Chemical Analysis for Alkali Ion-exchanged Glass Using Atom Probe Tomography.

The developing flexible ultrathin glass for use in foldable displays has attracted widespread attention as an alternative to rigid electronic smartphones. However, the detailed compositional effects of chemically strengthened glass are not well understood. Moreover, the spatially resolved chemistry and depth of the compression layer of tempered glass are far from clear. In this study, commonly used X-ray spectroscopy techniques and atom probe tomography (APT) were used comparatively to investigate the distribution of constituent elements in two representative smartphone glass samples: non- and chemically tempered. APT has enabled sub-nanoscale analyses of alkali metals (Li, Na, K, and Ca) and this demonstrates that APT can be considered as an alternative technique for imaging the chemical distribution in glass for mobile applications.

Insights into the performance and degradation of Ru@Pt core-shell catalysts for fuel cells by advanced (scanning) transmission electron microscopy.

Ru@Pt core-shell nanoparticles are currently being explored as carbon monoxide tolerant anode catalysts for proton exchange membrane fuel cells. However, little is known about their degradation under fuel cell conditions. In the present work, two types of Ru@Pt nanoparticles with nominal shell thicknesses of 1 (Ru@1Pt) and 2 (Ru@2Pt) Pt monolayers are studied as synthesized and after accelerated stress tests. These stress tests were designed to imitate the degradation occurring under fuel cell operating conditions. Our advanced (scanning) transmission electron microscopy characterization explains the superior initial electrochemical performance of Ru@1Pt. Moreover, the 3D reconstruction of the Pt shell by electron tomography reveals an incomplete shell for both samples, which results in a less stable Ru metal being exposed to an electrolyte. The degree of coverage of the Ru cores provides insights into the higher stability of Ru@2Pt during the accelerated stress tests. Our results explain how to maximize the initial performance of Ru@Pt-type catalysts, without compromising their stability under fuel cell conditions.

Evaluation of functional layers thinning of high temperature polymer electrolyte membrane fuel cells after long term operation.

The operation related degradation processes of high temperature polymer electrolyte membrane fuel cell operated with hydrogen-rich reformate gas are studied. CO impurities from the reformate gas are strongly adsorbed by the catalyst surface, leading to poisoning and thus, reduction of the overall performance of the cell. Most of the studies are performed in a laboratory set-up by applying accelerated stress tests. In the present work, a high temperature polymer electrolyte membrane fuel cell is operated in a realistic configuration for 12 000 h (500 days). The fuel cell contains as electrocatalyst Pt in the cathode and a Pt-Ru alloy in the anode. The study of the degradation occurring in the functional layers, i.e. in different regions of cathode, anode and membrane layer, is carried out by scanning electron microscopy, (scanning) transmission electron microscopy and energy dispersive X-ray spectroscopy. We observed a thinning of the functional layers and a redistribution of catalyst material. The thinning of the cathode side is larger compared to the anode side due to harsher operation conditions likely causing a degradation of the support material via C corrosion and/or due to a degradation of the catalyst via oxidation of Pt and Ru. A thinning of the membrane caused by oxidation agents is also detected. Moreover, during operation, catalyst material is dissolved at the cathode side and redistributed. Our results will help to design and develop fuel cells with higher performance.

Machine-learning-enhanced time-of-flight mass spectrometry analysis.

Mass spectrometry is a widespread approach used to work out what the constituents of a material are. Atoms and molecules are removed from the material and collected, and subsequently, a critical step is to infer their correct identities based on patterns formed in their mass-to-charge ratios and relative isotopic abundances. However, this identification step still mainly relies on individual users' expertise, making its standardization challenging, and hindering efficient data processing. Here, we introduce an approach that leverages modern machine learning technique to identify peak patterns in time-of-flight mass spectra within microseconds, outperforming human users without loss of accuracy. Our approach is cross-validated on mass spectra generated from different time-of-flight mass spectrometry (ToF-MS) techniques, offering the ToF-MS community an open-source, intelligent mass spectra analysis.

