SearcharxivSearch

arXiv subjects

N. Barrett

Publications and source records attributed to N. Barrett.

18 recordsLinked to original sources

Ferroelastic twin angles at the surface of CaTiO$_\mathrm{3}$ quantified by PhotoEmission Electron Microscopy

We use photoemission electron microscopy to measure the ferroelastic twin wall angles at the surface of CaTiO$_\mathrm{3}$(001) and deduce the strain ordering. We analyze the angular dependence of the photoelectron emission from different domain surfaces, each with their own characteristic tilt angle in the factory roof-like topography. By considering the surface topography as a field perturbation, the offset in the photoemission threshold can be directly related to the tilt angles. With knowledge of the symmetry allowed twin walls we quantify twin topography between 179.1{\deg} to 180.8{\deg}.

cond-mat.mtrl-sci

Surface enhanced covalency and Madelung potentials in Nb doped SrTiO$_3$ (100), (110) and (111) single crystals

The influence of surface enhanced covalency on the Madelung potential is experimentally investigated using angle-resolved photoemission for (100), (110) and (111) SrTiO$_3$ surfaces after annealing in UHV at 630 {\deg}C. Deconvolution of the core level spectra (O 1s, Sr 3d and Ti 2p) distinguishes bulk and surface components, which are interpreted in terms of surface enhanced covalency (SEC). By comparing the experimentally measured binding energies with theoretical calculations developed in the framework of the Localized-Hole Point-Ion Model, we quantitatively determine the effective electron occupancy at bulk and surface Sr and Ti sites. Our results confirm the essentially ionic character of Sr$-$O bond and the partially covalent character of Ti$-$O bond in bulk STO. The cation Ti and Sr electron occupation is greater for all the three surfaces than in the bulk. Surface covalency shifts the Madelung potential at the surface by {\Delta}EM. {\Delta}EM is a minimum for the (111) surface, and increases through (100), attaining a maximum for (110). The angle-resolved valence band spectra and the work function values also confirm this trend. The results are consistent with d$-$d charge fluctuations dominating at the surface, whereas metal-ligand charge transfers are more energetically favourable in the bulk.

cond-mat.mtrl-sci

Exploring interlayer Dirac cone coupling in commensurately rotated few-layer graphene on SiC(000-1)

We investigate electronic band-structure images in reciprocal space of few layer graphene epitaxially grown on SiC(000-1). In addition to the observation of commensurate rotation angles of the graphene layers, the k-space images recorded near the Fermi edge highlight structures originating from diffraction of the Dirac cones due to the relative rotation of adjacent layers. The 21.9{\deg} and 27{\deg} rotation angles between two sheets of graphene are responsible for a periodic pattern that can be described with a superlattice unit cells. The superlattice generates replicas of Dirac cones with smaller wave vectors, due to a Brillouin zone folding.

cond-mat.mtrl-sci

Full field electron spectromicroscopy applied to ferroelectric materials

The application of PhotoEmission Electron Microscopy (PEEM) and Low Energy Electron Microscopy (LEEM) techniques to the study of the electronic and chemical structure of ferroelectric materials is reviewed. Electron optics in both techniques gives spatial resolution of a few tens of nanometres. PEEM images photoelectrons whereas LEEM images reflected and elastically backscattered electrons. Both PEEM and LEEM can be used in direct and reciprocal space imaging. Together, they provide access to surface charge, work function, topography, chemical mapping, surface crystallinity and band structure. Examples of applications for the study of ferroelectric thin films and single crystals are presented.

cond-mat.mtrl-sci

Charge spill-out and work function of few-layer graphene on SiC(0001)

We report on the charge spill-out and work function of epitaxial few-layer graphene on 6H-SiC(0001). Experiments from high-resolution, energy-filtered X-ray photoelectron emission microscopy (XPEEM) are combined with ab initio Density Functional Theory calculations using a relaxed interface model. Work function values obtained from theory and experiments are in qualitative agreement, reproducing the previously observed trend of increasing work function with each additional graphene plane. Electrons transfer at the SiC/graphene interface through a buffer layer causes an interface dipole moment which is at the origin of the graphene work function modulation. The total charge transfer is independent of the number of graphene layers, and is consistent with the constant binding energy of the SiC component of the C 1s core-level measured by XPEEM. Charge leakage into vacuum depends on the number of graphene layers explaining why the experimental, layer-dependent C 1s-graphene core-level binding energy shift does not rigidly follow that of the work function. Thus, a combination of charge transfer at the SiC/graphene interface and charge spill-out into vacuum resolves the apparent discrepancy between the experimental work function and C1s binding energy.

