US20140161972A1 - Method for forming conductive film at room temperature - Google Patents
Method for forming conductive film at room temperature Download PDFInfo
- Publication number
- US20140161972A1 US20140161972A1 US13/709,006 US201213709006A US2014161972A1 US 20140161972 A1 US20140161972 A1 US 20140161972A1 US 201213709006 A US201213709006 A US 201213709006A US 2014161972 A1 US2014161972 A1 US 2014161972A1
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- United States
- Prior art keywords
- room temperature
- silver
- forming
- silver nanoparticles
- conductive film
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- Abandoned
Links
- 238000000034 method Methods 0.000 title claims abstract description 70
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 claims abstract description 75
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 74
- 239000000758 substrate Substances 0.000 claims abstract description 71
- -1 dodecanoate-protected silver Chemical class 0.000 claims abstract description 63
- 229910052709 silver Inorganic materials 0.000 claims abstract description 60
- 239000004332 silver Substances 0.000 claims abstract description 60
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000007864 aqueous solution Substances 0.000 claims abstract description 49
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000002105 nanoparticle Substances 0.000 claims abstract description 41
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 27
- 239000003446 ligand Substances 0.000 claims abstract description 26
- 239000002904 solvent Substances 0.000 claims abstract description 21
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims abstract description 19
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims abstract description 17
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 93
- 239000000203 mixture Substances 0.000 claims description 71
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 42
- 230000008569 process Effects 0.000 claims description 17
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 14
- POULHZVOKOAJMA-UHFFFAOYSA-M dodecanoate Chemical compound CCCCCCCCCCCC([O-])=O POULHZVOKOAJMA-UHFFFAOYSA-M 0.000 claims description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 11
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 11
- 229920002457 flexible plastic Polymers 0.000 claims description 10
- 239000012454 non-polar solvent Substances 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 238000007641 inkjet printing Methods 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 239000012279 sodium borohydride Substances 0.000 claims description 8
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 8
- 238000004528 spin coating Methods 0.000 claims description 8
- 239000011668 ascorbic acid Substances 0.000 claims description 7
- 229960005070 ascorbic acid Drugs 0.000 claims description 7
- 235000010323 ascorbic acid Nutrition 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- 238000009833 condensation Methods 0.000 claims description 5
- 230000005494 condensation Effects 0.000 claims description 5
- 239000011521 glass Substances 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 4
- 125000003944 tolyl group Chemical group 0.000 claims description 3
- 239000000243 solution Substances 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 2
- 230000035945 sensitivity Effects 0.000 abstract 1
- 239000010408 film Substances 0.000 description 69
- 238000004321 preservation Methods 0.000 description 8
- 230000007774 longterm Effects 0.000 description 6
- 238000007639 printing Methods 0.000 description 6
- 230000000087 stabilizing effect Effects 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000010017 direct printing Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229910001868 water Inorganic materials 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000003837 high-temperature calcination Methods 0.000 description 3
- 239000002082 metal nanoparticle Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000008439 repair process Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical class CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000001459 lithography Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1603—Process or apparatus coating on selected surface areas
- C23C18/1607—Process or apparatus coating on selected surface areas by direct patterning
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1646—Characteristics of the product obtained
- C23C18/165—Multilayered product
- C23C18/1651—Two or more layers only obtained by electroless plating
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1655—Process features
- C23C18/1658—Process features with two steps starting with metal deposition followed by addition of reducing agent
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1689—After-treatment
- C23C18/1692—Heat-treatment
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/42—Coating with noble metals
- C23C18/44—Coating with noble metals using reducing agents
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
- H01L21/283—Deposition of conductive or insulating materials for electrodes conducting electric current
- H01L21/288—Deposition of conductive or insulating materials for electrodes conducting electric current from a liquid, e.g. electrolytic deposition
Definitions
- the present invention relates to a method for forming a conductive film at room temperature, and more particularly to a method using a reducing agent to chemically reduce a film of dodecanoate-protected silver nanoparticles pre-coated on the flexible substrate into a conductive silver film at room temperature.
- Low-cost liquid direct printing technology can be applied to a variety of patterned and deposition processes, such as processes of integrated circuits (IC), glass substrate circuits of large-size liquid crystal display (LCD), surface circuits of LED wafer, repair of IC open circuits, electronic tags or radio frequency identification (RFID), etc.
- IC integrated circuits
- LCD liquid crystal display
- RFID radio frequency identification
- plating and etching to form a conductive patterned circuit are generally done by lithography processes.
- due to the many complex steps required to construct a layer of circuit it is relatively time-consuming and the manufacturing cost is higher.
- the technique is to quickly convert the metal nanoparticles into the low-resistance metal conductor to form a conductive circuit after removing the solvent and heat treatment.
- one of the direct printing technologies is to firstly mix metal nanoparticles and a solvent as a printing ink, and then spray the printing ink onto a substrate to form a conductive circuit by an inkjet method, wherein the metal nanoparticles is preferably selected from silver.
- Silver is more suitable than gold for being used in this art, because silver is the metal having the highest conductivity among all the metals.
- gold has excessive material cost which affects its applicability in the field of electronics.
- the inventors of the present patent previously disclosed a paper named “One-step synthesis of uniform silver nanoparticles capped by saturated decanoate: direct spray printing ink to form metallic silver films” published in the journal, Physical Chemistry Chemical Physics (2009, vol. 11, p. 6269-6275), on May 27, 2009, wherein it disclosed that the decanoate-protected silver nanoparticles (C 9 H 19 COO 2 —Ag) is used as a printing ink.
- the stability of the operation of the decanoate-protected silver nanoparticles at room temperature is only maintained for one day because of desorption by the carbon dioxide and other decomposition fragments.
- the decanoate-protected silver nanoparticles described above is coated on a rigid silicon substrate, and reduce the coating film of the silver nanoparticles into a high conductive silver film by using the high-temperature calcination above 150° C.
- the process of using high-temperature calcination also cannot be applied to the non-heat-resistant flexible plastic substrate and it takes longer process time.
- adding the hydrogen in the high temperature to process reduction reaction will increase the safety risk.
- a primary object of the present invention is to provide a method for forming a conductive film at room temperature, which includes steps of: firstly adding AgNO 3 into a solution of dodecanoic acid; sequentially dropping n-butylamine as a silver-ion ligand and a diluted aqueous solution of a reducing agent to reduce silver ions into silver nanoparticles to initially obtain silver nanoparticles stably protected by dodecanoate as a capping ligand; then using cyclohexane as a long-term stabilizing solvent to spin-coat or print silver nanoparticles using dodecanoate as a capping ligand onto the surface of the substrate to form a patterned silver nanoparticle film; finally immersing the substrate into a high concentrated aqueous solution of a reducing agent to chemically reduce the patterned film of silver nanoparticles into a conductive silver film.
- This method can not only be used to conveniently and rapidly print the patterned film or circuit on the substrate, but also significantly
- a secondary object of the present invention is to provide a method for forming a conductive film at room temperature, which includes steps of: firstly using cyclohexane containing 0.5 wt % dodecanoic acid as a solvent to mix with silver nanoparticles using dodecanoate as a capping ligand into a long-term stabilizing preservation solvent (30-day preservation period) with 5.0 to 15.0 wt % silver nanoparticles, so that silver nanoparticles in the cyclohexane solution containing 0.5 wt % dodecanoic acid is unable to generate mutual aggregation and condensation, and the size uniformity of the nanoparticles can be kept. Therefore, it can improve the printing quality of silver nanoparticles applied to inkjet printing process.
