Chemical modification, such as intercalation or doping of novel materials is of great importance for exploratory material science and applications in various fields of physics and chemistry. In the present work, we report the systematic intercalation of chemically exfoliated few-layer graphene with potassium while monitoring the sample resistance using microwave conductivity. We find that the conductivity of the samples increases by about an order of magnitude upon potassium exposure. The increased of number of charge carriers deduced from the ESR intensity also reflects this increment. The doped phases exhibit two asymmetric Dysonian lines in ESR, a usual sign of the presence of mobile charge carriers. The width of the broader component increases with the doping steps, however, the narrow components seem to have a constant line width.
We present electron energy-loss spectroscopic measurements of potassium (K) intercalated tungsten diselenide (WSe2). After exposure of pristine WSe2 films to potassium, we observe a charge carrier plasmon excitation at about 0.97 eV, which indicates a semiconductor to metal transition. Our data signal the formation of one particular doped K-WSe2 phase. A Kramers-Kronig analysis (KKA) allows the determination of the dielectric function and to estimate the composition of about K0.6WSe2. Momentum dependent measurements reveal a substantial plasmon dispersion to higher energies.
The electronic excitations of manganese phthalocyanine (MnPc) films were studied as a function of potassium doping using electron energy-loss spectroscopy in transmission. Our data reveal doping induced changes in the excitation spectrum, and they provide evidence for the existence of three doped phases: K$_1$MnPc, K$_2$MnPc, and K$_4$MnPc. Furthermore, the addition of electrons first leads to a filling of orbitals with strong Mn 3d character, a situation which also affects the magnetic moment of the molecule.
TEM specimens from potassium niobate single crystals were observed while being heated in a TEM. DWs and dislocations were observed; the DWs were mobile. In certain cases the DWs became pinned by the dislocations, at least for a short time, most likely due to interaction of strain fields. Both phase changes were observed with accompanying rapid appearance of new domain patterns.
The implementation of aberration-corrected electron beam lithography (AC-EBL) in a 200 keV scanning transmission electron microscope (STEM) is a novel technique that could be used for the fabrication of quantum devices based on 2D atomic crystals with single nanometer critical dimensions, allowing to observe more robust quantum effects. In this work we study electron beam sculpturing of nanostructures on suspended graphene field effect transistors using AC-EBL, focusing on the in situ characterization of the impact of electron beam exposure on device electronic transport quality. When AC-EBL i…
The strong geomagnetic influences on mechanical properties of crystals due to their exposure to ultralow crossed magnetic fields, the Earth's field (approx. 50 microTesla) and the AC field (approx. 3 microTesla) in the electron paramagnetic resonance scheme, are discussed. Resonance relaxation displacements of dislocations in NaCl crystals are found both for a harmonic pump field and for a pulse AC field of resonance duration approx. 0.5 microsec. Resonant changes have been also detected in the microhardness of ZnO, triglycine sulfate, and potassium acid phthalate crystals after their exposure…
Observation of a structurally driven, reversible topological phase transition in a distorted square net material
Princeton University（普林斯顿大学）；Nanyang Technological University（南洋理工大学）；Okinawa Institute of Science and Technology (OIST)（冲绳科学技术大学院大学）；University of Arkansas（阿肯色大学）；Johns Hopkins University（约翰斯·霍普金斯大学）；University of North Texas（北德克萨斯大学）；Wichita State University（威奇托州立大学）；Lawrence Berkeley National Laboratory（劳伦斯伯克利国家实验室）
The kinetics of E' centers induced in silica by 4.7eV laser irradiation was investigated observing in situ their optical absorption band at 5.8 eV. After exposure the defects decay due to reaction with diffusing molecular hydrogen of radiolytic origin. Hydrogen-related annealing is active also during exposure and competes with the photo-induced generation of the centers until a saturation is reached. The concentrations of E' and H2 at saturation are proportional, so indicating that the UV-induced generation processes of the two species are correlated. These results are consistent with a model …
Sequential infiltration synthesis (SIS) provides a successful route to grow inorganic materials into polymeric films by penetrating of gaseous precursors into the polymer, both in order to enhance the functional properties of the polymer creating an organic-inorganic hybrid material, and to fabricate inorganic nanostructures when infiltrating in patterned polymer films or in selfassembled block copolymers. A SIS process consists in a controlled sequence of metal organic precursor and co-reactant vapor exposure cycles of the polymer films in an atomic layer deposition (ALD) reactor. In this wor…
