ZnO nanorods: morphology control, optical properties, and nanodevice applications

Research interest in ZnO nanostructures derives from their excellent luminescent properties and availability of low cost fabricating and processing, which hold promise for the development of electronic and optoelectronic nanodevices. In this review, we focus on the progress in synthesis, properties and nanodevices of ZnO nanorod (NR) arrays and nanotetrapods (NTPs). Recent work done by the authors are also presented. After a brief introduction to the controlled fabrication methods for the highly-ordered ZnO NR arrays and NTPs, we present some aspects of the fundamental properties, especially optical performance, of ZnO NRs/NTPs. Then, we provide an overview of the applications to functional nanodevices based on individual NR and NTP of ZnO. It is demonstrated that different morphologies of ZnO nanostructures have salient effects on their properties and applications. Although much progress has been achieved in the fundamental and applied investigations of ZnO NRs/NTPs over the past decade, many obstacles still remain, hampering further development in this field. Finally, some longstanding problems that warrant further investigation are addressed.     

Thermoelectric and optical properties of CuAlO2 synthesized by direct microwave heating

A single phase of delafossite CuAlO₂ (CAO) was successfully synthesized by a 600 W microwave radiation for 20 min. The CAO sample was composed of quite distorted single-crystalline plates with 200–350 nm thick. Its atomic vibrations were detected at 760 and 550 cm⁻¹ belonging to Al–O and Cu–O stretching, respectively. The direct and indirect energy gaps were respectively determined to be 3.9 and 2.9 eV. The photoluminescence (PL) at room temperature was at 585 nm (2.12 eV) corresponding to the indirect energy gap and at 760 nm (1.63 eV) corresponding to the p-type native defect. For its thermoelectric (TE) properties, the Seebeck coefficient (S) was positive value, with holes as the majority of charge carriers. By increasing of the test temperature, both the electrical resistivity and absolute value of Seebeck coefficient were decreased, but the power factor was in the opposite manner. The dimensionless figure of merit (ZT) of the crystalline CAO was evaluated to be the maximum of 9 × 10⁻³ at 1073 K.     

X-ray analysis of ZnO nanorods grown by microwave irradiation heating on ZnO films

Utilizing microwave irradiation heating, 100-nm-diameter ZnO nanorods were grown from aqueous solution on sputtered ZnO films on glass substrates. Its out-of-plane X-ray diffraction (XRD) measurement indicated that the ZnO nanorods were grown with c-axis orientation, similar with the underlying ZnO films. In the in-plane XRD measurement, intensity of the () diffraction was comparable with that of the () one, suggesting their intensity ratio would contain useful information on nanorods density.     

Structural and optical properties of poly-vinylpyrrolidone modified ZnO nanorods synthesized through simple hydrothermal process

The synthesis of nanocrystalline zinc oxide (ZnO) in the presence of poly-vinylpyrrolidone (PVP) as capping agent through hydrothermal process, and their structural and optical properties were reported. PVP modified ZnO nanorods grown hydrothermally involve a heterogeneous chemical reaction in the presence of water as a solvent medium and reaction temperature of 100 °C for 7 h in a hot air oven and calcined in air at 500 °C for 3 h. Crystal structure, phase purity and average crystallite size of ZnO were studied by powder X-ray diffraction (PXRD). The strain associated with the as-prepared samples due to lattice deformation was estimated by Williamson–Hall (W–H) analysis. Structural morphology was investigated using scanning electron microscopy (SEM), which showed the formation of nanorods with PVP capping. The growth mechanism of ZnO nanorods and its capping by poly-vinylpyrrolidone are briefly discussed through FT-IR adsorption spectra. The optical behavior of the samples was analyzed through photoluminescence (PL) spectroscopy with an emission spectra in visible region ∼418 nm indicate the applicability of using it as a transport material in solar cells.     

