Self-Assembly of designed precursors: a route to crystallographically aligned new materials with controlled na no a r c hi t e c t u r e , Journal of Solid State Chemistry, http://dx.
ABSTRACTModulated elemental reactants is a method by which new and complex intergrowth compounds can be synthesized by the self-assembly of designed precursors prepared by physical vapor deposition. Careful calibration of the composition and thickness of the precursors ensures the formation of the desired product by precise control of local composition and diffusion lengths. Superstructures of increasing complexity can be realized using binary and ternary systems as starting points. The synthesis of systems based on three different binary compounds, either alloyed together or separated into distinct layers, expands the number of possible superstructures that can be formed using this technique, but provides analytical challenges. The synthesis of [(SnSe) 1.15 ] 1 ([Ta x V 1-x ]Se 2 ) 1 [(SnSe) 1.15 ] 1 ([V y Ta 1-y ]Se 2 ) 1 compound is used to illustrate the preparation of precursors and the challenges in both measuring and limiting the interdiffusion of layers during self-assembly. Systematic changes in the electrical properties of (SnSe) 1+δ (Ta x V 1-x )Se 2 alloys are observed as x is varied. The electrical resistivity of [(SnSe) 1.15 ] 1 ([Ta x V 1-x ]Se 2 ) 1 [(SnSe) 1.15 ] 1 ([V y Ta 1-y ]Se 2 ) 1 can be modeled as the two constituent layers in parallel.
INTRODUCTIONNew synthetic methods have been critical both to advance scientific understanding as well as to advance technology. Traditional approaches have historically focused on using thermodynamic control to make desired products, for example growing doped silicon crystals from a melt of fixed composition. Phase diagrams were determined to understand the thermodynamic relationships between compounds. Kinetic control, typically achieved by controlling temperature as a function of time, was used to influence the microstructure. The search for new materials focused on finding reaction conditions where new compounds would be thermodynamically stable. High temperature synthesis and the growth of new materials from melts were commonly used to overcome slow solid state diffusion rates and to form single crystals for structure determination. New compounds and new phenomena are discovered whenever new approaches are developed, such as vapor transport reactions in the 1960's, [1,2] or new adaptations, such as the use of low temperature fluxes, [3,4] are explored. A grand challenge in the field of materials discovery is the development of approaches to predict new structures and the properties associated with specific compositions, and the development of approaches that will enable their synthesis. Historically, serendipity played a significant role in most new discoveries as unexpected compounds formed in reaction mixtures.