The real-space imaging of small molecules is always challenging under the electron microscopes, but highly demanded for investigating various nanoscale interactions, such as hydrogen bond and van der Waals (vdW) force. Especially, identifying the host-guest interactions in porous materials directly at the molecular level will bring a deeper insight into the behaviors of guest molecules during the sorption, catalysis, gas separation and energy storage. In this work, we directly resolved the ordered configurations of p-xylenes (PXs) adsorbed in ZSM-5 frameworks by the scanning transmission electron microscopy (STEM) with the integrated differential phase contrast (iDPC) technique to identify the host-guest vdW interactions. Based on these observations, we revealed that the PXs in one straight channel modified the channel geometry with a coherent orientation. And the adjacent straight channels were deformed up to 8.8% along the different directions corresponding to three dominant PX configurations, resulting a negligible overall expansion of ZSM-5 lattices. Then, we could also image the disorder and desorption of PXs in ZSM-5 channels during the in situ heating. This work not only helped us to study the host-guest vdW interactions and the sorption behaviors of PXs in ZSM-5, but also provided an efficient tool for further imaging and studying other single-molecule behaviors under STEMs.
Directly imaging the configurations of small molecules at the ambient temperatures will greatly promote the study of their chemical and physical properties, including the host-guest interactions of organics in porous materials during the adsorption, catalysis and energy storage. However, due to the current challenges on the small-molecule imaging by the (scanning) transmission electron microscopy ((S)TEM), we still have a lack of the molecular-level understandings on the host-guest interactions and other molecular behaviors. Here, we achieved the STEM imaging of various small aromatics confine…
4-n-octyl-4-cyanobiphenyl (8CB) has been recently shown to display an unusual sequence of phases when confined into porous silicon (PSi). The gradual increase of oriented short-range smectic (SRS) correlations in place of a phase transition has been interpreted as a consequence of the anisotropic quenched disorder induced by confinement in PSi. Combining two quasielastic neutron scattering experiments with complementary energy resolutions, we present the first investigation of the individual molecular dynamics of this system. A large reduction of the molecular dynamics is observed in the confi…
Big pores, small pores, ordered pores, random pores, they all have a function and as is often found, show behaviour in new materials that is not always predicted or obvious at the outset. I started my research journey trying to put extremely thin films onto near-perfect III-V crystals to control (opto)electronic properties and when the first TEM on our campus showed remarkable pore growth and structure in InP almost 21 years ago, the electrochemical modification of the InP made more sense. In this paper, I will summarise a few aspects of research into porous materials and semiconductors, from …
There has been considerable interest in chalcogenide alloys with high concentrations of native vacancies that lead to properties desirable for thermoelectric and phase-change materials. Recently, vacancy ordering has been identified as the mechanism for metal-insulator transitions observed in GeSb2Te4 and an unexpectedly low thermal conductivity in Ga2Te3. Here, we report the direct observation of vacancy ordering in Ga2SeTe2 utilizing aberration-corrected electron microscopy. Images reveal a cation-anion dumbbell inversion associated with the accommodation of vacancy ordering across the entir…
Quantitative strain measurements of the 1:1 B-site cation ordered domains, antiphase boundaries and dislocations in a highly ordered Pb(Sc1/2Ta1/2)O3 ceramic have been carried out by high-resolution transmission electron microscopy and geometric phase analysis. A phase shift of PI between two adjacent ordered domains across an antiphase boundary are determined unambiguously. The maximum in-plane strain and lattice rotation induced by a dislocation are 9.5% and 5.4deg, respectively. In a defect-free antiphase boundary, the maximum in-plane strain and lattice rotation are 1.8% and 0.9deg, respec…
X-ray photoelectron spectroscopy and diffraction (XPS, XPD) and scanning tunneling microscopy (STM) have been used for study of NbOx-structures on the Nb(110) surface. It is shown that niobium atoms are ordered to form a two-dimensional superstructure with equidistant spacing between the chains of niobium atoms. Chemical shifts of Nb3d- and O1s-levels demonstrate that the oxide layer corresponds to niobium monoxide NbO and the most part of oxygen in chemisorbed state is localized on the surface. A model of quasi-ordered structure of NbO on the Nb(110) surface is proposed.
