Field emission from patterned SnO2 nanostructures

A simple and reliable method has been developed for synthesizing finely patterned tin dioxide (SnO₂) nanostructure arrays on silicon substrates. A patterned Au catalyst film was prepared on the silicon wafer by radio frequency (RF) magnetron sputtering and photolithographic patterning processes. The patterned SnO₂ nanostructures arrays, a unit area is of ∼500 μm × 200 μm, were synthesized via vapor phase transport method. The surface morphology and composition of the as-synthesized SnO₂ nanostructures were characterized by means of scanning electron microscopy (SEM) and X-ray diffraction (XRD). The mechanism of formation of SnO₂ nanostructures was also discussed. The measurement of field emission (FE) revealed that the as-synthesized SnO₂ nanorods, nanowires and nanoparticles arrays have a lower turn-on field of 2.6, 3.2 and 3.9 V/μm, respectively, at the current density of 0.1 μA/cm². This approach must have a wide variety of applications such as fabrications of micro-optical components and micropatterned oxide thin films used in FE-based flat panel displays, sensor arrays and so on.     

Structural characterization of La0.9Ba0.1MnO3/Y-ZrO2 film by X-ray diffraction

Perovskite manganite La_0.9Ba_0.1MnO₃(LBMO) films were deposited on (0 0 1)-oriented single crystal yttria-stabilized zirconia (YSZ) substrate by 90° off-axis radio frequency magnetron sputtering. The film thickness ranged from 10 nm to 100 nm. Grazing incidence X-ray diffraction technique and high resolution X-ray diffraction were applied to characterize the structure of LBMO films. The LBMO film mainly consisted of (0 0 1)-orientated grain as well as weakly textured (1 1 0)-orientated grain. The results indicated that an amorphous layer with thickness of about 4 nm was formed at the LBMO/YSZ interface. The strain in LBMO film was small and averaged to be about -0.14%. The strain in the film was not lattice mismatch-induced strain but residual strain due to the difference in thermal expansion coefficient between film and substrate.     

Detection of hydrogen with SnO2-coated ZnO nanorods

SnO₂-coated ZnO nanorods on c-plane sapphire substrates were synthesized by pulsed laser deposition. The thickness of the polycrystalline SnO₂ was ∼10 nm, as determined by high-resolution transmission electron microscopy, while the diameter of the ZnO nanorods was ∼30 nm. The sensitivity of the SnO₂/ZnO structures to hydrogen was tested by depositing Ti/Au Ohmic contacts on a random array of the nanorods and measuring the current at fixed voltage. There was no response to 500 ppm H₂ in N₂ at room temperature, but we obtained a sensitivity of ∼70% at 400 °C. The SnO₂/ZnO structures exhibit drift in their recovery characteristics and for sequential detection of hydrogen, as generally reported for SnO₂ thin film sensors.     

Synthesis and nonlinear optical characterization of SnO2 quantum dots

The present paper demonstrates the preparation and characterization of SnO₂ semiconductor quantum dots. Extremely small ∼1.1 and ∼1.4 nm SnO₂ samples were prepared by microwave assisted technique with a frequency of 2450 MHz. Based on XRD analysis, the phase, crystal structure and purity of the SnO₂ samples are determined. UV-vis measurements showed that, for the both size of SnO₂ samples, excitonic peaks are obtained at ∼238 and ∼245 nm corresponding to ∼1.1 nm (sample 1) and ∼1.4 nm (sample 2) sizes, respectively. STM analysis showed that, the quantum dots are spherical shaped and highly monodispersed. At first, the linear absorption coefficients for two different sizes of SnO₂ quantum dots were measured by employing a CW He-Ne laser at 632.8 nm and were obtained about 1.385 and 4.175 cm⁻¹, respectively. Furthermore, the nonlinear refractive index, n₂, and nonlinear absorption coefficient, β, were measured using close and open aperture Z-scan respectively using the same laser. As quantum dots have strong absorption coefficient to obtain purely effective n₂, we divided the closed aperture transmittance by the corresponding open aperture in the same incident beam intensity. The nonlinear refraction indices of these quantum dots were measured in order of 10⁻⁷ (cm²/W) with negative sign and the nonlinear absorption coefficients were obtained for both in order of 10⁻³ (cm/W) with positive sign.     

