Efficient synthesis of ZnO nanoparticles,nanowalls, and nanowires by thermal decomposition of zinc acetate at a low temperature

ZnO nanoparticles, nanowires, and nanowalls were synthesized rapidly on Si via thermal decomposition of zinc acetate by a modified chemical vapor deposition at a low substrate temperature of 200–250°C for the first time. The diameters of the synthesized nanoparticles and nanowires are around 100 and 30 nm, respectively, and the thickness of nanowalls is around 20 nm. High-resolution transmission electron microscopy shows that the nanowires as well as nanowalls are single-crystalline, and the nanoparticles are highly-textured poly-crystalline structures. Room-temperature photoluminescence spectra of the nanostructures show strong ultraviolet emissions centered at 368–383 nm and weak violet emissions at around 425 nm, indicating good crystal quality. The study provides a simple and efficient route to synthesize ZnO diverse nanostructures at low temperature.     

Nanocrystalline CaCu<Subscript>3</Subscript>Ti<Subscript>4</Subscript>O<Subscript>12</Subscript> powder by PVA sol–gel route: synthesis,characterization and its giant dielectric constant

Nanocrystalline CaCu₃Ti₄O₁₂ powders were synthesized by a simple PVA sol–gel route and calcined at 700 and 800°C in air for 8 h. The diameter of the powders ranges from 40–100 nm. The calcined CaCu₃Ti₄O₁₂ powders were characterized by TG-DTA, XRD, FTIR, SEM, and TEM. Sintering of the powders was conducted in air at 1100°C for 16 h. The XRD results indicated that all sintered samples had a typical perovskite CaCu₃Ti₄O₁₂ structure although the sintered samples contained some amount of CaTiO₃. SEM of the sintered CaCu₃Ti₄O₁₂ ceramics showed the average grain sizes of 13–15 μm. The samples exhibit a giant dielectric constant, ε′∼10⁵ at 150 to 200°C with weak temperature dependence below 1 kHz in the sample sintered using the powders calcined at 700°C. The Maxwell–Wagner polarization mechanism is used to explain the high permittivity in these ceramics. It is also found that all sintered samples have the same activation energy of grains, which is ∼0.122 eV.     

Surface enhanced Raman scattering and photoluminescence properties of catalytic grown ZnO nanostructures

Sword-like (diameter ranging from 40 nm to 300 nm) and needle-like zinc oxide (ZnO) nanostructures (average tip diameter ∼40 nm) were synthesized on annealed silver template over silicon substrate and directly on silicon wafer, respectively via thermal evaporation of metallic zinc followed by a thermal annealing in air. The surface morphology, microstructure, chemical analysis and optical properties of the grown samples were investigated by field emission scanning electron microscopy, X-ray diffraction, energy dispersive X-ray analysis, room temperature photoluminescence and Raman spectroscopy. The sword-like ZnO nanostructures grown on annealed silver template are of high optical quality compared to needle-like ZnO nanorods for UV emission and show enhanced Raman scattering.     

Self-aligned nanocrystalline ZnO hexagons by facile solid-state and co-precipitation route

In this study, we report the synthesis of well-aligned nanocrystalline hexagonal zinc oxide (ZnO) nanoparticles by facile solid-state and co-precipitation method. The co-precipitation reactions were performed using aqueous and ethylene glycol (EG) medium using zinc acetate and adipic acid to obtain zinc adipate and further decomposition at 450 °C to confer nanocrystalline ZnO hexagons. XRD shows the hexagonal wurtzite structure of the ZnO. Thermal study reveals complete formation of ZnO at 430 °C in case of solid-state method, whereas in case of co-precipitation method complete formation was observed at 400 °C. Field emission scanning electron microscope shows spherical morphology for ZnO synthesized by solid-state method. The aqueous-mediated ZnO by co-precipitation method shows rod-like morphology. These rods are formed via self assembling of spherical nanoparticles, however, uniformly dispersed spherical crystallites were seen in EG-mediated ZnO. Transmission electron microscope (TEM) investigations clearly show well aligned and highly crystalline transparent and thin hexagonal ZnO. The particle size was measured using TEM and was observed to be 50–60 nm in case of solid-state method and aqueous-mediated co-precipitation method, while 25–50 nm in case of EG-mediated co-precipitation method. UV absorption spectra showed sharp absorption peaks with a blue shift for EG-mediated ZnO, which demonstrate the mono-dispersed lower particle size. The band gap of the ZnO was observed to be 3.4 eV which is higher than the bulk, implies nanocrystalline nature of the ZnO. The photoluminescence studies clearly indicate the strong violet and weak blue emission in ZnO nanoparticles which is quite unique. The process investigated may be useful to synthesize other oxide semiconductors and transition metal oxides.     

