Different growth regimes in InP nanowire growth mediated by Ag nanoparticles.

We report on the existence of two different regimes in one-step Ag-seeded InP nanowire growth. The vapor-liquid-solid-mechanism is present at larger In precursor flows and temperatures, ∼500 °C, yielding high aspect ratio and pure wurtzite InP nanowires with a semi-spherical metal particle at the thin apex. Periodic diameter oscillations can be achieved under extreme In supersaturations at this temperature range, showing the presence of a liquid catalyst. However, under lower temperatures and In precursor flows, large diameter InP nanowires with mixed wurtzite/zincblende segments are obtained, similarly to In-assisted growth. Chemical composition analysis suggest that In-rich droplet formation is catalyzed at the substrate surface via Ag nanoparticles; this process might be facilitated by the sulfur contamination detected in these nanoparticles. Furthermore, part of the original Ag nanoparticle remains solid and is embedded inside the actual catalyst, providing an in situ method to switch growth mechanisms upon changing In precursor flow. Nevertheless, our Ag-seeded InP nanowires exhibit overall optical emission spectra consistent with the observed structural properties and similar to Au-catalyzed InP nanowires. We thus show that Ag nanoparticles may be a suitable replacement for Au in InP nanowire growth.

Interaction between lamellar twinning and catalyst dynamics in spontaneous core-shell InGaP nanowires.

Semiconductor nanowires oriented along the [211] direction usually present twins parallel to their axis. For group IV nanowires this kind of twin allows the formation of a catalyst-nanowire interface composed of two equivalent {111} facets. For III-V nanowires, however, the twin will generate two facets with different polarities. In order to keep the <211> orientation stable, a balance in growth rates for these different facets must be reached. We report here the observation of stable, micron-long <211>-oriented InGaP nanowires with a spontaneous core-shell structure. We show that stacking fault formation in the crystal region corresponding to the {111}A facet termination provides a stable NW/NP interface for growth along the <211> direction. During sample cool down, however, the catalyst migrates to a lateral {111}B facet, allowing the growth of branches perpendicular to the initial orientation. In addition to that, we show that the core-shell structure is non-concentric, most likely due to the asymmetry between the facets formed in the NW sidewall; this effect generates stress along the nanowire, which can be relieved through bending.

Photon bunching in cathodoluminescence.

We have measured the second order correlation function [g^{(2)}(τ)] of the cathodoluminescence intensity resulting from the excitation by fast electrons of defect centers in wide band-gap semiconductor nanocrystals of diamond and hexagonal boron nitride. We show that the cathodoluminescence second order correlation function g^{(2)}(τ) of multiple defect centers is dominated by a large, nanosecond zero-delay bunching (g^{(2)}(0)>30), in stark contrast to their flat photoluminescence g^{(2)}(τ) function. We have developed a model showing that this bunching can be attributed to the synchronized emission from several defect centers excited by the same electron through the deexcitation of a bulk plasmon into few electron-hole pairs.

Spatial modulation of above-the-gap cathodoluminescence in InP nanowires.

We report the observation of light emission on wurtzite InP nanowires excited by fast electrons. The experiments were performed in a scanning transmission electron microscope using an in-house-built cathodoluminescence detector. Besides the exciton emission, at 850 nm, emission above the band gap from 400 to 800 nm was observed. In particular, this broad emission presented systematic periodic modulations indicating variations in the local excitation probability. The physical origin of the detected emission is not clear. Measurements of the spatial variation of the above-the-gap emission points to the formation of leaky cavity modes of a plasmonic nature along the nanowire length, indicating the wave nature of the excitation. We propose a phenomenological model, which fits closely the observed spatial variations.

Spatially resolved quantum nano-optics of single photons using an electron microscope.

We report on the experimental demonstration of single-photon state generation and characterization in an electron microscope. In this aim we have used low intensity relativistic (energy between 60 and 100 keV) electrons beams focused in a ca. 1 nm probe to excite diamond nanoparticles. This triggered individual neutral nitrogen-vacancy centers to emit photons which could be gathered and sent to a Hanbury Brown-Twiss intensity interferometer. The detection of a dip in the correlation function at small time delays clearly demonstrates antibunching and thus the creation of nonclassical light states. Specifically, we have also demonstrated single-photon states detection. We unveil the mechanism behind quantum states generation in an electron microscope, and show that it clearly makes cathodoluminescence the nanometer scale analog of photoluminescence. By using an extremely small electron probe size and the ability to monitor its position with subnanometer resolution, we also show the possibility of measuring the quantum character of the emitted beam with deep subwavelength resolution.

Spontaneous periodic diameter oscillations in InP nanowires: the role of interface instabilities.

We have observed that thin InP nanowires generated by vapor-liquid-solid growth display spontaneous periodic diameter oscillations when large group III supersaturations are used. Diameter variations are associated with a large number of stacking faults and crystallographic phase changes(wurtzite/zinc-blende); also the axial distance between oscillations depends on the indium precursor flow used during the run. We attribute the morphology changes to a substantial deformation of the triple phase line (vapor-liquid-solid) at the catalyst nanoparticle edge originated from multistep nucleation during growth. The deformation alters the mechanical force balance acting on the nanoparticle during growth in such a way that the particle displaces from the nanowire top and wets the nanowire sidewall. Subsequently, as catalytic growth occurs at the sidewall, the associated increase in diameter will eventually push the NP back to its original wire-top position until the onset of a new instability at the triple phase line.

