Interfacial engineering of CuO nanorod/ZnO nanowire hybrid nanostructure photoanode in dye-sensitized solar cell

Developing efficient and cost-effective photoanode plays a vital role determining the photocurrent and photovoltage in dye-sensitized solar cells (DSSCs). Here, we demonstrate DSSCs that achieve relatively high power conversion efficiencies (PCEs) by using one-dimensional (1D) zinc oxide (ZnO) nanowires and copper (II) oxide (CuO) nanorods hybrid nanostructures. CuO nanorod-based thin films were prepared by hydrothermal method and used as a blocking layer on top of the ZnO nanowires’ layer. The use of 1D ZnO nanowire/CuO nanorod hybrid nanostructures led to an exceptionally high photovoltaic performance of DSSCs with a remarkably high open-circuit voltage (0.764 V), short current density (14.76 mA/cm² under AM1.5G conditions), and relatively high solar to power conversion efficiency (6.18%) . The enhancement of the solar to power conversion efficiency can be explained in terms of the lag effect of the interfacial recombination dynamics of CuO nanorod-blocking layer on ZnO nanowires. This work shows more economically feasible method to bring down the cost of the nano-hybrid cells and promises for the growth of other important materials to further enhance the solar to power conversion efficiency.     

Sputter-deposited ZnO thin films consisting of nano-networks for binder-free dye-sensitized solar cells

ZnO nano-network structures with high porosity were prepared for use in the photoelectrodes of binder-free dye-sensitized solar cells (DSSCs) by DC sputtering and subsequent thermal oxidation. Zn thin films prepared at 100 °C showed nano-network structures with high porosity, while those prepared at 25 °C did not. This was partially attributed to the high mobility of sputter-deposited particles that arrived at the surface of the substrate and partially to a supersaturation mechanism. The prepared nano-network Zn was successfully transformed to ZnO without a morphological change via subsequent annealing in air. The power conversion efficiency of DSSCs based on the ZnO nano-network structures exhibited 10 times higher efficiency than those based on ZnO film prepared at 25 °C because of its large surface area for adsorption of dye molecules. The thickness of the ZnO nano-network structures increased linearly at 10 μm h^?1 as a function of sputter time. As the film thickness increased, the power conversion efficiency of DSSCs increased from 1.09% to 1.82%.     

Dye-sensitized solar cells based on ZnO nanowire array/TiO2 nanoparticle composite photoelectrodes with controllable nanowire aspect ratio

The ZnO nanowire (NW) array/TiO₂ nanoparticle (NP) composite photoelectrode with controllable NW aspect ratio has been grown from aqueous solutions for the fabrication of dye-sensitized solar cells (DSSCs), which combines the advantages of the rapid electron transport in ZnO NW array and the high surface area of TiO₂ NPs. The results indicate that the composite photoelectrode achieves higher overall photoelectrical conversion efficiency (η) than the ZnO NW alone. As a result, DSSCs based on the ZnO NW array/TiO₂ NP composite photoelectrodes get the enhanced photoelectrical conversion efficiency, and the highest η is also achieved by rational tuning the aspect ratio of ZnO NWs. With the proper aspect ratio (ca. 6) of ZnO NW, the ZnO NW array/TiO₂ NP composite DSSC exhibits the highest conversion efficiency (5.5 %). It is elucidated by the dye adsorption amount and interfacial electron transport of DSSCs with the ZnO NW array/TiO₂ NP composite photoelectrode, which is quantitatively characterized using the UV-Vis absorption spectra and electrochemical impedance spectra. It is evident that the DSSC with the proper aspect ratio of ZnO NW displays the high dye adsorption amount and fastest interfacial electron transfer.     

