In this study, silicon solar cells with copper-plated front side metallisation were exposed to long-term reliability thermal stress conditions and the material integrity of the plated contacts after stress testing was investigated using imaging and electrical measurements. Significant voltage 'bend-back' was observed in Suns-V-oc measurements at high illumination intensities (> 1 Sun) following thermal stress testing at 200 degrees C for 500 h of laser ablated cells with a nickel/copper/silver plated front metal grid. Using a combination of focussed ion beam milling, high resolution imaging and energy dispersive X-ray spectroscopy, it was shown that large voids can form between the silver capping layer and the main copper stack during thermal annealing. However, even more revealing was the detection of a new metal layer comprising largely of diffused copper overlying the silver capping. The cause of the Schottky 'bend-back' behaviour was theorised to be due to increased contact resistance arising from the voids which are presumed to form as a result of grain boundary diffusion of copper through the silver capping layer. Errors of 5-10% in the determination of pFF from Suns-V-oc occur as a result, with the scale of the error dependent on the capping method and sintering conditions. Collapsing the voids was subsequently shown to remove the Schottky behaviour and improve reliability of the fitted diode parameters extracted from Suns-V-oc measurements.