Chemical instability at chalcogenide surfaces impacts chalcopyrite devices well beyond the surface.

The electrical and optoelectronic properties of materials are determined by the chemical potentials of their constituents. The relative density of point defects is thus controlled, allowing to craft microstructure, trap densities and doping levels. Here, we show that the chemical potentials of chalcogenide materials near the edge of their existence region are not only determined during growth but also at room temperature by post-processing. In particular, we study the generation of anion vacancies, which are critical defects in chalcogenide semiconductors and topological insulators. The example of CuInSe2 photovoltaic semiconductor reveals that single phase material crosses the phase boundary and forms surface secondary phases upon oxidation, thereby creating anion vacancies. The arising metastable point defect population explains a common root cause of performance losses. This study shows how selective defect annihilation is attained with tailored chemical treatments that mitigate anion vacancy formation and improve the performance of CuInSe2 solar cells.

Cryo-focused ion beam preparation of perovskite based solar cells for atom probe tomography.

Focused-ion beam lift-out and annular milling is the most common method used for obtaining site specific specimens for atom probe tomography (APT) experiments and transmission electron microscopy. However, one of the main limitations of this technique comes from the structural damage as well as chemical degradation caused by the beam of high-energy ions. These aspects are especially critical in highly-sensitive specimens. In this regard, ion beam milling under cryogenic conditions has been an established technique for damage mitigation. Here, we implement a cryo-focused ion beam approach to prepare specimens for APT measurements from a quadruple cation perovskite-based solar cell device with 19.7% efficiency. As opposed to room temperature FIB milling we found that cryo-milling considerably improved APT results in terms of yield and composition measurement, i.e. halide loss, both related to less defects within the APT specimen. Based on our approach we discuss the prospects of reliable atom probe measurements of perovskite based solar cell materials. An insight into the field evaporation behavior of the organic-inorganic molecules that compose the perovskite material is also given with the aim of expanding the applicability of APT experiments towards nano-characterization of complex organo-metal materials.

Calibration of Atom Probe Tomography Reconstructions Through Correlation with Electron Micrographs.

Although atom probe tomography (APT) reconstructions do not directly influence the local elemental analysis, any structural inferences from APT volumes demand a reliable reconstruction of the point cloud. Accurate estimation of the reconstruction parameters is crucial to obtain reliable spatial scaling. In the current work, a new automated approach of calibrating atom probe reconstructions is developed using only one correlative projection electron microscopy (EM) image. We employed an algorithm that implements a 2D cross-correlation of microstructural features observed in both the APT reconstructions and the corresponding EM image. We apply this protocol to calibrate reconstructions in a Cu(In,Ga)Se2-based semiconductor and in a Co-based superalloy. This work enables us to couple chemical precision to structural information with relative ease.

Crystalline structure, electronic and lattice-dynamics properties of NbTe2.

Layered-structure materials are currently relevant given their quasi-2D nature. Knowledge of their physical properties is currently of major interest. Niobium ditelluride possesses a monoclinic layered-structure with a distortion in the tellurium planes. This structural complexity has hindered the determination of its fundamental physical properties. In this work, NbTe2 crystals were used to elucidate its structural, compositional, electronic and vibrational properties. These findings have been compared with calculations based on density functional theory. The chemical composition and elemental distribution at the nanoscale were obtained through atom probe tomography. Ultraviolet photoelectron spectroscopy allowed the first determination of the work function of NbTe2. Its high value, 5.32 eV, and chemical stability allow foreseeing applications such as contact in optoelectronics. Raman spectra were obtained using different excitation laser lines: 488, 633, and 785 nm. The vibrational frequencies were in agreement with those determined through density functional theory. It was possible to detect a theoretically-predicted, low-frequency, low-intensity Raman active mode not previously observed. The dispersion curves and electronic band structure were calculated, along with their corresponding density of states. The electrical properties, as well as a pseudo-gap in the density of states around the Fermi energy are characteristics proper of a semi metal.

Tailoring Thermoelectric Transport Properties of Ag-Alloyed PbTe: Effects of Microstructure Evolution.

