Synthesis and field-emission of aligned SnO2 nanotubes arrays

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

UV-enhanced room-temperature gas sensing of ZnGa2O4 nanowires functionalized with Au catalyst nanoparticles

ZnGa₂O₄ nanowires were synthesized using a thermal evaporation technique. Scanning electron microscopy, transmission electron microscopy, and X-ray diffraction revealed that the nanowires were single crystals 30–200 nm in diameter and ranged up to ～100 μm in length. The sensing properties of multiple networked ZnGa₂O₄ nanowire sensors functionalized with Au catalyst nanoparticles with diameters of a few nanometers toward NO₂ gas at room temperature under UV irradiation were examined. The sensors showed a remarkably enhanced response and far reduced response and recovery times toward NO₂ gas at room temperature under 254 nm-ultraviolet (UV) illumination. The response of ZnGa₂O₄ nanowires to NO₂ gas at room temperature increased from ～100 to ～861 % with increasing the UV intensity from 0 to 1.2 mW/cm². The significant improvement in the response of ZnGa₂O₄ nanowires to NO₂ gas by UV irradiation is attributed to the increased change in resistance due to the increase in the number of electrons participating in the reactions with NO₂ molecules by photo-generation of electron–hole pairs.     

Cu-supported carbon networks containing SnO<Subscript>2</Subscript> as three-dimensional anodes for lithium-ion batteries

Cu-supported SnO₂@C composite coatings constructed by interconnected carbon-based porous branches were fabricated by annealing Cu foils with films formed by knife coating DMF solution containing SnCl₂, polyacrylonitrile (PAN), and poly(methyl methacrylate) (PMMA) on their surface in vacuum. The carbon-based porous branches consist of amorphous carbon matrices, SnO₂ nanoparticles with a size of 30–100 nm mainly encapsulated inside, and many micropores with a size of 1–5 nm. The three-dimensional (3D) porous network structures of the SnO₂@C composite were achieved by volatilization of PMMA and pyrolysis of SnCl₂. The SnO₂@C composite coatings demonstrate good cyclic performance with a high reversible capacity of 642 mA h g^?1 after 100 cycles at a current density of 50 mA g^?1 without apparent capacity fading during cycling and excellent rate performance with a capacity of 276 mA h g^?1 at a high current density up to 10 A g^?1.     

ZnO–SnO2 branch–stem nanowires based on a two-step process: Synthesis and sensing capability

ZnO–SnO₂ branch–stem nanostructures were realized on a basis of a two-step process. In step 1, SnO₂-stem nanowires were synthesized. In step 2, ZnO-branch nanowires were successfully grown on the SnO₂-stem nanowires through a simple evaporation technique. We have pre-deposited thin Au layers on the surface of SnO₂ nanowire stems and subsequently evaporated Zn powders on the nanowires. The ZnO branches, which sprouted from the SnO₂ stems, had diameters in a range of 30–35 nm. As-synthesized branches were of single crystalline hexagonal ZnO structures. Since the branch tips were comprised of Au-containing nanoparticles, the Au-catalyzed vapor–liquid–solid growth mechanism was more likely to control the growth process of the ZnO branches. To test a potential use of ZnO–SnO₂ branch–stem nanostructures in chemical gas sensors, their sensing performances with respect to NO₂ gas were investigated, showing the promising potential in chemical gas sensors.     

Magnetic behaviour and DCEMS study of SnO2 films implanted with 57Fe

Fe implanted SnO₂ films (5 × 10¹⁶ and 1 × 10^{17 57}Fe ions/cm²) characterized by conversion electron Mossbauer spectroscopy (CEMS) are reviewed. The substrate temperatures affect the growth of precipitated iron oxides. The Fe ion implanted film at room temperature (RT) shows no Kerr effect and no magnetic sextet in CEM spectra. The SnO₂ film implanted with ⁵⁷Fe at the substrate temperature of 300 °C show a small Kerr effect although the magnetic sextet is not observed, but post-annealing results in the disappearance of the Kerr effect. This magnetism is considered to be due to defect induced magnetism. Some samples were measured by CEMS at 15 K. SnO₂ (0.1 at %Sb and 3 at %Sb) films, implanted at 500 °C and the post-annealed samples, show RT ferromagnetism due to formation of clusters of magnetite and maghemite, respectively. The layer by layer analysis of these films within 100 nm in thickness has been done by depth sensitive CEMS (DCEMS) using a He + 5 % CH₄ gas counter. The structures and compositions of Fe implanted SnO₂ films, and the effects due to post-annealing were investigated.     

