Quantum size effect in low energy electron diffraction of thin films

Low energy electron microscopy (LEEM) is used to study the quantum size effect (QSE) in electron reflectivity from thin films. Strong QSE interference peaks are seen below 20 eV for Cu and Ag films on the W(1 1 0) surface and Sb films on the Mo(0 0 1) surface. Simple inspection of QSE interference peaks reveals that all three metals grow atomic layer-by-atomic layer. Layer-specific I(V) spectra obtained with LEEM permit structural analysis by full dynamical multiple scattering LEED calculations for a layer-by-layer view of thin film structure.     

Irradiation induced modifications in morphology and magnetic property of Mn/Si structure

Mn films of ∼50 nm has been deposited by electron beam evaporation technique on cleaned and etched Si [(1 0 0), 8–10 Ω cm] substrates to realize a Mn/Si interfacial structures. The structures have been irradiated from energetic (∼100 MeV) ion beam from Mn side. The irradiated and unirradiated structures have been characterized from atomic force microscopy, X-ray diffractometry, magnetic force microscopy, and vibrating sample magnetometer facilities. It has been found that surface/interfacial granular silicide phases (of Mn_xSi_y) are formed before and after the irradiation with a irradiation induced modifications of surface morphology and magnetic property. The surface/interface roughness has been found to increase on the irradiation from the atomic force microscopy data. The magnetic property on the irradiation shows an interesting and significant feature of an increased coercivity and a ferromagnetic like behavior in the Mn–Si structure. The observed increased coercivity has been related to the increased roughness on the irradiation. The ferromagnetism after the irradiation is a curious phenomenon which seems due to the formation of Mn–C–Si compound from the carbon dissolved in silicon.     

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.     

Annealing temperature dependent on structural,optical and electrical properties of indium oxide thin films deposited by electron beam evaporation method

In the present work the influence of annealing temperature on the structural and optical properties of the In₂O₃ films deposited by electron beam evaporation technique in the presence of oxygen was studied. The deposited films were annealed from 350 to 550 °C in air. The chemical compositions of In₂O₃ films were carried out by X-ray photoelectron spectroscopy (XPS). The film structure and surface morphologies were investigated as a function of annealing temperature by X-ray diffraction (XRD) and atomic force microscopy (AFM). The structural studies by XRD reveal that films exhibit preferential orientation along (2 2 2) plane. The refractive index (n), packing density and porosity (%) of films were arrived from transmittance spectral data obtained in the range 250–1000 nm by UV–vis-spectrometer. The optical band gap of In₂O₃ film was observed and found to be varying from 3.67 to 3.85 eV with the annealing temperature.     

Physical properties of vacuum evaporated CdTe thin films with post-deposition thermal annealing

This paper presents the physical properties of vacuum evaporated CdTe thin films with post-deposition thermal annealing. The thin films of thickness 500 nm were grown on glass and indium tin oxide (ITO) coated glass substrates employing thermal vacuum evaporation technique followed by post-deposition thermal annealing at temperature 450 °C. These films were subjected to the X-ray diffraction (XRD),UV-Vis spectrophotometer, source meter and atomic force microscopy (AFM) for structural, optical, electrical and surface morphological analysis respectively. The X-ray diffraction patterns reveal that the films have zinc-blende structure of single cubic phase with preferred orientation (111) and polycrystalline in nature. The crystallographic and optical parameters are calculated and discussed in brief. The optical band gap is found to be 1.62 eV and 1.52 eV for as-grown and annealed films respectively. The I–V characteristics show that the conductivity is decreased for annealed thin films. The AFM studies reveal that the surface roughness is observed to be increased for thermally annealed films.     

