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Bournonite (CuPbSbS3) and enargite (Cu3AsS4) have recently been used as absorber layers in thin-film photovoltaic devices due to their ideal bandgap and ferroelectric properties. An understanding of the ferroelectric domain structure in these materials is required so that the benefits of the internal depolarizing electric fields can be fully exploited. Here, the atomic structure and electronic properties of domain walls (DWs) are elucidated through a combined aberration-corrected scanning transmission electron microscopy and density functional theory study. ∼90° and 180° DWs are observed in bournonite. As the 180° DW is charge neutral, it cannot contribute to the anomalous photovoltaic effect that leads to high open circuit voltages. The ∼90° DW shows a slight offset across the boundary, but the contributions of this to the anomalous photovoltaic effect are negligible. The DWs are also electrically passive, i.e., they do not result in significant recombination and do not block charge carrier transport. A high density of stacking faults (SF) was, however, observed in enargite. The SFs have a large number of defect states within the bandgap, which would lower the device efficiency through Shockley–Read–Hall recombination. [ABSTRACT FROM AUTHOR]

The growth of Cu2ZnSnS4 (CZTS) polycrystals from solid state reaction over a range of compositions, including the regions which produce the highest efficiency photovoltaic devices, is reported. X-ray measurements confirm the growth of crystalline CZTS. Temperature and intensity dependent photoluminescence (PL) measurements show an increase in the energy of the main CZTS luminescence peak with both increasing laser power and increasing temperature. Analysis of the PL peak positions and intensity behavior demonstrates that the results are consistent with the model of fluctuating potentials. This confirms that the polycrystals are heavily doped with the presence of a large concentration of intrinsic defects. The behavior of the main luminescence feature is shown to be qualitatively similar over a broad range of compositions although the nature and amount of secondary phases vary significantly. The implications for thin-film photovoltaic devices are discussed. [ABSTRACT FROM AUTHOR]

The crystal structure identification of the photovoltaic material Cu2ZnSnSe4 (CZTSe) is challenging due to the distinguishing feature between the two polymorphs, kesterite and stannite, being the arrangement of Cu and Zn ions. Here an energy dispersive X-ray (EDX) technique, based on electron beam channeling along specific crystallographic planes in a transmission electron microscope (TEM), is used to identify the structure. Regions a few 100 nm in size can be analysed using this method, unlike neutron or anomalous X-ray scattering. The parent crystal structure of CZTSe, annealed on either side of the order–disorder transition temperature, was correctly identified as being kesterite. The presence of 1/2[110] (001) and 1/4[201] (101) anti-site boundaries (ASBs) has also been investigated. The density of ASBs is higher above the transition temperature, due to a smaller energy penalty for disordering on the 2c and 2d Wyckoff sites. A nearest neighbour cation analysis predicted the 1/2[110] (001) ASB to have the lowest formation energy. From density functional theory (DFT) simulations the 1/2[110] (001) ASB energy is only 43 mJ m−2 and furthermore it is not a recombination site or current blocking layer, so that photovoltaic device performance is not significantly degraded. [ABSTRACT FROM AUTHOR]

The synthesis of multinary compound films from layered precursors is only partially understood. Identical location microscopy resolves the multi-step synthesis of Cu2ZnSnSe4 from metallic stacks on the micron-scale. Large scale metal alloying and the seemingly illogical observation that ZnSe segregates preferentially on locations previously poor of zinc are revealed. [ABSTRACT FROM AUTHOR]

Electron-energy-loss spectroscopy is used to map composition and electronic states in epitaxial La2/3Ca1/3MnO3 (LCMO) films of various thicknesses grown on SrTiO3 (001) and (110) substrates. For relatively thick films (≥20 nm), epitaxial tensile strain in (001) films promotes a compositional La/Ca gradient across the film thickness, being the interface La rich, while the relaxed (110) films are chemically homogeneous. In contrast, much thinner (001) and (110) LCMO films display a different La/Ca distribution, being La rich at the free surface. The observed distinct thickness-dependent composition gradient behavior reflects a balance between strain-induced elastic energy minimization and kinetic effects during growth. [ABSTRACT FROM AUTHOR]

Extended abstract of a paper presented at Microscopy and Microanalysis 2010 in Portland, Oregon, USA, August 1 – August 5, 2010. [ABSTRACT FROM PUBLISHER]

Extended abstract of a paper presented at Microscopy and Microanalysis 2010 in Portland, Oregon, USA, August 1 – August 5, 2010. [ABSTRACT FROM PUBLISHER]

Experimental techniques that probe the electronic structure of crystalline solids are vital for exploring novel condensed matter phenomena. In coherent Compton scattering the Compton signal due to interference of an incident and Bragg diffracted beam is measured. This gives the projected, non-diagonal electron momentum density of the solid, a quantity that is sensitive to both the amplitude and phase of the electron wavefunction. Here coherent electron Compton scattering is demonstrated using electron energy loss spectroscopy in the transmission electron microscope. The technique has several advantages over coherent X-ray Compton scattering, such as a superior spatial resolution and the use of smaller specimens to generate Bragg beams of sufficient intensity. The conditions for a directly interpretable coherent electron Compton signal are established. Results are presented for the projected, non-diagonal electron momentum density for silicon under 004 and 2¯20 Bragg beam set ups., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 The Author(s). Published by Elsevier B.V. All rights reserved.)

