One-step solution synthesis and formation mechanism of flower-like ZnO and its structural and optical characterization

The regular hierarchical flower-like ZnO nanostructures assembled by nanosheets were successfully synthesized by one-step solution route with citrate assistance at room temperature. It was demonstrated that the concentration of citrate and the molar ratio of Zn²⁺/OH⁻ had strong effect on the formation of nanosheets and self-assembly flower-like nanostructures. A reasonable formation mechanism of the flower-like nanostructures was proposed. According to UV–vis spectrum, the flower-like ZnO nanostructures exhibited strong light absorption, and the value of band gap of the obtained ZnO was estimated to be 3.26 eV. Moreover, the room-temperature photoluminescence (PL) spectrum of the sample presented only a near-band edge emission at 382 nm.     

ZnO纳米棒水热法生长与表征

采用两步法在FTO导电玻璃衬底上制备ZnO纳米棒,首先利用浸渍-提拉法在FTO导电玻璃衬底上制备ZnO晶种层,然后把有ZnO晶种层的FTO衬底放入盛有生长溶液的反应釜中利用水热法制备ZnO纳米棒.研究了生长溶液的浓度、生长温度和生长时间对所制备的对ZnO纳米棒阵列的微结构和光致发光性能的影响,利用X射线衍射(XRD)、扫描电子显微镜(SEM)和光致发光谱(PL)研究了ZnO样品的结构、形貌和光学性质.实验结果表明:所制备的ZnO纳米棒呈现六方纤锌矿结构,沿(002)晶面择优取向生长,纳米棒的平均直径约为100 nm,长度约为2.5 μm.所制备的ZnO纳米棒在390 nm附近具有很强的紫外发光峰和在550 nm附近有较弱的宽绿光发光峰.     

Effect of chlorine ion concentration on morphology and optical properties of Cl-doped ZnO nanostructures

Effect of Cl^?1 concentration on morphology and optical properties of Cl-doped ZnO nanostructures was studied. The Cl-doped ZnO nanostructures and undoped ZnO microstructures were grown on Si(1 1 1) substrates using a physical vapor deposition method. The ZnO nanostructures have been doped with different concentrations of chlorine. The Cl-doped ZnO nanostructures with 6% atom Cl, showed a nanodisk morphology with a hexagonal shape, while the Cl-doped ZnO nanostructures with 9% atom Cl, exhibited a stacked nanoplate morphology with smaller thickness in comparison to the Cl-doped ZnO nanodisks. In addition, with increasing Cl content to 13%, morphology of the products changed to more stacked nanoplates with nanoflakes morphology. X-ray diffraction results clearly showed a hexagonal structure for the all samples. Raman spectroscopy results showed a strong crystalline quality for the undoped ZnO microdisks and Cl-doped ZnO nanodisks; while these results indicated a weak crystalline quality for the Cl-doped ZnO nanoplates and nanoflakes. Photoluminescence (PL) studies also confirmed the Raman results and it exhibited a lower optical property for the Cl-doped ZnO nanoplates and nanoflakes in comparison to the undoped ZnO microdisks and Cl-doped ZnO nanodisks. Furthermore, the UV peak of the Cl-doped ZnO nanostructures was blue-shifted with respect to that of the undoped ZnO.     

Effect of indium concentration on morphology and optical properties of In-doped ZnO nanostructures

In-doped ZnO nanostructures with different indium concentrations were grown using a thermal evaporation method. The In-doped ZnO nanostructures with a low concentration of indium exhibited a javelin shape, while the In-doped ZnO nanostructures with a high concentration of indium showed a flake shape. In addition, undoped ZnO nanojavelins were grown under the same conditions, but the sizes of these undoped ZnO nanojavelins were larger than the In-doped ZnO nanojavelins. It was shown that the In³⁺ cations played a crucial role in controlling the size. X-ray diffraction and Raman spectroscopy clearly showed hexagonal structures for all of the products. However, the Raman results demonstrated that the In-doped ZnO nanoflakes had a lower crystalline quality than the In-doped ZnO nanojavelins. Furthermore, photoluminescence (PL) measurements confirmed the Raman results. Moreover, the PL results demonstrated a larger band-gap for the In-doped ZnO nanostructures in comparison to the undoped ZnO.     

