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Raffaella Calarco

Publications and source records attributed to Raffaella Calarco.

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Spontaneous nucleation and growth of GaN nanowires: Fundamental role of crystal polarity

We experimentally investigate whether crystal polarity affects the growth of GaN nanowires in plasma-assisted molecular beam epitaxy and whether their formation has to be induced by defects. For this purpose, we prepare smooth and coherently strained AlN layers on 6H-SiC(0001) and SiC(000$\bar{1}$) substrates to ensure a well-defined polarity and an absence of structural and morphological defects. On N-polar AlN, a homogeneous and dense N-polar GaN nanowire array forms, evidencing that GaN nanowires form spontaneously in the absence of defects. On Al-polar AlN, we do not observe the formation of Ga-polar GaN NWs. Instead, sparse N-polar GaN nanowires grow embedded in a Ga-polar GaN layer. These N-polar GaN nanowires are shown to be accidental in that the necessary polarity inversion is induced by the formation of Si$_{x}$N. The present findings thus demonstrate that spontaneously formed GaN nanowires are irrevocably N-polar. Due to the strong impact of the polarity on the properties of GaN-based devices, these results are not only essential to understand the spontaneous formation of GaN nanowires but also of high technological relevance.

cond-mat.mtrl-sci

Carrier diffusion in GaN -- a cathodoluminescence study. I: Temperature-dependent generation volume

The determination of the carrier diffusion length of semiconductors such as GaN and GaAs by cathodoluminescence imaging requires accurate knowledge about the spatial distribution of generated carriers. To obtain the lateral distribution of generated carriers for sample temperatures between 10 and 300 K, we utilize cathodoluminescence intensity profiles measured across single quantum wells embedded in thick GaN and GaAs layers. Thin (Al,Ga)N and (Al,Ga)As barriers, respectively, prevent carriers diffusing in the GaN and GaAs layers to reach the well, which would broaden the profiles. The experimental cathodoluminescence profiles are found to be systematically wider than the energy loss distributions calculated by means of the Monte Carlo program CASINO, with the width monotonically increasing with decreasing temperature. This effect is observed for both GaN and GaAs and becomes more pronounced for higher acceleration voltages. We discuss this phenomenon in terms of both, the electron-phonon interaction controlling the energy relaxation of hot carriers, and the shape of the initial carrier distribution. Finally, we present a phenomenological approach to simulate the carrier generation volume that can be used for the investigation of the temperature dependence of carrier diffusion.

cond-mat.mtrl-sci

Carrier diffusion in GaN -- a cathodoluminescence study. II: Ambipolar vs. exciton diffusion

We determine the diffusion length of excess carriers in GaN by spatially resolved cathodoluminescence spectroscopy utilizing a single quantum well as carrier collector or carrier sink. Monochromatic intensity profiles across the quantum well are recorded for temperatures between 10 and 300 K. A classical diffusion model accounts for the profiles acquired between 120 and 300 K, while for temperatures lower than 120 K, a quantum capture process has to be taken into account in addition. Combining the diffusion length extracted from these profiles and the effective carrier lifetime measured by time-resolved photoluminescence experiments, we deduce the carrier diffusivity as a function of temperature. The experimental values are found to be close to theoretical ones for the ambipolar diffusivity of free carriers limited only by intrinsic phonon scattering. This agreement is shown to be fortuitous. The high diffusivity at low temperatures instead originates from an increasing participation of excitons in the diffusion process.

cond-mat.mtrl-sci

Carrier diffusion in GaN -- a cathodoluminescence study. III: Nature of nonradiative recombination at threading dislocations

