Reversible control of the chromium valence in chemically reduced Cr-doped SrTiO3 bulk powders.

The effect of chemical reduction by NaBH4 on the electronic structure of Cr-doped SrTiO3-δ bulk powders prepared by a solid-state reaction was systematically studied as a function of reduction temperature. Electron paramagnetic resonance (EPR) and diffuse reflectance spectroscopies (DRS) were utilized to monitor changes in the electronic structures of both intrinsic defects (oxygen vacancies and/or Ti(3+)) and extrinsic dopants (Cr(3+)) at different reduction temperatures. We identify the existence of two temperature regimes where changes occur within 30 min. The first temperature regime occurs between 300-375 °C and results in (1) reduction of oxygen-related surface defects, and (2) an increase in the concentration of Cr(3+) by over an order of magnitude, suggesting that EPR-silent Cr(4+) or Cr(6+) is being reduced to Cr(3+) by NaBH4. The second temperature regime occurs between 375-430 °C where we observe clear evidence of Ti(3+) formation by EPR spectroscopy that indicates chemical reduction of the SrTiO3 lattice. In addition, the oxygen-related surface defects observed in regime 1 are not formed in regime 2, but instead lattice oxygen vacancies (VO) are observed by EPR. The changes to the Cr-doped SrTiO3 electronic structure after chemical reduction in regime 1 are quantitatively reversible after aerobic annealing at 400 °C for 30 min. The internal oxygen vacancies formed during the higher temperature reductions in regime 2 require increased temperatures of at least 600 °C to be fully reoxidized in 30 min. The effect of these different oxygen-related defects on the EPR spectrum of substitutional Cr(3+) dopants is discussed. These results allow us to independently tune the dopant and host electronic structures of a technologically-relevant multifunctional material by a simple ex situ chemical perturbation.