Synthesis of multi-walled carbon nanotubes for NH3 gas detection

It has been recently demonstrated that carbon nanotubes (CNTs) represent a new type of chemical sensor capable of detecting a small concentration of molecules such as CO, NO₂, NH₃.In this work, CNTs were synthesized by chemical vapor deposition (CVD) on the SiO₂/Si substrate by decomposition of acetylene (C₂H₂) on sputtered Ni catalyst nanoparticles. Their structural properties are studied by atomic force microscopy, high-resolution scanning electron microscopy (HRSEM) and Raman spectroscopy. The CNTs grown at 700 °C exhibit a low dispersion in size, are about 1 μm long and their average diameter varies in the range 25–60 nm as a function of the deposition time. We have shown that their diameter can be reduced either by annealing in oxygen environment or by growing at lower temperature (less than 600 °C).We developed a test device with interdigital Pt electrodes on an Al₂O₃ substrate in order to evaluate the CNTs-based gas sensor capabilities. We performed room temperature current–voltage measurements for various gas concentrations. The CNT films are found to exhibit a fast response and a high sensitivity to NH₃ gas.     

The effect of Si surface nitridation on the interfacial structure and electrical properties of (La2O3)0.5(SiO2)0.5 high-k gate dielectric films

Thermal stability, interfacial structures and electrical properties of amorphous (La₂O₃)_0.5(SiO₂)_0.5 (LSO) films deposited by using pulsed laser deposition (PLD) on Si (1 0 0) and NH₃ nitrided Si (1 0 0) substrates were comparatively investigated. The LSO films keep the amorphous state up to a high annealing temperature of 900 °C. HRTEM observations and XPS analyses showed that the surface nitridation of silicon wafer using NH₃ can result in the formation of the passivation layer, which effectively suppresses the excessive growth of the interfacial layer between LSO film and silicon wafer after high-temperature annealing process. The Pt/LSO/nitrided Si capacitors annealed at high temperature exhibit smaller CET and EOT, a less flatband voltage shift, a negligible hysteresis loop, a smaller equivalent dielectric charge density, and a much lower gate leakage current density as compared with that of the Pt/LSO/Si capacitors without Si surface nitridation.     

The effects of hydrogen plasma pretreatment on the formation of vertically aligned carbon nanotubes

The effects of H₂ plasma pretreatment on the growth of vertically aligned carbon nanotubes (CNTs) by varying the flow rate of the precursor gas mixture during microwave plasma chemical vapor deposition (MPCVD) have been investigated in this study. Gas mixture of H₂ and CH₄ with a ratio of 9:1 was used as the precursor for synthesizing CNTs on Ni-coated TiN/Si(1 0 0) substrates. The structure and composition of Ni catalyst nanoparticles were investigated by using scanning electron microscopy (SEM) and cross-sectional transmission electron microscopy (XTEM). Results indicated that, by manipulating the morphology and density of the Ni catalyst nanoparticles via changing the flow rate of the precursor gas mixture, the vertically aligned CNTs could be effectively controlled. The Raman results also indicated that the intensity ratio of the G and D bands (I_D/I_G) is decreased with increasing gas flow rate. TEM results suggest H₂ plasma pretreatment can effectively reduce the amorphous carbon and carbonaceous particles and, thus, is playing a crucial role in modifying the obtained CNTs structures.     

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.     

Epitaxial growth of highly transparent and conducting Sc-doped ZnO films on c-plane sapphire by sol–gel process without buffer

Highly transparent and conductive scandium doped zinc oxide (ZnO:Sc) films were deposited on c-plane sapphire substrates by sol–gel technique using zinc acetate dihydrate [Zn(CH₃COO)₂·2H₂O] as precursor, 2-methoxyethanol as solvent and monoethanolamine as a stabilizer. The doping with scandium is achieved by adding 0.5 wt% of scandium nitrate hexahydrate [(ScNO₃·6H₂O)] in the solution. The influence of annealing temperature (300–550 °C) on the structural, optical and electrical properties was investigated. X-ray Diffraction study revealed that highly c-axis oriented films with full-width half maximum of 0.16° are obtained at an annealing temperature of 400 °C. The surface morphology of the films was judged by SEM and AFM images which indicated formation of grains. The average transmittance was found to be above 92% in the visible region. ZnO:Sc film, annealed at 400 °C exhibited minimum resistivity of 1.91 × 10⁻⁴ Ω cm. Room-temperature photoluminescence measurements of the ZnO:Sc films annealed at 400 °C showed ultraviolet peak at 3.31eV with a FWHM of 11.2 meV, which are comparable to those found in high-quality ZnO films. Reflection high-energy electron diffraction pattern confirmed the epitaxial nature of the films even without introducing any buffer layer.     

