Studies on structural and magnetic properties of Co-doped pyramidal ZnO nanorods synthesized by solution growth technique

Large-area arrays of highly oriented Co-doped ZnO nanorods with pyramidal hexagonal structure are grown on silica substrates by wet chemical decomposition of zinc–amino complex in an aqueous medium. In case of undoped ZnO with an equi-molar ratio of Zn²⁺/hexamethylenetetramine (HMT), highly crystalline nanorods were obtained, whereas for Co-doped ZnO, good quality nanorods were formed at a higher Zn²⁺/HMT molar ratio of 4:1. Scanning electron microscope (SEM) studies show the growth of hexagonal-shaped nanorods in a direction nearly perpendicular to the substrate surface with a tip size of ～50 nm and aspect ratio around 10. The XRD studies show the formation of hexagonal phase pure ZnO with c-axis preferred orientation. The doping of Co ions in ZnO nanorods was confirmed by observation of absorption bands at 658, 617 and 566 nm in the UV–vis spectra of the samples. The optical studies also suggest Co ions to be present both in +2 and +3 oxidation states. From the photoluminescence studies, a defect-related emission is observed in an undoped sample of ZnO at 567 nm. This emission is significantly quenched in Co-doped ZnO samples. Further, the Co-doped nanorods have been found to show ferromagnetic behavior at room temperature from vibrating sample magnetometer (VSM) studies.     

A study on morphology control and optical properties of ZnO nanorods synthesized by microwave heating

In this study, we present morphology control investigations on zinc oxide (ZnO) nanorods synthesized by microwave heating of a mixture of zinc nitrate hexahydrate and hexamethylenetetramine (HMTA) precursors in deionized water (DI water). To study the morphology and structural variations of the obtained ZnO nanorods in different molar ratio of zinc nitrate hexahydrate to HMTA, X-ray diffraction (XRD), scanning electron microscopy (SEM) images, Raman scattering, and photoluminescence (PL) spectroscopy were measured. XRD and SEM images are utilized to examine the crystalline quality as well as the morphological properties of the ZnO nanorods. It is found that morphology control can be achieved by simply adjusting the reactant concentrations and the molar ratio of zinc nitrate hexahydrate to HMTA. Raman scattering and PL spectroscopy measurements were demonstrated to study the size- and shape-dependent optical response of the ZnO nanorods. The Raman scattering result shows that the intensity of LO mode at around 576 cm^?1 decreases with the increase in the molar ratio of zinc nitrate hexahydrate to HMTA, indicating the reduction of defect concentrations in the synthesized ZnO nanorods. Room temperature PL spectrum of the synthesized ZnO nanorods reveals an ultraviolet (UV) emission peak and a broad visible emission. An enhancement of UV emission appears in the PL spectra as the molar ratio of zinc nitrate hexahydrate to HMTA increases, indicating that the defect concentration of the synthesized ZnO nanorods can be reduced by increasing the molar ratio.     

Influence of Sn-doping in hydrothermal methods on the optical property of the ZnO nanorods

Sn-doped ZnO nanorods with various Sn-doping concentrations were prepared using a low temperature hydrothermal method in an aqueous solution containing zinc nitrate, ammonium hydroxide, and tin acetate. With the increase in the concentration of tin acetate, more Sn atoms replaced Zn atoms in the ZnO lattice, and the amount of Sn in ZnO nanorods increased up to 14 at%. The relative intensity ratio of UV and deep level emission of ZnO nanorods was increased with the increase of Sn-doping level, and four times increase in the intensity ratio of UV to deep level emission was obtained for 14 at% Sn-doped ZnO nanorods compared with undoped ones. A blueshift of UV emission was observed up to 11 at% of Sn concentration, but redshift occurred when the amount of Sn was greater than that.     

Synthesis of defect-rich, (001) faceted-ZnO nanorod on a FTO substrate as efficient photocatalysts for dehydrogenation of isopropanol to acetone

Highly oriented ZnO nanorod was successfully synthesised on Ag nanoseed coated FTO substrate via a microwave hydrolysis approach. It was found that the morphology and the optical properties of the ZnO nanorod are strongly influenced by the power of the microwave irradiation used during the growth process. The aspect ratio of the nanorods changed from high to low with the increasing of microwave power. It was also found that the optical band gap of the ZnO nanorod red shifted with the increasing of the microwave power, reflecting an excellent tune ability of the optical properties of ZnO nanorods. The photocatalytic activity of these unique nanorod was evaluated by a dehydrogenation process of isopropanol to acetone in the presence of ZnO nanorod. It was found that the ZnO nanorod exhibited an excellent catalytic performance by showing an ability to accelerate the production of 0.031 mol L⁻¹ of acetone within only 35 min or 0.9 mmol L⁻¹ min⁻¹ from isopropyl alcohol dehydrogenation. It was almost no conversion from isopropyl alcohol when ZnO nanorods was absence during the reaction. In this report, a detailed mechanism of ZnO nanorod formation and the relationship between morphology and optical energy band gap are described.     

