Chemical vapor synthesis of nanocrystalline perovskites using laser flash evaporation of low volatility solid precursors.

One key requirement for the production of multinary oxide films by chemical vapor deposition (CVD) or nanocrystalline multinary oxides particles by chemical vapor synthesis (CVS) is the availability of precursors with high vapor pressure. This is especially the case for CVS where much higher production rates are required compared to thin films prepared by CVD. However, elements, which form low valent cations such as alkaline earth metals, are typically only available as solid precursors of low volatility, e.g., in form of beta-diketonates. This study describes laser flash evaporation as precursor delivery method for CVS of nanocrystalline perovskites. Laser flash evaporation exploits the nonequilibrium evaporation of solid metal organic precursors of low vapor pressure by absorption of the infrared radiation of a CO(2) laser. It is shown that stoichiometric, nanocrystalline particles consisting of SrZrO(3) and SrTiO(3) can be formed from corresponding mixtures of beta-diketonates which are evaporated nonselectively and with high rates by laser flash evaporation.

Multicomponent equiatomic rare earth oxides with a narrow band gap and associated praseodymium multivalency.

New multicomponent equiatomic rare earth oxides (ME-REOs) containing 3-7 rare earth elements (Ce, Gd, La, Nd, Pr, Sm and Y) in equiatomic proportions are synthesized using nebulized spray pyrolysis. All the systems crystallized as a phase pure fluorite type (Fm3[combining macron]m) structure in spite of the high chemical complexity. A nominal increase in the lattice parameter compared to CeO2 is observed in all ME-REOs. X-ray photoelectron spectroscopy performed on the ME-REOs confirmed that all the constituent rare earth elements are present in the 3+ oxidation state, except for Ce and Pr which are present in 4+ and in a mixed (3+/4+) oxidation state, respectively. The presence of Ce4+ contributes substantially to the observed stability of the single phase structure. These new oxide systems have narrow direct band gaps in the range of 1.95-2.14 eV and indirect band gaps in the range of 1.40-1.64 eV, enabling light absorption over the entire visible spectral range. Furthermore, the oxygen vacancy concentration rapidly increases and then saturates with the number of rare earth elements that are incorporated into the ME-REOs. The lowering of the band gap is found to be closely related to the presence of multivalent Pr. Interestingly, the band gap values are relatively invariant with respect to the composition or thermal treatments. Considering the high level of oxygen vacancies present and the observed low band gap values, these new material systems can be of importance where the presence of oxygen vacancies is essential or in applications where a narrow band gap is desirable.