CN101804458A - 经有机胺稳定的银纳米颗粒及其制备方法 - Google Patents
经有机胺稳定的银纳米颗粒及其制备方法 Download PDFInfo
- Publication number
- CN101804458A CN101804458A CN201010115500A CN201010115500A CN101804458A CN 101804458 A CN101804458 A CN 101804458A CN 201010115500 A CN201010115500 A CN 201010115500A CN 201010115500 A CN201010115500 A CN 201010115500A CN 101804458 A CN101804458 A CN 101804458A
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- Prior art keywords
- silver
- organic amine
- described solution
- solution
- organic
- Prior art date
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- 150000001412 amines Chemical class 0.000 title claims abstract description 57
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 38
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000002245 particle Substances 0.000 claims abstract description 25
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000003960 organic solvent Substances 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 51
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 43
- 229910052709 silver Inorganic materials 0.000 claims description 43
- 239000004332 silver Substances 0.000 claims description 42
- 239000002904 solvent Substances 0.000 claims description 13
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 239000000243 solution Substances 0.000 description 63
- 239000002105 nanoparticle Substances 0.000 description 34
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 29
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 27
- 239000004065 semiconductor Substances 0.000 description 15
- 239000000203 mixture Substances 0.000 description 12
- 239000011159 matrix material Substances 0.000 description 11
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 239000010409 thin film Substances 0.000 description 10
- FJLUATLTXUNBOT-UHFFFAOYSA-N 1-Hexadecylamine Chemical compound CCCCCCCCCCCCCCCCN FJLUATLTXUNBOT-UHFFFAOYSA-N 0.000 description 8
- 238000009826 distribution Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 230000004888 barrier function Effects 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 238000000151 deposition Methods 0.000 description 6
- 239000010408 film Substances 0.000 description 6
- 238000009413 insulation Methods 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 238000006722 reduction reaction Methods 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 4
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 229940071536 silver acetate Drugs 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- ZXSQEZNORDWBGZ-UHFFFAOYSA-N 1,3-dihydropyrrolo[2,3-b]pyridin-2-one Chemical compound C1=CN=C2NC(=O)CC2=C1 ZXSQEZNORDWBGZ-UHFFFAOYSA-N 0.000 description 2
- JPZYXGPCHFZBHO-UHFFFAOYSA-N 1-aminopentadecane Chemical compound CCCCCCCCCCCCCCCN JPZYXGPCHFZBHO-UHFFFAOYSA-N 0.000 description 2
- JKFYKCYQEWQPTM-UHFFFAOYSA-N 2-azaniumyl-2-(4-fluorophenyl)acetate Chemical compound OC(=O)C(N)C1=CC=C(F)C=C1 JKFYKCYQEWQPTM-UHFFFAOYSA-N 0.000 description 2
- OQXSRALAOPBHPM-UHFFFAOYSA-N 2-hydroxypropanoic acid;silver Chemical compound [Ag].CC(O)C(O)=O OQXSRALAOPBHPM-UHFFFAOYSA-N 0.000 description 2
- RBWNDBNSJFCLBZ-UHFFFAOYSA-N 7-methyl-5,6,7,8-tetrahydro-3h-[1]benzothiolo[2,3-d]pyrimidine-4-thione Chemical compound N1=CNC(=S)C2=C1SC1=C2CCC(C)C1 RBWNDBNSJFCLBZ-UHFFFAOYSA-N 0.000 description 2
