Vibrational study of silicon oxidation: H2O on Si(100)

The vibrational spectrum of water dissociatively adsorbed on Si(100) surfaces is obtained with surface infrared absorption spectroscopy. Low frequency spectra (< 1450 cm⁻¹ are acquired using a buried CoSi₂ layer as an internal mirror to perform external reflection spectroscopy. On clean Si(100), water dissociates into H and OH surface species as evidenced by EELS results [1] in the literature which show a Si---H stretching vibration (2082 cm⁻¹), and SiO---H vibrations (O---H stretch at 3660 cm⁻¹ and the Si---O---H bend and Si---O stretch of the hydroxyl group centered around 820 cm⁻¹). In this paper, infrared (IR) measurements are presented which confirm and resolve the issue of a puzzling isotopic shift for the Si---O mode of the surface hydroxyl group, namely, that the Si---O stretch of the O---H surface species formed upon H₂O exposure occurs at 825 cm⁻¹, while the Si---O stretch of the ---OD surface species formed upon D₂O exposure shifts to 840 cm⁻¹, contrary to what is expected for simple reduced mass arguments. The higher resolution of IR measurements versus typical EELS measurements makes it possible to identify a new mode at 898 cm⁻¹, which is an important piece of evidence in understanding the anomalous frequency shift. By comparing the results of measurements for adsorption of H¹⁶₂O, H¹⁸₂O and D₂O with the results from recently performed first-principles calculations, it can be shown that a strong vibrational interaction between the Si---O stretching and Si---O---H bending functional group vibrations of the hydroxyl group accounts for the observed isotopic shifts.     

On the luminescence of LiBaF3:Eu

From the temperature dependence of the line—band luminescence intensity ratio of LiBaF₃:Eu²⁺ a 4f−5d activation energy (Δ) of 800 cm⁻¹ is derived, being much higher than the value reported in the literature (100 cm⁻¹). The temperature dependence of the luminescence decay can be well described with Δ = 800 cm⁻¹ and with 4f−4f and 5d−4f radiative probabilities of 4×10²s⁻¹ and 6×10⁵s⁻¹, respectively.     

Measurement of the absolute oscillator strengths of gadolinium using an atomic vapor produced by electron beam heating

The absolute values of the oscillator strength ƒ were measured for the six spectral lines of Gd by means of laser absorption spectroscopy with the atomic vapor produced by electron beam heating. The ƒ values obtained for the transition are 0–17381 cm⁻¹, 215–17750 cm⁻¹, 533–17795 cm⁻¹, 999–18070 cm⁻¹, 999–17931 cm⁻¹, 1719–18070 cm⁻¹ were obtained to be 0.0036, 0.012, 0.014, 0.019, 0.0075 and 0.039, respectively. The error of ƒ values was 24% due to uncertainty of metastable states' density.     

Infrared microspectroscopy station at BL43IR of SPring-8

BL43IR of SPring-8 has been constructed for the infrared materials researches, and it covers a wide spectral range from 100 to 20,000 cm⁻¹. The microspectroscopy station of this BL has a spatial resolution smaller than 10 μm in diameter in the mid-infrared region without apertures. This station had been mainly used within mid-infrared region, and its performance in the far-infrared region had not been tested. In this paper, we examined the capability of the microscope in the far-infrared region and the spatial resolution is found to be almost at the diffraction limit. The microspectroscopy station has been revealed to have a good performance for doing materials researches in all the spectral range available.     

NIR-FT-SERS of 4″-trimethylsilylethylsulfanyl-4,4′-di(phenyleneethynylene)benzenethiol on Au nanospheres

Oligo(phenyleneethynylene) (OPE) compounds have been identified as promising molecular electronic bridges. Self-assembled monolayers of 4″-trimethylsilylethylsulfanyl-4,4′-phenyleneethynylenebenzene thiol (OPE′) on Au were characterized by surface-enhanced Raman scattering (SERS). The FT-Raman spectrum of OPE′ shows three C–S bands at 834, 1086, and 1131 cm⁻¹. From the FT-Raman to the SERS spectra, the 1086 cm⁻¹ band exhibits a 9 cm⁻¹ red shift. Chemisorption of OPE′ to the gold surface occurs via oxidative cleavage of the disulfide bond and the formation of the Au–S bond. The Au–S vibration is visible in the SERS spectra at 257 cm⁻¹. Peaks due to the S–S and S–H stretch are observed at 544 and 2519 cm⁻¹, respectively, in the FT spectrum, but are unobserved in the surface-enhanced spectra. The C–H stretching region (2700–3350 cm⁻¹) in the spectrum of neat OPE′ shows three distinct bands, whereas the SERS spectra show a single broad band. Assignments of vibrational bands were based on DFT calculations performed at the B3LYP level with good agreement between theoretical and experimental values. An average percent difference of 2.52 was obtained for the non-CH stretching frequencies.     

