Surface crystallography of thin films by electron diffraction in the stem

It is shown that by using STEM microdiffraction it is possible to obtain surface reflections from thin metallic films. The technique is demonstrated for a gold film. Reflections from the surface reproduce the (23 × 1) supernet for the (111) surface previously reported in the literature. It is also shown that the film surface consists of reconstructed (5 × 1) domains which when interlocking, produce the (23 × 1) pattern.     

Surface magnetic structure analysis of Ni(001) by polarized electron diffraction

For spin-polarized low-energy electrons diffracted from ferromagnetic Ni(001), the exchange-and the spin-orbit-induced scattering asymmetries A_ex and A_so of two diffracted beams have been simultaneously measured at T = 300 K and at T = 520 K for several constant energies as functions of the polar angle of incidence. Corresponding “rocking curves” calculated by dynamical theory are in generally good agreement with the data. Analysis of A_so shows firstly that an energy-dependent exchange approximation is adequate, secondly that the topmost interlayer spacing is essentially bulk-like with a possible slight outward relaxation (1%), and thirdly that 3p → 3d excitation is significant. From A_ex the following magnetic information is obtained: The surface magnetization for T = 300 K and 520 K is such as to imply, via extrapolation by mean field theory, a T = 0 value slightly enhanced (by + 5% ± 5%) with respect to the bulk magnetization. The spin asymmetries of localized and uniform inelastic processes are very small, leading, for incident electron energy 69 and 89 eV, to a combined inverse mean free path asymmetry of less than 0.3%.     

Surface segregation of InGaAs films by the evolution of reflection high-energy electron diffraction patterns

Surface segregation is studied via the evolution of reflection high-energy electron diffraction (RHEED) patterns under different values of As 4 BEP for InGaAs films. When the As 4 BEP is set to be zero, the RHEED pattern keeps a 4×3/(n×3) structure with increasing temperature, and surface segregation takes place until 470 C. The RHEED pattern develops into a metal-rich (4×2) structure as temperature increases to 495 C. The reason for this is that surface segregation makes the In inside the InGaAs film climb to its surface. With the temperature increasing up to 515 C, the RHEED pattern turns into a GaAs(2×4) structure due to In desorption. While the As 4 BEP comes up to a specific value (1.33×10 4 Pa–1.33×10 3 Pa), the surface temperature can delay the segregation and desorption. We find that As 4 BEP has a big influence on surface desorption, while surface segregation is more strongly dependent on temperature than surface desorption.     

Impedance and electron diffraction studies on single crystals of BINIVOX

Single crystals of the nominal composition Bi₂V_0.9Ni_0.1O_5.35 were prepared. They were studied by TGA/DTA, impedance spectroscopy and electron diffraction. The impedance of the crystals with Pt electrodes was measured in two directions: parallel and perpendicular to the layers of the intergrowth structure in the frequency range 10⁻²−10⁷ Hz at temperatures between 300 and 940 K. Arrhenius type plots for both directions show two linear regions with different activation energies. In the low temperature region the conductivity in the direction parallel to the layers was by a factor of about 1000 larger than in the perpendicular direction. In the high temperature region the ratio of conductivities was about 100. A time dependence of the conductivity in the perpendicular direction was observed during heating and cooling in limited temperature ranges. The electron diffraction experiments gave evidence that the superlattice spots present in the diffraction patterns at low temperature, disappear reversibly at temperatures higher than 650 K. The transition temperatures observed in the DTA and in the electron diffraction experiments correspond to the temperature of changes of the activation energy. An order-disorder transition of oxygen ions is considered to be responsible for this phenomenon. Paper presented at the 5th Euroconference on Solid State Ionics, Benalmádena, Spain, Sept. 13–20, 1998.     

Ultrafast electron diffraction

Ultrafast electron diffraction(UED) technique has proven to be an innovative tool for providing new insights in lattice dynamics with unprecedented temporal and spatial sensitivities. In this article, we give a brief introduction of this technique using the proposed UED station in the Synergetic Extreme Condition User Facility(SECUF) as a prototype. We briefly discussed UED's functionality, working principle, design consideration, and main components. We also briefly reviewed several pioneer works with UED to study structure-function correlations in several research areas. With these efforts,we endeavor to raise the awareness of this tool among those researchers, who may not yet have realized the emerging opportunities offered by this technique.     

Surface structure effects via photoexcited core electron diffraction for Na on Ni

Photoemission from the Na 2p core level has been measured in the range ?ω = 40–120 eV for a c(2×2) Na overlayer on a Ni(001). surface. Weak oscillations in the Na 2p emission intensity vs. wavelength were observed and are interpreted as due to photoelectron scattering. The observed peaks closely match, in energy, those derived in recent calculations which assume the Na occupies a hollow site 2.23Å above the Ni surface layer. The data therefore indicate that observation and calculation of such effects may allow surface structure determinations.     

