Photodesorption from powdered zinc oxide

Mass spectrometric measurements of photodesorption from powdered ZnO under controlled radiation are reported. Neutral carbon dioxide and atomic oxygen prevail as the desorbing species. From photodesorption rate decay curves we obtain cross sections for photodesorption of ~ 2 × 10^?17 cm² for O and ~4 × 10^?19 cm² for CO₂. Both species desorb only when the incoming photon energy exceeds the ZnO band gap energy (3.2 eV). The desorption rate is linear with incoming photon flux. All the data seem to support a substrate dependent process of photodesorption by neutralization of chemisorbed species by photogenerated holes. The temperature dependence of the photodesorption rate for CO₂ yields a value of 0.26 eV for the apparent binding energy of the physisorbed CO₂ molecule.     

Shuttle-like ZnO nano/microrods: Facile synthesis, optical characterization and high formaldehyde sensing properties

Shuttle-like ZnO nano/microrods were successfully synthesized via a low temperature (80 °C), “green” (without any organic solvent or surfactant) and simple hydrothermal process in the solution of zinc chloride and ammonia water. X-ray diffraction and Raman spectroscopy indicated that the ZnO nano/microrods are a well-crystallized hexagonal wurtzite structure. Yet photoluminescence analysis showed that abundant intrinsic defects (52.97% electron donor defects and 45.49% electron acceptor defects) exist on the surface of ZnO crystals. Gas sensors based on the shuttle-like ZnO nano/microrods exhibited high sensitivity, rapid response-recovery and good selectivity to formaldehyde in the range of 10-1000 ppm at an optimum operating temperature of 400 °C. Through applying linear fitting to the plot of sensitivity versus formaldehyde concentration in logarithmic forms, the chemisorbed oxygen species on the ZnO surface were found to be O²⁻ (highly active among O₂, O₂⁻ and O⁻ species). Notably, formaldehyde can be easily distinguished from acetaldehyde with a selectivity of about 3. The high formaldehyde sensitivity is mainly attributed to the synergistic effect of abundant electron donor defects (52.97%) and highly active oxidants (surface adsorbed O²⁻ species) co-existed on the surfaces of ZnO.     

Electrical conductivity and defect structure of Ni-doped and “CO-reduced” Ni-doped SrTiO3 single crystals

The electrical conductivities of Ni-doped and “CO-reduced” Ni-doped SrTiO₃ single crystals were measured at temperatures 700–1200°C and P_o2's of 10^?7–10^?1 atm. Plots of log σ vs $\text{1}\text{T}$ at constant P_o2's were found to be linear, and the activation energies appeared to be 0.92 eV for Ni-doped SrTiO₃ and 0.50 eV for “CO-reduced” Ni-doped SrTiO₃ single crystals, respectively. Plots of log σ vs log P_o2 at constant temperature were found to be linear with an average slope of ?$\text{1}\text{4}$ for SrTiO₃:Ni and of ?$\text{1}\text{6}$ for “CO-reduced” SrTiO₃:Ni single crystals, respectively. The electrical conductivity dependencies on P_o2 indicate that a triply ionized titanium interstitial and an oxygen vacancy model are applicable to Nidoped and “CO-reduced” Ni-doped SrTiO₃ single crystals, respectively. The small polaron conduction was suggested on “CO-reduced” Ni-doped SrTiO₃ single crystal from the temperature dependence of conductivity.     

New books

Under low energy sputtering conditions (e.g. Ar⁺ ions, 300 eV, 10^?8A cm^?2) the Secondary Ion Mass Spectra show almost only those polyatomic ions which correspond to the arrangement of the atoms in the crystal structure. This method for obtaining structural information is demonstrated on a single crystal of cubic ZnS. In the SIMS for this pure ZnS crystal mainly polyatomic ions such as (ZnS)⁺, (ZnS)^?, (ZnSZn)⁺, (SZnS)^?, etc. were observed. Other polyatomic ions such as (Zn₂)⁺ or (S₂^?), which are not originally present in the crystal, are observed only in a very low counting rate ratio. An increase in the energy of the primary ions causes larger clusters of atoms of the crystal to be taken off, as well as polyatomic ions which do not correspond to the original structure. These effects and the influence of the crystallographic orientations are demonstrated on single crystals of CaF₂. Two applications of this method are discussed: the determination of S₂ content in thin films of ZnS and the identification of “FeAl₂O₄” clusters in activated ammonia catalysts (α-Fe+ 3%Al₂O₃).     

