Thin Glass Film between Ultrafine Conductor Particles in Thick-Film Resistors

Thick-film resistors arc electrical composites containing ultrafine particles of ruthenate conductor (Pb₂Ru₂O₇ in the present materials) distributed in a highly modified silicate glass. We show that conductor particles remain flocced in the absence of any applied or capillary pressures, but are separated at equilibrium by a nanometer-thick film of glass. Microstructures show evidence for liquid-phase sintering, i.e., contact flattening of particles, under van der Waals attraction alone. Titania addition, which in dilute concentrations markedly increases the resistivity, decreases the temperature coefficient of resistance, and improves voltage stability and noise, is found to increase the equilibrium film thickness between particles by a few angstroms. STEM analyses show that the added titania preferentially concentrates in the silicate-rich grain boundary film, as well as at particle–glass interfaces. The roles of interparticle forces and adsorption on the glass film thickness with and without titania are discussed. The large increase in resistivity caused by titania additions is attributed to the increase in Film thickness as well as to local chemical changes of two possible types. Titania enrichment within the glass film itself is expected to decrease the local ruthenium ion solubility, and this along with the possible formation of a more insulating titania-substituted surface layer on ruthenate grains will decrease the tunneling conductivity between conductor grains.