Studies on surface graft polymerization of acrylic acid onto PTFE film by remote argon plasma initiation

The graft polymerization of acrylic acid (AAc) was carried out onto poly(tetrafluoroethylene) (PTFE) films that had been pretreated with remote argon plasma and subsequently exposed to oxygen to create peroxides. Peroxides are known to be the species responsible for initiating the graft polymerization when PTFE reacts with AAc. We chose different parameters of remote plasma treatment to get the optimum condition for introducing maximum peroxides (2.87 × 10⁻¹¹ mol/cm²) on the surface. The influence of grafted reaction conditions on the grafting degree was investigated. The maximum grafting degree was 25.2 μg/cm². The surface microstructures and compositions of the AAc grafted PTFE film were characterized with the water contact angle meter, Fourier-transform infrared spectroscopy (ATR-FTIR) and X-ray photoelectron spectroscopy (XPS). Contact angle measurements revealed that the water contact angle decreased from 108° to 41° and the surface free energy increased from 22.1 × 10⁻⁵ to 62.1 × 10⁻⁵ N cm⁻¹ by the grafting of the AAc chains. The hydrophilicity of the PTFE film surface was greatly enhanced. The time-dependent activity of the grafted surface was better than that of the plasma treated film.     

Investigation of the effect of power ultrasound on the nucleation of water during freezing of agar gel samples in tubing vials

Nucleation, as an important stage of freezing process, can be induced by the irradiation of power ultrasound. In this study, the effect of irradiation temperature (−2 °C, −3 °C, −4 °C and −5 °C), irradiation duration (0 s, 1 s, 3 s, 5 s, 10 s or 15 s) and ultrasound intensity (0.07 W cm⁻², 0.14 W cm⁻², 0.25 W cm⁻², 0.35 W cm⁻² and 0.42 W cm⁻²) on the dynamic nucleation of ice in agar gel samples was studied. The samples were frozen in an ethylene glycol-water mixture (−20 °C) in an ultrasonic bath system after putting them into tubing vials. Results indicated that ultrasound irradiation is able to initiate nucleation at different supercooled temperatures (from −5 °C to −2 °C) in agar gel if optimum intensity and duration of ultrasound were chosen. Evaluation of the effect of 0.25 W cm⁻² ultrasound intensity and different durations of ultrasound application on agar gels showed that 1 s was not long enough to induce nucleation, 3 s induced the nucleation repeatedly but longer irradiation durations resulted in the generation of heat and therefore nucleation was postponed. Investigation of the effect of ultrasound intensity revealed that higher intensities of ultrasound were effective when a shorter period of irradiation was used, while lower intensities only resulted in nucleation when a longer irradiation time was applied. In addition to this, higher intensities were not effective at longer irradiation times due to the heat generated in the samples by the heating effect of ultrasound. In conclusion, the use of ultrasound as a means to control the crystallization process offers promising application in freezing of solid foods, however, optimum conditions should be selected.     

Study of HfSiO film prepared by electron beam evaporation for high-k gate dielectric applications

The purpose of this paper is to report some experimental results with HfSiO films formed on silicon substrates by electron beam evaporation (EB-PVD) and annealed at different temperatures. The images of atomic force microscope (AFM) indicated that HfSiO film annealed at 900 °C was still amorphous, with a surface roughness of 0.173 nm. X-ray photoelectron spectroscopy (XPS) analysis revealed that the chemical composition of the film was (HfO₂)₃(SiO₂) and Hf-Si-O bonds existed in the annealed film. Electrical measurements showed that the equivalent oxide thickness (EOT) was 4 nm, the dielectric constant was around 6, the breakdown voltage was 10 MV/cm, the fixed charge density was −1.2 × 10¹² cm⁻², and the leakage current was 0.4 μA/cm² at the gate bias of 2 V for 6 nm HfSiO film. The annealing after deposition effectively reduced trapping density and the leakage current, and eliminated hysteresis in the C-V curves. Annealing also induced SiO₂ growth at the interface.     

Ag-N doped ZnO film and its p-n junction fabricated by ion beam assisted deposition

Ag-N doped ZnO film was synthesized by ion beam assisted deposition and its electrical properties and annealing property were investigated. The films remained p-type even after annealing at 400 °C in air for 10 min. While the annealing temperature went up to 500 °C, the conduction type of these films shifted from p-type to n-type. The p-type ZnO film revealed low resistivity (0.0016 Ω cm), low Hall mobility (0.65 cm² V⁻¹ s⁻¹) and high carrier concentration (5.8 × 10²⁰ cm⁻³). ZnO p-n homojunction consisting of a p-type layer (Ag-N doped ZnO film) and an n-type layer (In-doped ZnO film) had been fabricated by ion beam assisted deposition. With electrical measurement, its current-voltage curve had a typical rectifying characteristic with current rectification ratio of 25 at bias ±5 V and a reverse current of 0.01 mA at −5 V. The depletion width was estimated 3.8 nm by using p-n junction equation.     