Synthesis of nanocrystalline ZnO nanobelts via pyrolytic decomposition of zinc acetate nanobelts and their gas sensing behavior

The pyrolytic decomposition of layered basic zinc acetate (LBZA) nanobelts (NBs) into nanocrystalline ZnO NBs is investigated using scanning electron microscopy (SEM), atomic force microscopy (AFM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and photoluminescence (PL). We also report on the gas sensing response of the resulting ZnO nanomaterial to CO. The LBZA NBs are grown at 65 °C in an aqueous solution of zinc acetate dihydrate. AFM and SEM results show as-grown products possess the characteristic layered structure of the LBZA crystals. XRD and XPS results show that annealing as-grown products at 210 °C in air causes a transformation from zinc acetate to nanocrystalline ZnO NBs via thermal decomposition. The ZnO crystalline domain size increases with temperature from 9.2 nm at 200 °C to 94 nm at 1000 °C, as measured from XRD. SEM shows evidence of sintering at 600 °C. The thickness of the NBs, determined via AFM, ranges from 10 to 50 nm and remains approximately constant with annealing temperature. XPS confirmed the chemical transformation from zinc acetate to ZnO and showed a significant remaining zinc hydroxide component for the ZnO NBs consistent with published results. PL measurements at room temperature show a blue shift in peak emission as the nanobelts change from LBZA to ZnO at 200 °C. Above this transition temperature, the ZnO nanobelts possess strong band edge emission at 390 nm and little broad band emission in the visible region. The AFM and SEM images reveal that the crystallites within the nanobelts orientate in rows along the long axis during annealing. This structure provides a high surface area to volume ratio of aligned nanoparticles which is beneficial for gas sensing applications. Gas sensors fabricated from 400 °C annealed nanobelts showed a response of 1.62 when exposed to 200 ppm of CO in dry air at 400 °C, as defined by the ratio of resistance before and during exposure. This indicates that ZnO nanostructures obtained by thermal decomposition of LBZA NBs could provide a cost effective route to high sensitivity gas sensors.     

Study of Schottky contact between Au and NiO nanowire by conductive atomic force microscopy (C-AFM): The case of surface states

In this work, NiO nanowires have been synthesized by a hydrothermal reaction of NiCl₂ with Na₂C₂O₄ in the presence of ethylene glycol at 180 °C for 12 h, then calcinated at 400 °C for 2 h. The NiO nanowires were analyzed by means of scanning electron microscope (SEM), atomic force microscope (AFM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The resulting current–voltage (I–V) characteristics of the NiO nanowires exhibited a clear rectifying behavior. This rectify behavior was attributed to the formation of a Schottky contact between Au coated atomic force microscopy (AFM) tip and NiO nanowires (nano-M/SC) which was dominated by the surface states in NiO itself. Photo-assisted conductive AFM (PC-AFM) was used to demonstrate how the I–V characteristics are influenced by the surface states. Our I–V results also showed that the nano-M/SCs had a good photoelectric switching effect at reverse bias.     

Band diagram for chemical vapor deposition diamond surface conductive layer: Presence of downward band bending due to shallow acceptors

The properties of surface conductivity (SC) of impurity-non-doped CVD diamond (001) samples were studied by various methods of sheet-resistance (R_S) measurement, Hall-effect measurement, XPS, UPS, SES, SR-PES, PEEM and 1D band simulation taking into account special emphases on deriving the information about the surface band diagram (SBD). The R_S values in UHV conditions were determined after no-annealing or 200 ～ 300 °C annealing in UHV. C 1 s XPS profiles were measured in detail in bulk-sensitive and surface-sensitive modes of photoelectron detection. The energy positions of valence band top (E_V) relative to the Fermi level (E_F) in UHV conditions after no-annealing or 200 ～ 300 °C annealing in UHV were determined. One of the samples was subjected to SR-PES, PEEM measurements. The SBDs were simulated by a band simulator from the determined R_S and E_V ? E_F values for three samples based on the two models of surface conductivity, namely, so-called surface transfer doping (STD) model and downward band bending with shallow acceptor (DBB/SA) model. For the DBB/SA model, there appeared downward bends of SBDs toward the surface at a depth range of ～ 1 nm. C 1 s XPS profiles were then simulated from the simulated SBDs. Comparison of simulated C 1 s XPS profiles to the experimental ones showed that DBB/SA model reproduces the C 1 s XPS profiles properly. PEEM observation of a sample can be explained by the SBD based on the DBB/SA model. Mechanism of SC of CVD diamonds is discussed on the basis of these findings. It is suggested that the STD model combined with SBD of DBB/SA model explains the surface conductivity change due to environmental changes in actual cases of CVD diamond SC with the presence of surface E_F controlling defects.     