Evolution of the magnesium surface during oxidation studied by Metastable Impact Electron Spectroscopy

The evolution of a polycrystalline magnesium surface during oxidation at room temperature has been studied by Metastable Impact Electron Spectroscopy (MIES). This technique allowed us to follow the metal-to-insulator transformation of the top layer of the surface. An electronic signal corresponding to a metallic behavior of the surface evidences the presence of under-stoichiometric MgO species on the surface. The total covering by oxygen of the Mg surface uppermost layer, obtained at around 10 L of oxygen deposition, does not correspond to a fully insulating surface. An insulating surface is obtained after 30 L of oxygen deposition. Depositions of CO₂ on a clean and a preoxidized polycrystalline Mg surface have been analyzed to give information about the composition of the surface and its evolution. CO₂ adsorption in the form of CO₃²⁻ compounds on preoxidized Mg is more efficient than on clean Mg. Oxygen species, corresponding to chemisorbed oxygen less bounded than oxygen in the MgO lattice, allows the formation of CO₃²⁻. Therefore, it is concluded that during oxygen deposition at room temperature, MgO islands and chemisorbed oxygen species coexist on the surface. Moreover, the larger the oxygen predeposition is, the less CO₃²⁻ compounds are formed, meaning a decrease of available chemisorbed oxygen sites. From oxidation measurements at high temperature (420 K), we show that MgO islands and uncovered Mg domain coexist. Further, no under-stoichiometric compound features have been observed. The high temperature allows the direct formation of oxide MgO species in islands.     

ESR of adsorbates on single crystal metal surfaces under UHV conditions

Angular dependent electron spin resonance measurements were taken for paramagnetic molecules adsorbed on metallic single crystal surfaces in UHV. For the hydrated Cu(NO₃)₂ complex on a Cu[111] surface an angular dependent ESR signal is recorded. The plane ofthe molecule is found to lie preferentially out of the surface plane. Experiments on chemisorbed molecular O₂ on Ag[110] at 25 K and NO on Pt[111] at 110 K show no sharp ESR signal characteristic for well localized moments. If one assumes that NO on Pt (respectively Pd) carries an unpaired spin, one can estimate a lower limit for the spin flip rate of π^?1>2×10⁹s^?.     

UPS and XPS studies of the chemisorption of O2, H2 AND H2O on reduced and stoichiometric SrTiO3(111) surfaces; The effects of illumination

About one monolayer of Ti³⁺ species is detectable at the surface of reduced SrTiO₃(111) single crystals by XPS and UPS. O₂, H₂ and H₂O have been adsorbed in the dark and the decrease on the concentration of the Ti³⁺ species has been monitored as a function of the gas exposures. Subsequent band gap illumination partially restores the Ti³⁺ initial concentration in the cases of O₂ and H₂ exposures but not in the case of H₂O. The Ti³⁺ photogeneration on the oxygen covered surface is associated with oxygen photodesorption as indicated by XPS and UPS. UPS measurements give evidence for surface hydroxylation resulting from water and hydrogen adsorption. The activity of the stoichiometric SrTiO₃(111) crystal face for O₂ and H₂ adsorption is very low when compared with the reduced SrTiO₃ samples.     