Morphology and photoluminescence of ultrasmall size of Ge quantum dots directly grown on Si(0 0 1) substrate

High density and ultrasmall size of Ge quantum dots (QDs) have been achieved directly on Si(0 0 1) (2 × 1) reconstruction surface. Their detailed morphology was observed by atomic force microscope (AFM) and shows that small pyramids, small domes, huts, and multi-headed large domes coexist in the film grown at 400 °C, while small domes and multi-headed large domes formed at 450 °C. Their low temperature photoluminescence (PL) showed that a very strong non-phonon (NP) peak with a large blue shift of 0.19 eV at 14 K, which can be attributed to their very high areal density, 5.2 × 10¹¹ cm⁻², and sub-10-nm mean size, 7.6 ± 2.3 nm.     

A novel polyol method to synthesize colloidal silver nanoparticles by ultrasonic irradiation

A polyol synthesis of silver nanoparticles in the presence of ultrasonic irradiation was compared with other configurations (at ambient temperature, 120 °C, and 120 °C with injected solutions) in the absence of ultrasonic irradiation in order to obtain systematic results for morphology and size distribution. For applying ultrasonic irradiation, rather fine and uniform spherical silver particles (21 ± 3.7 nm) were obtained in a simple (at ambient temperature without mechanical stirring) and fast (within 4 min, 3.61 × 10⁻³ mol min⁻¹) manner than other cases (at ambient temperature (for 8 h, 0.03 × 10⁻³ mol min⁻¹): 86 ± 16.8 nm, 120 °C (for 12 min, 1.16 × 10⁻³ mol min⁻¹): 64 ± 14.9 nm, and 120 °C with injected solutions (during 12 min): 35 ± 6.8 nm; all other cases contained anisotropic shaped particles). Even though the temperature of polyol reaction reached only at 80 °C (<120 °C) in the presence of ultrasonic irradiation, a uniform mixing (i.e. enhanced collision between silver particle and surrounding components) by ultrasonic irradiation might induce a better formation kinetics and morphological uniformity.     

Temperature effect on water desorption from methylcellulose films studied by thermal FT-IR microspectroscopy

Temperature-induced desorption behavior of water from methylcellulose (MC) film was investigated by a novel microscopic Fourier transform infrared (FT-IR) spectroscopy equipped with thermal analyzer (thermal FT-IR microscopic system) and thermogravimetric analysis (TGA). The result indicates that the weight loss of water from MC film was markedly correlated to the IR spectral changes of OH stretching (3000-3800 cm⁻¹) and bending (1649 cm⁻¹) modes of water molecules. The shift of OH stretching mode from 3461 to 3481 cm⁻¹ was accompanied with the water loss from MC film induced by temperature effect. Two stages of water desorption from MC film were proposed: the first stage within the 35-65 °C had a dramatic IR peak shift from 3461 to 3477 cm⁻¹ and accompanied with a largest weight loss of water from MC film, which might be mainly due to the desorption of free water with minor weakly hydrogen-bonded water; the second stage beyond 65 °C would be desorption of moderately hydrogen-bonded bound water, due to the gradual IR spectral shift from 3477 to 3481 cm⁻¹ and a slower weight loss of water from MC film. The changes in peak area ratio of 1649 cm⁻¹/1374 cm⁻¹ with the temperature also confirmed the IR spectral peak shift of the OH stretching mode via the water loss from MC film. The temperature-dependent dissociation of intermolecular and intramolecular hydrogen bonds within water molecules and/or between water/MC interaction might be responsible for the desorption kinetics of water from MC film.     

The analysis of superconducting thin films modified by AFM lithography with a spectroscopic imaging technique

A practical application of nanolithography using atomic force microscopy (AFM) was accomplished in fabricating superconducting flux flow transistors (SFFTs). It was found that it is essential to oxidize a superconducting thin film, grown on LaAlO₃ substrates by a thermal CVD process, by an applied bias voltage between a conducting AFM tip and the films, since I/V characteristics of the device were mainly controlled by the modified gate area in the SFFT. After AFM lithography, the critical current of an YBCO thin film was found to be degraded. Raman lines in the modified YBCO film were observed at 340, 502, and 632 cm⁻¹ in Ar the laser system and 142, 225, and 585 cm⁻¹ in the He-Ne laser system. Raman fluorescence images were also produced by mapping the Raman peaks. A strain image of the peak at 142 cm⁻¹ was most clear, which means that a surface of the YBCO thin film was changed into the YBa₂Cu₃O₆ insulator. AFM nanolithography enables us to fabricate a channel between a source and a drain in SFFT in order to get I/V characteristics.     