A templateless surfactant-free seedless aqueous route to single-crystalline ZnO nanowires synthesis

Zinc oxide (ZnO) nanowires (NWs) have been synthesized using zinc nitrate and hexamethylenetetramine by templateless, surfactant-free and seedless aqueous solution route. The morphology of ZnO NWs was considerably affected by growth time: a longer reaction time results in the formation of ZnO NWs. Structural analysis of the synthesized NWs showed an average diameter of 20–30 nm length of several micrometers and single-crystalline wurtzite hexagonal structure. Photoluminescence studies of ZnO NWs showed a strong green emission peak at 585 nm.     

Excellent UV absorption in spin-coated thin films of oleic acid modified zinc oxide nanorods embedded in Polyvinyl alcohol

The aim of the study is to investigate the optical properties of spin-coated, highly transparent nanocomposite films of oleic acid modified ZnO (Zinc oxide) nanorods embedded in Polyvinyl alcohol (PVA) matrix. Pristine and oleic acid (OA) modified ZnO nanorods have been prepared by wet chemical synthesis and are characterized by X-ray diffraction, FESEM, TEM and FT–IR spectroscopy techniques. The optical properties of ZnO/PVA films are studied using UV–visible absorption and Photoluminescence (PL) spectroscopy. The results show that the optical absorption of the films in the UV region is quite high and more than 95% absorption is observed in films prepared from OA modified ZnO nanorods. The excellent UV absorption at around 300 nm offers prospects of applications of these films as efficient UV filters in this wavelength region. The PL spectrum of pristine ZnO nanorods shows almost white light emission whereas OA modified ZnO nanorods have a more intense peak centered in the blue region. The PL emission of OA modified ZnO/PVA film shows appreciable increase in intensity compared to the film obtained with pristine ZnO. The surface modification of ZnO by the polymer matrix removes defect states within ZnO and facilitates sharp near band edge PL emission at 364 nm.     

Synthesis of ZnO nanoplates decorated rhombus-shaped ZnO nanorods and their application in solar cells

Novel nanostructures of ZnF(OH) nanoplates decorated rhombus-shaped ZnF(OH) nanorods were fabricated. The obtained precursors were transformed by calcination to porous hierarchical ZnO nanostructures with the original morphologies retained. Field emission scanning electron microscope images exhibit that the nanoplates are grown in the interstices between the nanorods and on the top of the nanorods. The structure and composition of the obtained products have been confirmed by transmission electron microscope and X-ray diffraction measurements. The obtained ZnO nanostructures have been successfully used in solar cells. The light-to-electricity conversion results show that the complex nanostructures exhibit a power conversion efficiency of 1.36% with a photoelectrode thickness of 4.2 µm, which is comparable to those based on 40 µm vertically aligned hexagonal-shaped ZnO nanowire array photoelectrodes. These results indicate that the synthesized ZnO nanoplate decorated rhombus-shaped ZnO nanorod nanostructures are more suitable for application as a photoelectrode in solar cells.     

Strong temperature and substrate effect on ZnO nanorod flower structures in modified chemical vapor condensation growth

We have reported low temperature growth (300 °C) of ZnO nanorod flower structures by depositing zinc acetate vapor on Ge (100) substrate in the form of a jet using chemical vapor condensation technique. The flowers were comprised of hierarchical arrangement of highly crystalline ZnO nanorods oriented isotropically around a common nucleus. The temperature window for stability of these structures was found to be very narrow and the formation of the flowers was highly depended on the type of the substrates used. The flower morphology changed to a different hemispherical shape when the growth temperature was increased by only 50 °C while decreasing the growth temperature of the same degrees resulted in an amorphous deposition of ZnO. The temperature and substrate effect has been explained on the basis of adatom kinetics during growth. X-ray diffraction and TEM study revealed wurtzite ZnO nanorods with lattice constants a and c of 3.2 and 5.19 Å, respectively. The flower structures showed strong room temperature photoluminescence having pure excitonic transition at around 3.298 eV.     

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.     

Effect of growth time on Ti-doped ZnO nanorods prepared by low-temperature chemical bath deposition

Ti-doped ZnO nanorod arrays were grown onto Si substrate using chemical bath deposition (CBD) method at 93 °C. To investigate the effect of time deposition on the morphological, and structural properties, four Ti-doped ZnO samples were prepared at various deposition periods of time (2, 3.5, 5, and 6.5 h). FESEM images displayed high-quality and uniform nanorods with a mean length strongly dependent upon deposition time; i.e. it increases for prolonged growth time. Additionally, EFTEM images reveal a strong erosion on the lateral side for the sample prepared for 6.5 h as compared to 5 h. This might be attributed to the dissolution reaction of ZnO with for prolonged growth time. XRD analysis confirms the formation of a hexagonal wurtzite-type structure for all samples with a preferred growth orientation along the c-axis direction. The (100) peak intensity was enhanced and then quenched, which might be the result of an erosion on the lateral side of nanorods as seen in EFTEM. This study confirms the important role of growth time on the morphological features of Ti-doped ZnO nanorods prepared using CBD.     

