Dye-sensitized solar cells based on ZnO nanoflowers and TiO2 nanoparticles composite photoanodes

ZnO nanoflowers were synthesized by low temperature solution-phase method. ZnO nanoflowers/TiO₂ nanoparticles composite photoanodes with various mass ratios were prepared on transparent conductive fluorine-doped tin oxide substrates by doctor-blade technique. The dye-sensitized solar cells (DSSCs) were assembled. The morphology characteristics of ZnO nanoflowers and ZnO/TiO₂ composite photoanodes have been analyzed by scanning electron microscopy. The effect of the ZnO nanoflowers/TiO₂ nanoparticles mass ratio on the performance of DSSCs was systematically investigated by I–V characteristics and electrochemical impedance spectroscopy. Results show that the conversion efficiency of the dye-sensitized solar cell with a ZnO/TiO₂ mass ratio of 25:75 was increased by about 35 % compared to that of pure TiO₂-based solar cell. Addition of ZnO nanoflowers can enhance the light harvesting and improve electron transport.     

Growth of ZnO nanorods on TiO2 nanoparticles films and their application to the electrode of dye-sensitized solar cells

A ZnO nanorods (NRs)/TiO₂ nanoparticles (NPs) film has been prepared by electrochemical deposition of ZnO NRs growth on P25 TiO₂ NPs film surfaces. It was found that ZnO NRs/TiO₂ NPs could significantly improve the efficiency of dye-sensitized solar cells owing to its relatively enhanced light-scattering capability and efficient charge transport efficiency. The overall energy-conversion efficiency (η) of 3.48 % was achieved by the formation of ZnO NRs/TiO₂ NPs film, which is 33 % higher than that formed by TiO₂ NPs alone (η = 2.62 %). The charge recombination behavior of cells was investigated by electrochemical impedance spectra, and the results showed that ZnO NRs/TiO₂ NPs film has the longer electron lifetime than TiO₂ NPs alone, which could facilitate the reduction of recombination processes and thus would promote the photocatalysis and solar cell performance.     

Hydrothermal synthesis, characterization and properties of TiO2 nanorods on boron-doped diamond film

The rutile TiO₂ nanorods have been hydrothermally synthesized on boron-doped diamond (BDD) film with a ZnO buffer layer. It is demonstrated that the ZnO buffer layer plays a key role in increasing the density and improving the morphology of synthesized TiO₂ nanorods. The heterojunction of n-TiO₂ nanorods/p-BDD shows an evident rectifying behavior with a ratio of ∼ 180 at 6 V. Experimentally, the TiO₂ nanorod-covered BDD exhibits an improved electron field-emission property over that without using a ZnO buffer layer.     

White-light-controlled resistive switching and photovoltaic effects in TiO2/ZnO composite nanorods array at room temperature

White-light-controlled resistance switching and photovoltaic effects in TiO₂/ZnO composite nanorods array grown on fluorine-doped tin oxide (FTO) substrate by hydrothermal process were investigated. The average length of TiO₂/ZnO nanorods is about 3 μm, and the average diameter is about 200 nm. ZnO nanoparticles with size 5–10 nm are embedded in TiO₂ base material. The current–voltage characteristics of Ag/[TiO₂/ZnO]/FTO device demonstrate an outstanding rectifying property and bipolar resistive switching behavior. Specially, the resistive switching behavior can be regulated by white-light illuminating. In addition, this structure also exhibits a substantial white-light photovoltaic effect. This study is helpful for exploring the multifunctional materials and their applications in nonvolatile multistate memory devices and solar cells.     