The improvement of gas-sensing properties of SnO<Subscript>2</Subscript>/zeolite-assembled composite

SnO₂-impregnated zeolite composites were used as gas-sensing materials to improve the sensitivity and selectivity of the metal oxide-based resistive-type gas sensors. Nanocrystalline MFI type zeolite (ZSM-5) was prepared by hydrothermal synthesis. Highly dispersive SnO₂ nanoparticles were then successfully assembled on the surface of the ZSM-5 nanoparticles by using the impregnation methods. The SnO₂ nanoparticles are nearly spherical with the particle size of ~?10 nm. An enhanced formaldehyde sensing of as-synthesized SnO₂-ZSM-5-based sensor was observed whereas a suppression on the sensor response to other volatile organic vapors (VOCs) such as acetone, ethanol, and methanol was noticed. The possible reasons for this contrary observation were proposed to be related to the amount of the produced water vapor during the sensing reactions assisted by the ZSM-5 nanoparticles. This provides a possible new strategy to improve the selectivity of the gas sensors. The effect of the humidity on the sensor response to formaldehyde was investigated and it was found the higher humidity would decrease the sensor response. A coating layer of the ZSM-5 nanoparticles on top of the SnO₂-ZSM-5-sensing film was thus applied to further improve the sensitivity and selectivity of the sensor through the strong adsorption ability to polar gases and the “filtering effect” by the pores of ZSM-5.     

Structure and NO2 gas sensing properties of SnO2-core/In2O3-shell nanobelts

SnO₂-core/In₂O₃-shell nanobelts were fabricated by a two-step process comprising thermal evaporation of Sn powders and sputter-deposition of In₂O₃. Transmission electron microscopy and X-ray diffraction analyses revealed that the core of a typical core–shell nanobelt comprised a simple tetragonal-structured single crystal SnO₂ and that the shell comprised an amorphous In₂O₃. Multiple networked SnO₂-core/In₂O₃-shell nanobelt sensors showed the response of 5.35% at a NO₂ concentration of 10 ppm at 300 °C. This response value is more than three times larger than that of bare-SnO₂ nanobelt sensors at the same NO₂ concentration. The enhancement in the sensitivity of SnO₂ nanobelts to NO₂ gas by sheathing the nanobelts with In₂O₃ can be accounted for by the modulation of electron transport by the In₂O₃–In₂O₃ homojunction.     

Investigation of characteristic properties of Pr-doped SnO2 thin films

In the present work, an investigation study on the crystal structure, surface morphology, electrical conductivity and optical transparency of spray-deposited Pr-doped SnO₂ was made as a function of Pr doping content. The X-ray diffraction studies indicated that the films were grown at the (2 1 1) preferential orientation. The values of crystallite size and strain were determined using Williamson–Hall method and they varied between 71.47 and 208.76 nm, and 1.98 × 10^?3 – 2.78 × 10^?3. As seen from Scanning Electron Microscope micrographs, the films were composed of homogenous dispersed pyramidal-shaped grains. The n-type conductivity of films was confirmed with Hall Effect measurements, and the best electrical parameters were found for 3 at.% Pr doping level. The highest optical band gap and transmittance values were observed for undoped SnO₂ sample. The highest figure of merit (Φ), which is a significant parameter to interpret the usage efficiency of conductive and transparent materials in the optoelectronic and solar cell applications, was calculated to be 2.85 × 10^?5 Ω^?1 for 1 at.% Pr doping content. As a result of this study, it may be concluded that Pr-doped SnO₂ films with above properties can be used as a transparent conductor in various optoelectronic applications.     

Influence of CuO catalyst in the nanoscale range on SnO2 surface for H2S gas sensing applications

The dispersal of CuO catalyst on the surface of the semiconducting SnO₂ film is found to be of vital importance for improving the sensitivity and the response speed of a SnO₂ gas sensor for H₂S gas detection. Ultra-thin CuO islands (8 nm thin and 0.6 mm diameter) prepared by evaporating Cu through a mesh and subsequent oxidation yield a fast response speed and recovery. Ultimately nanoparticles of Cu (average size = 15 nm) prepared by a chemical technique using a reverse micelle method involving the reduction of Cu(NO₃)₂ by NaBH₄ exhibited significant improvement in the gas sensing characteristics of SnO₂ films. A fast response speed of ∼14 s and a recovery time of ∼60 s for trace level ∼20 ppm H₂S gas detection have been recorded. The sensor operating temperature (130° C) is low and the sensitivity (S = 2.06 × 10³) is high. It is found that the spreading over of CuO catalyst in the nanoscale range on the surface of SnO₂ allows effective removal of excess adsorbed oxygen from the uncovered SnO₂ surface due to spill over of hydrogen dissociated from the H₂S-CuO interaction.     