Purification of carbon nanotubes grown by thermal CVD

We show the results of a set of purifications on carbon nanotubes (CNT) by acid and basic treatments. CNTs were obtained by thermal decomposition of camphor at 850 °C in a CVD growth system, by means of a growth process catalyzed by iron clusters originating from the addition of ferrocene in the precursors mixture. The purification procedures involved HNO₃, H₂SO₄, HSO₃Cl and NaOH for different process temperatures.As-grown CNTs showed a consistent presence of metal catalyst (about 6 wt%), evidenced by TGA. The purification treatments led to a certain amount of opening of the CNT tips, with a consequent loss of metal catalyst encapsulated in tips. This is also confirmed by BET analysis, which showed an increase of the surface area density of CNT after the purification.FT-IR and XPS revealed the presence of carboxylic groups on the CNT surface chemically modified by the harsh environment of the purification process.Among the various treatments that have been tested, the 1:3 solution of nitric and sulphuric acid was the most effective in modifying the CNT surface and inducing the formation of functional groups.     

Effect of annealing temperature on microstructure, hardness and adhesion properties of TiSixNy superhard coatings

A series of TiSi_xN_y superhard coatings with different Si contents were prepared on M42 steel substrates using two Ti and two Si targets by reactive magnetron sputtering at 500 °C. These samples were subsequently vacuum-annealed at 500, 600, 700, 800 and 900 °C, respectively. X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), microindenter, Rockwell hardness tester and scratch tester were applied to investigate the microstructure, phase configuration, hardness and adhesion properties of as-deposited and annealed samples. The results indicated that there were two bonds, TiN and Si₃N₄, in all presently deposited TiSi_xN_y thin films, that structure was nanocomposite of nanocrystalline (nc-) TiN embedded into amorphous Si₃N₄ matrices. Annealing treatment below 900 °C played a little role in microstructure and hardness of the coatings although it greatly affected those of steel substrates. The film-substrate adhesion strength was slightly increased, followed by an abrupt decrease with increasing annealing temperature. Its value got to the maximum at 600 °C. Annealing had little effect on the friction coefficient with its value varying in the range of 0.39-0.40.     

Catalyst free rutile phase TiO2 nanorods as efficient hydrogen sensor with enhanced sensitivity and selectivity

Using a low-cost hydrothermal method, we demonstrated the fabrication of phase pure rutile phase high-density vertically aligned TiO₂ nanorods-based catalyst-free hydrogen (H₂) gas sensor. The synthesized TiO₂ nanorods on FTO are decorated with the aluminum interdigitated electrode pattern for electrical measurements. TiO₂ nanorods-based hydrogen sensor showed the optimum response of ∼53.18% at 150 ppm H₂ concentration relative to air at 100 °C. The measured response and recovery time of TiO₂ nanorods are 85 and 620 s, respectively. The TiO₂ nanorods-based H₂ gas sensor showed a relatively better response, good reproducibility, and stability at moderate temperatures, i.e., 50 and 100 °C. The electrochemical impedance measurements showed a small variation in the surface characteristics of TiO₂ nanorods before and after exposing H₂ gas. The carrier lifetime at 50 °C and 100 °C at 150 ppm are 5 μs and 3 μs, respectively. Interestingly, H₂ selectivity is also observed against H₂S, CO, and NH₃ gases, suggesting that high-density vertically aligned TiO₂ nanorods can be a good candidate for efficient hydrogen sensing at relatively low temperatures.     

