Fabrication and strain investigation of ZnO nanorods on Si composing sol–gel and chemical bath deposition method

High density vertically aligned ZnO nanorods arrays were prepared on Si substrate by the simple and facile sol–gel and chemical bath deposition combination technology. ZnO nanorods, preferentially oriented along the c-axis, were of the hexagonal wurzite structure. The lattice constants of ZnO nanorods a was shrunken by about 0.004 nm, which can result in about 1.29% mismatch between ZnO nanorods and Si substrate. The Raman spectrum was also analyzed in detail, and the result indicates that the stress between ZnO nanorods and Si substrate was about 0.227 GPa, which can be ascribed to the stress relaxation effect of the ZnO nanorods. The room temperature photoluminescence (PL) measurement result has shown a main deep level emission. The forming mechanism for ZnO nanorods was further analyzed.     

Effect of surface preparation on the morphology of ZnO nanorods

The effects of Si substrate orientation and surface treatment on the morphology and density of Zinc oxide (ZnO) nanorods were investigated. The size and density of ZnO nanorods were influenced by Si substrate orientation and surface preparation. ZnO nanorods synthesized on the ideally H-terminated Si(1 1 1) prepared with an NH₄F solution resulted in the biggest size and the lowest density. It is suggested that the smoother surface of the Si substrate and lattice shape match with a larger atomic distance result in the increase of the ZnO seedlayer's grain size, which in turn enhances the size of ZnO nanorods grown on it. The optical properties of the ZnO nanorods were affected by their size and crystallinity. The smallest ZnO nanorods with a preferential c-axis orientation synthesized on the HF-treated Si(1 1 1) surface showed the highest intensity ratio of UV to visible emission, and the biggest ZnO nanorods synthesized on the N₂-sparged NH₄F-treated Si(1 1 1) surface showed the lowest intensity ratio of UV to visible emission. Therefore, it can be concluded that Si substrate orientation and surface preparation significantly affect the optical properties of ZnO nanorods.     

Controllable vertically aligned ZnO nanorods on flexible polyethylene naphthalate (PEN) substrate using chemical bath deposition synthesis

Zinc oxide (ZnO) nanorods were successfully grown on polyethylene naphthalate substrates with a seed layer using a wet chemical bath deposition method at a low temperature. Using various precursor concentrations, the diameter, length, and density of the ZnO nanorods were controlled, and their optical and crystallinity properties were investigated. X-ray diffraction and field emission scanning electron microscopy were used to examine the structure and morphology of the ZnO nanorods. The obtained ZnO nanorods were hexagonal and grew vertically from the substrate in the (002) direction along the c-axis. The low compressive strain values confirmed the high-quality crystal structure of the synthesized ZnO nanorods. A 0.050 M precursor concentration resulted in nanorods with a uniform diameter along their entire length and diameters ranging from 10 nm to 40 nm. The photoluminescence results indicated that the ZnO nanorods grown using a 0.050 M precursor concentration exhibited the sharpest and most intense PL peaks in the UV range compared with the other samples. Therefore, the precursor concentration considerably influenced the growth of the ZnO nanorods. These ZnO nanorods can be greatly applied for the development of flexible, elastic electronic, and optoelectronic devices.     

A template-free sol-gel technique for controlled growth of ZnO nanorod arrays

The growth of ZnO nanorod arrays via a template-free sol-gel process was investigated. The nanorod is single-crystalline wurtzite structure with [0 0 0 1] growth direction determined by the transmission electron microscope. The aligned ZnO arrays were obtained directly on the glass substrates by adjusting the temperatures and the withdrawal speeds, without seed-layer or template assistant. A thicker oriented ZnO nanorod arrays was obtained at proper experimental conditions by adding dip-coating layers. Room temperature photoluminescence spectrum exhibits an intensive UV emission with a weak broad green emission as well as a blue double-peak emission located at 451 and 468 nm, respectively. Further investigation results show that the difference in the alignment of nanorods ascribes to the different orientations of the nanoparticles-packed film formed prior to nanorods on the substrate. Well ordered ZnO nanorods are formed from this film with good c-axis orientation. Our study is expected to pave a way for direct growth of oriented nanorods by low-cost solution approaches.     

Structural and optical properties of ZnO nanorods grown on MgxZn1−xO buffer layers

ZnO nanorod arrays were synthesized by chemical-liquid deposition techniques on Mg_xZn_1−xO (x = 0, 0.07 and 0.15) buffer layers. It is found that varying the Mg concentration could control the diameter, vertical alignment, crystallization, and density of the ZnO nanorods. The X-ray diffraction (XRD), transmission electron microscopy (TEM), and selected area electron diffraction (SAED) data show the ZnO nanorods prefer to grow in the (0 0 2) c-axis direction better with a larger Mg concentration. The photoluminescence (PL) spectra of ZnO nanorods exhibit that the ultraviolet (UV) emission becomes stronger and the defect emission becomes weaker by increasing the Mg concentration in Mg_xZn_1−xO buffer layers.     

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.     