- the present invention provides a method for forming a conductive film at room temperature, which comprises following steps of:
- the molar ratio of the silver ions of AgNO 3 and the dodecanoate group of dodecanoic acid is 1:2.
- the non-polar solvent is toluene.
- the molar ratio of the silver ions of AgNO 3 and n-butylamine is 1:2.
- the diluted aqueous solution of the reducing agent is selected from a diluted aqueous solution of hydrazine, ascorbic acid, NaBH 4 or dimethylformamide (DMF).
- the diluted aqueous solution of the reducing agent is the diluted aqueous solution of hydrazine, and the molar ratio of the silver ions of AgNO 3 and hydrazine of the diluted aqueous solution of hydrazine is 2:1.
- the range of average particle diameter of the dodecanoate-protected silver nanoparticles is 6.20 ⁇ 0.57 nanometer (nm).
- step (d) in the step (d), firstly adding acetone into the third mixture to deposit the dodecanoate-protected silver nanoparticles, and then adopting methanol and acetone to wash, centrifuge and dry by reduced pressure condensation, in order to obtain the dodecanoate-protected silver nanoparticles.
- the fourth mixture in the step (e), is: firstly using cyclohexane containing 0.5 wt % dodecanoate acid as a solvent to mix with the silver nanoparticles in the step (d) into the fourth mixture which has 5.0 to 15.0 wt % silver nanoparticles, wherein the fourth mixture is a long-term stabilizing preservation solvent (30-day preservation period) preferably having 10.0 wt % silver nanoparticles.
- the fourth mixture is selected to be applied onto the surface of the substrate by spin-coating or inkjet printing.
- the substrate is selected from the group consisting of a flexible plastic substrate, a glass substrate and a silicon wafer substrate; wherein the flexible plastic substrate is a polyethylene terephthalate (PET) substrate.
- PET polyethylene terephthalate
- the aqueous solution of the reducing agent is selected from an aqueous solution of hydrazine, ascorbic acid, NaBH 4 or dimethylformamide (DMF).
- the aqueous solution of the reducing agent is an aqueous solution of hydrazine
- the hydrazine concentration of the aqueous solution of hydrazine is between 70 and 90 wt %, such as 80 wt %.
- the processes in the steps (a) to (g) are all performed at room temperature in the range between 20 and 30° C., such as 25° C.
- the method further comprises: (g1) applying a heat-treatment to the conductive silver film at 100° C.
- the method further comprises: (h) repeating the steps (f) and (g) to further stack and form another conductive silver film on the original conductive silver film.
- the method further comprises: (h1) applying a heat-treatment to two of the stacked conductive silver films at 100° C.
- FIG. 1 is a schematic diagram of steps (a) to (d) of a method for forming a conductive film at room temperature according to a first embodiment of the present invention
- FIG. 2 is a schematic diagram of steps (e) to (g) of the method for forming the conductive film at room temperature according to the first embodiment of the present invention.
- FIG. 3 is a schematic diagram of steps (e) to (g) of a method for forming a conductive film at room temperature according to a second embodiment of the present invention.
- a method for forming a conductive film at room temperature mainly comprises the following steps: (a) adding AgNO 3 into a non-polar solvent containing dodecanoic acid (C 11 H 23 COOH, also known as n-dodecanoic acid) to be a first mixture; (b) dropping n-butylamine into the first mixture as a ligand of silver ions of silver nitrate to be a second mixture; (c) dropping a diluted aqueous solution of hydrazine (N 2 H 4 .H 2 O) into the second mixture to be a third mixture, wherein the hydrazine reduces silver ion into silver nanoparticles (NPs) and the dodecanoate group of dodecanoic acid is used as a capping ligand to be around and protect the silver nanoparticles; (d) separating the dodecanoate-protected silver nanoparticles (A)
- the first step (a) of the method for forming a conductive film at room temperature according to the first embodiment of the present invention is to add AgNO 3 into a non-polar solvent containing dodecanoic acid to be a first mixture.
- the present invention executes some sub-steps of: adopting 31.69 ml of toluene as a non-polar solvent and adding 3.3387 g (16.67 mmol) Idodecanoic acid into toluene; stirring it until it is dissolved, then adding 1.4156 g (8.33 mmol) of AgNO 3 , which contains 0.25 mol/L Ag + , wherein AgNO 3 in the first mixture is used as a precursor of silver ions, and in the following step (c), dodecanoic acid in the first mixture will be used as a capping ligand of the silver nanoparticles.
- dodecanoic acid doesn't yet react with AgNO 3 .
- the molar ratio of the silver ions of AgNO 3 and the dodecanoate group of dodecanoic acid substantially maintains at 1:2.
- the non-polar solvent preferably is selected from toluene, but it can still be selected from other similar non-polar solvents which have equivalent effect.
- the following step (b) of the method for forming a conductive film at room temperature according to the first embodiment of the present invention is to drop n-butylamine into the first mixture as a ligand of silver ions of AgNO 3 to be a second mixture.
- the present invention executes the way of dropping per second to add the 1.6473 ml (16.67 mmol) of n-butylamine.
- the second mixture then continues to react for 3.5 minutes and it gradually turned milky turbid suspension in the process of n-butylamine is temporarily used as a ligand of silver ions to separate silver ions from AgNO 3 firstly.
- the status of the milky turbid suspension shows that the second mixture includes the complex formed by coordinating silver ions and n-butylamine.
- the molar ratio of the silver ions of AgNO 3 and n-butylamine substantially maintains at 1:2.
- the following step (c) of the method for forming a conductive film at room temperature according to the first embodiment of the present invention is to drop a diluted aqueous solution of hydrazine (N 2 H 4 .H 2 O) into the second mixture to be a third mixture.
- the present invention executes the way of firstly adding 80 wt % a solution of hydrazine (N 2 H 4 .H 2 O) into 25 ml of a deionized water for diluting and mixing to be a diluted aqueous solution of hydrazine as a chemical redox fluid, which includes 0.2607 g (4.17 mmol) hydrazine.
- the step (b) n-butylamine in the step (b) reacted for 3.5 minutes, executing the way of dropping per second to add the prepared diluted aqueous solution of hydrazine into the second mixture to be a third mixture.
- the titration takes 15 minutes.
- the third mixture reacts again for 3 hours, wherein hydrazine reduces silver ions using n-butylamine as a temporary ligand into silver atoms in the metallic state.
- Silver atoms are further re-aggregated to be silver nanoparticles and the dodecanoate group of dodecanoic acid is used as a capping ligand to be around the silver nanoparticles.
- the molar ratio of the silver ions of AgNO 3 and hydrazine of the diluted aqueous solution of hydrazine is 2:1.
- step (c) silver ions using n-butylamine as a temporary ligand can be further reduced into silver atoms of the metallic state by hydrazine. And, a plurality of silver atoms of the metallic state is clustered with each other into nano-scale silver nanoparticles. After clustered, the average particle size of the silver nanoparticles is roughly in the range of 6.20 ⁇ 0.57 nm (nanometer), wherein each silver nanoparticles are actually formed by ten to hundreds of silver atoms clustered together.