- 229910017944 Ag—Cu Inorganic materials 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- 229920000544 Gore-Tex Polymers 0.000 description 2
- -1 Merlon Polymers 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- 229910021612 Silver iodide Inorganic materials 0.000 description 2
- PLZVEHJLHYMBBY-UHFFFAOYSA-N Tetradecylamine Chemical compound CCCCCCCCCCCCCCN PLZVEHJLHYMBBY-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 229910052946 acanthite Inorganic materials 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 2
- 229910002113 barium titanate Inorganic materials 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000012937 correction Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- TZMFJUDUGYTVRY-UHFFFAOYSA-N ethyl methyl diketone Natural products CCC(=O)C(C)=O TZMFJUDUGYTVRY-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000003808 methanol extraction Methods 0.000 description 2
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- 239000003607 modifier Substances 0.000 description 2
- GVWISOJSERXQBM-UHFFFAOYSA-N n-methylpropan-1-amine Chemical compound CCCNC GVWISOJSERXQBM-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- FJDUDHYHRVPMJZ-UHFFFAOYSA-N nonan-1-amine Chemical compound CCCCCCCCCN FJDUDHYHRVPMJZ-UHFFFAOYSA-N 0.000 description 2
- 229910052755 nonmetal Inorganic materials 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- DPBLXKKOBLCELK-UHFFFAOYSA-N pentan-1-amine Chemical compound CCCCCN DPBLXKKOBLCELK-UHFFFAOYSA-N 0.000 description 2
- HKOOXMFOFWEVGF-UHFFFAOYSA-N phenylhydrazine Chemical compound NNC1=CC=CC=C1 HKOOXMFOFWEVGF-UHFFFAOYSA-N 0.000 description 2
- 229940067157 phenylhydrazine Drugs 0.000 description 2
- 150000004031 phenylhydrazines Chemical class 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 238000004080 punching Methods 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- XQLMNMQWVCXIKR-UHFFFAOYSA-M silver bromate Chemical compound [Ag+].[O-]Br(=O)=O XQLMNMQWVCXIKR-UHFFFAOYSA-M 0.000 description 2
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 2
- 229910001958 silver carbonate Inorganic materials 0.000 description 2
- LKZMBDSASOBTPN-UHFFFAOYSA-L silver carbonate Substances [Ag].[O-]C([O-])=O LKZMBDSASOBTPN-UHFFFAOYSA-L 0.000 description 2
- SDLBJIZEEMKQKY-UHFFFAOYSA-M silver chlorate Chemical compound [Ag+].[O-]Cl(=O)=O SDLBJIZEEMKQKY-UHFFFAOYSA-M 0.000 description 2
- 229940071575 silver citrate Drugs 0.000 description 2
- 229940096017 silver fluoride Drugs 0.000 description 2
- YSVXTGDPTJIEIX-UHFFFAOYSA-M silver iodate Chemical compound [Ag+].[O-]I(=O)=O YSVXTGDPTJIEIX-UHFFFAOYSA-M 0.000 description 2
- 229940045105 silver iodide Drugs 0.000 description 2
- REYHXKZHIMGNSE-UHFFFAOYSA-M silver monofluoride Chemical compound [F-].[Ag+] REYHXKZHIMGNSE-UHFFFAOYSA-M 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- KKKDGYXNGYJJRX-UHFFFAOYSA-M silver nitrite Chemical compound [Ag+].[O-]N=O KKKDGYXNGYJJRX-UHFFFAOYSA-M 0.000 description 2
- 229910001923 silver oxide Inorganic materials 0.000 description 2
- FJOLTQXXWSRAIX-UHFFFAOYSA-K silver phosphate Chemical compound [Ag+].[Ag+].[Ag+].[O-]P([O-])([O-])=O FJOLTQXXWSRAIX-UHFFFAOYSA-K 0.000 description 2