Hydrothermal synthesis and characterization of ZnO films with different nanostructures

ZnO films with morphologies of nanorods, nanowires and nanosheets were grown on F-doped SnO₂ glass substrate, which may have potential application in solar cells. X-ray diffraction (XRD) and scanning electron microscopy (SEM) were employed to characterize the structures and morphologies of the as-synthesized samples. The photoluminescence (PL) and the photoelectrochemical properties of ZnO films were also measured. The results showed that ZnO nanorods preferentially oriented along the c-axis and had the largest photocurrent density which is as high as 60 μA/cm².     

The structural and optical properties of ZnO nanorod arrays

High quality vertical-aligned ZnO nanorod arrays were synthesized by a simple vapor transport process on Si (111) substrate at a low temperature of 520 °C. Field-emission scanning electron microscopy (FESEM) showed the nanorods have a uniform length of about 1 μm with diameters of 40-120 nm. X-ray diffraction (XRD) analysis confirmed that the nanorods are c-axis orientated. Selected area electron diffraction (SAED) analysis demonstrated the individual nanorod is single crystal. Photoluminescence (PL) measurements were adopted to analyze the optical properties of the nanorods both a strong UV emission and a weak deep-level emission were observed. The optical properties of the samples were also tested after annealing in oxygen atmosphere under different temperatures, deep-level related emission was found disappeared at 600 °C. The dependence of the optical properties on the annealing temperatures was also discussed.     

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.     

Catalyst-free synthesis and luminescence of aligned ZnO nanorods

Quasi-aligned undoped ZnO nanorods with diameter in the range 100–300 nm and length of several micrometers have been grown catalyst-free on Si(1 0 0) wafer in a one-step process by direct heating of Zn powders. All nanowires are single crystals and are aligned vertically to the substrate surface with c-axis preferred orientation. XRD, HRTEM and Raman studies revealed that the ZnO nanorods have wurtzite phase, are highly crystalline and well aligned with the lattice parameters a=0.32 nm and c=0.52 nm. The PL spectra measured at different temperatures are dominated by excitonic emission at 380 nm and less intense below band gap emission band centered at 520 nm.     

Effect of Mn doping on the microstructures and photoluminescence properties of CBD derived ZnO nanorods

Mn-doped ZnO nanorods were synthesized from aqueous solutions of zinc nitrate hexahydrate, manganese nitrate and methenamine by the chemical solution deposition method (CBD). Their microstructures, morphologies and optical properties were studied in detail. X-ray diffraction (XRD) results illustrated that all the diffraction peaks can be indexed to ZnO with the hexagonal wurtzite structure. Scanning electron microscope (SEM) results showed that the average diameter of Mn-doped ZnO nanorods was larger than that of the undoped one. Photoluminescence (PL) spectra indicated that manganese doping suppressed the emission intensity and caused the blue shift of UV emission position compared with the undoped ZnO nanorods. In the Raman spectrum of Mn-doped ZnO nanorods, an additional mode at about 525 cm⁻¹ appeared which was significantly enhanced and broadened with the increase of Mn doping concentration.     

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.     

Structural, morphological and photoluminescence properties of W-doped ZnO nanostructures

W-doped ZnO nanostructures were synthesized at substrate temperature of 600 °C by pulsed laser deposition (PLD), from different wt% of WO₃ and ZnO mixed together. The resulting nanostructures have been characterized by X-ray diffraction, scanning electron microscopy, atomic force microscopy and photoluminescence for structural, surface morphology and optical properties as function of W-doping. XRD results show that the films have preferred orientation along a c-axis (0 0 L) plane. We have observed nanorods on all samples, except that W-doped samples show perfectly aligned nanorods. The nanorods exhibit near-band-edge (NBE) ultraviolet (UV) and violet emissions with strong deep-level blue emissions and green emissions at room temperature.     

Effects of cooling rate and post-heat treatment on properties of ZnO thin films deposited by sol-gel method

Sol-gel spin-coated ZnO thin films are cooled with different rates after the pre-heat treatment. Atomic force microscopy (AFM), X-ray diffraction (XRD), Raman, and photoluminescence (PL) were carried out to investigate the effects of the cooling rate during pre-heat treatment on structural and optical properties of the ZnO thin films. The ZnO thin films cooled slowly exhibit mountain chain structure while the ones cooled rapidly have smooth surface. The ZnO thin films cooled rapidly have higher c-axis orientation compared to the ones cooled slowly. The narrower and the higher near-band-edge emission (NBE) peaks are observed in the ZnO thin films cooled rapidly.     

