Subscribe to the gold package and get unlimited access to Shamra Academy
Register a new userAnion vacancies as a source of persistent photoconductivity in II-VI and chalcopyrite semiconductors
172
0
0.0
(
0
)
Ask ChatGPT about the research
No Arabic abstract
Using first-principles electronic structure calculations we identify the anion vacancies in II-VI and chalcopyrite Cu-III-VI2 semiconductors as a class of intrinsic defects that can exhibit metastable behavior. Specifically, we predict persistent electron photoconductivity (n-type PPC) caused by the oxygen vacancy VO in n-ZnO, and persistent hole photoconductivity (p-type PPC) caused by the Se vacancy VSe in p-CuInSe2 and p-CuGaSe2. We find that VSe in the chalcopyrite materials is amphoteric having two negative-U like transitions, i.e. a double-donor transition e(2+/0) close to the valence band and a double-acceptor transition e(0/2-) closer to the conduction band. We introduce a classification scheme that distinguishes two types of defects (e.g., donors): type-alpha, which have a defect-localized-state (DLS) in the gap, and type-beta, which have a resonant DLS within the host bands (e.g., conduction band). In the latter case, the introduced carriers (e.g., electrons) relax to the band edge where they can occupy a perturbed-host-state (PHS). Type alpha is non-conducting, whereas type beta is conducting. We identify the neutral anion vacancy as type-alpha and the doubly positively charged vacancy as type-beta. We suggest that illumination changes the charge state of the anion vacancy and leads to a crossover between alpha- and beta-type behavior, resulting in metastability and PPC. In CuInSe2, the metastable behavior of VSe is carried over to the (VSe-VCu) complex, which we identify as the physical origin of PPC observed experimentally. We explain previous puzzling experimental results in ZnO and CuInSe2 in the light of this model.
rate research
Read More
Controlled chemical transformation of nanostructures is a promising technique to obtain precisely designed novel materials which are difficult to synthesize otherwise. We report high-temperature vapor phase anion exchange reactions to chemically transform II-VI semiconductor nanostructures (100-300 nm length scale) while retaining the single crystallinity, crystal structure, morphology and even defect distribution of the parent material via atomic templating. The concept of atomic templating is employed to obtain kinetically controlled, thermodynamically metastable structural phases such as zincblende CdSe and CdS from zincblende CdTe upon complete chemical replacement of Te with Se or S. The underlying transformation mechanisms are explained through first-principles density functional theory calculations. Atomic templating is a unique path to independently tune materials phase and composition at the nanoscale allowing synthesis of novel materials.
We demonstrate that X-ray irradiation can be used to induce an insulator-metal transition in Si-doped Al$_{0.35}$Ga$_{0.65}$As, a semiconductor with {it DX} centers. The excitation mechanism of the {it DX} centers into their shallow donor state was revealed by studying the photoconductance along with fluorescence. The photoconductance as a function of incident X-ray energy exhibits an edge both at the Ga and As K-edge, implying that core-hole excitation of Ga and As are efficient primary steps for the excitation of {it DX} centers. A high quantum yield ($gg 1$) suggests that the excitation is indirect and nonlocal, due to secondary electrons, holes, and fluorescence photons.
The Persistent Photoconductivity (PPC) effect was studied in individual tin oxide (SnO2) nanobelts as a function of temperature, in air, helium, and vacuum atmospheres, and low temperature Photoluminescence measurements were carried out to study the optical transitions and to determine of the acceptor/donors levels and their best representation inside the band gap. Under ultraviolet (UV) illumination and at temperatures in the range of 200 to 400K we observed a fast and strong enhancement of the photoconductivity, and the maximum value of the photocurrent induced increases as the temperature or the oxygen concentration decreases. By turning off the UV illumination the induced photocurrent decays with lifetimes up to several hours. The photoconductivity and the PPC results were explained by adsorption and desorption of molecular oxygen at the surface of the SnO2 nanobelts. Based on the temperature dependence of the PPC decay an activation energy of 230 meV was found, which corresponds to the energy necessary for thermal ionization of free holes from acceptor levels to the valence band, in agreement with the photoluminescence results presented. The molecular-oxygen recombination with holes is the origin of the PPC effect in metal oxide semiconductors, so that, the PPC effect is not related to the oxygen vacancies, as commonly presented in the literature.
Large and persistent photoconductivity (LPPC) in semiconductors is due to the trapping of photo-generated minority carriers at crystal defects. Theory has suggested that anion vacancies in II-VI semiconductors are responsible for LPPC due to negative-U behavior, whereby two minority carriers become kinetically trapped by lattice relaxation following photo-excitation. By performing a detailed analysis of photoconductivity in CdS, we provide experimental support for this negative-U model of LPPC. We also show that LPPC is correlated with sulfur deficiency. We use this understanding to vary the photoconductivity of CdS films over nine orders of magnitude, and vary the LPPC characteristic decay time from seconds to 10^4 seconds, by controlling the activities of Cd^{2+} and S^{2-} ions during chemical bath deposition. We suggest a screening method to identify other materials with long-lived, non-equilibrium, photo-excited states based on the results of ground-state calculations of atomic rearrangements following defect redox reactions, with a conceptual connection to polaron formation.
The interface between the band gap insulators LaAlO3 and SrTiO3 is known to host a highly mobile two-dimensional electron gas. Here we report on the fabrication and characterization of the NdGaO3/SrTiO3 interface, that shares with LaAlO3/SrTiO3 an all-perovskite structure, the insulating nature of the single building block and the polar-non polar character. Our work demonstrates that in NdGaO3/SrTiO3 a metallic layer of mobile electrons is formed, with properties comparable to LaAlO3/SrTiO3. The localization of the injected electrons at the Ti sites, within a few unit cells from the interface, was proved by Atomic-scale-resolved EELS analyses. The electric transport and photoconduction of samples were also investigated. We found that irradiation by photons below the SrTiO3 gap does not increase the carrier density, but slightly enhances low temperature mobility. A giant persistent photoconductivity effect was instead observed, even under irradiation by low energy photons, in highly resistive samples fabricated at non-optimal conditions. We discuss the results in the light of different mechanisms proposed for the two-dimensional electron gas formation. Both the ordinary and the persistent photoconductivity in these systems are addressed and analyzed.
Log in to be able to interact and post comments
comments
Fetching comments
Sign in to be able to follow your search criteria