Highly sintered nickel oxide: surface morphology and FTIR investigation of CO adsorbed at low temperature

The monolayer of CO molecules adsorbed at low temperature on highly sintered nickel oxide, gives rise to a very symmetric IR absorption band at 2136 cm⁻¹ (θ_max) with a full-width at half-maximum (FWHM) of 3.7 cm⁻¹. This band shifts to higher frequenc upon decreasing the coverage, reaching the 2152 cm⁻¹ value for θ→0. The observed shift is due to changes in the lateral interactions (dynamic and static) among the adsorbed molecules. The observed spectral simplicity implies that most of the adsorbed CO molecules occupy crystallographically identical sites with a similar environment. Moreover, the remarkably small half-width indicates that inhomogeneous broadening effects, due to surface defects, are very small and that NiO microcrystals behave as single crystals. The morphology of microcrystals has been studied by SEM, AFM and HRTEM techniques: it was concluded that the surface termination of the sample is mainly represented by the (100) and (111) faces.     

Lattice absorption of Ge in the far infrared

The lattice absorption at low frequency (100 cm⁻¹) and low temperature (50 K) of Ge is very small, yet it may influence the performance of the p---Ge hot hole far-infrared laser. We have measured by temperature-tuned laser interferometry.     

Dependence of the excitation wavelength on the Raman-active phonons of YBa2Cu3O7 Search for Landau damping in single-domain crystals

In single-domain crystals of YBa₂Cu₃O₇, we examine the dependence of phonon linewidth on wavevector by varying the wavelength of the exciting laser. In three crystals, we find the linewidths of the Raman-active phonons at 120 and 150 cm⁻¹ to be nearly invariant for excitation wavelengths between 647 and 413 nm. That is, we find no broadening of the phonon linewidths with increasing phonon wavevector (decreasing excitation wavelength), and thus no evidence of Landau damping in our crystals. In addition, the correlation between the intensity of the chain-related Raman feature at ≈232 cm⁻¹ and the temperature dependence of the B_1g-like phonon at 340 cm⁻¹ has been investigated. In all three crystals, we find a net sharpening of the 340 cm⁻¹ phonon below T_c and essentially no intensity for the ≈232 cm⁻¹ mode under resonance conditions.     

Optoacoustic study of the infrared multiphoton excitation of ethylene

The optoacoustic effect was used to detect the infrared multiphoton excitation of ethylene as a function of laser wave length and laser energy fluence. The strong absorptions were observed at 949 cm⁻¹, 953 cm⁻¹ and 939 cm⁻¹. The dependence of the energy absorption on the laser energy fluence shows that the absorption at 949 cm⁻¹ is due to the resonance of the single quantum transition whereas the absorptions at 953 cm⁻¹ and 939 cm⁻¹ are due to the resonance of the double quantum transitions. The energy shift of the later transitions was explained in terms of Fermi resonance of the overtones of v₇ and v₈ modes. The onset of highly multiple quantum transitions were observed at high laser energy fluence.     

HREELS of H/GaN(0001): evidence for Ga termination

Two issues relevant to the growth and processing of GaN are the termination of the GaN(0001) surface and its reaction with hydrogen. We have used high-resolution electron energy loss spectroscopy (HREELS), low-energy electron diffraction (LEED), and Auger electron spectroscopy (AES) to study the adsorption of hydrogen on MOCVD-grown GaN(0001). LEED of the sputtered and annealed surface shows evidence of facetting. No adsorbate vibrations are observed on the clean surface by HREELS, only Fuchs–Kliewer phonons at intervals of 700 cm⁻¹. Following exposure of the clean GaN surface to hydrogen atoms, HREEL spectra show adsorbate loss peaks at 2580, 3280, and 3980 cm⁻¹. The Ga–H stretching vibration at 1880 cm⁻¹ becomes evident when the HREEL spectrum is deconvoluted to remove the phonon multiple-loss peaks. We assign the 2580, 3280, and 3980 cm⁻¹ peaks to combination modes of the Ga–H stretch and phonon(s). Upon dosing with deuterium, the Ga–D bending mode is observed at 400 cm⁻¹. No vibrational peaks due to N–H (N–D) species are observed after H (D) exposure. We conclude that sputtered and annealed GaN(0001) is Ga-terminated.     

Radiative and nonradiative processes in LiGa5O8: Mn

The luminescence of LiGa₅O₈:Mn⁴⁺ was observed with measurements of decay times and intensities for different temperatures. The experimental results were analysed taking into account purely radiative, vibronic and radiationless transitions. It is shown that the nonradiative process involves 46 phonons, each with an energy of 304 cm⁻¹.     