Defect-dominated optical emission and enhanced ultraviolet photoconductivity properties of ZnO nanorods synthesized by simple and catalyst-free approach

We report on the defect-dominated light emission and ultraviolet (UV) photoconductivity characteristics of ZnO nanorods (NRs) fabricated using a facile, cost-effective, and catalyst-free thermal decomposition route under varying reaction temperatures. The morphological and structural studies reveal the formation of homogeneous quality nanorods in large scale at the highest reaction temperature of 600 ^°C. The luminescence feature of the nanorods is dominated by the defect related emission over the typical band edge emission. The variation of band-edge and native defect-related emission response of the samples has been correlated to the morphology and microstructure. In photoconductivity studies, the I–V characteristics of the ZnO NRs prepared at different reaction temperatures in dark and under UV illumination (λ=365 nm) follow the power law, i.e., IαV ^r . An enhanced ultraviolet photodetection has been observed in the nanorods fabricated at the highest reaction temperature of 600 ^°C. The sample prepared at highest reaction temperature of 600 ^°C exhibits UV photosensitivity value (photo-to-dark current ratio) of around 1.18×10³, which is much higher in magnitude compared to that of the samples prepared at lower reaction temperatures. The enhanced photoconductivity may be assigned to the development of uniformity and homogeneity of the nanorods. Further development of such ZnO nanostructures can form the basis of promising prototype luminescent and UV photodetecting devices.     

Growth and optical study of ZnO nanorods

ZnO nanorods were grown by a simple near room temperature, chemical solution method on ZnO-seeded silicon substrates. Study of the ZnO nanorods over different growth times by electron microscopy methods revealed that the resulting ZnO nanorods were single crystalline with a highly preferential growth perpendicular to the substrate and a very good c-axis alignment. The size of the nanorods increased with increasing growth time. The growth mechanism is briefly discussed. Post-annealing in oxygen slightly improved the surface roughness of the ZnO nanorods. Photoluminescence experiments at 1.6 K revealed a major emission peak of the nanorods at around 3.36 eV which is attributed to the band edge transition of ZnO, while defect-related emission is relatively weak.     

Ag-doped ZnO nanorods synthesized by two-step method

A two-step method is adopted to synthesize Ag-doped ZnO nanorods.A ZnO seed layer is first prepared on a glass substrate by thermal decomposition of zinc acetate.Ag-doped ZnO nanorods are then assembled on the ZnO seed layer using the hydrothermal method.The influences of the molar percentage of Ag ions to Zn ions(RAg/Zn) on the structural and optical properties of the ZnO nanorods obtained are carefully studied using X-ray diffractometry,scanning electron microscopy and spectrophotometry.Results indicate that Ag ions enter into the crystal lattice through the substitution of Zn ions.The<002>c-axis-preferred orientation of the ZnO nanorods decreases as RAg/Zn increases.At RAg/Zn >1.0%,ZnO nanorods lose their c-axis-preferred orientation and generate Ag precipitates from the ZnO crystal lattice.The average transmissivity in the visible region first increases and then decreases as R Ag/Zn increases.The absorption edge is first blue shifted and then red shifted.The influence of Ag doping on the average head face,and axial dimensions of the ZnO nanorods may be optimized to improve the average transmissivity at RAg/Zn <1.0%.     

Synthesis and optical properties of flower-like ZnO nanorods by thermal evaporation method

Flower-like ZnO nanorods have been synthesized by heating a mixture of ZnO/graphite powders using the thermal evaporation and vapor transport on Si (1 0 0) substrates without any catalyst. The structures, morphologies and optical properties of the products were characterized in detail by using X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), photoluminescence (PL) and Raman spectroscopy. The synthesized products consisted of large quantities of flower-like ZnO nanostructures in the form of uniform nanorods. The flower-like ZnO nanorods had high purity and well crystallized wurtzite structure, whose high crystalline quality was proved by Raman spectroscopy. The as-synthesized flower-like ZnO nanorods showed a strong ultraviolet emission at 386 nm and a weak and broad yellow-green emission in visible spectrum in its room temperature photoluminescence (PL) spectrum. In addition, the growth mechanism of the flower-like ZnO nanorods was discussed based on the reaction conditions.     

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.     