Monolayers of colloidally synthesized cobalt-platinum nanoparticles of different diameters characterized by TEM (transmission electron microscopy) were deposited on structured silicon oxide substrates and characterized by SEM (scanning electron microscopy), GISAXS (grazing incidence x-ray scattering), and electric transport measurements. The highly ordered nanoparticle films show a thermally activated electron hopping between spatially adjacent particles at room temperature and Coulomb blockade at low temperatures. We present a novel approach to experimentally determine the particles charging …
Zeolites have been used in industrial applications such as catalysts, ion exchangers, and molecular sieves because of their unique porous atomic structures. However, the direct observation of zeolitic local atomic structures via electron microscopy is difficult owing to their low resistance to electron irradiation. Subsequently, the fundamental relationships between these structures and their properties remain unclear. A novel low-electron-dose imaging technique, optimum bright-field scanning transmission electron microscopy (OBF STEM) has recently been developed. It reconstructs images with a…
Isothermal Close Space Sublimation (ICSS) technique was used for embedding porous silicon (PS) films with ZnTe. It was studied the influence of the preparation conditions and in particular of a chemical etching step before the ZnTe growth, on the composition profile and final porosity of ZnTe embedded PS. The structure of the embedded material was determined by x-ray diffraction analysis while the thickness of the samples was determined by scanning electron microscopy (SEM). Rutherford backscattering (RBS) and Energy Dispersive (EDS) spectrometries allowed determining the composition profiles.…
The composition and site occupancy of Mg within ordered δ precipitates in a model Al Mg Li alloy have been characterized by atom probe microscopy and first-principles simulations. The concentration in the precipitates is found to be almost the same as that of the matrix, however, we show evidence that Mg partitions to the sites normally occupied by Li in the L12 structure. Density functional calculations demonstrate that this partition is energetically favorable, in agreement with experimental results.
We report on experimental evidence for the formation of a two dimensional Si/Au(110) surface alloy. In this study, we have used a combination of scanning tunneling microscopy, low energy electron diffraction, Auger electron spectroscopy and ab initio calculations based on density functional theory. A highly ordered and stable Si-Au surface alloy is observed subsequent to growth of a sub-monolayer of silicon on an Au(110) substrate kept above the eutectic temperature.
Ice-templating is a well-established processing route for porous ceramics. Because of the structure/properties relationships, it is essential to better understand and control the solidification microstructures. Ice-templating is based on the segregation and concentration of particles by growing ice crystals. What we understand so far of the process is based on either observations by optical or X-ray imaging techniques, or on the characterization of ice-templated materials. However, in situ observations at particle-scale are still missing. Here we show that confocal microscopy can provide multi…
Polarized small-angle neutron scattering (PSANS) experimental results obtained on arrays of ferromagnetic Co nanowires ($ϕ\approx13$ nm) embedded in self-organized alumina (Al$_{2}$O$_{3}$) porous matrices are reported. The triangular array of aligned nanowires is investigated as a function of the external magnetic field with a view to determine experimentally the real space magnetization $\vec{M}(\vec{r})$ distribution inside the material during the magnetic hysteresis cycle. The observation of field-dependentSANSintensities allows us to characterize the influence of magnetostatic fields. The…
Fe$_{3}$Si/Ge(Fe,Si)/Fe$_{3}$Si thin film stacks were grown by a combination of molecular beam epitaxy and solid phase epitaxy (Ge on Fe$_{3}$Si). The stacks were analyzed using electron microscopy, electron diffraction, and synchrotron X-ray diffraction. The Ge(Fe,Si) films crystallize in the well oriented, layered tetragonal structure FeGe$_{2}$ with space group P4mm. This kind of structure does not exist as a bulk material and is stabilized by solid phase epitaxy of Ge on Fe$_{3}$Si. We interpret this as an ordering phenomenon induced by minimization of the elastic energy of the epitaxial f…
We present theory and experiments for the force-distance curve $F(z_0)$ of an atomic force microscope (AFM) tip (radius $R$) indenting a supported fluid bilayer (thickness $2d$). For realistic conditions the force is dominated by the area compressibility modulus $κ_A$ of the bilayer, and, to an excellent approximation, given by $F= πκ_A R z_0^2/(2d-z_0)^2$. The experimental AFM force curves from coexisting liquid ordered and liquid disordered domains in 3-component lipid bilayers are well-described by our model, and provides $κ_A$ in agreement with literature values. The liquid ordered phase h…
The ordered arrays of Ag nanowires and nanodots have been grown in ultra-high vacuum on the Si(5 5 7) surface containing regular steps of three bilayer height. Formation of Ag nanostructures have been studied by scanning tunneling microscopy, low energy electron diffraction and Auger electron spectroscopy at room temperature. It was shown that a sample exposure in the vacuum before Ag growth affects the shape of the forming Ag islands. This effect is caused by oxygen adsorption on the silicon surface from the residual atmosphere in the vacuum chamber. When Ag is deposited on the clean silicon …
Using low energy electron diffraction (LEED), scanning tunnelling microscopy (STM) and x-ray absorption spectroscopy (XAS) techniques, we have studied the first steps of silicon adsorption onto Cu (001) single crystal substrate. For low coverage (~ 0.5 ML) and after annealing at 100°C, STM images and LEED patterns reveal the formation of an ordered quasi commensurate superstructure. From a quantitative analysis of XAS data, we extract the Si-Cu distance and detail the local atomic arrangement of the structure.