Hydrothermal synthesis of ZnO–CdS nanocomposites: Structural,optical and electrical behavior

ZnO–CdS nanocomposites with three different molar ratios of 25:75, 50:50 and 75:25 were synthesized by simple hydrothermal technique. Powder X-ray diffraction patterns confirmed the phase formation of ZnO and CdS in ZnO–CdS nanocomposites. The calculated crystallite size was found in the range of 33–38 nm and 15–21 nm for ZnO and CdS respectively. HRSEM images revealed flake-like morphology for all samples. Energy dispersive X-ray spectra confirmed the presence of all the elements. The estimated optical bandgap was found in the range of 3.71–3.35 eV. IR spectra confirmed the formation of stretching vibration in ZnO and CdS. Dielectric analysis was performed in order to study Ac conductivity, dielectric constant and dielectric loss. Photoconductivity studies revealed that ZnO–CdS nanocomposites material exhibited sound photo-response characteristics.     

CdS／ZnO复合光催化剂催化分解硫化氢制氢研究

采用溶胶-凝胶-沉淀的方法,制备出CdS／ZnO复合光催化剂,并通过XRD和UV—Vis漫反射光谱对催化剂进行了表征。考察了ZnO制备过程中胶溶剂种类、CdS物质的量百分含量（X）和焙烧温度（T）对CdS／ZnO复合光催化剂的性质与光催化分解硫化氢制氢性能的影响。实验结果表明：CdS／ZnO复合催化剂中,ZnO和CdS为六方晶系,UV—Vis吸收边有不同程度的红移。当以氨水为胶溶剂,T为400℃,x为50时,制备出的CdS／ZnO复合催化剂,其光催化分解硫化氢制氢速率最大,可达35mmol／g·h。     

Effect of precursor concentration on structural,morphological and opto-electric properties of ZnO thin films prepared by spray pyrolysis

Sprayed ZnO films were grown on glass substrate at 400 °C using zinc chloride as precursor with different molar concentrations varying from 0.05 to 0.2 M. X-ray diffraction patterns reveal that ZnO films are polycrystalline with hexagonal wurtzite structure with preferred orientation in (002) plane. Optical measurements show that transmittance reaches a maximum value of 95% in the visible region for ZnO films prepared from precursor with 0.05 M concentration. The films obtained from the precursor with 0.1 M concentration have the highest electrical conductivity and photocurrent values.     

Enhanced optoelectrical performance of ultraviolet detectors based on self-assembled porous zinc oxide nanostructures

A templated self-assembly technique was utilized in the present study to grow porous zinc oxide nanostructures. The nanostructures were formed by the electrochemical deposition of ZnO through the interstitial spaces between polymer microsphere templates. After the deposition, polymer microspheres were removed by dissolving in chloroform solvent, leaving porous ZnO nanostructures. This technique is benefited from facile controllability of the pore morphology and size by varying the diameter of microspheres. X-ray diffraction analysis showed a dominant peak corresponding to the hexagonal ZnO structure. Moreover, no significant structural strain was observed after the removal of spheres unlike the other synthesis methods of porous materials. The improved photoluminescence (PL) properties revealed an enhancement in the light capturing capability of the systems due to the multiple scattering of light in the pore walls. The porous sample showed a PL blue-shift compared to the flat one, indicating a reduction in crystallite size of ZnO nanostructures. To assess the photonic applications of synthesized porous ZnO substrates, a metal-semiconductor-metal photodetector was developed via the metallization of ZnO nanostructures, and their optoelectrical properties were tested under UV radiation. The results showed an improvement in photosensitivity and quantum efficiency of devices based on porous ZnO substrates which can be assigned to the larger exposed area and elevated rates of electron-hole generation in this sample.     

