Adsorption of O2 and CO2 on the Si(111)-7 × 7 surfaces

The interaction of O₂ and CO₂ with the Si(111)-7 × 7 surface has been studied with X-ray photoelectron spectroscopy (XPS). It was found that both O₂ and CO₂ molecules can readily oxidize the Si(111)-7 × 7 surface to form thin oxide films. Two oxygen species were identified in the oxide film: oxygen atoms binding to on-top sites of adatom/rest atoms with an O 1s binding energy of ~ 533 eV as well as to bridge sites of adatom/rest atom backbonds at ~ 532 eV. These two oxygen species can be interconverted thermally during the annealing process. Due to the low oxidation capability, the silicon oxide film formed by CO₂ has a lower O/Si ratio than that of O₂.     

Preparation and characterization of highly conducting and transparent Al doped CdO thin films by pulsed laser deposition

Highly conducting and transparent aluminum doped CdO thin films were deposited using pulsed laser deposition technique. The effect of growth temperature on structural, electrical, and optical properties was studied. It is observed that the film orientation changes from preferred (1 1 1) plane to (2 0 0) plane with increase in growth temperature. The electrical resistivity of the films was found to increase with increase in growth temperature. The low resistivity of 4.3 × 10⁻⁵ Ω cm and high transparency (∼85%) was obtained for the film grown at 150 °C. The band gap of the films varies from 2.74 eV to 2.84 eV.     

Characterization of luminescent chromophore obtained from silica spheres

Blue light emitting chromophores have been separated from silica spheres by soaking them into acetone for 120 days. The luminescent chromophores were not obtained from other solvents, including ether, methanol, ethanol, 2-propanol, chloroform and tetrahydrofuran. According to the Fourier transform infrared spectrum, the luminescent material is composed of C–OH, –CH₂, –CH₃, C=O, and Si–O–Si. UV–visible absorption peak of the chromophore is at 5.17 eV (240 nm). Field emission scanning electron microscope images show small cracks on the surface of aged spheres. The luminescence peak was at 2.81 eV (441 nm) for excitation energy between 3.88 and 3.35 eV and slightly shifted toward lower energy for excitation energy lower than 3.35 eV. The deconvoluted luminescent spectrum shows two emission bands at 3.08 and 2.74 eV, which are well-matched the oxygen deficient center model. Compared to the absorption peak (5.17 eV) and the emission peak (2.81 eV), large Stokes shift (2.36 eV) is observed.     

Characterization on electron beam evaporated α-MoO3 thin films by the influence of substrate temperature

Electrochromic molybdenum oxide (MoO₃) thin films were prepared by electron beam evaporation technique using the dry MoO₃ pellets. The films were deposited on glass and fluorine doped tin oxide (SnO₂:F or FTO) coated glass substrates at different substrate temperatures like room temperature (RT, 30 °C), 100 °C and 200 °C. The influence of substrate temperature on the structural, surface morphological and optical properties of the films has been studied. The X-ray diffraction analysis showed that the films are having orthorhombic phase MoO₃ (α-MoO₃) with 〈1 1 0〉 preferred orientation. The laser Raman scattering spectrum shows the polycrystalline nature of MoO₃ films deposited at 200 °C. The Raman-active band at 993 cm⁻¹ is corresponding to Mo–O stretching mode that is associated with the unique character of the layered structure of orthorhombic MoO₃. Needle—like morphology was observed from the SEM analysis. The energy band gap of MoO₃ films was evaluated which lies between 2.8 and 2.3 eV depending on the substrate temperature and substrates. The decrease in band gap value with increasing substrate temperature is owing to the oxygen-ion vacancies. The absorption edge shift shows the coloration effect on the films.     

