An X-ray chamber for in situ structural studies of solvent-mediated nanoparticle self-assembly

Technical details and experimental examples are given for a novel sample environment allowing X-ray investigations of self-assembly phenomena induced by controlled bulk solvent evaporation and nanoscale solvent adsorption/desorption. Spontaneous ordering of nanoparticles (NPs) occurring as a consequence of solvent evaporation can yield highly ordered and extended NP superlattices bearing both fundamental scientific interest and potential for technological application. A versatile experimental chamber has been developed allowing (i) controlled in situ deposition of NP solutions on solid substrates, (ii) rate-controlled evaporation of the bulk solvent, and (iii) adsorption/desorption of nano-thick solvent films onto preformed NP assemblies. Within this hermetically sealed chamber all the stages of self-assembly, including macroscopic solution evaporation, NP thin-film formation and its subsequent structural transformation induced by nano-thick solvent films, can be characterized in situ by X-ray scattering techniques. Here, technical design and calibration details are provided, as well as three experimental examples highlighting the chamber's performances and potential. Examples include the controlled adsorption of thin toluene films on flat silicon wafers, the observation of transient accumulation of gold NPs near the toluene–vapour interface, and preliminary data on the structural effects of fast macroscopic solvent evaporation followed by nanoscale solvent adsorption/desorption from a vapour phase. By combining bulk evaporation rate control, fine tuning of the thickness of adsorbed solvent films and in situ X-ray characterization capabilities, this cell enables explorations of both near-to-equilibrium and far-from-equilibrium routes to NP self-assembly