WO2012103285A2 - Procédés et systèmes de réalisation d'un substrat sensiblement transparent et conducteur - Google Patents
Procédés et systèmes de réalisation d'un substrat sensiblement transparent et conducteur Download PDFInfo
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- WO2012103285A2 WO2012103285A2 PCT/US2012/022650 US2012022650W WO2012103285A2 WO 2012103285 A2 WO2012103285 A2 WO 2012103285A2 US 2012022650 W US2012022650 W US 2012022650W WO 2012103285 A2 WO2012103285 A2 WO 2012103285A2
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- WIPO (PCT)
- Prior art keywords
- substrate
- plate
- ink
- conductive
- pattern
- Prior art date
Links
- 239000000758 substrate Substances 0.000 title claims abstract description 137
- 238000000034 method Methods 0.000 title claims abstract description 69
- 238000007639 printing Methods 0.000 claims abstract description 25
- 239000002105 nanoparticle Substances 0.000 claims description 55
- 238000000151 deposition Methods 0.000 claims description 28
- 239000006185 dispersion Substances 0.000 claims description 11
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 8
- 239000004332 silver Substances 0.000 claims description 8
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 claims description 8
- 229910052709 silver Inorganic materials 0.000 claims description 7
- 230000000007 visual effect Effects 0.000 claims description 7
- 239000000853 adhesive Substances 0.000 claims description 6
- 230000001070 adhesive effect Effects 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 229910001923 silver oxide Inorganic materials 0.000 claims description 4
- 238000007646 gravure printing Methods 0.000 claims description 3
- 239000011159 matrix material Substances 0.000 claims description 3
- 239000000725 suspension Substances 0.000 claims description 2
- 239000000976 ink Substances 0.000 description 92
- 239000002245 particle Substances 0.000 description 15
- 239000004020 conductor Substances 0.000 description 14
- 239000000203 mixture Substances 0.000 description 13
- 238000012546 transfer Methods 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 239000003446 ligand Substances 0.000 description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- 239000010408 film Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 238000003825 pressing Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 125000005842 heteroatom Chemical group 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- KZNMRPQBBZBTSW-UHFFFAOYSA-N [Au]=O Chemical compound [Au]=O KZNMRPQBBZBTSW-UHFFFAOYSA-N 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- CXKCTMHTOKXKQT-UHFFFAOYSA-N cadmium oxide Inorganic materials [Cd]=O CXKCTMHTOKXKQT-UHFFFAOYSA-N 0.000 description 2
- CFEAAQFZALKQPA-UHFFFAOYSA-N cadmium(2+);oxygen(2-) Chemical compound [O-2].[Cd+2] CFEAAQFZALKQPA-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 229910000431 copper oxide Inorganic materials 0.000 description 2
- JAONJTDQXUSBGG-UHFFFAOYSA-N dialuminum;dizinc;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Al+3].[Al+3].[Zn+2].[Zn+2] JAONJTDQXUSBGG-UHFFFAOYSA-N 0.000 description 2
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 229910001922 gold oxide Inorganic materials 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 2
- 229910003437 indium oxide Inorganic materials 0.000 description 2
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 2
- 229910000457 iridium oxide Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910000480 nickel oxide Inorganic materials 0.000 description 2
- 229910052762 osmium Inorganic materials 0.000 description 2
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 2
- 229910000487 osmium oxide Inorganic materials 0.000 description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 2
- JIWAALDUIFCBLV-UHFFFAOYSA-N oxoosmium Chemical compound [Os]=O JIWAALDUIFCBLV-UHFFFAOYSA-N 0.000 description 2
- HBEQXAKJSGXAIQ-UHFFFAOYSA-N oxopalladium Chemical compound [Pd]=O HBEQXAKJSGXAIQ-UHFFFAOYSA-N 0.000 description 2
- MUMZUERVLWJKNR-UHFFFAOYSA-N oxoplatinum Chemical compound [Pt]=O MUMZUERVLWJKNR-UHFFFAOYSA-N 0.000 description 2
- SJLOMQIUPFZJAN-UHFFFAOYSA-N oxorhodium Chemical compound [Rh]=O SJLOMQIUPFZJAN-UHFFFAOYSA-N 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 229910003445 palladium oxide Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229910003446 platinum oxide Inorganic materials 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 229910003450 rhodium oxide Inorganic materials 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 229910001316 Ag alloy Inorganic materials 0.000 description 1
