Novel method for fabrication of room temperature polypyrrole–ZnO nanocomposite NO2 sensor

Nanocomposites of polypyrrole (PPy) and zinc oxide (ZnO) nanoparticles (NPs) were prepared by spin coating method. These nanocomposites were characterized by Fourier transform infrared (FTIR), Field emission scanning electron microscope (SEM), Atomic force microscopy (AFM), Transmission electron microscopy (TEM), X-ray diffraction (XRD) and UV–vis techniques, which proved the polymerization of pyrrole monomer and the strong interaction between polypyrrole and ZnO NPs. The nanocomposites were used for gas sensing to CH₃OH, C₂H₅OH, NH₃, H₂S and NO₂ at room temperature. It was revealed that PPy–ZnO nanocomposites with different ZnO weight ratios (10%, 20%, 30%, 40% and 50%) could detect NO₂ at low concentration with very higher selectivity and sensitivity at room temperature than the reported PPy. The PPy–ZnO nanocomposites responded to NO₂ at concentration as low as 10 ppm. PPy–ZnO nanocomposite containing ZnO (50%) showed the maximum sensitivity 38% with 92.10% stability to 100 ppm NO₂ gas at room temperature. The sensing mechanism of PPy–ZnO nanocomposites to NO₂ was presumed to be the effects of p–n junction between PPy and ZnO.     

Fabrication and field emission properties of boron nanowire bundles

We have successfully synthesized large-scale crystalline boron nanowire bundles (BNBs) by chemical vapor deposition method. Fe₃O₄ nanoparticles were used as catalysts spreading on ceramic substrate during the reaction process. The bundles consisted of many thin boron nanowires with a mean diameter of about 25 nm and a length of several micrometers. In addition, boron nanowires are single crystals with an α-tetragonal structure and grow along [0 0 1] orientation. These nanowires have a surface electron affinity of 3.76 eV and a work function of 4.54 eV. A turn-on field of 5.1 V/μm and a threshold field of 10.5 V/μm were found in the nanowire bundles, and stable field emission was recorded at the same time.     

Growth and field emission properties of ZnO nanostructures deposited by a novel pulsed laser ablation source on silicon substrates

Zinc oxide (ZnO) nanostructures were produced using a novel pulsed laser ablation apparatus comprising in-situ analysis of the plume by reflection time-of-flight mass spectrometry. Various morphologies of nano and microstructures were obtained for laser wavelengths of 1064 and 355 nm, and oxygen ambient pressures of 10⁻⁶ and 10⁻² mbar, respectively. None of the produced structures exhibited a particular type of self-organisation whereas all of them showed low aspect ratios and good field emission properties. Optimum values of 5.2 V μm⁻¹ and 2060 were obtained for the turn-on field and Fowler–Nordheim enhancement factor, respectively, for deposited nano-tipped microstructures presenting a high coverage of the substrate. The experimental data showed that for a given laser wavelength, higher field enhancement factors were obtained for the samples grown at the lower pressure of 10⁻⁶ mbar. In these conditions, the deposited materials showed distinct nanostructuring and comparison with existing data showed the corresponding ablation plumes to contain (ZnO)_n clusters, up to n=13. This work also shows that the electronic properties of the nanostructured ZnO produced in our conditions, as determined by the oxygen concentration during deposition, have an influence on the field emission properties in addition to the nanostructure morphology.     

Photo-enhanced field emission study of TiO2 nanotubes array

Aligned TiO₂ nanotubes were synthesized by simple anodization of the Ti foil surface. The as-anodized product is further characterized by SEM, XRD, and PL. The tube inner diameter is found to be ≈60-80 nm with the average wall thickness ≈30 nm and areal density ≈15×10⁶/ cm². FE studies of the aligned TiO₂ nanotubes are carried out at base pressure of ≈1×10⁻⁸ mbar. The turn-on field observed for an emission current density of ≈10 μA/cm² is found to be ≈1.7 V/μm and current density of ≈44 μA/cm² is obtained at an applied field of ≈2.3 V/μm. Photo-enhanced FE study is carried out by shining visible and UV light on the cathode. The aligned TiO₂ nanotubes show sensitivity to both the light sources. The FE current shows fast switching response to the visible light. The increment in the preset current upon UV illumination can be attributed to the band edge excitation of the electrons. The free excitons associated with band gap of the TiO₂ nanotubes array may be responsible for the visible light sensitivity. TiO₂ nanotubes are also grown on the Ti wire and exhibit similar photo-enhanced behavior. The FE and photo-enhanced FE properties demonstrate the applicability of the aligned TiO₂ nanotubes in the FE based micro/nanoelectronic devices.     