- the outermost layer of the silver nanoparticles reacts with dodecanoate to form ionic complex; wherein the outermost layer of the silver atoms will transform into positively charged silver ions to bond with negative charge dodecanoate groups (as shown in the right-most side of FIG. 1 ).
- the dodecanoate groups are used as capping ligands to be around and protect the silver nanoparticles (Ag—C 11 H 23 CO 2 ) for avoiding the neighboring silver nanoparticles from clustering with each other again to enlarge the particle size, and further it can effectively restrict the number of silver atoms clustered inside the silver nanoparticles is no longer increased to stabilize the particle size of silver nanoparticles.
- the advantage of this is that the particle size of the silver nanoparticles can be controlled stably. It can effectively avoid the problem that when forming the patterned circuit in the following steps, the conductive quality of the circuit will be affected because of large conductive particles.
- the following step (d) of the method for forming a conductive film at room temperature according to the first embodiment of the present invention is to separate the dodecanoate-protected silver nanoparticles (Ag—C 11 H 23 CO 2 ) from the third mixture.
- this step when the reaction of hydrazine is finished, adding 200 ml of acetone into the third mixture to deposit the dodecanoate-protected silver nanoparticles, followed by using the solution of methanol and acetone to wash, centrifuge and dry by reduced pressure condensation, so that dark blue powder of dodecanoate-protected silver nanoparticles can be obtained.
- the separation method of the present invention is not limited thereto; the present invention can also use other existing separation techniques or other solvents to separate the dodecanoate-protected silver nanoparticles from the third mixture.
- step (e) of the method for forming a conductive film at room temperature according to the first embodiment of the present invention is to use cyclohexane as a solvent to mix with the dodecanoate-protected silver nanoparticles to be a fourth mixture 10 .
- the present invention executes the way of firstly using cyclohexane containing 0.5 wt % dodecanoate as a solvent and adding silver nanoparticles of the step (d) into the solvent to mix to be a fourth mixture 10 which has 5.0 to 15.0 wt % silver nanoparticles; wherein the fourth mixture 10 is a long-term stabilizing preservation suspension, which preferably has 10.0 wt % silver nanoparticles. Because the fourth mixture 10 contains 0.5 wt % dodecanoate and cyclohexane, it is benefit to stably preserve silver nanoparticles using dodecanoate as the capping ligand at least about 30 days or more.
- the dodecanoate-protected silver nanoparticles can be stably suspended in the cyclohexane solvent containing 0.5 wt % dodecanoate, and hence the fourth mixture 10 not only can be used for the storage backup purposes, but also can avoid the problem that silver nanoparticles further cluster to expand the particle diameter during the preservation.
- the following step (f) of the method for forming a conductive film at room temperature according to the first embodiment of the present invention is to coat the fourth mixture 10 onto a surface of a substrate 20 by spin coating to form a film 11 of dodecanoate-protected silver nanoparticles.
- the fourth mixture 10 is selected to be applied onto the upper surface of the substrate 20 by spin coating via a spin-coating liquid distributor 30 ; wherein the substrate 20 is selected from the group consisting of a flexible plastic substrate, a glass substrate and a silicon wafer substrate and preferably selected from a flexible plastic substrate, for example, the substrate made of polyethylene terephthalate (PET) of non-heat-resistant and low cost.
- PET polyethylene terephthalate
- the present invention adopts the fourth mixture 10 containing 10 wt % dodecanoate-protected silver nanoparticles (Ag—C 11 H 23 CO 2 ) to execute spin coating wherein the substrate 20 is placed on the a turntable, and spin-coated for 15 seconds at 2000 round per minute, so that the mixture 10 can be uniformly coated on the substrate 20 (e.g., PET substrate). Until the substrate 20 is dried by nitrogen, so that cyclohexane in the fourth mixture is completely volatilized. The surface of the substrate 20 can be formed a film 11 of dodecanoate-protected silver nanoparticles.
- the following step (g) of the method for forming a conductive film at room temperature according to the first embodiment of the present invention is to immerse the substrate 20 into an aqueous solution of hydrazine to chemically reduce the film 11 of silver nanoparticles into a conductive silver film 12 .
- the concentration of hydrazine of the aqueous solution of hydrazine is obviously higher than that used in the step (c); wherein the concentration of hydrazine of the aqueous solution of hydrazine in the step is between 70 and 90 wt %, for example, preferably 80 wt %.
- the present invention immerses the coated film 11 of silver nanoparticles of the step (f) into the aqueous solution of hydrazine (N 2 H 4 ) at room temperature of 25° C. for one hour, and then chemically reduce it to obtain a conductive silver film 12 . Finally, deionized water is used to wash the surface of the conductive silver film 12 and the surface is blown dried by nitrogen gas (or by wind).
- the hydrazine can reduce silver ions on the surface of the silver nanoparticles in the film 11 of the silver nanoparticles to the silver atoms in the metal state, and desorb dodecanoate from silver nanoparticles. After reducing and desorption, silver nanoparticles only contain silver atoms in the metal state, and closely attach and combine to the upper surface of the substrate 20 .
- the processes in the steps (a) to (g) are all performed at room temperature.
- the room temperature of the present invention refers to the range between 0 and 50° C., and preferably between 10 and 40° C. and especially between 20 and 30° C., such as 21, 23, 25, 27 or 29° C.
- the conductive silver film 12 formed by the steps (a) to (g) are specially suitable to be applied to the integrated circuit (IC) on a wafer, a circuit design of a transparent conductive layer of a thin film transistor liquid crystal display (TFT-LCD) or repair of fine-pitch tiny opening defects.
- TFT-LCD thin film transistor liquid crystal display
- the second embodiment comprises the following steps: (a) adding AgNO 3 into a non-polar solvent containing dodecanoic acid (C 11 H 23 COOH) to be a first mixture; (b) dropping n-butylamine into the first mixture as a ligand of silver ions of silver nitrate to be a second mixture; (c) dropping a diluted aqueous solution of hydrazine (N 2 H 4 .H 2 O) into the second mixture to be a third mixture, wherein the hydrazine reduces silver ion into silver nanoparticles and uses the dodecanoate group of dodecanoic acid as a capping ligand to be around and protect the silver nanoparticles; (d) separating the dodecano
- the difference is that: as shown in FIG. 3 , the step (f) of the second embodiment further uses the way of inkjet printing to replace that of spin-coating.
- the fourth mixture 10 is selected to be applied onto the upper surface of the substrate 20 by inkjet printing via an inkjet liquid distributor 40 ; wherein the substrate 20 is selected from the group consisting of a flexible plastic substrate, a glass substrate and a silicon wafer substrate and preferably selected from a flexible plastic substrate, for example, the substrate formed by polyethylene terephthalate (PET) of non-heat-resistant and low cost.
- PET polyethylene terephthalate
- the present invention adopts the fourth mixture 10 containing 10 wt % dodecanoate-protected silver nanoparticles (Ag—C 11 H 23 CO 2 ) to inkjet printing; wherein the substrate 20 is placed on the a work platform or a mobile platform, and then the upper surface of the substrate 20 is inkjet-printed by the inkjet liquid distributor 40 , so that the mixture 10 can be uniformly inkjet-printed on the substrate 20 (e.g., PET substrate).
