silver wire and the molecular level of substrate when being conducive to brush
With reference to and preferably mutually overlap joint form conductive channel, so as to make the transparent conductive film product of preparation have higher light transmittance
And preferable electric conductivity.
As preparation method specific embodiment of the present invention, the AgNWs suspensions use the preparation of prior art routine
Method, the mass fraction for the AgNWs suspensions prepared is 0.5%-3%, and solvent is ethyl alcohol or isopropanol.
Referring to Fig. 4, as preparation method specific embodiment of the present invention, described the step of brushing nano silver wire, is：It will be saturating
Bright substrate 108 is placed on a pedestal 109, then platoon liquid will be used after prepared above-mentioned 106 ultrasound 20-30min of AgNWs suspensions
105 drop coating of rifle is on transparent substrates 108, then with machine or manually, makes the above-mentioned steps warp obtained for brushing element 107
Downward, the AgNWs suspensions 106 being located on transparent substrates are brushed, make Yin Na in the processed surface of surfactant carboxylated
Rice noodles are uniformly spread in transparent substrates 108.The step is core of the present invention, be can effectively ensure that in transparent substrates 108
Nano silver wire uniformly sprawls arrangement, so as to which finally formed transparent conductive film be made to have the superiority of light transmittance height and good conductivity
Energy.
As preparation method specific embodiment of the present invention, the drying steps are to place the transparent substrates for sprawling completion
In drying box, at a temperature of 60-80 DEG C of constant temperature dry 10min-15min or be placed in dried and clean avoid at direct sunlight from
So dry.Form a kind of high conductivity and the nano silver wire transparent conductive film compared with high transmittance, nano silver wire transparent conductive film
Sheet resistance 6-15 Ω/sq, it is seen that wavelength mean transmissivity is more than 70%, and nano silver wire is formed far better than untreated drop coating
Transparent conductive film, untreated drop coating form nano silver wire transparent conductive film sheet resistance 200-800 Ω/sq, it is seen that wavelength is average
Transmitance 50%-60%.
Fig. 5 illustrates scanning electron microscope after transparent conductive film prepared by nano silver wire raw material of the present invention,
Nano silver wire size diameter is in 53nm or so used in clear display.
In conclusion be only the part of present pre-ferred embodiments shown in the above embodiment of the present invention and attached drawing, it can not
The present invention is limited to this, under conditions of marrow of the present invention is not departed from, any modification that those skilled in the art are made equally is replaced
It changes and improves, all belong to protection scope of the present invention.
Claims (11)
1. a kind of transparent conductive film, which is characterized in that the brushing element handled using surface hydroxylation is brushed on a transparent substrate
Be made after nano silver wire slurry, it is described brush element include an at least surface be silica surface base material, the two of the base material
Silicon oxide surface is handled using surfactant hydroxylating, and light transmittance is more than 85%；The brushing element passes through solute
Molecular polarity power, the hydroxyl absorption connection that major part halogen constituent element element side has the one side of silica exposed with base material are formed, are made
There is silicon chip the one side of silica to form similar " hairbrush " shape structure, the molecular structure of the solute include backbone,
3 identical halogens of one methyl and a silicon Si connection.
2. transparent conductive film as described in claim 1, which is characterized in that the nano silver wire diameter 50-100nm, length are
30μm-80μm。
3. such as claim 1-2 any one of them electrically conducting transparent membrane preparation methods, which is characterized in that include the following steps：
The brushing element is subjected to standardization cleaning；
Surfactant carboxylated processing is carried out to the brushing element surface；
Prepare AgNWs suspensions；
The transparent substrates are horizontal positioned, then prepared AgNWs suspensions are dripped in the transparent substrates, and by institute
Nano silver wire is brushed in the transparent substrates in the surface for stating the process surfactant carboxylated processing for brushing element；
Processing is dried in the transparent substrates that brushing has nano silver wire, that is, forms transparent conductive film.
4. electrically conducting transparent membrane preparation method as claimed in claim 3, which is characterized in that the standardization cleaning step is by institute
The surface with silica for stating brushing element uses deionized water, acetone, isopropanol difference ultrasound 20-30mi n.
5. electrically conducting transparent membrane preparation method as claimed in claim 4, which is characterized in that the brushing element uses surface-active
Agent carboxylated processing step is by the corona treatment 2- of the surface with silica of the brushing element after cleaning
10mi n or UV ozone processing 20-30mi n, are then impregnated with silanes treatment fluid or ammonium class treatment fluid.