Dependence of the selectivity of SnO2 nanorod gas sensors on functionalization materials

Effects of functionalization materials on the selectivity of SnO₂ nanorod gas sensors were examined by comparing the responses of SnO₂ one-dimensional nanostructures functionalized with CuO and Pd to ethanol and H₂S gases. The response of pristine SnO₂ nanorods to 500 ppm ethanol was similar to 100 ppm H₂S. CuO-functionalized SnO₂ nanorods showed a slightly stronger response to 100 ppm H₂S than to 500 ppm ethanol. In contrast, Pd-functionalized SnO₂ nanorods showed a considerably stronger response to 500 ppm ethanol than to 100 ppm H₂S. In other words, the H₂S selectivity of SnO₂ nanorods over ethanol is enhanced by functionalization with CuO, whereas the ethanol selectivity of SnO₂ nanorods over H₂S is enhanced by functionalization with Pd. This result shows that the selectivity of SnO₂ nanorods depends strongly on the functionalization material. The ethanol and H₂S gas sensing mechanisms of CuO- and Pd-functionalized SnO₂ nanorods are also discussed.     

Electrodeposition of Ag nanoparticles onto bamboo-type TiO2 nanotube arrays to improve their lithium-ion intercalation performance

Bamboo-type TiO₂ nanotube arrays prepared via anodic oxidation are modified with Ag nanoparticles by pulsed electrochemical deposition, for improved lithium-ion intercalation property as the anode material in lithium-ion batteries. Heat treatment converts as-formed nanotubes into anatase for Ag deposition. Bare and Ag-modified nanotubes are cycled at a current density of 800 μA?cm^?2 between 1.0 and 2.6 V (vs. Li/Li⁺). All Ag-modified nanotubes exhibit significantly improved or even doubled areal discharge capacities and better cycleability compared to bare nanotubes. Particularly, the nanotubes modified using 100 Ag deposition cycles deliver the highest initial discharge capacity of 199.6 μA?h cm^?2 and the largest final discharge capacity of 131.7 μA?h cm^?2 after 50 electrochemical cycles, while bare nanotubes exhibit an initial capacity of 93.5 μA?h cm^?2 and a final discharge capacity of 54.8 μA?h cm^?2. The former also exhibits 10 % higher capacity retention efficiency than the latter. In addition, an increase in the capacity of modified nanotubes is observed with more Ag deposition, but superfluous Ag content yields reduced capacities due to slower Li-ion transfer inside. Finally, kinetic characteristics of TiO₂ nanotubes are explored using cyclic voltammetry to understand the origin of improvements in electrochemical properties of Ag-modified nanotubes.     

Synthesis and enhanced acetone gas-sensing performance of ZnSnO<Subscript>3</Subscript>/SnO<Subscript>2</Subscript> hollow urchin nanostructures

A kind of novel ZnSnO₃/SnO₂ hollow urchin nanostructure was synthesized by a facile, eco-friendly two-step liquid-phase process. The structure, morphology, and composition of samples were characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and nitrogen adsorption–desorption techniques. The results revealed that many tiny needle-like SnO₂ nanowires with the average diameter of 5 nm uniformly grew on the surface of the ZnSnO₃ hollow microspheres and the ZnSnO₃/SnO₂ hollow urchin nanostructures with different SnO₂ content also were successfully prepared. In order to comprehend the evolution process of the ZnSnO₃/SnO₂ hollow urchin nanostructures, the possible growth mechanism of samples was illustrated via several experiments in different reaction conditions. Moreover, the gas-sensing performance of as-prepared samples was investigated. The results showed that ZnSnO₃/SnO₂ hollow urchin nanostructures with high response to various concentration levels of acetone enhanced selectivity, satisfying repeatability, and good long-term stability for acetone detection. Specially, the 10 wt% ZnSnO₃/SnO₂ hollow urchin nanostructure exhibited the best gas sensitivity (17.03 for 50 ppm acetone) may be a reliable biomarker for the diabetes patients, which could be ascribed to its large specific surface area, complete pore permeability, and increase of chemisorbed oxygen due to the doping of SnO₂.     

