Structures, electronic and thermodynamic properties of NiB2n (n=7-11) and their anions: A theoretical study

Based on the Crystal structure Analysis by Particle Swarm Optimization (CALYPSO) searching method and density functional theory (DFT), theoretical studies about structures, electronic and thermodynamic properties have been investigated systematically at the TPSSh/6-311+G(d) level for NiB2n0/- (n=7-11) clusters. Results found that the lowest energy structures possess a Ni atom-centered double ring tubular boron structures, NiB180/- except. Relative stabilities were analyzed via computing their vertical ionization potentials (VIP), vertical electronic affinity (VEA), adiabatic electronic affinity (AEA), HOMO-LUMO gaps and hardness. The infrared spectra, Raman spectra and photoelectron spectra were computationally simulated to facilitate their experimental characterizations. At last, aromatic properties (Nucleus independent chemical shift) and thermodynamic properties (enthalpy and entropy) with temperature were discussed in detailed for studied systems.

Characterization of Ti/SnO2 Interface by X-ray Photoelectron Spectroscopy

The Ti/SnO2 interface has been investigated in situ via the technique of x-ray photoelectron spectroscopy. Thin films (in the range from 0.3 to 1.1 nm) of titanium were deposited on SnO2 substrates via the e-beam technique. The deposition was carried out at two different substrate temperatures, namely room temperature and 200 °C. The photoelectron spectra of tin and titanium in the samples were found to exhibit significant differences upon comparison with the corresponding elemental and the oxide spectra. These changes result from chemical interaction between SnO2 and the titanium overlayer at the interface. The SnO2 was observed to be reduced to elemental tin while the titanium overlayer was observed to become oxidized. Complete reduction of SnO2 to elemental tin did not occur even for the lowest thickness of the titanium overlayer. The interfaces in both the types of the samples were observed to consist of elemental Sn, SnO2, elemental titanium, TiO2, and Ti-suboxide. The relative percentages of the constituents at the interface have been estimated by curve fitting the spectral data with the corresponding elemental and the oxide spectra. In the 200 °C samples, thermal diffusion of the titanium overlayer was observed. This resulted in the complete oxidation of the titanium overlayer to TiO2 upto a thickness of 0.9 nm of the overlayer. Elemental titanium resulting from the unreacted overlayer was observed to be more in the room temperature samples. The room temperature samples showed variation around 20% for the Ti-suboxide while an increasing trend was observed in the 200 °C samples.

Surface Charge Transfer Doping of MoS2 Monolayer by Molecules with Aggregation-Induced Emission Effect

Surface charge transfer doping has attracted much attention in modulating the optical and electrical behavior of 2D transition metal dichalcogenides (TMDCs), where finding controllable and efficient dopants is crucial. Here, 1,1,2,2-tetraphenylethylene (TPE) derivative molecules with aggregation-induced emission (AIE) effect were selected as adjustable dopants. By designing nitro and methoxyl functional groups and surface coating, controlled p/n-type doping can be achieved on a chemical vapor deposition (CVD) grown monolayer, MoS2. We investigated the electron transfer behavior between these two dopants and MoS2 with fluorescence, Raman, X-ray photoelectron spectra and transient absorption spectra. 1,1,2,2-Tetrakis(4-nitrophenyl)ethane (TPE-4NO2) with a negative charge aggregation can be a donor to transfer electrons to MoS2, while 1,1,2,2-Tetrakis(4-methoxyphenyl)ethane (TPE-4OCH3) is the opposite and electron-accepting. Density functional theory calculations further explain and confirm these experimental results. This work shows a new way to select suitable dopants for TMDCs, which is beneficial for a wide range of applications in optoelectronic devices.

OPTIMIZED QUASIPARTICLE DENSITY FUNCTIONAL AND GREEN’S FUNCTIONS METHOD TO COMPUTING BOND ENERGIES OF DIATOMIC MOLECULES

It is presented an advanced approach to computing the energy and spectral parameters of the diatomic molecules, which is based on the hybrid combined density functional theory (DFT) and the Green’s-functions (GF) approach. The Fermi-liquid quasiparticle version of the density functional theory is modified and used. The density of states, which describe the vibrational structure in photoelectron spectra, is defined with the use of combined DFT-GF approach and is well approximated by using only the first order coupling constants in the optimized one-quasiparticle approximation. Using the combined DFT-GF approach to computing the spectroscopic factors of diatomic molecules leads to significant simplification of the calculation procedure and increasing an accuracy of theoretical prediction. As illustration, the results of computing the bond energies in a number of known diatomic molecules are presented and compared with alternative theoretical results, obtained within discrete-variational , muffin-tin orbitals and other methods.