- the substrate 20 e.g., PET substrate.
- the surface of the substrate 20 can be formed a film 13 of dodecanoate-protected silver nanoparticles, which can be the patterned shape of circuits.
- step (g) immerse the substrate 20 into the aqueous solution of hydrazine to reduce the film 13 of silver nanoparticles to the conductive silver film 14 .
- the steps (a) to (e) and (g) of the second embodiment are almost similar to the first embodiment, and therefore the description thereof is no longer to be repeated therein.
- the diluted aqueous solution of hydrazine in the step (c) of the first and second embodiments described above, can be replaced with the diluted aqueous solution of other reducing agents, such as diluted aqueous solution of ascorbic acid, NaBH 4 or dimethylformamide (DMF).
- the aqueous solution of the hydrazine in the step (g) can be replaced with the aqueous solution of other reducing agents, such as aqueous solution of ascorbic acid, NaBH 4 or dimethylformamide (DMF).
- the above agents are formulated into different concentrations of the reducing agents.
- the capabilities of electronic conduction of the silver conductive film are obtained by using various reducing agents, as shown in Table 1:
- Thickness Reductant Reaction time Resistivity ( ⁇ cm) (nm) 80 wt % Hydrazine 1 hr 4.80-9.90 60-250 1M ascorbic acid 1 hr 13.4-17.2 110-121 0.005M NaBH 4 1 min 91.2-112.9 175-240 50% DMF 2 hr 249.1-377.0 145-180
- the method can optionally further include a sub-step (g1): applying a heat-treatment to the conductive silver film at 100° C. for 1 hour to density the silver conductive film to enhance the conductivity of the film.
- the resistivity ( ⁇ cm) can be reduced from 4.80-9.90 ⁇ cm to 2.05-4.75 ⁇ cm.
- the method can optionally further include a step (h): repeating steps (f) and (g) to further stack and form another conductive silver film on the original conductive silver film to enhance the conductivity of the film by increasing the thickness and filling the holes of the first layer of conductive film.
- step (h) repeating steps (f) and (g) to further stack and form another conductive silver film on the original conductive silver film to enhance the conductivity of the film by increasing the thickness and filling the holes of the first layer of conductive film.
- the method can optionally further include a sub-step (h1): applying a heat-treatment to the conductive silver film at 100° C. for 1 hour to density the silver conductive film to enhance the conductivity of the film.
- 1-3 shows that firstly adding AgNO 3 into a solution of dodecanoic acid; sequentially dropping n-butylamine as a silver-ion ligand and a diluted aqueous solution of a reducing agent to reduce silver ions into silver nanoparticles to initially obtain dodecanoate-protected silver nanoparticles stably; then using cyclohexane as a long-term stabilizing solvent to spin-coat or print the dodecanoate-protected silver nanoparticles on the surface of the substrate to form a patterned silver nanoparticle film; finally immersing the substrate into a high concentrated aqueous solution of a reducing agent to chemically reduce the patterned film of silver nanoparticles into a conductive silver film.
- This method can not only be used to conveniently and rapidly print the patterned film or circuit on the substrate, but also significantly increase the application potential of silver nanoparticles on the flexible substrate (ie. PET substrate) which is non-heat-resistant and low cost.
- the present invention includes steps of: firstly using cyclohexane containing 0.5 wt % dodecanoic acid as a solvent to mix dodecanoate-protected silver nanoparticles into a long-term stabilizing preservation solvent (30-day preservation period) with 5.0 to 15.0 wt % silver nanoparticles, so that silver nanoparticles in the cyclohexane solution containing 0.5 wt % dodecanoic acid is unable to generate mutual aggregation and condensation, and the size uniformity of the nanoparticles can be kept. Therefore, it can improve the printing quality of silver nanoparticles applied to inkjet printing process.
Abstract
A method for forming a conductive film at room temperature is provided and includes steps of: adding AgNO3 into a first solution of dodecanoic acid; dropping n-butylamine and a diluted aqueous solution of a reducing agent into the first solution in turn, so as to initially obtain the dodecanoate-protected silver nanoparticles as a capping ligand; then using cyclohexane as a solvent to apply the silver nanoparticles onto a surface of a substrate to form a patterned film of silver nanoparticles; and finally immersing the substrate into a high concentrated aqueous solution of a reducing agent to chemically reduce the patterned film of silver nanoparticles into a conductive silver film. Thus, a patterned film or circuit can be conveniently and rapidly formed, and the silver nanoparticles can be applied to flexible substrates with low material cost and temperature sensitivity.
Description
- The present invention relates to a method for forming a conductive film at room temperature, and more particularly to a method using a reducing agent to chemically reduce a film of dodecanoate-protected silver nanoparticles pre-coated on the flexible substrate into a conductive silver film at room temperature.
- Low-cost liquid direct printing technology can be applied to a variety of patterned and deposition processes, such as processes of integrated circuits (IC), glass substrate circuits of large-size liquid crystal display (LCD), surface circuits of LED wafer, repair of IC open circuits, electronic tags or radio frequency identification (RFID), etc. Traditionally, plating and etching to form a conductive patterned circuit are generally done by lithography processes. However, due to the many complex steps required to construct a layer of circuit, it is relatively time-consuming and the manufacturing cost is higher. Therefore, for the related industry, it is necessary to simplify the process and reduce the manufacturing cost of the direct printing techniques, wherein the technique is to quickly convert the metal nanoparticles into the low-resistance metal conductor to form a conductive circuit after removing the solvent and heat treatment.
- Nowadays, one of the direct printing technologies is to firstly mix metal nanoparticles and a solvent as a printing ink, and then spray the printing ink onto a substrate to form a conductive circuit by an inkjet method, wherein the metal nanoparticles is preferably selected from silver. Silver is more suitable than gold for being used in this art, because silver is the metal having the highest conductivity among all the metals. And, gold has excessive material cost which affects its applicability in the field of electronics.
- For example, the inventors of the present patent previously disclosed a paper named “One-step synthesis of uniform silver nanoparticles capped by saturated decanoate: direct spray printing ink to form metallic silver films” published in the journal, Physical Chemistry Chemical Physics (2009, vol. 11, p. 6269-6275), on May 27, 2009, wherein it disclosed that the decanoate-protected silver nanoparticles (C9H19COO2—Ag) is used as a printing ink. However, the stability of the operation of the decanoate-protected silver nanoparticles at room temperature is only maintained for one day because of desorption by the carbon dioxide and other decomposition fragments. Therefore, there is a need to change other protective agents to stabilize the produced silver nanoparticles, or that will significantly affect the application of the silver nanoparticles in the direct printing technology. Furthermore, the decanoate-protected silver nanoparticles described above is coated on a rigid silicon substrate, and reduce the coating film of the silver nanoparticles into a high conductive silver film by using the high-temperature calcination above 150° C. However, the process of using high-temperature calcination also cannot be applied to the non-heat-resistant flexible plastic substrate and it takes longer process time. And, adding the hydrogen in the high temperature to process reduction reaction will increase the safety risk.
- It is therefore necessary to provide a method for forming a conductive film at room temperature to solve the problem of the conventional technology.
