A cathodoluminescence study of InP/InGaP axially heterostructured NWs for tandem solar cells.

Axially heterostructured nanowires (NWs) constitute a promising platform for advanced electronic and optoelectronic nanodevices. The presence of different materials in these NWs introduces a mismatch resulting in complex strain distributions susceptible of changing the band gap and carrier mobility. The growth of these NWs presents challenges related to the reservoir effect in the catalysts droplet that affect to the junction abruptness, and the occurrence of undesired lateral growth creating core-shell heterostructures that introduce additional strain. We present herein a cathodoluminescence (CL) analysis on axially heterostructured InP/InGaP NWs with tandem solar cell structure. The CL is complemented with micro Raman, micro photoluminescence (PL), and high resolution transmission electron microscopy measurements. The results reveal the zinc blende structure of the NWs, the presence of a thin InGaP shell around the InP bottom cell, along with its associated strain, and the doping distribution.

Measurements of Strain and Bandgap of Coherently Epitaxially Grown Wurtzite InAsP-InP Core-Shell Nanowires.

We report on experimental determination of the strain and bandgap of InAsP in epitaxially grown InAsP-InP core-shell nanowires. The core-shell nanowires are grown via metal-organic vapor phase epitaxy. The as-grown nanowires are characterized by transmission electron microscopy, X-ray diffraction, micro-photoluminescence (µPL) spectroscopy, and micro-Raman (µ-Raman) spectroscopy measurements. We observe that the core-shell nanowires are of wurtzite (WZ) crystal phase and are coherently strained with the core and the shell having the same number of atomic planes in each nanowire. We determine the predominantly uniaxial strains formed in the core-shell nanowires along the nanowire growth axis and demonstrate that the strains can be described using an analytical expression. The bandgap energies in the strained WZ InAsP core materials are extracted from the µPL measurements of individual core-shell nanowires. The coherently strained core-shell nanowires demonstrated in this work offer the potentials for use in constructing novel optoelectronic devices and for development of piezoelectric photovoltaic devices.

Anti-Stokes photoluminescence probing k-conservation and thermalization of minority carriers in degenerately doped semiconductors.

It has recently been found that anti-Stokes photoluminescence can be observed in degenerately n-doped indium phosphide nanowires, when exciting directly into the electron gas. This anti-Stokes mechanism has not been observed before and allows the study of carrier relaxation and recombination using standard photoluminescence techniques. It is important to know if this anti-Stokes photoluminescence also occurs in bulk semiconductors as well as its relation to carrier recombination and relaxation. Here we show that similar anti-Stokes photoluminescence can indeed be observed in degenerately doped bulk indium phosphide and gallium arsenide and is caused by minority carriers scattering to high momenta by phonons. We find in addition that the radiative electron-hole recombination is highly momentum-conserving and that photogenerated minority carriers recombine before relaxing to the band edge at low temperatures. These observations challenge the use of models assuming thermalization of minority carriers in the analysis of highly doped devices.

Photon upconversion in degenerately sulfur doped InP nanowires.

Radiative recombination in degenerately n-doped InP nanowires is studied for excitation above and below the Fermi energy of the electron gas, using photoluminescence. Laser-induced electron heating is observed, which allows absorption below the Fermi energy. We observe photon upconversion where photo-excited holes recombine with high |k| electrons. This can be attributed to hole scattering to high |k|-values, and the temperature dependence of this process is measured. We show that hole relaxation via phonon scattering can be observed in continuous wave excitation luminescence measurements.

Structural investigation of GaInP nanowires using X-ray diffraction.

In this work the structure of ternary Ga x In1 - x P nanowires is investigated with respect to the chemical composition and homogeneity. The nanowires were grown by metal-organic vapor-phase epitaxy. For the investigation of ensemble fluctuations on several lateral length scales, X-ray diffraction reciprocal space maps have been analyzed. The data reveal a complicated varying materials composition across the sample and in the nanowires on the order of 20%. The use of modern synchrotron sources, where beam-sizes in the order of several 10 µm are available, enables us to investigate compositional gradients along the sample by recording diffraction patterns at different positions. In addition, compositional variations were found also within single nanowires in X-ray energy dispersive spectroscopy measurements.

Particle-assisted Ga(x)In(1-x)P nanowire growth for designed bandgap structures.

Non-tapered vertically straight Ga(x)In(1-x)P nanowires were grown in a compositional range from Ga(0.2)In(0.8)P to pure GaP in particle-assisted mode by controlling the trimethylindium, trimethylgallium and hydrogen chloride flows in metal-organic vapor phase epitaxy. X-ray energy dispersive spectroscopy in transmission electron microscopy revealed homogeneous radial material composition in single nanowires, whereas variations in the material composition were found along the nanowires. High-resolution x-ray diffraction indicates a variation of the material composition on the order of about 19% measuring an entire sample area, i.e., including edge effects during growth. The non-capped nanowires emit room temperature photoluminescence strongly in the energy range of 1.43-2.16 eV, correlated with the bandgap expected from the material composition.