6. electrically conducting transparent membrane preparation method as claimed in claim 5, which is characterized in that the solute in the silanes treatment fluid
For at least one of following compounds：N-octadecane base trichlorosilane either hexadecane base trichlorosilane or positive 14
Alkyltrichlorosilanes either n-octadecane base trichlorosilane either n-octadecane base silicofluoroform or n-hexadecyl trifluoro
Silane either n-tetradecane base silicofluoroform either γ-chloropropyl trichloro-silane or γ-chloropropyl dichlorosilane,
Either γ-r-chloropropyl trimethoxyl silane either γ-chloropropyl triethoxysilane or chloromethyl triethoxysilane or
Person's gamma-aminopropyl-triethoxy-silane either γ-aminopropyltrimethoxysilane or γ-(β-aminoethyl) aminopropyl front three
Oxysilane either γ-urea propyl-triethoxysilicane either anilinomethyl triethoxysilane or anilinomethyl front three
Oxysilane or γ-(2,3- the third oxygen of epoxy) propyl trimethoxy silicane or γ-three second of (2,3- the third oxygen of epoxy) propyl
Oxysilane or γ-(2,3- the third oxygen of epoxy) hydroxypropyl methyl dimethoxysilane or β-(3,4- epoxycyclohexyl) ethyl
Trimethoxy silane either gamma-methyl allyl acyloxypropyl trichlorosilane or gamma-methyl allyl acyloxypropyl trimethoxy
Silane either gamma-methyl allyl acyloxypropyl methyldiethoxysilane or gamma-methyl allyl acyloxypropyl methyl dimethoxy
Oxysilane either γ-mercaptopropyl trimethoxysilane either gamma-mercaptopropyltriethoxysilane or double-(tri- ethoxies of 3-
Silicon propyl) tetrasulfide is either double-(tri- ethoxy silicon propyl of 3-) disulphide either vinyl trichlorosilane or vinyl
Triethoxysilane either vinyltrimethoxysilane either (2- methoxyethoxies) silane of vinyl three or vinyl
Triacetoxysilane either three tert-butyl peroxide silane of vinyl either vinyl methyl dichlorosilane or β-cyanogen second
Base trichlorosilane either β-cyanoethyl dimethyl dichlorosilane (DMCS) either β-cyanoethyl triethoxysilane or γ-cyanoethyl three
Methoxy silane or 3- isocyanatopropyl triethoxysilanes；
Solute in the ammonium class treatment fluid is at least one of following compounds：Or octadecyl-dimethyl-(3- tri-
Methoxy silicon propyl) ammonium chloride either 2- methylacryoyloxyethyls dimethyl-(3- trimethoxy silicon propyl) ammonium chloride or 4-
Ethylene benzyl dimethyl-(3- trimethoxy silicon propyl) ammonium chloride.
7. electrically conducting transparent membrane preparation method as claimed in claim 6, which is characterized in that the silanes treatment fluid or the ammonium
Solution in class treatment fluid is dry toluene, dimethylbenzene, chlorobenzene or one or two chlorobenzenes, a concentration of 0.05-0.5mo l/L.
8. electrically conducting transparent membrane preparation method as claimed in claim 5, which is characterized in that use the silanes treatment fluid or ammonium
After class treatment fluid impregnates, which is heated to 50 DEG C of -70 DEG C of holding 15-20mi n, then with dry toluene, dimethylbenzene, chlorine
Benzene or one or two chlorobenzenes rinse, and dried up with nitrogen, finally by the brushing element in 50 DEG C of -70 DEG C of heating 10-20mi n.
9. electrically conducting transparent membrane preparation method as claimed in claim 3, which is characterized in that the preparation AgNWs suspension steps
In, the mass fraction of the AgNWs suspensions is 0.5%-3%, and solvent is ethyl alcohol or isopropanol.
10. electrically conducting transparent membrane preparation method as claimed in claim 3, which is characterized in that described the step of brushing nano silver wire
It is by drop coating after the prepared AgNWs suspensions ultrasound 20-30mi n on the transparent substrates, then by the brushing
Element through the processed surface of surfactant carboxylated downward, brush be located at the transparent substrates on AgNWs it is suspended
Liquid makes nano silver wire uniformly spread in the transparent substrates.
11. electrically conducting transparent membrane preparation method as claimed in claim 3, which is characterized in that the drying steps are will to have sprawled
Into the transparent substrates be placed in drying box, the dry 10mi n-15mi n or to be placed in drying clean at a temperature of 70 DEG C of constant temperature
Only naturally dry at direct sunlight is avoided.
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| CN1472371A (en) * | 2003-06-30 | 2004-02-04 | �Ϻ���ͨ��ѧ | Modification method of flat single crystal silicon surface |
| CN1800068A (en) * | 2005-12-15 | 2006-07-12 | 南京工业大学 | Transparent heat insulation glass |
| CN101999408A (en) * | 2009-09-03 | 2011-04-06 | 财团法人工业技术研究院 | Long-acting antimicrobial nanowire composition and its antimicrobial film and spray |
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