Bottom-up Filling of Nanosized Trenches with Silver to Fabricate Transparent Conducting Electrodes
Authors: Bleiji Yorick , Dieperink Mees , Cordaro Andrea , Tabernig Stefan Wil , Höhn Oliver , Müller Ralph , Bläsi Bendikt , Polman Albert , Alarcón Lladó Esther 
Published: September 2023

Transparent conducting electrodes (TCEs) are essential in many optoelectronic devices including solar cells, sensors, displays, and LEDs. The use of transparent metal oxide layers, in particular Indium tin oxide (ITO), is the most common used approach. However, ITO comes with numerous drawbacks such as the relatively rarity of indium and hence high cost, fragility, strong UV absorption and relative high sheet resistance. An exciting alternative TCE is the use of interconnected metallic nanowires, where their sub-wavelength cross-sections makes them transparent to visible light, where especially silver nanowires are a good candidate because of their high conductivity.

Here we show a promising cost-effective method called selective-area electrochemical deposition (SAEC) for the fabrication of these metal nanostructures. SAEC is based on a through-the-mask electrochemical deposition method, where the mask is made using substrate conformal imprint lithography. Next to the inherent low fabrication cost of the electrochemical deposition, it has numerous advantages such as bottom-up growth, scalability, operate at ambient conditions, control over nucleation, and yields high purity deposits. While submicron sized features have been already demonstrated by SAEC, obtaining homogeneous void free filling of features below 100 nm using direct plating is a major challenge because of the terminal effect and the poor control of nucleation of the seed layer.

In this work, we have explored the SAEC fabrication of large area silver nanowire grids on ITO substrates and on TOPCon solar cells. We show that the nucleation density of the silver nanoparticles is the key parameter for the successful homogenous void-free filling of the trenches. The nucleation density namely determines the coalescence thickness, which sets a minimum thickness for the silver nanowires in order to be connected. We control the nucleation density of the silver nanoparticles by making use of the double pulse method, where a high overpotential nucleation pulse is applied for controlling the nucleation density. After nucleation, we merge the silver nuclei by applying a low overpotential growth pulse.

After the successful filling of the trenches, we have compared the optical and electrical performance of the SAEC fabricated silver nanowire grids to those using conventional thermal or e-beam evaporation followed by lift-off. The SAEC-fabricated TCEs show high transmission (>96%) and extreme low resistance (as low as 3 Ω/sq), resulting into a superior figure of merit (FoM). Due to the bottom-up nature of this technique, arbitrary high aspect ratio nanowires can be achieved and therefore the relationship of decreasing transmission with decreasing sheet resistance is broken.

Furthermore, we have also incorporated the silver NW grids in TOPCon cells and compared the performance to similar cells based on ITO. This work represents a low-cost and scalable strategy to fabricate sub 100 nm predefined metal structures, enabling the commercial viable fabrication of nanostructure based transparent conductive electrodes for optoelectronic devices.