Enhanced field emission from PbTiO3 nanodots prepared by phase separation approach

Uniformly distributed PbTiO₃ nanodots were successfully prepared by phase separation approach. A precursor sol film was first spin-coated on Si wafer and then spontaneously separated into two distinct phases owing to the Marangoni instability. PT nanodots with tailorable size and density were obtained after further heat treatment. X-ray diffraction analysis indicated that these nanodots showed a perovskite structure. An excellent room temperature field emission property of PbTiO₃ nanodots was observed: the minimum turn-on voltage was about 5.3 V/μm; while the emission current density reached about 270 μA cm⁻² at an applied field of about 9.25 V/μm.     

Synthesis, characterization and low field emission of CNx nanotubes

Aligned CN_x nanotubes were fabricated by pyrolyzing ethylenediamine on p-type Si(1 1 1) substrates using iron as the catalyst. Scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectrum (XPS) and Raman spectroscopy were used to characterize the CN_x nanotubes. The CN_x nanotubes with the average length of 20 μm and diameters in the range of 50–100 nm have the “bamboo-like” structure and worse crystalline order. The low-field emission measurements of the CN_x nanotubes indicated that 20 μA/cm² current densities were observed at an electric field of 1.4 V/μm and 1.280 mA/cm² were obtained at 2.54 V/μm. The CN_x nanotubes exhibit better field emission properties than the carbon nanotubes and the BCN nanotubes. The emission mechanism of CN_x nanotubes is also discussed.     

Spectral characterization and energy levels of Cr:Sc2(MoO4)3 crystal

This paper reports the spectral properties and energy levels of Cr³⁺:Sc₂(MoO₄)₃ crystal. The crystal field strength Dq, Racah parameter B and C were calculated to be 1408 cm⁻¹, 608 cm⁻¹ and 3054 cm⁻¹, respectively. The absorption cross sections σ_α of ⁴A₂→⁴T₁ and ⁴A₂→⁴T₂ transitions were 3.74×10⁻¹⁹ cm² at 499 nm and 3.21×10⁻¹⁹ cm² at 710 nm, respectively. The emission cross section σ_e was 375×10⁻²⁰ cm² at 880 nm. Cr³⁺:Sc₂(MoO₄)₃ crystal has a broad emission band with a broad FWHM of 176 nm (2179 cm⁻¹). Therefore, Cr³⁺:Sc₂(MoO₄)₃ crystal may be regarded as a potential tunable laser gain medium.     

Li ion conduction in TiO2 filled polyvinylidenefluoride-co-hexafluoropropylene based novel nanocomposite polymer electrolyte membranes with LiDFOB

This paper describes, nanocomposite polymer electrolyte (NCPE) based on polyvinylidenefluoride-co-hexafluoropropylene (PVdF-HFP), which comprises the novel lithium difluoro(oxalato)borate (LiDFOB). Ehtylene carbonate (EC) and diethyl carbonate (DEC) mixture was used as gelling agent and nanoparticulate TiO₂ used as filler. The NCPE membranes were subjected to a.c. impedance, tensile strength, Raman studies, TG/DTA and morphological studies. 5 wt% TiO₂ comprising membranes exhibited enhanced conductivity of 0.56 mS cm⁻¹and the Young’s modulus was increased from 1.32 to 2.74 MPa. The structural change of α to β phase was confirmed by Raman studies. The thermal stability of the NCPE membrane is found to be 130 °C. Calculation of activation energy and synthesis of LiDFOB has also been presented.     

In situ spectroelectrochemical surface-enhanced Raman scattering (SERS) investigations on composite Ag/TiO2-nanotubes/Ti substrates

A tubular array of TiO₂-nanotubes on a Ti substrate was used as a support for an Ag sputter-deposited layer intended for surface-enhanced Raman scattering (SERS) investigations. Composite samples of Ag/TiO₂-nanotube/Ti were studied with the aid of scanning electron microscopy (SEM) and Auger electron spectroscopy (AES) to reveal their characteristic morphological and chemical features. Raman spectra of pyridine (as a probe molecule) were measured at different cathodic potentials ranging from −0.2 down to −1.2 V after the pyridine had been adsorbed on the TiO₂-nanotube/Ti substrates covered with the Ag deposit. In addition, SERS spectra on a bulk electrochemically-roughened Ag reference substrate, were also measured.The SERS activity of the composite samples was strongly dependent on the amount of Ag deposit and, in some cases, was even higher than that for the Ag reference substrate. The SERS intensity vs. electrode potential dependences measured were interpreted in terms of the modified electronic structure of the Ag deposits due to the interaction of the Ag clusters with the TiO₂-nanotube/Ti substrate.     

