Pressure-induced crossover between diffusive and displacive mechanisms of phase transitions in single-crystalline alpha-GeO2

We present the first example of the phase transition occurring via the different kinetic mechanisms, displacive or diffusive, competing with each other in quartz-like alpha-GeO2 single crystals. Upon room-pressure heating, alpha-GeO2 transforms to the rutile-type phase (the alpha-->r transition) via the diffusive mechanism. With increase of the treatment pressure the diffusive mode of the temperature-induced alpha-->r transition is substituted at approximately 4 GPa by a displacive-like mode, and then at approximately 6 GPa the transition type changes from the alpha-->r sequence to a displacive martensitic-like transition to a distorted rutile-like phase (alpha-->r'. A crossover between diffusive and displacive transition modes suggests a new way to control the meso- and nanometer-scale morphology of high-pressure phases.