Excited Spin-State Trapping in Spin Crossover Complexes on Ferroelectric Substrates

MARCH, 2018

Christian Wackerlin, Fabio Donati, Aparajita Singha, Romana Baltic, Silvio Decurtins, Shi-Xia Liu, Stefano Rusponi, and Jan Dreiser
The Journal of Physical Chemistry C 122, 8202 (2018)

Description


Using X-ray absorption spectroscopy, we have studied thin films of Fe(II) spin crossover complexes deposited on differently poled ferroelectric PMN-PT substrates. The X-ray spectra reveal the temperature driven conversion between high-spin and low-spin states. X-rays induce excited spin-state trapping regime at 3 K, with large differences occurring between the two ferroelectric polarizations. We explain our findings by a modulation of the polarization-dependent efficiency of the scattering of X-ray-generated secondary electrons at the molecules. Our results provide a deep insight into the X-rays spin trapping mechanism and suggest that such molecules could be used as detectors for electrons traveling in the substrate at energies lower than the substrate electron affinity.

Abstract


We have studied thin films of Fe(II) spin crossover complexes deposited on differently poled ferroelectric PMN-PT ([Pb(Mg1/3Nb2/3)O3]1–x[PbTiO3]x, x = 0.32) substrates by X-ray absorption spectroscopy. The X-ray spectra reveal the temperature-driven conversion between high-spin and low-spin states without any observable effect of the ferroelectric polarization on the spin state of the molecules down to 100 K. In the soft X-ray-induced excited spin-state trapping (SOXIESST) regime at 3 K, large differences occur between the two ferroelectric polarizations. The efficiency of X-rays in exciting the molecules to the high-spin state is more than an order of magnitude larger when the ferroelectric dipoles of the substrate are pointing toward the surface compared to the opposite polarization. We explain our findings by a modulation of the polarization-dependent efficiency of the scattering of X-ray-generated secondary electrons at the molecules. Our results provide a deep insight into the SOXIESST mechanism and suggest that such molecules could be used as detectors for electrons traveling in the substrate at energies lower than the substrate electron affinity.
 
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