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Ultrafast Spin Crossover in a Room-Temperature Ferrimagnet: Element-Specific Spin Dynamics in Photoexcited Cobalt Ferrite

Journal Article · · Journal of Physical Chemistry. C
 [1];  [2];  [2];  [2];  [2];  [2];  [2];  [2];  [2];  [2]
  1. The Ohio State Univ., Columbus, OH (United States); The Ohio State University, Ohio (United States) - Department of Chemistry and Biochemistry
  2. The Ohio State Univ., Columbus, OH (United States)
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Transition metal complexes capable of photoinduced spin crossover have been greatly investigated because of their potential to enable ultrafast optical control of information processing. Yet, any real application of photoswitchable molecules requires that spin crossover be paired with additional functionality such as long-range magnetic order. Important advances combining these functions are notably reported for a number of bimetallic Prussian Blue analogues; however, to date, PBA-based magnetic photoswitches can only operate below 150 K due to loss of magnetic order. In contrast, cobalt ferrite is a ferrimagnetic semiconductor with a Curie temperature of 790 K and extremely favorable magnetic properties by comparison to state-of-the-art PBAs. The mixed valence electronic structure of cobalt ferrite is reminiscent of cobalt–iron PBA, which is a well-known photoswitch. To investigate the potential for photoswitching in this material, we employ transient XUV spectroscopy to probe charge and spin dynamics with element-specific resolution on the femtosecond time scale. Results show that 400 nm light excites a metal-to-metal charge transfer transition, which drives the crossover of high-spin Co2+ to low-spin Co3+ with a time constant of 405 ± 29 fs and an internal quantum efficiency of unity. This result establishes the existence of efficient photoswitching in a new class of robust ferrimagnetic spinel ferrites.
Research Organization:
The Ohio State Univ., Columbus, OH (United States)
Sponsoring Organization:
National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division
Grant/Contract Number:
SC0014051
OSTI ID:
1617194
Journal Information:
Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Journal Issue: 21 Vol. 124; ISSN 1932-7447
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

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