High-resolution transmission electron microscopy investigation of the nanostructure of undoped and Pt-doped nanocrystalline pulsed laser deposited SnO2 thin films

Pulsed laser deposition (PLD) was used to grow nanocrystalline SnO₂ thin films onto alumina substrates. The reactive PLD process was carried out at different substrate deposition temperatures (T_d) between 20 and 600 °C under an oxygen background pressure of 150 mtorr. The same PLD technique was used to produce SnO₂ films in situ-doped with Pt (at the level of ∼2 at. %) through the concomitant ablation of both SnO₂ target and Pt strips. Conventional and high-resolution transmission electron microscopy (HRTEM) observations have revealed that the microstructure of the PLD SnO₂ films is highly sensitive to their deposition temperature. Indeed, its changes from a porous granular structure with extremely fine equiaxed grains (∼4 nm diameter), at T_d=20 °C to a very compact and textured columnar structure characterized by SnO₂ columns (∼25 nm diameter) composed of grains of ∼12 nm of diameter, at T_d=600 °C. In addition, the PLD SnO₂ films were found to exhibit the highest nanoporosity at T_d=300 °C which also coincides with the granular-to-columnar microstructural transition. On the other hand, the microstructure of the Pt-doped SnO₂ films, deposited at 300 °C, was found to contain a high density of defects, such as twin boundaries and edge dislocations. By combining HRTEM and EDS microanalysis, we were able to show that the Pt-dopant self-organizes into spherical nanoparticles (1-2 nm diameter) randomly distributed at the SnO₂ grain boundaries. Finally, doping the films with such platinum nanoclusters is found to affect the SnO₂ nanostructure by particularly reducing the SnO₂ mean grain size (from ∼10 nm when undoped to ∼6 nm for the doped films).     

Synthesis and field-emission of aligned SnO2 nanotubes arrays

Aligned tin dioxide (SnO₂) nanotubes have been synthesized by high-frequency inductive heating. Nanotubes with high yield were grown on silicon substrates in less than 5 min, using SnO₂ and graphite as the source powder. Scanning electron microscopy and transmission electron microscopy showed nanotube with diameters from 50 to 100 nm and lengths up to tens of mircrometers. The SnO₂ nanotubes synthesized under the optimum condition have better field-emission characteristics. The turn-on field needed to produce a current density of 10 μA/cm² is found to be 1.64 V/μm. The samples show good field-emission properties with a fairly stable emission current. This type of SnO₂ nanotubes can be applied as field emitters in displays as well as vacuum electric devices.     

Extended X-ray absorption fine structure (EXAFS) and X-ray absorption near-edge structure (XANES) study of melt-spun Fe85Ga15 ribbons

The local structure in melt-spun Fe₈₅Ga₁₅ ribbons with a width ∼3 mm and thickness ∼60 μm produced in argon atmosphere was studied by analyzing EXAFS and XANES data. The following results were obtained: Ga–Ga bonds were not detected excluding the tendency to form clusters of Ga atoms; Ga substitutes Fe creating a local strain of about +1% on the first shell Fe–Ga bond, whereas on the second Fe–Ga shell strain quickly relaxes down to +0.3%; XANES spectra are compatible with a random substitution of Fe atoms by Ga atoms in the A2 structure. From the AFM investigation, we observed that at the surface (free side) of the ribbon the particles are elongated along the ribbon (∼2 μm×∼5 μm) and each particle is formed by small grains of average size of 200 nm.     

Pure UV photoluminescence from ZnO thin film by thermal retardation and using an amorphous SiO2 buffer layer

ZnO/SiO₂ thin films were fabricated on Si substrates by E-beam evaporation with thermal retardation. The as-prepared films were annealed for 2 h every 100 °C in the temperature range 400-800 °C under ambient air. The structural and optical properties were investigated by X-ray diffraction (XRD), atomic force microscopy (AFM) and photoluminescence (PL). The XRD analysis indicated that all ZnO thin films had a highly preferred orientation with the c-axis perpendicular to the substrate. From AFM images (AFM scan size is 1 μm×1 μm), the RMS roughnesses of the films were 3.82, 5.18, 3.65, 3.40 and 13.2 nm, respectively. PL measurements indicated that UV luminescence at only 374 nm was observed for all samples. The optical quality of the ZnO film was increased by thermal retardation and by using an amorphous SiO₂ buffer layer.     