An accurate dynamical electron diffraction algorithm for reflection high-energy electron diffraction

The conventional multislice method (CMS) method, one of the most popular dynamical electron diffraction calculation procedures in transmission electron microscopy, was introduced to calculate reflection high-energy electron diffraction (RHEED) as it is well adapted to deal with the deviations from the periodicity in the direction parallel to the surface. However, in the present work, we show that the CMS method is no longer sufficiently accurate for simulating RHEED with the accelerating voltage 3–100 kV because of the high-energy approximation. An accurate multislice (AMS) method can be an alternative for more accurate RHEED calculations with reasonable computing time. A detailed comparison of the numerical calculation of the AMS method and the CMS method is carried out with respect to different accelerating voltages, surface structure models, Debye–Waller factors and glancing angles.     

Order in amorphous polystyrenes as revealed by electron diffraction and diffraction microscopy

Ordered regions ranging in size between 15 and 45 Å have been established in several atactic polystyrenes of various molecular weights (4800; 51,000; and 1,800,000) as well as in an amorphous isotactic polystyrene by means of electron diffraction and high-resolution diffraction microscopy. The order is due to long-chain polymer molecules which tend to align more-or-less parallel to one another with a constant average spacing. The orderly chain packing can be disturbed upon cross-linking by electron irradiation, the disturbance being manifested in the irreversible changes in the d spacing and broadening of one of the diffuse rings which is inter-molecular in origin. From the results obtained, the high-resolution diffraction microscopy technique appears to have the potential for resolving the question regarding the presence of order in unoriented amorphous polymers. The technique can also differentiate between a broadened diffuse ring due to small crystallites and another due to paracrystals containing numerous defects.     

Measurement of surface defects by low-energy electron diffraction

Low-energy electron diffraction is capable of detection of non-periodic arrangements by spot profile analysis (SPA-LEED). All kinds of defects may be identified by a qualitative and nevertheless systematic evaluation of the diffraction pattern with respect to spot shape, background and energy dependance. It is shown that the kinematical approximation provides far reaching results. The importance and achievements of the newly developed high-resolution instrumentation is demonstrated. The quantitative evaluation provides data on defect density and distribution, which are not available otherwise, as demonstrated with examples. A comparison of imaging and diffraction techniques shows the special advandages of diffraction with respect to quantitative analysis.     

Low energy electron diffraction studies of high index crystal surfaces of platinum

Several high Miller Index crystal surfaces of platinum have been examined by low energy electron diffraction (LEED) and have been shown to consist of low index (111) or (100) terraces of constant width, linked by steps of monatomic height. The ordered stepped surfaces were found to be stable in ultra-high vacuum up to 1500 K, and the reasons for this remarkable stability are discussed. The presence of ordered atomic steps may be considered as a general structural property of high index surfaces regardless of the chemical bonding in the crystal. A nomenclature is suggested to identify the surface structures of stepped surfaces.     

Microstructural studies of composite Mughal period cannons of Daulatabad Fort,India, by electron backscattered diffraction and scanning electron microscopy

Historical data on ancient Indian cannons have systematically been researched, but there is lack of archaeometallurgical studies on bimetallic cannons. This study revolves around 16th–17th century bimetallic Indian cannons: copper barrel with inner iron sleeve at an approximate ratio of 5:1. Scanning electron microscopy and electron backscattered diffraction techniques have been employed to know the changes in the microstructures of the metals used in making cannons. Energy dispersive spectrometry confirmed that the outer copper barrel, with 4.5 wt% tin, had inclusions of cupric oxide (Cu₂O) and contained lead and sulfur. The inner sleeve, on the other hand, was primarily iron but contained fayalite (FeSiO₄) and inclusions with silicon and phosphorous. Both inner (bloomery iron) and outer (copper) material had strong signatures of plastic deformation, and the cannons were stipulated to be forge welded. Deformation twinning in recrystallized iron grains of inner iron sleeve and near-perfect extensive twinning in the inner copper barrel indicate exposures of the respective materials to such active usage. It is concluded from the deformed structures and from the presence of clear joints that the bimetallic cannons were made by a process of forge welding. This study brings actual manufacturing practices of bimetallic cannons in ancient India.     

