Crystal growth in nanoporous framework materials

Future applications of nanoporous materials will be in opto-electronic devices, magnetic and chemical sensors, shape-selective and bio-catalysis, structural materials and nuclear waste management. Crucially, in all such applications, an understanding of crystal growth to the same depth as has been achieved in semiconductor technology is needed. Therefore, defects, intergrowths, dopants and isomorphous substitution must be controlled, and crystal habit and size (e.g. single crystal films) must be fabricated with precision. These goals elude the community because of lack of understanding of crystal growth processes. Modern microscopy techniques including AFM, ultra-high resolution SEM and HREM coupled with theoretical calculations are beginning to reveal the details of these growth processes yielding the important thermodynamic data crucial to effect synthetic control such as: controlling defects; controlling intergrowths: introducing chirality; modifying surface access; altering diffusion pathways; controlling crystal habit; synthesising templated materials cheaply in order to render them economically viable; controlling crystal size for instance as single crystal films. In this paper we will discuss recent results including: the details of surface alteration processes in nanoporous materials, measured in situ, under different chemical environments and the ability to switch processes on and off by the control of growth conditions. Further we illustrate an approach to theoretically model the crystal growth in such complex systems which ultimately delivers activation energies for fundamental growth processes.