- 229910001020 Au alloy Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- LPXDKRZWFWKMST-UHFFFAOYSA-N aluminum;iron Chemical compound [Al+3].[Fe].[Fe].[Fe] LPXDKRZWFWKMST-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000005829 chemical entities Chemical class 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 230000003292 diminished effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 239000003353 gold alloy Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000007644 letterpress printing Methods 0.000 description 1
- 238000001459 lithography Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- VIKNJXKGJWUCNN-XGXHKTLJSA-N norethisterone Chemical compound O=C1CC[C@@H]2[C@H]3CC[C@](C)([C@](CC4)(O)C#C)[C@@H]4[C@@H]3CCC2=C1 VIKNJXKGJWUCNN-XGXHKTLJSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000006254 rheological additive Substances 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/1884—Manufacture of transparent electrodes, e.g. TCO, ITO
Definitions
- Manufacturing methods for creating a transparent, conductive substrate include depositing a transparent conductor such as indium tin oxide (ITO) on a substrate to create a conductive surface.
- ITO's conductive and transparent properties permit the creation of a substrate that is not only conductive, but that can maintain up to ninety five percent of the visual light transmission (%VLT) after deposition of ITO on the substrate.
- Methods for depositing ITO on a substrate can include sputter deposition, vapor deposition or other similar deposition methods.
- ITO can be patterned on a substrate.
- general methods for creating a pattern of conductive geometries can include depositing the ITO on a substrate and scoring or otherwise etching a pattern onto the substrate.
- Other transparent and conductive oxides may be used, e.g. aluminum zinc oxide (AZO).
- Using transparent, conductive oxides to manufacture substantially transparent, conductive substrates can be costly, difficult, and may produce a brittle substrate.
- the deposition methods used to deposit the transparent conductor are often process intensive, expensive and cannot be carried out in high volumes. Additionally, the conductive and structural integrity of substrates generated using ITO or other transparent conductors can be diminished when the substrate is folded or otherwise physically manipulated. The decrease or complete loss in integrity can be largely attributed to the brittle nature of the metal oxide.
- Methods, systems and compositions are therefore needed to generate a rugged and flexible, conductive, transparent substrate using a conductor other than ITO or similar conductive oxides. These methods, systems and compositions may use a conductive ink that can be deposited using a deposition method that allows direct patterned deposition and that can be performed inexpensively at high volumes.
- the resulting structure appears to be substantially transparent.
- the resulting structure although substantially transparent, contains geometric areas of conductor that are visible to the human eye.
- the resulting structure approaches transparency but is not truly transparent because it contains trace amounts of conductor that may be visible to the human eye. Reducing the amount of conductor deposited onto the substrate can affect the conductivity of the substrate and in this way the conductive and optical properties of the patterned surface can be tailored to various applications.
- Methods, systems and compositions are therefore needed for depositing a conductive solution onto a substrate in a pattern such that substantially the same amount of conductor is deposited onto the substrate while maintaining the transparency of the substrate by controlling the size and shape of the pattern.
- the ink can be deposited in any pattern using any print method.
- the print method can be a flexographic print method, a letterpress print method, any relief print method, or any combination thereof.
- FIG. 1 A depicts a transmission electron microscope ("TEM”) micrograph of one embodiment of silver nanoparticles
- FIG. IB illustrates an embodiment of a scanning electron microscope ("SEM") micrograph of a trace comprised of a composition of the metallic nanoparticles described herein cured for up to 1 minute at 100 degrees Celsius;
- SEM scanning electron microscope
- FIG. 1C depicts a SEM micrograph of a trace comprised of a composition of the present disclosure cured for up to 3 minutes at 85 degrees Celsius;
- FIGs. 2A-2C depict embodiments of a plate used to print metallic
- FIGs. 3A-3C depict embodiments of a substrate having a conductive ink printed thereon
- FIGs. 4A-4B illustrate embodiments of methods for printing an ink onto a substrate.