A simple thermal decomposition synthesis, magnetic properties, and cytotoxicity of La0.7Sr0.3MnO3 nanoparticles

This study reports the new and simple synthesis of magnetic La_0.7Sr_0.3MnO₃ (LSMO) nanoparticles by thermal decomposition method using acetate salts of La, Sr and Mn as starting materials. To obtain the LSMO nanoparticles, thermal decomposition of the precursor is carried out at the temperatures of 600, 700, 800, 900, and 1000°C for 6 hours. The synthesized LSMO nanoparticles were characterized by XRD, FT-IR, TEM and SEM. Structural characterization shows that the prepared particles consisted of two phases of LaMnO₃ (LMO) and LSMO with crystallite sizes ranging from 18 to 55 nm. All the prepared samples have a perovskite structure which changes from cubic to rhombohedral with the increase in the thermal decomposition temperature. Basic magnetic characteristics such as saturation magnetization (M _S) and coercive field (H _C) are evaluated by sample vibrating magnetometry at room temperature (20°C). The samples show soft ferromagnetic behavior with M _S values of ∼9–55 emu/g and H _C values of ∼8–37 Oe, depending on the crystallite size and thermal decomposition temperature. The relationship between the crystallite size and the magnetic properties is presented and discussed. The cytotoxicity of synthesized LSMO nanoparticles was also evaluated with NIH 3T3 cells and the result showed that the synthesized nanoparticles were not toxic to the cells as determined from cell viability in response to the liquid extraction of LSMO nanoparticles.     

Optimization of F-doped SnO2 electrodes for organic photovoltaic devices

Fluorine-doped tin oxide (FTO) thin films have been investigated as an alternative to indium tin oxide anodes in organic photovoltaic devices. The structural, electrical, and optical properties of the FTO films grown by pulsed laser deposition were studied as a function of oxygen deposition pressure. For 400 nm thick FTO films deposited at 300°C and 6.7 Pa of oxygen, an electrical resistivity of 5×10⁻⁴ Ω-cm, sheet resistance of 12.5 Ω/□, average transmittance of 87% in the visible range, and optical band gap of 4.25 eV were obtained. Organic photovoltaic (OPV) cells based on poly(3-hexylthiophene)/[6,6]-phenyl-C₆₁-butyric acid methyl ester bulk heterojunctions were prepared on FTO/glass electrodes and the device performance was investigated as a function of FTO film thickness. OPV cells fabricated on the optimum FTO anodes (∼300–600 nm thick) exhibited power conversion efficiencies of ∼3%, which is comparable to the same device made on commercial ITO/glass electrodes (3.4%).     

Structure and magnetic properties of Zn<Subscript>0.9</Subscript>Co<Subscript>0.1</Subscript>O nanorods synthesized by a simple sol–gel method using metal acetylacetonate and poly(vinyl alcohol)

Room-temperature ferromagnetism was observed in Zn_0.9Co_0.1O nanorods with diameters and lengths of ∼100–200 nm and ∼200–1000 nm, respectively. Nanorods were synthesized by a simple sol–gel method using metal acetylacetonate powders of Zn and Co and poly(vinyl alcohol) gel. The XRD, FT-IR and SAED analyses indicated that the nanorods calcined at 873–1073 K have the pure ZnO wurtzite structure without any significant change in the structure affected by Co substitution. Optical absorption measurements showed absorption bands indicating the presence of Co²⁺ in substitution of Zn²⁺. The specific magnetization of the nanorods appeared to increase with a decrease in the lattice constant c of the wurtzite unit cell with the highest value being at 873 K calcination temperature. This magnetic behavior is similar to that of Zn_0.9Co_0.1O nanoparticles prepared by polymerizable precursor method. We suggest that this behavior might be related to hexagonal c-axis being favorable direction of magnetization in Co-doped ZnO and the 873 K (energy of 75 meV) being close to the exciton/donor binding energy of ZnO.     