CdS-sensitized ZnO nanorod arrays coated with TiO2 layer for visible light photoelectrocatalysis

A novel ZnO/CdS/TiO₂ nanorod array composite structure was fabricated by depositing CdS-sensitized layer onto ZnO nanorod arrays via chemical bathing deposition and subsequently coated by TiO₂ protection layer via a vacuum dip-coating process. The films were characterized by x-ray diffraction, field emission scanning electron microscopy, energy dispersive spectrum, and UV–Vis diffuse reflectance spectroscopy. For the films severed as the photoanodes, linear sweep voltammetry and transient photocurrent (i _ph) were investigated in a three-electrode system. The photoelectrocatalytic activity was evaluated by the degradation of methylene blue (MB) under visible light irradiation. The results show that the oriented ZnO nanorods are adhered by relatively uniform CdS-sensitized layer and coated with TiO₂ layer. Both the coated and uncoated CdS-sensitized ZnO nanorod arrays exhibit the visible light response and the photoelectrocatalytic activity on the degradation of MB under visible light irradiation. The ZnO/CdS/TiO₂ nanorod array film possesses stable and superior photoelectrocatalytic performance owing to the TiO₂ thin layer protecting the CdS from photocorrosion.     

Synthesis and enhanced light absorption of alumina matrix nanocomposites containing multilayer oxide nanorods and silver nanoparticles

In this paper, multilayer oxide nanorods were deposited in the nanopores of anodic aluminum oxide (AAO) via solution infiltration followed by heat treatment. The nanorods have a core–shell structure. First, the shell (nanotube) with the thickness of about 40 nm was made of TiO₂ through the hydrolysis of (NH₄)₂TiF₆. Second, silver nanoparticles with the diameter of about 3 nm were added into the TiO₂ layer through thermal decomposition of AgNO₃ at elevated temperatures. Then, cylindrical cores (nanorods) of CoO and ZnO with 200 nm diameter were prepared, respectively. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) were used to characterize the structure and composition of the nanorods. UV–vis light absorption measurements in the wavelength range from 350 to 1000 nm were performed to study the effect of nanorod and nanoparticle addition on the light absorption property of the alumina nanocomposites. It is found that CoO nanorods increase the light absorption of the alumina matrix composite in the wavelength range from 500 nm to 800 nm, but the TiO₂ shell does not increase the light absorption much. The ZnO nanorods do not change the light absorption either. However, the addition of silver nanoparticles significantly enhances light absorption of both AAO/TiO₂/Ag/CoO and AAO/TiO₂/Ag/ZnO nanocomposites. This increase in the visible light absorption reveals that there exists surface plasmon around the fine silver nanoparticles in the nanorods.     

Microstructural,chemical and textural characterization of ZnO nanorods synthesized by aerosol assisted chemical vapor deposition

ZnO nanorods were synthesized by aerosol assisted chemical vapor deposition onto TiO₂ covered borosilicate glass substrates. Deposition parameters were optimized and kept constant. Solely the effect of different nozzle velocities on the growth of ZnO nanorods was evaluated in order to develop a dense and uniform structure. The crystalline structure was characterized by conventional X-ray diffraction in grazing incidence and Bragg–Brentano configurations. In addition, two-dimensional grazing incidence synchrotron radiation diffraction was employed to determine the preferred growth direction of the nanorods. Morphology and growth characteristics analyzed by electron microscopy were correlated with diffraction outcomes. Chemical composition was established by X-ray photoelectron spectroscopy. X-ray diffraction results and X-ray photoelectron spectroscopy showed the presence of wurtzite ZnO and anatase TiO₂ phases. Morphological changes noticed when the deposition velocity was lowered to the minimum, indicated the formation of relatively vertically oriented nanorods evenly distributed onto the TiO₂ buffer film. By coupling two-dimensional X-ray diffraction and computational modeling with ANAELU it was proved that a successful texture determination was achieved and confirmed by scanning electron microscopy analysis. Texture analysis led to the conclusion of a preferred growth direction in [001] having a distribution width Ω = 20° ± 2°.     

Optical and structural properties of ZnO/TiO2/ZnO multi-layers prepared via electron beam evaporation

We prepared a ZnO/TiO₂/ZnO multi-layer on quartz glass substrate via electron beam evaporation. Optical and structural properties of the ZnO/TiO₂/ZnO multi-layer were investigated. The TiO₂ buffer layer is found to improve the crystallinity of the ZnO thin film. A green emission of the ZnO thin film deposited on the TiO₂ buffer layer was significantly enhanced due to the increased defect concentration of oxygen vacancy. Photoluminesence spectra measured at 9 K revealed that a violet luminescence at 409 nm was attributed to the draft of the donor's defect levels in the ZnO thin film.     