A new aberration-corrected,energy-filtered LEEM/PEEM instrument. I. Principles and design

We describe a new design for an aberration-corrected low energy electron microscope (LEEM) and photo electron emission microscope (PEEM), equipped with an in-line electron energy filter. The chromatic and spherical aberrations of the objective lens are corrected with an electrostatic electron mirror that provides independent control over the chromatic and spherical aberration coefficients C_c and C₃, as well as the mirror focal length, to match and correct the aberrations of the objective lens. For LEEM (PEEM) the theoretical resolution is calculated to be ∼1.5 nm (∼4 nm). Unlike previous designs, this instrument makes use of two magnetic prism arrays to guide the electron beam from the sample to the electron mirror, removing chromatic dispersion in front of the mirror by symmetry. The aberration correction optics was retrofitted to an uncorrected instrument with a base resolution of 4.1 nm in LEEM. Initial results in LEEM show an improvement in resolution to ∼2 nm.     

Accurate conductance measurements of a pinhole orifice using a constant-pressure flowmeter

A pinhole orifice with a known conductance can be used as a secondary flow standard. Commercially available laser-drilled pinhole orifices with diameters ranging from 1.0 μm to 50 μm can have molecular-flow conductances ranging from about 0.1 μL/s to 200 μL/s for N₂ at 23 °C. Gas flows of 10⁻¹¹–10⁻⁶ mol/s can easily be produced by applying an upstream pressure in the range of 1–10⁵ Pa. Accurate measurements of the orifice conductance as a function of pressure are required to use the pinhole orifice as a basis of a flowmeter. We use a constant-pressure flowmeter to make accurate measurements of the conductance of a 20 μm orifice as a function of pressure for gas flows of Ar and N₂ into vacuum. We present results of these conductance measurements for an orifice with a nominal diameter of 20 μm. The N₂ conductance of this orifice ranged from 30 μL/s to 60 μL/s over the range of pressures investigated, and was measured with an uncertainty of better than 0.2% (k = 2) for upstream pressures greater than 10 Pa.     

Fabrication and characterization of ZnO thin film for hydrogen gas sensing prepared by RF-magnetron sputtering

A ZnO thin film-based gas sensor was fabricated using a SiO₂/Si substrate with an integrated platinum comb-like electrode and heating element. The structural characteristics, morphology, and surface roughness of the as-grown ZnO nanostructure were investigated. The optical properties were examined by UV–vis spectrophotometry. The film revealed the presence of a c-axis oriented (0 0 2) phase of 20.8 nm grain size. The sensor response was tested for hydrogen concentrations of 50, 70, 100, 200, 400, and 500 ppm at operating temperatures ranging from 250 °C to 400 °C. The sensitivity toward 50 and 200 ppm of hydrogen at the optimum operating temperature of 350 °C were about 78% and 98%, respectively. The response was linear within the range of 50–200 ppm of hydrogen concentration. Our results demonstrated the potential application of ZnO nanostructure for fabricating cost-effective and high-performance gas sensors.     

Probing non-dipole allowed excitations in highly correlated materials with nanoscale resolution

Here, we demonstrate that non-dipole allowed d–d excitations in NiO can be measured by electron energy loss spectroscopy (EELS) in transmission electron microscopes (TEM). Strong excitations from ³A_2g ground states to ³T_1g excited states are measured at 1.7 and 3 eV when transferred momentum are beyond 1.5 Å⁻¹. We show that these d–d excitations can be collected with a nanometrical resolution in a dedicated scanning transmission electron microscope (STEM) by setting a good compromise between the convergence angle of the electron probe and the collected transferred momentum. This work opens new possibilities for the study of strongly correlated materials on a nanoscale.     