Influence of annealing temperature on structural, optical and magnetic properties of Zn0.95Cu0.02Cr0.03O powders

Zn_0.95Cu_0.02Cr_0.03O powders have been synthesized by the sol-gel method and sintered in argon atmosphere under different temperatures. The structural, optical and magnetic properties of the powders were investigated by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), photoluminescence (PL) and vibrating sample magnetometer (VSM). The XRD results demonstrated that Cr and Cu ions are incorporated into ZnO successfully when annealing temperatures were 600 and 700 °C. But when the samples were annealed at 500 °C, the crystallinity of the samples was not very good. However, when the annealing temperature was increased to 800 °C, the secondary phase of Cu and ZnCr₂O₄ appeared in the samples. The PL spectra revealed that the position of the ultraviolet (UV) emission peak of the samples showed a blue shift and the green emission peak enhanced significantly with the annealing temperature increasing from 600 to 700 °C. Magnetic measurements indicated that the room temperature ferromagnetism of Zn_0.95Cu_0.02Cr_0.03O was intrinsic in nature. In addition, the saturation magnetization (Ms) increased from 0.0078 to 0.0088 emu/g with the annealing temperature increased from 600 to 700 °C.     

Influence of Al-doping on the structure and optical properties of ZnO films

Al-doped ZnO (ZnO:Al) thin films with c-axis preferred orientation were deposited on glass substrates using the radio frequency reactive magnetron sputtering technique. The effect of Al concentrations on the microstructure and the luminescence properties of the ZnO:Al thin films were studied by atomic force microscopy (AFM), X-ray diffraction (XRD), and fluorescence spectrophotometer. The results showed that the crystallization of the films was promoted by appropriate Al concentrations; the photoluminescence spectra (PL) of the samples were measured at room temperature. Strong blue peak located at 437 nm (2.84 eV) and two weak green peaks located at about 492 nm (2.53 eV) and 524 nm (2.37 eV) were observed from the PL spectra of the four samples. The origin of these emissions was discussed. In addition, absorption and transmittance properties of the samples were researched by UV spectrophotometer; the UV absorption edge shifted to a shorter wavelength first as Al was incorporated, and then to a longer wavelength with the increasing Al concentrations. The optical band gaps calculated based on the quantum confinement model are in good agreement with the experimental values.     

Laser initiation of a mixture of PETN with NiC nanoparticles at elevated temperatures

The temperature dependence of the probability of the explosion of pentaerythritol tetranitrate (PETN) with an admixture of NiC particles (0.3 wt %) initiated by laser pulses (1064 nm, 20 ns) was studied over the temperature range 295–450 K. At 295–350 K, a weak temperature dependence was observed. The determining contribution to explosion initiation was made by the absorption of laser radiation by nanoparticles. The threshold of explosive decomposition at 295 K decreased by ∼40 times compared with samples free of NiC nanoparticles. Over the temperature range 400–450 K, the threshold of the explosive decomposition of samples containing NiC nanoparticles decreased with the activation energy ∼0.4 eV. A decrease in the threshold of explosive decomposition with a ∼0.4 eV activation energy over the temperature range 340–440 K was also observed for laser action on PETN samples not containing NiC. A hypothesis was suggested according to which the absorption of a light quantum caused the transfer of an electron from the valence band of the crystal to a level in the forbidden band with subsequent thermal positive ion dissociation to the carbocation and NO₃ radical.     

A facile thermal evaporation route for large-area synthesis of tin oxide nanowires: Characterizations and their use for liquid petroleum gas sensor

In this paper, a very simple procedure was presented for the reproducible synthesis of large-area SnO₂ nanowires (NWs) on a silicon substrate by evaporating Sn powders at temperatures of 700, 750, and 800 °C. As-obtained SnO₂ NWs were characterized by field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), and Raman spectroscopy. They revealed that the morphology of the NWs is affected by growth temperature and the SnO₂ NWs are single-crystalline tetragonal. The band gap of the NWs is in the range of 4.2–4.3 eV as determined from UV/visible absorption. The NWs show stable photoluminescence with an emission peak centered at around 620 nm at room-temperature. The sensors fabricated from the SnO₂ NWs synthesized at 700 °C exhibited good response to LPG (liquefied petroleum gas) at an operating temperature of 400 °C.     