- mil means 1/1000 of an inch. 1 mil is also equivalent to 25.4 micrometers.
- sheet resistance means the electrical resistance divided by the number of squares.
- square means the length of a conductive film or layer of known dimension divided by the width of the conductive film or layer of known dimension.
- milli ohms refers to milli ohms, or 1/1000. sup.th ohm.
- aqueous means containing water.
- aqueous refers to a solution comprised substantially entirely of water.
- aqueous can refer to a solution comprised substantially entirely of water and containing limited amounts of additives that adjust either the rheology of the ink or the ability of the ink to bind to a substrate.
- bonding means covalently bonding, ionically bonding, hydrogen bonding, coordinate bonding, and the like.
- tail means a straight, branched, or cyclic chain of carbon atoms, wherein the chain may be aliphatic, and wherein the chain may have one or more additional groups bound to one or more of its member carbon atoms.
- An example would be a chain of aliphatic carbon atoms with an alcohol group attached to one of the chain members.
- hetero atomic head group means a group including at least one atom wherein at least one atom within the group is atom other than carbon.
- Examples include nitrogen, sulfur, or oxygen.
- cohesive means united as a single entity and resisting separation.
- complexing means forming coordinating bonds with a metal atom or ion.
- ligand means a molecule or a molecular group that binds to another chemical entity to form a larger complex. Examples include a molecular group that becomes bound to a metal or metal ion by a coordinate covalent bond through donating electrons from a lone electron pair of the ligand into an empty metal electron orbital.
- the term "agglomeration” means two or more particles reversibly clustered together, wherein the surfaces of the particles do not come into contact with one another.
- the term “floe” means two or more particles reversibly clustered together, wherein the surfaces of the particles do not come into contact with one another.
- the term "bulk resistivity" means the inherent resistivity of a material that makes up a specified object.
- the bulk resistivity of an ingot made of silver would be the inherent conductivity of silver.
- the bulk resistivity of an ingot made of an alloy comprising silver and gold would be the inherent conductivity of the silver and gold alloy.
- aggregate As used herein, the terms “aggregate”, “aggregation”, and similar forms mean a unified structure comprised of two or more particles irreversibly fused, connected, or necked together.
- corresponding metal means the metal or metals that comprise an object or objects.
- side printing can refer to the additional ink deposited on a substrate when a plate comprising a geometric relief is used to apply the ink to the substrate. Side printing can also be referred to as ghosting or drag-out.
- Section A describes synthesized metallic nanoparticles
- Section B describes a print process and apparatus
- Section C describes post process methods.
- metallic nanoparticles such as the metallic nanoparticles that can be used to create cohesive metallic shielding structures.
- the metallic nanoparticles can comprise at least one silver nanoparticle.
- the metallic nanoparticles can comprise any combination of the following compositions or elements: copper; gold, zinc; cadmium; palladium; iridium;
- the metallic nanoparticles in some embodiments, can have an average particle size of less than about 100 nm. In other embodiments, the metallic nanoparticles can have an average particle size of less than about 50 nm. In still other embodiments, the metallic nanoparticles can have an average particle size within the range of 50 nm to 75 nm, while in other embodiments the nanoparticles can have an average particle size within the range of 75 nm to 100 nm.
- the metallic nanoparticles in some embodiments, can have an average particle size within the range of 15 nm to 50 nm. While in some embodiments, the metallic nanoparticles can have an average particle size within the range of 30 nm to 50 nm.
- the metallic nanoparticles in one embodiment, can have an average cross- sectional dimension in a range of about 1 nm to about 100 nm.