Effects of the Verwey transition on the (100) surface of magnetite were studied using scanning tunelling microscopy and spin polarized low-energy electron microsccopy. On cooling through the transition temperature Tv, the initially flat surface undergoes a roof-like distortion with a periodicity of ~0.5 um due to ferroelastic twinning within monoclinic domains of the low-temperature monoclinic structure. The monoclinic c axis orients in the surface plane, along the [001]c directions. At the atomic scale, the charge-ordered sqrt2xsqrt2R45 reconstruction of the (100) surface is unperturbed by th…
Ordered Ag nanowire arrays with high aspect ratio and high density self-supporting Ag nanowire patterns were successfully prepared using potentiostatic electrodeposition within the confined nanochannels of a commercial porous anodic aluminium oxide (AAO) template. X-ray diffraction and selected area electron diffraction analysis show that the as-synthesized samples have preferred (220) orientation. Transmission electron microscopy and scanning electron microscopy investigation reveal that large-area and ordered Ag nanowire arrays with smooth surface and uniform diameter were synthesized. Surfa…
Using cryogenic transmission electron microscopy, we revealed three dimensional (3D) structural details of the electrochemically plated lithium (Li) flakes and their solid electrolyte interphase (SEI), including the composite SEI skin-layer and SEI fossil pieces buried inside the Li matrix. As the SEI skin-layer is largely comprised of nanocrystalline LiF and Li2O in amorphous polymeric matrix, when complete Li stripping occurs, the compromised SEI three-dimensional framework buckles, forming nanoscale bends and wrinkles. We showed that the flexibility and resilience of the SEI skin-layer play…
Ideal models of complex materials must satisfy all available information about the system. Generally, this information consists of experimental data, information implicit to sophisticated interatomic interactions and potentially other {\it a priori} information. By jointly imposing first-principles or tight-binding information in conjunction with experimental data, we have developed a method: Experimentally Constrained Molecular Relaxation (ECMR) that uses {\it all} of the information available. We apply the method to model medium range order in amorphous silicon using Fluctuation Electron mic…
Insight in the structure of nanoparticle assemblies up to a single particle level is key to understand the collective properties of these assemblies, which critically depend on the individual particle positions and orientations. However, the characterization of large, micron sized assemblies containing small, 10-500 nanometer, sized colloids is highly challenging and cannot easily be done with the conventional light, electron or X-ray microscopy techniques. Here, we demonstrate that focused ion beam-scanning electron microscopy (FIB-SEM) tomography in combination with image processing enables …
Metal-organic frameworks (MOFs) can provide exceptional porosity for molecular guest encapsulation useful for emergent applications in sensing, gas storage, drug delivery and optoelectronics. Central to the realisation of such applications however is the successful incorporation of a functional guest confined within the host framework. Here we demonstrate, for the first time, the feasibility of scattering-type scanning near-field optical microscopy (s-SNOM) and nano-Fourier transform infrared (nanoFTIR) spectroscopy, in concert with density functional theory (DFT) calculations to reveal the vi…