- YPNVIBVEFVRZPJ-UHFFFAOYSA-L silver sulfate Chemical compound [Ag+].[Ag+].[O-]S([O-])(=O)=O YPNVIBVEFVRZPJ-UHFFFAOYSA-L 0.000 description 2
- 229910000367 silver sulfate Inorganic materials 0.000 description 2
- 229940056910 silver sulfide Drugs 0.000 description 2
- XUARKZBEFFVFRG-UHFFFAOYSA-N silver sulfide Chemical compound [S-2].[Ag+].[Ag+] XUARKZBEFFVFRG-UHFFFAOYSA-N 0.000 description 2
- ZYXPMOIHQRKWGT-UHFFFAOYSA-N silver;2,2,2-trifluoroacetic acid Chemical compound [Ag].OC(=O)C(F)(F)F ZYXPMOIHQRKWGT-UHFFFAOYSA-N 0.000 description 2
- CLDWGXZGFUNWKB-UHFFFAOYSA-M silver;benzoate Chemical compound [Ag+].[O-]C(=O)C1=CC=CC=C1 CLDWGXZGFUNWKB-UHFFFAOYSA-M 0.000 description 2
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- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 1
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Abstract
公开了制备经有机胺稳定的银纳米颗粒的方法。所述方法包含:(a)形成一种包含一种有机溶剂和一种第一物量的有机胺的溶液;(b)向所述溶液中加入银盐颗粒;(c)向所述溶液中加入一种第二物量的有机胺;(d)向所述溶液中加入一种有机肼;和(e)使所述溶液反应以形成经有机胺稳定的银纳米颗粒。
Description
技术领域
本发明涉及稳定的高性能纳米颗粒组合物以及制备和/或使用所述组合物的方法和设备。
背景技术
使用液相沉积技术制作电子电路元件可能是有利的,因为这种技术为电子应用如薄膜晶体管(TFT)、发光二级管(LED)、RFID标签、光电器件等提供了常规主流非晶硅技术的潜在低成本替代物。然而,满足导电性、加工和成本的实际应用要求的功能电极、像素垫圈(pixel pad)和导电线路(trace)、导电路线(line)和导电通道(track)的沉积和/或布图已成为一个极大挑战。金属银(Ag)作为电子设备的导电元件引起了特别关注,因为银比金(Au)的成本低很多且其具有比铜(Cu)好很多的环境稳定性。
现有的实验室级制备银纳米颗粒的方法使用了多个步骤,并且费力费时。结果不可重现或不易放大以用于大规模生产。另外,所得的产品通常呈现为粘性糊状物,带来处理问题。还有,最终产品储存期限较短且纯度较低。
因此,迫切需要制备适用于制作电子设备的导电性元件的、适于液体加工且稳定的含银纳米颗粒组合物的较低成本方法,本公开的实施方案可满足这样的需要。
发明内容
本申请在多个示例性实施方案中公开了制备含银纳米颗粒组合物的方法以及由此制备的组合物。也公开了使用所述纳米颗粒组合物的设备,如薄膜晶体管。
实施方案中公开了一种制备经有机胺稳定的银纳米颗粒的方法,该方法包含:形成一种包含一种有机溶剂和一种第一物量的有机胺的热溶液;向所述溶液中加入银盐颗粒;向所述溶液中加入一种第二物量的有机胺;向所述溶液中加入有机肼;和使所述溶液反应以形成经有机胺稳定的银纳米颗粒。
所述银盐可选自乙酸银、硝酸银、氧化银、乙酰基丙酮酸银、苯甲酸银、溴酸银、溴化银、碳酸银、氯化银、柠檬酸银、氟化银、碘酸银、碘化银、乳酸银、亚硝酸银、高氯酸银、磷酸银、硫酸银、硫化银和三氟乙酸银。
所述有机溶剂可选自甲苯、庚烷、己烷、苯、环己烷、戊烷、溴苯、氯苯和烃类。
银盐与总的有机胺的摩尔比可以是从约1至约15。
所述溶液可被加热至从约50℃至约80℃的第一温度。所述溶液可在加入第二物量的有机胺之后冷却。所述溶液可冷却约30分钟或更长的时间。所述溶液可冷却至从约45℃至约60℃的温度。
有机溶剂与所述第一物量的有机胺的重量比可以为约1∶1。所述第一物量的有机胺与所述第二有机物量的有机胺的重量比可以为约1∶1。
所述有机肼可以具有式:
R6R7N-NR8R9
其中R6、R7、R8和R9独立地选自氢、烷基和芳基;且其中R6、R7、R8和R9中的至少一个可以不是氢。
生成的纳米颗粒可具有从约2纳米至约8纳米的平均直径,和/或约10纳米的颗粒大小分布。生成的纳米颗粒也可具有80%或更高的银含量。
所述方法还可包含:通过向所述溶液中加入异丙醇和一种非溶剂从所述溶液中分离所述银纳米颗粒;和洗涤所述银纳米颗粒。
所述非溶剂可包括丙酮、甲醇、乙醇、丙醇、甲基乙基酮、乙腈、异丁醇和它们的结合物。异丙醇与非溶剂的体积比可以为约0.4。
实施方案中还公开了一种制备经有机胺稳定的银纳米颗粒的方法,该方法包含:形成一种包含一种有机溶剂和一种第一物量的有机胺并具有第一温度的溶液;向所述溶液中加入银盐颗粒;向所述溶液中加入一种第二物量的有机胺;将所述溶液冷却至第二温度;向所述溶液中加入一种有机肼;使所述溶液反应以形成经有机胺稳定的银纳米颗粒;将所述溶液冷却至第三温度;向所述溶液中加入异丙醇;向所述溶液中加入一种非溶剂以从所述溶液中分离所述银纳米颗粒;和洗涤所述银纳米颗粒。
本申请公开的这些和其他非限制性特征更具体地公开于下文。
附图说明
下面是附图的简要说明,提供附图是为了示例说明而非限制本文所公开的示例性实施方案。
图1表示一种含本申请公开的纳米颗粒的薄膜晶体管的第一个实施方案。
图2表示一种含本申请公开的纳米颗粒的薄膜晶体管的第二个实施方案。
图3表示一种含本申请公开的纳米颗粒的薄膜晶体管的第三个实施方案。
图4表示一种含本申请公开的纳米颗粒的薄膜晶体管的第四个实施方案。
图5是一幅示出根据现有方法形成的纳米颗粒的颗粒大小和分布的图示。
图6是第一幅示出根据本申请公开的方法形成的纳米颗粒的颗粒大小和分布的图示。
图7是第二幅示出根据本申请公开的方法形成的纳米颗粒的颗粒大小和分布的图示。
具体实施方式
通过参照附图可更充分理解本文公开的组件、方法和装置。这些图示仅是出于方便以及易于说明本申请公开内容的示意图,因此并非意欲标示所述设备或其组件的相对大小和尺寸和/或限定或限制所示例的实施方案的范围。
尽管为清楚起见而在下面的描述中使用了专有术语,但这些术语仅是意在涉及附图中为示例说明而选择的实施方案的具体结构,并非意欲限定或限制本申请公开内容的范围。在附图和下面的描述中,应理解类似的数字名称是指类似功能的组件。
在“含银纳米颗粒”中所使用的术语“纳米”是指低于约1000nm的颗粒大小。在实施方案中,所述含银纳米颗粒具有从约0.5nm至约1000nm、从约1nm至约500nm、从约1nm至约100nm、以及特别是从约1nm至约20nm的颗粒大小。所述颗粒大小在本文中定义为所述含银颗粒的平均直径,用TEM(透射电子显微镜)测得。
与数量结合使用的修饰语“约”包括所述值并具有上下文指定的含义(例如,其至少包括与具体数量测量相关的误差程度)。当用于范围情况下时,修饰语“约”也应被认为是公开了由两个端点的绝对值限定的范围。例如,范围“从约2至约4”也公开了范围“从2至4”。
