Controlling energy deposition during the C60 bombardment of silicon: The effect of incident angle geometry

The profile of the energy deposition footprint is controlled during the C₆₀⁺ erosion of Si surfaces by varying the incident energy and/or incident angle geometry. Sputter yield, surface topography, and chemical composition of the eroded surfaces were characterized using atomic force microscopy (AFM) and secondary ion mass spectrometry (SIMS). The experiments show that the 10 keV, 40° incident C₆₀⁺ erosion of Si results in the formation of a C containing, mound-like structure on the solid surface. We find that the occurrence of this C feature can be avoided by increasing the incident energy of the C₆₀⁺ projectile or by increasing the incident angle of the C₆₀⁺ projectile. While both strategies allow for the Si samples to be eroded, the occurrence of topographical roughening limits the usefulness of C₆₀⁺ in ultra-high resolution semiconductor depth profiling. Moreover, we find that the relative effect of changing the incident angle geometry of the C₆₀⁺ projectile on the profile of the energy deposition footprint, and thus the sputter yield, changes according to the kinetic energy of the projectile and the material of the bombarded surface, a behavior that is quite different than what is observed for an atomic counterpart.     

Polyethylene terephthalate (PET) bulk film analysis using C60, Au3, and Au primary ion beams

The damage characteristics of polyethylene terephthalate (PET) have been studied under bombardment by C₆₀⁺, Au₃⁺ and Au⁺ primary ions. The observed damage cross-sections for the three ion beams are not dramatically different. The secondary ion yields however were significantly enhanced by the polyatomic primary ions where the secondary ion yield of the [M + H]⁺ is on average 5× higher for C₆₀⁺ than Au₃⁺ and 8× higher for Au₃⁺ than Au⁺. Damage accumulates under Au⁺ and Au₃⁺ bombardment while C₆₀⁺ bombardment shows a lack of damage accumulation throughout the depth profile of the PET thick film up to an ion dose of ∼1 × 10¹⁵ ions cm⁻². These properties of C₆₀⁺ bombardment suggest that the primary ion will be a useful molecular depth profiling tool.     

Weak water absorption lines around 1.455 and 1.66 μm by CW-CRDS

The absorption spectra of water vapor near 1.455 and 1.66 μm have been recorded with a typical absorption sensitivity of 5 × 10⁻¹⁰ cm⁻¹ by using CW-cavity ring down spectroscopy. A series of 18 distributed feed-back (DFB) lasers was used as sources and allowed for the coverage of the 5911.0-5922.5, 5926-5941.8, 5957.0-6121.6, and 6745-7015.6 cm⁻¹ spectral regions. These regions extend to lower and higher energies our previous study of the water spectrum in the important 1.5 μm transparency window [P. Macko, D. Romanini, S.N. Mikhailenko, O.V. Naumenko, S. Kassi, A. Jenouvrier, Vl.G. Tyuterev, J. Mol. Spectrosc. 227 (2004) 90-108]. The line parameters were determined with the help of an interactive least squares multi-lines fitting program which uses a Voigt function as line profile. More than 1900 water lines with intensities ranging between 10⁻²⁸ and 5 × 10⁻²⁴ cm/molecule at 296 K were measured, about 690 of them being reported for the first time. The rovibrational assignment was performed on the basis of previously determined energy levels and of the results of the variational global calculations [H. Partridge, D.W. Schwenke, J. Chem. Phys. 106 (1997) 4618-4639]. The assignment results were validated by using the Ritz combination principle together with previously reported water transitions. Several new energy levels were determined for the H₂¹⁶O, H₂¹⁷O, and HD¹⁶O isotopologues. The retrieved line lists of the H₂¹⁶O, H₂¹⁷O, H₂¹⁸O, and HD¹⁶O isotopologues are compared with the available calculated and experimental (FTS) databases for water.     