Seed/catalyst-free vertical growth of high-density electrodeposited zinc oxide nanostructures on a single-layer graphene

We report the seed/catalyst-free vertical growth of high-density electrodeposited ZnO nanostructures on a single-layer graphene. The absence of hexamethylenetetramine (HMTA) and heat has resulted in the formation of nanoflake-like ZnO structure. The results show that HMTA and heat are needed to promote the formation of hexagonal ZnO nanostructures. The applied current density plays important role in inducing the growth of ZnO on graphene as well as in controlling the shape, size, and density of ZnO nanostructures. High density of vertically aligned ZnO nanorods comparable to other methods was obtained. The quality of the ZnO nanostructures also depended strongly on the applied current density. The growth mechanism was proposed. According to the growth timing chart, the growth seems to involve two stages which are the formation of ZnO nucleation and the enhancement of the vertical growth of nanorods. ZnO/graphene hybrid structure provides several potential applications in electronics and optoelectronics such as photovoltaic devices, sensing devices, optical devices, and photodetectors.     

SURFACE MODIFICATION OF HYDROTHERMALLY GROWN ZnO NANOSTRUCTURES WITH PROCESS PARAMETERS

ZnO nanorods (NRs) were hydrothermally synthesized by using equimolar zinc nitrate hydrate (Zn(NO₃)₂ [sdot] 6H₂O) and hexamethylenetetramine (C₆H₁₂N₄) solutions. The shape of the nanostructures, obtained by aqueous method, was greatly influenced by the growth temperature and the molar concentrations. NRs grown at higher temperature (90°C) have rounded tips, whereas nanostructures of hexagonal flat-end shape were obtained at 75°C. Hardly any nanostructures were observed by further reducing the temperature to 60°C. In addition, solutions with higher molarity favored the appearance of nanoflowers. Scattered ZnO NRs were observed on silicon substrate, whereas aligned ZnO nanowires (NWs) 50–70 nm in diameter were obtained at 75°C by introducing sputtered ZnO film as a seed layer. High-resolution transmission electron microscopy (HRTEM) confirmed the growth of ZnO nanowires along [001] direction. A band-edge luminescence along with a broad visible spectrum was observed for the ZnO nanowires.     

Low-temperature synthesis of ZnO/CdS hierarchical nanostructure for photovoltaic application

Hierarchical nanostructures involving primary wide-band-gap nanowires and secondary narrow-band-gap branches are promising for photovoltaic application due to their excellent properties for light harvesting and fast carrier transport. In the present work, we developed a low-temperature process for facile synthesis of ZnO/CdS hierarchical nanowires, where the primary ZnO nanowires were first prepared via a hydrothermal route and then the secondary single-crystal CdS tips were grown on the ZnO nanowires by electrochemical deposition. The as-grown hierarchical ZnO/CdS nanowires are superior in charge separation as well as carrier transport, thus achieving higher open circuit voltage, short circuit current and final conversion efficiency than the common coaxial nanocables with CdS nanocrystal shell on core ZnO nanowires.     

Bottom-up self-assembly of macroporous ZnO nanostructures for photovoltaic applications

The present study utilized a template-assisted electrodeposition route for the bottom-up epitaxial growth of macroporous zinc oxide nanostructures. To this end, the ZnO seed layer was coated on the p-type silicon substrates using a radio frequency magnetron sputtering technique to form a p-n heterojunction. Then, polymer microspheres were implanted on ZnO/Si substrates to act as a template. Subsequently, ZnO nanostructures were electrodeposited through the interstitial spaces between the microspheres. After the deposition, the microspheres were removed by dissolving in chloroform solvent, forming a porous structure. The planar and cross-sectional electron microscopy analyses exhibited a uniform macroporous morphology with an average pore diameter of ∼1 μm. The pores were homogeneously distributed on the surface of the electrodeposited ZnO layer. The advantage of this technique over the top-down approaches, such as electrochemical etching, is that the porosity and size of pores can be easily adjusted by varying the concentration and diameter of microsphere templates. The optical investigations revealed enhancement in photon absorption and photoluminescence (PL) intensity due to multiple light scattering in the pore walls of the deposited ZnO nanostructures. For the templated sample, a PL blue shift was observed due to the reduction in crystallite size of ZnO nanostructures. A heterojunction thin film solar cell was designed by the metallization of ZnO/p-Si samples to study the power conversion capability of macroporous ZnO nanostructures. The photovoltaic performance of the developed devices was evaluated under a solar light simulator. The device based on the templated sample showed increased shunt resistance and reduced series resistance compared to the flat sample. The optoelectrical results indicated an efficiency improvement for the fabricated solar cells based on the macroporous ZnO sample due to its higher exposed area and increased rate of electron-hole generation.     