Compton scattering in electron energy loss spectroscopy (EELS) is used to quantify the momentum distribution of occupied electronic states in a solid. The Compton signal is a broad feature with a width of several hundred eV. Furthermore, the weak intensity results in a low peak-to-background ratio. Removing the background under the Compton profile is therefore particularly challenging, especially if there is an overlap with EELS core loss edges. Here an empirical background subtraction routine is proposed that uses input data from a bright-field EELS spectrum that does not have a Compton signal. The routine allows for multiple elastic-inelastic scattering within the EELS collection angles. Background subtraction is demonstrated on a Compton profile in silicon that overlaps with the Si L-edge. Systematic errors in the method are also discussed., Competing Interests: Declaration of Competing Interest The author declares that he has no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 The Authors. Published by Elsevier Ltd.. All rights reserved.)

The role of magnon inelastic scattering in high energy electron diffraction of spin unpolarised electron beams, including vortex beams, is investigated theoretically for a Heisenberg ferromagnet. The interaction is between the atomic magnetic dipoles in the specimen and orbital angular momentum (OAM) of the electron beam. Magnon inelastic scattering by vortex beams is allowed despite many atoms along the magnon spin wave experiencing mixed OAM states. The scattering cross-section is however independent of the vortex beam winding number. In the case of planes waves in ferromagnetic iron, the magnon diffuse scattered intensity is significantly smaller than phonons in the energy loss range currently accessible by state-of-the-art monochromated electron energy loss spectroscopy (EELS). Nevertheless, it is shown that the long-range magnetic field of the atomic dipoles has a similar role to dipole scattering in phonon excitation. This means that magnons could, in principle, be detected using aloof beam EELS, where long acquisition times can be realised without any specimen beam damage, an important pre-requisite for detecting the weak magnon signal., (Copyright © 2022. Published by Elsevier B.V.)

The feasibility of detecting magnetic excitations using monochromated electron energy loss spectroscopy in the transmission electron microscope is examined. Inelastic scattering cross-sections are derived using a semi-classical electrodynamic model, and applied to AC magnetic susceptibility measurements and magnon characterization. Consideration is given to electron probes with a magnetic moment, such as vortex beams, where additional inelastic scattering can take place due to the change in magnetic potential energy of the incident electron in a non-uniform magnetic field. This so-called 'Stern-Gerlach' energy loss can be used to enhance the strength of the scattering by increasing the orbital angular momentum of the vortex beam, and enables separation of magnetic from non-magnetic (i.e. dielectric) energy losses, thus providing a promising experimental route for detecting magnons. AC magnetic susceptibility measurements are however not feasible using Stern-Gerlach energy losses for a vortex beam., (Copyright © 2021 Elsevier B.V. All rights reserved.)

Electron Compton scattering is a technique that gives information on the electron momentum density of states and is used to characterize the ground state electronic structure in solids. Extracting the momentum density of states requires us to assume the so-called 'impulse approximation', which is valid for large energy losses. Here, the robustness of the impulse approximation in the low energy transfer regime is tested and confirmed on amorphous carbon films. Compared to traditional Compton measurements, this provides additional benefits of more efficient data collection and a simplified way to probe valence electrons, which govern solid state bonding. However, a potential complication is the increased background from the plasmon signal. To overcome this, a novel plasmon background subtraction routine is proposed for samples that are resistant to beam damage. LAY DESCRIPTION: Properties of solids depend on their electronic structure which can be studied using electron Compton scattering technique. Here, an electron beam is used to penetrate a very thin sample. During the interaction between the electrons in the beam and electrons in the sample, the former transfer a part of their energy to the latter, resulting in a measurable energy loss of the transmitted beam. The amount of the energy transfer depends on the angle of incidence between the beam and the sample. Typically, the experiments are carried out using high tilt angles and high energy transfer; however, in this work, we show that even smaller angles of incidence are suitable, which improve the signal quality and ease data processing procedures., (© The Authors. Journal of Microscopy published by John Wiley & Sons Ltd on behalf of Royal Microscopical Society.)

Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

Quantitative electron microscopy requires accurate simulation methods that take into account both elastic and inelastic scattering of the high energy electrons within the specimen. Here a method to combine plasmon excitations, the dominant energy loss mechanism in a solid, with conventional frozen phonon, multislice simulations is presented. The Monte Carlo based method estimates the plasmon scattering path length and scattering angle using random numbers and modifies the transmission and propagator functions in the multislice calculation accordingly. Comparison of energy filtered, convergent beam electron diffraction patterns in [110]-Si show good agreement between simulation and experiment. Simulations also show that plasmon excitation decreases the high angle annular dark field signal from atom columns, due to the plasmon scattering angle suppressing electron beam channeling along the atom columns. The effect on resolution and peak-to-background ratio of the atom columns is however small., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Cathodoluminescence (CL) is an important analytical technique for probing the optical properties of materials at high spatial resolution. Interpretation of CL spectra is however complicated by the fact that the spectrum depends on the carrier injection density of the incident electron beam. Here a generalised version of Planck's radiation law is used to uncover the evolution of CL spectra with injection under steady-state conditions. The importance of the quasi-Fermi level is highlighted and it is shown that steady-state luminescence is suppressed when the carrier distributions undergo a population inversion. The theory is consistent with some well-known luminescence phenomena, such as the blue shifting of donor-acceptor pair transitions with increased injection, and its predictions are experimentally verified on CdTe and GaN, which are exemplar thin-film solar cell and light emitting diode materials respectively. Furthermore, the discussion is broadened to include pulsed illumination in time resolved CL, where the carrier distribution is dynamically evolving with time., (Copyright © 2019 Elsevier B.V. All rights reserved.)

There is renewed interest in cathodoluminescence (CL) in the transmission electron microscope, since it can be combined with low energy loss spectroscopy measurements and can also be used to probe defects, such as grain boundaries and dislocations, at high spatial resolution. Transition radiation (TR), which is emitted when the incident electron crosses the vacuum-specimen interface, is however an important artefact that has received very little attention. The importance of TR is demonstrated on a wedge shaped CdTe specimen of varying thickness. For small specimen thicknesses (<250nm) grain boundaries are not visible in the panchromatic CL image. Grain boundary contrast is produced by electron-hole recombination within the foil, and a large fraction of that light is lost to multiple-beam interference, so that thicker specimens are required before the grain boundary signal is above the TR background. This is undesirable for high spatial resolution. Furthermore, the CL spectrum contains additional features due to TR which are not part of the 'bulk' specimen. Strategies to minimise the effects of TR are also discussed., (Copyright © 2016 Elsevier B.V. All rights reserved.)

Electron vortex beams are distorted by scattering within a crystal, so that the wavefunction can effectively be decomposed into many vortex components. Using a Bloch wave approach equations are derived for vortex beam decomposition at any given depth and with respect to any frame of reference. In the kinematic limit (small specimen thickness) scattering largely takes place at the neighbouring atom columns with a local phase change of π/2rad. When viewed along the beam propagation direction only one vortex component is present at the specimen entrance surface (i.e. the 'free space' vortex in vacuum), but at larger depths the probe is in a mixed state due to Bragg scattering. Simulations show that there is no direct correlation between vortex components and the 〈Lz〉 pendellösung, i.e. at a given depth probes with relatively constant 〈Lz〉 can be in a more mixed state compared to those with more rapidly varying 〈Lz〉. This suggests that minimising oscillations in the 〈Lz〉 pendellösung by probe channelling is not the only criterion for generating a strong electron energy loss magnetic circular dichroism (EMCD) signal., (Copyright © 2015 Elsevier B.V. All rights reserved.)

Two important applications of electron vortex beams are in electron magnetic chiral dichroism (EMCD) measurements and nanoparticle manipulation. In both cases orbital angular momentum (〈Lz〉) transfer between the vortex beam and the specimen due to dynamic scattering is critical. In general the 〈Lz〉 pendellösung consists of short and long wavelength oscillations. The former is due to interference between the tightly bound 1s and more dispersive non-1s Bloch states, while the latter is due to interference between the non-1s states. For EMCD experiments with ±ħ angular momentum beams, momentum transfer can be minimised by selecting the appropriate aperture size, so that the probe wavefunction approximately matches that of the 2p-type Bloch states. For manipulating nanoparticles with large angular momentum beams small apertures are required to excite the 1s state and thereby enhance the short wavelength oscillations in 〈Lz〉. This enables efficient momentum transfer to the specimen, provided the nanoparticle dimension corresponds to a minimum in the 〈Lz〉 pendellösung., (Copyright © 2014. Published by Elsevier B.V.)

Several electron microscopy techniques available for characterising thin-film solar cells are described, including recent advances in instrumentation, such as aberration-correction, monochromators, time-resolved cathodoluminescence and focused ion-beam microscopy. Two generic problems in thin-film solar cell characterisation, namely electrical activity of grain boundaries and 3D morphology of excitionic solar cells, are also discussed from the standpoint of electron microscopy. The opportunities as well as challenges facing application of these techniques to thin-film and excitonic solar cells are highlighted., (Copyright © 2011 Elsevier B.V. All rights reserved.)