Synthesis and photoluminescence properties of ZnO nanorods and nanotubes

Different morphologies of zinc oxide (ZnO) nanorods and nanotubes, which were grown under the same conditions but different dissolving processes, are prepared in our experiment through hydrothermal method. After the growth process, cooling down the reactor naturally or dissolving at a constant temperature of 40 °C, preferential dissolution will occur at different places on the tip of ZnO nanorods. During the dissolution process, different dissolution rates on the entire surface of nanorod will lead to different nanostructures. ZnO nanorods and nanotubes on Cu substrates display the same PL property with strong green emission but weak UV emission, while ZnO nanorods on Si substrates exhibits a relatively strong UV emission.     

Synthesis and field emission of novel ZnO nanorod chains

A new aqueous chemical growth method for generation of ZnO nanorod chains, transformed from ZnO micro dumbbell, has been developed. The novel structure and morphology of the as-synthesized ZnO micro dumbbell and ZnO nanorod chains are characterized using X-ray diffraction and scanning electron microscopies. Field emission characterization shows that the turn-on fields for the ZnO nanorod chains and micro dumbbell are 2.7 and 5.0 V/μm, respectively. The field enhancement factor β was estimated to be about 2194 for ZnO nanorod chains. The findings imply that ZnO nanorod chains may be suitable for cold-cathode electron source applications.     

Influence of solution parameters for the fast growth of ZnO nanostructures by laser-induced chemical liquid deposition

ZnO nanorods, nanoneedles, nanoparticles, and nanoballs were synthesized on fused quartz substrates upon irradiation of a droplet of methanolic zinc acetate dihydrate solution by an infrared (IR) continuous wave CO₂ laser for a few seconds. The addition of monoethanolamine and water to the solution improved the alignment of the nanorods and had a significant effect on the volume and morphology of the deposits. An increase of the zinc acetate concentration was found to lead to an increase of the thickness and area covered by the initial ZnO seed layer on which the nanostructures grew. By investigating the crystal structure of the deposits using X-ray and electron diffraction, we were able to show that the nanorods grow along the c axis with a high crystalline quality. Raman and photoluminescence spectroscopy confirmed the high quality of the grown ZnO nanostructures. As a matter of fact, their photoluminescence spectra are dominated by an intense UV emission around 390 nm.     

Study of Au/ZnO nanorods Schottky light-emitting diodes grown by low-temperature aqueous chemical method

High quality vertically aligned ZnO nanorods (NRs) were grown by low-temperature aqueous chemical technique on 4H-n-SiC substrates. Schottky light-emitting diodes (LEDs) were fabricated. The current-voltage (I–V) characteristics of Schottky diodes reveal good rectifying behavior. Optical properties of the ZnO nanorods (NRs) were probed by cathodoluminescence (CL) measurements at room temperature complemented with electroluminescence (EL). The room-temperature CL spectra of the ZnO NRs exhibit near band edge (NBE) emission as well as strong deep level emission (DLE) centered at 690 nm. At room temperature the CL spectra intensity of the DLE was enhanced with the increase of the electron beam penetration depth due to the increase of defect concentration at the interface and due to the conversion of self-absorbed UV emission. We observed a variation in the DLE along the nanorod depth. This indicates a relatively lower structural quality near the interface between ZnO NRs and n-SiC substrate. The room-temperature CL spectra of SiC show very weak emission, which confirms that most of the DLE is originating from the ZnO NRs, and SiC has a minute contribution to the emission.     

Depth-resolved cathodoluminescence study of zinc oxide nanorods catalytically grown on p-type 4H-SiC

Optical properties of ZnO nanorods (NRs) grown by vapour-liquid-solid (VLS) technique on 4H-p-SiC substrates were probed by cathodoluminescence (CL) measurements at room temperature and at 5 K complemented with electroluminescence. At room temperature the CL spectra for defect related emission intensity was enhanced with the electron beam penetration depth. We observed a variation in defect related green emission along the nanorod axis. This indicates a relatively poor structural quality near the interface between ZnO NRs and p-SiC substrate. We associate the green emission with oxygen vacancies. Analysis of the low-temperature (5 K) emission spectra in the UV region suggests that the synthesized nanorods contain shallow donors and acceptors.     