本申请公开的方法可制备经有机胺稳定的银纳米颗粒。所述方法包含:(a)形成一种包含一种有机溶剂和一种第一物量的有机胺的溶液;(b)向所述溶液中加入银盐颗粒;(c)向所述溶液中加入一种第二物量的有机胺;(d)向所述溶液中加入一种有机肼;和(e)使所述溶液反应以形成经有机胺稳定的银纳米颗粒。
所述有机胺可以是伯胺、仲胺或叔胺。示例性有机胺包括丙胺、丁胺、戊胺、己胺、庚胺、辛胺、壬胺、癸胺、十一胺、十二胺、十三胺、十四胺、十五胺、十六胺、十七胺、十八胺、N,N-二甲胺、N,N-二丙胺、N,N-二丁胺、N,N-二戊胺、N,N-二己胺、N,N-二庚胺、N,N-二辛胺、N,N-二壬胺、N,N-二癸胺、N,N-双十一基胺、N,N-双十二基胺、甲基丙胺、乙基丙胺、丙基丁胺、乙基丁胺、乙基戊胺、丙基戊胺、丁基戊胺、三乙胺、三丙胺、三丁胺、三戊胺、三己胺、三庚胺、三辛胺、1,2-乙二胺、N,N,N’,N’-四甲基乙二胺、丙-1,3-二胺、N,N,N’,N’-四甲基丙-1,3-二胺、丁-1,4-二胺、和N,N,N’,N’-四甲基丁-1,4-二胺等,或它们的混合物。在具体实施方案中,所述银纳米颗粒用十二胺、十三胺、十四胺、十五胺或十六胺稳定。
所述有机胺在两个步骤中加入。第一物量的有机胺在加入所述银盐颗粒之前就存在于所述溶液中,第二物量的有机胺在加入所述银盐颗粒之后加入所述溶液中。有机溶剂与第一物量的有机胺的重量比可以为约1∶1。第一物量的有机胺与第二物量的有机胺的重量比可以是约1∶1。
包含所述有机溶剂和所述第一物量的有机胺的溶液处于第一升高的温度下。所述第一升高的温度可以为从约50℃至约80℃。所述溶液通常维持在大气压力下,所述溶液也可被搅动(例如,搅拌)。所述溶液应被置于一个惰性环境层(例如氮气或氩气)中。
然后向该热溶液中加入银盐颗粒。示例性银盐包括乙酸银、硝酸银、氧化银、乙酰基丙酮酸银、苯甲酸银、溴酸银、溴化银、碳酸银、氯化银、柠檬酸银、氟化银、碘酸银、碘化银、乳酸银、亚硝酸银、高氯酸银、磷酸银、硫酸银、硫化银和三氟乙酸银。理想的银盐颗粒是细小的以均匀分散在所述溶液中,这有助于高效反应。银盐颗粒通常可迅速加入,因为其会快速溶解。
然后向所述溶液中加入第二物量的有机胺。银盐与加入的总有机胺的摩尔比可以为从约1至约15。可在加入第二物量的有机胺之后冷却所述溶液。所述溶液可被冷却约30分钟或更长的时间,如约45分钟。所述溶液可被冷却至从约45℃至约60℃的较低第二温度。发现该加入有机胺的两步法使得银盐颗粒可一致重现地溶解在所述溶液中,得到更高品质的银纳米颗粒。
接下来向所述溶液中加入一种有机肼。所述有机肼具有式:
R1R2N-NR3R4
其中R1、R2、R3和R4独立地选自氢、烷基和芳基;且其中R1、R2、R3和R4中的至少一个不是氢。在更具体的实施方案中,所述有机肼具有式R1R2N-NH2。示例性有机肼包括苯肼。
然后使包含银盐颗粒、有机胺和有机肼的溶液反应以形成经有机胺稳定的银纳米颗粒。所述反应可进行约5分钟至约2小时。在该反应期间也可混合或搅拌所述溶液。通常,在该反应期间所述溶液被维持在第二温度下。
生成的纳米颗粒具有10纳米或更小的平均直径。在更具体的实施方案中,所述纳米颗粒具有从约1纳米至约10纳米、包括从约2纳米至约8纳米的平均直径。在其他实施方案中,所述纳米颗粒也可具有约10纳米的较窄颗粒大小分布(即最大纳米颗粒的直径与最小纳米颗粒的直径之间的差值)。
所述纳米颗粒可具有80%或更高、包括从80%至约90%的银含量。该含量比通过常规方法制备的高。
然后可从所述溶液中分离经有机胺稳定的银纳米颗粒。所述溶液可被冷却至第三较低的温度,如从约35℃至约50℃。通过沉淀所述纳米颗粒而分离所述纳米颗粒。然后可洗涤所述银纳米颗粒。发现向所述溶液中加入异丙醇,接着加入第二非溶剂——即一种所述纳米颗粒不溶于其中的液体——改进了经有机胺稳定的银纳米颗粒的储存期限和纯度。示例性第二非溶剂包括丙酮、甲醇、乙醇、丙醇、甲基乙基酮、乙腈、异丁醇、其他酮和醇,以及它们的结合物。一种优选的非溶剂为甲醇。异丙醇与非溶剂的理想体积比为约0.4。
本申请公开的方法提供了经有机胺稳定的银纳米颗粒。生成的纳米颗粒也是纯的、粉末形式、易于分散的,并具有提高的储存期限和稳定性。因为所述纳米颗粒不是糊状物形式,所以它们不粘、更易处理且分散更均匀。此外,所述方法相对于现有方法可更一致地再现和放大。
在实施方案中,所述含银纳米颗粒由元素银或银复合物构成。除了银,所述银复合物可包括(i)一种或多种其他金属或者(ii)一种或多种非金属,或包括二者。合适的其他金属包括例如Al、Au、Pt、Pd、Cu、Co、Cr、In和Ni,特别是过渡金属例如Au、Pt、Pd、Cu、Cr、Ni,以及它们的混合物。示例性金属复合物有Au-Ag、Ag-Cu、Au-Ag-Cu和Au-Ag-Pd。所述金属复合物中合适的非金属包括例如Si、C和Ge。所述银复合物中的各种成分可以以例如从约0.01重量%至约99.9重量%,特别是从约10重量%至约90重量%的量存在。在实施方案中,所述银复合物是一种由银和一种、两种或多种其他金属构成的金属合金,所述银构成例如纳米颗粒的至少约20重量%、特别是大于纳米颗粒的约50重量%。
在实施方案中,还可以进行银纳米颗粒(用羧酸在其表面上)的加工,例如用液相沉积技术使它们相容(例如,用于制作一个电子设备)。这种对组合物的另外加工可以是,例如将所述含银纳米颗粒溶解或分散于合适的液体中。
由所述银纳米颗粒制作导电元件可以在实施方案中使用任何合适的液相沉积技术进行,包括i)印刷如丝网/模版印刷、冲压、微接触印刷、喷墨印刷等,和ii)涂布如旋涂、浸渍涂布、刮涂、浇铸、浸渍等。在该阶段沉积的银纳米颗粒可以具有或不具有导电性。
在低于约300℃、优选在或低于约250℃的温度下加热所沉积的纳米颗粒会使它们结合以形成适用作电子设备中的导电元件的导电层。所述加热进行例如从约一分钟至约10小时,特别是从约5分钟至约1小时。所述加热可在从约100℃至约300℃的温度下进行。在更具体的实施方案中,所述加热在从约120℃至约200℃、或从约170℃至约190℃的温度下进行。
通过加热所沉积的银纳米颗粒而制备的所得含银元件的导电率为,例如至少1000S/cm。在其他实施方案中,用四探针方法测得的导电率至少为10000S/cm。
生成的导电元件可用作电子设备中的导电电极、导电垫圈、导电路线、导电通道(track)等,所述电子设备如薄膜晶体管、有机发光二极管、RFID(射频辨识)标签、光电器件和需要导电元件或组件的其他电子设备。
在图1中,图示说明了一种薄膜晶体管(″TFT″)构造10,其由一个既作为基质又作为栅极的n型重掺杂的(heavily n-doped)硅片18和一个热生长氧化硅绝缘介电层14构成,在所述介电层14上沉积有两个金属接触点——源极20和漏极22。如本文说明的,在所述金属接触点20和22之上以及之间是一个半导体层12。
图2图示说明了另一种TFT构造30,其由一个基质36、一个栅极38、一个源极40和一个漏极42、一个绝缘介电层34和一个半导体层32构成。
图3图示说明了又一种TFT构造50,其由一个既作为基质又作为栅极的n型重掺杂的硅片56,一个热生长氧化硅绝缘介电层54和一个半导体层52构成,在所述半导体层52上沉积有一个源极60和一个漏极62。
图4图示说明了另一种TFT构造70,其由一个基质76、一个栅极78、一个源极80、一个漏极82、一个半导体层72和一个绝缘介电层74构成。
