Mid-gap Emission Research Articles

Impact of exciton fine structure on the energy transfer in magic-sized (CdSe)13 clusters

Magic-sized (CdSe)13 clusters (MSCs) represent a material class at the boundary between molecules and quantum dots that exhibit a pronounced and well separated excitonic fine structure. The characteristic photoluminescence is composed of exciton bandgap emission and a spectrally broad mid-gap emission related to surface defects. Here, we report on a thermally activated energy transfer from fine-structure split exciton states to surface states by using temperature dependent photoluminescence excitation spectroscopy. We demonstrate that the broad mid-gap emission can be suppressed by a targeted Mn-doping of the MSC leading to the characteristic orange luminescence of the 4T1 → 6A1 Mn2+ transition. The energy transfer to the Mn2+ states is found to be significantly different than the transfer to the surface defect states, as the activation of the dopant emission requires a spin-conserving charge carrier transfer that only dark excitons can provide.

60Co γ-irradiation of AlGaN UVC light-emitting diodes

270 nm AlGaN UV Light-Emitting Diodes (LEDs) were exposed to 1–5 Mrad fluences of Co-60 γ-rays. The effect of the exposure to radiation was a ∼40% reduction in optical output after the highest fluence. No significant midgap emission was induced in the electro-luminescence spectra of the irradiated LEDs. We ascribe the decrease in optical output to creation of non-radiative states within the active regions. There were small (5–10%) increases in forward and reverse current as a result of irradiation with an effective carrier removal rate of <1 cm−1. The irradiation did not produce any increase in degradation rate of the LEDs output power under high drive current (95 mA) compared to unirradiated devices, which is consistent with the lack of midgap emission. The relatively small changes in electrical and optical properties, along with the resistance of the AlxGa1-xN/AlN to displacement damage effects indicate these devices may be well-suited to harsh terrestrial and space radiation applications.

Size and Quality Enhancement of 2D Semiconducting Metal-Organic Chalcogenolates by Amine Addition.

The use of two-dimensional (2D) materials in next-generation technologies is often limited by small lateral size and/or crystal defects. Here, we introduce a simple chemical strategy to improve the size and overall quality of 2D metal-organic chalcogenolates (MOCs), a new class of hybrid organic-inorganic 2D semiconductors that can exhibit in-plane anisotropy and blue luminescence. By inducing the formation of silver-amine complexes during a solution growth method, we increase the average size of silver phenylselenolate (AgSePh) microcrystals from <5 μm to >1 mm, while simultaneously extending the photoluminescence lifetime and suppressing mid-gap emission. Mechanistic studies using 77Se NMR suggest dual roles for the amine in promoting the formation of a key reactive intermediate and slowing down the final conversion to AgSePh. Finally, we show that amine addition is generalizable to the synthesis of other 2D MOCs, as demonstrated by the growth of single crystals of silver 4-methylphenylselenolate (AgSePhMe), a novel member of the 2D MOC family.

Mercury Chalcogenide Nanoplatelet-Quantum Dot Heterostructures as a New Class of Continuously Tunable Bright Shortwave Infrared Emitters.

Despite broad applications in imaging, energy conversion, and telecommunications, few nanoscale moieties emit light efficiently in the shortwave infrared (SWIR, 1000-2000 nm or 1.24-0.62 eV). We report quantum-confined mercury chalcogenide (HgX, where X = Se or Te) nanoplatelets (NPLs) can be induced to emit bright (QY > 30%) and tunable (900-1500+ nm) infrared emission from attached quantum dot (QD) "defect" states. We demonstrate near unity energy transfer from NPL to these QDs, which completely quench NPL emission and emit with a high QY through the SWIR. This QD defect emission is kinetically tunable, enabling controlled midgap emission from NPLs. Spectrally resolved photoluminescence demonstrates energy-dependent lifetimes, with radiative rates 10-20 times faster than those of their PbX analogues in the same spectral window. Coupled with their high quantum yield, midgap emission HgX dots on HgX NPLs provide a potential platform for novel optoelectronics in the SWIR.

Preparation of highly emissive and reproducible Cu–In–S/ZnS core/shell quantum dots with a mid-gap emission character

Copper indium sulfide (CIS) quantum dots (QDs) are one of the newest types of luminescent semiconductors with low-toxicity and earth-abundant features. The present work reports the successful aqueous synthesis of CIS/ZnS core/shell QDs using dual-stabilizing agents of N-acetyl-l-cysteine and trisodium citrate. Off-stoichiometric QDs with In-rich compositions were found to be very small and highly emissive after coating by a shell of wide bandgap ZnS. The effect of various experimental parameters was evaluated to achieve highly reproducible QDs with bright reddish emission. Results showed a significant contribution of mid-gap defect states in the recombination processes (based on the gradual increase in absorbance recorded for samples, relatively high Urbach energy, large Stokes shift, large FWHM value in PL spectra, as well as the long-lived PL decay time). In addition, the chemical stability of samples was investigated using highly oxidant H2O2 agent and results demonstrate their superior stability. The combination of low-toxicity, intense and stable emission, along with synthetic advantages demonstrates that the present aqueous-soluble and emissive QDs can be considered as an excellent bio-photonic structure suitable for different fields of biological imaging and diagnostics.