Nanostructure materials for destruction of warfare agents and eco-toxins prepared by homogeneous hydrolysis with thioacetamide: Part 1—zinc oxide

Zinc sulphide (ZnS) nanoparticles were prepared by homogeneous hydrolysis of zinc sulphate and thioacetamide (TAA) at 80 °C. After annealing at temperature above 400 °C in oxygen atmosphere, zinc oxide (ZnO) nanoparticles were obtained. The ZnS and ZnO nanoparticles were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), high resolution transmission microscopy (HRTEM), selected area electron diffraction (SAED), by BET and BJH methods used for surface area and porosity determination. The photocatalytic activity of the as-prepared ZnO samples was determined by the decomposition of Orange II in the aqueous solution under UV irradiation of 365 nm of wavelength.     

High c-axis preferred orientation ZnO thin films prepared by oxidation of metallic zinc

Thin films of zinc oxide were grown on glass substrates by thermal oxidation. The metallic zinc films were thermally oxidized at different temperatures ranging from 300 to 600 °C to yield ZnO thin films. The structural property of the thin films was characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The X-ray diffraction measurements showed that the films oxidized at 300 °C were not oxidized entirely, and the films deposited at 600 °C had better crystalline quality than the rest. When the oxidation temperature increased above 400 °C, the films exhibited preferred orientation along (002) and high transmittance ranging from 85% to 98% in vis–near-infrared band. Meanwhile, the films showed a UV emission at about 377 nm and green emission. With the increasing of oxidation temperature, the intensity of green emission peak was enhanced, and then decreased, disappearing at 600 °C, and the case of UV emission increased. Furthermore, a strong green emission was observed in the film sintered in pure oxygen atmosphere.     

Influence of ultrasonication times on the tunable colour emission of ZnO nanophosphors for lighting applications

This paper reports on the sonochemical synthesis of zinc oxide (ZnO) nanophosphors (NPr) at different ultrasonication times (5 min, 30 min, 1 h, 5 h, 10 h and 15 h) for near white light emission applications. X-ray photoelectron spectroscopy indicated that the O1s peak consists of two components. These were O1 (ZnO) and O2 (deficient oxygen; OH groups) centred at 529.7 ± 0.3 eV and 531.1 ± 0.3 eV, respectively. All samples showed UV and defect level emission (DLE). The DLE enhancement was due to the increase in oxygen related defects such as oxygen vacancies/interstitials. Due to the combination of near UV and DLE near white light emission in ZnO NPr was obtained. The emission could be tuned with different ultrasonic times. It was found that the ultrasonication time influenced the growth mechanism and luminescence properties of the ZnO NPr.     

Enhanced power efficiency of ZnO based organic/inorganic solar cells by surface modification

We present series of strategies to enhance efficiency of ZnO nanorods based organic/inorganic solar cells with spin-coated P3HT:PCBM blend as active layer. The performance of the as-fabricated devices is improved by controlling the size of ZnO nanorods, annealing temperature and time of active layer, surface modification of ZnO with PSBTBT. Optimized device of ITO/ZnO nanorod/P3HT:PCBM/Ag device with PSBTBT surface modification and air exposure reaches an efficiency of 2.02% with a short-circuit current density, open-circuit voltage and fill factor of 13.23 mA cm⁻², 0.547 V and 28%, respectively, under AM 1.5 irradiation of 100 mW m⁻², the increase in efficiency is 7-fold of the PSBTBT surface modified ITO/ZnO nanorods/P3HT:PCBM/Ag device compared with the unmodified one, which is own to the increased interface contact, expanded light absorption, tailored band alignment attributed to PSBTBT. We found exposure to air and surface modification is crucial to improve the device performance, and we discussed the mechanisms that affect the performance of the devices in detail.     

Synthesis,characterization and photoluminescence of ZnO:Cd rosette-like nanostructures using solution process

Well crystalline undoped and Cd-doped ZnO rosette-like structures were successfully synthesized at low temperature (80 °C) via solution process technique during 30 min. Zinc nitrate, cadmium nitrate, sodium hydroxide and hexamine were used as starting materials. The morphology and microstructure were determined by field emission scanning electron microscopy (FE-SEM), X-ray diffraction (XRD), transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy (EDX) and photoluminescence (PL) spectroscopy. X-ray diffraction indicated that the structure has a single phase with wurtzite structure. FESEM indicated that rosette like structures have been formed. This rosette consists of nanorods with length 210 and 460 nm and diameter 50 and 74 nm for undoped and Cd doped ZnO, respectively. HRTEM showed a decrease in the lattice parameter after the Cd doping. EDX showed that the amount of Cd incorporated into ZnO is 6.4 wt.%. Photoluminescence measurements taken on both doped and undoped samples showed that, in the Cd-doped ZnO nanostructures, the band-edge UV emission is blue shifted and the broad green emission intensity decreased.