所述基质可以由例如硅、玻璃板、塑料膜或塑料片构成。对于结构柔性设备,可使用塑料基质,例如聚酯、聚碳酸酯、聚酰亚胺片等。基质厚度可以为从约10微米至超过10毫米,一个示例性厚度尤其是对于柔性塑料基质为从约50微米至约2毫米,对于刚性基质如玻璃或硅为从约0.4至约10毫米。
所述栅极、源极和漏极通过本申请公开的实施方案制作。所述栅极层的厚度例如在从约10至约2000nm范围变化。源极和漏极的厚度通常为例如从约40nm至约1微米,更具体的厚度为约60至约400nm。
所述绝缘介电层通常可以是一种无机材料膜或一种有机材料膜。适用作绝缘层的无机材料的示例性实例包括氧化硅、氮化硅、氧化铝、钛酸钡、钛酸钡锆(barium zirconium titanate)等;用于绝缘层的有机聚合物的示例性实例包括聚酯、聚碳酸酯、聚(乙烯基苯酚)、聚酰亚胺、聚苯乙烯、聚(甲基丙烯酸酯)、聚(丙烯酸酯)、环氧树脂等。所述绝缘层的厚度为例如从约10nm至约500nm,这取决于使用的介电材料的介电常数。所述绝缘层的一个示例性厚度为从约100nm至约500nm。所述绝缘层可具有例如低于约10-12S/cm的电导率。
位于例如所述绝缘层和所述源极/漏极之间并与之接触的是半导体层,其中所述半导体层的厚度通常为例如约10nm至约1微米、或约40至约100nm。任何半导体材料都可用以形成该层。示例性半导体材料包括区域规则的聚噻吩、低聚噻吩(oligthiophene)、并五苯,以及美国专利No.6,621,099、6,770,904和6,949,762;和C.D.Dimitrakopoulos和P.R.L.Malenfant的“Organic Thin Film Transistors for Large AreaElectronics”,Adv.Mater.,第12卷,No.2,99-117页(2002)中公开的半导体聚合物,所述文献的公开内容通过引用全部纳入本文。任何合适的技术可用以形成所述半导体层。一种这样的方法是给包含基质和容纳粉末形式的化合物的源容器的室施以约10-5至10-7托的真空。加热所述容器直至所述化合物升华至所述基质上。所述半导体层通常也可通过溶液方法如旋涂、浇注、丝网印刷、冲压或喷涂一种所述半导体的溶液或分散体制作。
所述绝缘介电层、栅极、半导体层、源极和漏极以任意顺序排列,特别是其中在实施方案中所述栅极和半导体层均接触所述绝缘层,且所述源极和漏极均接触所述半导体层。词组“以任意顺序”包括顺次排列和并列排列。例如,所述源极和漏极可以并列或顺次排列。薄膜晶体管的构成、制作和操作描述于Bao等人的美国专利6,107,117中,该专利的公开内容通过引用全部纳入本文。所述银纳米颗粒可以以层的形式沉积于任合合适的表面,如所述基质、介电层或半导体层。
下列实施例是为进一步说明本发明的公开内容。所述实施例仅用于示例说明,并非意欲用本文详述的材料、条件或过程参数限制根据本公开内容制备的设备。
实施例
比较例1
将48.3克1-十六胺(200毫摩尔)、3.34克乙酸银(20毫摩尔)和5mL甲苯的溶液在65℃下加热使之变成透明液体。然后在剧烈搅拌下向所述溶液中滴加甲苯稀释的苯肼。在65℃下再搅拌所述溶液15分钟,然后滴加甲醇,形成黑色沉淀。在65℃下再搅拌所述溶液10分钟,然后冷却至40-50℃。滤出所述沉淀,用甲醇冲洗,并真空烘箱干燥两小时。获得一种蓝色固体,通常银产率>95%。
实施例1
以1L规模合成经十六胺稳定的银纳米颗粒:
在初始的瓶子中将十六胺预加热至50-60℃以熔化。在氮气层下的1L的夹套式反应器中,搅拌下将144.6克1-十六胺(600毫摩尔,Aldrich,90%)和160ml甲苯加热至约65℃。然后在2分钟内向该反应器中加入20克乙酸银(120毫摩尔,Alfa Aesar,99%);乙酸银迅速溶解。将第二部分的十六胺(144.6克)倒入该反应器并在45分钟内将所述溶液冷却至55℃。在10分钟内将用10ml甲苯稀释的7.13克苯肼(66毫摩尔,Aldrich,97%)加入反应器。溶液变成黑红色,表明银颗粒还原并形成银纳米颗粒。再混合所述溶液15分钟以确保还原反应完成。然后将反应器冷却至50℃以下,通过向反应器中加入240ml异丙醇、接着加入560ml甲醇沉淀产物。所述溶液变成深蓝紫色。将所述溶液混合5分钟,然后卸料并转移至使用配有0.5μm Gortex膜的3英寸直径过滤器的真空过滤单元。将金属蓝色滤饼分散于200ml异丙醇中,并洗涤30分钟以除去所述反应的任意残余胺和副产物。使用相同的过滤介质过滤所述混合物。接着进行三次50ml甲醇冲洗以从所述颗粒表面除去异丙醇。然后在30-40℃下在真空烘箱中过夜干燥所述颗粒。产物的最终产量为15.21克(理论值的94.4%),包含81%的银(用TGA分析评估)。
实施例2
以6L规模合成经十六胺稳定的银纳米颗粒:
在常规烘箱中将十六胺预加热至50-60℃以熔化。在氮气层下的6L的夹套式反应器中,搅拌下将723克1-十六胺(3摩尔,Aldrich,90%)和700ml甲苯加热至约65℃。然后在4分钟内向该反应器中加入100克乙酸银(0.6摩尔,Alfa Aesar,99%),接着再加入100ml甲苯。将第二部分的十六胺(723克)加入该反应器并在还原前45分钟内将所述溶液冷却至55℃。在20分钟内将用60ml甲苯稀释的35.63克苯肼(0.33摩尔,Aldrich,97%)加入反应器。溶液变成黑红色,表明银颗粒还原。再混合所述溶液15分钟以确保还原反应完成。然后将反应器冷却至50℃以下,通过加入1200ml异丙醇、接着加入2800ml甲醇沉淀产物。所述溶液变成深蓝紫色。将所述溶液混合15分钟,然后卸料并转移至使用配有0.5μm Gortex膜的8英寸直径过滤器的真空过滤单元。将金属蓝色滤饼分散于1500ml异丙醇中,并混合1小时,然后在异丙醇中静置过夜以除去所述反应的任意残余胺和副产物。第二天早晨使用相同的过滤介质过滤溶液。再次将滤饼分散于异丙醇洗涤半小时,并使用相同的过滤单元过滤。接着用甲醇三次冲洗以从产物中除去异丙醇(共750ml甲醇)。然后在30-40℃下在真空烘箱中过夜干燥剩余产物。产物的最终产量为65克(理论值的84%),包含84%的银(用TGA分析评估)。
试验及结果
测试了比较例1、实施例1和实施例2的银纳米颗粒的平均颗粒大小和银含量。还由这些纳米颗粒通过沉积和在140℃下退火10分钟制备膜。测定所述膜的电导率。还评价了所述银纳米颗粒的稳定性。结果示于表1中。
表1.
| 试样 | 平均颗粒大小(nm ) | 电导率(S/m) | 银含量(%) | 稳定性 |
| 比较例1 | 4.0 | 3.529x104 | 75 | 10天 |
| 实施例1 | 4.0 | 2.756x104 | 81 | 30天 |
| 实施例2 | 5.0 | 2.935x104 | 84 | >30天 |
图5示出了比较例1中形成的纳米颗粒的颗粒大小分布。图6示出了实施例1中形成的纳米颗粒的颗粒大小分布。图7示出了实施例2中形成的纳米颗粒的颗粒大小分布。
结果显示实施例1和2的方法制备的纳米颗粒具有类似的电导率,但具有较高的银含量和较高的稳定性(即更好的纯度和储存期限)。在两个步骤中加入有机胺和应用其中使用异丙醇和一种非溶剂(MeOH)的两步沉淀过程均有助于该结果。
尽管已描述了具体的实施方案,但申请人或其他的本领域技术人员可提出目前未预见或可能未预见的各种替代、修正、变型、改进和基本等效方案。因此,提交的并可能会被修改的附随权利要求意欲涵盖所有此类替代、修正、变型、改进和基本等效方案。
Claims (10)
1.一种制备经有机胺稳定的银纳米颗粒的方法,包含:
形成一种包含一种有机溶剂和一种第一物量的有机胺的热溶液;