Spectrally and spatially resolved cathodoluminescence of nanodiamonds: local variations of the NV(0) emission properties.

Here we report the spectrally and spatially resolved cathodoluminescence of diamond nanoparticles using focused fast electron beams in a transmission electron microscope. We demonstrate the possibility of quickly detecting various individual colour centres of different kinds on wide areas (several micrometres square) contained in nanoparticles separated by subwavelength distances. Among them, nanoparticles containing one or more neutral nitrogen-vacancy (NV(0)) intensity maxima have been seen, attributable to individual emitters. Thanks to a spatial resolution which is solely limited by charge carrier diffusion in the case of a fast electron (80 keV) setup, the spectra of two individual NV(0) emitters separated by 80 nm inside a nanoparticle have been spatially discerned. A shift of the zero phonon line (ZPL) between the two emitters, which we attribute to internal stress, is shown to arise even within the same nanoparticle. Detailed emission spectra (ZPL, phonon lines and Huang-Rhys factor, directly linked to the relaxation energy of the colour centre) in 51 individual NV(0) centres have been measured in 39 particles. The ZPL and Huang-Rhys factor are found to be measurably dispersed, while the phonon energies keep constant.

Enhanced Eshelby twist on thin Wurtzite InP nanowires and measurement of local crystal rotation.

We have performed a detailed study of the lattice distortions of InP wurtzite nanowires containing an axial screw dislocation. Eshelby predicted that this kind of system should show a crystal rotation due to the dislocation induced torque. We have measured the twisting rate and the dislocation Burgers vector on individual wires, revealing that nanowires with a 10-nm radius have a twist up to 100% larger than estimated from elasticity theory. The strain induced by the deformation has a Mexican-hat-like geometry, which may create a tube-like potential well for carriers.

Spatial carrier distribution in InP/GaAs type II quantum dots and quantum posts.

We performed a detailed investigation of the structural and optical properties of multi-layers of InP/GaAs quantum dots, which present a type II interface arrangement. Transmission electronic microscopy analysis has revealed relatively large dots that coalesce forming so-called quantum posts when the GaAs layer between the InP layers is thin. We observed that the structural properties and morphology affect the resulting radiative lifetime of the carriers in our systems. The carrier lifetimes are relatively long, as expected for type II systems, as compared to those observed for single layer InP/GaAs quantum dots. The interface intermixing effect has been pointed out as a limiting factor for obtaining an effective spatial separation of electrons and holes in the case of single layer InP/GaAs quantum-dot samples. In the present case this effect seems to be less critical due to the particular carrier wavefunction distribution along the structures.

Characterization of interface abruptness and material properties in catalytically grown III-V nanowires: exploiting plasmon chemical shift.

We have studied the assessment of chemical composition changes in III-V heterostructured semiconductor nanowires (NWs) with nanometric spatial resolution using transmission electron microscopy methods. These materials represent a challenge for conventional spectroscopy techniques due to their high sensitivity to electron beam irradiation. Radiation damage strongly limits the exposure time to a few (5-10) s, which reduces the sensitivity of the traditionally used x-ray spectroscopy. The rather low counting statistics results in significant errors bars for EDS chemical quantification (5-10%) and interface width determination (few nanometers). Plasmon chemical shift is ideal in this situation, as its measurement requires very short exposure times (approximately 100 ms) and the plasmon peak energy can be measured with high precision (approximately 20 meV in this work). This high sensitivity allows the detection of subtle changes (1-2%) in composition or even the detection of a small plasmon energy (33 +/- 7) meV change along usually assumed pure and homogeneous InAs segments. We have applied this approach to measure interface widths in heterostructure InAs/InP NWs grown using metal catalysts and also to determine the timescale (approximately 10 s) in which beam irradiation induces material damage in these wires. In particular, we have detected small As concentrations (4.4 +/- 0.5)% in the final InP segment close to the Au catalyst, which leads to the conclusion that As diffuses through the metal nanoparticle during growth.

III-V semiconductor nanowire growth: does arsenic diffuse through the metal nanoparticle catalyst?

The synthesis of III-V semiconductor nanowires (NWs) is based on the delivery of atoms from a vapor phase to a catalytic metal nanoparticle (NP). Although there has been extensive work on such systems, the incorporation pathways of group V atoms remain an open issue. Here, we have performed a detailed structural and chemical analysis of the catalyst NP in NWs where we switch the V atomic element during growth (heterostructured InP/InAs/InP NWs). Our experimental results indicate a group V pathway where these atoms actually diffuse through the catalytic NP by formation of a stable phase containing As under growth conditions. We have observed distinct NW growth behavior within a narrow temperature range (30 degrees C) suggesting a transition between vapor-liquid-solid and vapor-solid-solid growth modes.