Synthesis and field emission of patterned ZnO nanorods

A simple and self-catalytic method has been developed for synthesizing finely patterned ZnO nanorods on ITO-glass substrates under a low temperature of 500 °C. The patterned ZnO nanorod arrays, a unit area is of 400 × 100 μm², are synthesized via vapor phase transport method. The surface morphology and composition of the as-synthesized ZnO nanorods are characterized by means of scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDX). The mechanism of formation of ZnO nanorods is also discussed. The measurement of field emission (FE) reveals that the as-synthesized ZnO nanorods arrays have a turn-on field of 3.3 V/μm at the current density of 0.1 μA/cm² and a low threshold field of 6.2 V/μm at the current density of 1 mA/cm². So this approach must have a potential application of fabricating micropatterned oxide thin films used in FE-based flat panel displays.     

Photoelectrochemical property and photocatalytic activity of N-doped TiO2 nanotube arrays

N-doped TiO₂ nanotube arrays (NTN) were prepared by anodization and dip-calcination method. Hydrazine hydrate was used as nitrogen source. The surface morphology of samples was characterized by SEM. It showed that the mean size of inner diameter was 65 nm and wall thickness was 15 nm for NTN. The ordered TiO₂ nanotube arrays on Ti substrate can sustain the impact of doping process and post-heat treatment. The atomic ratio of N/Ti was 8/25, which was calculated by EDX. Photoelectrochemical property of NTN was examined by anodic photocurrent response. Results indicated the photocurrent of NTN was nearly twice as that of non-doped TiO₂ nanotube arrays (TN). Photocatalytic activity of NTN was investigated by degrading dye X-3B under visible light. As a result, 99% of X-3B was decomposed by NTN in 105 min, while that of TN was 59%.     

Effect of annealing temperature on microstructure, optical and electrical properties of sputtered Ba0.9Sr0.1TiO3 thin films

Ba_0.9Sr_0.1TiO₃ (BST) thin films were deposited on fused quartz and Pt/TiN/Si₃N₄/Si substrates by radio frequency magnetron sputtering technique. Microstructure and chemical bonding states of the BST films annealed at 700 °C were characterized by field emission scanning electron microscopy, X-ray photoelectron spectroscopy, glancing angle X-ray diffraction and Raman spectrum. Optical constants including refractive indices, extinction coefficients and bandgap energies of the as-deposited BST film and the BST films annealed at 650, 700 and 750 °C, respectively, were determined from transmittance spectra by envelope method and Tauc relation. Dielectric constant and remnant polarization for the BST films increase with increasing annealing temperature. Leakage current density-applied voltage (J–V) data indicate that the dominant conduction mechanism for all the BST capacitors is the interface-controlled Schottky emission under the conditions of 14 V < V < 30 V and −30 V < V < −14 V. Furthermore, the inequipotential J–V characteristics for the BST films annealed at various temperatures are mainly attributed to the combined effects of the different thermal histories, relaxed stresses and strains, and varied Schottky barrier heights in the BST/Pt and Pt/BST interfaces.     

Surface-enhanced Raman scattering (SERS) activity of Ag, Au and Cu nanoclusters on TiO2-nanotubes/Ti substrate