On the Etching Mechanism of Highly Hydrogenated SiN Films by CF4/D2 Plasma: Comparison with CF4/H2

With the increasing interest in dry etching of silicon nitride, utilization of hydrogen-contained fluorocarbon plasma has become one of the most important processes in manufacturing advanced semiconductor devices. The correlation between hydrogen-contained molecules from the plasmas and hydrogen atoms inside the SiN plays a crucial role in etching behavior. In this work, the influences of plasmas (CF4/D2 and CF4/H2) and substrate temperature (Ts, from −20 to 50 °C) on etch rates (ERs) of the PECVD SiN films were investigated. The etch rate performed by CF4/D2 plasma was higher than one obtained by CF4/H2 plasma at substrate temperature of 20 °C and higher. The optical emission spectra showed that the intensities of the fluorocarbon (FC), F, and Balmer emissions were stronger in the CF4/D2 plasma in comparison with CF4/H2. From X-ray photoelectron spectra, a thinner FC layer with a lower F/C ratio was found in the surface of the sample etched by the CF4/H2 plasma. The plasma density, gas phase concentration and FC thickness were not responsible for the higher etch rate in the CF4/D2 plasma. The abstraction of H inside the SiN films by deuterium and, in turn, hydrogen dissociation from Si or N molecules, supported by the results of in situ monitoring of surface structure using attenuated total reflectance-Fourier transform infrared spectroscopy, resulted in the enhanced ER in the CF4/D2 plasma case. The findings imply that the hydrogen dissociation plays an important role in the etching of PECVD-prepared SiN films when the hydrogen concentration of SiN is higher. For the films etched with the CF4/H2 at −20 °C, the increase in ER was attributed to a thinner FC layer and surface reactions. On the contrary, in the CF4/D2 case the dependence of ER on substrate temperature was the consequence of the factors which include the FC layer thickness (diffusion length) and the atomic mobility of the etchants (thermal activation reaction).

X-ray Photoelectron Spectroscopy of Surface Layers of Faceted Zinc Oxide Nanorods

The control of the nanomaterials surface’s hydrophilic properties is of interest for various applications, including optics, photocatalysis, and spintronics. In this work, techniques for designing the defective structure of the surface layers of faceted zinc oxide nanorods during sacrificial doping with iodine by hydrothermal synthesis were considered. The features of the chemical composition of the surface of the obtained layers were studied using X-ray photoelectron spectroscopy (XPS). It was found that peaks corresponding to the binding energy of iodine were not observed in the X-ray photoelectron spectra. An additional peak with a binding energy of 531.8 eV, corresponding to the oxygen of OH groups, was observed in the O 1s level spectrum for zinc oxide nanorods doped with iodine. During the heat treatment of the synthesized layers, iodine evaporates, which leads to a change in the surface composition and an increase in the oxygen content of the surface hydroxyl groups. A model has been proposed to explain the experimental results. It has been established that XPS techniques are effective for analyzing the defective surface structure of functional layers based on faceted zinc oxide nanorods.

Good Vibrations: Calculating Excited State Frequencies Using Ground State Self-Consistent Field Models

△SCF methods have proven to be reliable computational tools for the assignment and interpretation of photoelectron spectra of isolated molecules. These results have increased the interest in △SCF techniques for electronic excited states based on improved algorithms that prevent convergence to ground states. In this work, one of these △SCF improved algorithms is studied to demonstrate its ability to explore the molecular properties for excited states. Results from △SCF calculations for a set of representative molecules are compared with results obtained using time-dependent density functional theory and single substitution configuration interaction method. For the △SCF calculations, the efficacy of a spin-purification technique is explored to remedy some of the spin-contamination presented in some of the SCF solutions. The obtained results suggest that the proposed projection-based SCF scheme, in many cases, alleviates the spin--contamination present in the SCF single determinants, and provides a computational alternative for the efficient exploration of the vibrational properties of excited states molecules.

Data analysis procedures for time-resolved x-ray photoelectron spectroscopy at a SASE free-electron-laser

The random nature of self-amplified spontaneous emission (SASE) is a well-known challenge for x-ray core level spectroscopy at SASE free-electron lasers (FELs). Especially in time-resolved experiments that require a combination of good temporal and spectral resolution the jitter and drifts in the spectral characteristics, relative arrival time as well as power fluctuations can smear out spectral-temporal features. We present a combination of methods for the analysis of time-resolved photoelectron spectra based on power and time corrections as well as self-referencing of a strong photoelectron line. Based on sulfur 2p photoelectron spectra of 2-thiouracil taken at the SASE FEL FLASH2, we show that it is possible to correct for some of the photon energy drift and jitter even when reliable shot-to-shot photon energy data is not available. The quality of pump-probe difference spectra improves as random jumps in energy between delay points reduce significantly. The data analysis allows to identify coherent oscillations of 1 eV shift on the mean photoelectron line of 4 eV width with an error of less than 0.1 eV.