We investigate the impact of threading dislocations with an edge component (a or a+c-type) on carrier recombination and diffusion in GaN(0001) layers close to the surface as well as in the bulk. To this end, we utilize cathodoluminescence imaging of the top surface of a GaN(0001) layer with a deeply buried (In,Ga)N quantum well. Varying the acceleration voltage of the primary electrons and comparing the signal from the layer and the quantum well enables us to probe carrier recombination at depths ranging from the close vicinity of the surface to the position of the quantum well. Our experiments are accompanied by fully three-dimensional Monte Carlo simulations of carrier drift, diffusion, and recombination in the presence of the surface, the quantum well, and the dislocation, taking into account the dislocation strain field and the resulting piezoelectric field at the dislocation outcrop. Near the surface, this field establishes an exciton dead zone around the dislocation, the extent of which is not related to the carrier diffusion length. However, reliable values of the carrier diffusion length can be extracted from the dipole-like energy shift observed in hyperspectral cathodoluminescence maps recorded around the dislocation outcrop at low acceleration voltages. For high acceleration voltages, allowing us to probe a depth where carrier recombination is unaffected by surface effects, we observe a much stronger contrast than expected from the piezoelectric field alone. This finding provides unambiguous experimental evidence for the strong nonradiative activity of edge threading dislocations in bulk GaN and hence also in buried heterostructures.

cond-mat.mtrl-sci

Room-temperature ferroelectric switching of spin-to-charge conversion in GeTe

Since its birth in the 1990s, semiconductor spintronics has suffered from poor compatibility with ferromagnets as sources of spin. While the broken inversion symmetry of some semiconductors may alternatively allow for spin-charge interconversion, its control by electric fields is volatile. Ferroelectric Rashba semiconductors stand as appealing materials unifying semiconductivity, large spin-orbit coupling, and non-volatility endowed by ferroelectricity. However, their potential for spintronics has been little explored. Here, we demonstrate the non-volatile, ferroelectric control of spin-to-charge conversion at room temperature in epitaxial GeTe films. We show that ferroelectric switching by electrical gating is possible in GeTe despite its high carrier density. We reveal a spin-to-charge conversion as effective as in Pt, but whose sign is controlled by the orientation of the ferroelectric polarization. The comparison between theoretical and experimental data suggests that spin Hall effect plays a major role for switchable conversion. These results open a route towards devices combining spin-based logic and memory integrated into a silicon-compatible material.

cond-mat.mtrl-sci

Influence of Mg doping on In adsorption and In incorporation in (In,Ga)N superlattices

We present a detailed investigation of the mechanisms at play for the incorporation of In and Mg on the GaN(0001) surface during plasma-assisted molecular beam epitaxy (PAMBE). First, we have studied the kinetics of In desorption in the presence of Mg either without or with N supply from the plasma cell by quadrupole mass spectrometry (QMS) in the line of sight. Second, we have explored the effect of Mg doping at a different time along the cycle of (InN/GaN) supply repeated 10 times to form (In,Ga)N/GaN superlattices (SLs). By the complementary ex-situ investigation of these SLs by X-ray diffraction (XRD) and secondary ion mass spectrometry (SIMS), we found that in monolayer-thick (In,Ga)N layer, the In content was maximized when Mg was not supplied simultaneously to In, but it drastically decreased otherwise. In contrast, the Mg concentration strongly increased in the (In,Ga)N monolayers compared to the GaN barriers. We attribute this finding to the surfactant effect of In for Mg, which decreases the binding energy of Mg in GaN in presence of N.

cond-mat.mtrl-sci

InN and GaN/InN monolayers grown on ZnO {0001}

Thin InN and GaN/InN films were grown on oxygen-polar (O) (000-1) and zinc-polar (Zn) (0001) zinc oxide (ZnO) by plasma-assisted molecular beam epitaxy (PAMBE). The influence of the growth rate (GR) and the substrate polarity on the growth mode and the surface morphology of InN and GaN/InN was investigated in situ by reflection high-energy electron diffraction (RHEED) and ex situ by atomic force microscopy (AFM). During InN deposition, a transition from two dimensional to three dimensional (2D-3D) growth mode is observed in RHEED. The critical thickness for relaxation increases with decreasing GR and varies from 0.6 ML (GR: 1.0 ML/s) to 1.2 MLs (GR: 0.2 ML/s) on O-ZnO and from 1.2 MLs (GR: 0.5 ML/s) to 1.7 MLs (GR: 0.2 ML/s) on Zn-ZnO. The critical thickness for relaxation of GaN on top of 1.2 MLs and 1.5 MLs thick InN is close to zero on O-ZnO and 1.6 MLs on Zn-ZnO, respectively.

