Nanoscale x-ray investigation of composition fluctuations in AlGaN nanowires.

In the present study we combined, in the same synchrotron x-ray experiment, reciprocal space mapping, multiwavelength anomalous diffraction and diffraction anomalous fine structure, to determine the strain, crystallographic polarity, alloy composition and ordering at the atomic scale in [0001]-oriented AlGaN nanowires grown by molecular beam epitaxy on GaN nanowire bases. The information that we obtained was averaged over a macroscopic ensemble of NWs. We found from the diffraction anomalous fine structure that there were an isotropic increased number of Ga-Ga pairs in the Ga next nearest coordination shell (cation sublattice) with respect to what is expected for the AlGaN alloy composition determined by anomalous diffraction. This significant deviation from random alloy atomic distribution is present whatever the AlN molar fraction and growth conditions. Our results are consistent with nanoscale composition fluctuations expected from both alloy disorder or kinematically driven spontaneous ordering, both effects being suspected to account for the physical properties of AlGaN ternary alloys.

Growth, structural and optical properties of AlGaN nanowires in the whole composition range.

We report on the growth of AlxGa1-xN nanowires by plasma-assisted molecular beam epitaxy for x in the 0.3-0.8 range. Based on a combination of macro- and micro-photoluminescence, Raman spectroscopy, x-ray diffraction and scanning electron microscopy experiments, it is shown that the structural and optical properties of AlGaN NWs are governed by the presence of compositional fluctuations associated with strongly localized electronic states. A growth model is proposed, which suggests that, depending on growth temperature and metal adatom density, macroscopic composition fluctuations are mostly of kinetic origin and are directly related to the nucleation of the AlGaN nanowire section on top of the GaN nanowire base which is used as a substrate.

The structural properties of GaN/AlN core-shell nanocolumn heterostructures.

The growth and structural properties of GaN/AlN core-shell nanowire heterostructures have been studied using a combination of resonant x-ray diffraction, Raman spectroscopy and high resolution transmission electron microscopy experiments. For a GaN core of 20 nm diameter on average surrounded by a homogeneous AlN shell, the built-in strain in GaN is found to agree with theoretical calculations performed using a valence force field model. It is then concluded that for an AlN thickness up to at least 12 nm both core and shell are in elastic equilibrium. However, in the case of an inhomogeneous growth of the AlN shell caused by the presence of steps on the sides of the GaN core, plastic relaxation is found to occur. Consistent with the presence of dislocations at the GaN/AlN interface, it is proposed that this plastic relaxation, especially efficient for AlN shell thickness above 3 nm, is promoted by the shear strain induced by the AlN inhomogeneity.

Nucleation mechanism of GaN nanowires grown on (111) Si by molecular beam epitaxy.

We have performed a real-time in situ x-ray scattering study of the nucleation of GaN nanowires grown by plasma-assisted molecular beam epitaxy on AlN(0001)/Si(111). The intensity variation of the GaN diffraction peak as a function of time was found to exhibit three different regimes: (i) the deposition of a wetting layer, which is followed by (ii) a supralinear regime assigned to nucleation of almost fully relaxed GaN nanowires, eventually leading to (iii) a steady-state growth regime. Based on scanning electron microscopy and electron microscopy analysis, it is proposed that the granular character of the thin AlN buffer layer may account for the easy plastic relaxation of GaN, establishing that three-dimensional islanding and plastic strain relaxation of GaN are two necessary conditions for nanowire growth.

Strain, size, and composition of InAs quantum sticks embedded in InP determined via grazing incidence x-ray anomalous diffraction.

We have used x-ray anomalous diffraction to recover the model-independent Fourier transform (x-ray structure factor) of InAs quantum sticklike islands embedded in InP. The average height of the quantum sticks, as deduced from the width of the structure factor profile, is 2.54 nm. The InAs out-of-plane deformation, relative to InP, is 6.1%. Diffraction anomalous fine structure provides evidence of pure InAs quantum sticks. Finite difference method calculations reproduce well the diffraction data, and give the strain along the growth direction. The chemical mixing at interfaces is also analyzed.

Diffraction anomalous fine-structure spectroscopy at beamline BM2 at the European Synchrotron Radiation Facility.