Variable-temperature FT-IR studies on the thermodynamics of carbon dioxide adsorption on a faujasite-type H-Y zeolite

Adsorption of carbon dioxide on a faujasite-type H-Y zeolite (Si:Al = 2.6:1) was studied by variable-temperature (200-290 K range) infrared spectroscopy. Adsorbed CO₂ molecules interact with the Brønsted acid Si(OH)Al groups located inside the zeolite supercage, bringing about a characteristic bathochromic shift of the O-H stretching mode from 3645 cm⁻¹ (free OH group) to 3540 cm⁻¹ (hydrogen-bonded CO₂ adsorption complex). Simultaneously, the asymmetric (ν₃) mode of adsorbed CO₂ is observed at 2353 cm⁻¹. From the observed variation of the integrated intensity of the 3645 and 2353 cm⁻¹ IR absorption bands upon changing temperature, corresponding values of standard adsorption enthalpy and entropy were found to be ΔH° = −28.5(±1) kJ mol⁻¹ and ΔS° = −129(±10) J mol⁻¹ K⁻¹. Comparison with the reported values of ΔH° for CO₂ adsorption on other zeolites is briefly discussed.     

The sodium diffusion in aluminium-oxide

The transport of Na through the polycrystalline ceramic arc tube of high intensity discharge lamps has been investigated. This complex process consists of several steps: solution in the ceramics, diffusion through the ceramics, leaving the bulk phase, evaporation from the surface. Among the listed processes the kinetics of the diffusion was examined in the temperature range 400-1200 °C, separately from other disturbing effects. X-ray photoelectron spectroscopy (XPS) and secondary ion mass spectroscopy (SIMS) were used to determine the concentration depth profiles. The obtained results confirmed that the grain boundary diffusion plays an important role in the transport process of sodium through the ceramic wall. The bulk and the grain boundary diffusion coefficients and the temperature dependencies of these transport processes have been determined. The activation energy of Na bulk diffusion is 56.5 ± 6.7 kJ/mol at 900-1200 °C, respectively the activation energies of Na grain boundary diffusion amount to 97.5 ± 21.6 kJ/mol in the temperature range 700-1100 °C and 7.7 ± 4.0 × 10⁻² kJ/mol at 400-700 °C. The preexponential factor of the bulk diffusion was found to be D_o = 5.1 × 10⁻¹⁵ ± 9.5 × 10⁻¹⁷ cm²/s in the temperature range 900-1200°C, whereas the preexponential factors of grain boundary diffusion are D_o = 1.1 × 10⁻¹⁰ ± 1.1 × 10⁻¹¹ cm²/s at 700-1100 °C and D_o = 7.5 × 10^-15 ± 1.5 × 10⁻¹⁷ cm²/s at 400-700 °C.     

An atomic force microscopy study of DNA hairpin probes monolabelled with gold nanoparticle: Grafting and hybridization on oxide thin films

First and original results are reported regarding the surface evolution of two kinds of oxide film after covalent grafting and hybridization of hairpin oligonucleotide probes. These hairpin probes were monolabelled with a 1.4 nm gold nanoparticle. One kind of oxide film was rough Sb doped SnO₂ oxide film and the other kind was smooth SiO₂ film. Same process of covalent grafting, involving a silanization step, was performed on both oxide surfaces. Atomic force microscopy (AFM) was used to study the evolution of each oxide surface after different steps of the process: functionalization, probe grafting and hybridization. In the case of rough SnO₂ films, a slight decrease of the roughness was observed after each step whereas in the case of smooth SiO₂ films, a maximum of roughness was obtained after probe grafting. Step height measurements of grafted probes could be performed on SiO₂ leading to an apparent thickness of around 3.7 ± 1.0 nm. After hybridization, on the granular surface of SnO₂, by coupling AFM with SEM FEG analyses, dispersed and well-resolved groups of gold nanoparticles linked to DNA duplexes could be observed. Their density varied from 6.6 ± 0.3 × 10¹⁰ to 2.3 ± 0.3 × 10¹¹ dots cm⁻². On the contrary, on smooth SiO₂ surface, the DNA duplexes behave like a dense carpet of globular structures with a density of 2.9 ± 0.5 × 10¹¹ globular structures cm⁻².     