Synthesis and optical properties of ZnO nanorods on indium tin oxide substrate

ZnO nanorods with uniform diameter and length have been synthesized on an indium-tin oxide (ITO) substrate by using a simple thermal evaporation method which is suitable to larger scale production and without any catalyst or additives. The samples were characterized with X-ray diffraction (XRD), scanning electron microscopy (SEM), ultraviolet-vis (UV-vis) absorption spectrum, photoluminescence (PL) spectrum and Raman spectrum. The single-phase ZnO nanorods grow well-oriented along the c-axis of its wurtzite structure on ITO substrate. The ZnO nanorods shows sharp and strong UV emission located at 380 nm without notable visible light emission in the PL spectrum, which suggests the good crystallinity of the nanorods, which was also testified by their Raman spectrum. The photodegradation of methylene orange (MO) in aqueous solution reveals that the well-arranged c-axis growth of ZnO nanorods possess evidently improved photocatalytic performance and these properties enable the ZnO nanorods potential application in UV laser.     

Galvanic deposition of ZnO nanorods and thermal annealing effects on their optical properties

The effects of NaCl electrolyte concentrations in the range 6-48 mM on the galvanic deposition of ZnO in Zn(Ac)₂ electrolyte is presented. Effects of thermal annealing on their structural and optical properties have been investigated by using scanning electron microscopy (SEM), X-ray diffraction (XRD) and energy-dispersive X-ray (EDX) microanalysis and photoluminescence (PL). The results show that the increase of NaCl electrolyte concentration not only results in the increase of the diameter of ZnO nanorods, but also promotes the blue-shift of UV emission of ZnO. After air annealing at 200 °C, 300 °C and 400 °C, the UV emission is first enhanced then quenched sharply, while the visible emission tends to be enhanced tremendously. It can be ascribed to the new defect states introduced in ZnO after annealing at high temperature.     

Structural and optical properties of the S-doped ZnO particles synthesized by hydrothermal method

Sulfur-doped ZnO particles have been synthesized by hydrothermal method. The structural and optical properties were studied systematically by XRD, scanning electron microscopy (SEM), and photoluminescence. SEM results show that the particle is hexagonal and the average size decreases with increasing sulfur doping, which means a retardant effect of sulfur on the growth of S-doped ZnO. XRD results show that the lattice parameters increase with more sulfur, which means an effective sulfur doping and increasing strain. Optical characterization also shows that the effective sulfur doping will enhance the green emission and suppress the near bandgap emissions.     

Electrical and optical properties of Sb-doped ZnO thin films synthesized by sol–gel method

Sb-doped ZnO thin films with different values of Sb content （from 0 to 1.1 at.%） are deposited by the sol-gel dip- coating method under different sol concentrations. The effects of Sb-doping content, sol concentration, and annealing ambient on the structural, optical, and electrical properties of ZnO films are investigated. The results of the X-ray diffraction and ultraviolet-visible spectroscopy （UV-VIS） spectrophotometer indicate that each of all the films retains the wurtzite ZnO structure and possesses a preferred orientation along the c axis, with high transmittance （〉 90%） in the visible range. The Hall effect measurements show that the vacuum annealed thin films synthesized in the sol concentration of 0.75 mol/L each have an adjustable n-type electrical conductivity by varying Sb-doping density, and the photoluminescence （PL） spectra revealed that the defect emission （around 450 nm） is predominant. However, the thin films prepared by the sol with a concentration of 0.25 mol/L, despite their poor conductivity, have priority in ultraviolet emission, and the PL peak position shows first a blue-shift and then a red-shift with the increase of the Sb doping content.     

固相反应法制备Co掺杂ZnO的磁性和光学性能研究

研究了以固相反应法制备Co掺杂ZnO粉体的磁性和光学性能，测试结果表明对于均匀掺杂的Zn_0.95Co_0.05O粉体，Co²⁺随机取代Zn²⁺的位置进入ZnO晶格.Co²⁺之间的3d自旋电子耦合交换作用使得近邻的Co²⁺自旋反平行，Zn_0.95Co_0.05O粉体在3—300K表现为顺磁性，而非铁磁性. 关键词： ZnO 固相反应 稀磁半导体 顺磁性     

Enhanced optical and field emission properties of CTAB-assisted hydrothermal grown ZnO nanorods

We have developed a simple N-cetyl-N,N,N-trimethyl ammonium bromide (CTAB)-assisted hydrothermal route for the production of ZnO one-dimensional (1D) nanostructures on zinc foil at reaction temperature of 160 °C. With the increase of CTAB concentration, the one-dimensional structures change from microrod to a mixture of nano- and microrod and finally to nanorods. X-ray diffraction studies confirmed the proper phase formation of the grown nanostructures. The room temperature photoluminescence spectra showed that ZnO nanostructures prepared with increased CTAB concentration exhibited enhanced band edge UV emission and also blue shift of the emission peak. All the samples show no defect related green emission. Field emission property of the 1D structures has been investigated in detail. By tuning the CTAB concentration, the field emission property was optimized. The nanorods synthesized with high CTAB showed turn-on and threshold fields of 3.2 and 5 V/μm, respectively, which are comparable to the values for vapour phase synthesized high field emitting ZnO nanostructures.     