Enhanced performance of Al2O3 coated ZnO nanorods in CdS/CdSe quantum dot-sensitized solar cell

CdS/CdSe quantum dot-sensitized solar cells (QDSCs) based on ZnO nanorods, 4.55 μm in length, were studied. Many studies have shown that the performance of QDSCs is limited by a recombination process. Therefore, the interface layer was fabricated on the surface of the ZnO nanorods to retard recombination at the interface between the semiconductor and electrolyte. Overall, the performance of the QDSCs was improved by a surface coating of aluminum isopropoxide (Al₂O₃) on the ZnO nanorod, which facilitates a decrease in electron recombination and increased adsorption of CdS/CdSe QDs on the ZnO nanorods.     

Optical properties of ZnO-based core-shell nanostructures

ZnO nanorods were prepared by electrodeposition, and the effect of different shells (MgO and TiO_x) on their optical properties has been studied. Shells have also been prepared using a simple solution based method. The two types of shells exhibited different effects on the optical properties of ZnO nanorods, mainly due to different annealing temperature required for synthesis process. The improvement in the emission intensity from the samples under optical excitation did not result in changes in the emission spectra or increase in emission intensity under electrical excitation for the same bias voltage. However, improved luminance for the same bias current was observed for most core-shell structures.     

Facile synthesis of highly branched jacks-like ZnO nanorods and their applications in dye-sensitized solar cells

Highly branched, jacks-like ZnO nanorods architecture were explored as a photoanode in dye-sensitized solar cells, and their photovoltaic performance was compared with that of branch-free ZnO nanorods photoanodes. The highly branched network and large pores of the jacks-like ZnO nanorods electrodes enhances the charge transport, and electrolyte penetration. Thus, the jacks-like ZnO nanorods DSSCs render a higher conversion efficiency of η = 1.82% (V_oc = 0.59 V, J_sc = 5.52 mA cm⁻²) than that of the branch-free ZnO nanorods electrodes (η = 1.08%, V_oc = 0.49 V, J_sc = 4.02 mA cm⁻²). The incident photon-to-current conversion efficiency measurements reveal that the jacks-like ZnO nanorods DSSCs exhibit higher internal quantum efficiency (∼59.1%) than do the branch-free ZnO nanorods DSSC (∼52.5%). The charge transfer resistances at the ZnO/dye/electrolyte interfaces investigated using electrochemical impedance spectroscopy showed that the jacks-like ZnO nanorods DSSC had high charge transfer resistance and a slightly longer electron lifetime, thus improving the solar-cell performance.     

Fabrication of TiO<Subscript>2</Subscript>/ZnO composite nanofibers with enhanced photocatalytic activity

TiO₂/ZnO composite nanofibers have been successfully prepared by electrospinning technique. X-ray diffraction, scanning electron microscopy, energy-dispersive X-ray spectroscopy, transmission electron microscopy, Raman spectrum, X-ray photoelectron spectroscopy and UV–Vis diffuse reflectance spectroscopy, were used to characterize the as-synthesized nanofibers. The photocatalytic studies revealed that the TiO₂/ZnO nanofibers exhibited enhanced photocatalytic efficiency of photodegradation. Additionally, the recycling experiment of TiO₂/ZnO nanofibers had been done, demonstrating that TiO₂/ZnO nanofibers have high efficiency and stability.     

Deposition and characterization of a novel integrated ZnO nanorods/thin film structure

One-dimensional (1-D) ZnO (zinc oxide) nanostructures have received a lot of attention due to their superior properties. Various techniques have been developed to synthesize ZnO nanorods at high-temperature process using vapor–liquid–solid (VLS) mechanism. In this paper, we report a novel process to synthesize integrated ZnO nanorods/thin film structures using an RF magnetron sputter deposition under different deposition parameters and substrate conditions. The substrate used was glass plated with electroless Cu prepared using various conditions. The resulting specimens are analyzed using scanning electron microscopy (SEM), transmission electron microscopy (TEM), and X-ray diffraction (XRD). The effect of the copper surface roughness was found to be significant. ZnO nanorods were found only when the copper layer is rough enough. The roughness of the copper in general increases with the plating time and/or the ratio of V_HCHO/V_Cu used in the plating bath. Post-plating annealing of the copper was also found to increase the surface roughness of the copper.     