ZnO nanostructures decorated hollow glass microspheres as near infrared reflective pigment

Hollow glass microsphere/ZnO composite pigments were successfully prepared by a facile sol-gel method. ZnO coating layers composed of nanosheets, nanoplates, or nanoparticles were anchored at the surface of hollow glass microspheres by formation of Zn-O-Si bond. A reasonable growth mechanism for elucidating the formation of ZnO nanocoating was proposed. The results indicated that the near-infrared reflectance property of the composite pigments was strongly affected by the morphology of ZnO nanostructures. The nanoparticles structures exhibited higher near-infrared reflectance than that of nanosheets and nanoplates structures. The near-infrared solar reflectance of hollow glass microsphere/ZnO composite pigments was 95.7%, while the total solar reflectance of the composite pigment was as high as 97.2%. An approximately 11.1 °C decrease in outer surface temperature was obtained for the heat box coated with composite pigments. Therefore, hollow glass microsphere/ZnO composites are excellent near infrared reflective pigments for efficient solar reflective coatings designed for building facades and roofs.     

Growth and optical properties of hierarchical flower-like ZnO nanostructures

The integration of low dimensions nanoscale building blocks into 3D architectures has attracted great scientific attention. We have obtained the novel hierarchical flower-like ZnO nanostructures self-assembled by nanorods via a facile hydrothermal method. The as-synthesized samples were characterized with various technologies. The field emission scanning electron microscope (FESEM) images indicated that hydroxide ions play a significant role on the formation of hierarchical flower-like ZnO nanostructures. The X-ray diffraction (XRD) result proved that the nanocrystals were well crystallized hexagonal wurtzite structure. A possible growth mechanism of the nanostructures was proposed based on the effects of hydroxide ions. And the TEM imagines provided some important evidence for the proposed growth mechanism. UV–vis adsorption and photoluminescence (PL) spectra results indicated that the obtained ZnO nanostructurs have a good optical-absorption and photoluminescence property. The as-synthesized ZnO nanostructures exhibited superior photocatalytic performance, which was higher than that of commercially available ZnO.     

Structural,optical and magnetic behavior of (Pr,Fe) co-doped ZnO based dilute magnetic semiconducting nanocrystals

The development of ZnO-based dilute magnetic semiconductor nanostructures co-doped with rare-earth and transition metals has attracted substantial attention for spintronics application. In this work, Pr (1%) and Fe (1%, 3%, and 5%) co-doped ZnO nanoparticles (NPs) were synthesized via co-precipitation method, and their structural, morphological, optical, photoluminescence, and magnetic properties were investigated. The single-phase wurtzite hexagonal crystal structure of all samples was detected via X-ray diffraction. Morphological analysis revealed spherical shape of the NPs with an average size in 20–50 nm range. The ultraviolet (UV)–visible measurements showed a redshift in the UV band and a slight change in the bandgap of the co-doped NPs. Fourier transform infrared analysis proved the existence of different functional groups in all synthesized NPs. X-ray photoelectron spectroscopy confirmed that Pr and Fe ions incorporated in the host ZnO lattice exhibit Pr³⁺ and Fe³⁺ oxidation states, respectively. Photoluminescence analysis showed that incorporated ions induce characteristic emission bands and structural defects in the synthesized NPs. Magnetic characterization indicated that the ZnO NPs exhibit a diamagnetic nature. However, the (Pr, Fe) co-doped NPs exhibit ferromagnetism at room temperature because of the interactions between Pr³⁺ and Fe³⁺ ions and trapped electrons mediated by bound magnetic polarons. Excellent optical and magnetic properties of synthesized samples may render them promising candidates for spintronics applications.     

