Unconventional Crystal Structure of the High-Pressure Superconductor La_{3}Ni_{2}O_{7}.

The discovery of high-temperature superconductivity in La_{3}Ni_{2}O_{7} at pressures above 14 GPa has spurred extensive research efforts. Yet, fundamental aspects of the superconducting phase, including the possibility of a filamentary character, are currently subjects of controversial debates. Conversely, a crystal structure with NiO_{6} octahedral bilayers stacked along the c-axis direction was consistently posited in initial studies on La_{3}Ni_{2}O_{7}. Here, we reassess this structure in optical floating zone-grown La_{3}Ni_{2}O_{7} single crystals that show signs of filamentary superconductivity. Employing scanning transmission electron microscopy and single-crystal x-ray diffraction under high pressures, we observe multiple crystallographic phases in these crystals, with the majority phase exhibiting alternating monolayers and trilayers of NiO_{6} octahedra, signifying a profound deviation from the previously suggested bilayer structure. Using density functional theory, we disentangle the individual contributions of the monolayer and trilayer structural units to the electronic band structure of La_{3}Ni_{2}O_{7}, providing a firm basis for advanced theoretical modeling and future evaluations of the potential of the monolayer-trilayer structure for hosting superconductivity.

Imaging the atomic structure and local chemistry of platelets in natural type Ia diamond.

In the past decades, many efforts have been devoted to characterizing {001} platelet defects in type Ia diamond. It is known that N is concentrated at the defect core. However, an accurate description of the atomic structure of the defect and the role that N plays in it is still unknown. Here, by using aberration-corrected transmission electron microscopy and electron energy-loss spectroscopy we have determined the atomic arrangement within platelet defects in a natural type Ia diamond and matched it to a prevalent theoretical model. The platelet has an anisotropic atomic structure with a zigzag ordering of defect pairs along the defect line. The electron energy-loss near-edge fine structure of both carbon K- and nitrogen K-edges obtained from the platelet core is consistent with a trigonal bonding arrangement at interstitial sites. The experimental observations support an interstitial aggregate mode of formation for platelet defects in natural diamond.

Long-range charge-density-wave proximity effect at cuprate/manganate interfaces.

The interplay between charge density waves (CDWs) and high-temperature superconductivity is currently under intense investigation. Experimental research on this issue is difficult because CDW formation in bulk copper oxides is strongly influenced by random disorder, and a long-range-ordered CDW state in high magnetic fields is difficult to access with spectroscopic and diffraction probes. Here we use resonant X-ray scattering in zero magnetic field to show that interfaces with the metallic ferromagnet La2/3Ca1/3MnO3 greatly enhance CDW formation in the optimally doped high-temperature superconductor YBa2Cu3O6+δ (δ ∼ 1), and that this effect persists over several tens of nanometres. The wavevector of the incommensurate CDW serves as an internal calibration standard of the charge carrier concentration, which allows us to rule out any significant influence of oxygen non-stoichiometry, and to attribute the observed phenomenon to a genuine electronic proximity effect. Long-range proximity effects induced by heterointerfaces thus offer a powerful method to stabilize the charge-density-wave state in the cuprates and, more generally, to manipulate the interplay between different collective phenomena in metal oxides.

Strain and size combined effects on the GaN band structure: VEELS and DFT study.

A nanoscale study of combined strain/size effects has been performed using monochromated valence electron energy-loss spectroscopy and density functional theory (DFT) calculations to locally explore the valence and conduction bands of a strained 2 nm GaN quantum well inserted between two fully relaxed AlN thick layers. Two main electronic transitions from the valence to the conduction band were experimentally detected and interpreted. The first transition was shown to be a collective oscillation (or plasmon), which was significantly blue-shifted in energy mainly due to the widening of the valence-band top-part. The second, however, had a single-particle character, that is: Ga-3d → Ga-4p, and was weakly affected by strain and size. In addition, our DFT calculations showed that strain and size can be adjusted separately to tune the GaN band-gap energy.

Inline electron holography and VEELS for the measurement of strain in ternary and quaternary (In,Al,Ga)N alloyed thin films and its effect on bandgap energy.

We present the use of (1) dark-field inline electron holography for measuring the structural strain, and indirectly obtaining the composition, in a wurtzite, 4-nm-thick InAlGaN epilayer on a AlN/GaN/AlN/GaN multinano-layer heterosystem, and (2) valence electron energy-loss spectroscopy to study the bandgap value of five different, also hexagonal, 20-50-nm-thick InAlGaN layers. The measured strain values were almost identical to the ones obtained by other techniques for similarly grown materials. We found that the biaxial strain in the III-N alloys lowers the bandgap energy as compared to the value calculated with different known expressions and bowing parameters for unstrained layers. By contrast, calculated and experimental values agreed in the case of lattice-matched (almost unstrained) heterostructures.

