Optical Study of p-Doping in GaAs Nanowires for Low-Threshold and High-Yield Lasing.

Semiconductor nanowires suffer from significant non-radiative surface recombination; however, heavy p-type doping has proven to be a viable option to increase the radiative recombination rate and, hence, quantum efficiency of emission, allowing the demonstration of room-temperature lasing. Using a large-scale optical technique, we have studied Zn-doped GaAs nanowires to understand and quantify the effect of doping on growth and lasing properties. We measure the non-radiative recombination rate ( knr) to be (0.14 ± 0.04) ps-1 by modeling the internal quantum efficiency (IQE) as a function of doping level. By applying a correlative method, we identify doping and nanowire length as key controllable parameters determining lasing behavior, with reliable room-temperature lasing occurring for p ≳ 3 × 1018 cm-3 and lengths of ≳4 µm. We report a best-in-class core-only near-infrared nanowire lasing threshold of ∼10 µJ cm-2, and using a data-led filtering step, we present a method to simply identify subsets of nanowires with over 90% lasing yield.

Effect of a High Density of Stacking Faults on the Young's Modulus of GaAs Nanowires.

Stacking faults (SFs) are commonly observed crystalline defects in III-V semiconductor nanowires (NWs) that affect a variety of physical properties. Understanding the effect of SFs on NW mechanical properties is critical to NW applications in nanodevices. In this study, the Young's moduli of GaAs NWs with two distinct structures, defect-free single crystalline wurtzite (WZ) and highly defective wurtzite containing a high density of SFs (WZ-SF), are investigated using combined in situ compression transmission electron microscopy and finite element analysis. The Young's moduli of both WZ and WZ-SF GaAs NWs were found to increase with decreasing diameter due to the increasing volume fraction of the native oxide shell. The presence of a high density of SFs was further found to increase the Young's modulus by 13%. This stiffening effect of SFs is attributed to the change in the interatomic bonding configuration at the SFs.

Zn3As2 nanowires and nanoplatelets: highly efficient infrared emission and photodetection by an earth abundant material.

The development of earth abundant materials for optoelectronics and photovoltaics promises improvements in sustainability and scalability. Recent studies have further demonstrated enhanced material efficiency through the superior light management of novel nanoscale geometries such as the nanowire. Here we show that an industry standard epitaxy technique can be used to fabricate high quality II-V nanowires (1D) and nanoplatelets (2D) of the earth abundant semiconductor Zn3As2. We go on to establish the optoelectronic potential of this material by demonstrating efficient photoemission and detection at 1.0 eV, an energy which is significant to the fields of both photovoltaics and optical telecommunications. Through dynamical spectroscopy this superior performance is found to arise from a low rate of surface recombination combined with a high rate of radiative recombination. These results introduce nanostructured Zn3As2 as a high quality optoelectronic material ready for device exploration.

Carrier thermalization dynamics in single zincblende and wurtzite InP Nanowires.

Using transient Rayleigh scattering (TRS) measurements, we obtain photoexcited carrier thermalization dynamics for both zincblende (ZB) and wurtzite (WZ) InP single nanowires (NW) with picosecond resolution. A phenomenological fitting model based on direct band-to-band transition theory is developed to extract the electron-hole-plasma density and temperature as a function of time from TRS measurements of single nanowires, which have complex valence band structures. We find that the thermalization dynamics of hot carriers depends strongly on material (GaAs NW vs InP NW) and less strongly on crystal structure (ZB vs WZ). The thermalization dynamics of ZB and WZ InP NWs are similar. But a comparison of the thermalization dynamics in ZB and WZ InP NWs with ZB GaAs NWs reveals more than an order of magnitude slower relaxation for the InP NWs. We interpret these results as reflecting their distinctive phonon band structures that lead to different hot phonon effects. Knowledge of hot carrier thermalization dynamics is an essential component for effective incorporation of nanowire materials into electronic devices.

Phase separation induced by Au catalysts in ternary InGaAs nanowires.

We report a novel phase separation phenomenon observed in the growth of ternary In(x)Ga(1-x)As nanowires by metalorganic chemical vapor deposition. A spontaneous formation of core-shell nanowires is investigated by cross-sectional transmission electron microscopy, revealing the compositional complexity within the ternary nanowires. It has been found that for In(x)Ga(1-x)As nanowires high precursor flow rates generate ternary In(x)Ga(1-x)As cores with In-rich shells, while low precursor flow rates produce binary GaAs cores with ternary In(x)Ga(1-x)As shells. First-principle calculations combined with thermodynamic considerations suggest that this phenomenon is due to competitive alloying of different group-III elements with Au catalysts, and variations in elemental concentrations of group-III materials in the catalyst under different precursor flow rates. This study shows that precursor flow rates are critical factors for manipulating Au catalysts to produce nanowires of desired composition.