Synthesis and characterization of sulfur-containing polyacetylene derivative: Synthesis of poly(phenyl propargyl sulfide) and its electro-optical properties

Sulfur-containing conjugated polymer was synthesized by the polymerization of phenyl propargyl sulfide by transition metal catalysts such as PdCl₂, RuCl₃, (NBD)PdCl₂, WCl₆, and MoCl₅. The polymerization proceeded well in homogeneous manner to give a moderate yield of polymer. The chemical structure of poly(phenyl propargyl sulfide) was characterized by NMR (¹H–, ¹³C–), IR, and UV–visible spectroscopy, and elemental analysis to have the conjugated polymer backbone with the designed moieties. The FT-IR spectra of the polymer did not show the acetylenic CC bond stretching (2119 cm⁻¹) and acetylenic C–H bond stretching (3293 cm⁻¹) frequencies of the monomer. The thin polymer film exhibited reversible electrochemical behaviors between the doping and undoping peaks. Poly(phenyl propargyl sulfide) showed the characteristic UV–visible absorption band at 360 nm and blue PL spectrum at 460 nm, corresponding to the photon energy of 2.70 eV. The energy band gap of poly(PPS) was estimated to be 2.77 eV from the analysis of the absorption edge.     

High quality nitrogen-doped zinc oxide thin films grown on ITO by sol–gel method

Highly transparent N-doped ZnO thin films were deposited on ITO coated corning glass substrate by sol–gel method. Ammonium nitrate was used as a dopant source of N with varying the doping concentration 0, 0.5, 1.0, 2.0 and 3.0 at%. The DSC analysis of prepared NZO sols is observed a phase transition at 150 °C. X-ray diffraction pattern showed the preferred (002) peak of ZnO, which was deteriorated with increased N concentrations. The transmittance of NZO thin films was observed to be ~88%. The bandgap of NZO thin films increased from 3.28 to 3.70 eV with increased N concentration from 0 to 3 at%. The maximum carrier concentration 8.36×10¹⁷ cm⁻³ and minimum resistivity 1.64 Ω cm was observed for 3 at% N doped ZnO thin films deposited on glass substrate. These highly transparent ZnO thin films can be used as a window layer in solar cells and optoelectronic devices.     

Modifications in physical,optical and electrical properties of tin oxide by swift heavy Au8+ ion bombardment

Tin oxide thin films were deposited by a novel technique called as modified-SILAR. The preparative parameters were optimized to obtain good quality thin films. As-deposited films were annealed in O₂ atmosphere for 1 h at 500 °C. The annealed films were irradiated using Au⁸⁺ ions with energy of 100 MeV at different fluencies of 1 × 10¹¹, 1 × 10¹², 5 × 10¹² and 1 × 10¹³ ions/cm² using tandem pelletron accelerator. The irradiation-induced modifications in tin oxide thin films were studied using XRD, AFM, optical band gap, photoluminescence and I–V measurements. XRD studies showed formation of tin oxide with tetragonal structure. AFM revealed uniform deposition of the material with increase in grain size after irradiation. Decrease in band gap from 3.51 eV to 2.82 eV was seen with increases in fluency. A decrease in PL intensity, and an additional peak was observed after irradiation. I–V measurements showed a decrease in resistance with fluency.     

Oxygen species on the silver surface oxidized by MW-discharge: Study by photoelectron spectroscopy and DFT model calculations

A polycrystalline silver surface has been studied by synchrotron radiation photoelectron spectroscopy after deep oxidation by microwave discharge in an O₂ atmosphere. Oxidized structures with high oxygen content, AgO_x with x > 1, have been found on the silver surface after oxidation at 300–400 K. The line shapes observed in the O1s spectra were decomposed into five components and indicated that complex oxidized species were formed. An analysis of the oxidized structures with binding energies, Е_b(O1s), greater than 530 eV pointed to the presence of both Ag–O and O–O bonds. We have carried out a detailed experimental study of the valence band spectra in a wide spectral range (up to 35 eV), which has allowed us to register the multicomponent structure of spectra below Ag4d band. These features were assigned to the formation of Ag–O and O–O bonds composed of molecular (associative) oxygen species. DFT model calculations showed that saturation of the defect oxidized silver surface with oxygen leads to the formation of associative oxygen species, such as superoxides, with electrophilic properties and covalent bonding. The high stability of oxygen-rich silver structures, AgO_x, can be explained by the formation of small silver particles during the intensive MW oxidation, which can stabilize such oxygen species.     