Electrical conductivity of magnesium oxide single crystal below 1200 K

Using 2-, 3- and 4-electrodes configurations the direct current conductivity of MgO single crystals of nominally highest purity (with respect to cation impurities), grown by arc-fusion, was studied in argon or oxygen between 500–1200 K with special reference to both hysteresis effects during heating and cooling cycles and conductivity phenomena which occur underneath the surface in a thin subsurface zone. The samples contained 250–2500 at.-ppm carbon and typically 800 at.-ppm hydrogen.Below 1000 K the low temperature (LT) conductivity mechanism is characterized by an activation energy of 1.1 ± 0.2eV, distinctly lower than that of the high temperature region (HT) approximately 2.4 eV. By annealing at 300 K the LT mechanism progressively builds up and causes a very pronounced conductivity increase between 700–900 K, unaffected or even enhanced by O₂. Above 900 K, O₂ decreases the conductivity.The LT mechanism is proposed to be due to defect electrons on anion sites corresponding to O^? in the O^2? structure which are a consequence of the presence of carbon and hydrogen dissolved in the MgO and formally derived from the dissolution of traces of CO₂ and H₂O [J. Chem. Phys. Solids43, 129 (1982)].The dissolved carbon is known to segregate into the elastically relaxed subsurface zone (J. Chem. Phys. Solids43, 59 1982). The conductivity data suggest that between 700–900 K, defect species of C + 2O^?, the dipolar CO^?₂, which become strongly enriched in the subsurface zone upon annealing at 300 K, dissociate according to the equation CO₂^2?→CO^? + O^?, thus generating the defect electrons responsible for the LT mechanism.     

An initial study of the growth and defect analysis on hydrated 2-benzoyl benzoic acid crystal

In the present study, single crystals of hydrated 2-benzoyl benzoic acid were grown by the slow evaporation solution growth method. Single crystal and powder X-ray diffraction studies confirm the triclinic structure of the grown crystals. The defect in crystalline perfection has been defined by rocking curve analysis. The FTIR spectrum of the crystal displays carbonyl stretching of the carboxylic group at 1685 cm^?1 and of keto group at 1661 cm^?1. It shows a merged medium band around 3450 cm^?1 due to OH stretching and does not distinguish clearly between OH of COOH and H₂O held up in the crystal. The existence of additional bands appears at 1590 cm^?1 due to vibration of H₂O in the compound. The photoluminescence excitation studies were carried out for the grown crystals for wide wavelength range between 300 nm and 700 nm at room temperature. The range of percentage of optical absorption of the crystal has been ascertained by UV?vis spectral characterization. The mechanical strength has been determined by Vickers's microhardness measurement for different loads with constant dwell time.     

Work function changes during low pressure oxidation of aluminum at room temperature

The oxidation kinetics of clean bulk aluminum surfaces exposed to low oxygen pressures (10^?8 to 2 × 10^?6 torr) at room temperature were followed by measurement of work function changes. The interaction of oxygen with aluminum resulted in a decrease in the work function, indicating that the chemisorbed surface oxygen was unstable and incorporation into the subsurface region took place even at very small surface coverages. A “stable layer” of constant work function was finally formed on the aluminum surface. The limiting work functio nchange (work function change to form the “stable layer”) became less negative with increase in oxygen pressure. It was not possible to explain these results on the basis of previously published oxygen uptake models. A new model based on a pressure dependent limiting amount of outer surface and incorporated oxygen is proposed to explain the pressure dependence of the limiting work function change.     

Growth, Characterization and Theoretical Study of a Novel Organometallic Nonlinear Optical Crystal: CdHg(SCN)4(C2H5NO)2

