Microbubble formation from plasma polymers.

We document the formation of liquid-like particles in a toluene glow discharge that subsequently solidify via a process that releases hydrogen to form a solid microbubble with micrometer-size diameter, nanometer-size shell thickness, and high volume fraction, in excess of 90%. Liquid-like particles are produced in a toluene plasma under conditions that promote low degree of cross-linking (low power, high pressure). When these are transferred for observation in TEM, they are seen to transform under irradiation by the electron beam into solid bubbles with diameter of about 3 μm. This transformation also takes place under laser irradiation of sufficient power and under heating. We present evidence that the formation of these microbubbles is due to solidification of the liquid-like precursor that is accompanied by release of hydrogen. This mechanism is supported by a geometric model that provides a quantitative description of the particle size before and after solidification. These unique stimuli-responsive particles exhibit the potential of using temperature, electron beam, or laser as a source to change their size and structure which may find application in thermal insulators, lightweight materials, and light scattering agents.