cond-mat.mtrl-sci

Mapping the band structure of GeSbTe phase change alloys around the Fermi level

Phase change alloys are used for non-volatile random access memories exploiting the conductivity contrast between amorphous and metastable, crystalline phase. However, this contrast has never been directly related to the electronic band structure. Here, we employ photoelectron spectroscopy to map the relevant bands for metastable, epitaxial GeSbTe films. The constant energy surfaces of the valence band close to the Fermi level are hexagonal tubes with little dispersion perpendicular to the (111) surface. The electron density responsible for transport belongs to the tails of this bulk valence band, which is broadened by disorder, i.e., the Fermi level is 100 meV above the valence band maximum. This result is consistent with transport data of such films in terms of charge carrier density and scattering time. In addition, we find a state in the bulk band gap with linear dispersion, which might be of topological origin.

cond-mat.mtrl-sci

Sub-nanometre resolution of atomic motion during electronic excitation in phase-change materials

Phase-change materials based on Ge-Sb-Te alloys are widely used in industrial applications such as nonvolatile memories, but reaction pathways for crystalline-to-amorphous phase-change on picosecond timescales remain unknown. Femtosecond laser excitation and an ultrashort x-ray probe is used to show the temporal separation of electronic and thermal effects in a long-lived ($>$100 ps) transient metastable state of Ge$_{2}$Sb$_{2}$Te$_{5}$ with muted interatomic interaction induced by a weakening of resonant bonding. Due to a specific electronic state, the lattice undergoes a reversible nondestructive modification over a nanoscale region, remaining cold for 4 ps. An independent time-resolved x-ray absorption fine structure experiment confirms the existence of an intermediate state with disordered bonds. This newly unveiled effect allows the utilization of non-thermal ultra-fast pathways enabling artificial manipulation of the switching process, ultimately leading to a redefined speed limit, and improved energy efficiency and reliability of phase-change memory technologies.

cond-mat.mtrl-sci

Individual electron and hole localization in submonolayer InN quantum sheets embedded in GaN

We investigate sub-monolayer InN quantum sheets embedded in GaN(0001) by temperature-dependent photoluminescence spectroscopy under both continuous-wave and pulsed excitation. Both the peak energy and the linewidth of the emission band associated with the quantum sheets exhibit an anomalous dependence on temperature indicative of carrier localization. Photoluminescence transients reveal a power law decay at low temperatures reflecting that the recombining electrons and holes occupy spatially separate, individual potential minima reminiscent of conventional (In,Ga)N(0001) quantum wells exhibiting the characteristic disorder of a random alloy. At elevated temperatures, carrier delocalization sets in and is accompanied by a thermally activated quenching of the emission. We ascribe the strong nonradiative recombination to extended states in the GaN barriers and confirm our assumption by a simple rate-equation model.

cond-mat.mes-hall

Interband characterization and electronic transport control of nanoscaled GeTe/Sb$_2$Te$_3$ superlattices

The extraordinary electronic and optical properties of the crystal-to-amorphous transition in phase-change materials led to important developments in memory applications. A promising outlook is offered by nanoscaling such phase-change structures. Following this research line, we study the interband optical transmission spectra of nanoscaled GeTe/Sb$_2$Te$_3$ chalcogenide superlattice films. We determine, for films with varying stacking sequence and growth methods, the density and scattering time of the free electrons, and the characteristics of the valence-to-conduction transition. It is found that the free electron density decreases with increasing GeTe content, for sub-layer thickness below $\sim$3 nm. A simple band model analysis suggests that GeTe and Sb$_2$Te$_3$ layers mix, forming a standard GeSbTe alloy buffer layer. We show that it is possible to control the electronic transport properties of the films by properly choosing the deposition layer thickness and we derive a model for arbitrary film stacks.

cond-mat.mes-hall

Insights into ultrafast Ge-Te bond dynamics in a phase-change superlattice

A long-standing question for avant-grade data storage technology concerns the nature of the ultrafast photoinduced phase transformations in the wide class of chalcogenide phase-change materials (PCMs). Overall, a comprehensive understanding of the microstructural evolution and the relevant kinetics mechanisms accompanying the out-of-equilibrium phases is still missing. Here, after overheating a phase-change chalcogenide superlattice by an ultrafast laser pulse, we indirectly track the lattice relaxation by time resolved X-ray absorption spectroscopy (tr-XAS) with a sub-ns time resolution. The novel approach to the tr-XAS experimental results reported in this work provides an atomistic insight of the mechanism that takes place during the cooling process, meanwhile a first-principles model mimicking the microscopic distortions accounts for a straightforward representation of the observed dynamics. Finally, we envisage that our approach can be applied in future studies addressing the role of dynamical structural strain in phase-change materials.

