Noble metal coated silver nanowires, methods for performing the coating
Metal nanowires with uniform noble metal coatings are described. Two methods, galvanic exchange and direct deposition, are disclosed for the successful formation of the uniform noble metal coatings. Both the galvanic exchange reaction and the direct deposition method benefit from the inclusion of appropriately strong binding ligands to control or mediate the coating process to provide for the formation of a uniform coating. The noble metal coated nanowires are effective for the production of stable transparent conductive films, which may comprise a fused metal nanostructured network.
1. A method for forming noble metal coated silver nanowires by direct metal deposition, the method comprising:
gradually adding a coating solution comprising dissolved non-silver noble metal ions and a metal ion complexing ligand into a reaction solution comprising dispersed silver nanowires and a reducing agent to form the noble metal coating on the silver nanowires, wherein the gradual addition is performed over a period from about 5 minutes to about 5 hours and
harvesting noble metal coated silver nanowires having a root mean square roughness of no more than about 1 nm.
2. The method of claim 1 wherein the metal ion complexing ligand is selected from the group consisting of nitrite, diethyl amine, ethylene diamine, nitrilotriacetic acid, iminobis(methylene phosphonic acid), aminotris(methylene phosphonic acid), ethylene diamine tetraacetic acid (EDTA), 1,3-propylenediaminetetraacetic acid (1,3-PDTA), triethylene tetramine, tri(2-aminoethyl) amine, diethylenetriaminepentaacetic acid, 1,2-cyclohexanediaminotetraacetic acid, iminodiacetic acid, methyliminodiacetic acid, N-(2-acetamide) iminoacetic acid, N-(2-carboxyethyl) iminodiacetic acid, N-(2-carboxymethyl)imino dipropionic acid, picolinic acid, dipicolinic acid, histidine, combinations thereof.
3. The method of claim 1 wherein the coating solution has a molar ratio of at least about 2 ligands per noble metal ion.
4. The method of claim 1 wherein the reaction solution further comprises a capping polymer, wherein the coating solution comprises noble metal ions at from about 0.0001 M to about 5 M and wherein the reaction solution comprises from about 0.02 wt % to about 3.5 wt % silver nanowires, from about 0.01 wt % to about 1.5 wt % capping polymer and from about 1 micromolar to about 1 millimolar reducing agent.
5. The method of claim 1 further comprising harvesting noble metal coated silver nanowires having from about 0.05 wt % to about 15 wt % noble metal.
6. The method of claim 1 wherein the reducing agent comprises hydrazine.
7. The method of claim 1 wherein the reducing agent comprises NaBH 4 , LiAlH 4 , ascorbic acid, oxalic acid, or formic acid.
8. The method of claim 1 wherein the coating solution comprises gold ions or platinum ions.
9. The method of claim 1 wherein the coating solution comprises comprise noble ions in amounts generally ranging from about 0.1 at % to about 30 at % as a fraction of the total coated nanowire.
10. The method of claim 1 wherein the coating solution comprises from about 0.0001 M to about 0.025 M noble metal ions, a molar ratio of ligands to metal ions at least about 0.8, and from about 0.001 wt % to about 5 wt % polyvinylpyrrolidone.
11. The method of claim 1 wherein the reaction solution comprises from about 0.03 wt % to about 2.5 wt % silver nanowires, from about 0.02 wt % to about 1 wt % polyvinylpyrrolidone and from about 1 micromolar to about 1 millimolar reducing agent.
12. The method of claim 1 wherein as a result of the addition of the coating solution a coating reaction is allowed to proceed without adding heat.
13. The method of claim 1 wherein the gradual addition of the coating solution is performed at an approximate constant rate.
14. The method of claim 1 wherein the coated nanowires are harvested and washed.
15. The method of claim 1 further comprising harvesting noble metal coated silver nanowires having a standard deviation in diameter of no more than about 6% relative to the average diameter.
16. The method of claim 1 further comprising harvesting noble metal coated silver nanowires having from about 0.9 wt % to about 40 wt % noble metal.