Diffraction anomalous fine-structure (DAFS) spectroscopy uses resonant elastic X-rays scattering as an atomic, shell and site-selective probe that provides information on the electronic structure and the local atomic environment as well as on the long-range-ordered crystallographic structure. A DAFS experiment consists of measuring the Bragg peak intensities as a function of the energy of the incoming X-ray beam. The French CRG (Collaborative Research Group) beamline BM2-D2AM (Diffraction Diffusion Anomale Multi-longueurs d'Onde) at the ESRF (European Synchrotron Radiation Facility) has developed a state-of-the-art energy scan diffraction set-up. In this article the requirements for obtaining reliable DAFS data are presented and recent technical achievements are reported.

Valence selective DAFS measurements of Mn in La1/3Ca2/3MnO3.

The manganese perovskite system La(1-x)Ca(x)MnO3 displays a complex phase diagram of structural, magnetic, and transport properties with varying Ca concentration. At x = 2/3 and at low temperature, the system is antiferromagnetic with Mn4+ and Mn3+ ions occupying special positions in a charge-ordered supperlattice. The charge ordering transition at about 260 K is characterized by the appearance of satellite peaks around certain strong normal lattice reflections. The normal lattice reflections are due to scattering from planes containing Mn4+ and Mn3+ ions in nearly stoichiometric proportion, however the superlattice reflections are due to scattering from planes containing only Mn4+ ions. By measuring Diffraction Anomalous Fine-Structure spectral on a superlattice reflection and its associated normal lattice reflection, it is possible to isolate absorption-like spectra for the two Mn sites. Due to the weak intensity of these superlattice reflections, we were unable to obtain high quality near-edge spectra for the superlattice reflection measured. However, the data offer useful information about the local electronic structures of the two Mn ions.

Diffraction anomalous fine structure of forbidden Bragg reflections: charge localization and structure of the octahedral site in magnetite.

Resonant X ray scattering has been used to investigate charge localization on the octahedral iron atoms in magnetite below and above the Verwey temperature. We have measured the DAFS spectra of the 002 and 006 "forbidden" Bragg reflections permitted by the anisotropy of the iron anomalous scattering factor. We performed ab initio calculations which are in fair agreement with the experiment in the near edge region and demonstrate the sensitivity of the DAFS spectra to tiny structural and electronic changes. No change is observed, in the energy and azimuthal dependences, when the sample is cooled down below the Verwey temperature. Charge ordering can be definitely excluded and different charge localisation schemes discarded. Ab initio simulations, performed by using the refined crystallographic structure proposed for the room temperature phase, do not show a good agreement with the experiment in the extended region of the DAFS spectrum. This point is being investigated.

Glancing-angle diffraction anomalous fine structure of InAs quantum dots and quantum wires.

We have performed Diffraction Anomalous Fine Structure measurements at the As K-edge of self-growth InAs/InP(001) Quantum Wires and InAs/GaAs(001) Quantum Dots. The samples have been grown by Molecular Beam Epitaxy and their equivalent thickness is of 2.5 monolayers. We have measured the (440) and (420) Bragg reflections in glancing-angle scattering geometry, at incidence angles close to the substrate critical angle. We demonstrate the feasibility of the experiment reporting, for the first time. Diffraction Anomalous Fine Structure spectra of such low coverage epitaxial layers, and we show that the analysis of the Diffraction Anomalous Fine Structure lineshape together with the analysis of oscillatory part of the signal, can provide information about composition and strain of the nanostructures.

A Fe(x)Mn1-x/Ir(001) multilayer probed by EXAFS and DAFS.

Diffraction Anomalous Fine Structure (DAFS) and EXAFS measurements have been performed on a (Fe0.7Mn0.3)/Ir(100)40 super-lattice at the K-edges of Fe and Mn. Theoretical EXAFS spectra have been refined: a slight difference in the first neighbor distance suggests a non homogeneous distribution of the Mn in the alloy. The smooth features of the DAFS spectra have been modeled to study the composition and the strain profile along the growth axis.

Resonant "forbidden" reflections in magnetite.

Resonant x-ray scattering was used to investigate electronic fluctuations of the octahedral iron atoms in magnetite. We measured the (002) and (006) "forbidden" x-ray diffraction reflections permitted by the anisotropy of the iron anomalous scattering factor. The energy and azimuthal angle dependencies of these reflections, and the polarization analysis, are shown and discussed. The results clearly show p and d iron empty states ordering in magnetite at room temperature. Moreover, the octahedral iron atoms are electronically equivalent in a time scale lower than 10(-16) sec. Therefore, magnetite should be considered as an itinerant magnet and not as a fluctuating mixed valence material.