Structural manifestation of the delocalization error of density functional approximations: C(4N+2) rings and C(20) bowl, cage, and ring isomers.

The ground state structure of C(4N+2) rings is believed to exhibit a geometric transition from angle alternation (N < or = 2) to bond alternation (N > 2). All previous density functional theory (DFT) studies on these molecules have failed to reproduce this behavior by predicting either that the transition occurs at too large a ring size, or that the transition leads to a higher symmetry cumulene. Employing the recently proposed perspective of delocalization error within DFT we rationalize this failure of common density functional approximations (DFAs) and present calculations with the rCAM-B3LYP exchange-correlation functional that show an angle-to-bond-alternation transition between C(10) and C(14). The behavior exemplified here manifests itself more generally as the well known tendency of DFAs to bias toward delocalized electron distributions as favored by Huckel aromaticity, of which the C(4N+2) rings provide a quintessential example. Additional examples are the relative energies of the C(20) bowl, cage, and ring isomers; we show that the results from functionals with minimal delocalization error are in good agreement with CCSD(T) results, in contrast to other commonly used DFAs. An unbiased DFT treatment of electron delocalization is a key for reliable prediction of relative stability and hence the structures of complex molecules where many structure stabilization mechanisms exist.

Threshold reduction and yield improvement of semiconductor nanowire lasers via processing-related end-facet optimization.

Both gain medium design and cavity geometry are known to be important for low threshold operation of semiconductor nanowire lasers. For many applications nanowire lasers need to be transferred from the growth substrate to a low-index substrate; however, the impact of the transfer process on optoelectronic performance has not been studied. Ultrasound, PDMS-assisted and mechanical rubbing are the most commonly used methods for nanowire transfer; each method may cause changes in the fracture point of the nanowire which can potentially affect both length and end-face mirror quality. Here we report on four common approaches for nanowire transfer. Our results show that brief ultrasound and PDMS-assisted transfer lead to optimized optoelectronic performance, as confirmed by ensemble median lasing threshold values of 98 and 104 µJ cm-2 respectively, with nanowires transferred by ultrasound giving a high lasing yield of 72%. The mean threshold difference between samples is shown to be statistically significant: while a significant difference in mean length from different transfer methods is seen, it is shown by SEM that end-facet quality is also affected and plays an important role on threshold gain for this nanowire architecture.

Optimized effective potentials from arbitrary basis sets.

We investigate the use of a regularized optimized effective potential (OEP) energy functional and L-curve procedure [T. Heaton-Burgess, F. A. Bulat, and W. Yang, Phys. Rev. Lett. 98, 256401 (2007)] for determining physically meaningful OEPs from arbitrary combinations of finite orbital and potential basis sets. The important issue of the manner in which the optimal regularization parameter is determined from the L-curve perspective is reconsidered with the introduction of a rigorous measure of the quality of the potential generated-that being, the extent to which the Ghosh-Parr exchange energy virial relation is satisfied along the L-curve. This approach yields nearly identical potentials to our previous work employing a minimum derivative condition, however, gives rise to slightly lower exact-exchange total energies. We observe that the ground-state energy and orbital energies obtained from this approach, either with balanced or unbalanced basis sets, yield meaningful potentials and energies which are in good comparison to other (a priori balanced) finite basis OEP calculations and experimental ionization potentials. As such, we believe that the regularized OEP functional approach provides a computationally robust method to address the numerical stability issues of this often ill-posed problem.

3D Atomic-Scale Insights into Anisotropic Core-Shell-Structured InGaAs Nanowires Grown by Metal-Organic Chemical Vapor Deposition.

III-V ternary InGaAs nanowires have great potential for electronic and optoelectronic device applications; however, the 3D structure and chemistry at the atomic-scale inside the nanowires remain unclear, which hinders tailoring the nanowires for specific applications. Here, atom probe tomography is used in conjunction with a first-principles simulation to investigate the 3D structure and chemistry of InGaAs nanowires, and reveals i) the nanowires form a spontaneous core-shell structure with a Ga-enriched core and an In-enriched shell, due to different growth mechanisms in the axial and lateral directions; ii) the shape of the core evolves from hexagon into Reuleaux triangle and grows larger, which results from In outward and Ga inward interdiffusion occurring at the core-shell interface; and iii) the irregular hexagonal shell manifests an anisotropic growth rate on {112}A and {112}B facets. Accordingly, a model in terms of the core-shell shape and chemistry evolution is proposed, which provides fresh insights into the growth of these nanowires.