Tubular arrays of TiO₂ nanotubes (ranging in diameter from 40 to 110 nm) on a Ti substrate were used as a support for Ag, Au or Cu deposits obtained by the sputter deposition technique, where the amount of metal varied from 0.01 to 0.2 mg/cm². Those composite supports were intended for surface-enhanced Raman scattering (SERS) investigations. Composite samples were studied with the aid of scanning electron microscopy (SEM) and Auger electron spectroscopy (AES) to reveal their characteristic morphological and chemical features. Raman spectra of pyridine (as a probe molecule) were measured at different cathodic potentials ranging from −0.2 down to −1.2 V after the pyridine had been adsorbed on the metal-covered TiO₂ nanotube/Ti substrates. In addition, SERS spectra on a bulk standard activated Ag, Au and Cu substrates were also measured. The SERS activity of the composite samples was strongly dependent on the amount of metal deposit, e.g. at and above 0.06 mg Ag/cm², the intensity of SERS signal was even higher than that for the Ag reference substrate. The high activity of these composites is mainly a result of their specific morphology. The high SERS sensitivity on the surface morphology of the substrate made it possible to monitor very small temporal changes in the Ag metal clusters. This rearrangement was not detectable with microscopic (SEM) or microanalytical (AES) methods. The SERS activity of Au or Cu clusters was distinctly lower than those of Ag. The spectral differences exhibited by the three kinds of composites as compared to the reference metal samples are discussed.     

A study on photo-generated charges property in highly ordered TiO2 nanotube arrays

In this study TiO₂ nanotube arrays were fabricated by potentiostatic anodization of titanium sheet. The X-ray diffraction (XRD) pattern and field emission scanning electron microscopy (FE-SEM) image indicated the TiO₂ nanotube arrays were of pure anatase form and highly ordered. The properties of the photo-generated charges in the nanotube arrays were investigated by transient photovoltage (TPV) technique and surface photovoltage (SPV) technique based on lock-in amplifier with dc bias, in comparison with the commercial powder derived film. The separation processes of the photo-induced charges in the system of TiO₂ nanotubes on Ti have been demonstrated to be correlated with the incident light intensity, surface trapping states, and the interfacial electric field between Ti and TiO₂. The results also show that the highly ordered nanotube film could generate much stronger SPV responses under external electric field than the commercial powder derived film.     

Structure, ferroelectric and piezoelectric properties of (Bi1−x−yNa0.925−x−yLi0.075)0.5BaxSryTiO3 lead-free piezoelectric ceramics

Lead-free multi-component ceramics (Bi_1−x−yNa_{0.925−x−y}Li_0.075)_0.5Ba_xSr_yTiO₃ have been prepared by an ordinary sintering technique and their structure and electrical properties have been studied. All the ceramics can be well-sintered at 1100 °C. X-ray diffraction patterns shows that Li⁺, Ba²⁺ and Sr²⁺ diffuse into the Bi_0.5Na_0.5TiO₃ lattices to form a new solid solution with a pure perovskite structure, and a morphotropic phase boundary (MPB) is formed at 0.04 < x < 0.08. As compared to pure Bi_0.5Na_0.5TiO₃ ceramic, the coercive field E_C of the ceramics decreases greatly and the remanent polarization P_r of the ceramics increases significantly after the formation of the multi-component solid solution. Due to the MPB, lower E_C and higher P_r, the piezoelectricity of the ceramics is greatly improved. For the ceramics with the compositions near the MPB (x = 0.04–0.08 and y = 0.02–0.04), piezoelectric coefficient d₃₃ = 133–193 pC/N and planar electromechanical coupling factor k_P = 16.2–32.1%. The depolarization temperature T_d reaches a minimum value near the MPB. The temperature dependences of the ferroelectric and dielectric properties suggest that the ceramics may contain both the polar and non-polar regions at temperatures near/above T_d.     

Comparative in vitro cytotoxicity assessment of some manufacturednanoparticulate materials characterized by transmissionelectron microscopy

A range of manufactured nanoparticulate materials, including Ag, TiO₂, Fe₂O₃, Al₂O₃, ZrO₂, Si₃N₄, and a range of carbonaceous nanoparticulate materials: single-wall and multi-wall carbon nanotube aggregates and aggregated nanoparticles of black carbon, as well as commercial (mineral grade) chrysotile asbestos nanotube aggregates, have been rigorously characterized by transmission electron microscopy. These nanoparticulate materials ranged in primary particle sizes from roughly 3 to 150 nm (except for the nanotube materials with lengths in excess of 15 μm). Aggregate sizes ranged from 25 nm to 20 μm. Comparative cytotoxicological assessment of these nanomaterials was performed utilizing a murine (lung) macrophage cell line. Considering the chrysotile asbestos to be a positive control, and assigning it a relative cytotoxicity index of unity (1.0), relative cytotoxicity indexes were observed as follows at concentrations of 5 μg/ml: 1.6 and ∼ 0.4 for Ag and TiO₂, respectively; 0.7–0.9 for the Fe₂O₃, Al₂O₃ and ZrO₂, 0.4 for the Si₃N₄, 0.8 for the black carbon, and 0.9 to 1.1 for the carbon nanotube aggregate samples. Observations of a cytotoxic response, nearly identical to that for chrysotile asbestos, for multi-wall carbon nanotube aggregates which very closely resemble anthropogenic multi-wall carbon nanotubes in the environment, raise some concern for potential health effects, especially for long-term exposure.     