Transmission electron microscopy characterization of Au/Pt/Ti/Pt/GaAs ohmic contacts for high power GaAs/InGaAs semiconductor lasers.

We report on transmission electron microscopy studies of Au/Pt/Ti/Pt(10-30 nm) contact structures for high power GaAs/InGaAs semiconductor lasers. The studies showed that annealing at 450 degrees C of contact structures causes the reaction of whole Pt with substrate components (Ga and As) and the formation of Pt-GaAs interlayers with smooth interfaces as required for such structures. Annealing of the structures at 470 and 490 degrees C unfavourably affects the contact structure. At this condition, the strong downward diffusion of Au and Pt from the top layers causes a formation of Au-Pt pits, which break the Ti barrier. Transmission electron microscopy observation revealed that Au/Pt/Ti/Pt(10-30 nm) system annealed at 450 degrees C is appropriate for practical applications. The EDS technique used to identify the phase composition in the Pt(30 nm)/GaAs structure (specially produced for the EDS analysis) annealed at 450 degrees C showed that two layers were formed as a result of the reaction of the whole Pt layer with GaAs, and they consist of Ga, Pt and As. The top layer has the highest concentration of Ga. However, the bottom layer, which is close to the substrate, has the highest concentration of As.

Transmission electron microscopy study of erbium silicide formation from Ti/Er stack for Schottky contact applications.

In this paper, we present results of transmission electron microscopy studies on erbium silicide structures fabricated under various thermal conditions. A titanium cap has been used as a protective layer against oxidation during rapid thermal annealing of an erbium layer in a temperature range of 300-700 degrees C. Both layers (200 nm Ti and 25 nm Er) were deposited by electron-beam sputtering. The investigations have shown that the transformation of the 25-nm-thick erbium into erbium silicide is completed after annealing at 500 degrees C. At higher temperatures, the formation of a titanium silicide layer above erbium silicide is observed. The lowest Schottky barrier has been measured in the sample annealed at 700 degrees C.

Structure and chemistry of interfaces between ceria and yttria-stabilized zirconia studied by analytical STEM.

Epitaxial undoped and Gd2O3-doped ceria films were grown by pulsed laser deposition on (1 1 1) faced Y2O3-stabilized zirconia (YSZ). Highly localized cerium reduction at the film-substrate interfaces is revealed by atomically resolved valence EELS mapping using Cs aberration-corrected scanning transmission electron microscopy. The chemical profiles reveal interdiffusion of Ce, (Gd), Y, Zr, forming an intermixing zone at the interface 7-9 (1 1 1) lattice planes wide. In its vicinity, the fraction of Ce3+ raises gradually over 6-8 lattice planes from zero in the bulk ceria to ≈100% in one single plane at the interface. Beyond this plane the Ce3+ fraction drops sharply within the YSZ substrate. In the vicinity of the interface systematic scan deflections are observed during EELS line scans. The advancing electron probe experiences a retarding force at the ceria side, and an accelerating force at the YSZ side, irrespective of the scan direction. This behavior is suggestive of coulombic interactions between the electron probe and a charged interface. This is interpreted as an indication of the presence of a space-charge situation at the YSZ/ceria interface, resulting from an excess negative charge at the ceria side (due to Ce3+cations) and an excess positive charge at the YSZ side (due to oxygen vacancies).

High-temperature superconductivity at the lanthanum cuprate/lanthanum-strontium nickelate interface.

The utilization of interface effects in epitaxial systems at the nanoscale has emerged as a very powerful approach for engineering functional properties of oxides. Here we present a novel structure fabricated by a state-of-the-art oxide molecular beam epitaxy method and consisting of lanthanum cuprate and strontium (Sr)-doped lanthanum nickelate, in which interfacial high-temperature superconductivity (Tc up to 40 K) occurs at the contact between the two phases. In such a system, we are able to tune the superconducting properties simply by changing the structural parameters. By employing electron spectroscopy and microscopy combined with dedicated conductivity measurements, we show that decoupling occurs between the electronic charge carrier and the cation (Sr) concentration profiles at the interface and that a hole accumulation layer forms, which dictates the resulting superconducting properties. Such effects are rationalized in the light of a generalized space-charge theory for oxide systems that takes account of both ionic and electronic redistribution effects.

Electron microscopy of polyoxometalate ions on graphene by electrospray ion beam deposition.