cond-mat.mtrl-sci

Polarization sensitive surface band structure of doped BaTiO3(001)

We present a spatial and wave-vector resolved study of the electronic structure of micron sized ferroelectric domains at the surface of a BaTiO3(001) single crystal. The n-type doping of the BaTiO3 is controlled by in-situ vacuum and oxygen annealing, providing experimental evidence of a surface paraelectric-ferroelectric transition below a critical doping level. Real space imaging of photoemission threshold, core level and valence band spectra show contrast due to domain polarization. Reciprocal space imaging of the electronic structure using linearly polarized light provides unambiguous evidence for the presence of both in and out-of plane polarization with two and fourfold symmetry, respectively. The results agree well with first principles calculations.

cond-mat.mtrl-sci

Enhancement of photovoltaic efficiency by insertion of a polyoxometalate layer at the anode of an organic solar cell

In this article the Wells-Dawson polyoxometalate K6[P2W18O62] is grown as an interfacial layer between indium tin oxide and bulk heterojunction of poly(3-hexylthiophene) (P3HT) and [6,6]-phenyl-C61-butyric acid methyl ester (PCBM). The structure of the POM layers depends on the thickness and shows a highly anisotropic surface organization. The films have been characterized by atomic force microscopy and X-ray photoelectron spectroscopy (XPS) to gain insight into their macroscopic organization and better understand their electronic properties. Then, they were put at the anodic interface of a P3HT:PCBM organic solar cell and characterized on an optical bench. The photovoltaic efficiency is discussed in terms of the benefit of the polyoxometalate at the anodic interface of an organic photovoltaic cell.

physics.app-ph

Influence of the ferroelectric polarization on the electronic structure of BaTiO3 thin films

Micrometric domains of precise ferroelectric polarization have been written into a 20 nm thick epitaxial thin film of BaTiO3(001) (BTO) on a Nb doped SrTiO3 (STO) substrate using PiezoForce Microscopy (PFM). The domain dependent electronic structure has been studied using fully energy-filtered PhotoEmission Microscopy (PEEM) and synchrotron radiation. Shifts, induced by ferroelectric polarization, of up to 300 meV are observed in the work function of the sample. The surface is Ba-O terminated. Polarization-induced distortion of the electronic structure is observed in the valence band and on the Ba 3d, Ti 2p and O 1s core levels of BTO. Polarization dependent surface adsorption is observed. A simple electrostatic model based on net surface charge is not sufficient to explain the observed modifications in the electronic levels.

cond-mat.mtrl-sci

Control of surface potential at polar domain walls in a nonpolar oxide

Ferroic domain walls could play an important role in microelectronics, given their nanometric size and often distinct functional properties. Until now, devices and device concepts were mostly based on mobile domain walls in ferromagnetic and ferroelectric materials. A less explored path is to make use of polar domain walls in nonpolar ferroelastic materials. Indeed, while the polar character of ferroelastic domain walls has been demonstrated, polarization control has been elusive. Here, we report evidence for the electrostatic signature of the domain-wall polarization in nonpolar calcium titanate (CaTiO3). Macroscopic mechanical resonances excited by an ac electric field are observed as a signature of a piezoelectric response caused by polar walls. On the microscopic scale, the polarization in domain walls modifies the local surface potential of the sample. Through imaging of surface potential variations, we show that the potential at the domain wall can be controlled by electron injection. This could enable devices based on nondestructive information readout of surface potential.

cond-mat.mtrl-sci

Time-resolved PhotoEmission Spectroscopy on a Metal/Ferroelectric Heterostructure