Visible photoluminescence from silicon nanoclusters embedded in silicon nitride films prepared by remote plasma-enhanced chemical vapor deposition

The photoluminescence (PL) of silicon nanoclusters embedded in silicon nitride films grown by remote plasma-enhanced chemical vapor deposition at 200 °C, using mixtures of SiCl₄/H₂/Ar/NH₃ is investigated. It was found that the color and the intensity of the PL of the as-grown samples depend on the H₂ flow rate, and there is an optimum flow for which a maximum luminescence is obtained. A strong improvement of the PL intensity and change in color was obtained with annealing treatments in the range of 500–1000 °C. The changes in the composition, structure and optical properties of the films, as a function of H₂ flow rate and thermal treatments, were studied by means of Fourier-transform infrared spectroscopy, X-ray photoelectron spectroscopy, ellipsometry and ultraviolet–visible transmission measurements. We conclude that the PL can be attributed to quantum confinement effect in silicon nanoclusters embedded in silicon nitride matrix, which is improved when a better passivation of the nanoclusters surface is obtained.     

Dimensional evolution of silicon nanowires synthesized by Au–Si island-catalyzed chemical vapor deposition

This study explores the nucleation and morphological evolution of silicon nanowires (Si-NWs) on Si (0 0 1) and (1 1 1) substrates synthesized using nanoscale Au–Si island-catalyzed rapid thermal chemical vapor deposition. The Au–Si islands are formed by Au thin film (1.2–3.0 nm) deposition at room temperature followed by annealing at 700 °C, which are employed as a liquid-droplet catalysis during the growth of the Si-NWs. The Si-NWs are grown by exposing the substrates with Au–Si islands to a mixture of gasses SiH₄ and H₂. The growth temperatures and the pressures are 500–600 °C and 0.1–1.0 Torr, respectively. We found a critical thickness of the Au film for Si-NWs nucleation at a given growth condition. Also, we observed that the dimensional evolution of the NWs significantly depends on the growth pressure and temperature. The resulting NWs are 30–100 nm in diameter and 0.4–12.0 μm in length. For Si (0 0 1) substrates 80% of the NWs are aligned along the 1 1 1 direction which are 30° and 60° with respect to the substrate surface while for Si (1 1 1) most of the NWs are aligned vertically along the 1 1 1 direction. In particular, we observed that there appears to be two types of NWs; one with a straight and another with a tapered shape. The morphological and dimensional evolution of the Si-NWs is significantly related to atomic diffusion kinetics and energetics in the vapor–liquid–solid processes.     

Transient-enhanced Si diffusion on natural-oxide-covered Si(0 0 1) nano-structures during vacuum annealing

The morphology of annealed patterned Si(0 0 1) wire templates was studied by several techniques. We found an enormous Si-mass transport on the Si surface at usual oxide desorption temperatures around 900°C under UHV conditions. Heat treatment of 5 min transforms the initially rectangular wire profiles with a height of 300 nm to flat (<100 nm) and faceted triangular ridges exhibiting thermodynamically preferred {1 1 1}- and {3 1 1}-facets.It was found that the natural SiO₂ on the predefined wire pattern must be responsible for the degradation of the wire structure. Removing the SiO₂ layer from the Si wires ex situ with an HF dip preserves the rectangular structures during high-temperature annealing. The Si–SiO₂ interface was investigated with high-resolution transmission electron microscopy to image the Si wire surface and the natural oxide layer in detail.     

Photoluminescence from amorphous silica nanowires synthesized using TiN/Ni/SiO2/Si and TiN/Ni/Si substrates

Photoluminescence characteristics of amorphous silica nanowires (a-SiONWs) grown on TiN/Ni/Si and TiN/Ni/SiO₂ substrates have been studied. A-SiONWs grown on TiN/Ni/Si substrates show a Si-rich composition compared to those grown from TiN/Ni/SiO₂/Si. The emission characteristics of the nanowires were found to depend on the type of substrate. By annealing the a-SiONWs grown on TiN/Ni/Si in air, emission bands shift from blue to green bands. It is likely that silicon to oxygen ratio is an important factor in deciding the types of defects and emission bands of amorphous silica nanowires.     