- These metallic nanoparticles in some embodiments, can comprise at least one ligand bound to its surface, where the ligand can include a heteroatom head group bound to the nanoparticle surface and a tail bound to the heteroatom head group.
- the metallic nanoparticles can be substantially spherical in shape, while in other embodiments the nanoparticles can be any of the following shapes: kidney-shaped; circular; triangular; rectangular; trapezoidal; typaniform; or any other suitable shape.
- each nanoparticle within a plurality or population of metallic nanoparticles can have a substantially uniform shape. In other embodiments, each
- nanoparticle within a plurality or population of metallic nanoparticles can have a substantially uniform size.
- a plurality of nanoparticles or nanoparticle population can include particle agglomerates that include two or more individual nanoparticles.
- a plurality of nanoparticles can include a nanoparticle floe that includes two or more individual nanoparticles.
- a plurality of nanoparticles can include any combination of particle agglomerate and a nanoparticle floe.
- the ratio by weight of the population of individual metallic nanoparticles to particle agglomerate can be within a range of about 1 :99 to 99: 1. In other embodiments, the ratio, by weight, of the population of individual metallic
- nanoparticles to particle floe can be in the range of from about 1 :99 to 99: 1.
- a nanoparticle agglomerate or floe can have an average cross-sectional dimension in the range of from about 100 nm to about 10,000 nm.
- Individual metallic nanoparticles within the nanoparticle agglomerate or floe can comprise any of the above-described compositions or elements.
- the individual metallic nanoparticles can comprise silver nanoparticles.
- the individual nanoparticles can comprise any combination of the following: silver, copper, gold, zinc, cadmium, palladium, iridium, ruthenium, osmium, aluminum, rhodium, platinum, iron, nickel, cobalt, indium, silver oxide, copper oxide, gold oxide, zinc oxide, cadmium oxide, palladium oxide, iridium oxide, ruthenium oxide, osmium oxide, aluminum oxide, rhodium oxide, platinum oxide, iron oxide, nickel oxide, cobalt oxide, and indium oxide.
- the metallic nanoparticles can be present within a composition in the range of from about 0.5 wt % to about 70 wt %.
- Ligand can be present in the range of from about 0.5 wt % to about 75 wt %, and the medium is present in the range of from about 30 to about 98 wt %.
- the medium in some embodiments, is an aqueous solution comprising water.
- a composition can be formed from the metallic nanoparticles and an aqueous solution such as any of the aqueous solutions described herein.
- the composition can be capable of forming a cohesive structure of less than about 10 micrometers in thickness formed when the metallic nanoparticles are heated at a low temperature.
- This low temperature in some embodiments, can be a temperature of less than about 140 degrees Celsius.
- the metallic nanoparticles are heated at the low temperature for a period of time less than about 60 seconds.
- the resulting cohesive shielding structure in some embodiments, can have a resistivity in the range of from about 2 times to about 15 times the bulk resistivity of the corresponding metal used in the metallic
- a continuous network film is created once the metallic nanoparticles are heated at a low temperature.
- the low temperature can be a temperature less than about 140 degrees Celsius.
- This film can form any number of shapes, marks, lines, figures and can occupy an area having various dimensions and configurations.
- the nanoparticles, when heated do not create a monolayer but rather an agglomerate of nanoparticles.
- the nanoparticles, when heated can form a continuous porous network of cured nanoparticles.
- the network in some embodiments, can be referred to as a matrix, network, web, grid or pattern of cured metallic nanoparticles.
- Section B Print Process and Apparatus
- Illustrated in Figure 2A is a side-view of an embodiment of a plate 200 that can be used to deposit or print a conductive ink onto a substrate.
- the plate 200 can have a top 205 and a bottom 210 where at least a portion of the plate top 205 physically makes contact with a substrate for the purpose of depositing a conductive ink onto the substrate.
- the plate 200 can be a plate 200 for any relief print method.
- the plate 200 can be a plate 200 used in flexographic print methods, in other embodiments the plate 200 can be a plate 200 used in letterpress print methods.
