The second hyperpolarizability of CdTe nanocrystals using polarization-resolved degenerate four-wave mixing

Polarization-resolved forward degenerate four-wave mixing (DFWM) in a nonresonant region revealed the effective third-order nonlinear susceptibility of colloidal CdTe nanocrystals (NCs) with the size near the Bohr radius and various concentrations. The second hyperpolarizabilities, and , of the CdTe NCs were ∼1.15 × 10⁻⁴¹ m⁵/V² and ∼3.01 × 10⁻⁴² m⁵/V² from the measurement of the concentration-dependent third-order nonlinear susceptibility of CdTe NCs, respectively. The ratio (/) of the hyperpolarizabilities was ∼0.26, which indicated a large contribution of an electronic polarization process to the third-order nonlinearity of CdTe NCs.     

Reaction of cyanide ions with copper on Si surfaces and its use for Si cleaning

A Si cleaning method has been developed by use of potassium cyanide (KCN) dissolved in methanol. When silicon dioxide (SiO₂)/Si(1 0 0) specimens with 10¹⁴ atom/cm² order copper (Cu) contaminants are immersed in 0.1 M KCN solutions of methanol at 25 °C, the Cu concentration is reduced to below the detection limit of total X-ray fluorescence spectrometer of ∼3 × 10⁹ atoms/cm². X-ray photoelectron spectra show that the thickness of the SiO₂ layers is unchanged after cleaning with the KCN solutions. 10¹⁴ cm⁻² order Cu contaminants on the Si surface can also be removed below ∼3 × 10⁹ atoms/cm², without causing contamination by potassium ions. UV spectra show that Cu-cyano complex ions are formed in the KCN solutions after the cleaning. The main Cu species in the KCN solutions is ions with the concentration of []:[Cu⁺] = 1:1.6 × 10²³. Even when the KCN solutions are contaminated with 64 ppm Cu²⁺ ions in the solutions, which form ions, the cleaning ability does not decrease, showing that ions are not re-adsorbed. The KCN solutions can also passivate defect states such as Si/SiO₂ interface states, leading to the improvement of characteristics of Si devices.     

Secondary ion emission from polymer layers by atomic and molecular ion bombardment: Data evaluation based on linear-cascade sputtering theory

This paper constitutes an attempt to rationalise impact-energy dependent yields of molecular secondary ions emitted from polymer samples under bombardment with atomic and molecular primary ions. The evaluation was based upon a comparison with sputtering yields calculated from linear-cascade sputtering theory, including threshold effects. To explore general trends, sputtering yields for carbon, silicon and silver were calculated under impact of normally incident C, F, S, Ga, Xe, Au, SF₅, C_11, C₆₀ and Au₅. The yields of carbon, for example, bombarded with C₆₀ are larger than for Ga by factors of ∼5 and ∼10 at 10 and 100 keV, respectively. However, owing to the fact that the effective threshold energy for sputtering increases with the number of constituents of the projectile, the yields for molecular ion impact start to exceed the yields for atomic ions only at energies between 0.5 and 5 keV. The analysed experimental results relate to molecular ion emission from one monolayer (1 ML) and 9 ML films of polymethacrylate on silver bombarded with Xe and SF₅ ions at energies E between 0.5 and 10 keV. Comparison of (initial) secondary ion yields S⁺ (m/z 143) with calculated sputtering yields suggests that S⁺ constitutes the sum of two contributions. The first, labelled , prevails at low energies and appears to reflect molecule ejection due to the mean effect of nuclear energy deposition (“ordinary” linear-cascade sputtering). The second contribution, , dominates at E > 1.5 keV, increases with a high power of E, but does not correlate with the calculated sputtering yield. It is suggested that is a measure of those impact events which occasionally generate a very high energy density at the surface, thus providing optimum conditions for very efficient ejection of molecules that are located at the rim of the agitated area. The SF₅/Xe secondary ion yield ratios are distinctly different for the two contributions, only about 0.3 for but ∼4 (1 ML) and ∼20 (9 ML) for . The pronounced secondary ion “yield enhancement” frequently reported in the literature for molecular versus atomic ion bombardment appears to be due to an enlargement of the contribution, more so the higher the impact energy and the more massive the projectile. The total (integrated) secondary ion yields, estimated by making use of the reported damage cross sections, were found to be the same for SF₅ bombardment of the 1-ML and the 9-ML samples. This finding calls for more attention towards obtaining high secondary ion yields at minimum sample consumption.     

