Main effect of phosphorus in studied materials is creation of a
luminescence center responsible for UV luminescence. It provide
broad band at 4–5 eV, which is sensitive to conditions of excitation
and time of detection. Thus, we observe a fast component, which
possesses similar thermal behavior in P doped α-quartz crystal
and phosphor–silicate glass. The nature of electronic transitions in
center responsible for UV luminescence in studied materials could
be explained as intra-center transitions. Indeed, the case of P
doped α-quartz crystal there is correspondence between thermal
dependence of intensity and decay parameters, Fig. 7. In the case
of phosphate glasses the reason is observed in [3] polarization of
luminescence for excitation with polarized light. In the case of
phospho-silicate crystal and glass the intra-center nature of the
transitions could be argued by observation of slowing decay and
increasing intensity for decreasing temperature. The behavior of
3150 3200 3250 3300 3350
-200
0
200
γ-irr. 105
rad
annealed at 400 C
ArF irradiated 18 min
after anealing
intensity (arb.units)
Phosphorus doped (0.01%) α- quartz,
magnetic field (gauss)
Fig. 14. Thermal annealing of ESR spectra of phosphorus doped α-quartz and
influence of ArF irradiation.
400 500 600 700 800
0
8
16
414 cm
293 K
9 K
PL intensity (arb.units)
550 C treated P-doped α-quartz ArF irradiated & excited
WAVELENGTH (nm)
903 cm
0 10 20 30 40 50
10
10
647 nm, 9K
τ=18 μs
TIME μs)
Fig. 15. ArF laser induced PL spectra of P doped α-quartz 2 h annealed at 550 °C.
Measurements are performed at 9 K under pulses of ArF laser. Sharp line at 647 nm
is ascribed to zero phonon line of induced non-bridging oxygen luminescence
center. Lines shifted from ZPL are 75 cm1
, 414 cm1 and 903 cm1
. Sharp lines
labeled in cm1 correspond to shift of those lines form zero phonon line. Inset –
decay kinetics curve under ArF laser at 9 K and exponential fit of this curve.
352 A.N. Trukhin et al. / Journal of Luminescence 166 (2015) 346–355
recombination luminescence should be opposite. If the nature of
luminescence excitation process could be recombination of electron
and holes, the decreasing temperature should slow down
decay duration and decreased luminescence intensity. So, experimental
data underline intra-center nature of electronic transitions.
Using exponential approximation we were able compare PL
intensity and time constant thermal dependences, Fig. 7. The
effects related to singlet and triplet states were discovered. Those
are the zero magnetic field splitting of the triplet state and singlet–
triplet splitting of UV PL band. In this our studied phosphorus
containing materials correlates with observation of singlet triplet
nature of self-trapped exciton luminescence in scandium orthophosphate
[6–8]. The STE in scandium orthophosphate was
assumed as hole component on PO4 tetrahedron whereas electron
spread over scandium. Similar model of UV luminescence center
created by phosphorus in silicon dioxide could be proposed.
Excited state of this center could be imagined as electron transition
from PO4 tetrahedron to states of silicon. Remarkable is that
heat treatment of P-doped quartz to 550 °C does not destroy
completely UV luminescence. Oppositely, this treatment completely
removes yellow luminescence and strongly affects IR
absorption related to water and OH groups. Therefore corresponding
UV luminescence center should be connected to phosphorus
situated in position far from water and OH groups. In that
UV luminescence center is similar to UV luminescence of ScPO4,
where water and OH groups were not observed by direct measurement
of IR absorption.
In the case of studied glasses, where concentration of phosphorus
is high, some additional peculiarities may be observed in
the case of disordered materials. That is structural non-equivalence
of centers with corresponding transformation of single decay
kinetics (exponent) to a wide distribution of parameters.
Center responsible for UV luminescence participates in
recombination processes. It is seen in thermally stimulated luminescence,
Fig. 11.
Main effect of phosphorus in studied materials is creation of aluminescence center responsible for UV luminescence. It providebroad band at 4–5 eV, which is sensitive to conditions of excitationand time of detection. Thus, we observe a fast component, whichpossesses similar thermal behavior in P doped α-quartz crystaland phosphor–silicate glass. The nature of electronic transitions incenter responsible for UV luminescence in studied materials couldbe explained as intra-center transitions. Indeed, the case of Pdoped α-quartz crystal there is correspondence between thermaldependence of intensity and decay parameters, Fig. 7. In the caseof phosphate glasses the reason is observed in [3] polarization ofluminescence for excitation with polarized light. In the case ofphospho-silicate crystal and glass the intra-center nature of thetransitions could be argued by observation of slowing decay andincreasing intensity for decreasing temperature. The behavior of3150 3200 3250 3300 3350-2000200γ-irr. 105 rad annealed at 400 C ArF irradiated 18 min after anealingintensity (arb.units)Phosphorus doped (0.01%) α- quartz,magnetic field (gauss)Fig. 14. Thermal annealing of ESR spectra of phosphorus doped α-quartz andinfluence of ArF irradiation.400 500 600 700 8000816414 cm 293 K 9 KPL intensity (arb.units)550 C treated P-doped α-quartz ArF irradiated & excitedWAVELENGTH (nm)903 cm0 10 20 30 40 5010
10
647 nm, 9K
τ=18 μs
TIME μs)
Fig. 15. ArF laser induced PL spectra of P doped α-quartz 2 h annealed at 550 °C.
Measurements are performed at 9 K under pulses of ArF laser. Sharp line at 647 nm
is ascribed to zero phonon line of induced non-bridging oxygen luminescence
center. Lines shifted from ZPL are 75 cm1
, 414 cm1 and 903 cm1
. Sharp lines
labeled in cm1 correspond to shift of those lines form zero phonon line. Inset –
decay kinetics curve under ArF laser at 9 K and exponential fit of this curve.
352 A.N. Trukhin et al. / Journal of Luminescence 166 (2015) 346–355
recombination luminescence should be opposite. If the nature of
luminescence excitation process could be recombination of electron
and holes, the decreasing temperature should slow down
decay duration and decreased luminescence intensity. So, experimental
data underline intra-center nature of electronic transitions.
Using exponential approximation we were able compare PL
intensity and time constant thermal dependences, Fig. 7. The
effects related to singlet and triplet states were discovered. Those
are the zero magnetic field splitting of the triplet state and singlet–
triplet splitting of UV PL band. In this our studied phosphorus
containing materials correlates with observation of singlet triplet
nature of self-trapped exciton luminescence in scandium orthophosphate
[6–8]. The STE in scandium orthophosphate was
assumed as hole component on PO4 tetrahedron whereas electron
spread over scandium. Similar model of UV luminescence center
created by phosphorus in silicon dioxide could be proposed.
Excited state of this center could be imagined as electron transition
from PO4 tetrahedron to states of silicon. Remarkable is that
heat treatment of P-doped quartz to 550 °C does not destroy
completely UV luminescence. Oppositely, this treatment completely
removes yellow luminescence and strongly affects IR
absorption related to water and OH groups. Therefore corresponding
UV luminescence center should be connected to phosphorus
situated in position far from water and OH groups. In that
UV luminescence center is similar to UV luminescence of ScPO4,
where water and OH groups were not observed by direct measurement
of IR absorption.
In the case of studied glasses, where concentration of phosphorus
is high, some additional peculiarities may be observed in
the case of disordered materials. That is structural non-equivalence
of centers with corresponding transformation of single decay
kinetics (exponent) to a wide distribution of parameters.
Center responsible for UV luminescence participates in
recombination processes. It is seen in thermally stimulated luminescence,
Fig. 11.
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