The Impact of Morphology and Composition on the Resistivity and Oxidation Resistance of Metal Nanostructure Films
Printed electronics, including transparent conductors, currently rely on expensive materials to generate high conductivity devices. Conductive inks for thick film applications utilizing inkjet, aerosol, and screen printing technologies are often comprised of expensive and rare silver particles. Thin film applications such as organic light emitting diodes (OLEDs) and organic photovoltaics (OPVs) predominantly employ indium tin oxide (ITO) as the transparent conductive layer which requires expensive and wasteful vapor deposition techniques. Thus an alternative to silver and ITO with similar performance in printed electronics warrants considerable attention. Copper nanomaterials, being orders of magnitude cheaper and more abundant than silver or indium, solution-coatable, and exhibiting a bulk conductivity only 6 % less than silver, have emerged as a promising candidate for incorporation in printed electronics.
First, we examine the effect of nanomaterial shape on the conductivity of thick films. The inks used in such films often require annealing at elevated temperature in order to sinter the silver nanoparticles together and obtain low resistivities. We explore the change in morphology and resistivity that occurs upon heating thick films of silver nanowires (of two different lengths, Ag NWs), nanoparticles (Ag NPs), and microflakes (Ag MFs) deposited from water at temperatures between 70 and 400 °C. At the lowest temperatures, longer Ag NWs exhibited the lowest resistivity (1.8 × 10-5 Ω cm), suggesting that the resistivity of thick films of silver nanostructures is dominated by the contact resistance between particles.
This result supported previous research showing that junction resistance between Ag NWs in thin film conductors also dominates optoelectronic performance. Since the goal is to replace silver with copper, we perform a similar analysis by using a pseudo-2D rod network modeling approach that has been modified to include lognormal distributions in length that more closely reflect experimental data collected from the nanowire transparent conductors. In our analysis, we find that Cu NW-based transparent conductors are capable of achieving comparable electrical performance to Ag NW transparent conductors with similar dimensions. We also synthesize high aspect ratio Cu NWs (as high as 5700 in an aqueous based synthesis taking less than 30 minutes) and show that this increase in aspect ratio can result results in transparent conducting films with a transmittance >95% at a sheet resistance <100 Ω sq−1, optoelectronic properties similar to that for ITO.
Two of the major barriers preventing the further use of Cu NWs in printed electronics are the necessity to anneal the nanowires under H2¬ at higher temperatures and copper’s susceptibility to oxidation. The former issue is solved by removing the insulating oxide along the Cu NWs with acetic acid and pressing the nanowires together to make H2 annealing obsolete. Finally, several methods of preventing copper oxidation in the context of transparent conductors were successfully developed such as electroplating zinc, tin, and indium and electrolessly plating benzotriazole (BTAH), nickel, silver, gold, and platinum. While all of the shells lessened or prevented oxidation both in dry and humid conditions, it was found that a thin layer of silver confers identical optoelectronic properties to the Cu NWs as pure Ag NWs. These results are expected provide motivation to replace pure silver and ITO in printed electronics.
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