- the plate 200 can be manufactured from any material suitable for receiving a conductive substance.
- the plate bottom 210 in some embodiments, can comprise structures for attaching the plate 200 to a machine that can be used to apply the plate 200 to a substrate.
- the machine can be any machine capable of physically moving the plate 200 in any number of directions relative to a surface.
- the machine can cause the plate 200 to make contact with a substrate and can further cause the plate 200 to apply pressure to the substrate.
- the top of the plate 205 makes contact with a substrate; in other embodiments the sides of the plate 200 may also make contact with a substrate.
- the top of the plate 205 can be considered the portion of the plate 200 located vertically parallel to the portion of the plate 200 that connects to a machine able to manipulate the position of the plate 200.
- a plate 200 can be used to apply, deposit or print a conductive ink onto a substrate.
- the top portion of the plate 205 can be used to apply, deposit or print the conductive ink onto the substrate.
- An ink can be applied to or secreted from the top portion of the plate 205 such that the plate top 205 comprises a layer of ink.
- the ink can be cured to create a conductive geometry.
- the plate top 205 can then make contact with a substrate so as to cause at least a portion of the ink to transfer from the plate top 205 to the substrate.
- causing the plate top 205 to physically connect with the substrate can include causing the plate top 205 to apply a predetermined amount of pressure to the substrate.
- a predetermine amount of ink transfers from the plate top 205 to the substrate.
- the amount of ink transferred to the substrate in some embodiments, can be directly proportional to the amount of pressure the plate top 205 applies to the substrate.
- FIG. 2B Illustrated in Figure 2B is a top view of an embodiment of a plate 200 that can be used to apply, deposit or print a conductive ink onto a substrate.
- the plate top 205 can comprise a geometric relief 240 that can begin at the plate edge 235 and can span the length of the plate 200.
- the geometric relief 240 can include geometric elements 215 spaced apart by a predetermined length 220 and overlapping by a predetermined length 230. In some instances, the geometric elements 215 can include edges 225 that are horizontally parallel with the length of the plate 200.
- the plate top 205 can comprise a geometric relief 240.
- This relief 240 can extend vertically from the surface of the plate top 205 a predetermined length. In some embodiments, the relief 240 can be generated by eliminating a portion of the surface of the plate top 205. In other embodiments, the relief 240 can be a separate structure affixed to the plate top 205. The relief 240 can span substantially the entire length of the plate 200; while in other
- the relief 240 can span a portion of the length of the plate 200. In some embodiments, the geometric relief 240 can be uniformly distributed over the surface of the plate top 205. In other embodiments the geometric relief 240 can be sporadically distributed over the surface of the plate top 205.
- geometric relief 240 can be one or more geometric elements 215. These geometric elements 215 can be the same size and shape, while in other embodiments the geometric elements 215 can vary in size and shape. While Figure 2B illustrates a plate having a geometric relief 240 comprising diamond-shaped geometric elements 215, the geometric elements 215 can be any of the following shapes or forms:
- the geometric elements 215 can be a non-symmetrical shape.
- the shape of the geometric elements 215 can vary throughout the length of the geometric relief 240.
- the geometric relief 240 can include more than one geometric element 215, while in other embodiments the geometric relief 240 can include a single geometric element 215.
- the shapes can be open or closed such that the ink shape transferred to the substrate is a dot.
- the dot can be circular, while in other embodiments the dot can be any shape described herein.
- Each geometric element 215, in some embodiments, can be separated by a predetermined length 220. This length can span from the center of on geometric element 215 to the center of an adjacent geometric element 215. In some embodiments the length 220 between geometric elements 215 can be substantially uniform throughout the length of the relief 240. In other embodiments, the length 220 between geometric elements 215 can vary throughout the length of the relief 240.
- Each geometric element 215, in some embodiments, can overlap by a predetermined length 230. This length can extend from the overlapping edge of one geometric element 215 to the overlapping edge of an adjacent geometric element 215. In some embodiments, the overlap length 230 can directly affect the number of geometric elements included in the geometric relief 240. In these embodiments, the number of geometric elements can further affect the number of geometric element edges 225 that span the length of the plate 200. Each geometric element edge 225 extends vertically from the surface of the plate top 205, and has a surface that is parallel to the side of the plate 200.