Gaining in-situ access to relaxation dynamics of radiation induced defects will lead to a better understanding of materials and is important for the verification of theoretical models and simulations. We show preliminary results from experiments at the new Neutralized Drift Compression Experiment (NDCX-II) at Lawrence Berkeley National Laboratory that will enable in-situ access to defect dynamics through pump-probe experiments. Here, the unique capabilities of the NDCX-II accelerator to generate intense, nanosecond pulsed ion beams are utilized. Preliminary data of channeling experiments using…
W-based granular metals have been prepared by electron beam induced deposition from the tungsten-hexacarbonyl W(CO)6 precursor. In situ electrical conductivity measurements have been performed to monitor the growth process and to investigate the behavior of the deposit under electron beam post irradiation and by exposure to air. During the first part of the growth process, the electrical conductivity grows non-linearly, independent of the electron beam parameters. This behavior is interpreted as the result of the increase of the W-particles diameter. Once the growth process is terminated, the …
We report, for the first time, a comprehensive study involving in situ Raman spectroscopy supported by quantum mechanical calculations to exactly monitor the covalent binding to graphene with unprecedented precision. As a model reaction we have chosen the hydrogenation of reduced graphite ($KC_8$) with $H_2O$ and compared it with the corresponding exposure to $H_2$ and $O_2$. The early stages of graphene hydrogenation are accompanied by the evolution of a series of so far undiscovered D-bands ($D_1$-$D_5$). Using quantum mechanical calculations, we were able to unambiguously assign these bands…
Bismuth selenide Bi$_2$Se$_3$ was grown by molecular beam epitaxy while carrier density and mobility were measured directly \emph{in situ} as a function of film thickness. Carrier density shows high interface n-doping (1.5 x 10$^{13}$ cm$^{-2}$) at the onset of film conduction, and bulk dopant density of $\sim$5 x 10$^{18}$ cm$^{-3}$, roughly independent of growth temperature profile. Mobility depends more strongly on the growth temperature and is related to the crystalline quality of the samples quantified by \emph{ex-situ} AFM measurements. These results indicate that Bi$_2$Se$_3$ as prepare…
Recently the graphene/SiC interface has emerged as a versatile platform for the epitaxy of otherwise unstable, monoelemental, two-dimensional (2D) layers via intercalation. Intrinsically capped into a van der Waals heterostructure with overhead graphene, they compose a new class of quantum materials with striking properties contrasting their parent bulk crystals. Intercalated silver presents a prototypical example where 2D quantum confinement and inversion symmetry breaking entail a metal-to-semiconductor transition. However, little is known about the associated unoccupied states, and control …
Controllable doping of two-dimensional materials is highly desired for ideal device performance in both hetero- and p-n homo-junctions. Herein, we propose an effective strategy for doping of MoS2 with nitrogen through a remote N2 plasma surface treatment. By monitoring the surface chemistry of MoS2 upon N2 plasma exposure using in-situ X-ray photoelectron spectroscopy, we identified the presence of covalently bonded nitrogen in MoS2, where substitution of the chalcogen sulfur by nitrogen is determined as the doping mechanism. Furthermore, the electrical characterization demonstrates that p-typ…
Defects and microstructural features spanning the atomic level to the microscale play deterministic roles in the expressed properties of materials. Yet studies of material evolution in response to environmental stimuli most often correlate resulting performance with one dominant microstructural feature only. Here, the dynamic evolution of swelling in a series of Ni-based concentrated solid solution alloys under high-temperature irradiation exposure is observed using continuous, in situ measurements of thermoelastic properties in bulk specimens. Unlike traditional evaluation techniques which ac…
While the basal plane of graphene is inert, defects in it are centers of chemical activity. An attractive application of such defects is towards controlled functionalization of graphene with foreign molecules. However, the interaction of the defects with reactive environment, such as ambient, decreases the efficiency of functionalization and makes it poorly controlled. Here, we report a novel approach to generate, monitor with time resolution, and functionalize the defects $\textit{in situ}$ without ever exposing them to the ambient. The defects are generated by an energetic Argon plasma and t…