Aberration-corrected high-resolution transmission electron microscopy (AC-HRTEM) has enabled atomically resolved imaging of molecules adsorbed on low-dimensional materials like carbon nanotubes, graphene oxide and few-layer-graphene. However, conventional methods for depositing molecules onto such supports lack selectivity and specificity. Here, we describe the chemically selective preparation and deposition of molecules-like polyoxometalate (POM) anions [PW12O40]3- using electrospray ion-beam deposition (ES-IBD) along with high-resolution TEM imaging. This approach provides access to sub-monolayer coatings of intact molecules on freestanding graphene, which enables their atomically resolved ex situ characterization by low-voltage AC-HRTEM. The capability to tune the deposition parameters in either soft or reactive landing mode, combined with the well-defined high-vacuum deposition conditions, renders the ES-IBD based method advantageous over alternative methods such as drop-casting. Furthermore, it might be expanded towards depositing and imaging large and nonvolatile molecules with complex structures.

High-temperature superconductivity in space-charge regions of lanthanum cuprate induced by two-dimensional doping.

The exploitation of interface effects turned out to be a powerful tool for generating exciting material properties. Such properties include magnetism, electronic and ionic transport and even superconductivity. Here, instead of using conventional homogeneous doping to enhance the hole concentration in lanthanum cuprate and achieve superconductivity, we replace single LaO planes with SrO dopant planes using atomic-layer-by-layer molecular beam epitaxy (two-dimensional doping). Electron spectroscopy and microscopy, conductivity measurements and zinc tomography reveal such negatively charged interfaces to induce layer-dependent superconductivity (Tc up to 35 K) in the space-charge zone at the side of the planes facing the substrate, where the strontium (Sr) profile is abrupt. Owing to the growth conditions, the other side exhibits instead a Sr redistribution resulting in superconductivity due to conventional doping. The present study represents a successful example of two-dimensional doping of superconducting oxide systems and demonstrates its power in this field.

Massive Dirac Fermion Observed in Lanthanide-Doped Topological Insulator Thin Films.

The breaking of time reversal symmetry (TRS) in three-dimensional (3D) topological insulators (TIs), and thus the opening of a 'Dirac-mass gap' in the linearly dispersed Dirac surface state, is a prerequisite for unlocking exotic physical states. Introducing ferromagnetic long-range order by transition metal doping has been shown to break TRS. Here, we present the study of lanthanide (Ln) doped Bi2Te3, where the magnetic doping with high-moment lanthanides promises large energy gaps. Using molecular beam epitaxy, single-crystalline, rhombohedral thin films with Ln concentrations of up to ~35%, substituting on Bi sites, were achieved for Dy, Gd, and Ho doping. Angle-resolved photoemission spectroscopy shows the characteristic Dirac cone for Gd and Ho doping. In contrast, for Dy doping above a critical doping concentration, a gap opening is observed via the decreased spectral intensity at the Dirac point, indicating a topological quantum phase transition persisting up to room-temperature.

Hybridization approach to in-line and off-axis (electron) holography for superior resolution and phase sensitivity.

Holography--originally developed for correcting spherical aberration in transmission electron microscopes--is now used in a wide range of disciplines that involve the propagation of waves, including light optics, electron microscopy, acoustics and seismology. In electron microscopy, the two primary modes of holography are Gabor's original in-line setup and an off-axis approach that was developed subsequently. These two techniques are highly complementary, offering superior phase sensitivity at high and low spatial resolution, respectively. All previous investigations have focused on improving each method individually. Here, we show how the two approaches can be combined in a synergetic fashion to provide phase information with excellent sensitivity across all spatial frequencies, low noise and an efficient use of electron dose. The principle is also expected to be widely to applications of holography in light optics, X-ray optics, acoustics, ultra-sound, terahertz imaging, etc.

Toward quantitative core-loss EFTEM tomography.

Core-loss EFTEM tomography provides three-dimensional structural and chemical information. Multiple inelastic scattering occurring in thick specimens as well as orientation-dependent diffraction contrast due to multiple elastic scattering, however, often limit its applications. After demonstrating the capability of core-loss EFTEM tomography to reconstruct just a few monolayers thin carbon layer covering a Fe catalyst particle we discuss its application to thicker samples. We propose an approximate multiple-scattering correction method based on the use of zero-loss images and apply it successfully to copper whiskers, providing a significant improvement of the reconstructed 3D elemental distribution. We conclude this paper by a general discussion on experimental parameters affecting the accuracy of EFTEM 3D elemental mapping.

Direct imaging of surface plasmon resonances on single triangular silver nanoprisms at optical wavelength using low-loss EFTEM imaging.

Using low-loss energy-filtering transmission electron microscopy (EFTEM) imaging, we map surface plasmon resonances (SPRs) at optical wavelengths on single triangular silver nanoprisms. We show that EFTEM imaging combining high spatial sampling and high energy resolution enables the detection and for the first time, to the best of our knowledge, mapping at the nanoscale of an extra multipolar SPR on these nanoparticles. As illustrated on a 276.5 nm long nanoprism, this eigenmode is found to be enhanced on the three edges where it exhibits a two-lobe distribution.