- FIG. 2C Illustrated in Figure 2C is a perspective view of an embodiment of a plate 200 having a geometric relief 240 installed on the top of the plate 205.
- the perspective view illustrates the geometric relief 240 extending vertically from the plate top 205.
- the geometric relief 240 can extend vertically a predetermined distance 245.
- Figures 3A-3C Illustrated in Figures 3A-3C are embodiments of a substrate 300 having a conductive ink printed thereon in a pattern. Each of Figures 3A-3C illustrates a different pattern 305, 310 and 315. While Figures 3A-3C illustrate three different types of patterns, other patterns can be used. In some embodiments, the pattern printed on the substrate 300 can be symmetrical, while in others the pattern is not symmetrical.
- the substrate 300 can be any substrate described herein.
- the substrate 300 can be a thin film of polyester, in other embodiments the substrate 300 can be a conductive or non-conductive polymer.
- the substrate can be any plastic film like PET with a continuous coating applied thereon that improves the wettability of the conductive ink onto the substrate.
- each pattern contains one or more deposited, applied or printed conductive areas. These areas can be formed by applying the top of the plate 200 illustrated in Figures 2A-2C to the substrate 300. Applying the top of the plate 205 can include using any mechanical means necessary to cause the substrate 300 to come into contact with the top of the plate 205.
- the portion of the plate 200 that comes into contact with the substrate 300 can be a geometric relief 240 or relief spanning at least a portion of the surface area of the plate top 205.
- the relief 240 can comprise any pattern and in some embodiments can be any relief 240 described herein.
- the ink distributed over the surface area of the plate top 205 can transfer from the top of the plate 205 to the substrate 300.
- this transfer can be accomplished by applying pressure to either the plate 200 or the substrate 300. Applying pressure can cause the sides of the plate 200 to also make contact with the substrate 300 such that side -printing occurs.
- the shape created by the transferred ink can have measurements larger than the surface area of the top of the plate 205. For example, if the surface area of the top of the plate has a width of 25 microns, side-printing can cause the shape of ink transferred to the substrate to have a width of 30 microns.
- Illustrated in Figure 3A is one embodiment of a pattern of ink deposited on a substrate 300.
- the pattern in Figure 3 A comprises one or more circular areas 305.
- the width of the circles' 305 lines can be within a range of 25 to 10 microns.
- the circular areas 305 can be placed throughout the surface of the substrate 300 in any ordered or non-ordered pattern.
- the circular areas 305 can be closed such that the entire area is filled with ink, in other embodiments the circular areas 305 can be open such that the areas are rings.
- the diameter of the circular areas 305 can vary or can be uniform and can be any size.
- the diameters of the circular areas 305 and the width of the ring that defines the circular areas can be predetermined values. These values can be chosen such that the resulting pattern causes the substrate 300 to be conductive and substantially transparent.
- Illustrated in Figure 3B is another embodiment of a pattern of ink deposited on a substrate 300.
- the pattern in Figure 3B comprises a grid pattern 310 created by depositing a series of horizontal lines and a series of vertical lines.
- the lines of the grid pattern 310 can have a width within a range of 5 to 75 microns.
- Figure 3B illustrates a grid pattern having vertical lines that are parallel with the side edges of the substrate 300 and horizontal lines that are parallel with the top and bottom edges of the substrate 300, in other embodiments the grid pattern 310 can be oriented in any direction on the substrate 300.
- FIG. 3C Illustrated in Figure 3C is yet another embodiment of a pattern of ink deposited on a substrate 300.
- This embodiment depicts lines drawn in a circular pattern 315 on the substrate 300.
- the lines of the pattern 315 can have a width within a range of 25 to 10 microns.
- the spacing between each line can be any distance.