Low energy electron diffraction studies of chemisorbed gases on stepped surfaces of platinum

The chemisorption of hydrogen, oxygen, carbon, carbon monoxide and ethylene was studied by low-energy electron diffraction on ordered stepped surfaces of platinum which were cut at angles less than 10° from the (111) face. The chemisorption characteristics of stepped platinum surfaces are markedly different from those of low index platinum surfaces and they are also different from each other. Hydrogen and oxygen which do not chemisorb easily on the (111) and (100) crystal faces chemisorb readily and at relatively low temperatures and pressures on the stepped platinum surfaces used in this study. In contrast to the ordered adsorption of carbon monoxide and ethylene on low index faces, the adsorption was disordered on the stepped surfaces and there is evidence for dissociation of the molecule. Carbon formed several ordered surface structures and caused faceting on the stepped surface, which are not observed on low index platinum surfaces. There appears to be a much stronger interaction of chemisorbed gases with stepped surfaces than with low index planes that must be caused by the differing atomic structures at the steps. Evidence for the differing reactivities of the two stepped surfaces are also discussed.     

Spin polarization in low-energy electron diffraction: Surface analysis of Pt(111)

Transverse and longitudinal spin polarization components arising in the diffraction of unpolarized low-energy electrons from Pt(111) have been studied as functions of energy and diffraction geometry. Experimental data measured by means of a Mott detector are in good agreement with theoretical results obtained by relativistic LEED calculations. A detailed investigation of the selective sensitivity of the calculated polarization profiles to the surface relaxation δ₁₂ and to various non-structural model features firstly supports an ion-core potential involving an energy-dependent exchange approximation (by discriminating against two band structure potentials), and secondly establishes the geometry of Pt(111) as unreconstructed with a possible slight outward relaxation of the topmost atomic layer (δ₁₂ = 0.5% ± 1.0% of the bulk interlayer distance). A surface Debye temperature is found close to the bulk value 230 K.     

Surface energy modification by electron beam

We observe a pronounced variation of wettability properties in solid state materials induced by a low-energy electron beam. The phenomenon occurs in several stages characterized by various mechanisms. We show that for low electron doses the irradiation leads to decrease in the wetting of a dielectric surface due to induced surface electric potential. The higher electron charge leads to formation of a chemical monolayer on material’s surface. It has been found that the electron irradiation strongly modifies the surface free energy of SiO₂ by decreasing its total surface free energy value, almost twice. However, electron-induced variations of dispersive and polar components of the surface free energy are quite different and depend of incident electron charge.     

Low energy electron diffraction and auger electron spectroscopy studies of the structure of adsorbed gases on solid surfaces

Low energy electron diffraction (LEED) studies of the structure of adsorbed molecules on crystal surfaces revealed that ordered surface structures predominate under most conditions of the experiments. In the absence of chemical reactions with the substrate, the degree of ordering depends on the heats of adsorption, ΔH_ads, and the activation energies for surface diffusion, ΔE_D1. Since ΔH_ads is usually markedly larger than ΔE_D1, small changes of substrate temperature facilitate ordering without appreciable increase in desorption rates. The surface structures of adsorbed gases that have been reported so far have been tabulated. For molecules whose size is compatible with the interatomic distance of the substrate, rules of ordering can be proposed that permit prediction of the structure of the adsorbed layer that is likely to form. These rules indicate close packing due to attractive interactions in the adsorbed layer, and that the rotational multiplicity of the substrate is likely to be maintained by the adsorbate structure. When molecules whose dimensions are larger than the substrate interatomic distance are adsorbed, the conditions that control ordering are more complex and simple rules may not be readily applicable.The surface structures of adsorbed gases have also been studied on high Miller Index substrate surfaces. These surfaces are characterized by ordered steps separated by terraces of low index surface orientation. Many gases have different ordering characteristics on stepped surfaces than on low index crystal faces due to the stronger substrate-adsorbate interactions in these surfaces. The dissociation of diatomic molecules at steps induces the formation of new types of surface structures (frequently one-dimensional) and the dehydrogenation of hydrocarbons at steps induces the formation of ordered carbonaceous surface structures that would not nucleate on low index substrate planes.So far, mostly work function changes upon adsorption gave indication of the magnitude of charge transfer upon adsorption and on forming of new surface chemical bonds. Most recently, chemical shifts of the Auger transitions of the substrate atoms and of the adsorbed molecules upon chemisorption, have been found to provide additional information on charge redistribution during adsorption.     

Structural studies of liquid alcohols by neutron diffraction

Neutron diffraction measurements have been made on methyl alcohol at room temperature for an incident wavelength of 0·94 Å. Cross sections have been obtained for CD₃OD, CD₃OH, and mixtures of these compounds. These data are subtracted to obtain the separated structure factors for intermolecular H₀H₀, the hydroxyl components, and the non-hydroxyl components. The Fourier transformations of the structure factors show components of both intra- and intermolecular distribution functions. Width parameters obtained from model fits are too large for thermal vibrations and are interpreted as geometrical broadening due to the stretching of bonds, variations in bond angles, and rotation of the methyl group. Differences in the real space distribution function between hydrogen and deuterium are noted.