Dynamical LEED analyses of the clean and the NO-adsorbed Ir(111) surface

The adsorption structure of nitric oxide (NO) on Ir(111) was studied by thermal desorption spectroscopy (TDS) and dynamical analyses of low-energy electron diffraction (LEED). At the saturation coverage at about 100 K, a 2 × 2 pattern was observed by LEED and two peaks appeared at 365 and 415 K in TDS. No change in the LEED I–V curves was observed by annealing at 280 K, which means that the NO-saturated surface was retained at this temperature. On the contrary, partial desorption and changes of the LEED I–V curves were observed by annealing at 360 K. Combined with previous vibrational studies, it is suggested that one adsorption species is not affected, while another species is partially desorbed and the rest of them are dissociated by annealing at 360 K. Dynamical analyses of LEED were performed for the 280 K-annealed and the 360 K-annealed surfaces, which correspond to the NO-saturated and the NO-dissociated Ir(111) surfaces, respectively. These revealed that NO occupies the atop, fcc-hollow and hcp-hollow sites (atop-NO + fcc-NO + hcp-NO) for the NO-saturated Ir(111) surface with the saturation coverage of 0.75 ML. For the 360 K-annealed surface, the atop-NO is not affected but the fcc-NO and the hcp-NO are partially desorbed as NO and partially dissociated to N and O, both of which occupy the fcc-hollow site on the surface.     

Ultrasonic assisted synthesis,characterization and influence factors of monodispersed dumbbell-like YF3 nanostructures

In the present paper, we reported the successful synthesis of dumbbell-like YF₃ nanostructures with a high yield in a mixed system of water/N,N-dimethylformamide (DMF) under the assistance of ultrasound waves of 40 kHz with the ultrasonic power of 100% (200 W) at 65 °C for 2 h, employing Y₂O₃ (99.99%) and NH₄F as the starting reactants. The product was characterized by means of powder X-ray diffraction (XRD), energy dispersive spectrometry (EDS), transmission electron microscopy (TEM), selected area electron diffraction (SAED) pattern and field-emission scanning electron microscopy (SEM). Some factors influencing the morphology of YF₃ nanostructures, including the ultrasonic time and power, the amount of NH₄F, and the ratio of water/DMF, were systematically investigated. Research showed that the morphology of YF₃ could be tuned by the volume ratio of water/DMF. The roles of DMF and the ultrasonic wave in the formation of YF₃ nanostructures were discussed.     

Effect of Fe doping on the structural and gas sensing properties of ZnO porous microspheres

Fe-doped ZnO porous microspheres composed of nanosheets were prepared by a simple hydrothermal method combined with post-annealing, and characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), Brunauer–Emmett–Teller N₂ adsorption–desorption measurements and photoluminescence (PL) spectra. In this paper we report Fe doping induced modifications in the structural, photoluminescence and gas sensing behavior of ZnO porous microspheres. Our results show that the crystallite size decreases and specific surface area increases with the increase of Fe doping concentration. The PL spectra indicate that the 4 mol% Fe-doped ZnO has higher ratio of donor (V_O and Zn_i) to acceptor (V_Zn) than undoped ZnO. The 4 mol% Fe-doped ZnO sample shows the highest response value to ppb-level n-butanol at 300 °C, and the detected limit of n-butanol is below 10 ppb. In addition, the 4 mol% Fe -doped ZnO sample exhibits good selectivity to n-butanol. The superior sensing properties of the Fe-doped porous ZnO microspheres are contributed to higher donor defects contents combined with larger specific surface area.     

Effect of nanocrystallization on the electronic conductivity of vanadate–phosphate glasses

Electronically conducting glasses of the composition xV₂O₅·(100 − x)P₂O₅ for 60 < x < 90 were prepared. The glasses of the composition corresponding to x = 90 exhibited the highest electrical conductivity and they were studied in more detail. The effects of the annealing of the samples on their electrical conductivity, structure and other characteristics were studied by impedance spectroscopy, X-ray diffractometry, DSC and SEM microscopy. It was shown that, at temperatures close to the crystallization temperature T_c (determined from DSC), these glasses turned into nanomaterials consisting of crystalline grains of V₂O₅ (average size 25–35 nm) embedded in the glassy matrix. Their electrical conductivity was higher and the temperature stability was better than those of the starting glasses. It is postulated that the major role in this conductivity enhancement is played by the interfacial regions between crystalline and amorphous phases. The annealing at temperatures exceeding T_c led to massive crystallization and to a conductivity drop. The XRD and SEM observations have shown that the material under study undergoes structural changes: from amorphous at the beginning, to partly crystalline after the annealing at 340 °C and to polycrystalline after the annealing at 530 °C.The obtained results are in agreement with those of our earlier studies on mixed electronic–ionic conducting glasses of the ternary Li₂O–V₂O₅–P₂O₅ system.     

