Preparation and characterization of spin crossover thin solid films

Abstract

Iron(II) spin crossover complexes display a reversible transition from low-spin (LS) state to high-spin (HS) state by e.g. variation of temperature, pressure or by irradiation with light. Therefore, these systems are promising candidates for information storage materials. In view of practical device applications thin films of these materials are needed. The SCO-compound [Fe(Htrz)2(trz)] (BF4) (1) switches between the LS and the HS state with a 50 K wide thermal hysteresis loop above room temperature. We have prepared thin films of 1 on a SiO2 substrate by spin coating. The spin states of the films have been characterized by Mossbauer spectroscopy in reflection mode using a MIMOS II spectrometer. A low quadrupole splitting (LS state) at 300 K and a high quadrupole splitting (HS state) at 400 K were found for the film, as well as for bulk powder of 1. This confirms that a spin crossover occurs above room temperature. Furthermore, synchrotron based nuclear resonance scattering measurements from 80 K to 400 K indicate that the hyperfine parameters are similar to those of the bulk powder of 1. DFT calculations reproduce the experimentally determined Fe-vibrational density of states of the bulk and of the thin film sample of 1. These results indicate that a higher fraction of HS Fe atoms is present in the film of 1. Therefore, we conclude different SCO properties of the thin film and the bulk material of 1.