向所述溶液中加入银盐颗粒;
向所述溶液中加入一种第二物量的有机胺;
向所述溶液中加入一种有机肼;和
使所述溶液反应以形成经有机胺稳定的银纳米颗粒。
2.权利要求1的方法,其中银盐与总的有机胺的摩尔比为从约1至约15。
3.权利要求1的方法,其中所述溶液在加入所述第二物量的有机胺之后冷却。
4.权利要求1的方法,其中所述有机溶剂与所述第一物量的有机胺的重量比为约1∶1。
5.权利要求1的方法,其中所述第一物量的有机胺与所述第二物量的有机胺的重量比为约1∶1。
6.权利要求1的方法,其中所述有机肼具有式:
R6R7N-NR8R9
其中R6、R7、R8和R9独立地选自氢、烷基和芳基;且其中R6、R7、R8和R9中的至少一个不是氢。
7.权利要求1的方法,还包含:
通过向所述溶液中加入异丙醇和一种非溶剂从所述溶液中分离所述银纳米颗粒;和
洗涤所述银纳米颗粒。
8.权利要求7的方法,其中所述异丙醇与非溶剂的体积比为约0.4。
9.通过权利要求1的方法制备的银纳米颗粒。
10.一种制备经有机胺稳定的银纳米颗粒的方法,包含:
形成一种包含一种有机溶剂和一种第一物量的有机胺并具有第一温度的溶液;
向所述溶液中加入银盐颗粒;
向所述溶液中加入一种第二物量的有机胺;
将所述溶液冷却至第二温度;
向所述溶液中加入一种有机肼;
使所述溶液反应以形成经有机胺稳定的银纳米颗粒;
将所述溶液冷却至第三温度;
向所述溶液中加入异丙醇;
向所述溶液中加入一种非溶剂以从所述溶液中分离所述银纳米颗粒;和
洗涤所述银纳米颗粒。
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104010752A (zh) * | 2011-12-28 | 2014-08-27 | 户田工业株式会社 | 银微粒及其制造方法、以及含有该银微粒的导电性糊、导电性膜和电子器件 |
| TWI476202B (zh) * | 2012-07-19 | 2015-03-11 | Nof Corp | Silver-containing compositions and substrates |
| CN104471652A (zh) * | 2012-07-17 | 2015-03-25 | 日油株式会社 | 含银组合物及银成分形成基材 |
| CN104470659A (zh) * | 2012-07-19 | 2015-03-25 | 日油株式会社 | 银纳米微粒及其制备方法、银纳米微粒分散液及形成银成分的基材 |
| CN105081306A (zh) * | 2014-05-16 | 2015-11-25 | 施乐公司 | 用于3d打印的经稳定的金属纳米粒子 |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8366971B2 (en) | 2010-04-02 | 2013-02-05 | Xerox Corporation | Additive for robust metal ink formulations |
| KR101284714B1 (ko) | 2010-09-20 | 2013-07-17 | 엘지디스플레이 주식회사 | 액정 표시장치와 이의 제조방법 |
| TWI462791B (zh) | 2011-07-08 | 2014-12-01 | Benq Materials Corp | 奈米銀粒子的形成方法 |
| US9353460B2 (en) * | 2013-09-24 | 2016-05-31 | Xerox Corporation | Method for forming metal structures |
| US9752040B2 (en) | 2015-01-12 | 2017-09-05 | Xerox Corporation | Nanosilver ink compositions comprising polystyrene additives |
| CN105779981A (zh) * | 2016-04-22 | 2016-07-20 | 广东南海启明光大科技有限公司 | 一种环保化学镀银液制备方法 |
| US10492297B2 (en) | 2017-02-22 | 2019-11-26 | Xerox Corporation | Hybrid nanosilver/liquid metal ink composition and uses thereof |
Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4403072A (en) * | 1981-09-09 | 1983-09-06 | Dynapol | Alkoxyethanols as solvents for coupling sulfonyl halides to polymeric amines |
| CN1493421A (zh) * | 2002-11-01 | 2004-05-05 | 中国科学院理化技术研究所 | 一维纳米银材料的制备方法 |
| US20050139144A1 (en) * | 2002-03-27 | 2005-06-30 | Muller Bernd W. | Method for the production and the use of microparticles and nanoparticles by constructive micronisation |
| WO2005088652A1 (ja) * | 2004-03-10 | 2005-09-22 | Asahi Glass Company, Limited | 金属含有微粒子、金属含有微粒子分散液および導電性金属含有材料 |
| US20060073667A1 (en) * | 2004-10-05 | 2006-04-06 | Xerox Corporation | Stabilized silver nanoparticles and their use |
| JP2006219693A (ja) * | 2005-02-08 | 2006-08-24 | Harima Chem Inc | 金属銀微粒子の製造方法 |
| JP2006291347A (ja) * | 2005-03-18 | 2006-10-26 | Seiko Epson Corp | 金属粒子分散液、金属粒子分散液の製造方法、導電膜形成基板の製造方法、電子デバイスおよび電子機器 |
| JP2007039718A (ja) * | 2005-08-01 | 2007-02-15 | Dowa Holdings Co Ltd | 銀粒子粉末の製造法 |
| WO2007024697A2 (en) * | 2005-08-19 | 2007-03-01 | Nanosys, Inc. | Electronic grade metal nanostructures |
| WO2007034922A1 (ja) * | 2005-09-22 | 2007-03-29 | Nippon Shokubai Co., Ltd. | 金属ナノ粒子、金属ナノ粒子コロイド、金属ナノ粒子コロイドの保存方法、及び金属被膜 |
| US20070190323A1 (en) * | 2006-02-15 | 2007-08-16 | Samsung Electro-Mechanics Co., Ltd. | Method of producing metal nanoparticles |