CW-Cavity Ring Down Spectroscopy of O3. Part 3: Analysis of the 6490–6900 cm region and overview comparison with the O3 main isotopologue

This paper is devoted to the third part of the analysis of the very weak absorption spectrum of the ¹⁸O₃ isotopologue of ozone recorded by CW-Cavity Ring Down Spectroscopy between 5930 and 6900 cm⁻¹. In the two first parts [A. Campargue, A. Liu, S. Kassi, D. Romanini, M.-R. De Backer-Barilly, A. Barbe, E. Starikova, S.A. Tashkun, Vl.G. Tyuterev, J. Mol. Spectrosc. (2009), doi: 10.1016/j.jms.2009.02.012 and E. Starikova, M.-R. De Backer-Barilly, A. Barbe, Vl.G. Tyuterev, A. Campargue, A.W.Liu, S. Kassi, J. Mol. Spectrosc. (2009) doi: 10.1016/j.jms.2009.03.013], the effective operators approach was used to model the spectrum in the 6200–6400 and 5930–6080 cm⁻¹ regions, respectively. The analysis of the whole investigated region is completed by the present investigation of the 6490–6900 cm⁻¹ upper range. Three sets of interacting states have been treated separately. The first one falls in the 6490–6700 cm⁻¹ region, where 1555 rovibrational transitions were assigned to three A-type bands: 3ν₂ + 5ν₃, 5ν₁ + ν₂ + ν₃ and 2ν₁ + 3ν₂ + 3ν₃ and one B-type band: ν₁ + 3ν₂ + 4ν₃. The corresponding line positions were reproduced with an rms deviation of 18.4 × 10⁻³ cm⁻¹ by using an effective Hamiltonian (EH) model involving eight vibrational states coupled by resonance interactions. In the highest spectral region – 6700–6900 cm⁻¹ – 389 and 183 transitions have been assigned to the ν₁ + 2ν₂ + 5ν₃ and 4ν₁ + 3ν₂ + ν₃ A-type bands, respectively. These very weak bands correspond to the most excited upper vibrational states observed so far in ozone. The line positions of the ν₁ + 2ν₂ + 5ν₃ band were reproduced with an rms deviation of 7.3 × 10⁻³ cm⁻¹ by using an EH involving the {(054), (026), (125)} interacting states. The coupling of the (431) upper state with the (502) dark state was needed to account for the observed line positions of the 4ν₁ + 3ν₂ + ν₃ band (rms = 5.7 × 10⁻³ cm⁻¹).The dipole transition moment parameters were determined for the different observed bands. The obtained set of parameters and the experimentally determined energy levels were used to generate a complete line list provided as Supplementary Materials.The results of the analyses of the whole 5930–6900 cm⁻¹ spectral region were gathered and used for a comparison of the band centres to their calculated values. The agreement achieved for both ¹⁸O₃ and ¹⁶O₃ (average difference on the order of 1 cm⁻¹) indicates that the used potential energy surface provides accurate predictions up to a vibrational excitation approaching 80% of the dissociation energy. The comparison of the ¹⁸O₃ and ¹⁶O₃ band intensities is also discussed, opening a field of questions concerning the variation of the dipole moments and resonance intensity borrowing by isotopic substitution.     

