Evolution Of Defect States Research Articles

Variation in defects and properties in composite of ZnO and α-Fe2O3 for sustainable wastewater treatment

Defects in nanostructures play a pivotal role in determining their properties and performance in the desired applications. Herein, the defect states and structural properties of the bi-metal oxide composite of ZnO and α-Fe2O3 (ZF-W) are varied by annealing the composite at different temperatures. The changes in defects, structures, and phase are evaluated thoroughly using transmission electron microscopy, x-ray diffraction, photoluminescence, and Mössbauer spectroscopy techniques. The defect-rich ZF-W composite is found to be composed of defect-deficient ZnFe2O4 attaining the equilibrium state when as-synthesized ZF-W is annealed at 500 °C [ZF-W(500)]. Further annealing at 1000 °C, ZF-W(1000), a non-stoichiometric and highly defected ZnFe2O4 is evidenced in the composite. The changes in the composite with the annealing temperature are correlated with the cationic migration and evolution of defect states. Moreover, the transition associated with the vacancy defects, which trapped the excited electron and dispel the free electrons, thereby inhibiting fast electron–hole pair recombination, is corroborated from the photoluminescence spectra. When implemented for methyl blue adsorption/degradation without the assistance of any external sources, the degradation efficiency of ZF-W, ZF-W(300), ZF-W(500), and ZF-W(1000) is found to be 86%, 84%, 68%, and 82%, respectively. The prepared samples are highly stable and can be used repeatedly without losing effectiveness. The simultaneous evolution of defects and structural properties of the composite are attributed for the variation in methyl blue adsorption/degradation. The present study reveals the importance of defects present in the mixed metal oxide composite in obtaining high-performance dye degradation/adsorption properties for sustainable wastewater treatment.

Revealing the Degradation and Self-Healing Mechanisms in Perovskite Solar Cells by Sub-Bandgap External Quantum Efficiency Spectroscopy.

Ion dissociation has been identified to determine the intrinsic stability of perovskite solar cells (PVSCs), but the underlying degradation mechanism is still elusive. Herein, by combining highly sensitive sub-bandgap external quantum efficiency (s-EQE) spectroscopy, impedance analysis, and theoretical calculations, the evolution of defect states in PVSCs during the degradation can be monitored. It is found that the degradation of PVSCs can be divided into three steps: 1) dissociation of ions from perovskite lattices, 2) migration of dissociated ions, and 3) consumption of I- by reacting with metal electrode. Importantly, step (3) is found to be crucial as it will accelerate the first two steps and lead to continuous degradation. By replacing the metal with more chemically robust indium tin oxide (ITO), it is found that the dissociated ions under light soaking will only saturate at the perovskite/ITO interface. Importantly, the dissociated ions will subsequently restore to the corresponding vacancies under dark condition to heal the perovskite and photovoltaic performance. Such shuttling of mobile ions without consumption in the ITO-contact PVSCs results in harvesting-rest-recovery cycles in natural day/night operation. It is envisioned that the mechanism of the intrinsic perovskite material degradation reported here will lead to clearer research directions toward highly stable PVSCs.

Shallow defect states in two-dimensional photonic crystals

We investigate localized defect states near the edge of a band gap in a two-dimensional photonic crystal. An asymptotic approach based on Green's functions leads to analytical results both for the frequency and for the spatial behavior of the defect states. In particular, we find a simple exponential law which relates the change in frequency of the defect states to the relative change in electrical energy of the Bloch modes on the band edge, and to the density of states in the photonic crystal. We find that the symmetries of the Bloch modes at band extrema play an important role in the manifestation and evolution of defect states. We confirm the analysis with numerical simulations based on the fictitious source superposition method.

Metastable defect creation in tritiated hydrogenated amorphous silicon and the Staebler–Wronski effect

Defect creation through tritium decay in tritiated hydrogenated amorphous silicon provides a unique technique for the study of defect dynamics in hydrogenated amorphous silicon (a-Si:H). Isothermal Capacitance Transient Spectroscopy (ICTS) and Constant Photocurrent Method (CPM) were used to measure the positively charged, D+, and negatively charged, D−, states in the gap of a-Si:H:T, respectively. The samples were thermally annealed prior to the measurement of defect state densities. The ICTS experiments showed a decrease in the concentration of positively charged dangling bonds while the CPM measurements showed an increase in the density of D− states with time. This increase was much larger than the concentration of decayed tritium atoms. The CPM results also showed that the Urbach energy decreased with time. The decrease in Urbach energy indicates a decrease in the concentration of weak bonds in the valence band tail and suggests weak bond to dangling bond conversion. CPM experiments carried out under bias confirm the role of excess carriers in the defect creation process. The dynamic defect pool model was developed to quantitatively explain the experimental data. The defect evolution in a-Si:H:T is similar to the evolution of defect states in light exposure studies, supporting the interpretation of the Staebler–Wronski effect in terms of weak bond to dangling bond conversion.

Effect of Fermi Level Position in Intrinsic a-Si:H on the Evolution of Defect States under Light Exposure.

AbstractThe evolution of the programmed defect-state distributions in intrinsic hydrogenated amorphous silicon (a-Si:H) due to light soaking was qualitatively determined from charge deep-level transient spectroscopy. The defect-state distribution in a-Si:H was programmed by applying a particular bias voltage on the metal-oxide-semiconductor structure while annealing the structure above the equilibration temperature. The programmed distributions simulate defect-state distributions in different parts of an actual a-Si:H solar cell, particularly in the intrinsic regions close to the p/i and i/n interfaces.The defect-state distribution in the bulk of the intrinsic layer is characterized by comparable contributions from the positively charged defect states above midgap, Dh, neutral states, Dz, and negatively charged states below midgap, De. In the programmedp-type (n-type) defect-state distribution there is an excess of the Dh (De) states. Light exposure modifies the p-type distribution that evolves to a broad distribution of states with a maximum around midgap. This distribution is dominated by Dz states with substantial contributions from Dh and De states. In case of n-type distribution light soaking only slightly influences the distribution by removing a part of the Dh states and by a small increase of Dz and De states.

Evolution of defect states in doped polythiophene: A study based on the method of simulated annealing

AbstractA modified Su–Schrieffer–Heeger Hamiltonian‐based model is used to compute the electronic and geometric structures of fairly long polythiophene (PT) chains, neutral as well as doped. The geometry optimization is carried out by the simulated annealing method. Both Metropolis and Glauber functions are used for sampling. It is shown that a bipolaron can be structurally represented by a fragment of the PT chain containing 14 thiophene units. As a series of bipolaronic defects are introduced in a long PT chain (50–100 rings), the highest occupied molecular orbital (HOMO)–lowest unoccupied molecular orbital (LUMO) gap energy (Δ) becomes vanishingly small, a feature not present in the PT chains of similar sizes containing polaronic defects. The Fermi energy level (EF) also moves into the valency band and nonzero density of states at ϵ = EF are created. Once again, this feature is shown to be missing in PT chains containing polaronic defects. Implications of these findings are analyzed. © 2003 Wiley Periodicals, Inc. Int J Quantum Chem, 2003