Strong violet emission from zinc oxide dumbbell-like microrods and nanowires

ZnO of different morphologies with controlled size and aspect ratio (l/d) such as dumbbell-like microrods, thick nanowires and thin nanowires were prepared by a hydrothermal method. Possible mechanisms for the formation of ZnO crystals with the different morphologies were discussed. Strong violet photoluminescence bands at～413 nm (3.0 eV) without band edge emission were observed from the dumbbell-like ZnO microrods and thick nanowires. Correspondingly, the thin nanowires showed a weak shoulder UV photoluminescence band at～390 nm. Such result indicates that the photoluminescence properties could be improved by the morphologies or aspect ratio (l/d) and the potential fabrication violet-light-emitting devices.     

Synthesis of nanocrystalline ZnO nanobelts via pyrolytic decomposition of zinc acetate nanobelts and their gas sensing behavior

The pyrolytic decomposition of layered basic zinc acetate (LBZA) nanobelts (NBs) into nanocrystalline ZnO NBs is investigated using scanning electron microscopy (SEM), atomic force microscopy (AFM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and photoluminescence (PL). We also report on the gas sensing response of the resulting ZnO nanomaterial to CO. The LBZA NBs are grown at 65 °C in an aqueous solution of zinc acetate dihydrate. AFM and SEM results show as-grown products possess the characteristic layered structure of the LBZA crystals. XRD and XPS results show that annealing as-grown products at 210 °C in air causes a transformation from zinc acetate to nanocrystalline ZnO NBs via thermal decomposition. The ZnO crystalline domain size increases with temperature from 9.2 nm at 200 °C to 94 nm at 1000 °C, as measured from XRD. SEM shows evidence of sintering at 600 °C. The thickness of the NBs, determined via AFM, ranges from 10 to 50 nm and remains approximately constant with annealing temperature. XPS confirmed the chemical transformation from zinc acetate to ZnO and showed a significant remaining zinc hydroxide component for the ZnO NBs consistent with published results. PL measurements at room temperature show a blue shift in peak emission as the nanobelts change from LBZA to ZnO at 200 °C. Above this transition temperature, the ZnO nanobelts possess strong band edge emission at 390 nm and little broad band emission in the visible region. The AFM and SEM images reveal that the crystallites within the nanobelts orientate in rows along the long axis during annealing. This structure provides a high surface area to volume ratio of aligned nanoparticles which is beneficial for gas sensing applications. Gas sensors fabricated from 400 °C annealed nanobelts showed a response of 1.62 when exposed to 200 ppm of CO in dry air at 400 °C, as defined by the ratio of resistance before and during exposure. This indicates that ZnO nanostructures obtained by thermal decomposition of LBZA NBs could provide a cost effective route to high sensitivity gas sensors.     

Structural and photoluminescence analysis of Zn1 − xMnxO nanocrystalline powders

This Letter reports on structural and photoluminescence properties of Zn_1 − xMn_xO nanocrystalline powders, which were synthesized by using oxalate precursor decomposition method. From the XRD features, we have noticed that all samples exhibit wurtzite crystal structure. The origin of photoluminescence properties of Mn doped and undoped ZnO have been discussed.     

Strong violet luminescence from ZnO nanocrystals grown by the low-temperature chemical solution deposition

The luminescence properties of zinc oxide (ZnO) nanocrystals grown from solution are reported. The ZnO nanocrystals were characterized by scanning electron microscopy, X-ray diffraction, cathodo- and photoluminescence (PL) spectroscopy. The ZnO nanocrystals have the same regular cone form with the average sizes of 100-500 nm. Apart from the near-band-edge emission around 381 nm and a weak yellow-orange band around 560-580 nm at 300 K, the PL spectra of the as-prepared ZnO nanocrystals under high-power laser excitation also showed a strong defect-induced violet emission peak in the range of 400 nm. The violet band intensity exhibits superlinear excitation power dependence while the UV emission intensity is saturated at high excitation laser power. With temperature raising the violet peak redshifts and its intensity increases displaying unconventional negative thermal quenching behavior, whereas intensity of the UV and yellow-orange bands decreases. The origin of the observed emission bands is discussed.     

Strong blue excitonic emission from CdS nanocrystallites prepared by LB technique

CdS nanocrystallites formed in ordered fatty acid LB multilayers exhibited strong surface states emission ∼550 nm and weak excitonic emission ∼400 nm. Treatment with aqueous CdCl₂ resulted in the suppression of surface states emission and enhancement of the blue excitonic emission. Subsequent annealing in air at 200°C caused an order of magnitude enhancement of excitonic emission. The growth of nanocrystallites during annealing as seen from the red-shift of excitonic absorption and emission is suppressed by the CdCl₂ treatment. The hindered growth of nanocrystallites, the significant enhancement of excitonic emission from CdS, and the suppression of surface states emission are attributed to surface passivation of CdS nanocrystallites by surface oxide formation.     

