The energy level diagram of the Cr3+ ion in an octahedral crystal
field consists of the ground 4
A2 state and the 2
E and 2
T1 doublet
state and two 4
T2 and 4
T1 quartet states. The spin allowed 4
A2 ? 4
T2 and 4
A2 ? 4
T1 transitions are responsible for most intense
two broad absorption bands in visible range of Cr3+ ion.
The spin-forbidden absorption transitions are recorded as some
weak features in absorption spectrum of Cr3+ ion. We have tried
to measure the absorption spectra of Cr3+:MgAl2O4 nanocrystalline
powders however their quality was very poor. Therefore, to get insight
into their structure we have measured the excitation spectra
of Cr3+:MgAl2O4 samples. The respective excitation spectra of
Cr3+:MgAl2O4 nanocrystalline powders sintered at different
annealing temperatures were measured at room temperature
(see Fig. 4). For comparison it was taken the absorption spectrum
of Cr3+:MgAl2O4 synthetic spinel crystal [7]. The respective energy
features of observed absorption bands are given in Table 1. A simple
comparison of the absorption transitions bands in excitation
and absorption spectra points on different distribution of the
intensities – in absorption spectrum the intensity of 4
A2 ? 4
T2
band is lower than 4
A2 ? 4
T1 band whereas in excitation spectra
their distribution is quite opposite. The intensity of 4
T1 band is very
low, practically absent for the nanocrystals characterized by smallest
sizes. It means that main contribution to the 2
E ? 4
A2 phosphorescence
comes from the 4
T2 ? 2
E intersystem crossing. Moreover,
it is interesting to note that with increasing the grain size a contribution
of the 4
T1 band to overall phosphorescence intensity
increases.
To discuss the observed effect we have calculated the intensity
ratio between the intensities of both quartet states b = I(
4
T2)/
I(4
T1). The dependence of intensity ratio on average size of
Cr3+:MgAl2O4 nanocrystals is shown in Fig. 5. One can observe
that with increasing the grain size D the intensity ratio decreases
linearly. This result seems to be surprising and its elucidation
needs further more elaborated experimental and theoretical studies.
We suppose that for the smallest grain the electron–phonon
interaction is reduced due to confinement effect [18] leading to
diminishing the multiphonon relaxation from the 4
T1 state to
the 4
T2 and 2
E states.
The respective energy features measured in the excitation spectra
of Cr3+:MgAl2O4 samples and their assignments are listed in Table
1. One can note, that with increasing the grain size the maxima
of the absorption bands and phosphorescence are shifted into the
blue. This effect was smaller for the spin-forbidden phosphorescence
however for the spin allowed absorption transitions was significant.
It means that with increasing the grain size the crystal
field strength increases.