- A primary object of the present invention is to provide a method for forming a conductive film at room temperature, which includes steps of: firstly adding AgNO3 into a solution of dodecanoic acid; sequentially dropping n-butylamine as a silver-ion ligand and a diluted aqueous solution of a reducing agent to reduce silver ions into silver nanoparticles to initially obtain silver nanoparticles stably protected by dodecanoate as a capping ligand; then using cyclohexane as a long-term stabilizing solvent to spin-coat or print silver nanoparticles using dodecanoate as a capping ligand onto the surface of the substrate to form a patterned silver nanoparticle film; finally immersing the substrate into a high concentrated aqueous solution of a reducing agent to chemically reduce the patterned film of silver nanoparticles into a conductive silver film. This method can not only be used to conveniently and rapidly print the patterned film or circuit on the substrate, but also significantly increase the application potential of silver nanoparticles on the flexible substrate (i.e. PET substrate) which is non-heat-resistant and low cost.
- A secondary object of the present invention is to provide a method for forming a conductive film at room temperature, which includes steps of: firstly using cyclohexane containing 0.5 wt % dodecanoic acid as a solvent to mix with silver nanoparticles using dodecanoate as a capping ligand into a long-term stabilizing preservation solvent (30-day preservation period) with 5.0 to 15.0 wt % silver nanoparticles, so that silver nanoparticles in the cyclohexane solution containing 0.5 wt % dodecanoic acid is unable to generate mutual aggregation and condensation, and the size uniformity of the nanoparticles can be kept. Therefore, it can improve the printing quality of silver nanoparticles applied to inkjet printing process.
- To achieve the above object, the present invention provides a method for forming a conductive film at room temperature, which comprises following steps of:
-
- (a) adding AgNO3 into a non-polar solvent containing dodecanoic acid to be a first mixture;
- (b) dropping n-butylamine into the first mixture as a ligand of silver ions of silver nitrate to be a second mixture;
- (c) dropping a diluted aqueous solution of a reducing agent into the second mixture to be a third mixture, wherein the reducing agent reduces silver ion into silver nanoparticles and dodecanoate group of dodecanoic acid is used as a capping ligand to be around and protect the silver nanoparticles;
- (d) separating the dodecanoate-protected silver nanoparticles from the third mixture;
- (e) using cyclohexane as a solvent to mix with the dodecanoate-protected silver nanoparticles to be a fourth mixture;
- (f) applying the fourth mixture onto a surface of a substrate to form a film of the dodecanoate-protected silver nanoparticles; and
- (g) immersing the substrate into an aqueous solution of a reducing agent to chemically reduce the film of silver nanoparticles into a conductive silver film;
- wherein the processes in the steps (a) to (g) are all performed at room temperature.
- In one embodiment of the present invention, in the step (a), the molar ratio of the silver ions of AgNO3 and the dodecanoate group of dodecanoic acid is 1:2.
- In one embodiment of the present invention, in the step (a), the non-polar solvent is toluene.
- In one embodiment of the present invention, in the step (b), the molar ratio of the silver ions of AgNO3 and n-butylamine is 1:2.
- In one embodiment of the present invention, in the step (c), the diluted aqueous solution of the reducing agent is selected from a diluted aqueous solution of hydrazine, ascorbic acid, NaBH4 or dimethylformamide (DMF).
- In one embodiment of the present invention, in the step (c), the diluted aqueous solution of the reducing agent is the diluted aqueous solution of hydrazine, and the molar ratio of the silver ions of AgNO3 and hydrazine of the diluted aqueous solution of hydrazine is 2:1.
- In one embodiment of the present invention, in the step (c), the range of average particle diameter of the dodecanoate-protected silver nanoparticles is 6.20±0.57 nanometer (nm).
- In one embodiment of the present invention, in the step (d), firstly adding acetone into the third mixture to deposit the dodecanoate-protected silver nanoparticles, and then adopting methanol and acetone to wash, centrifuge and dry by reduced pressure condensation, in order to obtain the dodecanoate-protected silver nanoparticles.
- In one embodiment of the present invention, in the step (e), the fourth mixture is: firstly using cyclohexane containing 0.5 wt % dodecanoate acid as a solvent to mix with the silver nanoparticles in the step (d) into the fourth mixture which has 5.0 to 15.0 wt % silver nanoparticles, wherein the fourth mixture is a long-term stabilizing preservation solvent (30-day preservation period) preferably having 10.0 wt % silver nanoparticles.
- In one embodiment of the present invention, in the step (f), the fourth mixture is selected to be applied onto the surface of the substrate by spin-coating or inkjet printing.
- In one embodiment of the present invention, in the step (f), the substrate is selected from the group consisting of a flexible plastic substrate, a glass substrate and a silicon wafer substrate; wherein the flexible plastic substrate is a polyethylene terephthalate (PET) substrate.
- In one embodiment of the present invention, in the step (f), the aqueous solution of the reducing agent is selected from an aqueous solution of hydrazine, ascorbic acid, NaBH4 or dimethylformamide (DMF).
- In one embodiment of the present invention, in the step (f), the aqueous solution of the reducing agent is an aqueous solution of hydrazine, and the hydrazine concentration of the aqueous solution of hydrazine is between 70 and 90 wt %, such as 80 wt %.
- In one embodiment of the present invention, the processes in the steps (a) to (g) are all performed at room temperature in the range between 20 and 30° C., such as 25° C. In one embodiment of the present invention, after the step (g), the method further comprises: (g1) applying a heat-treatment to the conductive silver film at 100° C.
- In one embodiment of the present invention, after the step (g), the method further comprises: (h) repeating the steps (f) and (g) to further stack and form another conductive silver film on the original conductive silver film.
- In one embodiment of the present invention, after the step (h), the method further comprises: (h1) applying a heat-treatment to two of the stacked conductive silver films at 100° C.
-
FIG. 1 is a schematic diagram of steps (a) to (d) of a method for forming a conductive film at room temperature according to a first embodiment of the present invention; -
FIG. 2 is a schematic diagram of steps (e) to (g) of the method for forming the conductive film at room temperature according to the first embodiment of the present invention; and -
FIG. 3 is a schematic diagram of steps (e) to (g) of a method for forming a conductive film at room temperature according to a second embodiment of the present invention. - The structure and the technical means adopted by the present invention to achieve the above and other objects can be best understood by referring to the following detailed description of the preferred embodiments and the accompanying drawings. Furthermore, directional terms described by the present invention, such as upper, lower, front, back, left, right, inner, outer, side, longitudinal/vertical, transverse/horizontal, and etc., are only directions by referring to the accompanying drawings, and thus the used directional terms are used to describe and understand the present invention, but the present invention is not limited thereto.
