Effect of ZnO seed layers on the solution chemical growth of ZnO nanorod arrays

High density ZnO nanorod arrays were grown on Si substrates coated with ZnO seed layers via aqueous solution route. The ZnO seed layers were deposited on the substrate using DC reactive sputtering and RF magnetron sputtering. It was found that ZnO seed layer with (1 0 3) preferred orientation, prepared using DC reactive sputtering, did not facilitate the formation of ZnO nanorods in the solution grown process. Prior seeding of the surface by ZnO layer with (0 0 2) preferred orientation, deposited using RF magnetron sputtering, leads to nucleation sites on which ZnO nanorod arrays can grow in a highly aligned fashion. ZnO nanorods with well-defined hexagonal facets (0 0 2) were grown almost vertically over the entire substrate. The uniformity and alignment of the nanorod arrays are strongly related to the properties of underneath ZnO seed layers.     

Controllable growth of ZnO nanorod arrays with different densities and their photo-electric properties

ABSTRACT: Since the photo-electric response and charge carriers transport can be influenced greatly by the density and spacing of the ZnO nanorod arrays, controlling of these geometric parameters precisely is highly desirable but rather challenging in practice. Here, we fabricated patterned ZnO nanorod arrays with different density and spacing distance on silicon (Si) substrate by electron beam lithography (EBL) method combined with the subsequent hydrothermal reaction process. By using the EBL method, patterned ZnO seed layers with different areas and spacing distances were obtained firstly. ZnO nanorod arrays with different density and various morphologies were obtained by the subsequent hydrothermal growth process. The combination of EBL and hydrothermal growth process was very attractive and made us could control the geometric parameters of ZnO nanorod arrays expediently. Finally, the vertical transport properties of the patterned ZnO nanorod arrays were investigated through the micro probe station equipment and the I-V measurement results indicated that back-to-back Schottky contacts with different barriers height were formed in dark conditions. Under UV light illumination, the patterned ZnO nanorod arrays showed a high UV light sensitivity, and the response ratio was about 104. The controllable fabrication of patterned ZnO nanorod arrays and understanding for their photo-electric transport properties were helpful to improve the performance of nanodevices based on them.     

Defect-controlled ZnO nanorod arrays for enhanced photoelectrochemical performance

In this work, we demonstrated the effect of crystal defects on the photoelectrochemical properties of ZnO nanorod arrays (NRAs). Vertically aligned ZnO NRAs with different defect contents were grown on F doped SnO₂ (FTO) glass substrate via facile electrochemical process and annealing treatement.     

Growth and optical properties of ZnO nanorod arrays on Al-doped ZnO transparent conductive film

ZnO nanorod arrays (NRAs) on transparent conductive oxide (TCO) films have been grown by a solution-free, catalyst-free, vapor-phase synthesis method at 600°C. TCO films, Al-doped ZnO films, were deposited on quartz substrates by magnetron sputtering. In order to study the effect of the growth duration on the morphological and optical properties of NRAs, the growth duration was changed from 3 to 12 min. The results show that the electrical performance of the TCO films does not degrade after the growth of NRAs and the nanorods are highly crystalline. As the growth duration increases from 3 to 8 min, the diffuse transmittance of the samples decreases, while the total transmittance and UV emission enhance. Two possible nanorod self-attraction models were proposed to interpret the phenomena in the sample with 9-min growth duration. The sample with 8-min growth duration has the highest total transmittance of 87.0%, proper density about 75 μm⁻², diameter about 26 nm, and length about 500 nm, indicating that it can be used in hybrid solar cells.     

Effects of preparing conditions on the electrodeposition of well-aligned ZnO nanorod arrays

By using a potentiostatic electrodeposition method, well-aligned ZnO nanorod arrays (ZNAs) were synthesized under different conditions. The effects of preparing conditions on the electrodeposition of ZNAs were systematically studied by scanning electron microscopy (SEM), X-ray diffraction (XRD) and absorbance spectroscopy. It is indicated that the electrodeposition parameters, such as electrodeposition potential, electrolyte pH, concentration of precursors, temperature of solution and electrodeposition time, have significant influence on the morphology, diameter, density and growth rate of ZNAs. The ZNAs, with well-defined crystallization, can be only obtained when the applied potential is controlled from −0.4 to −1.0 V. The growth temperature has great impact on the morphology of ZnO nanostructure but it is weakly related to the band gap (E_g) of ZNAs. The rod diameters can be monitored to some extent only by changing the concentration of the precursors. The electrolyte pH value has relative influence on the diameter of ZNAs. With the growth time increasing, ZNAs with high aspect ratio can be gained.     