| US20080011125A1 (en) * | 2006-07-11 | 2008-01-17 | Fujifilm Corporation | Method for producing metallic nanoparticles, metallic nanoparticles, and dispersion of the same |
| CN101157127A (zh) * | 2006-10-05 | 2008-04-09 | 施乐公司 | 具有置换稳定剂的含银纳米颗粒 |
| WO2008061632A1 (de) * | 2006-11-21 | 2008-05-29 | Bayer Technology Services Gmbh | Verfahren zur synthese von nanoskaligen metallhaltigen nanopartikel und nanopartikeldispersionen |
| CN101357403A (zh) * | 2007-07-30 | 2009-02-04 | 三星电机株式会社 | 用于制造金属纳米颗粒的方法 |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6107117A (en) | 1996-12-20 | 2000-08-22 | Lucent Technologies Inc. | Method of making an organic thin film transistor |
| US6348295B1 (en) | 1999-03-26 | 2002-02-19 | Massachusetts Institute Of Technology | Methods for manufacturing electronic and electromechanical elements and devices by thin-film deposition and imaging |
| WO2003060596A2 (en) * | 2001-10-24 | 2003-07-24 | The Regents Of The University Of California | Semiconductor liquid crystal composition and methods for making the same |
| US6949762B2 (en) | 2002-01-11 | 2005-09-27 | Xerox Corporation | Polythiophenes and devices thereof |
| US6621099B2 (en) | 2002-01-11 | 2003-09-16 | Xerox Corporation | Polythiophenes and devices thereof |
| US6770904B2 (en) | 2002-01-11 | 2004-08-03 | Xerox Corporation | Polythiophenes and electronic devices generated therefrom |
| US7160525B1 (en) | 2003-10-14 | 2007-01-09 | The Board Of Trustees Of The University Of Arkansas | Monodisperse noble metal nanocrystals |
| US20050129843A1 (en) | 2003-12-11 | 2005-06-16 | Xerox Corporation | Nanoparticle deposition process |
| US7306969B2 (en) | 2005-07-22 | 2007-12-11 | Xerox Corporation | Methods to minimize contact resistance |
| WO2007064301A1 (en) * | 2005-11-30 | 2007-06-07 | Agency For Science, Technology And Research | Nanoparticle and methods therefor |
| TW200811055A (en) | 2006-04-12 | 2008-03-01 | Nanomas Technologies Inc | Nanoparticles, methods of making, and applications using same |
| US8460584B2 (en) * | 2008-10-14 | 2013-06-11 | Xerox Corporation | Carboxylic acid stabilized silver nanoparticles and process for producing same |
-
2009
- 2009-02-12 US US12/369,861 patent/US8834965B2/en active Active
-
2010
- 2010-02-02 EP EP10152362.9A patent/EP2223756B1/en not_active Not-in-force
- 2010-02-05 CA CA2692067A patent/CA2692067C/en not_active Expired - Fee Related
- 2010-02-10 JP JP2010027894A patent/JP5616648B2/ja not_active Expired - Fee Related
- 2010-02-10 TW TW099104115A patent/TWI593633B/zh not_active IP Right Cessation
- 2010-02-11 CN CN201010115500.1A patent/CN101804458B/zh not_active Expired - Fee Related
- 2010-02-11 KR KR1020100012803A patent/KR101541930B1/ko not_active Expired - Fee Related
Patent Citations (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4403072A (en) * | 1981-09-09 | 1983-09-06 | Dynapol | Alkoxyethanols as solvents for coupling sulfonyl halides to polymeric amines |
| US20050139144A1 (en) * | 2002-03-27 | 2005-06-30 | Muller Bernd W. | Method for the production and the use of microparticles and nanoparticles by constructive micronisation |
| CN1493421A (zh) * | 2002-11-01 | 2004-05-05 | 中国科学院理化技术研究所 | 一维纳米银材料的制备方法 |