- Please refer to
FIGS. 1 to 3 , a method for forming a conductive film at room temperature according to a first embodiment of the present invention mainly comprises the following steps: (a) adding AgNO3 into a non-polar solvent containing dodecanoic acid (C11H23COOH, also known as n-dodecanoic acid) to be a first mixture; (b) dropping n-butylamine into the first mixture as a ligand of silver ions of silver nitrate to be a second mixture; (c) dropping a diluted aqueous solution of hydrazine (N2H4.H2O) into the second mixture to be a third mixture, wherein the hydrazine reduces silver ion into silver nanoparticles (NPs) and the dodecanoate group of dodecanoic acid is used as a capping ligand to be around and protect the silver nanoparticles; (d) separating the dodecanoate-protected silver nanoparticles (Ag—C11H23CO2) from the third mixture; (e) using cyclohexane as a solvent to mix with the dodecanoate-protected silver nanoparticles to be a fourth mixture; (f) coating the fourth mixture onto a surface of a substrate by spin-coating to form a film of dodecanoate-protected silver nanoparticles; and (g) immersing the substrate into an aqueous solution of hydrazine to chemically reduce the silver nanoparticles into a conductive silver film; wherein the processes in the steps (a) to (g) are all performed at room temperature.FIGS. 1-3 of the present invention will be used to describe the implementation details and reaction principles of each step of the first and second embodiments. - Please refer to
FIG. 1 , the first step (a) of the method for forming a conductive film at room temperature according to the first embodiment of the present invention is to add AgNO3 into a non-polar solvent containing dodecanoic acid to be a first mixture. In the step, the present invention executes some sub-steps of: adopting 31.69 ml of toluene as a non-polar solvent and adding 3.3387 g (16.67 mmol) Idodecanoic acid into toluene; stirring it until it is dissolved, then adding 1.4156 g (8.33 mmol) of AgNO3, which contains 0.25 mol/L Ag+, wherein AgNO3 in the first mixture is used as a precursor of silver ions, and in the following step (c), dodecanoic acid in the first mixture will be used as a capping ligand of the silver nanoparticles. However, in the step, dodecanoic acid doesn't yet react with AgNO3. Furthermore, in the step (a), the molar ratio of the silver ions of AgNO3 and the dodecanoate group of dodecanoic acid substantially maintains at 1:2. The non-polar solvent preferably is selected from toluene, but it can still be selected from other similar non-polar solvents which have equivalent effect. - Please referring to
FIG. 1 , the following step (b) of the method for forming a conductive film at room temperature according to the first embodiment of the present invention is to drop n-butylamine into the first mixture as a ligand of silver ions of AgNO3 to be a second mixture. In the step, the present invention executes the way of dropping per second to add the 1.6473 ml (16.67 mmol) of n-butylamine. After finishing dropping within 2.5 minutes, the second mixture then continues to react for 3.5 minutes and it gradually turned milky turbid suspension in the process of n-butylamine is temporarily used as a ligand of silver ions to separate silver ions from AgNO3 firstly. And, the status of the milky turbid suspension shows that the second mixture includes the complex formed by coordinating silver ions and n-butylamine. In the step (b), the molar ratio of the silver ions of AgNO3 and n-butylamine substantially maintains at 1:2. - Please refer to
FIG. 1 , the following step (c) of the method for forming a conductive film at room temperature according to the first embodiment of the present invention is to drop a diluted aqueous solution of hydrazine (N2H4.H2O) into the second mixture to be a third mixture. In the step, the present invention executes the way of firstly adding 80 wt % a solution of hydrazine (N2H4.H2O) into 25 ml of a deionized water for diluting and mixing to be a diluted aqueous solution of hydrazine as a chemical redox fluid, which includes 0.2607 g (4.17 mmol) hydrazine. Then, until n-butylamine in the step (b) reacted for 3.5 minutes, executing the way of dropping per second to add the prepared diluted aqueous solution of hydrazine into the second mixture to be a third mixture. The titration takes 15 minutes. After that, the third mixture reacts again for 3 hours, wherein hydrazine reduces silver ions using n-butylamine as a temporary ligand into silver atoms in the metallic state. Silver atoms are further re-aggregated to be silver nanoparticles and the dodecanoate group of dodecanoic acid is used as a capping ligand to be around the silver nanoparticles. In the step (c), the molar ratio of the silver ions of AgNO3 and hydrazine of the diluted aqueous solution of hydrazine is 2:1. - In more detail, in step (c), silver ions using n-butylamine as a temporary ligand can be further reduced into silver atoms of the metallic state by hydrazine. And, a plurality of silver atoms of the metallic state is clustered with each other into nano-scale silver nanoparticles. After clustered, the average particle size of the silver nanoparticles is roughly in the range of 6.20±0.57 nm (nanometer), wherein each silver nanoparticles are actually formed by ten to hundreds of silver atoms clustered together. And, the outermost layer of the silver nanoparticles reacts with dodecanoate to form ionic complex; wherein the outermost layer of the silver atoms will transform into positively charged silver ions to bond with negative charge dodecanoate groups (as shown in the right-most side of
FIG. 1 ). The dodecanoate groups are used as capping ligands to be around and protect the silver nanoparticles (Ag—C11H23CO2) for avoiding the neighboring silver nanoparticles from clustering with each other again to enlarge the particle size, and further it can effectively restrict the number of silver atoms clustered inside the silver nanoparticles is no longer increased to stabilize the particle size of silver nanoparticles. The advantage of this is that the particle size of the silver nanoparticles can be controlled stably. It can effectively avoid the problem that when forming the patterned circuit in the following steps, the conductive quality of the circuit will be affected because of large conductive particles. - Please refer to
FIG. 1 , the following step (d) of the method for forming a conductive film at room temperature according to the first embodiment of the present invention is to separate the dodecanoate-protected silver nanoparticles (Ag—C11H23CO2) from the third mixture. In this step, when the reaction of hydrazine is finished, adding 200 ml of acetone into the third mixture to deposit the dodecanoate-protected silver nanoparticles, followed by using the solution of methanol and acetone to wash, centrifuge and dry by reduced pressure condensation, so that dark blue powder of dodecanoate-protected silver nanoparticles can be obtained. However, the separation method of the present invention is not limited thereto; the present invention can also use other existing separation techniques or other solvents to separate the dodecanoate-protected silver nanoparticles from the third mixture. - Please refer to
FIG. 2 , the following step (e) of the method for forming a conductive film at room temperature according to the first embodiment of the present invention is to use cyclohexane as a solvent to mix with the dodecanoate-protected silver nanoparticles to be afourth mixture 10. In the step, the present invention executes the way of firstly using cyclohexane containing 0.5 wt % dodecanoate as a solvent and adding silver nanoparticles of the step (d) into the solvent to mix to be afourth mixture 10 which has 5.0 to 15.0 wt % silver nanoparticles; wherein thefourth mixture 10 is a long-term stabilizing preservation suspension, which preferably has 10.0 wt % silver nanoparticles. Because thefourth mixture 10 contains 0.5 wt % dodecanoate and cyclohexane, it is benefit to stably preserve silver nanoparticles using dodecanoate as the capping ligand at least about 30 days or more. The dodecanoate-protected silver nanoparticles can be stably suspended in the cyclohexane solvent containing 0.5 wt % dodecanoate, and hence thefourth mixture 10 not only can be used for the storage backup purposes, but also can avoid the problem that silver nanoparticles further cluster to expand the particle diameter during the preservation. - Please refer to