Cu-doped ZnO nanorod arrays: the effects of copper precursor and concentration

Cu-doped ZnO nanorods have been grown at 90°C for 90 min onto a quartz substrate pre-coated with a ZnO seed layer using a hydrothermal method. The influence of copper (Cu) precursor and concentration on the structural, morphological, and optical properties of ZnO nanorods was investigated. X-ray diffraction analysis revealed that the nanorods grown are highly crystalline with a hexagonal wurtzite crystal structure grown along the c-axis. The lattice strain is found to be compressive for all samples, where a minimum compressive strain of −0.114% was obtained when 1 at.% Cu was added from Cu(NO₃)₂. Scanning electron microscopy was used to investigate morphologies and the diameters of the grown nanorods. The morphological properties of the Cu-doped ZnO nanorods were influenced significantly by the presence of Cu impurities. Near-band edge (NBE) and a broad blue-green emission bands at around 378 and 545 nm, respectively, were observed in the photoluminescence spectra for all samples. The transmittance characteristics showed a slight increase in the visible range, where the total transmittance increased from approximately 80% for the nanorods doped with Cu(CH₃COO)₂ to approximately 90% for the nanorods that were doped with Cu(NO₃)₂.     

Enhanced piezo-phototronic effect of ZnO nanorod arrays for harvesting low mechanical energy

In this paper, ZnO photocatalytic activity was enhanced by a built-in piezoelectric field due to the piezoelectric effect of ZnO nanorods (NRs). A simple, practical, and self-powered device was designed to simulate and harvest the very low energy of ocean waves. By testing the degradation efficiency of ZnO for different polar dyes (methyl orange, natural red and rhodamine B), the role of the dynamic built-in electric field in the photocatalytic process was illustrated. The changing piezoelectric field acts as a “photo-induced carrier storage” in that the photo-induced carriers would be separated, stored, and released on the ZnO NR surfaces incessantly, improving the separation efficiency of photo-induced carriers in the ZnO NR array. The intensity and frequency of the built-in oscillating piezoelectric field are proportional to the ZnO NR array photocatalytic efficiency. The sustainable piezo-photocatalytic performance of the ZnO NR arrays should promote further applications of ZnO photocatalyst in pollution degradation.     

Novel ZnO microflowers on nanorod arrays: local dissolution-driven growth and enhanced light harvesting in dye-sensitized solar cells

ZnO nanostructures were manipulated, via a low-temperature solution process, from pure nanorod arrays to complex nanostructures of microflowers on nanorod arrays with adjusted quantities of flowers. We proposed the mechanism of local dissolution-driven growth to rationally discuss the novel growth process. These nanostructures were used as photoanodes in dye-sensitized solar cells. Compared to pure nanorod arrays, the nanorod array-microflower hierarchical structures improved the power conversion efficiency from 0.41% to 0.92%, corresponding to a 124% efficiency increase. The enhancement of the efficiency was mainly ascribed to the synergistic effect of the enhanced surface area for higher dye loading and the improved light harvesting from efficient light scattering. Present results provide a promising route to improve the capability of light-harvesting for ZnO nanorod array-based DSSCs.     

Synthesis of well-aligned ZnO nanorod arrays from mixed sulfide-oxide lead and zinc ore

A novel process of recovery of zinc from mixed sulfide-oxide lead and zinc ore was presented in this paper. ZnO nanorod arrays (ZNRAs) on FTO substrate pre-coated with a layer of ZnO seeds was synthesized successfully from the mixed ore via the oxidative ammoniacal leaching process and a two-step process including precipitation and hydrothermal synthesis. The characterization results from the XRD, SEM and UV–vis spectrophotometer analysis showed that the as-prepared ZNRAs was well-aligned, large-scale, perpendicular to the FTO substrate and had a reduced band gap energy of 3.03 eV. XPS analysis indicated that the grown ZNRAs were doped by a small quantity of carbon and did not contain any other impurities particularly Fe and Pb. The total zinc extraction can reach 92.4% after the oxidative ammoniacal leaching process and the precipitation process. The elimination of conventional purification process in zinc production was achieved due to the efficient and selective oxidative ammoniacal leaching process.     

Tuning of defects in ZnO nanorod arrays used in bulk heterojunction solar cells

With particular focus on bulk heterojunction solar cells incorporating ZnO nanorods, we study how different annealing environments (air or Zn environment) and temperatures impact on the photoluminescence response. Our work gives new insight into the complex defect landscape in ZnO, and it also shows how the different defect types can be manipulated. We have determined the emission wavelengths for the two main defects which make up the visible band, the oxygen vacancy emission wavelength at approximately 530 nm and the zinc vacancy emission wavelength at approximately 630 nm. The precise nature of the defect landscape in the bulk of the nanorods is found to be unimportant to photovoltaic cell performance although the surface structure is more critical. Annealing of the nanorods is optimum at 300°C as this is a sufficiently high temperature to decompose Zn(OH)₂ formed at the surface of the nanorods during electrodeposition and sufficiently low to prevent ITO degradation.     