The influence of the annealing conditions on the photoluminescence of ion-implanted SiO2:Si nanosystem at additional phosphorus implantation

The influence of P ion doping on the photoluminescence (PL) of the system of nanocrystals in SiO₂ matrix (SiO₂:Si) both without annealing and after annealing at various temperatures (provided before and after additional P implantation) is investigated. The Si and P implantation was carried out with ion energies of 150 keV and doses Φ_Si=10¹⁷ cm⁻² and Φ_P=(0.1–300)×10¹⁴ cm⁻² (current density j3 μAcm⁻²). The system after Si implantation was formed at 1000°C and 1100°C (2 h). For the case of SiO₂:Si system as-implanted by P, the intensity of PL was drastically quenched, but partially retained. As for the step-by-step annealing (at progressively increased temperatures) carried out after P implantation, the sign and degree of doping effect change with annealing temperature. The possible mechanisms of these features are discussed.     

Temperature and carbon source effects on methane–air flame synthesis of CNTs

We have conducted experimental and numerical studies on flame synthesis of carbon nanotubes (CNTs) to investigate the effects of three key parameters – selective catalyst, temperature and available carbon sources – on CNT growth. Two different substrates were used to synthesize CNTs: Ni-alloy wire substrates to obtain curved and entangled CNTs and Si-substrates with porous anodic aluminum oxide (AAO) nanotemplates to grow well-aligned, self-assembled and size-controllable CNTs, each using two different types of laminar flames, co-flow and counter-flow methane–air diffusion flames. An appropriate temperature range in the synthesis region is essential for CNTs to grow on the substrates. Possible carbon sources for CNT growth were found to be the major species CO and those intermediate species C₂H₂, C₂H₄, C₂H₆, and methyl radical CH₃. The major species H₂, CO₂ and H₂O in the synthesis region are expected to activate the catalyst and help to promote catalyst reaction.     

Si-nanostructures formation in amorphous silicon nitride SiNx:H deposited by remote PECVD

The formation of silicon nanoclusters embedded in amorphous silicon nitride (SiN_x:H) can be of great interest for optoelectronic devices such as solar cells. Here amorphous SiN_x:H layers have been deposited by remote microwave-assisted chemical vapor deposition at 300 °C substrate temperature and with different ammonia [NH₃]/silane [SiH₄] gas flow ratios (R=0.5−5). Post-thermal annealing was carried out at 700 °C during 30 min to form the silicon nanoclusters. The composition of the layers was determined by Rutherford back scattering (RBS) and elastic recoil detection analysis (ERDA). Fourier transform infrared spectroscopy (FTIR) showed that the densities of SiH (2160 cm⁻¹) and NH (3330 cm⁻¹) molecules are reduced after thermal annealing for SiN:H films deposited at flow gas ratio R>1.5. Breaking the SiH bonding provide Si atoms in excess in the bulk of the layer, which can nucleate and form Si nanostructures. The analysis of the photoluminescence (PL) spectra for different stoichiometric layers showed a strong dependence of the peak characteristics (position, intensity, etc.) on the gas flow ratio. On the other hand, transmission electron microscopy (TEM) analysis proves the presence of silicon nanoclusters embedded in the films deposited at a gas flow ratio of R=2 and annealed at 700 °C (30 min).     

Influence of vacuum annealing on structures and mechanical properties of Al–Ti–N films deposited by multi-arc ion plating

The Al–Ti–N films deposited by multi-arc ion plating have been annealed in vacuum within the range of 700–1100 °C. X-ray diffraction results showed that the structure of the films underwent the formation of coherent c-TiN and c-AlN for the annealing temperatures were up to 900 °C. A new phase AlTi_x (x = 0.50, 0.56, 3) was observed after annealing. The X-ray photoelectron spectroscopy results showed the intensity of Ti–Al bonds decreased as annealing temperatures increased, indicating the decomposition of (Al, Ti)N into c-TiN and c-AlN were at the expense of Ti–Al bonds. Differential scanning calorimetry experiments were used to investigate the dynamic behavior of the films during annealing process and the results showed that the N₂ formed as a consequence of the phase transformation process. The release of the N₂ resulted in the peeling of the films from the substrates. The film exhibited a maximum hardness of 39 GPa after 900 °C annealing due to the formation of coherent c-TiN and c-AlN phases. In addition, we also investigated the influence of vacuum annealing on adhesive strength.     