Electric field gradient in nanostructured SnO2 studied by means of PAC spectroscopy using 111Cd or 181Ta as probe nuclei

Electric quadrupole interactions were studied in pure and Mn-doped powder samples and thin films of SnO₂ using perturbed γγ angular correlation spectroscopy (PAC). The powder samples were prepared by Sol gel method and the thin film were prepared on the Si (100) substrate by sputtering technique using Sn in the oxygen atmosphere. The samples were characterized by x-ray diffraction, energy dispersive spectroscopy and scanning electron microscopy. The thickness of the film was 100 nm. The average particle size of the SnO₂ powder samples was determined to be smaller than 60 nm. The radioactive ¹¹¹In and ¹⁸¹Hf tracers were introduced in the powder samples during the sol gel chemical process. Radioactive ¹¹¹In was implanted on the SnO₂ thin films using the University of Bonn ion implanter (BONIS). PAC measurements were carried out in a four BaF₂ detector spectrometer in the temperature range of 77–973 K for samples annealed at different temperatures. The PAC results for both nuclear probes show the presence of two electric quadrupole interactions. The major fractions in both cases correspond to the substitutional sites in the rutile phase of SnO₂. The results are compared with previous PAC measurements.     

UV-activated gas sensing properties of ZnS nanorods functionalized with Pd

Pd-functionalized ZnS nanorods were prepared for use as gas sensors. Scanning electron microscopy revealed the diameters and lengths of the nanorods ranging from 30 to 80 nm and from 2 to 5 μm, respectively. The diameter of Pd nanoparticles ranged from 2 to 5 nm. Transmission electron microscopy revealed that ZnS nanorods and Pd nanoparticles were monocrystalline and amorphous, respectively. The responses of multiple networked ZnS nanorods sensors to 1–5 ppm NO₂ were increased substantially by a combination of Pd functionalization and UV irradiation. Pristine ZnS nanorod sensors at room temperature in the dark showed a response (∼100%) almost independent of NO₂ concentration in a NO₂ concentration range of 1–5 ppm. Pristine ZnS nanorod sensors showed enhanced responses of 214–603% to 1–5 ppm NO₂ at room temperature under UV illumination. Pd-functionalized ZnS nanorods sensors showed further enhanced responses of 355–1511% to 1–5 ppm NO₂ at room temperature under UV illumination. The NO₂ gas sensing mechanism of the Pd-functionalized ZnS nanorods sensors under UV illumination is discussed in depth.     

Synthesis and optoelectrical properties of SnO2 nanospheres derived by microwave-assisted hydrothermal method

SnO₂ nanospheres have been synthesized by microwave-assisted hydrothermal method from the starting materials of citric acid and tin metallic particles. From the results of SEM and TEM images, it can be found that the SnO₂ nanospheres are uniform with diameter of ~100 nm and aggregated by SnO₂ nanocrystals with size of 8–10 nm. The photoluminescence spectrum of the nanospheres shows a peak at ~330 nm and a cutoff wavelength of around 400 nm. The pronounced photocurrent was recoded from the as-prepared SnO₂ nanospheres assembled on a Mo thin sheet under the UV illumination, which is suggested for the potential application of UV photodetector.     

Development of high sensitivity ethanol gas sensor based on Co-doped SnO2 nanoparticles by microwave irradiation technique

We have successfully synthesized Co doped SnO₂ nanoparticles by a simple microwave irradiation technique. Powder X-ray diffraction results reveal that the SnO₂ doped with cobalt concentration from 0 to 5 wt % crystallizes in tetragonal rutile-type structure. The products were annealed at 600 °C for 5 h in ambient atmosphere in order to improve crystallinity and structural perfection. Transmission electron microscopy (TEM) studies illustrate that both the undoped and Co doped SnO₂ crystallites form in spherical shapes with an average diameter of 30–15 nm, which is in good agreement with the average crystallite sizes calculated by Scherrer's formula. A considerable red shift in the absorbing band edge was observed with increasing of Co content (0–5 wt %) by using UV–Vis diffuse reflectance spectroscopy (DRS). Oxygen-vacancies, tin interstitial and structural defects were analyzed using photoluminescence (PL) spectroscopy. Electron paramagnetic resonance (EPR) spectroscopic studies clearly showed that the Co²⁺ was incorporated into the SnO₂ host lattice. Ethanol gas sensitivity of pure and Co-doped (5 wt %) SnO₂ nanoparticles were experimented at ambient temperature using optical fiber based on clad-modified method. By modifying the clad exposure to ethanol vapor, the sensitivities were estimated to be 18 and 30 counts/100 ppm for undoped and Co-doped SnO₂ nanoparticles, respectively. These results show that the Co doping into SnO₂ enhances its ethanol gas sensitivity significantly.     