Electrodeposition of flexible stainless steel mesh supported ZnO nanorod arrays with enhanced photocatalytic performance

Large scale well oriented ZnO nanorod arrays (ZNRAs) were electrodeposited on flexible stainless steel mesh (SSM) substrate pre-treated by Al doped ZnO (AZO) seed layers. The effects of substrate pre-treatment conditions such as Al doping and spin coating times of the colloid on the morphology characteristics and photocatalytic properties of as-prepared ZNRAs were systematically studied. The results showed that by introducing Al into ZnO colloid solution, well aligned ZNRAs with relatively higher specific surface area (higher growth density and smaller rod diameter) could be obtained on the premodified SSM substrate. In addition, increasing spin coating times of AZO colloid solution would decrease the average diameter of ZNRAs. Under the optimum preparing conditions, the formed flexible SSM supported ZNRAs exihibited enhanced photocatalytic performance of 93.42% and remarkable photocatalytic stability under the UV-lamp for degradation of Rhodamine B.     

Significant enhancement of yellow-green light emission of ZnO nanorod arrays using Ag island films

Surface plasmon (SP) mediated emission from ZnO nanorod arrays (NRAs)/Ag/Si structures has been investigated. The ratio of visible emission to UV emission can be increased by over 30 times via coupling with SP without deterioration of the crystal quality. The fact that the effect of SP crucially depends on the size of Ag island films provides the feasibility to significantly enhance the yellow-green emission of the ZnO nanostructures without sacrificing the crystallinity of ZnO.     

Evaluation of ZnO nanorod arrays with dandelion-like morphology as negative electrodes for lithium-ion batteries

In this study, ZnO nanorod arrays have been evaluated for the negative electrodes of lithium-ion batteries. The ZnO nanorod arrays with dandelion-like morphology were directly grown on copper substrates by a hydrothermal synthesis process at 80 °C. X-ray diffraction, scanning electron microscopy, galvanostatic discharge-charge, and cyclic voltammetry were employed to characterize the structure and electrochemical property of the arrays. The array electrodes showed a stable capacity over 310 mAh g⁻¹ after 40 cycles, and good capacity retention as the anodes of lithium-ion batteries. It was believed that the unique dandelion-like binary-structure played an important role in the electrochemical performance of the array electrodes. The present finding opens the possibility to fabricate micro/nanometer hierarchical ZnO films that might be applied in lithium-ion batteries.     

Well-integrated ZnO nanorod arrays on conductive textiles by electrochemical synthesis and their physical properties

We reported well-integrated zinc oxide (ZnO) nanorod arrays (NRAs) on conductive textiles (CTs) and their structural and optical properties. The integrated ZnO NRAs were synthesized by cathodic electrochemical deposition on the ZnO seed layer-coated CT substrate in ultrasonic bath. The ZnO NRAs were regularly and densely grown as well as vertically aligned on the overall surface of CT substrate, in comparison with the grown ZnO NRAs without ZnO seed layer or ultrasonication. Additionally, their morphologies and sizes can be efficiently controlled by changing the external cathodic voltage between the ZnO seed-coated CT substrate and the counter electrode. At an external cathodic voltage of −2 V, the photoluminescence property of ZnO NRAs was optimized with good crystallinity and high density.     

Synthesis and photocatalysis of hierarchical heteroassemblies of ZnO branched nanorod arrays on Ag core nanowires

In this paper, hierarchical heteroassemblies made of interwoven Ag core nanowires (NWs) covered by ZnO branched nanorods (ZnO BNRs) are successfully prepared on a large scale via a solution bottom-up strategy coupling with a templating method. Briefly, heteroepitaxial growth of ZnO nanorods (ZnO NRs) on ZnO seed-coated Ag NWs is first conducted to form fluffy worm-like heteroassemblies. Then, by templating these, ZnO BNRs with exposed high-energy (001) planes on Ag NWs are fabricated with preserved morphology through the second nucleation and growth processes. When evaluated with UV-induced photo-degradation of rhodamine B (RhB), the heteroassemblies of Ag NWs-ZnO BNRs exhibit high photocatalytic properties, due to the decisive roles of the synergistic effect of the unique metal-semiconductor heterojunction and the hierarchical fluffy worm-like morphologies as well as the (001) plane-dominant surface of ZnO BNRs which are attractive for highly efficient photocatalysis.     

