C. Lewis Reynolds

Progress in ZnO Acceptor Doping: What Is the Best Strategy?

This paper reviews the recent progress in acceptor doping of ZnO that has been achieved with a focus toward the optimum strategy. There are three main approaches for generating p-type ZnO: substitutional group IA elements on a zinc site, codoping of donors and acceptors, and substitution of group VA elements on an oxygen site. The relevant issues are whether there is sufficient incorporation of the appropriate dopant impurity species, does it reside on the appropriate lattice site, and lastly whether the acceptor ionization energy is sufficiently small to enable significant p-type conduction at room temperature. The potential of nitrogen doping and formation of the appropriate acceptor complexes is highlighted although theoretical calculations predict that nitrogen on an oxygen site is a deep acceptor. We show that an understanding of the growth and annealing steps to achieve the relevant acceptor defect complexes is crucial to meet requirements.

Morphology and chain aggregation dependence of optical gain in thermally annealed films of the conjugated polymer poly[2-methoxy-5-(2′-ethylhexyloxy)-p-phenylene vinylene]

Aggregate formation in conjugated polymer films is one of the most important phenomena thought to influence the photophysical properties of optical devices based on these materials. In the current work, we report the results of a detailed investigation on the morphology and chain aggregation dependence of optical gain in spin-coated thin films of the conjugated polymer poly[2-methoxy-5-(2′-ethylhexyloxy)-p-phenylene vinylene] (MEH-PPV). Extensive gain measurements are performed using the variable stripe length technique with picosecond pulse excitation. The polymer morphology and extent of aggregate formation in the films are controlled by thermal annealing, which is relevant to the fabrication and optimization of conjugated polymer-based optical devices. The aggregation state of the polymer chains increases with the annealing temperature, which results in a decrease in luminescence efficiency at low excitation density (≤1018 cm−3). However, the increase in aggregate formation with increasing annealing te...

Enhancement of optical gain and amplified spontaneous emission due to waveguide geometry in the conjugated polymer poly[2-methoxy-5-(2′-ethylhexyloxy)-p-phenylene vinylene]

We report enhanced amplified spontaneous emission (ASE) and optical gain performance in a conjugated polymer (CP)-based thin film waveguide (WG) Si(100)/SiO2/poly[2-methoxy-5-(2′-ethylhexyloxy)-p-phenylene vinylene] (MEH-PPV) by encapsulating the active layer with a transparent dielectric film of poly(methyl methacrylate) (PMMA). With index matched SiO2 and PMMA claddings, symmetric WGs are formed that exhibit increased mode confinement and reduced propagation loss enabling lower ASE threshold (40%) and higher optical gain (50%) compared to Si(100)/SiO2/MEH-PPV/air asymmetric WGs. An extremely large net gain coefficient of 500 cm−1 is achieved under picosecond pulse excitation, which is >4× larger than values previously reported in the literature. Fabrication of symmetric WGs requires no complex processing techniques, thus offering a simple, low-cost approach for effectively controlling the ASE behavior of CP-based WGs and related optical devices.

Bandgap Tuning of GaAs/GaAsSb Core-Shell Nanowires Grown by Molecular Beam Epitaxy

Semiconductor nanowires have been identified as a viable technology for next-generation infrared (IR) photodetectors with improved detectivity and detection across a range of energies as well as for novel single-photon detection in quantum networking. The GaAsSb materials system is especially promising in the 1.3–1.55 μm spectral range. In this work we present band-gap tuning up to 1.3 μm in GaAs/GaAsSb core–shell nanowires, by varying the Sb content using Ga-assisted molecular beam epitaxy. An increase in Sb content leads to strain accumulation in shell manifesting in rough surface morphology, multifaceted growths, curved nanowires, and deterioration in the microstructural and optical quality of the nanowires. The presence of multiple PL peaks for Sb compositions ≥12 at.% and degradation in the nanowire quality as attested by broadening of Raman and x-ray diffraction peaks reveal compositional instability in the nanowires. Transmission electron microscope (TEM) images show the presence of stacking faults and twins. Based on photoluminescence (PL) peak energies and their excitation power dependence behavior, an energy-band diagram for GaAs/GaAsSb core–shell nanowires is proposed. Optical transitions are dominated by type II transitions at lower Sb compositions and a combination of type I and type II transitions for compositions ≥12 at.%. Type I optical transitions as low as 0.93 eV (1.3 μm) from the GaAsSb for Sb composition of 26 at.% have been observed. The PL spectrum of a single nanowire is replicated in the ensemble nanowires, demonstrating good compositional homogeneity of the latter. A double-shell configuration for passivation of deleterious surface states leads to significant enhancement in the PL intensity resulting in the observation of room temperature emission, which provides significant potential for further improvement with important implications for nanostructured optoelectronic devices operating in the near-infrared regime.