Diffusion and chemical composition of TiNxOy thin films studied by Rutherford Backscattering Spectroscopy

Thickness and chemical composition of the TiN_xO_y thin films deposited by reactive magnetron sputtering from Ti target at controllable oxygen flow rate were determined by Rutherford Backscattering Spectroscopy (RBS) using 2 MeV He⁺ ions. The films were deposited on carbon foils and amorphous silica (a-SiO₂) substrates at 25 °C and 250 °C. The estimated film thickness is of 75-100 nm. The O/Ti atomic ratio in the films increases up to 1.5 with increasing oxygen flow rate, while that of N/Ti decreases from about 1.1 for TiN to 0.4 at the highest oxygen flow rate. Substantial out-diffusion of carbon from the substrate is observed which is independent of the substrate temperature. Films grown onto a-SiO₂ substrates can be treated as homogeneous single layers without interdiffusion. It is more difficult to determine the nitrogen and oxygen content due to superposition of RBS signals arising from film and substrate. RBS analysis of the depth profile indicates that for the investigated films the carbon diffusion and oxidation not only at the topmost surface layers but over the bulk of the films were found. Comparison with XPS results indicates substantial oxygen adsorption at the surface of TiN_x thin films obtained at zero oxygen flow rate.     

Structural and optical properties of La-doped BaSnO3 thin films grown by PLD

In this study the structural and optical properties of lanthanum-doped BaSnO₃ powder samples and thin films deposited on fused silica were investigaed using laser ablation. Under an oxygen pressure of 5×10⁻⁴ mbar, phase pure BaSnO₃ films with a lattice constant of 0.417 nm and grain size of 21 nm were prepared at 630 °C. The band gap of BaSnO3 powder sample and thin films was calculated to be 3.36 eV and 3.67 eV, respectively. There was a progressive increase in conductivity for thin films of BaSnO₃ doped with 0~7 at% of La. The highest conductivity, 9 Scm⁻¹, was obtained for 7 at% La-doped BaSnO₃. Carrier concentration, obtained from Burstein-Moss (B-M) shift, nearly matches the measured values except for 3 at% and 10 at% La-doped BaSnO₃ thin films.     

Influence of rapid thermal annealing on electrical and structural properties of double metal structure Au/Ni/n-InP (1 1 1) diodes

The effect of rapid thermal annealing on the electrical and structural properties of Ni/Au Schottky contacts on n-InP have been investigated by current–voltage (I–V), capacitance–voltage (C–V), auger electron spectroscopy (AES) and X-ray diffraction (XRD) techniques. The Au/Ni/n-InP Schottky contacts are rapid thermally annealed in the temperature range of 200–500 °C for a duration of 1 min. The Schottky barrier height of as-deposited Ni/Au Schottky contact has been found to be 0.50 eV (I–V) and 0.86 eV (C–V), respectively. It has been found that the Schottky barrier height decreased with increasing annealing temperature as compared to as-deposited sample. The barrier height values obtained are 0.43 eV (I–V), 0.72 eV (C–V) for the samples annealed at 200 °C, 0.45 eV (I–V) and 0.73 eV (C–V) for those at 400 °C. Further increase in annealing temperature to 500 °C the barrier height slightly increased to 0.46 eV (I–V) and 0.78 eV (C–V) compared to the values obtained for the samples annealed at 200 °C and 400 °C. AES and XRD studies showed the formation of indium phases at the Ni/Au and InP interface and may be the reason for the increase in barrier height. The AFM results showed that there is no significant degradation in the surface morphology (rms roughness of 1.56 nm) of the contact even after annealing at 500 °C.     