Conversion of VUV to UV and visible in K5Li2LnF10 containing rare-earth from cerium group (Ln=La, Ce, Pr, Nd)

The potential of single crystals K₅Li₂LnF₁₀, for applications as VUV excited phosphors has been examined. The crystals were doped with lanthanide ions (Ce³⁺–Nd³⁺) with concentrations up to 100 at%. The self-quenching of luminescence is strongly reduced in this material. Luminescence spectra in the 50,000–10,000 cm⁻¹ range and excitation spectra in the 40,000–250,000 cm⁻¹ spectral range have been recorded at room and low temperature. Intense visible emission has been observed for Nd³⁺ and Pr³⁺. For the Pr³⁺ ions strong the ¹S₀–¹I₆ transition has been recorded only for concentrated crystals. Efficient conversion of VUV excitation to UV–VIS emission was observed in crystals doped with 3 and 100 at% of cerium. In both cerium-activated crystals the lifetimes of f–d transitions were equal to 32 ns.     

Vibrational spectroscopy of ordered oxygen adiayers on Ni/Cu(001) and Co/Cu(001) thin film systems

We report surface vibrations in c(2 × 2) oxygen adlayers on Ni and Co thin films on a Cu(001) substrate measured at gG by high resolution EELS. For the Ni thin film surface, one phonon peak is measured for varying film thicknesses from 1.3 ML (monolayer) to 6 ML with a constant energy of 221 cm⁻¹. For the Co thin film surface, three loss peaks are found, whose relative intensities change as the film thicknesses are varied. One loss peak at ˜520 cm⁻¹ is tentatively assigned to the Fuchs-Kliewer mode of cobalt oxide (CoO). The other two peaks at 317 and 376 cm⁻¹ are likely related to different bonding sites. Surface phonons on the p(2 × 2) Co thin film (389 cm⁻¹) and a bulk resonance mode (115 cm⁻¹) are also reported.     

Davydov splitting and two-photon excitation of cadmium tungstate (CdWO4) single crystal phosphorescence

Phosphorescence characteristics of CdWO₄ excited by one-photon (λ = 308 nm) and two-photon (λ = 570–590 nm) processes were measured. A Davydov splitting of 120 ± 20 cm⁻¹ was obtained in the phosphorescence spectra, suggesting a diffusion coefficient of about 1.2 × 10⁻² cm² s⁻¹, and a diffusion length of about 3.1 × 10⁻⁴ cm for the room temperature measured lifetime of 8μs. The phosphorescence quantum efficiency was less than 2% at low temperatures (only 0.25% at room temperature), indicating that the dominant decay mechanism was radiationless. The radiative lifetime was thus estimated as 1–2 ms. The two-photon phosphorescence excitation is characterized by an absorption cross-section of the order of 10⁻⁴⁹cm⁴s.     

Defect versus nanocrystal luminescence emitted from room temperature and hot-implanted SiO2 layers

Silicon nanocrystals have been synthesized in SiO₂ matrix using Si ion implantation. Si ions were implanted into 300-nm-thick SiO₂ films grown on crystalline Si at energies of 30–55 keV, and with doses of 5×10¹⁵, 3×10¹⁶, and 1×10¹⁷ cm⁻². Implanted samples were subsequently annealed in an N₂ ambient at 500–1100°C during various periods. Photoluminescence spectra for the sample implanted with 1×10¹⁷ cm⁻² at 55 keV show that red luminescence (750 nm) related to Si-nanocrystals clearly increases with annealing temperature and time in intensity, and that weak orange luminescence (600 nm) is observed after annealing at low temperatures of 500°C and 800°C. The luminescence around 600 nm becomes very intense when a thin SiO₂ sample is implanted at a substrate temperature of 400°C with an energy of 30 keV and a low dose of 5×10¹⁵ cm⁻². It vanishes after annealing at 800°C for 30 min. We conclude that this luminescence observed around 600 nm is caused by some radiative defects formed in Si-implanted SiO₂.     

Influence of the Sb dopant distribution on far infrared photoconductivity in Ge:Sb blocked impurity band detectors

Extended long wavelength response to 200 μm (50 cm⁻¹) has been observed in Ge:Sb blocked impurity band (BIB) detectors with N_D1×10¹⁶ cm⁻³. The cut-off wavelength increases from 150 μm (65 cm⁻¹) to 200 μm (50 cm⁻¹) with increasing bias. The responsivity at long wavelengths was lower than expected. This can be explained by considering the observed Sb diffusion profile in a transition region between the blocking layer and active layer. BIB modeling is presented which indicates that this Sb concentration profile increases the electric field in the transition region and reduces the field in the blocking layer. The depletion region consists partially of the transition region between the active and blocking layer, which could contribute to the reduced long wavelength response. The field spike at the interface is the likely cause of breakdown at a lower bias than expected.     