Comparison of the Stability of Functionalized GaN and GaP

Surface functionalization via 1 H,1 H,2 H,2H-perfluoro octanephosphonic acid was done in the presence of phosphoric acid to provide a simplified surface passivation technique for gallium nitride (GaN) and gallium phosphide (GaP). In an effort to identify the leading causes of surface instabilities, hydrogen peroxide was utilized as an additional chemical modification to cap unsatisfied bonds. The stability of the surfaces was studied in an aqueous environment and subsequently characterized. A physical characterization was carried out to evaluate the surface roughness and water hydrophobicity pre and post stability testing via atomic force microscopy and water goniometry. Surface-chemistry changes and solution leaching were quantified by X-ray photoelectron spectroscopy and inductively coupled plasma mass spectrometry. The results indicate a sensitivity to hydroxyl terminated species for both GaN and GaP under aqueous environments, as the increase of the degree of leaching was more significant for hydrogen peroxide treated samples. The results support the notion that hydroxyl species act as precursors to gallium oxide formation and lead to subsequent instability in aqueous solutions.

Self-assembled three-dimensional Cu–Ge nanoweb composite

The inexpensive combination of cryogenically milled Cu(3)Ge powders sonochemically processed in a standard ultrasonic cleaner has led to the prototype of a heretofore undescribed class of material. This prototype is a nanostructured composite composed of 4.5 nm diameter Cu nanocrystals embedded in a three-dimensional (3D) amorphous CuGeO(3) polyhedron web matrix. The diameters of the wires comprising the matrix are typically 5-15 nm. Complete structural and compositional characterization is reported to provide additional insight and firm designation on the observation of this previously undescribed class of material. The large surface to volume ratio of these nanoweb composites may offer unique advantages based on altered optical or electronic and magnetic properties. For example, quantum confinement of the Cu dots in the amorphous 3D nanowebs is possible. Nanostructures in general have altered properties compared to those of bulk materials and the same is expected in nanostructured composites.

Self-catalyzed growth of dilute nitride GaAs/GaAsSbN/GaAs core-shell nanowires by molecular beam epitaxy

Bandgap tuning up to 1.3 μm in GaAsSb based nanowires by incorporation of dilute amount of N is reported. Highly vertical GaAs/GaAsSbN/GaAs core-shell configured nanowires were grown for different N contents on Si (111) substrates using plasma assisted molecular beam epitaxy. X-ray diffraction analysis revealed close lattice matching of GaAsSbN with GaAs. Micro-photoluminescence (μ-PL) revealed red shift as well as broadening of the spectra attesting to N incorporation in the nanowires. Replication of the 4K PL spectra for several different single nanowires compared to the corresponding nanowire array suggests good compositional homogeneity amongst the nanowires. A large red shift of the Raman spectrum and associated symmetric line shape in these nanowires have been attributed to phonon localization at point defects. Transmission electron microscopy reveals the dominance of stacking faults and twins in these nanowires. The lower strain present in these dilute nitride nanowires, as opposed to GaAsSb nanowires having the same PL emission wavelength, and the observation of room temperature PL demonstrate the advantage of the dilute nitride system offers in the nanowire configuration, providing a pathway for realizing nanoscale optoelectronic devices in the telecommunication wavelength region.

Intrinsic optical gain in thin films of a conjugated polymer under picosecond excitation

A strong excitation pulse width dependence on optical gain is reported in thin films of the conjugated polymer poly[2-methoxy-5-(2′-ethylhexyloxy)-p-phenylene vinylene] (MEH-PPV), which suggests that previously reported gain measurements have occurred in an excitation regime that cause damage to the polymer. Symmetric waveguides Si(100)/SiO2/MEH-PPV/poly(methyl methacrylate) are fabricated and optically pumped using laser pulses having temporal widths shorter and longer than the PL decay time, resulting in transient and quasi-steady-state excitation conditions, respectively. Under quasi-steady-state conditions (8 ns pulses), a maximum gain coefficient of ∼135 cm−1 is achieved at a fluence of 2250 μJ/cm2. However, extremely large optical gain is observed under transient pumping (25 ps), reaching 700 cm−1 at a fluence of only 85 μJ/cm2; this 5× improvement in optical gain performance is achieved at the same excitation density as that for ns pulses. It is clear that our ps gain measurements more accurately r...

A Two-Step Growth Pathway for High Sb Incorporation in GaAsSb Nanowires in the Telecommunication Wavelength Range

Self-catalyzed growth of axial GaAs1−xSbx nanowire (NW) arrays with bandgap tuning corresponding to the telecommunication wavelength of 1.3 µm poses a challenge, as the growth mechanism for axial configuration is primarily thermodynamically driven by the vapor-liquid-solid growth process. A systematic study carried out on the effects of group V/III beam equivalent (BEP) ratios and substrate temperature (Tsub) on the chemical composition in NWs and NW density revealed the efficacy of a two-step growth temperature sequence (initiating the growth at relatively higher Tsub = 620 °C and then continuing the growth at lower Tsub) as a promising approach for obtaining high-density NWs at higher Sb compositions. The dependence of the Sb composition in the NWs on the growth parameters investigated has been explained by an analytical relationship between the effective vapor composition and NW composition using relevant kinetic parameters. A two-step growth approach along with a gradual variation in Ga-BEP for offsetting the consumption of the droplets has been explored to realize long NWs with homogeneous Sb composition up to 34 at.% and photoluminescence emission reaching 1.3 µm at room temperature.