The formation of V–Al–N thin films by reactive ion beam mixing of V/Al interfaces

The reactive ion beam mixing (IBM) of V/Al interfaces by low-energy N₂⁺ ions at room temperature leads to the formation of V–Al–N ternary nitride thin films. The kinetics, growth mechanisms, composition and electronic structure of those films have been studied using X-ray photoelectron spectroscopy, ultraviolet photoelectron spectroscopy, Factor Analysis and Monte Carlo TRIDYN simulations. The comparison of experimental results with those obtained from TRIDYN simulations suggests that the chemical reaction with the nitrogen partial pressure and processes driven by residual defects are the rate-controlling mechanisms during the reactive IBM of V/Al interfaces. The kinetics of mixing is characterized by two stages. During the first stage (≤4×10¹⁶ ions/cm²), the formation of vanadium nitride is observed. In the second stage, vanadium nitride is transformed into a V–Al–N ternary nitride due to Al incorporation in the near surface region. Moreover, the V/Al ratio can be varied in a broad range, whereas the nitrogen concentration slightly decreases with increasing the aluminium content of the film.     

Critical power for self-focussing of a femtosecond laser pulse in helium

The critical power for self-focussing of a femtosecond laser pulse in helium has been measured using the moving focus method. The experimental value is (1 atm) ∼268 GW. Using this value, the nonlinear refractive index is inferred to be  ∼ 3.6 × 10^-21 cm²/W. In addition, the plots of the electron densities versus energy and pressure have also been used to determine the critical power of helium, based on the intensity clamping of the filamentation process. The value agrees well with the one by the moving focus method.     

Dynamics of NF3 in a condensed film on Au(1 1 1) as studied by electron-stimulated desorption

We report a low-temperature dynamics study of condensed layers of NF₃ on Au(1 1 1) by time-of-flight electron-stimulated desorption ion angular distribution (TOF-ESDIAD), temperature-programmed desorption (TPD) and low-temperature scanning tunneling microscopy (LT-STM). Upon adsorption at 30 K, molecular NF₃ adsorption occurs first at the step edges and at minor terrace defect sites with the formation of 2D islands. Within the islands, NF₃ is adsorbed in an upright conformation via the nitrogen lone pair electrons projecting fluorine atoms away from the surface as judged by the presence of only a sharp F⁺ central beam in the ESDIAD pattern. At higher coverages, 3D islands start to populate the surface. Electron bombardment of a thick NF₃ (∼6 ML) layer adsorbed on the Au(1 1 1) surface leads to emission of F⁺, N⁺, NF⁺, and ions as observed in the TOF-ESD distribution. Upon heating to ∼37 K, a sudden decrease of the and ion yield, which is not related to thermal desorption, is observed which reflects the surface migration of NF₃ molecules, leading to local thinning of the film. The thinning process occurs at the temperature of onset of molecular rotations and self-diffusion in the bulk NF₃ crystal. In this process, some NF₃ molecules move closer to the surface which results in higher efficiency for ion neutralization by the underlying metal surface. In the TPD spectra, the monolayer desorption is observed to begin at ∼65 K, exhibiting zero-order kinetics with an activation energy of 21 kJ/mol.     

