| dc.description.abstract | Despite the large number of successful commercial applications of chalcogenide glasses (ChGs)
ranging from memory devices to photonics and medical imaging detectors, the understanding of a
fundamental property – photo-induced structural metastability is not yet complete. The inherent
trend of amorphous chalcogenides to convert to its crystalline counterpart, can on the one hand, be
directly utilized in phase-change memories, while on the other hand can degrade glass properties
for applications in sensing. Furthermore, because the structure of amorphous semiconductors is not
fixed by thermodynamic equilibrium conditions, its transformation can be triggered by optical/X-ray
excitation and influenced by thermal heating or applied electric field. Each case has its own
peculiarities of transformation. Thus, to ensure effective application of a given ChG, a solid
understanding of the causes for the structural transformation on the microscopic level has to be
developed.
This thesis is devoted to the study of photo-induced metastability of the most widely used ChG –
amorphous selenium (a-Se), and archetypal a-GexSe100-x glass compounds relevant for applications in
sensing. We focus on the research of defect creation and defect relaxation processes in these
materials since it is hypothesized to be the root cause for structural transformations affecting
stability. The detailed experimental and theoretical study is carried out to reveal the pathways
from a micro-level, i.e. defect creation/relaxation, to the macro-level photo-induced effects
formation, namely photodarkening (PD), photobleaching (PB) and photo-induced crystallization (PC)
and their kinetics.
The effects of temperature and energy of excitation on PD kinetics are studied in a- Se. Distinctly
different PD effects are observed in the case of sub-bandgap and above- bandgap excitation. It is
found that above-bandgap excitation causes only transient photodarkening with a temperature
independent relaxation time and no significant structural rearrangements. In contrast, sub-bandgap
excitation causes both transient and metastable PD effects. Whereas the mechanism responsible for
transient PD for sub- bandgap excitation is analogous to that in the case of
above-bandgap excitation,
metastable PD is controlled by the formation of self-trapped excitons resulting in
structural transformations into configuration defects. Subsequent relaxation in the latter case is
shown to be a thermally activated process at elevated temperatures; or configuration tunneling
below the room temperature. It is confirmed that if left unrestored, metastable PD acts as a
precursor for photo-induced crystallization.
Detailed investigation of the effects of different substrates and temperature on photo- induced
crystallization in a-Se demonstrates that the onset of PC is suppressed by softening of the
film-substrate interface and/or by operating at temperatures near the glass transition.
Further, photodarkening and photobleaching effects are investigated in a-GexSe100-x as a function
of composition across the glass forming region. The Ge:Se ratio is found to play a decisive role in
the observed effects. The critical concentration of Ge ≈30% is highlighted to correspond to the
crossover from transient PB to a mixture of transient PD and metastable PB. The underlying
microscopic mechanism is governed by the availability of lone pair (LP) states at Se atoms. For
low-Ge content films (x<20%) LPs are primarily involved in photoexcitation, causing a
photodarkening effect (like in a-Se). As Ge concentration reaches 30%, Ge-Se bond breakage becomes
prevalent under light exposure, which results in the generation of dangling bonds and the
saturation of the available LP states. This is found to be responsible for the transient PB effect.
With further increase of Ge %, the amount of homopolar Ge-Ge bonds starts to increase along with
the obvious deficiency of lone pairs. This leads to Ge-Ge bond breakage upon excitation, which
causes transient photodarkening. In the post-excitation period, however, it initiates transition to
a more ordered state with the main feature of the formation of 3D nanostructures. This is reflected
in a bandgap increase and an experimentally observed metastable photobleaching effect.
Finally, our understanding of a-Se properties allowed us to extend its application in low-energy
nuclear medicine devices. A novel fluence integrating gamma camera is proposed, which if
commercialized, will be used to guide advanced breast cancer treatment that involves the placement
of low-energy radioactive seeds. The feasibility of the proposed approach is confirmed in realistic
breast phantom studies. Our results demonstrate the potential of the gamma camera to fulfill the
clinical requirements of both
spatial resolution and sensitivity. | en_US |