FIG. 2 , the following step (f) of the method for forming a conductive film at room temperature according to the first embodiment of the present invention is to coat thefourth mixture 10 onto a surface of asubstrate 20 by spin coating to form afilm 11 of dodecanoate-protected silver nanoparticles. In the embodiment, thefourth mixture 10 is selected to be applied onto the upper surface of thesubstrate 20 by spin coating via a spin-coating liquid distributor 30; wherein thesubstrate 20 is selected from the group consisting of a flexible plastic substrate, a glass substrate and a silicon wafer substrate and preferably selected from a flexible plastic substrate, for example, the substrate made of polyethylene terephthalate (PET) of non-heat-resistant and low cost. In this step, the present invention adopts thefourth mixture 10 containing 10 wt % dodecanoate-protected silver nanoparticles (Ag—C11H23CO2) to execute spin coating wherein thesubstrate 20 is placed on the a turntable, and spin-coated for 15 seconds at 2000 round per minute, so that themixture 10 can be uniformly coated on the substrate 20 (e.g., PET substrate). Until thesubstrate 20 is dried by nitrogen, so that cyclohexane in the fourth mixture is completely volatilized. The surface of thesubstrate 20 can be formed afilm 11 of dodecanoate-protected silver nanoparticles. - Please refer to
FIG. 2 , the following step (g) of the method for forming a conductive film at room temperature according to the first embodiment of the present invention is to immerse thesubstrate 20 into an aqueous solution of hydrazine to chemically reduce thefilm 11 of silver nanoparticles into aconductive silver film 12. In the step, the concentration of hydrazine of the aqueous solution of hydrazine is obviously higher than that used in the step (c); wherein the concentration of hydrazine of the aqueous solution of hydrazine in the step is between 70 and 90 wt %, for example, preferably 80 wt %. In the embodiment, the present invention immerses thecoated film 11 of silver nanoparticles of the step (f) into the aqueous solution of hydrazine (N2H4) at room temperature of 25° C. for one hour, and then chemically reduce it to obtain aconductive silver film 12. Finally, deionized water is used to wash the surface of theconductive silver film 12 and the surface is blown dried by nitrogen gas (or by wind). In more detail, the hydrazine can reduce silver ions on the surface of the silver nanoparticles in thefilm 11 of the silver nanoparticles to the silver atoms in the metal state, and desorb dodecanoate from silver nanoparticles. After reducing and desorption, silver nanoparticles only contain silver atoms in the metal state, and closely attach and combine to the upper surface of thesubstrate 20. - It is worthy to note that the processes in the steps (a) to (g) are all performed at room temperature. The room temperature of the present invention refers to the range between 0 and 50° C., and preferably between 10 and 40° C. and especially between 20 and 30° C., such as 21, 23, 25, 27 or 29° C. Furthermore, the
conductive silver film 12 formed by the steps (a) to (g) are specially suitable to be applied to the integrated circuit (IC) on a wafer, a circuit design of a transparent conductive layer of a thin film transistor liquid crystal display (TFT-LCD) or repair of fine-pitch tiny opening defects. - Please refer to
FIG. 3 , the method for forming a conductive film at room temperature according to the second embodiment of the present invention is illustrated and similar to the first embodiment, so that the second embodiment uses similar terms or numerals of the first embodiment. However, compared with the first embodiment, the second embodiment comprises the following steps: (a) adding AgNO3 into a non-polar solvent containing dodecanoic acid (C11H23COOH) to be a first mixture; (b) dropping n-butylamine into the first mixture as a ligand of silver ions of silver nitrate to be a second mixture; (c) dropping a diluted aqueous solution of hydrazine (N2H4.H2O) into the second mixture to be a third mixture, wherein the hydrazine reduces silver ion into silver nanoparticles and uses the dodecanoate group of dodecanoic acid as a capping ligand to be around and protect the silver nanoparticles; (d) separating the dodecanoate-protected silver nanoparticles (Ag—C11H23CO2) from the third mixture; (e) using cyclohexane as a solvent to mix with the dodecanoate-protected silver nanoparticles to be a fourth mixture; (f) inkjet printing the fourth mixture onto a surface of a substrate to form a film of dodecanoate-protected silver nanoparticles; and (g) immersing the substrate into an aqueous solution of hydrazine to chemically reduce the silver nanoparticles into a conductive silver film; wherein the processes in the steps (a) to (g) are all performed at room temperature. - In the second embodiment of the present invention, the difference is that: as shown in
FIG. 3 , the step (f) of the second embodiment further uses the way of inkjet printing to replace that of spin-coating. In the second embodiment of the present invention, thefourth mixture 10 is selected to be applied onto the upper surface of thesubstrate 20 by inkjet printing via aninkjet liquid distributor 40; wherein thesubstrate 20 is selected from the group consisting of a flexible plastic substrate, a glass substrate and a silicon wafer substrate and preferably selected from a flexible plastic substrate, for example, the substrate formed by polyethylene terephthalate (PET) of non-heat-resistant and low cost. - In this step (f), the present invention adopts the
fourth mixture 10 containing 10 wt % dodecanoate-protected silver nanoparticles (Ag—C11H23CO2) to inkjet printing; wherein thesubstrate 20 is placed on the a work platform or a mobile platform, and then the upper surface of thesubstrate 20 is inkjet-printed by theinkjet liquid distributor 40, so that themixture 10 can be uniformly inkjet-printed on the substrate 20 (e.g., PET substrate). Until thesubstrate 20 is dried by nitrogen (or by wind) so that cyclohexane in thefourth mixture 10 is completely volatilized, the surface of thesubstrate 20 can be formed afilm 13 of dodecanoate-protected silver nanoparticles, which can be the patterned shape of circuits. In the following step (g), immerse thesubstrate 20 into the aqueous solution of hydrazine to reduce thefilm 13 of silver nanoparticles to theconductive silver film 14. The steps (a) to (e) and (g) of the second embodiment are almost similar to the first embodiment, and therefore the description thereof is no longer to be repeated therein. - On the other hand, according to other embodiments of the present invention, in the step (c) of the first and second embodiments described above, the diluted aqueous solution of hydrazine can be replaced with the diluted aqueous solution of other reducing agents, such as diluted aqueous solution of ascorbic acid, NaBH4 or dimethylformamide (DMF). Meanwhile, the aqueous solution of the hydrazine in the step (g) can be replaced with the aqueous solution of other reducing agents, such as aqueous solution of ascorbic acid, NaBH4 or dimethylformamide (DMF). The above agents are formulated into different concentrations of the reducing agents. The capabilities of electronic conduction of the silver conductive film are obtained by using various reducing agents, as shown in Table 1:
-
TABLE 1 Thickness Reductant Reaction time Resistivity (μΩcm) (nm) 80 wt % Hydrazine 1 hr 4.80-9.90 60-250 1M ascorbic acid 1 hr 13.4-17.2 110-121 0.005M NaBH4 1 min 91.2-112.9 175-240 50% DMF 2 hr 249.1-377.0 145-180 - In addition, after the step (g), the method can optionally further include a sub-step (g1): applying a heat-treatment to the conductive silver film at 100° C. for 1 hour to density the silver conductive film to enhance the conductivity of the film. For example, the resistivity (μΩcm) can be reduced from 4.80-9.90 μΩcm to 2.05-4.75 μΩcm.