Formation of silicon oxide nanowires directly from Au/Si and Pd–Au/Si substrates

Amorphous silicon oxide (SiO_x) nanowires were directly grown by thermal processing of Si substrates. Au and Pd–Au thin films with thicknesses of 3 nm deposited on Si (0 0 1) substrates were used as catalysts for the growth of nanowires. High-yield synthesis of SiO_x nanowires was achieved by a simple heating process (1000–1150 °C) in an Ar ambient atmosphere without introducing any additional Si source materials. The as-synthesized products were characterized by field-emission scanning electron microscopy, energy-dispersive X-ray spectroscopy, and transmission electron microscopy measurements. The SiO_x nanowires with lengths of a few and tens of micrometers had an amorphous crystal structure. The solid–liquid–solid model of nanowire formation was shown to be valid.     

Carbon nanotube diameter tuning using hydrogen amount and temperature on SiO2/Si substrates

Carbon nanotubes (CNTs) were grown on thin iron (Fe) films on SiO₂/Si substrates by chemical vapor deposition (CVD) at four different hydrogen (H₂)/methane (CH₄) ratios at temperatures ranging from 925 to 1000°C. The effects of temperature and the amount of hydrogen gas on the mean diameter at increasing temperature were examined. We demonstrated that the mean diameter and its distribution depend not only on temperature but also on the H₂ amount. We showed that increasing H₂ amount strongly affects the structure of CNTs, especially at high growth temperature; the mean diameter at 1000°C reduced from about 383 to 34 nm by increasing H₂ amount from 24 to 50 sccm. We observed that at high temperature growth the mean diameter was decreasing very fast initially with increasing H₂ amount suggesting the dominance of H₂ over the growth temperature. A decrease in the slope of diameter vs. H₂ amount with further increment in H₂ amount implied that the temperature was, then, deciding the CNT diameter through catalyst particle coarsening. The statistical analysis presented implies that the H₂ amount has to be adjusted according to the growth temperature for given CH₄ amount to keep CNT diameter under control, and the large diameter distributions at high temperature and high H₂ amount can be associated with the large variation in the catalyst particle sizes.     

Annealing effect on the superconductivity of In2O3–ZnO thin films

We have investigated the relation among ρ–T characteristics, superconductivity, annealing conditions and the crystallinity of polycrystalline (In₂O₃)_1−x–(ZnO)_x films. We annealed as-grown amorphous films in air by changing annealing temperature and time. It is found that the films annealed at 200 °C or 300 °C for a time over 0.5 h shows the superconductivity. Transition temperature T_c and the carrier density n are T_c < 3.3 K and n ≈ 10²⁵–10²⁶ m⁻³, respectively. Investigations for films with x = 0.01 annealed at 200 °C have revealed that the T_c, n and crystallinity depend systematically on annealing time. Further, we consider that there is a suitable annealing time for sharp resistive transition because the transition width becomes wider with longer annealing times. We studied the upper critical magnetic field H_c2(T) for the film with different annealing time. From the slope of dH_c2/dT for all films, we have obtained the resistivity ρ dependence of the coherence length ξ(0) at T = 0 K.     

Structural properties and electrical characteristics of high-k Dy2O3 gate dielectrics

This paper describes the structural properties and electrical characteristics of thin Dy₂O₃ dielectrics deposited on silicon substrates by means of reactive sputtering. The structural and morphological features of these films after postdeposition annealing were studied by X-ray diffraction and X-ray photoelectron spectroscopy. It is found that Dy₂O₃ dielectrics annealed at 700 °C exhibit a thinner capacitance equivalent thickness and better electrical properties, including the interface trap density and the hysteresis in the capacitance-voltage curves. Under constant current stress, the Weibull slope of the charge-to-breakdown of the 700 °C-annealed films is about 1.6. These results are attributed to the formation of well-crystallized Dy₂O₃ structure and the reduction of the interfacial SiO₂ layer.