The effects of substrate temperature on the structure, morphology and photoluminescence properties of pulsed laser deposited SrAl2O4:Eu,Dy thin films

In this study, SrAl₂O₄:Eu²⁺,Dy³⁺ thin film phosphors were deposited on Si (1 0 0) substrates using the pulsed laser deposition (PLD) technique. The films were deposited at different substrate temperatures in the range of 40-700 °C. The structure, morphology and topography of the films were determined by using X-ray diffraction (XRD), atomic force microscopy (AFM), scanning electron microscopy (SEM) and high resolution transmission electron microscopy (HRTEM). Photoluminescence (PL) data was collected in air at room temperature using a 325 nm He-Cd laser as an excitation source. The PL spectra of all the films were characterized by green phosphorescent photoluminescence at ∼530 nm. This emission was attributed to 4f⁶5d¹→4f⁷ transition of Eu²⁺. The highest PL intensity was observed from the films deposited at a substrate temperature of 400 °C. The effects of varying substrate temperature on the PL intensity were discussed.     

Growth of highly-oriented CaCu3Ti4O12 thin films on SrTiO3 (1 0 0) substrates by a chemical solution route

Highly-oriented CaCu₃Ti₄O₁₂ (CCTO) thin films deposited directly on SrTiO₃ (1 0 0) substrates have been developed successfully using a chemical solution coating method. X-ray diffraction (XRD), scanning electron microscopy (SEM), and atomic force microscopy (AFM) were employed to characterize the structure and the morphology. It was observed that the CCTO thin films had the 1 μm × 1 μm domain-like microstructure that consists of compact grains of about 0.1 μm in size. The cross sectional SEM image shows that the CCTO grains grow regularly close to the clear interface between the CCTO film and the SrTiO₃ substrate. The result was discussed in terms of lattice mismatch between CCTO and SrTiO₃.     

Writing of two-dimensional crystal curved lines at the surface of Sm2O3-Bi2O3-B2O3 glass by samarium atom heat processing

Two-dimensional crystal curved lines consisting of the nonlinear optical Sm_xBi_1−xBO₃ phase are fabricated at the surface of 8Sm₂O₃·37Bi₂O₃·55B₂O₃ glass by continuous wave Nd:YAG laser (wavelength: 1064 nm) irradiation (samarium atom heat processing) with a power of ∼0.9 W and a laser scanning speed of 5 μm/s. The curved lines with bending angles of 0-90° or with sine-shapes are written by just changing the laser scanning direction. The polarized micro-Raman scattering spectra for the line after bending are the same as those for the line before bending, indicating that the crystal plane of Sm_xBi_1−xBO₃ crystals to the crystal growth direction might be maintained even after the change in the laser scanning direction. It is found from laser scanning microscope observations that the crystal lines at the surface are swelled out smoothly, giving a height of about 10 μm.     

Morphological and structural characterizations of CrSi2 nanometric films deposited by laser ablation

The structure and morphology of chromium disilicide (CrSi₂) nanometric films grown on 〈1 0 0〉 silicon substrates both at room temperature (RT) and at 740 K by pulsed laser ablation are reported. A pure CrSi₂ crystal target was ablated with a KrF excimer laser in vacuum (∼3 × 10⁻⁵ Pa). Morphological and structural properties of the deposited films were investigated using Rutherford backscattering spectrometry (RBS), grazing incidence X-ray diffraction (GID), X-ray reflectivity (XRR), scanning (SEM) and transmission electron microscopy (TEM). From RBS analysis, the films’ thickness resulted of ∼40 nm. This value is in agreement with the value obtained from XRR and TEM analysis (∼42 and ∼38 nm, respectively). The films’ composition, as inferred from Rutherford Universal Manipulation Program simulation of experimental spectra, is close to stoichiometric CrSi₂. GID analysis showed that the film deposited at 740 K is composed only by the CrSi₂ phase. The RT deposited sample is amorphous, while GID and TEM analyses evidenced that the film deposited at 740 K is poorly crystallised. The RT deposited film exhibited a metallic behaviour, while that one deposited at 740 K showed a semiconductor behaviour down to 227 K.     