Using wide spectral range in situ spectroscopic ellipsometry with systematic ultra high vacuum annealing and in situ exposure to oxygen, we report the complex dielectric function of MoS$_2$ isolating the environmental effects and revealing the crucial role of unpassivated and passivated sulphur vacancies. The spectral weights of the A ($1.92$ eV) and B ($2.02$ eV) exciton peaks in the dielectric function reduce significantly upon annealing, accompanied by spectral weight transfer in a broad energy range. Interestingly, the original spectral weights are recovered upon controlled oxygen exposure…
Ultra-high vacuum Raman platform for in situ characterization of graphene nanoribbons
Department of Information Technology and Electrical Engineering, ETH Zürich - Swiss Federal Institute of Technology Zürich（苏黎世联邦理工学院信息与电气工程系）；Karlsruhe Institute of Technology（卡尔斯鲁厄理工学院）；Max Planck Institute for Polymer Research（马克斯·普朗克聚合物研究所）；Faculty of Chemistry and Food Chemistry & Center for Advanced Electronics Dresden, TUD - Dresden University of Technology（德累斯顿工业大学化学与食品化学学院及先进电子中心）；Max Planck Institute of Microstructure Physics（马克斯·普朗克微观结构物理研究所）
Two-dimensional black phosphorus has been configured as field-effect transistors, showing an intrinsic symmetric ambipolar transport characteristic. Here, we demonstrate the strongly modulated ambipolar characteristics of few-layer black phosphorus in oxygen. Pure oxygen exposure can dramatically decrease the electron mobility of black phosphorus without degrading the hole transport. The transport characteristics can be nearly recovered upon annealing in Argon. This reveals that oxygen molecules are physisorbed on black phosphorus. In contrast, oxygen exposure upon light illumination exhibits …
Photopolymerization processes are exploited in light exposure-based 3D printing technologies, where either a focused laser beam or a patterned light sheet allows layers of a UV curable, liquid pre-polymer to be solidified. Here we focus on the crucial, though often neglected, role of the layer thickness on photopolymerization. The temporal evolution of polymerization reactions occurring in droplets of acrylate-based oligomers and in photoresist films with varied thickness is investigated by means of an optical system, which is specifically designed for in-situ and real-time monitoring. The tim…
Study of amorphous alumina coatings for next-generation nuclear reactors: hightemperature in-situ and post-mortem Raman spectroscopy and X-ray diffraction
We present detailed multi frequency resonant Raman measurements of potassium graphite intercalation compounds (GICs). From a well controlled and consecutive in-situ intercalation and high temperature de-intercalation approach the response of each stage up to stage VI is identified. The positions of the G and 2D lines as a function of staging depend on the charge transfer from K to the graphite layers and on the lattice expansion. Ab-initio calculations of the density and the electronic band-structure demonstrate that most (but not all) of the transferred charge remains on the graphene sheets a…
In the majority of cases nanostructures prepared by focused electron beam induced deposition (FEBID) employing an organometallic precursor contain predominantly carbon-based ligand dissociation products. This is unfortunate with regard to using this high-resolution direct-write approach for the preparation of nanostructures for various fields, such as mesoscopic physics, micromagnetism, electronic correlations, spin-dependent transport and numerous applications. Here we present an in-situ cleaning approach to obtain pure Co-FEBID nanostructures. The purification procedure lies in the exposure …
Picometre-scale real-time drift correction in TEM and STEM by dynamic control of the specimen stage for atomic-resolution imaging
Université de Toulouse, CNRS, CEMES（图卢兹大学，法国国家科学研究中心，电子显微镜中心）；CNRS, Centre de Microcaracterisation Raimond Castaing（法国国家科学研究中心，雷蒙·卡斯特兰微 characterization 中心）
Black phosphorus (bP) has been recently investigated for next generation nanoelectronic multifunctional devices. However, the intrinsic instability of exfoliated bP (the bP nanoflakes) towards both moisture and air has so far overshadowed its practical implementation. In order to contribute to fill this gap, we report here the preparation of new hybrid polymer-based materials where bP nanoflakes exhibit a significantly improved stability. The new materials have been prepared by different synthetic paths including: i) the mixing of conventionally liquid-phase exfoliated bP (in DMSO) with PMMA s…
Quasi-two-dimensional (Quasi-2D) van der Waals (vdW) materials can be mechanically or chemically exfoliated down to monolayer because of their strong intralayer bonding and the weak interlayer vdW interaction. Thanks to this unique property, one can often find exotic thickness-dependent electronic properties from these quasi-2D vdW materials, which can lead to band gap opening, emerging superconductivity, or enhanced charge density waves with decreasing thickness. Surface-sensitive scanning tunneling microscopy (STM) can provide direct observation of structural and electronic characteristics o…