Disorder driven optical processes in nanocrystalline ZnO

A systematic study on the modification of optical properties in mechanically milled ZnO powder has been reported here. The average grain size of the powder becomes ～20 nm within 4 h of milling. Fluctuations of average grain size have been noticed at the initial stage of milling (within 15 min). Changes in grain morphology with milling have also been noticed in scanning electron micrographs of the samples. Room temperature optical absorption data shows a systematic red shift of absorption band edge (～3.25 eV). The band tail parameter (extracted from the optical absorption just below the band edge) follows a simple exponential relation with the inverse of the average grain size. Significant increase of the band tail parameter has been noticed at low grain size regime. It has been analyzed that high values of band tail parameter is a representative of V_Zn–V_O type divacancy clusters. Room temperature photoluminescence spectra show decrease (except for 120 min milling) of band edge emission intensity with increase of milling time. Subsequent decrease of sub-band edge emission is, however, less prominent. The variation of PL intensity ratio (intensity at band edge peak with that at 2.3 eV) follows simple exponential decrease with the increase of band tail parameter. This indeed shows that band edge emission in ZnO is related with the overall disorder in the system, not grain size induced only.     

Preparation of magnetic FeCo nanoparticles by coprecipitation route

Magnetic FeCo nanoparticles with high saturation magnetization (M_s = 148 emu/g) at 15 kOe were prepared by a coprecipitation route. The value of M_s for FeCo nanoparticles depends on the ratio of Fe to Co components. The size of the nanoparticles was confirmed by transmission electron microscopy (TEM) images, and morphology of the nanoparticles was obtained by field emission scanning electron microscopy (FE-SEM) images. The crystal structure of the nanoparticles dependent on annealing was characterized by X-ray diffraction data. The magnetic properties were characterized by saturation magnetization from a hysteresis loop by VSM.     

Dielectric,optical and structural properties of Bi4V2−xSrxO11−δ (0.05≤x≤0.20)

Composition Bi₄V_2−xSr_xO_11−δ (0.05≤x≤0.20) is synthesized by melt quench technique followed by heat treatment at 800 °C for 12 h. These compounds are characterised by X-ray diffraction, Fourier transform infrared (FTIR) spectroscopy, UV–visible spectroscopy, impedance spectroscopy and scanning electron microscopy. X-ray diffraction patterns of all the samples show γ-phase stabilization at room temperature except x=0.05 heat treated sample. The optical band gap of all the samples is observed in semiconducting range. The lowest and the highest optical band gap is 2.39 eV and 2.57 eV for x=0.10 heat treated and x=0.20 quenched samples, respectively. The highest value of dielectric constant is obtained ~10⁷ with very low dielectric loss for x=0.15 and 0.20 samples at ~350 °C and below 10 Hz. The grain size increases with dopant concentration leads to increase the dielectric constant.     

Atomic surface diffusion on Pt nanoparticles quantified by high-resolution transmission electron microscopy

Aberration-corrected high-resolution transmission electron microscopy allows for the delocalization-free observation of atomic motions on metallic surfaces and thus enables measurements of the diffusion of single atoms on the surfaces of nanoscopic objects such as nanoparticles. Using this recently introduced method, the diffusion coefficient for surface self-diffusion of Pt nanoparticles is determined through the fluctuating occupation of the particle's atomic columns. This diffusion coefficient is determined to lie in the range D ∼ (10⁻¹⁷ … 10⁻¹⁶) cm²/s.     