Growth of ZnO nanostructures: Cones,rods and hallow-rods,by microwave assisted wet chemical growth and their characterization

ZnO nanostructures were grown by microwave assisted wet-chemical growth, at different microwave powers and for different growth durations. The grown nanostructures were analysed for their morphological, structural, compositional and optical characteristics. The total microwave power per growth run (product of microwave power and growth duration, with units in watt-min), has a linear relationship with most of the characteristics of the grown ZnO nanostructures. It is shown that by altering the microwave power per growth run, the morphology of the individual ZnO nanostructure can be changed from cones with hexagonal cross section, to faceted hexagonal nanorods, to hollow hexagonal nanorods. It is observed that, while the fast growth rate along the high energy polar faces (0001) and (000ī) of ZnO is the reason behind the formation of one dimensional ZnO structures (cones and rods), the process of formation of hallow ZnO rods is due to further etching/material-removal from the tip of the rods, at high microwave power conditions at long growth durations.     

Preparation and photoelectrochemical properties of CdS quantum dot-sensitized ZnO nanotube arrays

CdS/ZnO nanotubes (NTs) arrays were synthesized on a transparent conductive glass (FTO) substrate by hydrothermal method, chemical bath etching and successive ionic layer adsorption and reaction (SILAR) method, which were used in semiconductor-sensitized photoelectrochemical cells (PECs). The crystal structure, morphology and photoelectrochemical conversion properties of different photoanodes were investigated by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), transmission electron microscope (TEM), high resolution transmission electron microscope (HRTEM), and electrochemical workstation. The results show a heterojunction has been formed between ZnO and CdS QDs. The ZnO NTs and CdS QDs played a remarkable controllability for PEC performances. The photoelectrochemical conversion efficiency of ZnO NTs photoanodes was 3 times that of ZnO nanorods (NRs) arrays photoanodes. After sensitization of CdS quantum dots, the photoelectrochemical conversion efficiency of CdS/ZnO NRs was improved by 7 times and the CdS/ZnO NTs was increased by 4 times. These results demonstrate that the CdS/ZnO core-shell structure can provide a facile and compatible frame for the potential applications in nanotube-based solar cells.     

Fabrication and characterization of hexagonally patterned quasi-1D ZnO nanowire arrays

Quasi-one-dimensional (quasi-1D) ZnO nanowire arrays with hexagonal pattern have been successfully synthesized via the vapor transport process without any metal catalyst. By utilizing polystyrene microsphere self-assembled monolayer, sol–gel-derived ZnO thin films were used as the periodic nucleation sites for the growth of ZnO nanowires. High-quality quasi-1D ZnO nanowires were grown from nucleation sites, and the original hexagonal periodicity is well-preserved. According to the experimental results, the vapor transport solid condensation mechanism was proposed, in which the sol–gel-derived ZnO film acting as a seed layer for nucleation. This simple method provides a favorable way to form quasi-1D ZnO nanostructures applicable to diverse fields such as two-dimensional photonic crystal, nanolaser, sensor arrays, and other optoelectronic devices.     

Growth and formation mechanism of sea urchin-like ZnO nanostructures on Si

Sea urchin-like nanostructures of ZnO consisting of ZnO nanowires with blunt faceted ends were grown on Si (100) substrates by oxidation of metallic Zn at 600 °C. ZnO nanowires having a diameter of 30–60 nm and length of 2–4 Μm were in similar shape with uniform diameter along its entire length with well faceted blunt ends. X-ray diffraction and transmission electron microscope analysis showed that the as-grown nanostructures were highly crystalline with wurtzite hexagonal structure having lattice constants of a=b=3.25 å and c=5.21 å. Room temperature photoluminescence (PL) measurements showed a weak near band-edge emission at 380 nm, but a strong green emission at 500–530 nm. A model for vapor-solid (VS) growth mechanism of ZnO nanowires was presented, in which nucleation of ZnO is crucial for the growth of the nanostructures.