The effect of incident angle on the C60 bombardment of molecular solids

The effect of incident angle on the quality of SIMS molecular depth profiling using C₆₀⁺ was investigated. Cholesterol films of ∼300 nm thickness on Si were employed as a model and were eroded using 40 keV C₆₀⁺ at an incident angle of 40° and 73° with respect to the surface normal. The erosion process was characterized by determining at each angle the relative amount of chemical damage, the total sputtering yield of cholesterol molecules, and the interface width between the film and the Si substrate. The results show that there is less molecule damage at an angle of incidence of 73° and that the total sputtering yield is largest at an angle of incidence of 40°. The measurements suggest reduced damage is not necessarily dependent upon enhanced yields and that depositing the incident energy nearer the surface by using glancing angles is most important. The interface width parameter supports this idea by indicating that at the 73° incident angle, C₆₀⁺ produces a smaller altered layer depth. Overall, the results show that 73° incidence is the better angle for molecular depth profiling using 40 keV C₆₀⁺.     

Quantitative O imaging towards oxygen consumption study in tumor bearing mice at 7 T

¹⁷O magnetic resonance imaging (MRI) using a conventional pulse sequence was explored as a method of quantitative imaging towards regional oxygen consumption rate measurement for tumor evaluation in mice. At 7 T, fast imaging with steady state (FISP) was the best among gradient echo, fast spin echo and FISP for the purpose. The distribution of natural abundance H₂¹⁷O in mice was visualized under spatial resolution of 2.5 × 2.5 mm² by FISP in 10 min. The signal intensity by FISP showed a linear relationship with ¹⁷O quantity both in phantom and mice. Following the injection of 5% ¹⁷O enriched saline, ¹⁷O re-distribution was monitored in temporal resolution down to 5 sec with an image quality sufficient to distinguish each organ. The image of labeled water produced from inhaled ¹⁷O₂ gas was also obtained. The present method provides quantitative ¹⁷O images under sufficient temporal and spatial resolution for the evaluation of oxygen consumption rate in each organ. Experiments using various model compounds of R-OH type clarified that the signal contribution of body constituents other than water in the present in vivo¹⁷O FISP image was negligible.     

Luminescence of Ce and Pr doped Sr2Mg(BO3)2 under VUV-UV and X-ray excitation

This report presents the luminescence properties of Ce³⁺ and Pr³⁺ activated Sr₂Mg(BO₃)₂ under VUV-UV and X-ray excitation. The five excitation bands of crystal field split 5d states are observed at about 46 729, 44 643, 41 667, 38 314 and 29 762 cm⁻¹ (i.e. 214, 224, 240, 261 and 336 nm) for Ce³⁺ in the host lattice. The doublet Ce³⁺ 5d→4f emission bands were found at about 25 840 and 24 096 cm⁻¹ (387 and 415 nm). The influence of doping concentration and temperature on the emission characteristics and the decay time of Ce³⁺ in Sr₂Mg(BO₃)₂ were investigated. For Pr³⁺ doped samples, the lowest 5d excitation band was observed at about 42017 cm⁻¹ (238 nm), a dominant band at around 35714 cm⁻¹ (280 nm) and two shoulder bands were seen in the emission spectra. The excitation and emission spectra of Ce³⁺ and Pr³⁺ were compared and discussed. The X-ray excited luminescence studies show that the light yields are ∼3200±230 and ∼1400±100 photons/MeV of absorbed X-ray energy for the samples Sr_1.86Ce_0.07Na_0.07Mg(BO₃)₂ and Sr_1.82Pr_0.09Na_0.09Mg(BO₃)₂ at RT, respectively.     

Studies of the electrochemical reduction processes of Bi, HTeO2 and their mixtures

The reduction process of Bi³⁺, HTeO₂⁺ and their mixtures on Au electrode surface was studied by cyclic voltammetry, linear sweep voltammetry, electrochemical impedance spectroscopy and chronoamperometry. XRD and EDS methods were also used to measure the reductive products prepared under different potentials and provide the evidences of the reactions. The results indicate that the reduction of HTeO₂⁺ occurs at more positive potential than that of Bi³⁺, but its reduction rate is slower and adsorption phenomenon exists during its reduction process. Bi₂Te₃ compound can be obtained potentiostatically at a proper potential in all the mixed solutions with concentration ratio CHTe+O₂/CBi3+ in our research range (0.1-10). But pure Bi₂Te₃ compound can only be obtained at 42 mV in the solution with concentration ratio CHTe+O₂/CBi3+ equaling to 1. And the formation of Bi₂Te₃ compound is an inductive co-depositing process: (1) HTeO₂⁺ + 4e⁻ + 3H⁺ → Te⁰ + 2H₂O, (2) 3Te⁰ + 2Bi³⁺ + 6e⁻ → Bi₂Te₃.     