In thin film ferroelectric capacitor the chemical and electronic structure of the electrode/FE interface can play a crucial role in determining the kinetics of polarization switching. We investigate the electronic structure of a Pt/BaTiO3/SrTiO3:Nb capacitor using time-resolved photoemission spectroscopy. The chemical, electronic and depth sensitivity of core level photoemission is used to probe the transient response of different parts of the upper electrode/ferroelectric interface to voltage pulse induced polarization reversal. The linear response of the electronic structure agrees quantitatively with a simple RC circuit model. The non-linear response due to the polarization switch is demonstrated by the time-resolved response of the characteristic core levels of the electrode and the ferroelectric. Adjustment of the RC circuit model allows a first estimation of the Pt/BTO interface capacitance. The experiment shows the interface capacitance is at least 100 times higher than the bulk capacitance of the BTO film, in qualitative agreement with theoretical predictions from the literature.

cond-mat.mtrl-sci

Hydrostatic strain enhancement in laterally confined SiGe nanostripes

Strain-engineering in SiGe nanostructures is fundamental for the design of optoelectronic devices at the nanoscale. Here we explore a new strategy, where SiGe structures are laterally confined by the Si substrate, to obtain high tensile strain avoiding the use of external stressors, and thus improving the scalability. Spectro-microscopy techniques, finite element method simulations and ab initio calculations are used to investigate the strain state of laterally confined Ge-rich SiGe nano-stripes. Strain information is obtained by tip enhanced Raman spectroscopy with an unprecedented lateral resolution of ~ 30 nm. The nano-stripes exhibit a large tensile hydrostatic strain component, which is maximum at the center of the top free surface, and becomes very small at the edges. The maximum lattice deformation is larger than the typical values of thermally relaxed Ge/Si(001) layers. This strain enhancement originates from a frustrated relaxation in the out-of-plane direction, resulting from the combination of the lateral confinement induced by the substrate side walls and the plastic relaxation of the misfit strain in the (001) plane at the SiGe/Si interface. The effect of this tensile lattice deformation at the stripe surface is probed by work function mapping, performed with a spatial resolution better than 100 nm using X-ray photoelectron emission microscopy. The nano-stripes exhibit a positive work function shift with respect to a bulk SiGe alloy, quantitatively confirmed by electronic structure calculations of tensile strained configurations. The present results have a potential impact on the design of optoelectronic devices at a nanometer length scale.

cond-mat.mes-hall

Interface Electronic Structure in a Metal/Ferroelectric Heterostructure under Applied Bias

The effective barrier height between an electrode and a ferroelectric (FE) depends on both macroscopic electrical properties and microscopic chemical and electronic structure. The behavior of a prototypical electrode/FE/electrode structure, Pt/BaTiO3/Nb-doped SrTiO3, under in-situ bias voltage is investigated using X-Ray Photoelectron Spectroscopy. The full band alignment is measured and is supported by transport measurements. Barrier heights depend on interface chemistry and on the FE polarization. A differential response of the core levels to applied bias as a function of the polarization state is observed, consistent with Callen charge variations near the interface.

cond-mat.mtrl-sci

Thickness-dependent polarization of strained BiFeO3 films with constant tetragonality

We measure the remnant polarization of ferroelectric domains in BiFeO3 films down to 3.6 nm using low energy electron and photoelectron emission microscopy. The measured polarization decays strongly below a critical thickness of 5-7 nm predicted by continuous medium theory whereas the tetragonal distortion does not change. We resolve this apparent contradiction using first-principles-based effective Hamiltonian calculations. In ultra thin films the energetics of near open circuit electrical boundary conditions, i.e. unscreened depolarizing field, drive the system through a phase transition from single out-of-plane polarization to a nanoscale stripe domains, giving rise to an average remnant polarization close to zero as measured by the electron microscopy whilst maintaining the relatively large tetragonal distortion imposed by the non-zero polarization state of each individual domain.

cond-mat.mtrl-sci

Full field chemical imaging of buried native sub-oxide layers on doped silicon patterns

Fully energy-filtered X-ray photoelectron emission microscopy is used to analyze the spatial distribution of the silicon sub-oxide structure at the SiO2/Si interface as a function of underlying doping pattern. Using a spectroscopic pixel-by-pixel curve fitting analysis, we obtain the sub-oxide binding energy and intensity distributions over the full field of view. Binding energy maps for each oxidation state are obtained with a spatial resolution of 120 nm. Within the framework of a five-layer model, the experimental data are used to obtain quantitative maps of the sub-oxide layer thickness and also their spatial distribution over the p-n junctions. Variations in the sub-oxide thicknesses are found to be linked to the level and type of doping. The procedure, which takes into account instrumental artefacts, enables the quantitative analysis of the full 3D dataset.