Magnetic properties of iron nanoparticles in a polymer film

We systematically synthesized self-aggregated iron nanoparticles in the perfluorinated sulfo-cation membrane (MF-4SK) by ion-exchange method. Our experimental results show that iron nanoparticles in MF-4SK exhibit superparamagnetic properties above the blocking temperature. Field-cooled and zero-field-cooled magnetization data show the blocking temperature, T_B≅120 K for the iron concentration of 5×10¹⁹ atoms per 1 g of polymer film at 500 Oe applied field. This result is well matched with the calculation based on the temperature dependence of the coercivity, which shows T_B≅110 K, with the zero temperature coercivity (H_C0) ≅ 420 Oe. The radius of the typical iron particle is determined to be ∼2 nm from transmission electron microscopy (TEM), showing good agreement with the value acquired by Langevin function fit. These experimental evidences suggest that iron nanoparticles in the polymer film obey a single-domain theory.     

Improved electrical parameters of vacuum annealed Ni/4H-SiC (0 0 0 1) Schottky barrier diode

The reported work has been focused on the improvement of electrical parameters of Schottky diode using vacuum annealing at mild temperature in Ar gas ambient. Nickel Schottky barrier diodes were fabricated on 50 μm epitaxial layer of n-type 4H-SiC (0 0 0 1) substrate. The values of leakage current, Schottky barrier height (?_B), ideality factor (η) and density of interface states (N_SS) were obtained from experimentally measured current–voltage (I–V) and capacitance–voltage (C–V) characteristics before and after vacuum annealing treatment. The data revealed that ?_B, η and reverse leakage current for the as-processed diodes are 1.25 eV, 1.6 and 1.2 nA (at ?100 V), respectively, while for vacuum annealed diodes these parameters are 1.36 eV, 1.3 and 900 pA (at same reverse voltage). Improved characteristics have been resulted under the influence of vacuum annealing because of lesser number of minority carrier generation due to incessant reduction of number of available discrete energy levels in the bandgap of 4H-SiC substrate and lesser number of interface states density at Ni/4H-SiC (0 0 0 1) interface.     

The role of passive potential in ultrasonic cavitation erosion of titanium in 1 M HCl solution

The influence of the applied passive potential on the ultrasonic cavitation erosion of Ti specimen in 1 M HCl solution was investigated by mass loss experiment, scanning electron microscopy (SEM), electrochemical impedance spectra (EIS) and Mott–Schottky plot. The results showed that Ti was in the passive state within the potential region from −0.3 V_SCE to 1.5 V_SCE under ultrasonic cavitation erosion. The applied passive potential can obviously decrease the mass loss of Ti caused by ultrasonic cavitation erosion in 1 M HCl solution. The resistance of the passive film increased, the flat band potential moved to positive direction, and the donor density of the passive film decreased with increasing the passive potential. Finally, a physical model was provided to explain the experimental results based on energy band and semi-conductive theories.     

Effect of calcination temperature on phase transformation,structural and optical properties of sol–gel derived ZrO2 nanostructures

Zirconia (ZrO₂) nanostructures of various sizes have been synthesized using sol–gel method followed by calcination of the samples from 500 to 700 °C. The calcined ZrO₂ powder samples were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), Fourier-transform infra-red spectroscopy (FT-IR), UV–visible spectroscopy (UV–vis.), Raman spectroscopy (RS) and thermogravimetric analysis (TGA). The phase transformation from tetragonal (t) to monoclinic (m) was observed. The average diameter of the ZrO₂ nanostructures calcined at 500, 600 and 700 °C was calculated to be 8, 17 and 10 nm, respectively. The ZrO₂ sample calcined at 500 °C with tetragonal phase shows a direct optical band gap of 5.1 eV. The value of optical band gap is decreased to 4.3 eV for the ZrO₂ calcined at 600 °C, which contains both tetragonal (73%) and monoclinic (27%) phases. On further calcination at 700 °C, where the ZrO₂ nanostructures have 36% tetragonal and 64% monoclinic phases, the optical band gap is calculated to be 4.8 eV. The enhancement in optical band gap for ZrO₂ calcined at 700 °C may be due to the rod like shape of ZrO₂ nanostructures. The tetragonal to monoclinic phase transformation was also confirmed by analyzing Raman spectroscopic data. The TG analysis revealed that the ZrO₂ nanostructure with dominance of monoclinic phase is found to be more stable over the tetragonal phase. In order to confirm the phase stability of the two phases of ZrO₂, single point energy is calculated corresponding to its monoclinic and tetragonal structures using density functional theory (DFT) calculations. The results obtained by theoretical calculations are in good agreement with the experimental findings.