- Furthermore, after the step (g) or (g1), the method can optionally further include a step (h): repeating steps (f) and (g) to further stack and form another conductive silver film on the original conductive silver film to enhance the conductivity of the film by increasing the thickness and filling the holes of the first layer of conductive film. And, the results are shown in Table 2 as follows:
-
TABLE 2 Reductant Reaction Resistivity of two layer Thickness of two (In the step time in of conductivity Ag film layer of conductivity h) the step h (μΩcm) Ag film (nm) 80 wt % 1 hr 3.23-4.62 183-349 Hydrazine 1M ascorbic 1 hr 4.34-5.95 203-278 acid 0.005M 1 min 6.50-10.9 181-256 NaBH4 50% DMF 2 hr 52.3-78.3 165-237 - Similarly, after the step (h), the method can optionally further include a sub-step (h1): applying a heat-treatment to the conductive silver film at 100° C. for 1 hour to density the silver conductive film to enhance the conductivity of the film.
- As described above, compared with the conditional method of forming a conductive film using decanoate-protected silver nanoparticles at room temperature, the stability of nanoparticles is poor, and high temperature calcination over 150° C. is adopted to reduce the coated film of silver nanoparticles on the rigid silicon substrate to high conductive silver film, and it is not suitable to the flexible plastic substrate of non-heat-resistance and has the shortcomings of the process time-consuming and high safety risk.
FIG. 1-3 according the present invention shows that firstly adding AgNO3 into a solution of dodecanoic acid; sequentially dropping n-butylamine as a silver-ion ligand and a diluted aqueous solution of a reducing agent to reduce silver ions into silver nanoparticles to initially obtain dodecanoate-protected silver nanoparticles stably; then using cyclohexane as a long-term stabilizing solvent to spin-coat or print the dodecanoate-protected silver nanoparticles on the surface of the substrate to form a patterned silver nanoparticle film; finally immersing the substrate into a high concentrated aqueous solution of a reducing agent to chemically reduce the patterned film of silver nanoparticles into a conductive silver film. This method can not only be used to conveniently and rapidly print the patterned film or circuit on the substrate, but also significantly increase the application potential of silver nanoparticles on the flexible substrate (ie. PET substrate) which is non-heat-resistant and low cost. - Furthermore, the present invention includes steps of: firstly using cyclohexane containing 0.5 wt % dodecanoic acid as a solvent to mix dodecanoate-protected silver nanoparticles into a long-term stabilizing preservation solvent (30-day preservation period) with 5.0 to 15.0 wt % silver nanoparticles, so that silver nanoparticles in the cyclohexane solution containing 0.5 wt % dodecanoic acid is unable to generate mutual aggregation and condensation, and the size uniformity of the nanoparticles can be kept. Therefore, it can improve the printing quality of silver nanoparticles applied to inkjet printing process.
- The present invention has been described with a preferred embodiment thereof and it is understood that many changes and modifications to the described embodiment can be carried out without departing from the scope and the spirit of the invention that is intended to be limited only by the appended claims.
Claims (18)
1. A method for forming a conductive film at room temperature, comprising:
(a) adding AgNO3 into a non-polar solvent containing dodecanoic acid to be a first mixture;
(b) dropping n-butylamine into the first mixture as a ligand of silver ions of silver nitrate to be a second mixture;
(c) dropping a diluted aqueous solution of a reducing agent into the second mixture to be a third mixture, wherein the reducing agent reduces silver ion into silver nanoparticles and dodecanoate group of dodecanoic acid is used as a capping ligand to be around and protect the silver nanoparticles;
(d) separating the silver nanoparticles using dodecanoate as the capping ligand from the third mixture;
(e) using cyclohexane as a solvent to mix with silver nanoparticles using dodecanoate as the capping ligand to be a fourth mixture;
(f) applying the fourth mixture onto a surface of a substrate to form a film of silver nanoparticles using dodecanoate as the capping ligand; and
(g) immersing the substrate into an aqueous solution of a reducing agent to chemically reduce the film of silver nanoparticles into a conductive silver film;
wherein the processes in the steps (a) to (g) are all performed at room temperature.
2. The method for forming a conductive film at room temperature according claim 1 , wherein in the step (a), the molar ratio of the silver ions of AgNO3 and the dodecanoate group of dodecanoic acid is 1:2.
3. The method for forming a conductive film at room temperature according claim 1 , wherein in the step (a), the non-polar solvent is toluene.
4. The method for forming a conductive film at room temperature according claim 1 , wherein in the step (b), the molar ratio of the silver ions of AgNO3 and n-butylamine is 1:2.
5. The method for forming a conductive film at room temperature according to claim 1 , wherein in the step (c), the diluted aqueous solution of the reducing agent is selected from a diluted aqueous solution of hydrazine, ascorbic acid, NaBH4 or dimethylformamide (DMF).
6. The method for forming a conductive film at room temperature according to claim 5 , wherein in the step (c), the diluted aqueous solution of the reducing agent is the diluted aqueous solution of hydrazine, and the molar ratio of the silver ions of AgNO3 and hydrazine of the diluted aqueous solution of hydrazine is 2:1.
7. The method for forming a conductive film at room temperature according ti claim 1 , wherein in the step (c), the range of average particle diameter of the dodecanoate-protected silver nanoparticles is 6.20±0.57 nm.
8. The method for forming a conductive film at room temperature according to claim 1 , wherein in the step (d), firstly adding acetone into the third mixture to deposit the dodecanoate-protected silver nanoparticles as the capping ligand, and then adopting methanol and acetone to wash, centrifuge and dry by reduced pressure condensation, in order to obtain the dodecanoate-protected silver nanoparticles.
9. The method for forming a conductive film at room temperature according to claim 1 , wherein in the step (e), the fourth mixture is treated by firstly using cyclohexane containing 0.5 wt % dodecanoate acid as a solvent to mix silver nanoparticles in the step (d) into the fourth mixture which has 5.0 to 15.0 wt % silver nanoparticles.
10. The method for forming a conductive film at room temperature according to claim 1 , wherein in the step (f), the fourth mixture is selected to apply onto the surface of the substrate by spin-coating or inkjet printing.
11. The method for forming a conductive film at room temperature according to claim 1 , wherein in the step (f), the substrate is selected from the group consisting of a flexible plastic substrate, a glass substrate and a silicon wafer substrate.
12. The method for forming a conductive film at room temperature according to claim 11 , wherein the flexible plastic substrate is a polyethylene terephthalate substrate.
13. The method for forming a conductive film at room temperature according to claim 1 , wherein in the step (f), the aqueous solution of the reducing agent is selected from an aqueous solution of hydrazine, ascorbic acid, NaBH4 or dimethylformamide (DMF).
14. The method for forming a conductive film at room temperature according to claim 13 , wherein in the step (f), the aqueous solution of the reducing agent is an aqueous solution of hydrazine, and the hydrazine concentration of the aqueous solution of hydrazine is between 70 and 90 wt %.
15. The method for forming a conductive film at room temperature according to claim 1 , wherein the processes in the steps (a) to (g) are all performed at room temperature in the range between 20 and 30° C.
16. The method for forming a conductive film at room temperature according to claim 1 , wherein after the step (g), the method further comprises:
(g1) applying a heat-treatment to the conductive silver film at 100° C.
17. The method for forming a conductive film at room temperature according to claim 1 , wherein after the step (g), the method further comprises:
(h) repeating the steps (f) and (g) to further stack and form another conductive silver film on the original conductive silver film.
18. The method for forming a conductive film at room temperature according to claim 17 , wherein after the step (h), the method further comprises:
(h1) applying a heat-treatment to two of the stacked conductive silver film at 100° C.
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