Size-dependent luminescence of Sm3+ doped SnO2 nano-particles dispersed in sol-gel silica glass

Sol-gel glasses with composition (100?x)SiO₂–xSnO₂ doped with 0.4 mol% of Sm³⁺, with x ranging from 1 to 10, have been successfully synthesized. Transparent doped nano-glass-ceramics were prepared by thermal treatment of the precursor glasses at 900°C during 4 hours, leading to nanocomposites comprising SnO₂ nanocrystals embedded into an amorphous SiO₂ phase. A structural analysis in terms of X-ray Diffraction and High Resolution Transmission Electron Microscopy confirms the precipitation of SnO₂ nanocrystals within the glassy matrix. The mean radius of the obtained SnO₂ nanocrystals, ranging from 2.1 to 4.7 nm calculated by the Scherrer and Brus equations, similar to the Bohr’s exciton radius, constitutes a wide band-gap semiconductor quantum-dot system. Energy transfer from SnO₂ nanocrystal host to Sm³⁺ ions is confirmed by luminescence spectra and analyzed as a function of SnO₂ concentration, showing an evolution that could be ascribed to selective excitation of nanocrystal sets with predetermined size. Besides, a study of the luminescence as a function of temperature helps to clarify the involved energy transfer mechanisms.     

Analysis of fiber optic SPR sensor utilizing platinum based nanocomposites

SPR based fiber optic sensor using nanocomposite is presented. Nanocomposites comprising of Pt nanoparticles with various volume fractions embedded in dielectric matrices of TiO₂ and SnO₂ are considered. Sensitivity enhances with increase in thickness of nanocomposite and volume fraction of nanoparticles for both nanocomposites. Optimized thicknesses are obtained to be 40 and 50 nm for Pt–TiO₂ and Pt–SnO₂ nanocomposites respectively while optimized volume fraction is found to be 0.85 for both nanocomposites. 40 nm thick Pt–TiO₂ nanocomposite based sensor with 0.85 volume fraction possesses utmost sensitivity.     

Enhanced NO2 gas sensing properties of WO3 nanorods encapsulated with ZnO

The influence of the encapsulation of WO₃ nanorods with ZnO on the NO₂ gas sensing properties was examined. WO₃-core/ZnO-shell nanorods were fabricated by a two-step process comprising the catalyst-free thermal evaporation of a mixture of WO₃ and graphite powders in an oxidizing atmosphere and atomic layer deposition of ZnO. Multiple networked WO₃-core/ZnO-shell nanorod sensors showed the response of 281?% at 5 ppm NO₂ at 300?°C. This response value was approximately 9 times larger than that of bare WO₃ nanorod sensors at 5 ppm NO₂. The response values obtained from the WO₃-core/ZnO-shell nanorods in this study were more than 5 times higher than those obtained previously from the SnO₂-core/ZnO-shell nanofibers at the same NO₂ concentration range. The significant enhancement in the response of WO₃ nanorods to NO₂ gas by encapsulating them with ZnO can be accounted for based on the space-charge model.     

Highly sensitive ethanol sensors based on nanocrystalline SnO2 thin films

This paper reports on a simple and inexpensive ultrasonic spray pyrolysis method to synthesize agglomerate-free nanosized SnO₂ particles with a size smaller than 10 nm. Scanning electron microscopy, transmission electron microscopy and high resolution X-ray diffraction studies were used to characterize the morphology, crystallinity, and structure of the SnO₂ particles. Under the optimized experimental conditions, the prepared SnO₂ sensor shows the high response (S = 491) towards 100 ppm ethanol gas at 300 °C, linearity in the range of 100–500 ppm, quick response time (2 s), recovery time (60 s) and selectivity against other gases. The response of the sensor was monitored in a 250–450 °C temperature range. The seven fold enhancement in gas response and selective detection of C₂H₅OH in the presence of other gases such as CH₃OH and CH₃CHOHCH₃ are the significant points in this investigation. These results demonstrate that pure nanocrystalline SnO₂ thin film can be used as the sensing material for fabricating high performance ethanol sensors.