Effect of pre-readout annealing treatments on TL mechanism in tellurite glasses at therapeutic radiation doses level

The higher sensitization for thermal annealing on TL mechanism in the region 550–600 °C for 80(TeO₂)–5(TiO₂)–(15 − x) (WO₃)–(x) A_nO_m where A_nO_m = Nb₂O₅, Nd₂O₃, Er₂O₃ and x = 5 mol% has been measured. The behavior of trap centers and luminescence centers has been investigated for tellurite glasses doped with rare earth oxides irradiated at 0.5 up to 2 Gy and annealed at different temperatures in the range 350–700 °C. The behavior of the three types of tellurite glasses is analyzed regarding to their kinetic parameters and luminescence emission which enhance the claim of tellurite glasses for use as TLD material at therapeutic radiation doses.     

Thermal sensors based on p-Pb0.925Yb0.075Te:Te and n-Pb0.925Yb0.075Se0.2Te0.8 thin films grown using thermal evaporation method

We utilize p-Pb_0.925Yb_0.075Te:Te and n-Pb_0.925Yb_0.075Se_0.2Te_0.8 ingots in a standard solid-state microwave synthesis route to fabricate thermally evaporated thin films. The nanostructure and composition of the films were studied through X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), and energy dispersive X-ray spectroscopy (EDX). The Seebeck coefficient and electrical conductivity were measured at a temperature range of 298–523 K. The micro-thermoelectric devices were composed of 20 pairs and 10 pairs of p-Pb_0.925Yb_0.075Te:Te and n-Pb_0.925Yb_0.075Se_0.2Te_0.8 thin films on glass substrates, respectively. The dimensions of the thin films thermoelectric generators which comprised of 10-pair were 12 mm × 10 mm, whereas, 20-pair were 23 mm × 20 mm, respectively of legs connected through aluminum electrodes. The serial 20-pair p–n thermocouples generated a maximum output open-circuit voltage of 275.3 mV and a maximum output power of 54.37 nW at a temperature difference of ΔT = 162 K; the values are 109.4 mV and 16.68 nW at ΔT = 162 K for the 10-pair thermocouples, respectively.     

A system for gas sensing employing correlation spectroscopy and wavelength modulation techniques with a multimode diode laser

A tunable multi-mode diode laser system based on correlation spectroscopy and wavelength modulation spectroscopy (TMDL–COSPEC–WMS) is designed and demonstrated for the concentration measurements of oxygen using A-band absorption lines of oxygen around 760 nm. The O₂ concentrations are conversed from the relation between the normalized WMS-2f signal peak heights of the measurement and reference signals which selected based on high signal to noise ratio and correlation coefficient. The correlation and the fitted slope between the measured and actual O₂ concentration are 0.9987 and of 1.025 ± 0.012 respectively over the tested range, which indicate the high linearity and accuracy of the system. A sensitivity of 350 ppm m is approved using 30 successive measurements with each measurement time taking ∼20 s during 30 min. A continuous measurement for oxygen in ambient air during approximately 200 min confirms the stability and the capability of the system.     

Study of structures at the boundary and defects in organic thin films of perchlorocoronene by high-resolution and analytical transmission electron microscopy

Both the periodic and non-periodic structures of perchlorocoronene (C₂₄Cl₁₂) crystals were characterized by high-resolution transmission electron microscopy (HRTEM), electron diffraction (ED), electron energy-loss spectroscopy (EELS), and energy-filtered transmission electron microscopy (EFTEM). The HRTEM images at the boundary of the C₂₄Cl₁₂ crystals exhibit the flexibility of defect structures, where molecules align to compensate for the discontinuity between two different domains. Emphasized by the filtered images, it was found that the non-periodic regions are created everywhere with a small electron beam irradiation (∼10⁶ electrons nm⁻²) and then spread over the entire regions to completely destroy the periodic structures after a higher electron dose (∼2×10⁶ electrons nm⁻²). The effect of the electron beam irradiation was monitored by ED, EELS, and EFTEM, where periodic structures and content elements are well preserved up to 10⁶ electrons nm⁻², but chlorine atoms decreased with a much higher electron dose. This is explained by the breakage of the C–Cl bond to detach chlorine atoms, confirmed by energy-loss near the edge structures (ELNES) of carbon π? peaks and chlorine loss at the edge of the specimen, as well as by theoretical simulation. The detachment of chlorine is localized at the peripheral edge around a hole confirmed by core-loss EFTEM imaging.     