Model multilayer structures for three-dimensional cell imaging

The prospects for SIMS three-dimensional analysis of biological materials were explored using model multilayer structures. The samples were analyzed in a ToF-SIMS spectrometer equipped with a 20 keV buckminsterfullerene (C₆₀⁺) ion source. Molecular depth information was acquired using a C₆₀⁺ ion beam to etch through the multilayer structures at specified time intervals. Subsequent to each individual erosion cycle, static SIMS spectra were recorded using a pulsed C₆₀⁺ ion probe. Molecular intensities in sequential mass spectra were monitored as a function of primary ion fluence. The resulting depth information was used to characterize C₆₀⁺ bombardment of biological materials. Specifically, molecular depth profile studies involving dehydrated dipalmitoyl-phosphatidylcholine (DPPC) organic films indicate that cell membrane lipid materials do not experience significant chemical damage when bombarded with C₆₀⁺ ion fluences greater than 10¹⁵ ions/cm². Moreover, depth profile analyses of DPPC-sucrose frozen multilayer structures suggest that biomolecule information can be uncovered after the C₆₀⁺ sputter removal of a 20 nm overlayer with no appreciable loss of underlying molecular signal. The experimental results support the potential for three-dimensional molecular mapping of biological materials using cluster SIMS.     

High sensitivity CW-CRDS of O enriched water near 1.6 μm

The absorption spectrum of ¹⁸O enriched water has been recorded by continuous wave cavity ring down spectroscopy between 5905.7 and 6725.7 cm⁻¹ using a series of fibred DFB lasers. The investigated spectral region corresponds to the important 1.55 μm transparency window of the atmosphere where water absorption is very weak. The typical CRDS sensitivity (noise equivalent absorption of 5×10⁻¹⁰ cm⁻¹) allowed for the detection of lines with intensity as low as 10⁻²⁸ cm/molecule while the minimum intensity value provided by HITRAN in the considered spectral region is 1.7×10⁻²⁴ cm/molecule. The line parameters were retrieved with the help of an interactive least squares multi-lines fitting program assuming a Voigt function as line profile. Overall, 4510 absorption lines belonging to the H₂¹⁸O, H₂¹⁶O, HD¹⁸O, HD¹⁶O and H₂¹⁷O water isotopologues were measured. Their intensities range between 3×10⁻²⁹ and 5×10⁻²³ cm/molecule at 296 K and the typical accuracy on the line positions is 1×10⁻³ cm⁻¹. 2074 of the observed lines attributed to H₂¹⁸O, HD¹⁸O and H₂¹⁷O are reported for the first time. The transitions were assigned on the basis of variational calculations resulting in 288, 135 and 38 newly determined rovibrational energy levels for the H₂¹⁸O, HD¹⁸O and H₂¹⁷O isotopologues, respectively. The new data set includes the band origin of the 4ν₂ bending overtone of H₂¹⁸O at 6110.4239 cm⁻¹ and rovibrational levels corresponding to J and K_a values up to 18 and 12, respectively, for the strongest bands of H₂¹⁸O: 4ν₂, ν₁+2ν₂, 2ν₂+ν₃, 2ν₁, ν₁+ν₃, and ν₂+ν₃. The obtained experimental results have been compared to the spectroscopic parameters provided by the HITRAN database and to the recent IUPAC critical review of the rovibrational spectrum of H₂¹⁸O and H₂¹⁷O as well as to variational calculations. Large discrepancies between the 4ν₂ variationally predicted and experimental intensities have been evidenced for the H₂¹⁸O and H₂¹⁶O molecules.     