Capturing and converting waste heat into electrical power through thermoelectric generators based on the Seebeck effect is a promising alternative energy source. Among thermoelectric compounds, PbTe can be alloyed and form precipitates by aging at elevated temperatures, thus reducing thermal conductivity by phonon scattering. Here, PbTe is alloyed with Ag to form Ag-rich precipitates having a number density controlled by heat treatments. We employ complementary scanning transmission electron microscopy and atom probe tomography to analyze the precipitate number density and the PbTe-matrix composition. We measure the temperature-dependent transport coefficients and correlate them with the microstructure. The thermal and electrical conductivities, as well as the Seebeck coefficients, are found to be highly sensitive to the microstructure and its temporal evolution, e.g., the number density of Ag-rich precipitates increases by ca. 3 orders of magnitude and reaches (1.68 ± 0.92) × 1024 m-3 upon aging at 380 °C for 6 h, which is pronounced by reduction in thermal conductivity to a value as low as 0.85 W m-1 K-1 at 300 °C. Our findings will help to guide predictive tools for further design of materials for energy harvesting.

Sodium enhances indium-gallium interdiffusion in copper indium gallium diselenide photovoltaic absorbers.

Copper indium gallium diselenide-based technology provides the most efficient solar energy conversion among all thin-film photovoltaic devices. This is possible due to engineered gallium depth gradients and alkali extrinsic doping. Sodium is well known to impede interdiffusion of indium and gallium in polycrystalline Cu(In,Ga)Se2 films, thus influencing the gallium depth distribution. Here, however, sodium is shown to have the opposite effect in monocrystalline gallium-free CuInSe2 grown on GaAs substrates. Gallium in-diffusion from the substrates is enhanced when sodium is incorporated into the film, leading to Cu(In,Ga)Se2 and Cu(In,Ga)3Se5 phase formation. These results show that sodium does not decrease per se indium and gallium interdiffusion. Instead, it is suggested that sodium promotes indium and gallium intragrain diffusion, while it hinders intergrain diffusion by segregating at grain boundaries. The deeper understanding of dopant-mediated atomic diffusion mechanisms should lead to more effective chemical and electrical passivation strategies, and more efficient solar cells.

Atom probe tomography studies on the Cu(In,ga)Se2 grain boundaries.

Compared with the existent techniques, atom probe tomography is a unique technique able to chemically characterize the internal interfaces at the nanoscale and in three dimensions. Indeed, APT possesses high sensitivity (in the order of ppm) and high spatial resolution (sub nm). Considerable efforts were done here to prepare an APT tip which contains the desired grain boundary with a known structure. Indeed, site-specific sample preparation using combined focused-ion-beam, electron backscatter diffraction, and transmission electron microscopy is presented in this work. This method allows selected grain boundaries with a known structure and location in Cu(In,Ga)Se2 thin-films to be studied by atom probe tomography. Finally, we discuss the advantages and drawbacks of using the atom probe tomography technique to study the grain boundaries in Cu(In,Ga)Se2 thin-film solar cells.

New generation of transvenous left ventricular leads - first experience with implantation of multipolar left ventricular leads.

BACKGROUND: Aside from unfavourable anatomy, inacceptable pacing thresholds and phrenic nerve stimulation represent major obstacles for successful left ventricular (LV) lead placement for cardiac resynchronization therapy (CRT). OBJECTIVE: To implant, for the first time, a new generation of transvenous multipolar LV leads (a quad-electrode lead) in combination with a CRT-cardioverter defibrillator, and to demonstrate that this combination allows for 10 different pacing vectors to combat the problems cited above. METHODS: Thirty patients were selected for CRT-cardioverter defibrillator implantation. At implantation, standard lead parameters were recorded. The reason for choosing a vector other than the standard bipolar vector for LV pacing, the LV lead implantation time, x-ray exposure time required for lead placement, and the reason for and number of repositions were documented. Before hospital discharge, a system inspection was performed. RESULTS: The implantation lead parameters were satisfactory. In 17 patients, a vector other than the standard bipolar vector was chosen to avoid phrenic nerve stimulation or to establish a better pacing threshold. In seven cases, the LV lead was repositioned (three phrenic nerve stimulations, two inacceptable pacing captures and two nonstable lead positions). Phrenic nerve stimulation was noted in eight cases; however, in five, this was eliminated by changing the stimulation vector. At hospital discharge, two-thirds of patients retained the implantation stimulation vector and in one-third, the vector was modified to further optimize the system. CONCLUSIONS: The quad-electrode lead provides good handling and may reduce the risk of inacceptable pacing thresholds and phrenic nerve stimulation. Consequently, implantation time, x-ray exposure and contrast agent load may be decreased, leading to lower kidney stress. Furthermore, the option for vector change after implantation may reduce the number of necessary reinterventions resulting from the pacing threshold and impedance increase.