Doping-enhanced radiative efficiency enables lasing in unpassivated GaAs nanowires.

Nanolasers hold promise for applications including integrated photonics, on-chip optical interconnects and optical sensing. Key to the realization of current cavity designs is the use of nanomaterials combining high gain with high radiative efficiency. Until now, efforts to enhance the performance of semiconductor nanomaterials have focused on reducing the rate of non-radiative recombination through improvements to material quality and complex passivation schemes. Here we employ controlled impurity doping to increase the rate of radiative recombination. This unique approach enables us to improve the radiative efficiency of unpassivated GaAs nanowires by a factor of several hundred times while also increasing differential gain and reducing the transparency carrier density. In this way, we demonstrate lasing from a nanomaterial that combines high radiative efficiency with a picosecond carrier lifetime ready for high speed applications.

Twinning superlattice formation in GaAs nanowires.

Semiconductor nanowires have proven a versatile platform for the realization of novel structures unachievable by traditional planar epitaxy techniques. Among these, the periodic arrangement of twin planes to form twinning superlattice structures has generated particular interest. Here we demonstrate twinning superlattice formation in GaAs nanowires and investigate the diameter dependence of both morphology and twin plane spacing. An approximately linear relationship is found between plane spacing and nanowire diameter, which contrasts with previous results reported for both InP and GaP. Through modeling, we relate this to both the higher twin plane surface energy of GaAs coupled with the lower supersaturation relevant to Au seeded GaAs nanowire growth. Understanding and modeling the mechanism of twinning superlattice formation in III-V nanowires not only provides fundamental insight into the growth process, but also opens the door to the possibility of tailoring twin spacing for various electronic and mechanical applications.

Size extensivity of the direct optimized effective potential method.

We investigate the size extensivity of the direct optimized effective potential procedure of Yang and Wu [Phys. Rev. Lett. 89, 143002 (2002)]. The choice of reference potential within the finite basis construction of the local Kohn-Sham potential can lead to a method that is not size extensive. Such a situation is encountered when one employs the Fermi-Amaldi potential, which is often used to enforce the correct asymptotic behavior of the exact exchange-correlation potential. The size extensivity error with the Fermi-Amaldi reference potential is shown to behave linearly with the number of electrons in the limit of an infinite number of well separated monomers. In practice, the error tends to be rather small and rapidly approaches the limiting linear behavior. Moreover, with a flexible enough potential basis set, the error can be decreased significantly. We also consider one possible reference potential, constructed from the van Leeuwen-Baerends potential, which provides a size extensive implementation while also enforcing the correct asymptotic behavior.

Spin-potential functional formalism for current-carrying noncollinear magnetic systems.

We develop a formalism dual to spin-current-density functional theory (CDFT) where minimization with respect to the scalar and vector spin potentials is used. In this way we circumvent the issues surrounding the nonuniqueness of the mapping between spin potentials and ground-state wave functions, and the v representability issue of current-density functionals. The approach applied within the Kohn-Sham formalism provides the foundations for the optimized effective potential method for CDFT.

Optimized effective potentials in finite basis sets.

The finite basis optimized effective potential (OEP) method within density functional theory is examined as an ill-posed problem. It is shown that the generation of nonphysical potentials is a controllable manifestation of the use of unbalanced, and thus unsuitable, basis sets. A modified functional incorporating a regularizing smoothness measure of the OEP is introduced. This provides a condition on balanced basis sets for the potential, as well as a method to determine the most appropriate OEP and energy from calculations performed with any finite basis set.

Optimized effective potentials from electron densities in finite basis sets.

The Wu-Yang method for determining the optimized effective potential (OEP) and implicit density functionals from a given electron density is revisited to account for its ill-posed nature, as recently done for the direct minimization method for OEP's from a given orbital functional [T. Heaton-Burgess, F. A. Bulat, and W. Yang, Phys. Rev. Lett. 98, 256401 (2007)]. To address the issues on the general validity and practical applicability of methods that determine the Kohn-Sham (local) multiplicative potential in a finite basis expansion, a new functional is introduced as a regularized version of the original work of Wu and Yang. It is shown that the unphysical, highly oscillatory potentials that can be obtained when unbalanced basis sets are used are the controllable manifestation of the ill-posed nature of the problem. The new method ensures that well behaved potentials are obtained for arbitrary basis sets.