Annealing effects on electrical and optical properties of ZnO thin films synthesized by the electrochemical method

Microstructural and electrical properties of potentiostatically electrodeposited ZnO thin films from an aqueous bath were investigated after annealing at different temperatures in Ar and 5% H₂/Ar atmospheres. It is confirmed that the bandgap energy of ZnO thin films decreased with annealing from 3.42 to 3.27-3.29 eV by calculating the wavelength of the absorption region. The annealing at temperatures as low as 200 °C decreased the sheet resistance of ZnO thin films because of the extinction of Zn(OH)₂ in the atmosphere. In addition, the sheet resistance of ZnO thin films decreased by annealing in a 5% H₂ atmosphere, which caused an increase of carrier concentration by hydrogen reduction.     

Ti-incorporated ZnO films synthesized via magnetron sputtering and its optical properties

Undoped and Ti-doped ZnO films were deposited using radio frequency reactive magnetron sputtering at various sputtering powers. The crystal structures, surface morphology, chemical state and optical properties in Ti-doped ZnO films were systematically investigated via X-ray diffraction (XRD), atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS) and ultraviolet visible (UV–Vis) spectrophotometer. Results indicated that titanium atoms may replace zinc atomic sites substitutionally or incorporate interstitially in the hexagonal lattices, and a moderate quantity of Ti atoms exist in the form of sharing the oxygen with Zn atoms and hence improve the (0 0 2) orientation. The photoluminescence (PL) spectra of the Ti-doped ZnO films contain one main blue peak, whose intensity increased with the increase of sputtering power. Our results indicated that a higher compressive stress in Ti-doped ZnO films results in a lower optical band gap and a lower transmittance, and various Ti impurities can affect the concentration of the interstitial Zn and O vacancies.     

Room-temperature magnetic properties of SiC based nanowires synthesized via microwave heating method

Two kinds of ferromagnetic SiC based nanowires with and without Ni catalyst were successfully synthesized by employing microwave heating method. The comprehensive characterizations and vibrating sample magnetometer (VSM) have been applied to investigate the micro-structures and magnetic properties of as-grown nanowires. For the nanowires synthesized without using Ni catalyst, the diameters and lengths are in the range of 20–60 nm and dozens of micrometers, respectively. Particularly, the results of transmission electron microscopy (TEM) show that the nanowires consist of SiC core and SiO_x shell. The SiC/SiO_x coaxial nanowires exhibit room-temperature ferromagnetism with saturation magnetization (Ms) of 0.2 emu/g. As to the nanowires obtained using Ni catalyst, the scanning electron microscopy (SEM) results indicate that the Ni catalyzed nanowires have a nano-particle attached on the tip and a uniform diameter of approximately 50 nm. The vapor-liquid-solid (VLS) growth mechanism can be used to explain the formation of the Ni catalyzed nanowires. The detection result of VSM indicates that the Ni catalyzed nanowires possess the paramagnetism and the ferromagnetism, simultaneously. The enhancement of the ferromagnetism, compared with the SiC/SiO_x coaxial nanowires, could be attributed to the Ni₂Si and NiSi phases.     

Effect of Mn doping on the nanostructure and optical properties of ZnO films synthesized by magnetron sputtering

We investigated the microstructure and optical properties of Zn_1−xMn_xO films synthesized by the magnetron sputtering technique. Structural analyses suggest that Mn occupied the Zn sites successfully and did not change the wurtzite structure of ZnO. In addition, nanoscale columnar grain arrays were found in the Mn-doped ZnO films. The experimental results indicate that moderate Mn doping could enhance the photoluminescence emission of ZnO. The possible origin of the emissions from our samples was also explored.