Performance of polymer/ZnO hybrid photovoltaic devices determined by reaction time for oriented ZnO nanorod growth

The performance of hybrid polymer/metal oxide photovoltaic devices based on poly(2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene) and oriented ZnO nanorods is studied. The ZnO nanorods on indium tin oxide-coated glass were prepared by hydrothermal method, where the length and the defect concentration of ZnO nanorods were controlled by the reaction time (T_r) for nanorod growth. Increasing T_r results in longer ZnO nanorods and higher defect concentration. Results show that both photocurrent and electron lifetime have strong dependence on the nanorod length (i.e., growth time) due to the exponential attenuation of incident light intensity in the device, offering a peak conversion efficiency of 0.337% under 1.5 AM illumination for T_r = 120 min. Combinational analyses of the data in this experiment and the previous data for the electrodeposited ZnO nanorods provide the insights into the dependence of the device performance on the intrinsic property of the ZnO nanorods.     

Synthesis of cluster like TiO<Subscript>2</Subscript> mesoporous spheres and nanorods and their applications in dye-sensitized solar cells

Cluster like mesoporous TiO₂ spheres, nanorods and nanoparticles were synthesized by simple wet chemical method. The TiO₂ mesoporous spheres, nanorods and nanoparticles were characterized by powder X-ray diffraction, Raman spectroscopy, ultraviolet visible spectroscopy, Fourier transform infrared spectroscopy, field emission scanning electron microscopy and transmission electron microscopy. Accordingly, a possible growth mechanism of mesoporous spheres, nanorods and nanoparticles were discussed. The changes of the dye-sensitized solar cell (DSSC) performance with the variation of the nanostructures of TiO₂ which were used in photoanodes have been investigated. The TiO₂ mesoporous sphere based DSSC with the film thickness of 20 μm was assembled and a conversion efficiency of 6.69% was obtained.     

Perovskite Solar Cells with ZnO Electron‐Transporting Materials

Perovskite solar cells (PSCs) have developed rapidly over the past few years, and the power conversion efficiency of PSCs has exceeded 20%. Such high performance can be attributed to the unique properties of perovskite materials, such as high absorption over the visible range and long diffusion length. Due to the different diffusion lengths of holes and electrons, electron transporting materials (ETMs) used in PSCs play a critical role in PSCs performance. As an alternative to TiO₂ ETM, ZnO materials have similar physical properties to TiO₂ but with much higher electron mobility. In addition, there are many simple and facile methods to fabricate ZnO nanomaterials with low cost and energy consumption. This review focuses on recent developments in the use of ZnO ETM for PSCs. The fabrication methods of ZnO materials are briefly introduced. The influence of different ZnO ETMs on performance of PSCs is then reviewed. The limitations of ZnO ETM‐based PSCs and some solutions to these challenges are also discussed. The review provides a systematic and comprehensive understanding of the influence of different ZnO ETMs on PSCs performance and potentially motivates further development of PSCs by extending the knowledge of ZnO‐based PSCs to TiO₂‐based PSCs.     

A simple one-step solvothermal synthesis of hierarchically structured ZnO hollow spheres for enhanced selective ethanol sensing properties

A simple one-step solvothermal method, using ethanolamine as solvent without any additives except zinc source, has been employed to synthesize hierarchically structured ZnO hollow spheres consisting of numerous orderly and radical nanorods with diameter of several tens nanometers and length of 2–3 μm. The ethanolamine and the solvothermal process play the critical role in the synthesis of the ZnO hollow spheres by the primary formation of ZnO crystal nucleus and subsequent transformation into nanorods, which self-assemble into hollow spheres. The morphology and structure of the spheres have been characterized by transmission electron microscopy, field emission scanning electron microscopy, X-ray powder diffraction, high-resolution transmission electron microscopy, and Brunauer–Emmett–Teller N₂ adsorption–desorption analyses. The results also indicate that the sensor based on the prepared ZnO hollow spheres exhibit good ethanol sensing performance, which can be attributed to its structural defects and high surface-to-volume ratio that significantly facilitate the absorption of oxygen species and diffusion of target gas. Besides, the sensor shows high selectivity to ethanol because ZnO as a basic oxide is favored for dehydrogenation of ethanol.     