| WO2005088652A1 (ja) * | 2004-03-10 | 2005-09-22 | Asahi Glass Company, Limited | 金属含有微粒子、金属含有微粒子分散液および導電性金属含有材料 |
| US7270694B2 (en) * | 2004-10-05 | 2007-09-18 | Xerox Corporation | Stabilized silver nanoparticles and their use |
| JP2006104576A (ja) * | 2004-10-05 | 2006-04-20 | Xerox Corp | 安定化された銀のナノ粒子及びそれらの利用法 |
| US20060073667A1 (en) * | 2004-10-05 | 2006-04-06 | Xerox Corporation | Stabilized silver nanoparticles and their use |
| JP2006219693A (ja) * | 2005-02-08 | 2006-08-24 | Harima Chem Inc | 金属銀微粒子の製造方法 |
| JP2006291347A (ja) * | 2005-03-18 | 2006-10-26 | Seiko Epson Corp | 金属粒子分散液、金属粒子分散液の製造方法、導電膜形成基板の製造方法、電子デバイスおよび電子機器 |
| JP2007039718A (ja) * | 2005-08-01 | 2007-02-15 | Dowa Holdings Co Ltd | 銀粒子粉末の製造法 |
| JP2009507998A (ja) * | 2005-08-19 | 2009-02-26 | ナノシス・インク. | 電子グレード金属ナノ構造 |
| WO2007024697A2 (en) * | 2005-08-19 | 2007-03-01 | Nanosys, Inc. | Electronic grade metal nanostructures |
| WO2007034922A1 (ja) * | 2005-09-22 | 2007-03-29 | Nippon Shokubai Co., Ltd. | 金属ナノ粒子、金属ナノ粒子コロイド、金属ナノ粒子コロイドの保存方法、及び金属被膜 |
| US20070190323A1 (en) * | 2006-02-15 | 2007-08-16 | Samsung Electro-Mechanics Co., Ltd. | Method of producing metal nanoparticles |
| US20080011125A1 (en) * | 2006-07-11 | 2008-01-17 | Fujifilm Corporation | Method for producing metallic nanoparticles, metallic nanoparticles, and dispersion of the same |
| CN101157127A (zh) * | 2006-10-05 | 2008-04-09 | 施乐公司 | 具有置换稳定剂的含银纳米颗粒 |
| WO2008061632A1 (de) * | 2006-11-21 | 2008-05-29 | Bayer Technology Services Gmbh | Verfahren zur synthese von nanoskaligen metallhaltigen nanopartikel und nanopartikeldispersionen |
| CN101357403A (zh) * | 2007-07-30 | 2009-02-04 | 三星电机株式会社 | 用于制造金属纳米颗粒的方法 |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104010752A (zh) * | 2011-12-28 | 2014-08-27 | 户田工业株式会社 | 银微粒及其制造方法、以及含有该银微粒的导电性糊、导电性膜和电子器件 |
| CN104471652A (zh) * | 2012-07-17 | 2015-03-25 | 日油株式会社 | 含银组合物及银成分形成基材 |
| CN104471652B (zh) * | 2012-07-17 | 2016-10-26 | 日油株式会社 | 含银组合物及银成分形成基材 |
| US10017655B2 (en) | 2012-07-17 | 2018-07-10 | Nof Corporation | Silver-containing composition, and base for use in formation of silver element |
| TWI476202B (zh) * | 2012-07-19 | 2015-03-11 | Nof Corp | Silver-containing compositions and substrates |
| CN104470659A (zh) * | 2012-07-19 | 2015-03-25 | 日油株式会社 | 银纳米微粒及其制备方法、银纳米微粒分散液及形成银成分的基材 |
| CN104470659B (zh) * | 2012-07-19 | 2016-01-27 | 日油株式会社 | 银纳米微粒及其制备方法、银纳米微粒分散液及形成银成分的基材 |
| US9496069B2 (en) | 2012-07-19 | 2016-11-15 | Nof Corporation | Silver nanoparticles, method for producing same, silver nanoparticle dispersion liquid, and base provided with silver material |
| CN105081306A (zh) * | 2014-05-16 | 2015-11-25 | 施乐公司 | 用于3d打印的经稳定的金属纳米粒子 |
Also Published As
| Publication number | Publication date |
|---|---|
| TWI593633B (zh) | 2017-08-01 |
| KR20100092392A (ko) | 2010-08-20 |
| TW201034971A (en) | 2010-10-01 |
| CA2692067C (en) | 2013-12-10 |
| JP2010185140A (ja) | 2010-08-26 |
| KR101541930B1 (ko) | 2015-08-04 |
| JP5616648B2 (ja) | 2014-10-29 |
| EP2223756B1 (en) | 2014-12-03 |
| CA2692067A1 (en) | 2010-08-12 |
| US8834965B2 (en) | 2014-09-16 |
| US20100203333A1 (en) | 2010-08-12 |
| EP2223756A1 (en) | 2010-09-01 |
| CN101804458B (zh) | 2015-08-19 |
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