cond-mat.mtrl-sci

Picosecond strain dynamics in Ge$_{2}$Sb$_{2}$Te$_{5}$ monitored by time-resolved x-ray diffraction

Coherent phonons (CP) generated by laser pulses on the femtosecond scale have been proposed as a means to achieve ultrafast, non-thermal switching in phase-change materials such as Ge$_{2}$Sb$_{2}$Te$_{5}$(GST). Here we use ultrafast optical pump pulses to induce coherent acoustic phonons and stroboscopically measure the corresponding lattice distortions in GST using 100 ps x-ray pulses from the ESRF storage ring. A linear-chain model provides a good description of the observed changes in the diffraction signal, however, the magnitudes of the measured shifts are too large to be explained by thermal effects alone implying the presence of transient non-equilibrium electron heating in addition to temperature driven expansion. The information on the movement of atoms during the excitation process can lead to greater insight into the possibilities of using CP-induced phase-transitions in GST.

cond-mat.mtrl-sci

Evidence for topological band inversion of the phase change material Ge2Sb2Te5

We present an angle-resolved photoemission study of a ternary phase change material, namely Ge2Sb2Te5, epitaxially grown on Si(111) in the metastable cubic phase. The observed upper bulk valence band shows a minimum at Gamma-bar being 0.3 eV below the Fermi level E_F and a circular Fermi contour around Gamma-bar with a dispersing diameter of 0.27-0.36 Anstroms^-1. This is in agreement with density functional theory calculations of the Petrov stacking sequence in the cubic phase which exhibits a topological surface state. The topologically trivial cubic KH stacking shows a valence band maximum at Gamma in line with all previous calculations of the hexagonal stable phase exhibiting the valence band maximum at Gamma for a trivial Z_2 topological invariant nu_0 and away from Gamma for non-trivial nu_0. Scanning tunneling spectroscopy exhibits a band gap of 0.4 eV around E_F.

cond-mat.mes-hall

Coupling of exciton states as the origin of their biexponential decay dynamics in GaN nanowires

Using time-resolved photoluminescence spectroscopy, we explore the transient behavior of bound and free excitons in GaN nanowire ensembles. We investigate samples with distinct diameter distributions and show that the pronounced biexponential decay of the donor-bound exciton observed in each case is not caused by the nanowire surface. At long times, the individual exciton transitions decay with a common lifetime, which suggests a strong coupling between the corresponding exciton states. A system of non-linear rate-equations taking into account this coupling directly reproduces the experimentally observed biexponential decay.

cond-mat.mtrl-sci

Current path in light emitting diodes based on nanowire ensembles

Light emitting diodes (LEDs) were fabricated using ensembles of free-standing (In,Ga)N/GaN nanowires (NWs) grown on Si substrates in the self-induced growth mode by molecular beam epitaxy. Electron beam induced current analysis, cathodoluminescence as well as biased $μ$-photoluminescence spectroscopy, transmission electron microscopy, and electrical measurements indicate that the electroluminescence of such LEDs is governed by the differences in the individual current densities of the single-NW LEDs operated in parallel, i.e. by the inhomogeneity of the current path in the ensemble LED. In addition, the optoelectronic characterization leads to the conclusion that these NWs exhibit N-polarity and that the (In,Ga)N quantum well states in the NWs are subject to a non-vanishing quantum confined Stark effect.

cond-mat.mes-hall

GaN and InN nanowires grown by MBE: a comparison

Morphological, optical and transport properties of GaN and InN nanowires grown by molecular beam epitaxy (MBE) have been studied. The differences between the two materials in respect to growth parameters and optimization procedure was stressed. The nanowires crystalline quality has been investigated by means of their optical properties. A comparison of the transport characteristics was given. For each material a band schema was shown, which takes into account transport and optical features and is based on Fermi level pinning at the surface.

cond-mat.mtrl-sci