High- and low-frequency noise in Cs and in liquid metal ion sources

Fundamental Physics space missions set rigid thrust noise limits for liquid metal ion thrusters used as actuators on drag-free platforms aboard the spacecraft. We have measured current-, voltage- and thrust noise of Cs and In LMIS, foreseen as prime candidates in these missions. In the high-frequency range, quasiperiodic oscillations around ∼10⁵ Hz can be observed for both types of emitters with frequency depending on emission current. In the low-frequency range (1–10⁻³ Hz), which is particularly important for drag-free control, different types of noise events are observed, which in some instances show definite signs of deterministic chaos (period doubling, self-similarity). High-frequency current oscillations are generally ascribed to electro-hydrodynamic oscillations of the TAYLOR cone and the jet at its apex, with concomitant emission of charged nanodroplets. Comparison of theory and experiment shows unsatisfactory agreement in predicted vs. measured current oscillation frequencies and large disagreement in droplet emission frequencies. No theory is presently available for describing low-frequency noise events. In terms of a linearized Mair theory it is, however, shown that these noise events can be efficiently described by spontaneous variations in electrical emitter impedance. In spite of this impedance noise, the mission requirements for thrust noise (<0.1 μN/Hz^1/2) can be met by a thrust-stabilized In emitter.     

Polypyrrole-NiO hybrid nanocomposite: Structural,morphological, optical and electrical transport studies

Polypyrrole (PPy)-nickel oxide (NiO) hybrid nanocomposite thin films have been prepared by spin coating method. The PPy–NiO hybrid nanocomposites were characterized for structural, morphological, optical and electrical analysis, and the results were compared with the pure PPy films. The structural and optoelectronic properties of PPy–NiO hybrid nanocomposites are quite different from those of pure PPy and NiO nanoparticles, which were attributed to the strong interaction between the PPy and NiO nanoparticles. The XRD pattern shows that broad peak of PPy becoming weaker on increasing the content of NiO nanoparticles in the PPy–NiO hybrid nanocomposites. Also the diffraction peaks of NiO nanoparticles in PPy–NiO (10–50 wt%) nanocomposites were found to shift to lower 2θ values. The morphological studies revealed that the transformation of granular morphology of PPy to the nanospheres and clusters in the PPy–NiO hybrid nanocomposites. FTIR spectra of PPy–NiO hybrid nanocomposites, revealed that the main absorption at 1204 cm⁻¹ and 1559 cm⁻¹ are affected by the presence of NiO nanoparticle in pure PPy and get shifted to 1216 cm⁻¹ and 1570 cm⁻¹ respectively indicates, insertion of NiO nanoparticles in the PPy–NiO hybrid nanocomposite. UV–vis absorption spectrum of PPy corresponding to λ_max = 442 nm is blue shifted to λ_max = 375 nm in the PPy–NiO hybrid nanocomposites, reveals strong interaction between PPy and NiO nanoparticles. The room temperature dc electrical conductivity is increased from 8.66 × 10⁻⁹ to 4.08 × 10⁻⁷ (Ω/cm)⁻¹ as the content of NiO nanoparticles increased from 10 to 50 in wt% in the PPy–NiO hybrid nanocomposites.     

Friction and Wear Properties of IF–MoS2 as Additive in Paraffin Oil

Inorganic fullerene-like (IF) MoS₂ nanoparticles with diameters ranging from 70 to 120 nm were synthesized by desulphurizing the MoS₃ precursor and characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM). Tribological properties of the IF–MoS₂, as lubricating oil additive, were evaluated using a MMW-1 four-ball tribotester. The wear scar was examined with an optical microscope and scanning electron microscopy (SEM). The wear resistance of the paraffin oil was improved and the friction coefficient of the oil was decreased by addition of the IF–MoS₂ nanoparticles. The mechanism of friction and wear of the IF–MoS₂ nanoparticles was discussed.     

Transmission electron microscopy at 20 kV for imaging and spectroscopy

The electron optical performance of a transmission electron microscope (TEM) is characterized for direct spatial imaging and spectroscopy using electrons with energies as low as 20 keV. The highly stable instrument is equipped with an electrostatic monochromator and a C_S-corrector. At 20 kV it shows high image contrast even for single-layer graphene with a lattice transfer of 213 pm (tilted illumination). For 4 nm thick Si, the 200 reflections (271.5 pm) were directly transferred (axial illumination). We show at 20 kV that radiation-sensitive fullerenes (C₆₀) within a carbon nanotube container withstand an about two orders of magnitude higher electron dose than at 80 kV. In spectroscopy mode, the monochromated low-energy electron beam enables the acquisition of EELS spectra up to very high energy losses with exceptionally low background noise. Using Si and Ge, we show that 20 kV TEM allows the determination of dielectric properties and narrow band gaps, which were not accessible by TEM so far. These very first results demonstrate that low kV TEM is an exciting new tool for determination of structural and electronic properties of different types of nano-materials.     