A study of H and D doped ZnO epitaxial films grown by pulsed laser deposition

We examine the crystal structure and electrical and optical properties of ZnO epitaxial films grown by pulsed laser deposition in a H2 or D2 ambient. n-type electrical conductivity is enhanced by three orders of magnitude as a result of growing in H2 (D2) compared to ZnO films grown in O2. Hall effect measurements reveal very small carrier activation energies and carrier concentrations in the mid-1018 cm−3 range. Optical absorption measurements show that the enhanced conductivity is not a result of ZnO reduction and interstitial Zn formation. Photoluminescence spectra suggest excitonic emission associated with exciton-hydrogen donor complex formation and show no evidence for midgap emission resulting from defects. We have modeled the transport properties of H (D) doped ZnO films using variable range hopping and surface layer conductivity models, but our data do not fit well with these models. Rather, it appears that growth in H2 (D2) promotes the formation of an exceedingly shallow donor state not seen in ZnO crystals annealed in H2 after growth. This new state may be associated with H (D) substitution at O sites in the lattice.

High-temperature ferromagnetism in Mn-doped ZnO nanowires

We have observed ferromagnetism in dilute (∼1–4at.%) Mn-doped crystalline ZnO nanowires at temperatures up to 400K. Arrays of freestanding single crystal ZnO:Mn nanowires were fabricated by Au-catalyzed vapor-liquid-solid growth. Structure and compositional analyses revealed that Mn was incorporated into the ZnO lattice. From the observed saturation magnetization, the magnetic moment per Mn atom is estimated to be between 0.3μB and 1.2μB. Photoluminescence measurements show a strong suppression of defect related midgap emission, indicative of an interplay between Mn doping and native point defects.

The Effect of Nitrogen Ion Damage on the Optical and Electrical Properties of MBE GaN Grown on MOCVD GaN/sapphire Templates

We have established a correlation between localized states responsible for mid-gap optical emission and film mobility of GaN grown under different nitrogen conditions. By imposing a deflector voltage at the tip of the plasma source, we varied the ion/neutral flux ratio to determine how N ions affect mid-gap luminescence and electrical mobility. Low energy electron-excited nanometer scale luminescence (LEEN) spectroscopy in ultrahigh vacuum (UHV) showed mid-gap emission intensities in the bulk that decreased in the ratio, 50 : 1.3 : 1 with increasing deflector voltage. Hall measurements indicated over a factor of two increase in mobility, and a factor of 8 decrease in residual charge density with increasing deflector voltage. The correlation of optical and electrical properties with a reduction in N ion flux suggests the primary role of native defects, such as N or Ga vacancies, in the mid-gap emissions.

The Effect of Nitrogen Ion Damage on the Optical and Electrical Properties of MBE GaN Grown on MOCVD GaN/Sapphire Templates

AbstractWe have established a correlation between localized states responsible for mid-gap optical emission and film mobility of GaN grown under different nitrogen conditions. By imposing a deflector voltage at the tip of the plasma source, we varied the ion/neutral flux ratio to determine how N ions affect mid-gap luminescence and electrical mobility. Low energy electron-excited nanometer scale luminescence (LEEN) spectroscopy in ultrahigh vacuum (UHV) showed mid-gap emission intensities in the bulk that decreased in the ratio, 50 : 1.3 : 1 with increasing deflector voltage. Hall measurements indicated over a factor of two increase in mobility, and a factor of 8 decrease in residual charge density with increasing deflector voltage. The correlation of optical and electrical properties with a reduction in N ion flux suggests the primary role of native defects, such as N or Ga vacancies, in the mid-gap emissions.

Properties of low-pressure chemical vapor epitaxial GaN films grown using hydrazoic acid (HN3)

We have grown high-quality GaN films on sapphire using a new nitrogen precursor, hydrazoic acid (HN3). Films were grown at 600 °C on (0001) sapphire substrates in a low-pressure chemical-vapor-deposition system using triethylgallium and hydrazoic acid as precursors. Subsequently, we have conducted a complete study of the surface, structural, electrical, and optical properties of these GaN films, and our early results are very encouraging. All films were of wurtzite crystal structure, slightly polycrystalline, and n type at about 2×1017 cm−3. We find the films to be efficient light emitters in the near-band edge region of the spectrum. Analysis of the emission energies and kinetics suggests that the midgap emission results from a superimposed deep-donor-to-shallow-acceptor emission and a deep-donor-to-valence-band emission, where the deep donor consists of a distribution of energy levels, thereby yielding a broad emission band.

Photoluminescence studies of heteroepitaxial gaas on si

We present a systematic study of the photoluminescence of undoped GaAs layers deposited by MOCVD on Si substrates. The study includes an examination of substrate and layer thickness effects in thin GaAs layers, and a detailed investigation of the stress effects on the intrinsic band-edge transitions in thicker samples. For sample thickness,t ≤ 0.5(μm), we observe strong midgap emission bands associated with defects close to the interface. These bands depend strongly on the nature of the Si substrate. The crystal quality improves with sample thickness, and fort ≥ 0.5 μm the emission is dominated by lines in the band edge region which are relatively independent of substrate preparation. Photoluminescence excitation spectra reveal that the highest energy line is due to an intrinsic exciton transition, and that a splitting of this line observed fort ≥ 2 μm reflects the presence of two different regions of strain in the material. The magnitude of the strain is estimated from the shift of the exciton lines relative to unstrained GaAs, and is found to be consistent with an upper limit provided by the thermal expansion mismatch between GaAs and Si.