Triton and alpha-particle contribution from LiF converter for neutron dosimeter

A personnel neutron dosimeter prototype based on chemical and electrochemical etched CR-39 detector, combined with LiF converter, has been calibrated using an ICRP-like phantom, under a heavy-water moderated Californium source neutron spectra; A conversion factor of 1.052±126 spots cm⁻² mSv⁻¹ was obtained. The sealing properties of the detector holder showed a ten-fold reduction in radon background when it was tested in a high radon atmosphere. A convenient mechanical shock resistance was achieved in LiF converters by sintering to 11 tons pressure LiF powder at 650°C, during one hour.     

The adsorption of CO on Ir(111) investigated with FT-IRAS

The adsorption of CO on Ir(111) has been investigated with Fourier transform infrared reflection-absorption spectroscopy, temperature programmed desorption, and low-energy electron diffraction. At sample temperatures between 90 and 350 K, only a single absorption band, above 2000 cm⁻¹, has been observed at all CO coverages. For fractional coverages above approximately 0.2, the bandwidth becomes as narrow as 5.5 cm⁻¹. The linewidth is attributed mainly to inhomogeneous broadening at low CO coverages and to the creation of electron-hole pairs at higher CO coverages. The coverage-dependent frequency shift of the IR band can be described quantitatively using an improved dipolar coupling model. The contribution of the dipole shift and the chemical shift to the total frequency shift were separated using isotopic mixtures of CO. The chemical shift is positive with a constant value of approximately 12 cm⁻¹ for all coverages, whereas the dipole shift increases with coverage up to a value of 36 cm⁻¹ at a coverage of 0.5 ML.     

Raman study of HgBa2Can−1CunO2n+2+δ (n=1,2,3,4 and 5) superconductors

Polarized micro-Raman scattering measurements have been performed on the five members of the HgBa₂Ca_n−1Cu_nO_2n+2+δ (n=1,2,3,4 and 5) high-T_c superconductor family using different laser frequencies. Local laser annealing measurements were carried out to investigate the variation of the Raman spectra with the excess oxygen content, δ. A systematic evolution of the spectra, which display mainly peaks near 590, 570, 540 and 470 cm⁻¹, with increasing number of CuO₂ layers has been observed; its origin has been shown to lie in the variation of the interstitial oxygen content. In addition to confirming that the 590 cm⁻¹ mode represents vibration of apical oxygens in the absence of neighboring excess oxygen, the 570 cm⁻¹ mode, which may be composed of some finer structures, has been assigned to the vibration of the apical oxygen modified by the presence of the neighboring excess oxygens. The 540 and 470 cm⁻¹ modes may represent the direct vibration of excess oxygens. The implication of possible different distribution sites of excess oxygens is discussed. All other observed lower-frequency modes are also assigned.     

The IR spectra of Mg5C(CO) complexes on the (0 0 1) surfaces of polycrystalline and single crystal MgO

The FTIR spectroscopy of carbon monoxide adsorbed on polycrystalline MgO smoke has been investigated as a function of the CO equilibrium pressure at constant temperature (60 K) (optical isotherm) and of the temperature (in the 300–60 K range) at constant CO pressure (optical isobar). In both cases the spectra fully reproduce those of CO adsorbed on the (0 0 1) surface of UHV cleaved single crystals [Heidberg et al., Surf. Sci. 331–333 (1995) 1467]. This result, never attained in previous investigations on dispersed MgO, contribute to bridging the gap which is commonly supposed to exist between surface science and the study of “real” (defective) systems. Depending on the surface coverage θ the main spectral features due to the CO/MgO smoke interaction are a single band shifting from 2157.5 (at θ→0) to 2150.2 cm⁻¹ (at θ=1/4) or a triplet, at 2151.5, 2137.2 and 2132.4 cm⁻¹ (at θ>1/4). These manifestations are due to the ν(CO) modes of Mg_5C²⁺· · · CO adducts formed on the (0 0 1) terminations of the cubic MgO smoke microcrystals. The formation of the CO monolayer is occurring in two different phases: (i) a first phase with CO oscillators perpendicularly oriented to the surface (2157–2150 cm⁻¹) and (ii) a second phase constituted by an array of coexisting perpendicular and tilted species (triplet at 2151.5, 2137.2 and 2132.4 cm⁻¹). A much weaker feature at 2167.5–2164 cm⁻¹ is assigned to Mg_4C²⁺· · · CO adducts at the edges of the microcrystals. The heat of adsorption of the perpendicular Mg_5C²⁺· · · CO complex in the first phase has been estimated from the optical isobar and results to be 11 kJ mol⁻¹.