A novel potentially useful second harmonic generation (SHG) organometallic nonlinear optical (NLO) crystal: cadmium mercury thiocyanate bis(N-methylformamide), CdHg(SCN)₄(C₂H₅NO)₂ (CMTN), has been prepared, and large high-optical-quality single crystals with dimensions up to 30 ×27×9 mm³ have been grown by the temperature-lowering method. Its structural, physicochemical and optical properties are characterized by elemental analyses, X-ray powder diffraction, Fourier transform infrared and Raman spectroscopy, thermal analysis, powder SHG measurements and UV/Vis/NIR transmission. The specific heat has been determined to be 515.5 J?mol^?1?K^?1 at 300 K. CMTN possesses good physicochemical stability up to 128.5^°C, exhibits powder SHG efficiencies 0.8 times that of urea and its UV transparency cutoff is 358 nm. By the use of the DFT/B3LYP/6-31G(d) method, the microscopic second order NLO behavior of CMTN has been investigated by computing the first-order hyperpolarizability together with that of CdHg(SCN)₄ (CMTC) and CdHg(SCN)₄(C₃H₈O₂) (CMTG) crystals. The results have been explained based on their crystal structures.     

Growth of high-quality ZnO thin films on (11\bar{2}0) a-plane sapphire substrates by plasma-assisted molecular beam epitaxy

High-quality ZnO thin films were grown on a-plane sapphire substrates by plasma-assisted molecular beam epitaxy. X-ray diffraction and transmission electron microscopy reveal that the ZnO films have high structural quality and an atomically sharp ZnO/Al₂O₃ interface. The full width at half maximum values of the 0002 and $30\bar{3}2$ ZnO ω-rocking curves are 467.8 and 813.5 arc sec for a 600 nm thick ZnO film. A screw dislocation density of 4.35×10⁸ cm^?2 and an edge dislocation density of 3.38×10⁹ cm^?2 are estimated by X-ray diffraction. The surface of the ZnO epilayers contains hexagonal pits, which can be observed in the Zn-polar ZnO. The films have a resistivity of 0.119 Ω?cm, an electron concentration of 6.85×10¹⁷ cm^?3, and a mobility of 76.5 cm²?V^?1?s^?1 at room temperature. Low temperature photoluminescence measurements show good optical properties comparable to ZnO single crystals.     

Diffusionskonstante und charakteristische Absorption vor der Bandkante von Mn in ZnO-Kristallen

ZnO single crystals were doped with Mn and Co by diffusion. In the temperature range from 1400–1600 K the Mn and Co-diffusion-constants were determined:D _Mn=3.2 · 10^?3 exp (?2.87 eV/kT) cm² sec^?1 andD _Co=1·10exp(?3.98 eV/kT) cm² sec^?1. The Mn doped ZnO crystals show a characteristic colour due to an absorption near the intrinsic absorption edge. The corresponding absorption spectra were measured forE⊥c andE∥c. A discussion of different absorption mechanism shows that a charge-transfer transition is responsible for this absorption.     

Electron beam effects on oxygen exposed aluminum surfaces

The damaging effects of electron beams during the acquisition of electron spectra have long been an obstacle in surface analysis. In order to understand the physico-chemical processes which take place under electron irradiation in an AlO system, we have carried out an experiment in which artifices, such as heating, charging, and gas contamination, were absent. We have observed with Auger Electron Spectra increases of the oxidation extent and the oxygen concentration on an oxygen exposed (111) textured polycrystalline surface under electron irradiation (5 keV, 9 × 10^?5 A/cm²). These increases were not observed on a clean surface, and were very feeble on a (100) single crystal surface. The increase of oxygen concentration was independent of residual gas pressure (3 × 10^?9 to 6 × 10^?10 Torr) and its composition; and therefore cannot be explained by gas contamination during the experimental period (about 70 min). We attribute the increase of oxidation degree to the transition of chemisorbed oxygen atoms into oxide through direct momentum transfer from the incident electrons. We suggest that the increase of oxygen within the irradiated area is due to the surface diffusion of chemisorbed oxygen atoms from outside the irradiated area. These oxygen atoms are excited by the electrons scattered from the vacuum chamber walls and gain energy through Franck-Condon type mechanism. The absence of chemisorbed oxygen atoms on (100) surface explains the near absence of these increases on this surface.     

