<i>In situ</i> high energy x-ray synchrotron diffraction study of the synthesis and stoichiometry of LaFeAsO and LaFeAsO1−xFy

Abstract

The reaction path for the synthesis of LaFeAsO and LaFeAsO1−xFy by solid state reaction was studied by in situ high temperature x-ray diffraction technique and differential thermal analysis in the temperature interval 100°C⩽T⩽1150°C. Starting with LaAs, Fe2O3, Fe, and LaF3 as precursors, the results show that the synthesis is characterized by three temperature intervals: (1) Below 500°C the sequential reduction of Fe2O3 and Fe3O4 takes place through the oxidization of LaAs. Below 400°C, Fe2O3 is reduced to Fe3O4 by LaAs and then at 400°C&amp;lt;T&amp;lt;500°C Fe3O4 is further reduced to Fe. (2) In the temperature interval 500°C&amp;lt;T&amp;lt;800°C, multiple intermediate reactions take place resulting in the formation of FeAs and La2O3. (3) The formation of LaFeAsO based phase could be unambiguously resolved above 800°C. For both LaFeAsO and LaFeAsO1−xFy, FeAs is a primary impurity at high temperatures that melts at ∼1040°C. Possible reaction pathways and the difference between F-free and F-doped samples are discussed.