High sensitivity ICLAS of H2O in the 12,580-13,550 cm transparency window

High-sensitivity Intracavity Laser Absorption Spectroscopy (ICLAS) is used to measure the high resolution absorption spectrum of H₂¹⁸O between 12,580 and 13,550 cm⁻¹. This spectral region covers the 3v+δ polyad of very weak absorption. Four isotopologues of water (H₂¹⁸O, H₂¹⁶O, H₂¹⁷O, HD¹⁸O) are found to contribute to the observed spectrum. Spectrum analysis is performed with the aid of variational calculations and allowed for assigning 1126 lines belonging to H₂¹⁸O, while only 160 H₂¹⁸O lines are included in the HITRAN-2008 database. Altogether, 823 accurate energy levels of H₂¹⁸O are determined from transitions attributed to 26 upper vibrational states, 438 of them being reported for the first time. New information includes energy levels of four newly observed vibrational states of H₂¹⁸O: (2 4 0), (1 4 1), (0 4 2) and (2 3 1) at 13,167.718, 13,212.678, 13,403.71 and 15,073.975 cm⁻¹, respectively. H₂¹⁸O transitions involving highly excited bending states like (1 6 0), (0 6 1), (0 7 1), (1 7 0), (0 9 0) and even (0 10 0) have been identified as a result of an intensity borrowing from stronger bands via high-order resonance interactions. Thirty-six new energy levels of H₂¹⁷O, present with a 2% relative concentration in our sample, could be determined. The rotational structure of the (0 2 3) state of HD¹⁸O at 13,245.497 cm⁻¹ is also reported for the first time.     

Thermoluminescent and stuctural properties of BaAl2O4:Eu,Nd,Gdphosphors prepared by combustion method

BaAl₂O₄:Eu²⁺,Nd³⁺,Gd³⁺ phosphors were prepared by a combustion method at different initiating temperatures (400–1200 °C), using urea as a comburent. The powders were annealed at different temperatures in the range of 400–1100 °C for 3 h. X-ray diffraction data show that the crystallinity of the BaAl₂O₄ structure greatly improved with increasing annealing temperature. Blue-green photoluminescence, with persistent/long afterglow, was observed at 498 nm. This emission was attributed to the 4f⁶5d¹–4f⁷ transitions of Eu²⁺ ions. The phosphorescence decay curves were obtained by irradiating the samples with a 365 nm UV light. The glow curves of the as-prepared and the annealed samples were investigated in this study. The thermoluminescent (TL) glow peaks of the samples prepared at 600 °C and 1200 °C were both stable at ∼72 °C suggesting that the traps responsible for the bands were fixed at this position irrespective of annealing temperature. These bands are at a similar position, which suggests that the traps responsible for these bands are similar. The rate of decay of the sample annealed at 600 °C was faster than that of the sample prepared at 1200 °C.     

Effects of electron beam current density and temperature on peak height ratios Dj/D0 for cathodoluminescence of Ln2O2S:Eu

The change in the initial and steady state (∼0 and 5 s after initiation of electron beam irradiation) peak heights from the ⁵D₂⇒⁷F₃, ⁵D₁⇒⁷F₃ and ⁵D₀⇒⁷F₂ cathodoluminescent transitions from Eu³⁺ have been studied for Ln₂O₂S:Eu³⁺ (Ln=La, Gd) phosphors. Specifically, the intensity ratio of these transitions, designated as ⁵D₁/⁵D₀, increased and then decreased for both La₂O₂S:Eu³⁺ (0.1 mole%) and Gd₂O₂S:Eu³⁺ (0.4 mole%), as the current density was changed from 10 towards a 1000 μA/cm². These effects were shown to be consistent with feeding from the higher ⁵D₂ excited state to the lower energy ⁵D₁ excited state, resulting in an increase of the ⁵D₁/⁵D₀ ratio at low current densities. At higher current densities, energy was funneled from the ⁵D₁-⁵D₀ states, resulting in a decrease of the ⁵D₁/⁵D₀ ratio. These effects of feeding versus funneling were dependent on both the Eu³⁺ concentration and current density, and changed with time (i.e., approached a steady state after ∼5 s) due to increased activator interactions from induced internal electric fields. The magnitude of thermal quenching versus interaction quenching was investigated using changes of the peak height ratios of ⁵D₂/⁵D₀ and ⁵D₁/⁵D₀.     