Ion angular distributions in electron stimulated desorption: Oxygen and CO on W(111)

The ion angular distributions resulting from electron stimulated desorption (ESD) of oxygen and carbon monoxide chemisorbed on a tungsten (111) crystal have been determined. The O⁺ ions released during ESD of adsorbed oxygen exhibit three-fold symmetric angular distributions in orientational registry with the W(111) substrate. The CO⁺ and O⁺ ions released during ESD of a monolayer of CO are desorbed normal to the (111) surface. Models for both oxygen and CO adsorption are discussed. The data for CO are consistent with adsorption of CO in “standing up” carbonyl structures in the virgin and α-CO binding states.     

The transition from the ordered to the merohedral disordered phase in oxygenated solid C60

C₆₀ powder, pellets and single crystals were oxygenated at 0.11 kbar and then studied with MAS ¹³C NMR, DSC and XRD. In agreement with reports by other authors, powder samples exhibited minor NMR resonances, indicative of blocking of fullerene rotation by interstitial oxygen, the distribution of which had yet to attain the equilibrium state. Also, as reported by others, DSC showed two endothermic peaks near 260 K, and both, we found, corresponded to a discontinuous change in the lattice parameter. The peak on the low-temperature side moved up in temperature with elapsed time. Pellets, in which presumably oxygen diffused easily, displayed only one peak but shifted in the same manner. Single crystals, in contrast, had only the higher-temperature “immobile” peak. We suggest that the shifting endotherm originates from the transition of oxygen-intercalated C₆₀ to a merohedral disordered phase, in which the rotation of fullerene molecules is partially impeded by oxygen. A phenomenological model is proposed for this transition.     

Photodesorption studies of adsorbate covered aluminum surfaces

Strong low photon energy photodesorption has been observed from aluminum samples exposed to CO and CO₂ and on aluminum oxide samples with carbon contamination. For these systems only CO₂ has been observed to photodesorb with similar energy thresholds (≈ 3.65 eV) and similar yields (≈ 5 × 10⁻⁵ molecules/photon) for all samples. The data does not support the band-gap mechanism for desorption from semiconductors/insulators.     

Interaction of O2 with low index faces of α-CuZn

The adsorption of O₂ and initial step of oxidation have been investigated, mainly at room temperature, for three different α-CuZn (75%Cu/25%Zn) surfaces ((110), (100) and (111)) by XPS. XAES, LEED, CPD and HREELS. No superstructures were detected on the LEED patterns during O₂ admission for the three faces, and from the beginning of adsorption Zn segregated to the surface. For (110), the interaction of oxygen follows the sequence: (1) dissociative chemisorption (up to ~ 20 L), accompanied by an increase of the work function and a single site occupancy as revealed by HREELS; (2) nucleation of ZnO only, indicated by a decrease of the work function, a shift of the Zn L₃M₄₅M₄₅ Auger transition and an emergence of a vibration at 550 cm^?1. corresponding to the surface phonon of ZnO. The (111) face follows the same scheme, except that the sticking coefficient for oxygen is very low. For (100), it is clear that two states of oxygen exist simultaneously, even at the beginning, as revealed by HREELS and CPD measurements. No copper oxides are ever detected, even after heat treatment. In addition, different bonding properties of OH groups on the three surfaces are reported.     

Dynamics of fractoluminescence and electromagnetic and acoustic emission upon an impact against the marble surface

The blow of a steel striker against the marble surface induces strain waves and electromagnetic emission. Simultaneously, microcracks appear in the marble single crystal with excited free CO ₂ ^? radicals at the microcrack banks. Relaxation of electronic excitation leads to the emergence of fractoluminescence bursts. The burst intensity is proportional to the area of the microcrack surfaces. Measurements show that the linear size of the microcracks varies from ～2 to ～47 μm.     

Angular distribution of the desorption of CO2 produced on Pt(111) surface at low temperatures

A new CO₂ formation process was observed in the CO oxidation over Pt(111) surface below 200 K. The desorption flux of the product CO₂, which is formed from the interaction between chemisorbed CO and adsorbed oxygen molecules O₂^2? (a), showed a very sharp angular distribution along the surface normal.