The use of telescoping guide catheters for coronary sinus cannulation and sub-selecting tributaries in left ventricular lead placement.

INTRODUCTION: Failure to enter the coronary sinus (CS) with a guiding catheter and entering its tributaries remains challenging in left ventricle (LV) pacing lead implants for cardiac resynchronization therapy (CRT). A dual telescoping catheter system (8F outer/6F inner) is designed to provide the ability to adjust the catheter curve size, shape and/or reach to the patients' anatomy avoiding the need for catheter change. METHODS: Five different designs for CS cannulation were randomly tested in 64 patients scheduled for CRT device implant. RESULTS: In 33 consecutive patients three adaptable telescoping guiding catheter systems were tested per patient, the adaptable catheters had higher overall cannulation success rates (68, 63 and 62%) compared to the fixed shape catheter (46%) and an greater cannulation success rate when the CS location was not known (70, 53 and 72% vs 33% for the fixed shape). In a second group of 31 CRT patients the two telescoping catheters had similar high levels of success (71-80%), with or without using the inner catheter. CONCLUSIONS: The telescopic system is adaptable to a wide range of anatomical variations in patients and can result in a higher CS cannulation success rate due to its adjustability in the RA in search for the CS ostium. On top of this the inner catheter allows for sub-selecting the CS tributaries.

Prospective randomized comparison of two defibrillation safety margins in unipolar, active pectoral defibrillator therapy.

Various techniques are used to establish defibrillation efficacy and to evaluate defibrillation safety margins in patients with an ICD. In daily practice a safety margin of 10 J is generally accepted. However, this is based on old clinical data and there are no data on safety margins using current ICD technology with unipolar, active pectoral defibrillators. Therefore, a randomized study was performed to test if the likelihood of successful defibrillation at defibrillation energy requirement (DER) + 5 J and + 10 J is equivalent. Ninety-six patients (86 men; age 61.0 +/- 10.3 years; ejection fraction 0.341 +/- 0.132; coronary artery disease [n = 65], dilated cardiomyopathy [n = 18], other [n = 13]) underwent implantation of an active pectoral ICD system with unidirectional current pathway and a truncated, fixed tilt biphasic shock waveform. The defibrillation energy requirement (DER) was determined with the use of a step-down protocol (delivered energy 15, 10, 8, 6, 4, 3, 2 J). The patients were then randomized to three inductions of ventricular fibrillation at implantation and three at predischarge testing with shock strengths programmed to DER + 5 J at implantation and + 10 J at predischarge testing or vice versa. The mean DER in the total study population was 7.88 +/- 2.96 J. The number of defibrillation attempts was 288 for + 5 J and 288 for + 10 J. The rate of successful defibrillation was 94.1% (DER + 5 J) and 98.9% (DER + 10 J; P < 0.01 for equivalence). Charge times for DER + 5 J were significantly shorter than for DER + 10 J (3.65 +/- 1.14 vs 5.45 +/- 1.47 s; P < 0.001). A defibrillation safety margin of DER + 5 J is associated with a defibrillation probability equal to the standard DER + 10 J. In patients in whom short charge times are critical for avoidance of syncope, a safety margin of DER + 5 J seems clinically safe for programming of the first shock energy.