K. V. Adarsh

Coexistence of fast photodarkening and slow photobleaching in Ge19As21Se60 thin films

We experimentally demonstrate the coexistence of two opposite photo-effects, viz. fast photodarkening (PD) and slow photobleaching (PB) in Ge(19)As(21)Se(60) thin films, when illuminated with a laser of wavelength 671 nm. PD appears to begin instantaneously upon light illumination and saturates in tens of seconds. By comparison, PB is a slower process that starts only after PD has saturated. Both PD and PB follow stretched exponential dependence on time. Modeling of overall change as a linear sum of two contributions suggests that the changes in As and Ge parts of glass network respond to light effectively independent of each other.

Origin of Unusual Excitonic Absorption and Emission from Colloidal Ag2S Nanocrystals: Ultrafast Photophysics and Solar Cell.

Colloidal Ag2S nanocrystals (NCs) typically do not exhibit sharp excitonic absorption and emission. We first elucidate the reason behind this problem by preparing Ag2S NCs from nearly monodisperse CdS NCs employing cation exchange reaction. It was found that the defect-related midgap transitions overlap with excitonic transition, blurring the absorption spectrum. On the basis of this observation, we prepared nearly defect-free Ag2S NCs using molecular precursors. These defect-free Ag2S NCs exhibit sharp excitonic absorption, emission (quantum yield 20%) in near-infrared (853 nm) region, and improved performance of Ag2S quantum-dot-sensitized solar cells (QDSSCs). Samples with lower defects exhibit photoconversion efficiencies >1% and open circuit voltage of ∼0.3 V, which are better compared with prior reports of Ag2S QDSSCs. Femtosecond transient absorption shows pump-probe two-photon absorption above 630 nm and slow-decaying excited state absorption below 600 nm. Concomitantly, open-aperture z-scan shows strong two-photon absorption at 532 nm (coefficient 55 ± 3 cm/GW).

Role of Ge:As ratio in controlling the light-induced response of a-GexAs35-xSe65 thin films

In this paper, we present interesting results on the quantification of photodarkening (PD), photobleaching (PB) and transient PD (TPD) in a-GexAs35−xSe65 thin films as a function of network rigidity. Composition dependent light-induced responses of these samples indicate that there exist two parallel competing mechanisms of instantaneous PD arising from the As part of the network, and PB arising from the Ge part of the network. Raman spectra of the as-prepared and illuminated samples provide first direct evidence of the light-induced structural changes: an increase in AsSe3/2 pyramidal and GeSe4/2 corner-sharing tetrahedra units together with new Ge-O bond formation and decrease in energetically unstable edge sharing GeSe4/2 tetrahedra. Importantly, for a fixed Se concentration, Ge:As ratio plays the critical role in controlling the net light-induced response rather than the much believed rigidity of the glassy network.

Role of rigidity and temperature in the kinetics of photodarkening in Ge x As (45-x) Se 55 thin films

We present insightful results on the kinetics of photodarkening (PD) in Ge(x)As(45-x)Se55 glasses at the ambient and liquid helium temperatures when the network rigidity is increased by varying x from 0 to 16. We observe a many fold change in PD and its kinetics with decreasing network flexibility and temperature. Moreover, temporal evolution of PD shows a dramatic change with increasing x.

Crossover from photodarkening to photobleaching in a-Ge x Se 100-x thin films

In this Letter, we present the interesting results of photodarkening (PD), transition toward photostability, and a slow crossover from PD to photobleaching when composition of the chalcogenide glassy thin film changes from Ge-deficient to rich. A subsequent Raman analysis on these as-prepared and irradiated samples provide the direct evidence of photoinduced structural rearrangement, i.e., photocrystallization of Se and the removal of edge-sharing GeSe4 tetrahedra. Further, our experimental results clearly demonstrate that light-induced effects can be effectively controlled by choosing the right composition and provide valuable information on synthesizing photostable/sensitive glasses.

Photoinduced transparency of effective three-photon absorption coefficient for femtosecond laser pulses in Ge16As29Se55 thin films

We report a dramatic change in effective three-photon absorption coefficient of amorphous Ge16As29Se55 thin films, when its optical band gap decreases by 10 meV with 532 nm light illumination. This large change provides valuable information on the higher excited states, which are otherwise inaccessible via normal optical absorption. The results also indicate that photodarkening in chalcogenide glasses can serve as an effective tool to tune the multiphoton absorption in a rather simple way

Ultrafast light induced unusually broad transient absorption in the sub-bandgap region of GeSe2 thin film.

In this paper, we show for the first time that ultrafast light illumination can induce an unusually broad transient optical absorption (TA), spanning of ≈ 200 nm in the sub-bandgap region of chalcogenide GeSe2 thin films, which we interpret as being a manifestation of creation and annihilation of light induced defects. Further, TA in ultrashort time scales show a maximum at longer wavelength, however blue shifts as time evolves, which provides the first direct evidence of the multiple decay mechanisms of these defects. Detailed global analysis of the kinetic data clearly demonstrates that two and three decay constants are required to quantitatively model the experimental data at ps and ns respectively.

Nanosecond light induced, thermally tunable transient dual absorption bands in a-Ge 5 As 30 Se 65 thin film

In this article, we report the first observation of nanosecond laser induced transient dual absorption bands, one in the bandgap (TA1) and another in the sub-bandgap (TA2) regions of a-Ge5As30Se65 thin films. Strikingly, these bands are thermally tunable and exhibit a unique contrasting characteristic: the magnitude of TA1 decreases while that of TA2 increases with increasing temperature. Further, the decay kinetics of these bands is strongly influenced by the temperature, which signifies a strong temperature dependent exciton recombination mechanism. The induced absorption shows quadratic and the decay time constant shows linear dependence on the laser beam fluence.

Engineering the optical response of a-Se thin films by employing morphological disorder

In this article, we experimentally demonstrate for the first time that photobleaching (PB) can be induced in morphologically disordered a-Se thin film, an observation which is opposite of the previously well-known photodarkening (PD) effects in morphologically ordered films. Further, the optical response of the film shows many fold increase with increase in control beam intensity. To explain the observed extraordinary phenomenon, we have proposed a model based on the morphological disorder of a modified surface and its subsequent photo-annealing. Our results demonstrate an efficient and yet simple new method to engineer the optical response of photosensitive thin films. We envision that this process can open up many avenues in optical field-enhanced absorption-based technologies.

Light induced diffusion driven self assembly of Ag nanoparticles in a-Se/Ag bi-layer thin film with ultrafast optical response

In this Letter, we demonstrate that femtosecond light-induced interdiffusion of Ag driven by the electrostatic attraction between photo-excited Ag+ ions and negatively charged amorphous layer can act as an efficient single step method for hybrid integration of spatially ordered and interconnected nanoparticles on the surface of amorphous films. Such self assembled complex hybrid structures of silver nanoparticles via bottom-up nano-construction method on a-Se thin film show an ultrafast optical response over an unusually broad wavelength range that can be used to construct optical modulators operating at switching speed of ∼5 ps.