Near-infrared luminescence of OH and Cl doped Bi4Ge3O12 crystals

OH⁻ and Cl⁻ doped Bi₄Ge₃O₁₂ (BGO) single crystals had been grown by Vertical Bridgman (VB) method. The structure of these crystals was determined by XRD, the transmittance and emission spectra in near infrared region (NIR) were measured at room temperature. 5% OH⁻ doped BGO shows a significant emission band peaking around 1181 nm under 808 nm laser diodes (LDs) excitation, and the 5% Cl⁻ doped BGO exhibits a relatively weak emission band as well. 100% and 5% OH⁻ doped BGO show noticeable emission band centered at about 1346 nm under 980 nm LDs excitation.     

The ν12 band of ethylene-1-C (CCH4) by high-resolution FTIR spectroscopy

The Fourier transform infrared (FTIR) spectrum of the ν₁₂ fundamental band of ethylene-1-¹³C (or ¹³C¹²CH₄) was recorded with an unapodized resolution of 0.0063 cm⁻¹ in the wavenumber region of 1360-1520 cm⁻¹. Rovibrational constants for the upper state (ν₁₂ = 1) up to five quartic and two sextic centrifugal distortion terms were derived for the first time by assigning and fitting a total of 879 infrared transitions using a Watson’s A-reduced Hamiltonian in the I^r representation. The root-mean-square deviation of the fit was 0.00066 cm⁻¹. The ground state rovibrational constants were also determined by a fit of 523 combination-differences from the present infrared measurements, with a rms deviation of 0.00090 cm⁻¹. The A-type ν₁₂ band which is centred at 1439.34607 ± 0.00004 cm⁻¹ was found to be relatively free from local frequency perturbations. From the ν₁₂ = 1 rovibrational constants obtained, the inertial defect Δ₁₂ was found to be 0.242826 ± 0.000002 μŲ.     

The ν1 + 3ν2 + 3ν3 and 4ν1 + ν2 + ν3 bands of ozone by CW-cavity ring down spectroscopy between 5900 and 5960 cm

The absorption spectrum of ozone, ¹⁶O₃, has been recorded in the 5903-5960 cm⁻¹ region by high sensitivity CW-cavity ring down spectroscopy (α_min ∼ 5 × 10⁻¹⁰ cm⁻¹). The ν₁ + 3ν₂ + 3ν₃ and 4ν₁ + ν₂ + ν₃ A-type bands centred at 5919.15 and 5947.07 cm⁻¹ were newly observed. A set of 173 and 168 energy levels could be experimentally determined for the (1 3 3) and (4 1 1) states, respectively. Except for a few K_a = 5 levels of the (4 1 1) state, the rotational structure of the two states was found mostly unperturbed. The spectroscopic parameters were determined from a fit of the corresponding line positions by considering the (1 3 3) and (4 1 1) states as isolated. The determined effective Hamiltonian and transition moment operators were used to generate a list of 785 transitions given as Supplementary Material.     

Analysis of the first triad of interacting states (0 2 0), (1 0 0), and (0 0 1) of D2O from hot emission spectra

The far-infrared and middle-infrared emission spectra of deuterated water vapour were measured at temperatures 1370, 1520, and 1940 K in the ranges 320-860 and 1750-3400 cm⁻¹. The measurements were performed in an alumina cell with an effective length of hot gas of about 50 cm. More than 3550 new measured lines for the D₂¹⁶O molecule corresponding to transitions from highly excited rotational levels of the (0 2 0), (1 0 0), and (0 0 1) vibrational states are reported. These new lines correspond to rotational states with higher values of the rotational quantum numbers compared to previously published determinations: J_max = 29 and K_a(max) = 22 for the (0 2 0) state, J_max = 29 and K_a(max) = 25 for the (1 0 0) state, and J_max = 30 and K_a(max) = 23 for the (0 0 1) state. The extended set of 1987 experimental rotational energy levels for the (0 2 0), (1 0 0), and (0 0 1) vibration states including all previously available data has been determined. For the data reduction we used the generating function model. The root mean square (RMS) deviation between observed and calculated values is 0.004 cm⁻¹ for 1952 rovibrational levels of all three vibration states. A comparison of the observed energy levels with the best available values from the literature and with the global predictions from molecular electronic potential energy surfaces of water isotopic species [H. Partridge, D.W. Schwenke, J. Chem. Phys. 106 (1997) 4618] is discussed. The latter confirms a good consistency of mass-dependent DBOC corrections in the PS potential function with new experimental rovibrational data.     