Surface treatments toward obtaining clean GaN(0 0 0 1) from commercial hydride vapor phase epitaxy and metal-organic chemical vapor deposition substrates in ultrahigh vacuum

We studied processes of cleaning GaN(0 0 0 1) surfaces on four different types of wafers: two types were hydride vapor phase epitaxy (HVPE) free-standing substrates and two types were metal-organic chemical vapor deposition (MOCVD) films grown on these HVPE substrates and prepared by annealing and/or Ar ion sputtering in ultra high vacuum. We observed the surfaces through treatments using in situ low-energy electron diffraction (LEED), reflection high-energy electron diffraction (RHEED), scanning tunneling microscopy (STM), and Auger electron spectroscopy, and also using ex situ temperature programmed desorption, X-ray photoelectron spectroscopy, X-ray diffraction, and secondary ion mass spectrometry. For HVPE samples, we obtained relatively clean surfaces under optimized three-step annealing conditions (200 °C for 12 h + 400 °C for 1 h + 500 °C for 5 min) without sputtering, after which the surface contamination of oxide and carbide was reduced to ∼20% of that before annealing. Clear GaN(0 0 0 1)1×1 patterns were obtained by LEED and RHEED. STM images showed flat terraces of ∼10 nm size and steps of ∼0.5 nm height. Upon annealing the HVPE-GaN samples at a much higher temperature (C), three-dimensional (3D) islands with facets were formed and the surface stoichiometry was broken down with the desorption of nitrogen in the form of ammonia, since the samples include hydrogen as an impurity. Ar⁺ sputtering was effective for removing surface contamination, however, postannealing could not recover the surface roughness but promoted the formation of 3D islands on the surface. For MOCVD/HVPE homoepitaxial samples, the surfaces are terminated by hydrogen and the as-introduced samples showed a clear 1×1 structure. Upon annealing at 500-600 °C, the surface hydrogen was removed and a 3×3 reconstruction structure partially appeared, although a 1×1 structure was dominant. We summarize the structure differences among the samples under the same treatment and clarify the effect of crystal quality, such as dislocations, the concentration of hydrogen impurities, and the residual reactant molecules in GaN films, on the surface structure.     

X-ray initiated molecular photochemistry of Cl-containing adsorbates on a Si(1 0 0) surface using synchrotron radiation

X-ray initiated molecular photochemistry for SiCl₄ and CCl₄ adsorbed on Si(1 0 0) at ∼90 K following Cl 2p core-level excitation is investigated by photon stimulated ion desorption and ion kinetic energy distribution measurements. The Cl excitation of solid SiCl₄ induces the significant enhancement (∼900%) of the Cl⁺ yield, while the Cl excitation of condensed CCl₄ leads to a moderate enhancement (∼500%) of the Cl⁺ yield. The enhancement of Cl⁺ yield at the specific core-excited states is strongly correlated to the ion escaped energy. Upon X-ray exposure for CCl₄ adsorbed on Si(1 0 0) (20-L exposure), the Cl⁺ yields at resonances decrease and new structures at higher photon energies are observed. Cl⁺ yields at these new resonances are significantly enhanced compared to those at other resonances. These changes are the results of desorption and surface reaction of the CCl₄-Si surface complex due to X-ray irradiation. We have demonstrated that state-specific enhancement of ion desorption can be successfully applied to characterize the reaction dynamics of adsorbates adsorbed on surfaces by X-ray irradiation.     

Experimental and theoretical studies on X-ray induced secondary electron yields in Ti and TiO2

Generation of X-ray induced secondary electrons in Ti and TiO₂ was studied from both experimental and theoretical approaches, using X-ray photoelectron spectroscopy (XPS) attached to a synchrotron radiation facility and Monte Carlo simulation, respectively.The experiment revealed that the yields of secondary electrons induced by X-rays (electrons/photon) at photon energies to 4950 and 5000 eV for Ti and TiO₂ are δ_Ti(4950 eV) = 0.002 and δ_Ti(5000 eV) = 0.014 while those for TiO₂ are δTiO₂(4950 eV)=0.003 and δTiO₂(5000 eV)=0.018.A novel approach to obtain the escape depth of secondary electrons has been proposed and applied to Ti and TiO₂. The approach agreed very well with the experimental data reported so far. The Monte Carlo simulation predicted; and while and .An experimental examination on the contribution of X-ray induced secondary electrons to photocatalysis in TiO₂ has also been proposed.     

