Modulation of intrinsic defects in vertically grown ZnO nanorods by ion implantation.

Intrinsic defects created by chemically inert gas (Xe) ion implantation in vertically grown ZnO nanorods are studied by optical and X-ray absorption spectroscopy (XAS). The surface defects produced due to dynamic sputtering by ion beams control the fraction of O and Zn with ion fluence, which helps in tuning the optoelectronic properties. The forbidden Raman modes related to Zn interstitials and oxygen vacancies are observed because of the weak Fröhlich interaction, which arises due to disruption of the long-range lattice order. The evolution of the lattice disorder is identified by O K-edge and Zn K-edge scans of XAS. The hybridization strength between the O 2p and Zn 4p states increases with ion fluence and modulates the impact of intrinsic defects. The ion irradiation induced defects also construct intermediate defects bands which reduce the optical bandgap. Density functional theory (DFT) calculations are used to correlate the experimentally observed trend of bandgap narrowing with the origin of electronic states related to Zn interstitial and O vacancy defects within the forbidden energy gap in ZnO. Our finding can be beneficial to achieve enhanced conductivity in ZnO by accurately varying the intrinsic defects through ion irradiation, which may work as a tuning knob to control the optoelectronic properties of the system.

Temperature-dependent excitonic emission characteristics of lead-free inorganic double perovskites and their third-order optical nonlinearities.

We report temperature-dependent photoluminescence (PL) in the temperature range between 77 K and 300 K, and room temperature nonlinear optical (NLO) properties of solution processed lead-free Cs2NaBiI6 (CNBI) and Cs2KBiI6 (CKBI) perovskite films. The de-convolution analysis of temperature-dependent PL spectra showed thermal quenching behavior of free-exciton (FX) emission, an unusual blue-shift of PL emission, and line broadening with increasing temperature as a consequence of strong exciton-phonon interaction. The nonlinear refractive index (n2) and nonlinear absorption coefficient (ß) of both the CNBI and CKBI films are determined using a closed aperture (CA) and open aperture (OA) Z-scan technique, respectively. Both the CNBI and CKBI perovskites exhibited features of saturable absorption (SA) with ß âˆ¼ -6.23 × 10-12 cm W-1, and -1.14× 10-12 cm W-1, respectively. The CA measurements depicted a self-defocusing effect in both the samples with n2 values ∼-1.06 × 10-14 cm2 W-1 and -1.337× 10-14 cm2 W-1, respectively. With such emission and NLO characteristics, CNBI and CKBI perovskite films can be used for designing eco-friendly optoelectronic and NLO devices.

Suppression of near band edge emission in specially engineered ZnO twin nanorods.

We report the synthesis of a unique zinc oxide nanorod structure in which an amorphous ZnO layer is sandwiched between two identical crystalline segments of ZnO. A simple hydrothermal reaction method was used for this purpose, which allowed us to tune the amorphous and crystalline sections of the nanorods via reaction temperature. A systematic study of the morphology and dimensions of the nanorods grown under various conditions was performed using a combination of scanning and transmission electron microscopy. Transmission electron microscopy (TEM) clearly showed an amorphous separation between the two crystalline segments. UV-vis absorption spectroscopy of the twin nanorods (TNRs) showed a redshift in the optical band gap as a function of the growth duration, indicating slightly stressed growth of the crystalline segments. For a longer growth duration, as the amorphous gap starts to get bridged by crystalline growth, redshift in optical band gap becomes constant. This confirms a true mechanical gap between the two crystalline segments of the nanorods. Temperature dependent photoluminescence (PL) spectra of the TNRs showed a variation in free exciton (FX) emission energy, which fitted very well to a model incorporating lattice dilation in addition to the standard electron-phonon interactions. At low temperatures (below ∼180 K) we observed the appearance of visible emission peaks due to localization of defect levels. A loss in the near band edge emission intensity was observed at low temperatures, commensurate with the appearance of defect emission in the visible range.

Nanoscale interface engineering in ZnO twin nanorods for proposed phonon tunnel devices.

Zinc oxide twin nanorods, with two identical crystalline sections connected by an amorphous layer, were reproducibly grown using a simple one-step hydrothermal technique. The thickness of the amorphous layer between the crystalline segments was tunable with growth parameters, as confirmed by high resolution transmission electron microscopy. The photoluminescence spectra of these twin nanorods exhibit strong near band edge emission in the UV range, with convoluted phonon sidebands. De-convolution analyses of these spectra showed that the amorphous interlayers act as effective phonon barriers beyond a certain thickness. Such oriented grown individual crystalline-amorphous-crystalline structures may be a suitable test system for fundamental studies of phonon tunneling in the nanostructure. While physical vapor deposition techniques are seriously constrained in realizing crystalline-amorphous-crystalline structures, our results show the viability of engineering embedded interfaces via chemical routes.