Blue luminescence in Tm-doped KGd(WO4)2 single crystals

Up-conversion blue emissions of trivalent thulium ions in monoclinic KGd(WO₄)₂ single crystals at 454 and 479 nm are reported for a single pump laser source at 688 nm. We grew thulium-doped KGd(WO₄)₂ single crystals at several concentrations from 0.1% to 10%. We recorded a polarized optical absorption spectrum for the ³F₂+³F₃ energy levels of thulium at room temperature and low temperature (6 K). From the low temperature emission spectra we determined the splitting of the ³H₆ ground state. The blue emissions are characterized as a function of the dopant concentration and temperature from 10 K to room temperature. To our knowledge, this is the first time that sequential two-photon excitation process (STEP) generated blue emissions in thulium-doped single crystals with a single excitation wavelength.     

Photoluminescence properties and effects of dopant concentration in Bi2ZnB2O7:Tb phosphor

A novel green phosphor, Tb³⁺ doped Bi₂ZnB₂O₇ was synthesized by conventional solid state reaction method. The phase of synthesized materials was determined using the XRD, DTA/TG and FTIR. The photoluminescence characteristics were investigated using spectrofluorometer at room temperature. Bi₂ZnB₂O₇:Tb³⁺ phosphors excited by 270 nm and 485 nm wavelengths. The emission spectra were composed of three bands, in which the dominated emission of green luminescence Bi₂ZnB₂O₇:Tb³⁺ attributed to the transition ⁵D₄ → ⁷F₅ is centered at 546 nm. The dependence of the emission intensity on the Tb³⁺ concentration for the Bi_2−xTb_xZnB₂O₇ (0.01 ≤ x ≤ 0.15) was studied and observed that the optimum concentration of Tb³⁺ in phosphor was 13 mol% for the highest emission intensity at 546 nm.     

Preparation and photoluminescence characteristics of Eu-doped MgAl1.8Y0.2O4 nanocrystals

A simple combustion route was employed for the preparation of Eu³⁺-doped MgAl_1.8Y_0.2−xO₄ nanocrystals using metal nitrates as precursors and urea as a fuel in a preheated furnace at 500 °C. The powders thus obtained were then fired at 1000 °C for 3 h to get better luminescent properties. The incorporation of Eu³⁺ activator in these nanocrystals was checked by luminescence characteristics. These nanocrystals displayed bright red color on excitation under 254 nm UV source. The main emission peak was assigned to the transition [⁵D₀→⁷F₂] at 615 nm. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) studies were carried out to understand surface morphological features and the particle size. Crystal structures of the nanocrystals were investigated by the X-ray diffraction (XRD) technique. The crystallite size of the as-prepared nanocrystals was around 29 nm, which was evaluated from the broad XRD peaks. The crystallite size increased to ∼45 nm on further heat treatment at 1000 °C.     

Auger electron/X-ray photoelectron and cathodoluminescent spectroscopic studies of pulsed laser ablated SrAl2O4:Eu,Dy thin films

Auger electron/X-ray photoelectron and cathodoluminescent (CL) spectroscopic studies were conducted on pulsed laser deposited SrAl₂O₄:Eu²⁺,Dy³⁺ thin films and the correlation between the surface chemical reactions and the decrease in the CL intensity was determined. The Auger electron and the CL data were collected simultaneously in a vacuum chamber either maintained at base pressure or backfilled with oxygen gas. The data were collected when the films were irradiated for 14 h with 2 keV electrons. The CL emission peak attributed to the 4f⁶5d¹ → 4f⁷ transitions was observed at ∼521 nm and the CL intensity of the peaks degraded at different rates in different vacuum conditions. X-ray photoelectron spectroscopy (XPS) data collected from degraded films suggest that strontium oxide (SrO) and aliminium oxide (Al₂O₃) were formed on the surface of the film as a result of electron stimulated surface chemical reaction (ESSCR).