Optical transitions of Dy in tellurite glass: observation of upconversion

Dy³⁺ doped tellurite glasses were prepared and its optical absorption, fluorescence and upconversion have been studied. The absorption data has been used to calculate the Judd-Ofelt parameters, oscillator strengths along with transition probability, branching ratio, etc. The lifetime of the level is found to be 0.66 ms for 1.0 mol% of Dy³⁺ doped in tellurite glass. NIR to visible upconversion has been observed at room temperature. The increase in upconversion luminescence at lower temperature indicates that upconversion is not due to a thermally activated process. The quantum efficiency of the transition is found to be ∼0.17 and the upconversion efficiency is ∼0.022. The strong dependence of the upconversion efficiency on the Dy³⁺ concentration reveals that the upconversion is due to energy transfer interaction.     

The formaldehyde cation: Rovibrational energy level structure and Coriolis interaction near the adiabatic ionization threshold

Rotationally resolved pulsed-field-ionization zero-kinetic-energy photoelectron spectra of the 0⁰, 6¹ and 4¹ vibrational levels of the ground electronic state of the formaldehyde cation were recorded using a resonant three-color three-photon excitation scheme. The first adiabatic ionization energy of CH₂O (87793.33(1.30) cm⁻¹) and the rigid-rotor rotational constants (A⁺ = 8.874(8) cm⁻¹, B⁺ = 1.342(15) cm⁻¹, C⁺ = 1.148(18) cm⁻¹) of the vibronic ground state of CH₂O⁺ were derived. A strong a-type Coriolis interaction between the 6¹ and 4¹ vibrational levels was observed. The Coriolis coupling parameter and the deperturbed fundamental vibrational frequencies of the in-plane-rocking mode ν₆ and the out-of-plane bending mode ν₄ were determined to be 8.70(10) cm⁻¹, 823.67(30) cm⁻¹ and 1036.50(30) cm⁻¹, respectively. The intensity distribution of the photoelectron spectra was analyzed in the realm of a simple photoionization model.     

Influence of the vacuum level upon the growth of carbon nanotubes on silicon carbide surface

We have investigated the influence of the vacuum level upon the growth of carbon nanotubes (CNTs) on 6H-SiC () surface.CNTs of about 160 nm in length were formed densely and uniformly on the 6H-SiC surface during annealing at 1700 °C in a high vacuum (∼10⁻² Pa). CNTs of about 1 μm in length were formed during annealing at 1700 °C in an ultra-high vacuum (∼10⁻⁷ Pa). However, CNTs were not formed and SiO₂ layers were formed on the SiC surface at 1700 °C in air. It is found that longer CNTs can grow up in an ultra-high vacuum, moreover, a little aligned and low-density graphite layers, or carbon nanofibers can also grow up.     

Quantitative determination of the local structure of thymine on Cu(1 1 0) using scanned-energy mode photoelectron diffraction

The local adsorption structures of the surface species formed by interaction of thymine with a Cu(1 1 0) surface at room temperature, and after heating to ∼530 K, have been investigated. Initial characterisation by soft-X-ray photoelectron spectroscopy and O K-edge near-edge X-ray absorption fine structure (NEXAFS) indicates the effect of sequential dehydrogenation of the NH species and provides information on the molecular orientation. O 1s and N 1s scanned-energy mode photoelectron diffraction shows the species at both temperatures bond to the surface through both carbonyl O atoms and the deprotonated N atom between them, each bonding atom adopting near-atop sites on the outermost Cu surface layer. The associated bondlengths are 1.96 ± 0.03 Å for Cu-N and 1.91 ± 0.03 Å and 2.03 ± 0.03 Å for the two inequivalent Cu--O bonds. The molecular plane lies almost exactly in the close-packed azimuth, but with a tilt relative to the surface normal of approximately 20°. Heating to ∼530 K, or deposition at this temperature, appears to lead to dehydrogenation of the second N atom in the ring, but no significant change in the adsorption geometry.     

