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.
ผลหลักของฟอสฟอรัสในวัสดุศึกษาเป็นการสร้างความศูนย์ luminescence ชอบ UV luminescence มันให้วงกว้างใน 4-5 eV ซึ่งเป็นเงื่อนไขในการกระตุ้นและเวลาของการตรวจสอบ ดังนั้น เราสังเกตส่วนประกอบได้อย่างรวดเร็ว ซึ่งมีลักษณะคล้ายร้อนใน P doped คริสตัลด้วยกองทัพและแก้ว phosphor – ซิลิเคท ธรรมชาติของการเปลี่ยนทางอิเล็กทรอนิกส์ในไม่ชอบ luminescence UV ในวัสดุศึกษาศูนย์สามารถอธิบายเป็นช่วงภายในศูนย์ จริง กรณี Pคริสตัลควอตซ์ด้วยกองทัพ doped มีเป็นจดหมายโต้ตอบระหว่างความร้อนอาศัยของพารามิเตอร์ความเข้มและผุ Fig. 7 ในกรณีของแก้วฟอสเฟต เหตุผลจะพบในโพลาไรซ์ [3] ของluminescence การในการกระตุ้นแสงโพลาไรซ์ ในกรณีของซิลิเคท phospho คริสตัลและแก้วศูนย์ภายในลักษณะของการเปลี่ยนที่ไม่สามารถโต้เถียง โดยการสังเกตของช้าผุ และเพิ่มความเข้มในการลดอุณหภูมิ ลักษณะการทำงานของ3150 3200 3250 3300 3350-2000200Γ-irr 105 rad annealed ที่ 400 C ArF irradiated 18 นาที หลังจาก anealingความเข้ม (arb.units)Doped ฟอสฟอรัส (0.01%) ด้วยกองทัพ - ควอตซ์สนามแม่เหล็ก (เกาส์)Fig. 14 การอบเหนียวระบายความร้อนของแรมสเป็คตรา ESR ของฟอสฟอรัส doped ด้วยกองทัพ และอิทธิพลของวิธีการฉายรังสีของ ArF400 500 600 700 8000816ซม. 414 293 K 9 KPL ความเข้ม (arb.units)550 C ถือว่า ArF P doped ด้วยกองทัพควอตซ์ irradiated และตื่นเต้นความยาวคลื่น (nm)903 cm0 10 20 30 40 501010 647 nm, 9Kτ=18 μsTIME 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 nmis ascribed to zero phonon line of induced non-bridging oxygen luminescencecenter. Lines shifted from ZPL are 75 cm1, 414 cm1 and 903 cm1. Sharp lineslabeled 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) 346–355recombination luminescence should be opposite. If the nature ofluminescence excitation process could be recombination of electronand holes, the decreasing temperature should slow downdecay duration and decreased luminescence intensity. So, experimentaldata underline intra-center nature of electronic transitions.Using exponential approximation we were able compare PLintensity and time constant thermal dependences, Fig. 7. Theeffects related to singlet and triplet states were discovered. Thoseare the zero magnetic field splitting of the triplet state and singlet–triplet splitting of UV PL band. In this our studied phosphoruscontaining materials correlates with observation of singlet tripletnature of self-trapped exciton luminescence in scandium orthophosphate[6–8]. The STE in scandium orthophosphate wasassumed as hole component on PO4 tetrahedron whereas electronspread over scandium. Similar model of UV luminescence centercreated by phosphorus in silicon dioxide could be proposed.Excited state of this center could be imagined as electron transitionfrom PO4 tetrahedron to states of silicon. Remarkable is thatheat treatment of P-doped quartz to 550 °C does not destroycompletely UV luminescence. Oppositely, this treatment completelyremoves yellow luminescence and strongly affects IRabsorption related to water and OH groups. Therefore correspondingUV luminescence center should be connected to phosphorussituated in position far from water and OH groups. In thatUV luminescence center is similar to UV luminescence of ScPO4,where water and OH groups were not observed by direct measurementof IR absorption.In the case of studied glasses, where concentration of phosphorusis high, some additional peculiarities may be observed inthe case of disordered materials. That is structural non-equivalenceof centers with corresponding transformation of single decaykinetics (exponent) to a wide distribution of parameters.Center responsible for UV luminescence participates inrecombination processes. It is seen in thermally stimulated luminescence,Fig. 11.
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