Highly conductive, nanoparticulate thick films processed at low processing temperatures
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Applications such as device interconnects require thick, patterned films that are currently produced by screen printing pastes consisting of metallic particles and subsequently sintering the films. For Ag films, achieving adequate electrical conductivity requires sintering temperatures in excess of 700˚C. New applications require highly conductive films that can be processed at lower processing temperatures. Although sintering temperatures have been reduced by utilizing finer nanoparticles (NPs) in place of conventional micron-size particles (MPs), realization of theoretically achievable sintering kinetics is yet to be achieved. The major factors that inhibit NP sintering are 1) the presence of organic molecules on the NP surfaces, 2) the dominance of the non-densifying surface diffusion over grain boundary or lattice diffusion 3) agglomeration of NPs, and 4) low initial density of the NPs. Here, we report a film fabrication technique that is capable of eliminating these deleterious factors and produces near fully dense Ag films that exhibit an order of magnitude higher conductivity when compared to other film fabrication techniques at processing temperatures of 150 – 250 °C. The observed results establish the benefits of NP diffusion kinetics to be far more profound when the deleterious factors to sintering are eliminated. The sintering behavior exhibits two distinct temperature regimes – one above 150 ᵒC where grain boundary diffusion-dominated densification is dominant and one below 100 ᵒC where surface diffusion-dominated coarsening is dominant. An analytical model is developed by fitting the experimental data to the existing models of simultaneous densification and grain growth, and combining this model with existing models of the dependence of conductivity on grain boundary scattering and pore scattering. The combined model successfully describes the evolution of density, grain size and conductivity of nanoparticulate films as a function of annealing treatment, with reasonable accuracy. The model was also used to evaluate the effect of initial NP size and initial relative density of films on the final sintered properties and conductivity of films.