Surface stoichiometry of La0.7Sr0.3MnO3 during in vacuo preparation; A synchrotron photoemission study

We present a study of the surface stoichiometry and contamination of La_0.7Sr_0.3MnO₃ thin films following exposure to air and subsequent in vacuo preparation. Samples were studied using both soft X-ray synchrotron photoemission (hν = 150 to 350 eV) and traditional Mg-Kα XPS (hν = 1253.6 eV) whilst annealing incrementally to ≈ 510°C in low pressures of O₂. In all cases, a Mn depleted and Sr rich surface oxide layer is observed, it is of reduced crystalline quality and is charge depleted. This surface layer is weakly affected by subsequent annealing, and is partially reversed by annealing in higher O₂ pressure. Surface carbon contamination is incrementally removed by annealing at increased temperatures, and at 270 °C, it is reduced to ≈ 0.4% of the topmost unit cell. The modification of the surface stoichiometry and electronic properties is consistent with the reported loss of magnetic properties in thin LSMO films.     

Relative reactivities of amino and ethenyl groups in allylamine on Si(100)2 × 1: Temperature-dependent X-ray photoemission and thermal desorption studies of a common linker molecule

The room-temperature adsorption and thermal evolution of allylamine on Si(100)2 × 1 have been investigated by using temperature-dependent X-ray photoelectron spectroscopy (XPS) and thermal desorption spectrometry (TDS). The presence of a broad N 1 s feature at 398.9 eV, attributed to a N―Si bond, indicates N―H dissociative adsorption. On the other hand, the presence of C 1 s features at 284.6 eV and 286.2 eV, corresponding to C═C and C―N, respectively, and the absence of the Si―C feature expected at 283.2 eV shows that [2 + 2] C═C cycloaddition does not occur at room temperature. These XPS data are consistent with the unidentate staggered and eclipsed allylamine conformer adstructures arising from N―H dissociation and not [2 + 2] C═C cycloaddition. The apparent conversion of the N 1 s feature for Si―N(H)―C

at 398.9 eV to that for Si―N(H) at 397.7 eV and the total depletion of C 1 s feature for C―N at 286.2 eV near 740 K indicates cleavage of the C―N bond, leaving behind a Si―N(H) radical. Furthermore, the C═C C 1 s feature at 284.6 eV undergoes steep intensity reduction between 740 K and 825 K, above which a new C 1 s feature at 283.2 eV corresponding to SiC is found to emerge. These spectral changes suggest total dissociation of the ethenyl fragment and the formation of SiC. Moreover, while the total N 1 s intensity undergoes a minor reduction (24%) upon annealing up to 1090 K, a considerable reduction (43%) is found in the overall C 1 s intensity. This observation is consistent with our TDS data, which shows the desorption of C-containing molecules including propene and ethylene at 580 K and of acetylene at 700 K. The lack of N-containing desorbates suggests that the dissociated N species are likely bonded to multiple surface Si atoms or diffused into the bulk. Interestingly, both the staggered and eclipsed N―H dissociative adstructures are found to have a less negative adsorption energy than the [N, C, C] tridentate or the [2 + 2] C═C cycloaddition adstructures by our DFT calculations, which suggests that the observed formation of N―H dissociative adstructures is kinetically favored on the Si(100)2 × 1 surface.     