Unit cell parameters of wurtzite InP nanowires determined by x-ray diffraction.

High resolution x-ray diffraction is used to study the structural properties of the wurtzite polytype of InP nanowires. Wurtzite InP nanowires are grown by metal-organic vapor phase epitaxy using S-doping. From the evaluation of the Bragg peak position we determine the lattice parameters of the wurtzite InP nanowires. The unit cell dimensions are found to differ from the ones expected from geometric conversion of the cubic bulk InP lattice constant. The atomic distances along the c direction are increased whereas the atomic spacing in the a direction is reduced in comparison to the corresponding distances in the zinc-blende phase. Using core/shell nanowires with a thin core and thick nominally intrinsic shells we are able to determine the lattice parameters of wurtzite InP with a negligible influence of the S-doping due to the much larger volume in the shell. The determined material properties will enable the ab initio calculation of electronic and optical properties of wurtzite InP nanowires.

The electrical and structural properties of n-type InAs nanowires grown from metal-organic precursors.

The electrical and structural properties of 111B-oriented InAs nanowires grown using metal-organic precursors have been studied. On the basis of electrical measurements it was found that the trends in carbon incorporation are similar to those observed in the layer growth, where an increased As/In precursor ratio and growth temperature result in a decrease in carbon-related impurities. Our results also show that the effect of non-intentional carbon doping is weaker in InAs nanowires compared to bulk, which may be explained by lower carbon incorporation in the nanowire core. We determine that differences in crystal quality, here quantified as the stacking fault density, are not the primary cause for variations in resistivity of the material studied. The effects of some n-dopant precursors (S, Se, Si, Sn) on InAs nanowire morphology, crystal structure and resistivity were also investigated. All precursors result in n-doped nanowires, but high precursor flows of Si and Sn also lead to enhanced radial overgrowth. Use of the Se precursor increases the stacking fault density in wurtzite nanowires, ultimately at high flows leading to a zinc blende crystal structure with strong overgrowth and very low resistivity.

Local and anisotropic excitation of surface plasmon polaritons by semiconductor nanowires.

We demonstrate a novel functionality of semiconductor nanowires as local sources for surface plasmon polaritons (SPPs). Photoexcited semiconductor nanowires decay non-radiatively exciting SPPs when they are on top of a metallic surface. We have investigated the anisotropic excitation of SPPs by nanowires by placing individual InP nanowires inside gold bullseye gratings. The gratings serve to couple SPPs to free space radiation that is detected with a scanning confocal microscope. The circular geometry of the grating allows to conclude that SPPs are preferentially generated in the direction along the nanowire axis.

Precursor evaluation for in situ InP nanowire doping.

The use of tetraethyltin (TESn) and dimethylzinc (DMZn) as in situ n- and p-dopant precursors during particle-assisted growth of InP nanowires is reported. Gate voltage dependent transport measurements demonstrate that the nanowires can be predictably synthesized as either n- or p-type. These doped nanowires can be characterized based on their electric field response and we find that n-type doping scales over a range from 10(17) to 10(19) cm(-3) with increasing input TESn dopant molar fraction. On the other hand, the p-type doping using DMZn saturates at low levels, probably related to a strong increase in nanowire growth rate with increasing DMZn molar fractions. By optimizing growth conditions with respect to tapering, axial pn-junctions exhibiting rectifying behavior were fabricated. The pn-junctions can be operated as light emitting diodes.

Modification of the photoluminescence anisotropy of semiconductor nanowires by coupling to surface plasmon polaritons.

We demonstrate efficient modification of the polarized light emission from single semiconductor nanowires by coupling this emission to surface plasmon polaritons on a metal grating. The polarization anisotropy of the emitted photoluminescence from single nanowires is compared for wires deposited on silica, a flat gold film, and a shallow gold grating. By varying the orientation of the nanowire with respect to the grating grooves, the large intrinsic polarization anisotropy can be either suppressed or enhanced. This modification is interpreted by the appearance of an additional emission channel induced by surface plasmon polaritons and their conversion to p-polarized radiation at the grating.

Remote p-doping of InAs nanowires.

We report on remote p-type doping of InAs nanowires by a p-doped InP shell grown epitaxially on the core nanowire. This approach addresses the challenge of obtaining quantitative control of doping levels in nanowires grown by the vapor-liquid-solid (VLS) mechanism. Remote doping of III-V nanowires is demonstrated here with the InAs/InP system. It is especially challenging to make p-type InAs wires because of Fermi level pinning around 0.1 eV above the conduction band. We demonstrate that shielding with a p-doped InP shell compensates for the built-in potential and donates free holes to the InAs core. Moreover, the off-current in field-effect devices can be reduced up to 6 orders of magnitude. The effect of shielding critically depends on the thickness of the InP capping layer and the dopant concentration in the shell.