Carbon nano dots scale by focused ion beam system for MIS diode nano devices

Metal-insulator-semiconductor (MIS) structures with a nanocrystal carbon (nc-C) embedded in SiO₂ thin films were fabricated using a focused ion beam (FIB) system with a precursor of low-energy Ga⁺ ion and carbon source. The crystallinity of nc-C was investigated by Raman spectroscopy and atomic force microscopy (AFM). Raman spectra indicate the evidence of crystallization of nc-C after annealed at 600 °C by the sharp peak at 1565 cm⁻¹ in graphite (sp²), while no peak of diamond (sp³) could be seen at 1333 cm⁻¹. The AFM images showed the nc-C dots controlled with diameter of 100 nm, 200 nm and 300 nm, respectively. The above results revealed that the nc-C dots had sufficiently stuck onto SiO₂ films. The hysterisis loop in the capacitance-voltage characteristics appeared in the MIS device with SiO₂/nc-C/SiO₂ structure in which voltage shift is 0.32 V for radical oxidation and 0.14 V for dry oxidation, respectively.     

Infrared emission spectrum of hot D2O

An emission spectrum of hot D₂O (1500 °C) has been analyzed in the 2077-4323 cm⁻¹ region. A considerable number of new vibration-rotation energy levels have been determined and two new vibrational levels identified. The new (0 4 1) and (0 2 2) vibrational levels have estimated band origins of 7343.93 ± 0.01 and 7826.38 ± 0.02 cm⁻¹, respectively.     

Effects of swift heavy ion irradiation on the electrical characteristics of Au/n-GaAs Schottky diodes

Metal-semiconductor diode of Au/n-GaAs is studied under the irradiation of swift heavy ion (SHI) beam (80 MeV ¹⁶O⁶⁺), using in situ current-voltage characterization technique. The diode parameters like ideality factor, barrier height, and leakage current are observed to vary with irradiation fluence. Significantly, the diode performance improves at a high fluence of 2 × 10¹³ ions cm⁻² with a large decrease of reverse leakage current in comparison to the original as deposited sample. The Schottky barrier height (SBH) also increases with fluence. At a high irradiation fluence of 5 × 10¹³ ions cm⁻² the SBH (0.62 ± 0.01 eV) is much larger than that of the as deposited sample (0.55 ± 0.01 eV). The diode parameters remain stable over a large range of irradiation up to fluence of 8 × 10¹³ ions cm⁻². A prominent annealing effect of the swift ion beam owing to moderate electronic excitation and high ratio of electronic energy loss to the nuclear loss is found to be responsible for the improvement in diode characteristics.     

Electrical properties of La2O3 thin films grown on TiN/Si substrates via atomic layer deposition

The electrical as well as the structural properties of La₂O₃ thin films on TiN substrates were investigated. Amorphous stoichiometric La₂O₃ thin films were grown at 300 °C via atomic layer deposition technique by using lanthanum 2,2,6,6-tetramethyl-3,5-heptanedione [La(TMHD)₃] and H₂O as precursors. Post-annealing of the grown film induced dramatic changes in structural and the electrical properties. Crystalline phases of the La₂O₃ film emerged with the increase of the post-annealing temperature. Metal-insulator-metal (MIM) capacitor was fabricated to measure the electrical properties of the grown film. The dielectric constant of the La₂O₃ thin films increased with annealing temperature to reach the value of 17.3 at 500 °C. The leakage current density of the film post-annealed at 400 °C was estimated to be 2.78 × 10⁻¹⁰ and 2.1 × 10⁻⁸ A/cm² at ±1 V, respectively.     

Evolution of surface morphology of NiO thin films under swift heavy ion irradiation

NiO nanoparticle thin films grown on Si substrates were irradiated by 107 MeV Ag⁸⁺ ions. The films were characterized by glancing angle X-ray diffraction and atomic force microscopy. Ag ion irradiation was found to influence the shape and size of the nanoparticles. The pristine NiO film consisted of uniform size (∼100 nm along major axis and ∼55 nm along minor axis) elliptical particles, which changed to also of uniform size (∼63 nm) circular shape particles on irradiation at a fluence of 3 × 10¹³ ions cm⁻². Comparison of XRD line width analysis and AFM data revealed that the particles in the pristine films are single crystalline, which turn to polycrystalline on irradiation with 107 MeV Ag ions.     

