SrCoO2
.5 (SCO) bulk is found to be a charge-transfer insulator with
a positive
value of charge-transfer energy (Δ) and 3d6 ground
state, which achieves the antiferromagnetic nature through conventional
Co3+–O–Co3+ superexchange interaction.
However, in the epitaxial SCO thin film, it is observed, with the
help of resonant photoemission spectroscopy and X-ray absorption spectroscopy,
that substrate-induced strain modifies the ground state of SCO film
to 3d7
L (L: O-2p hole), causing a negative value of Δ. The presence of
the O-2p hole in the negative Δ SCO film arises because of strong
O 2p–Co 3d hybridization and induces charge disproportionation
(CD) in the system. Consequently, the Co3+–O–Co3+ superexchange interaction is modified, and a hole-mediated
unconventional ferromagnetic (or ferrimagnetic) ordering is observed
in the SCO film. The magnetic moment is found to depend on the values
of Δ and CD, which are controlled by the lattice-induced strain.
This is manifested from the strain-dependent valence band and conduction
band spectra of the SCO films. Because of the negative Δ and
CD, additional spectral features appear in the Co L-edge of the films,
which are absent in its bulk counterpart. The energy positions and
intensities of such features vary with the film thickness, divulging
the role of strain in modifying Δ (and CD). Tuning SCO from
the positive Δ regime in the bulk to the negative Δ regime
in the thin film provides an opportunity to modulate the electronic
structure vis-à-vis magnetic property via strain
engineering with huge technological potential applications.