Size-selected growth of transparent well-aligned ZnO nanowire arrays

This paper reports the effect of precursor concentration, growth temperature, and growth time on the size and density of ZnO nanowire arrays (ZNAs). The well-aligned ZNAs were grown on indium tin oxide substrate using a facile chemical bath deposition method. The results showed that the ZnO nanowires could be tailored to the desired sizes with a simple variation of the growth parameters. Optical transmission spectra revealed a sufficient transparency of the ZNAs, qualifying them for photovoltaic and other optoelectronic applications. An inverted hybrid solar cell was fabricated using the ZNAs as the electron collecting layer, and the solar cell exhibited a power conversion efficiency of 0.91%.     

The effect of TiN deposition time on the field-emission performance coated on ZnO nanorod arrays

ZnO nanorod arrays (NRs) with a large number of sharp tips and uniform shapes were grown on the carbon cloth (CC) by a simple hydrothermal method. Titanium nitride (TiN) nanoparticles with various thicknesses were deposited on the ZnO NRs by magnetron sputtering to obtain ZnO/TiN core-shell arrays. Field emission (FE) performance of ZnO NRs show close dependence on TiN coating thickness. The turn-on field first decreases and then increases with increasing TiN coating thickness from 60 nm to 300 nm. The arrays with a design architecture can strike a balance between increased emission sites and limited field shielding effects. ZnO/TiN240 core-shell NRs have the lower turn-on electric field at 0.79 V/μm and the higher current densities at 9.39 mA/cm². The field enhancement factor (β) of ZnO/TiN240 is about 3.2 times that of the bare ZnO NRs. On the other hand, the electrochemical properties were improved due to the formation of core-shell heterojunction on the ZnO/TiN interface and porous structure, which makes the ion and charge transport more convenient. Hence, this work not only revealed that the ZnO/TiN core-shell structure exhibited excellent improvement in both FE and supercapacitors applications, but also that growing arrays on CC was expected to achieve flexible display.     

Room-temperature ferromagnetism in graphitic petal arrays

We report room-temperature ferromagnetism of graphitic petal arrays grown on Si substrates by microwave plasma chemical vapor deposition without catalyst. The samples have been characterized by Raman and X-ray photoelectron spectroscopy to confirm the absence of possible ferromagnetic impurities. The petals exhibit ferromagnetic hysteresis with saturation magnetization of ～4.67 emu cm(-3) and coercivity of ～105 Oe at 300 K, comparable to the reported behavior of few-layer graphene. Upon O2 annealing the saturation magnetization and coercivity decreased to 2.1 emu cm(-3) and ～75 Oe respectively. The origin of ferromagnetism is believed to arise from the edge defects and vacancies in the petals.     

A close correlation between nucleation sites,growth and final properties of ZnO nanorod arrays: Sol-gel assisted chemical bath deposition process

Different ZnO seed layers are synthesized by changing sol-gel parameters, including precursor concentration, type of solvent, and type of additive in order to systematically investigate the importance of seed layer properties on the nucleation, growth, and final properties of zinc oxide (ZnO) nanorod (NR) arrays. The X-ray diffraction (XRD) and field emission scanning electron microscope (FESEM) show the importance of the seed layer on ZnO NRs properties. Results verify that the relative intensity (RI factor) of (002) polar planes in the XRD patterns of ZnO nanoparticles (NPs) together with the aspect ratio, density, and alignment of ZnO NRs control the structural characteristics of those arrays. For instance, the RI factor of ZnO NPs and NRs follow the same trend when changing precursor concentration in sol preparation step. However, the importance of other parameters, including aspect ratio, density, and alignment of NRs is confirmed by changing solvent and additive. In addition, FESEM images show that the density of ZnO NRs is proportional to NPs density and inversely proportional to the size of ZnO NPs in the seed layers. Besides, the significant role of wrinkled inter-layer on NRs properties, together with the formation mechanism of that inter-layer are profoundly investigated.     

Growth temperature dependent properties of ZnO nanorod arrays on glass substrate prepared by wet chemical method

In this work, ZnO nanorod arrays were grown on glass substrate by the wet chemical method, and the effect of synthesis temperature on the properties was investigated. The grown nanorods were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), Raman and Photoluminescence (PL) measurements. XRD pattern showed that nanorod prepared at 80 °C and 90 °C has high crystallinity with wurtzite structure and orientated along the c-axis. However, nanorods were not formed at 60 °C and 70 °C due to less energy supply for the growth of the ZnO. FE-SEM results showed that the morphology and the size of ZnO can be effectively controlled. In particular, as the temperature increased, diameter of the nanorod was increased while length decreased. Raman scattering spectra of ZnO nanorod arrays revealed the characteristic E₂^high mode that is related to the vibration of oxygen atoms in the wurtzite ZnO. Room-temperature PL spectra of the ZnO nanorods revealed a near-band-edge (NBE) emission peak. The NBE (UV light emission) band at ~383 nm might be attributed to the recombination of free exciton. The narrow full-width at half-maximum (FWHM) of the UV emission indicated that ZnO nanorods had high crystallinity.