Annealing induced microstructural evolution of electrodeposited electrochromic tungsten oxide films

A significant influence of microstructure on the electrochromic and electrochemical performance characteristics of tungsten oxide (WO₃) films potentiostatically electrodeposited from a peroxopolytungstic acid (PPTA) sol has been evaluated as a function of annealing temperature. Powerful probes like X-ray diffractometry (XRD), transmission electron microscopy (TEM), UV-vis spectrophotometry, multiple step chronoamperometry and cyclic voltammetry have been employed for the thin film characterization. The as-deposited and the film annealed at 60 °C are composed of nanosized grains with a dominant amorphous phase, as well as open structure which ensues from a nanoporous matrix. This ensures a greater number of electroactive sites and a higher reaction area thereby manifesting in electrochromic responses superior to that of the films annealed at higher temperatures. The films annealed at temperatures ≥250 °C are characterized by a prominent triclinic crystalline structure and a hexagonal phase co-exists at temperatures ≥400 °C. The deleterious effect on the electrochromic properties of the film with annealing is ascribed to the loss of porosity, densification and the increasing crystallinity and grain size. Amongst all films under investigation, the film annealed at 60 °C exhibits a high transmission modulation (ΔT ∼ 68%) and coloration efficiency (η ∼ 77.6 cm² C⁻¹) at λ = 632.8 nm, charge storage capacity (Q_ins ∼ 21 mC cm⁻²), diffusion coefficient (6.08 × 10⁻¹⁰ cm² s⁻¹), fast color-bleach kinetics (t_c ∼ 275 s and t_b ∼ 12.5 s) and good electrochemical activity, as well as reversibility for the lithium insertion-extraction process upon cycling. The remarkable potential, which the film annealed at 60 °C has, for practical “smart window” applications has been demonstrated.     

Thermodynamics of nitrogen adsorption on the zeolite H-FER

Adsorption (at a low temperature) of nitrogen on the protonic zeolite H-FER results in hydrogen bonding of the adsorbed N₂ molecules with the zeolite Si(OH)Al Brønsted acid groups. This hydrogen bonding interaction leads to activation, in the IR, of the fundamental NN stretching mode, which appears at 2331 cm⁻¹. From the infrared spectra taken over a temperature range, while simultaneously recording integrated IR absorbance, temperature and nitrogen equilibrium pressure, the thermodynamics of the adsorption process was studied. The standard adsorption enthalpy and entropy resulted to be ΔH° = −20(±1) kJ mol⁻¹ and ΔS° = −131(±10) J mol⁻¹ K⁻¹, respectively.     

Nonlinear optical properties of CNHP4 nanofibers: Molecular dipole orientations and two photon absorption cross-sections

Polarized second harmonic measurements are used to determine the in- and out-of plane orientations of molecular dipoles in optical active, elongated, surface bound nanoaggregates. As a specific example, nonlinear optical active nanofibers grown from CNHP4 molecular dipoles on muscovite mica are investigated. The orientation of the dipoles relative to the substrate is found to be 7 ± 5°, whereas that of the dipoles relative to the long nanofiber axes is ± 13 ± 5°. Following 780 nm femtosecond laser excitation, the two photon action potential ησ₂ for CNHP4 is determined to be 4.7 × 10⁻⁵⁴ cm⁴ s/photon. For comparison, ησ₂ for para-hexaphenylene nanofibers is measured to be 12 × 10⁻⁵⁴ cm⁴ s/photon.     

Effect of swift (∼100 MeV) heavy ion irradiation on surface morphology and electronic transport in Fe film on Si substrate

Fe film (∼50 nm) have been deposited on pSi substrate by electron beam evaporation technique. The bilayers have been irradiated by 100 MeV Fe⁷⁺ ions having fluences of 1 × 10¹³, 1 × 10¹⁴ and 5 × 10¹⁴ ions cm⁻². SEM study of the unirradiated devices show surface modifications having a annular structures. From XRD study of the bilayer, it is observed that grain size has reduced from 70 to 25 nm after the irradiation for a fluence of 1 × 10¹⁴ ions cm⁻². Moreover electronic transport data of the bilayer show practically no effect on the current flow for a fluence of 1 × 10¹³ ions cm⁻² irradiation whereas for 1 × 10¹⁴ ions cm⁻² fluence, there is very significant change in current flow (by two orders in magnitude) across the bilayer. However, for a higher fluence of irradiation 5 × 10¹⁴ ions cm⁻², the bilayer becomes highly resistive. It has been found from the above observations that the fluence of 1 × 10¹⁴ ions cm⁻² of swift heavy ion irradiation is a optimum fluence.