Comparative study of multilayered ZnO/TiO<Subscript>2</Subscript>/ZnO and TiO<Subscript>2</Subscript>/ZnO/TiO<Subscript>2</Subscript> thin films prepared by sol–gel dip coating method

The aim of this research work is to represent the comparative study of ZnO/TiO₂/ZnO (ZTZ) and TiO₂/ZnO/TiO₂ (TZT) thin films deposited by sol–gel dip coating on FTO substrates. After deposition, the films were annealed at 500 °C for 1 h. Structural, surface morphology, optical and electrical properties of these films were studied by X-ray diffractrometer (XRD), Raman spectra, atomic force microscope (AFM), photoluminescence spectra (PL) and four point probe technique respectively. XRD and Raman spectra confirmed the anatase, brookite phases of TiO₂ and cubic phase of ZnO. AFM confirmed the formation of nano particles with average sizes of 18.4 and 47.2 nm of TZT and ZTZ films respectively. According to PL spectra, both the multilayer films slowdown the electron hole recombination rate and enhances the optoelectronic properties of the materials. Also it showed the peaks in the visible region of spectrum. The four point probe results showed that the average sheet resistivity of the films is 450 and 120 (ohm-m) respectively.     

Heterostructured TiO2 Nanorod@Nanobowl Arrays for Efficient Photoelectrochemical Water Splitting

Heterostructured TiO₂ nanorod@nanobowl (NR@NB) arrays consisting of rutile TiO₂ nanorods grown on the inner surface of arrayed anatase TiO₂ nanobowls are designed and fabricated as a new type of photoanodes for photoelectrochemical (PEC) water splitting. The unique heterostructures with a hierarchical architecture are readily fabricated by interfacial nanosphere lithography followed by hydrothermal growth. Owing to the two‐dimensionally arrayed structure of anatase nanobowls and the nearly radial alignment of rutile nanorods, the TiO₂ NR@NB arrays provide multiple scattering centers and hence exhibit an enhanced light harvesting ability. Meanwhile, the large surface area of the NR@NB arrays enhances the contact with the electrolyte while the nanorods offer direct pathways for fast electron transfer. Moreover, the rutile/anatase phase junction in the NR@NB heterostructure improves charge separation because of the facilitated electron transfer. Accordingly, the PEC measurements of the TiO₂ NR@NB arrays on the fluoride‐doped tin oxide (FTO) substrate show significantly enhanced photocatalytic properties for water splitting. Under AM1.5G solar light irradiation, the unmodified TiO₂ NR@NB array photoelectrode yields a photocurrent density of 1.24 mA cm^–2 at 1.23 V with respect to the reversible hydrogen electrode, which is almost two times higher than that of the TiO₂ nanorods grown directly on the FTO substrate.     

Three-dimensional (3D) sea-urchin-like hierarchical TiO2 microspheres: growth mechanism and highly enhanced photocatalytic activity

Three-dimensional (3D) sea-urchin-like hierarchical TiO₂ microspheres were synthesized by a template-free hydrothermal method. The effects of preparation parameters on the microstructure of 3D sea-urchin-like hierarchical TiO₂ were investigated using scanning electron microscopy (SEM), transmission electron microscopy, X-ray diffractometer, energy-dispersive X-ray spectrometer and Brunauer–Emmett–Teller technologies. The growth mechanism and photocatalytic activity of 3D sea-urchin-like TiO₂ microspheres were discussed. The results of electron microscopy characterizations SEM showed that the microspheres were consisted of numerous one-dimensional (1D) nanorods. A three-step growth model: oxygenated to be 1D nanorods, self-assembly and protonation, was proposed to illustrate the growth mechanism of sea-urchin-like structures. The synthesized 3D sea-urchin-like hierarchical TiO₂ microspheres exhibited a better photocatalytic activity for photodegradation of rhodamine B under sunlight irradiation compared to that of P25, which was attributed to the special 3D hierarchical nanostructure, the increased number of surface active sites and anatase crystal structure.