We present a new approach to ensure the low contact resistivity of a silver paste at a metal/semiconductor interface over a broad range of peak firing temperatures by using a solid-to-liquid phase transitional metallo-organic silver, that is, silver neodecanoate. Silver nanoclusters, thermally derived from silver neodecanoate, are readily dissolved into the melt of metal oxide glass frit even at low temperatures, at which point the molten metal oxide glass frit lacks the dissociation capability of bulk silver into Ag(+) ions. In the presence of O(2-) ions in the melt of metal oxide glass frit, the redox reaction from Ag(+) to Ag(0) augments the noble-metal-assisted etching capability to remove the passivation layer of silicon nitride. Moreover, during the cooling stage, the nucleated silver atoms enrich the content of silver nanocolloids in the solidified metal oxide glass layer. The resulting contact resistivity of silver paste with silver neodecanoate at the metal/semiconductor interface thus remains low-between 4.12 and 16.08 mΩ cm(2)-whereas without silver neodecanoate, the paste exhibits a contact resistivity between 2.61 and 72.38 mΩ cm(2) in the range of peak firing temperatures from 750 to 810 °C. The advantage of using silver neodecanoate in silver paste becomes evident in that contact resistivity remains low over the broad range of peak firing temperatures, thus providing greater flexibility with respect to the firing temperature required in silicon solar cell applications.
Keywords: contact resistivity; metallo-organic silver; noble-metal-assisted etching; phase transition; silicon solar cell; silver nanocolloids.