Characteristic properties of Y2SiO5:Ce thin films grown with PLD

Three different gases (nitrogen (N₂), oxygen (O₂) and argon (Ar)) were used as background gases during the growth of pulsed laser deposition (PLD) Y₂SiO₅:Ce thin films. A Krypton fluoride laser (KrF), 248 nm was used for the PLD of the films on silicon (Si) (1 0 0) substrates. The effect of the background gases on the surface morphology, crystal growth and luminescent properties were investigated. All the experimental parameters, the gas pressure (455 mT), the substrate temperature (600 °C), the pulse frequency (8 Hz), the number of pulses (4000) and the laser fluence (1.6±0.2) J/cm² were kept constant. The only parameter that was changed during the deposition was the ambient gas species. The surface morphology and average particle sizes were monitored with scanning electron microscopy (SEM) and atomic force microscopy (AFM). X-ray diffraction (XRD) and Auger electron spectroscopy (AES) were used to determine the crystal structure and composition, respectively. Cathodo- (CL) and photoluminescence (PL) were used to measure the luminescent intensities for the different phosphor thin films. The nature of the particles, ablated on the substrate, is related to the collisions between the ejected particles and the ambient gas particles. The CL and PL intensities also depend on the particle sizes. A 144 h (coulomb dose of 1.4×10⁴ C cm⁻²) electron degradation study on the thin films ablated in the Ar gas environment resulted in a decrease in the main CL intensity peak at 440 nm and to the development of a new very broad luminescent peak spectra ranging from 400 to 850 nm due to the growth of a SiO₂ layer on the surface.     

Laser frequency stabilization at 1.5 microns using ultranarrow inhomogeneous absorption profiles in Er:LiYF4

Single-frequency diode lasers have been frequency stabilized to 1.5 kHz Allan deviation over 0.05-50 s integration times, with laser frequency drift reduced to less than 1.4 kHz/min, using the frequency reference provided by an ultranarrow inhomogeneously broadened Er³⁺:⁴I_15/2→⁴I_13/2 optical absorption transition at a vacuum wavelength of 1530.40 nm in a low-strain LiYF₄ crystal. The 130 MHz full-width at half-maximum (FWHM) inhomogeneous line width of this reference transition is the narrowest reported for a solid at 1.5 μm. Strain-induced inhomogeneous broadening was reduced by using the single isotope ⁷Li and by the very similar radii of Er³⁺ and the Y³⁺ ions for which it substitutes. To show the practicability of cryogen-free cooling, this laser stability was obtained with the reference crystal at 5 K; moreover, this performance did not require vibrational isolation of either the laser or crystal frequency reference. Stabilization is feasible up to T=25 K where the Er³⁺ absorption thermally broadens to ∼500 MHz. This stabilized laser system provides a tool for interferometry, high-resolution spectroscopy, real-time optical signal processing based on spatial spectral holography and accumulated photon echoes, secondary frequency standards, and other applications such as quantum information science requiring narrow-band light sources or coherent detection.     

Effects of deposition temperature on the structural and morphological properties of SnO2 films fabricated by pulsed laser deposition

Tin oxide (SnO₂) thin films were grown on Si (1 0 0) substrates using pulsed laser deposition (PLD) in O₂ gas ambient (10 Pa) and at different substrate temperatures (RT, 150, 300 and 400 °C). The influence of the substrate temperature on the structural and morphological properties of the films was investigated using X-ray diffraction (XRD), atomic force microscopy (AFM) and scanning electron microscopy (SEM). XRD measurements showed that the almost amorphous microstructure transformed into a polycrystalline SnO₂ phase. The film deposited at 400 °C has the best crystalline properties, i.e. optimum growth conditions. However, the film grown at 300 °C has minimum average root mean square (RMS) roughness of 3.1 nm with average grain size of 6.958 nm. The thickness of the thin films determined by the ellipsometer data is also presented and discussed.     

Laser-induced forward transfer technique for maskless patterning of amorphous V2O5 thin film

A laser-induced forward transfer technique has been applied for the maskless patterning of amorphous V₂O₅ thin films. A sheet beam of a frequency doubled (SHG) Q-switched Nd:YAG laser was irradiated on a transparent glass substrate (donor), the rear surface of which was pre-coated with a vacuum-deposited V₂O₅ 180 nm thick film was either in direct contact with a second glass substrate (receiver) or a 0.14 mm air-gap was maintained between the donor film and the receiving substrate. Clear, regular stripe pattern of the laser-induced transferred film was obtained on the receiver. The pattern was characterized using X-ray diffraction (XRD), optical absorption spectroscopy, scanning electron microscopy (SEM), energy dispersive analysis of X-ray (EDAX), atomic force microscopy (AFM), etc.     