Correlation between sintering temperature and properties of ZnO ceramic varistors

The effect of sintering temperature on ZnO varistor properties is investigated in the range of 700–1400 °C. The increase of sintering temperature does not influence the well-known peaks related to hexagonal wurtzite structure of ZnO ceramics, whereas the average grain size is increased from (1.08 to 2.1 μm). With increasing sintering temperature up to 1200 °C, the nonlinear region is clearly observed in the I–V characteristics, whereas this region is completely absent only for the sample sintered at 1400 °C. As the sintering temperature increased, the breakdown field decreased over a wide range from 2838.7 to 6.41 V/cm, while the nonlinear coefficient is increased in the range of (23.86–47.76). Furthermore, the barrier height decreased from 1.76 to 0.974 eV, whereas electrical conductivity is improved. On the other hand, the optical band gap is gradually decreased in the range of 3.08–2.70 eV with increasing sintering temperature. These results showed a strong correlation between sintering temperature and the properties of ZnO ceramic varistor.     

Influence of ultrasonication times on the tunable colour emission of ZnO nanophosphors for lighting applications

This paper reports on the sonochemical synthesis of zinc oxide (ZnO) nanophosphors (NPr) at different ultrasonication times (5 min, 30 min, 1 h, 5 h, 10 h and 15 h) for near white light emission applications. X-ray photoelectron spectroscopy indicated that the O1s peak consists of two components. These were O1 (ZnO) and O2 (deficient oxygen; OH groups) centred at 529.7 ± 0.3 eV and 531.1 ± 0.3 eV, respectively. All samples showed UV and defect level emission (DLE). The DLE enhancement was due to the increase in oxygen related defects such as oxygen vacancies/interstitials. Due to the combination of near UV and DLE near white light emission in ZnO NPr was obtained. The emission could be tuned with different ultrasonic times. It was found that the ultrasonication time influenced the growth mechanism and luminescence properties of the ZnO NPr.     

A spectroscopic ellipsometry study of TiO2 thin films prepared by ion-assisted electron-beam evaporation

Film characterization based on variable-angle spectroscopic ellipsometry (VASE) is desirable in order to understand physical and optical characteristics of thin films. A number of TiO₂ film samples were prepared by ion-assisted electron-beam evaporation with 200-nm nominal thickness, 2.0 Å/s deposition rate and 8 sccm oxygen flow rate. The samples were maintained at 250 °C during the deposition, and annealed in air atmosphere afterwards. As-deposited and annealed films were analyzed by VASE, spectrophotoscopy and X-ray diffractometry. From ellipsometry modeling process, the triple-layer physical model and the Cody–Lorentz dispersion model offer the best results. The as-deposited films are inhomogeneous, with luminous transmittance and band gap of 62.37% and 2.95 eV. The 300 °C and 500 °C are transition temperatures toward anatase and rutile phases, respectively. Increasing temperature results in an increase of refractive index, transmittance percentage and band gap energy. At 500 °C, the highest refractive index and band gap energy are obtained at 2.62 and 3.26 eV, respectively. The developed VASE-modeling process should be able to characterize other TiO₂ films, using similar physical and optical modeling considerations.     

Simple one-step ultrasonic synthesis of anatase titania/polypyrrole nanocomposites

In this work, hybrid nanocomposites based on anatase titania:polypyrrole (TiO₂:PPy) were directly obtained from a simple, one-step, ultrasonic (UT)-assisted synthesis. The properties of these crystalline nanocomposites were compared with those of others fabricated using cold (Cold)-assisted synthesis without any UT assistance, which required a hydrothermal treatment (HT) to yield crystalline anatase titania in the nanocomposite (TiO₂:PPy) at low temperature (130 °C) and in a short time (3 h). The SEM results demonstrated that the UT-assisted synthesis is a feasible method to obtain anatase TiO₂:PPy nanocomposites with controlled morphology using low energy. The Fourier transform infrared (FT-IR) bands of the crystalline nanocomposites exhibited a shift with respect to neat components, which was attributed to the strong interaction between the secondary amine groups (N–H) of PPy and the oxygen from TiO₂. The acceptable absorption in the visible region (λ_max = 670 nm) indicates that these nanocomposites are good candidates for harvesting energy in solar cells. Devices based on these nanocomposites were built to evaluate their electrical properties. An increase in the photocurrent was observed for the devices prepared with the nanocomposites from the UT-assisted synthesis.     