Observation of record flux pinning in melt-textured NEG-123 superconductor doped by Nb, Mo, and Ti nanoparticles

Flux pinning in melt-processed (Nd_0.33Eu_0.33Gd_0.33)Ba₂Cu₃O_y “NEG-123” + 35 mol% Gd₂BaCuO₅ “NEG-211” (70 nm in size) composite doped by TiO₃, MoO₃ and Nb₂O₅ achieved record values. The optimum values of all three dopands were found to be around 0.1 mol%. Transmission electron microscope (TEM) analysis found clouds of <10 nm sized particles in the NEG-123 matrix, shifting the pinning particle size distribution to significantly lower values. TEM by energy dispersive X-ray spectroscopy (EDX) analysis clarified that these nanoparticles contained a significant amount of Nb, Mo, and Ti. Appearance of nanometer-sized defects correlated with a significantly improved flux pining at low and medium magnetic fields, which was particularly significant at high temperatures. In the Nb-doped sample, a record J_c value of 925 kA/cm² at the secondary peak field (4.5 T) was achieved at 65 K, 640 kA/cm² at zero field at 77 K, and 100 kA/cm² at 90.2 K, the last value having been up to now considered as a good standard for REBa₂Cu₃O_y “RE-123” materials at 77 K. The greatly improved J_c–B performance in Nb/Mo/Ti doped samples can be easily translated to large-scale LRE-123 (LRE = light rare earths, Nd, Eu, Gd, Sm) blocks intended for real superconducting super-magnets applications.     

IR-induced nonlinear optics in Ge-doped Bi12TiO20 large-sized nanocrystallites

Photoinduced non-linear optical effects in large-sized (up to 25 nm) nanocrystallites (NC) of Ge-doped Bi₁₂TiO₂₀ (BTO:Ge) incorporated within olygoether photopolymer matrix have been studied. Photoinduced second harmonic generation (PISHG) was measured. Nd:YAG pulsed laser (λ=1.06 μm) was used as a source of photoinducing light. As a fundamental light source for the SHG and two-photon absorption, Er:LiYF₄ laser (λ=2.065 μm) was used. We have found that with increasing IR pump power density, the output doubled frequency SHG signal (λ=1.03 μm) increases and achieves its maximum value at the pump power density about 0.45 GW/cm² and NC size about 12 nm.The values of second-order optical susceptibilities were almost 20% larger than for the pure BTO NC single crystals. With decreasing temperature below 60 K, the SHG signal increases achieving maximal value at LHeT.     

Synthesis and characterization of TiO2/Fe2O3 core-shell nanocomposition film and their photoelectrochemical property

TiO₂/Fe₂O₃ core-shell nanocomposition film has been fabricated via two-step method. TiO₂ nanorod arrays are synthesized by a facile hydrothermal method, and followed by Fe₂O₃ nanoparticles deposited on TiO₂ nanorod arrays through an ordinary chemical bath deposition. The phase structures, morphologies, particle size, chemical compositions of the composites have been characterized by X-ray diffraction (XRD), field emission scanning electron microscope (FESEM) and ultraviolet-visible (UV-vis) spectrophotometer. The results confirm that Fe₂O₃ nanoparticles of mean size ca. 10 nm coated on the surface of TiO2 NRs. After depositing Fe₂O₃, UV-vis absorption property is induces the shift to the visible-light range, the annealing temperature of 600 °C is the best condition for UV-vis absorption property of TiO₂/Fe₂O₃ nanocomposite film, and increasing Fe content, optical activity are enhanced one by one. The photoelectrochemical (PEC) performances of the as-prepared composite nanorods are determined by measuring the photo-generated currents under illumination of UV-vis light. The TiO₂ NRs modified by Fe₂O₃ show the photocurrent value of 1.36 mA/cm² at 0 V vs Ag/AgCl, which is higher than those of unmodified TiO₂ NRs.     

Applying the statistical experimental method to evaluate the process conditions of TiO2 nanotube arrays by anodization method

Vertically oriented TiO₂ nanotube arrays were successfully produced by the anodization technique in NH₄F/H₃PO₄ electrolyte. The structure and morphology were characterized by X-ray diffraction (XRD) and field emission scanning electron microscopy (FE-SEM). It is found that TiO₂ nanotube arrays annealed at 500 °C containing 100% anatase phase and entirely converted into rutile at 800 °C. The response surface methodology (RSM) and Box-Behnken design were applied to find the optimal factor conditions in production of TiO₂ nanotube arrays. Based on the results in preliminary experiments, we selected anodization time, anodization voltage and NH₄F concentration as the key factors to investigate their effects on responses. The regression models were built by fitting the experimental results with a second-order polynomial. By using the regression models, the optimal factor conditions were obtained as follows: anodization time of 300 min; anodization voltage of 15.39 V; NH₄F concentration of 0.50 M. Corresponding to the optimal factor conditions, the predicted average length and diameter of nanotube array were 1429 nm and 33 nm, respectively. Confirmation experiments using the optimized conditions were performed: TiO₂ nanotube arrays were obtained with an average tube length of 1420 nm and average tube diameter of 36 nm. The experimental results are in good agreement with the predicted results.     