- the lines of the pattern 315 can be separated by a predetermined distance such that the resulting pattern causes the substrate 300 to be conductive and substantially transparent.
- the patterns can comprise dots or areas of printed ink.
- the lines of the patterns can be a continuous line of connected dots, areas or geometries. In other embodiments, the lines of the patterns can be a non-continuous line of dots, areas or geometries.
- Illustrated in Figure 4A is one embodiment of a method for applying an ink to a substrate. The method can include applying an ink to the top of a plate (Step 405) and applying pressure to the top of the plate to cause the top of the plate to come into contact with the substrate 300 (Step 410). The plate is then pulled away from the substrate 300 after a predetermined period of time (Step 415) and the ink is permitted to cure (Step 420).
- ink is applied to the top of the plate (Step 405).
- the ink can be any ink described herein.
- the ink can be a conductive nanoink comprising conductive, metallic nanoparticles. Any method can be used to apply the ink to the top of the plate.
- ink can be wiped, sprayed or otherwise deposited onto the plate.
- the plate can be any plate 200 described herein.
- the plate 200 can be a plate 200 used in flexographic printing, letterpress printing or any hybrid printing technology that utilizes a plate 200.
- the plate 200 can then be applied to the substrate 300 so that the ink transfers from the plate 200 to the substrate 300 (Step 410). In some embodiments substantially all of the ink transfers from the plate 200 to the substrate 300. In other embodiments only a portion of the ink transfers from the plate 200 to the substrate 300. In these embodiments, the plate 200 retains a portion of the ink deposited onto the surface of the plate 200. Applying the plate 200 to the substrate 300 can include causing the plate 200 to come into contact with the substrate 300 and applying pressure to the plate 200. The application of pressure to the plate 200 causes the ink to adhere to the substrate 300 thereby causing the ink to be deposited onto the substrate 300.
- the plate 200 can be in contact with the substrate 300 for any period of time. In some embodiments, this period of time can be any period of time needed to deposit a sufficient amount of ink onto the substrate 300. After this period of time elapses, the plate 200 can be pulled away from the substrate 300 (Step 415). Pulling the plate 200 away from the substrate 300 can include moving the plate 200 away from the substrate 300 or moving the substrate 300 away from the plate 200. In some embodiments, this step can include removing pressure from the top of the plate 200 so that the plate 200 and the substrate 30 no longer are in contact.
- the process of applying the plate 200 to the substrate 300 can result in the deposition of ink onto the substrate 300.
- the ink can be allowed to cure (Step 420).
- the time required to cure the ink can depend on the properties of the ink. In some embodiments, the time and temperature required to cure the ink can be any of the time and temperature combinations described herein.
- Illustrated in Figure 4B is another method of depositing an ink onto a substrate 300.
- the method can include depositing the ink onto a substrate 300 in a pattern (Step 452) and permitting the ink to cure (Step 454).
- the ink can be deposited onto the substrate 452 using the method described in Figure 4A.
- the ink can be deposited onto the substrate using any of the following printing processes: screen printing; gravure printing; letterpress; intaglio; offset lithography; offset lithographic printing; offset gravure printing; rotogravure printing; or flexographic printing, or any relief printing method.
- Still further embodiments can include depositing the ink using any hybrid print process comprising any of the print or ink deposition processes described herein.
- one print process can include using a letterpress type of print plate on a flexographic print process.
- the ink When the ink is deposited onto the substrate 300, the ink can be deposited in any pattern described herein. In some embodiments, the ink can be deposited in any pattern. In other embodiments, the ink can be deposited in any pattern described in Figures 3A-3C. The ink can be deposited in a pattern such that the resulting substrate is both conductive and substantially transparent. The pattern, in some embodiments, can be designed to control the amount of ink deposited onto the substrate 300 and further control the print resolution.
- Controlling this property of the ink can further allow one to control how much ink is deposited from the plate 200 or print medium to the substrate 300.