Fabrication of Cu2O nanocrystalline thin films photosensor prepared by RF sputtering technique

Cuprous oxide (Cu₂O) nanocrystalline thin films were prepared on two types of substrates known as crystalline silicon and amorphous glass, by radio frequency reactive magnetron sputtering method. Scanning electron microscopy images confirmed that Cu₂O particles covered the entire surface of both substrates with smoothing distribution. The root mean square surface roughness for the prepared Cu₂O thin films on glass and Si (111) substrates is 4.16, and 3.36 nm, respectively. Meanwhile, X-ray diffraction results demonstrated that the two phases of Cu₂O and CuO were produced on Si (111) and glass substrates. The optical bandgap of Cu₂O thin films synthesised on glass substrate is 2.42 eV. Furthermore, the prepared Cu₂O nanocrystalline thin films have showed low reflectance value in the visible spectrum. Metal-Semiconductor-Metal photodetector based Cu₂O nanocrystalline thin films deposited onto Si (111) was fabricated using aluminium and platinum, with the current-voltage and photoresponse characteristic investigated under various applied bias voltages. The fabricated Metal-Semiconductor-Metal (M-S-M) photodetector had shown 126% sensitivity in the presence of 10 mW/cm² of 490 nm light with 1.0 V bias, displaying 90 and 100 ms response and recovery times, respectively. These findings have demonstrated the suitability of M-S-M Cu₂O photodetector as an affordable photosensor in the future.     

Activation of methyl acetate on Pd(111)

The adsorption and activation of methyl acetate (CH₃COOCH₃), one of the simplest carboxylic esters, on Pd(111) have been studied using self-consistent periodic density functional theory calculations. Methyl acetate adsorbs weakly through the carbonyl oxygen. Its activation occurs via dehydrogenation, instead of direct C–O bond dissociation, on clean Pd(111): It is much more difficult to dissociate the C–O bonds (E_a ≈ 2.0 eV for the carbonyl and acetate–methyl bonds; E_a = 1.0 eV for the acetyl–methoxy bond) than to dissociate the C–H bonds to produce enolate (CH₂COOCH₃; E_a = 0.74 eV) or methylene acetate (CH₃COOCH₂; E_a = 0.82 eV). The barriers for C–H and C–O bond dissociation are directly calculated for enolate and methylene acetate, and estimated for further dehydrogenated derivatives (CH₃COOCH, CH₂COOCH₂, and CHCOOCH₃) based on the Brønsted–Evans–Polanyi linear energy relations formed by the calculated steps. The enolate pathway leads to successive dehydrogenation to CCOOCH₃, whereas methylene acetate readily dissociates to yield acetyl. The selectivity for dissociating the acyl–alkoxy C–O bond, which is desired for alcohol formation, is therefore fundamentally limited by the facility of dehydrogenation under vacuum/low-pressure conditions on Pd(111).     

High c-axis preferred orientation ZnO thin films prepared by oxidation of metallic zinc

Thin films of zinc oxide were grown on glass substrates by thermal oxidation. The metallic zinc films were thermally oxidized at different temperatures ranging from 300 to 600 °C to yield ZnO thin films. The structural property of the thin films was characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The X-ray diffraction measurements showed that the films oxidized at 300 °C were not oxidized entirely, and the films deposited at 600 °C had better crystalline quality than the rest. When the oxidation temperature increased above 400 °C, the films exhibited preferred orientation along (002) and high transmittance ranging from 85% to 98% in vis–near-infrared band. Meanwhile, the films showed a UV emission at about 377 nm and green emission. With the increasing of oxidation temperature, the intensity of green emission peak was enhanced, and then decreased, disappearing at 600 °C, and the case of UV emission increased. Furthermore, a strong green emission was observed in the film sintered in pure oxygen atmosphere.