cond-mat.mtrl-sci

Microscopic correlation between chemical and electronic states in epitaxial graphene on SiC(000-1)

We present energy filtered electron emission spectromicroscopy with spatial and wave-vector resolution on few layer epitaxial graphene on SiC$(000-1) grown by furnace annealing. Low energy electron microscopy shows that more than 80% of the sample is covered by 2-3 graphene layers. C1s spectromicroscopy provides an independent measurement of the graphene thickness distribution map. The work function, measured by photoelectron emission microscopy (PEEM), varies across the surface from 4.34 to 4.50eV according to both the graphene thickness and the graphene-SiC interface chemical state. At least two SiC surface chemical states (i.e., two different SiC surface structures) are present at the graphene/SiC interface. Charge transfer occurs at each graphene/SiC interface. K-space PEEM gives 3D maps of the k_|| pi - pi* band dispersion in micron scale regions show that the Dirac point shifts as a function of graphene thickness. Novel Bragg diffraction of the Dirac cones via the superlattice formed by the commensurately rotated graphene sheets is observed. The experiments underline the importance of lateral and spectroscopic resolution on the scale of future electronic devices in order to precisely characterize the transport properties and band alignments.

cond-mat.mtrl-sci

Skin layer of BiFeO3 single crystals

A surface layer ("skin") that is functionally and structurally different from the bulk was found in single crystals of BiFeO3. Impedance analysis indicates that a previously reported anomaly at T* ~ 275 \pm 5 ^/circC corresponds to a phase transition confined at the surface of BiFeO3. X-ray photoelectron spectroscopy and X-ray diffraction as a function of both incidence angle and photon wavelength unambiguously confirm the existence of a skin with an estimated skin depth of few nanometres, elongated out-of-plane lattice parameter, and lower electron density. Temperature-dependent x-ray diffraction has revealed that the skin's out of plane lattice parameter changes abruptly at T*, while the bulk preserves an unfeatured linear thermal expansion. The distinct properties of the skin are likely to dominate in large surface to volume ratios scenarios such as fine grained ceramics and thin films, and should be particularly relevant for electronic devices that rely on interfacial couplings such as exchange bias.

cond-mat.mtrl-sci

Three-dimensional band structure of layered TiTe2: Photoemission final-state effects

Three-dimensional band structure of unoccupied and occupied states of the prototype layered material TiTe2 is determined focusing on the GammaA line of the Brillouin zone. Dispersions and lifetimes of the unoccupied states, acting as the final states in the photoemission process, are determined from a very-low-energy electron diffraction experiment supported by first-principles calculations based on a Bloch waves treatment of multiple scattering. The experimental unoccupied states of TiTe2 feature dramatic non-free-electron effects such as multiband composition and non-parabolic dispersions. The valence band layer-perpendicular dispersions are then determined from a photoemission experiment consistently interpreted on the basis of the experimental final states to achieve control over the 3-dimensional wavevector. The experimental results demonstrate the absence of the Te 4pz* Fermi surface pocket at the Gamma point and significant self-energy renormalization of the valence band dispersions. Photoemission calculations based on a novel Bloch waves formalism within the one-step theory reveal limitations of understanding photoemission from layered materials such as TiTe2 in terms of direct transitions.

cond-mat.str-el

Band Mapping in One-Step Photoemission Theory: Multi-Bloch-Wave Structure of Final States and Interference Effects

A novel Bloch-waves based one-step theory of photoemission is developed within the augmented plane wave formalism. Implications of multi-Bloch-wave structure of photoelectron final states for band mapping are established. Interference between Bloch components of initial and final states leads to prominent spectral features with characteristic frequency dispersion experimentally observed in VSe_2 and TiTe_2. Interference effects together with a non-free-electron nature of final states strongly limit the applicability of the common direct transitions band mapping approach, making the tool of one-step analysis indispensable.

cond-mat.mtrl-sci