- substantially transparent conductive structure the method comprising: depositing a dispersion of metallic nanoparticles on a substrate in a pattern, wherein the pattern comprises lines having a width less than 50 microns; and curing the deposited dispersion to create a substantially transparent conductive structure, wherein greater than eighty percent of visual light transmits through the structure.
- the method may further comprise depositing an adhesive on the substrate prior to depositing the dispersion.
- the adhesive may be a conductive adhesive.
- At least one of the metallic nanoparticles of the dispersion comprises any combination of silver, silver oxide and copper.
- the pattern may comprise lines having a width less than 10 microns.
- a pattern comprising lines having a width of less than 5 microns is specifically mentioned.
- greater than ninety percent of visual light may transmit through the metallic structure.
- a metallic structure wherein greater than ninety- five percent of visual light transmits through the metallic structure is specifically mentioned.
- the method may further comprise depositing a conductive coating onto the substantially transparent structure after curing the deposited dispersion.
- a conductive coating comprises an inorganic suspension of conductive components in an organic matrix is specifically mentioned.
- a transparent conductive substrate can be created by printing a conductive ink onto a substrate.
- the ink can be deposited using a letterpress plate in a flexographic print process.
- the plate can be any plate 200 described herein and can be configured to substantially reduce side printing.
- Ink can be deposited onto the substrate 300 using the plate 200.
- the ink can be deposited in an ordered pattern of ordered geometric areas to create a substrate that is conductive and substantially transparent.
- a transparent conductive substrate can be created by printing a conductive ink onto a substrate.
- the ink can be deposited using any print process that uses a plate such as any plate 200 described herein.
- the plate 200 can be configured to substantially reduce side printing.
- Ink can be deposited onto the substrate 300 in a random pattern of geometric areas such as bubbles or rings.
- the resulting substrate can be both conductive and substantially transparent.
- a conductive structure that has no non-conductive areas can be formed by depositing a conductive ink onto a conductive substrate or conductive material (e.g. a conductive polymer.)
- the ink can be deposited using any of the print processes described herein and can be deposited in any pattern described herein.
- the resulting substrate can be a fully conductive substrate, (e.g. both the printed ink areas and the areas between the printed ink areas are conductive.)
- the processes described herein for depositing ink onto a substrate can include one or more post process methods. These methods can include post etching to improve line resolution and reduce line width.
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Abstract
Selon l'invention, des procédés et des systèmes d'impression d'une encre conductrice sur un substrat pour réaliser un substrat transparent et conducteur peuvent comprendre un appareil d'impression d'encre sur un substrat. L'encre peut être imprimée ou déposée sur le substrat en un motif, au moyen d'un quelconque procédé d'impression compatible. Dans certains modes de réalisation, le motif d'encre peut être conçu pour contrôler la conductivité et la transparence du substrat.
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US201161437624P | 2011-01-29 | 2011-01-29 | |
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KR20060012545A (ko) * | 2002-07-03 | 2006-02-08 | 나노파우더스 인더스트리어스 리미티드. | 저온 소결처리한 전도성 나노 잉크 및 이것의 제조 방법 |
KR20100084991A (ko) * | 2009-01-19 | 2010-07-28 | 히다치 막셀 가부시키가이샤 | 투명도전막 및 그 제조방법 |
KR20100114040A (ko) * | 2007-12-20 | 2010-10-22 | 시마 나노 테크 이스라엘 리미티드 | 충전제 재료를 포함하는 투명한 전도성 코팅 |
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KR20060012545A (ko) * | 2002-07-03 | 2006-02-08 | 나노파우더스 인더스트리어스 리미티드. | 저온 소결처리한 전도성 나노 잉크 및 이것의 제조 방법 |
KR20100114040A (ko) * | 2007-12-20 | 2010-10-22 | 시마 나노 테크 이스라엘 리미티드 | 충전제 재료를 포함하는 투명한 전도성 코팅 |
KR20100084991A (ko) * | 2009-01-19 | 2010-07-28 | 히다치 막셀 가부시키가이샤 | 투명도전막 및 그 제조방법 |
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