Repulsive and bound parts of the interatomic potentials of the lowest singlet electronic energy states of the MeRg complexes (Me = Zn, Cd; Rg = He, Ne, Ar, Kr, Xe)

Laser-induced fluorescence excitation spectra of MeRg (Me = Zn, Cd; Rg = He, Ne, Ar, Kr, Xe) complexes were recorded using the D¹ ← X¹ free ← bound transition. The complexes were produced in their ground state in a free-jet expansion beam and excited with a dye-laser beam directly to the excited state. Analysis of free ← bound unstructured profiles provided a shape of the repulsive part of the D¹-state potentials. Valence ab initio calculations of the ZnRg and CdRg ground- and excited-state potentials and electronic transition dipole moments for the studied transition were performed, taking scalar relativistic and spin-orbit effects into account. Results of the calculations show regularities and correlations in the repulsive branches and bound wells of the X¹- and D¹-state potentials as well as provide information on the bonding character in both electronic energy states. The trends were compared with available experimental results for ZnRg and CdRg as well as for MgRg and HgRg.     

Reactivity to sulphur of clean and pre-oxidised Cu(1 1 1) surfaces

The reactivity of clean and pre-oxidised Cu(1 1 1) surfaces exposed to sulphur (H₂S) has been studied at room temperature by Auger electron spectroscopy, low energy electron diffraction and scanning tunneling microscopy. On the clean surface, the sulphur-saturated surface structure is dominated by the or so-called “zigzag” superstructure. It is shown that a single orientation domain is favoured by the slight misorientation (∼2°) of the surface with respect to the (1 1 1) plane. Scanning tunneling microscopy measurements also revealed two minority structures. Pre-oxidation was performed by exposure to 1.5 × 10⁴ L of O₂ at 300 °C. Under exposure to H₂S (1 × 10⁻⁷ mbar) at room temperature, the oxygen is totally substituted by sulphur. Once initiated, sulphur adsorption seems to propagate to cover the whole surface on the O-covered surface faster than on the clean Cu(1 1 1). At saturation by adsorbed sulphur, the surface is completely covered by the superstructure of highest coverage. This enhanced uptake of sulphur is assigned to the surface reconstruction of the copper surface induced by the pre-oxidation, causing a stronger reactivity of the Cu atoms released by the decomposition of the oxide.     

Epitaxial growth of titanium oxide thin films on c-cut and α-cut sapphire substrates

C-cut and α-cut sapphire substrates are used to grow epitaxial titanium oxide films by pulsed-laser deposition at 700 °C under a controlled oxygen pressure in the 10⁻¹-10⁻⁵ mbar range. The rutile phase is evidenced in films whatever the substrate and the oxygen pressure while the anatase phase is only observed on c-cut sapphire substrate and for oxygen pressure down to 10⁻³ mbar. No other titanium oxide phases (i.e. TiO, Ti₂O₃ or Magneli phases) are identified despite the oxygen-deficiency observed in films grown at low oxygen pressure. According to asymmetric X-ray diffraction measurements performed on films, the main axis growth and the in-plane epitaxial relationships between titanium oxide films and sapphire substrates are found to be depending on the orientation of the sapphire basal plane and on the oxygen pressure. The anatase crystallites are highly oriented with the following epitaxial relationship . The rutile phase is (2 0 0) oriented on c-cut sapphire substrate and displays two distinct in-plane relationships: . The use of α-cut sapphire substrate leads to the growth of rutile crystallites (2 0 0) or (1 0 1) oriented. In these cases, the in-plane orientations are , respectively. For the two substrates used, schematic views of atomic arrangement of the different interfaces are proposed.