Facile synthesis and phase control of copper chalcogenides with different morphologies

A series of stoichiometric and nonstoichiometric copper–chalcogenide nanocrystallines with different morphologies, e.g., extremely high aspect ratio nanofibers (Cu₉S₈), tubular structure (Cu _x S (x=∼1.86–1.96), nanorods (CuS, Cu₃₁S₁₆), platelets (β-CuSe, Cu₃Se₂), rope-like Cu₃Se₂, as well as spherical nanoparticles (Cu₇Se₄, Cu_2−x Se), have been successfully synthesized in 20 vol% water and 80 vol% organic solvents mixture under mild conditions. The products were characterized by various techniques, including X-ray powder diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), electronic diffraction (ED), and high-resolution transmission electron microscopy (HRTEM). The studies of the optical properties revealed that the copper chalcogenides have a wide absorption in the range of about 400–700 nm, with accessional IR band. Systematic studies showed that the mixture of 20 vol% water and 80 vol% organic solvents played a key role in controlling the copper chalcogenides with different morphologies and phases.     

Self-assembly and photoluminescence of molybdenum oxide nanoparticles

We report on the synthesis of self-assembled hillock shaped MoO₃ nanoparticles on thin films exhibiting intense photoluminescence (PL) by RF magnetron sputtering and subsequent oxidation. MoO₃ nanocrystals of size ∼29 nm are self-assembled into uniform nanoparticles with diameter ∼174 nm. The mechanism of the intense PL behaviour from MoO₃ nanoparticles is investigated and systematically discussed. The films exhibit two bands; a near-band-edge UV emission and a defect related deep level visible emission. The enhancement in PL intensity with annealing is not only by the improvement in crystallinity and grain size but also by the increase in the rms surface roughness and porosity of the films. The PL intensity is thermally activated with activation energy 1.07 and 0.87 eV respectively for the UV and visible emissions. The UV band exhibits a blue shift according to the band gap with increasing post-annealing temperatures, which suggests the possibility to tune the UV photoluminescence band by varying the oxidation temperature.     

Identification of about 100-meV acceptor level in?ZnO?nanostructures by photoluminescence

ZnO nanorod arrays and nanowires were grown by hydrothermal and vapor phase deposition methods, respectively. At low temperature, the photoluminescence (PL) spectra of both samples are dominated by a broad peak around 3.34 eV. Combined with excitation density-dependent PL spectra and surface passivation process, it is indicated from temperature-dependent PL results that the 3.34 eV emission could be attributed to free electron-to-neutral acceptor transitions. The acceptor level is estimated to be ∼100 meV.     

Characterization and luminescent properties of SiO2:ZnS:Mn and ZnS:Mn nanophosphors synthesized by a sol-gel method

ZnS and SiO₂-ZnS nanophosphors, with or without different concentration of Mn²⁺ activator ions, were synthesized by using a sol-gel method. Dried gels were annealed at 600 °C for 2 h. Structure, morphology and particle sizes of the samples were determined by using X-ray diffraction (XRD), highresolution transmission electron microscopy (HRTEM) and field emission scanning electron microscopy (FESEM). The diffraction peaks associated with the zincblende and the wurtzite structures of ZnS were detected from as prepared ZnS powders and additional diffraction peaks associated with ZnO were detected from the annealed powders. The particle sizes of the ZnS powders were shown to increase from 3 to 50 nm when the powders were annealed at 600 °C. An UV-Vis spectrophotometer and a 325 nm He-Cd laser were used to investigate luminescent properties of the samples in air at room temperature. The bandgap of ZnS nanoparticles estimated from the UV-Vis data was 4.1 eV. Enhanced orange photoluminescence (PL) associated with ⁴T₁→⁶A₁ transitions of Mn²⁺ was observed from as prepared ZnS:Mn²⁺and SiO₂-ZnS:Mn²⁺ powders at 600 nm when the concentration of Mn²⁺ was varied from 2-20 mol%. This emission was suppressed when the powders were annealed at 600 °C resulting in two emission peaks at 450 and 560 nm, which can be ascribed to defects emission in SiO₂ and ZnO respectively. The mechanism of light emission from Mn²⁺, the effect of varying the concentration on the PL intensity, and the effect of annealing are discussed.