Femtosecond Z-scan measurement of third-order optical nonlinearities in anatase TiO2 thin films

Anatase phase TiO₂ films have been grown on fused silica substrate by pulsed laser deposition technique at substrate temperature of 750 °C under the oxygen pressure of 5 Pa. From the transmission spectra, the optical band gap and linear refractive index of the TiO₂ films were determined. The third-order optical nonlinearities of the films were measured by Z-scan method using a femtosecond laser (50 fs) at the wavelength of 800 nm. The real and imaginary parts of third-order nonlinear susceptibility χ⁽³⁾ were determined to be −7.1 × 10⁻¹¹esu and −4.42 × 10⁻¹²esu, respectively. The figure of merit, T, defined by T=βλ/n₂, was calculated to be 0.8, which meets the requirement of all-optical switching devices. The results show that the anatase TiO₂ films have great potential applications for nonlinear optical devices.     

The role of the dopant in the magnetism of Fe-doped SnO2 films

Transparent pure and Fe-doped SnO₂ thin films were grown by pulsed laser deposition technique on LaAlO₃ substrates. X-ray diffraction shows that the films are polycrystalline and have the rutile structure. Surprisingly, the pure film presents magnetic-like behavior at room temperature with a saturated magnetization of almost one-third of the doped film (∼3.6 and 11.3 emu/g, respectively) and its magnetization could not be attributed to any impurity phase. Taking into account the magnetic moment measured in the pure film, the effective contribution of the impurity in the doped one can be inferred to be ∼2 μ_B per Fe atom. A large magnetic moment was also predicted by an ab initio calculation in the doped system, which increases if an oxygen vacancy is present near the Fe impurity.     

Chemical spray pyrolysis deposition and characterization of p-type CuCr1−xMgxO2 transparent oxide semiconductor thin films

A chemical spray pyrolysis technique for deposition of p-type Mg-doped CuCrO₂ transparent oxide semiconductor thin films using metaloorganic precursors is described. As-deposited films contain mixed spinel CuCr₂O₄ and delafossite CuCrO₂ structural phases. Reduction in spinel CuCr₂O₄ fraction and formation of highly crystalline films with single phase delafossite CuCrO₂ structure is realized by annealing at temperatures ?700 °C in argon. A mechanism of synthesis of CuCrO₂ films involving precursor decomposition, oxidation and reaction between constituent oxides in the spray deposition process is presented. Post-annealed CuCr_0.93Mg_0.07O₂ thin films show high (?80%) visible transmittance and sharp absorption at band gap energy with direct and indirect optical band gaps 3.11 and 2.58 eV, respectively. Lower (∼450 °C) substrate temperature formed films are amorphous and yield lower direct (2.96 eV) and indirect (2.23 eV) band gaps after crystallization. Electrical conductivity of CuCr_0.93 Mg_0.07O₂ thin films ranged 0.6-1 S cm⁻¹ and hole concentration ∼2×10¹⁹ cm⁻³ determined from Seebeck analysis. Temperature dependence of conductivity exhibit activation energies ∼0.11 eV in 300-470 K and ∼0.23 eV in ?470 K region ascribed to activated conduction and grain boundary trap assisted conduction, respectively. Heterojunction diodes of the structure Au/n-(ZnO)/p-(CuCr_0.93Mg_0.07O₂)/SnO₂ (TCO) were fabricated which show potential for transparent wide band gap junction device.     

Direct conversion of a metal organic compound to epitaxial Sb-doped SnO2 film on a (0 0 1) TiO2 substrate using a KrF laser, and its resulting electrical properties

Epitaxial Sb-doped SnO₂ (0 0 1) thin film on a TiO₂ (0 0 1) substrate was successfully prepared by laser-assisted metal organic deposition at room temperature. The effects of the precursor thin film and laser fluence on the resistivity, carrier concentration, and mobility of the Sb-doped SnO₂ film were investigated. The resistivity of the Sb-doped SnO₂ film prepared by direct irradiation to metal organic film is one order of magnitude lower than that of film prepared by irradiation to amorphous Sb-doped SnO₂ film. From an analysis of Hall measurements, the difference between the resistivity of the Sb-doped SnO₂ film prepared using the metal organic precursor film and that of amorphous precursor film appears to be caused by the mobility. Direct conversion of the metal organic compound by excimer laser irradiation was found to be effective for preparing epitaxial Sb-doped SnO₂ film with low resistivity.