Charge compensation by in-situ heating for insulating ceramics in scanning electron microscope

With a steady temperature increase under high vacuum (HV) in an environmental scanning electronic microscope, we observed charge-free characterization and fine secondary electron (SE) images in focus for insulating ceramics (alumina (Al₂O₃), aluminum nitride (AlN), pure magnesium silicate (Mg₂SiO₄)). The sample current I_sc increased from −8.18×10⁻¹³ to 2.76×10⁻⁷ A for Al₂O₃ and −9.28×10⁻¹² to 2.77×10⁻⁶ A for AlN with the temperature increased from 298 to 633 K. The surface conductance σ increased from 5.6×10⁻¹³ to 5.0×10⁻¹¹/Ω for Al₂O₃ and 1.1×10⁻¹² to 1.0×10⁻⁷/Ω for AlN with the temperature increased from 363 to 593 K. The SE image contrast obtained via heating approach in high vacuum with an Everhart–Thornley SE-detector was better than that via conventional approach of electron–ion neutralization in low vacuum (LV) with a gaseous SE-detector. The differences of compensation temperatures for charge effects indicate dielectric and thermal properties, and band structures of insulators. The charge compensation mechanisms of heating approach mainly relate to accelerated release of trapped electrons on insulating surface and to increase of electron emission yield by heating.     

The calibration and error compensation techniques for an Articulated Arm CMM with two parallel rotational axes

The calibration and error compensation techniques for an Articulated Arm Coordinate Measuring Machine (AACMM) with two parallel rotational axes are proposed. An improved six-parameter D–H model is established. The reversal techniques are used to calibrate the parallelism errors, arm lengths and zero position of the AACMM. The effects of the bending and torsion deformations caused by the gravity of the arms are removed. The experiments prove that the calibration method is simple and the measurement expanded uncertainty (_2uc$2_{u_c}$) of the developed AACMM with a measuring range of (∅200–∅1000 mm) × 250 mm is less than 10 μm after error compensation.     

Medium-range order in molecular materials: Fluctuation electron microscopy for detecting fullerenes in disordered carbons

During a fluctuation electron microscopy (FEM) study of disordered carbons, we found that samples containing C₆₀ exhibit a normalized variance peak at 7.1 nm⁻¹ that appears to be a unique indicator of tight curvature in layered materials. This peak is associated with the characteristic in-plane carbon–carbon bond distance of ∼0.14 nm in graphene. Diffraction from this spacing is normally forbidden in planar graphene (and graphite), but becomes allowed when the layer structure is interrupted. Such interruptions arise at the edges of graphite fragments and also when 5-rings are incorporated into a layer. We show that the curvature induced by a high density of 5-rings, such as that in C₆₀, can dominate the variance peak at 7.1 nm⁻¹. FEM simulations reveal that the variance peak at ∼7.1 nm⁻¹, which we label F₁, is one of several fullerene-signature peaks, with others occurring at Q values of 10.6 nm⁻¹ (F₂) and 12.4 nm⁻¹ (F₃). We conclude that FEM is a sensitive method for detecting dilute quantities of highly curved pentagon-rich fullerenes, such as C₆₀, when dispersed within disordered graphitic carbon.     

Structural imaging of β-Si3N4 by spherical aberration-corrected high-resolution transmission electron microscopy

Modern transmission electron microscopes (TEM) allow utilizing the spherical aberration coefficient as an additional free parameter for optimizing resolution and contrast. By tuning the spherical aberration coefficient of the objective lens, isolated nitrogen atom columns as well as the Si–N dumbbells within the six-membered ring were imaged in β-Si₃N₄ along [0 0 0 1] and [0 0 0 1¯] projections with a dumbbell spacing of 0.94 Å in white atom contrast. This has been obtained with negative or positive spherical aberration coefficient. We clarify contrast details in β-Si₃N₄ by means of extended image calculations. A simple procedure has been shown for pure phase imaging, which is restricted to linear imaging conditions.