Effect of annealing temperature and annealing atmosphere on the structure and optical properties of ZnO thin films on sapphire (0 0 0 1) substrates by magnetron sputtering

ZnO thin films were epitaxially grown on sapphire (0 0 0 1) substrates by radio frequency magnetron sputtering. ZnO thin films were then annealed at different temperatures in air and in various atmospheres at 800 °C, respectively. The effect of the annealing temperature and annealing atmosphere on the structure and optical properties of ZnO thin films are investigated by X-ray diffraction (XRD), atomic force microscopy (AFM), photoluminescence (PL). A strong (0 0 2) diffraction peak of all ZnO thin films shows a polycrystalline hexagonal wurtzite structure and high preferential c-axis orientation. XRD and AFM results reveal that the better structural quality, relatively smaller tensile stress, smooth, uniform of ZnO thin films were obtained when annealed at 800 °C in N₂. Room temperature PL spectrum can be divided into the UV emission and the Visible broad band emission. The UV emission can be attributed to the near band edge emission (NBE) and the Visible broad band emission can be ascribed to the deep level emissions (DLE). By analyzing our experimental results, we recommend that the deep-level emission correspond to oxygen vacancy (V_O) and interstitial oxygen (O_i). The biggest ratio of the PL intensity of UV emission to that of visible emission (I_NBE/I_DLE) is observed from ZnO thin films annealed at 800 °C in N₂. Therefore, we suggest that annealing temperature of 800 °C and annealing atmosphere of N₂ are the most suitable annealing conditions for obtaining high quality ZnO thin films with good luminescence performance.     

Nanocrystalline ZnO film deposited by ultrasonic spray on textured silicon substrate as an anti-reflection coating layer

A ZnO thin film was successfully synthesized on glass, flat surface and textured silicon substrates by chemical spray deposition. The textured silicon substrate was carried out using two solutions (NaOH/IPA and Na₂CO₃). Textured with Na₂CO₃ solution, the sample surface exhibits uniform pyramids with an average height of 5 μm. The properties and morphology of ZnO films were investigated. X-ray diffraction (XRD) spectra revealed a preferred orientation of the ZnO nanocrystalline film along the c-axis where the low value of the tensile strain 0.26% was obtained. SEM images show that all films display a granular, polycrystalline morphology. The morphology of the ZnO layers depends dramatically on the substrate used and follows the contours of the pyramids on the substrate surface. The average reflectance of the textured surface was found to be around 13% and it decreases dramatically to 2.57% after deposition of a ZnO antireflection coating. FT-IR peaks arising from the bonding between Zn–O are clearly represented using a silicon textured surface. A very intense photoluminescence (PL) emission peak is observed for ZnO/textured Si, revealing the good quality of the layer. The PL peak at 380.5 nm (UV emission) and the high-intensity PL peak at 427.5 nm are observed and a high luminescence occurs when using a textured Si substrate.     

Studies of luminescence properties of ZnO and ZnO:Zn nanorods prepared by solution growth technique

Pyramidal ZnO nanorods with hexagonal structure having c-axis preferred orientation are grown over large area silica substrates by a simple aqueous solution growth technique. The as-grown nanorods were studied using XRD, SEM and UV-vis photoluminescence (PL) spectroscopy for their structural, morphological and optical properties, respectively. Further, the samples have also been annealed under different atmospheric conditions (air, O₂, N₂ and Zn) to study the defect formation in nanorods. The PL spectra of the as-grown nanorods show narrow-band excitonic emission at 3.03 eV and a broad-band deep-level emission (DLE) related to the defect centers at 2.24 eV. After some mild air annealing at 200 °C, fine structures with peaks having energy separation of ∼100 meV were observed in the DLE band and the same have been attributed to the longitudinal optical (LO) phonon-assisted transitions. However, the annealing of the samples under mild reducing atmospheres of N₂ or zinc at 550 °C resulted in significant modifications in the DLE band wherein high intensity green emission with two closely spaced peaks with maxima at 2.5 and 2.7 eV were observed which have been attributed to the V_O and Zn_i defect centers, respectively. The V-I characteristic of the ZnO:Zn nanorods shows enhancement in n-type conductivity compared to other samples. The studies thus suggest that the green emitting ZnO:Zn nanorods can be used as low voltage field emission display (FED) phosphors with nanometer scale resolution.     

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.     

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.     

Nanoporous structures on ZnO thin films

Porous structures were formed on ZnO thin films which were grown by an electrochemical deposition (ECD) method. The growth processes were carried out in a solution of dimethylsulfoxide (DMSO) zinc perchlorate, Zn(ClO₄)₂, at 120 ^°C on indium tin oxide (ITO) substrates. Optical and structural characterizations of electrochemically grown ZnO thin films have shown that the films possess high (0002) c$c$-axis orientation, high nucleation, high intensity and low FWHM of UV emission at the band edge region and a sharp UV absorption edge. Nanoporous structures were formed via self-assembled monolayers (SAMs) of hexanethiol (C₆SH) and dodecanethiol (C₁₂SH). Scanning electron microscope (SEM) measurements showed that while a nanoporous structure (pore radius 20 nm) is formed on the ZnO thin films by hexanathiol solution, a macroporous structure (pore radius 360 nm) is formed by dodecanethiol solution. No significant variation is observed in X-ray diffraction (XRD) measurements on the ZnO thin films after pore formation. However, photoluminescence (PL) measurements showed that green emission is observed as the dominant emission for the macroporous structures, while no variation is observed for the thin film nanoporous ZnO sample.