In-plane gate transistors in AlxGa1−xN/GaN heterostructures written by focused ion beams

Focused ion beam implantation of gallium and dysprosium was used to locally insulate the near-surface two-dimensional electron gas of Al_xGa_1−xN/GaN heterostructures. The threshold dose for insulation was determined to be 2×10¹⁰ cm⁻¹ for 90 keV Ga⁺ and 1×10⁹ cm⁻¹ for 200 keV Dy²⁺ at 4.2 K. This offers a tool not only for inter-device insulation but also for direct device fabrication. Making use of “open-T” like insulating line patterns, in-plane gate transistors have been fabricated by focused ion beam implantation. An exemplar with a geometrical channel width of 1.5 μm shows a conductance of 32 μS at 0 V gate voltage and a transconductance of around 4 μS, which is only slightly dependent on the gate voltage.     

Highly ordered anodic TiO2 nanotube arrays and their stabilities as photo(electro)catalysts

Highly ordered TiO₂ nanotube arrays with an average diameter of 230 nm, a wall thickness of 30 nm and a length of 1.8 μm were fabricated within a large domain by electrochemically anodizing of a titanium foil in a mixed solution of glycerol and NH₄F aqueous electrolyte. The TiO₂ nanotubes exhibit an anatase structure after annealing at 450 °C in air for 3 h. The direct photolysis (DP), photocatalytic (PC), electrocatalytic (EC) and photoelectrocatalytic (PEC) activities of the TiO₂ nanotube arrays were investigated using methyl orange (MO) as the model pollutant. The degradation of MO in PC process is faster than that in DP process, which confirms the photocatalysis of TiO₂ nanotube arrays. The degradation rate in PEC process is much higher than those in EC and PC processes, which demonstrates the synergetic effect between PC and EC processes. The synergetic factor is 4.1, which suggests that the synergetic effect is strong. Moreover, the stabilities of morphology, structure and photo(electro)catalytic degradation performance of the TiO₂ nanotube arrays were studied in order to evaluate their applicability as photo(electro)catalysts. The photo(electro)catalytic experiments bring neither morphological nor structural modifications to the nanotube arrays. The photo(electro)catalytic degradation rates of the TiO₂ nanotube arrays maintain stable in 10 cycles, which indicates that the TiO₂ nanotube arrays are appropriate to be applied as photo(electro)catalysts.     

Lithium ion conductive glass–ceramics with Li3Fe2(PO4)3 and YAG laser-induced local crystallization in lithium iron phosphate glasses

The glasses with the composition of 37.5Li₂O–(25 − x)Fe₂O₃–xNb₂O₅–37.5P₂O₅ (mol%) (x = 5,10,15) are prepared, and it is found that the addition of Nb₂O₅ is effective for the glass formation in the lithium iron phosphate system. The glass–ceramics consisting of Nasicon-type Li₃Fe₂(PO₄)₃ crystals with an orthorhombic structure are developed through conventional crystallization in an electric furnace, showing electrical conductivities of 3 × 10^− 6 Scm^− 1 at room temperature and the activation energies of 0.48 eV (x = 5) and 0.51 eV (x = 10) for Li⁺ ion conduction in the temperature range of 30–200 °C. A continuous wave Nd:YAG laser (wavelength: 1064 nm) with powers of 0.14–0.30 W and a scanning speed of 10 μm/s is irradiated onto the surface of the glasses, and the formation of Li₃Fe₂(PO₄)₃ crystals is confirmed from XRD analyses and micro-Raman scattering spectra. The crystallization of the precursor glasses is considered as new route for the fabrication of Li₃Fe₂(PO₄)₃ crystals being candidates for use as electrolyte materials in lithium ion secondary batteries.