Improvement in Dielectric Tunability of Ba0.6Sr0.4TiO4-Mg2TiO4 Composite Ceramics via Heterogeneous Nucleation Processing

Dielectric tunable composite ceramics Ba0.6Sr0.4 TiO4-Mg2 TiO4 （BST-MT） are prepared with a heterogeneous nucleation sol-gel approach. The Mg2 TiO4 powders are synthesized by the conventionM solid-state reaction method. The micro-sized MT powders with dispersant Ciba-4010 are introduced into Ba-Sr-Ti sol to obtain uniform and homogeneous mixture compounds with nano-sized BST particles synthesized via heterogeneous nucleation （HN） in the sol-gel process. Thus, the mierostructural and dielectric properties can be tailored. The dielectric constants of BST-MT composite ceramics can be adjusted in a larg＇e range from 294 to 1790, and the dielectric tunability can be adjusted from 29.4% to 37.0% with different MT contents from 60wt% to 20wt%. Compared to the samples prepared by the conventional solid-state （SS） process, the BST-MT composite ceramics by the heterogeneous nucleation sol-gel process exhibit a more uniform microstructure, and improve dielectric properties.     

Enhanced Efficiency of Polymer： Fullerene Bulk Heterojunction Solar Cells with the Insertion of Thin TiO2 Layer near the LiF/A1 Electrode

The insertion layer of TiO2 between polymer-fullerene blend and LiF/AI electrode is used to enhance the shortcircuit current Isc and fill factor （FF）. The solar cell based on the blend of poly[2-methoxy-5-（2＇-ethylhexyloxy）- 1,4-phenylenevinylene] （MEH-PPV） and C60 with the modifying layer of TiO2 （about 20nm） shows the open- circuit Voc of about 0.62 V, short circuit current Isc of about 2.35 mA/cm^2, filling factor FF of about 0.284, and the power conversion efficiency （PCE） of about 2.4% under monochromatic light （50Onto） photoexcitation of about 17mW/cm^2. Compared to ceils without the TiO2 layer, the power conversion efficiency increases by about 17.5%. Similar effect is also obtained in cells with the undoped MEH-PPV structure of ITO/PEDOT：PASS/MEH- PPV/（TiO2）LiF/AI. The improved solar cell performance can be attributed to enhanced carrier extraction efficiency at the active layer/electrode interfaces when TiO2 is inserted.     

Effect of aging time of ZnO sol on the structural and optical properties of ZnO thin films prepared by sol-gel method

In this work, ZnO thin films were prepared by sol-gel method and the effect of aging time of ZnO sol on the structural and optical properties of the films was studied. The structural characteristics of the samples were analyzed by an atomic force microscope and an X-ray diffractometer. The optical properties were studied by a UV-vis spectrophotometer and a fluorophotometer. The results show that the ZnO thin film prepared by the as-synthesized ZnO sol had relatively poor crystalline quality, low optical transmittance in the visible range and relatively weak ultraviolet emission performance. After the as-synthesized ZnO sol was aged for 24 h, the degree of the preferred crystal orientation along the c-axis of the ZnO thin film prepared by this aged sol was improved. At the same time, this film had a very smooth surface with uniform grains and both its visible range transmittance and ultraviolet emission intensity were obviously increased. These results suggest that appropriate aging of ZnO sol is very important for the improvement of structural and optical quality of ZnO thin films derived from sol-gel method.     

Zinc oxide nanostructures for applications as ethanol sensors and dye-sensitized solar cells

ZnO nanostructures were prepared by thermal oxidation technique for applying as ethanol sensors and dye-sensitized solar cells. To improve sensitivity of the sensor based on ZnO nanostructures, gold doping was performed in ZnO nanostructures. Gold-doped with 0%, 5%, and 10% by weight were investigated. The improvement of sensor sensitivity toward ethanol due to gold doping was observed at entire operating temperature and ethanol concentration. The sensitivity up to 145 was obtained for 10% Au-doped ZnO sensor. This can be explained by an increase of the quantity of oxygen ion due to catalytic effect of gold. Also, it was found that oxygen ion species at the surface of the Au-doped ZnO sensor remained O²⁻ as pure ZnO sensor. For dye-sensitized solar cell application, the dye-sensitized solar cell structure based on ZnO as a photoelectrode was FTO/ZnO/Eosin-Y/electrolyte/Pt counter electrode. ZnO with different morphologies of nanobelt, nano-tetrapod, and powder were investigated. It was found that DSSCs with ZnO powder showed higher photocurrent, photovoltage and overall energy conversion efficiencies than that of ZnO nanobelt and ZnO nano-tetrapod. The best results of DSSCs were the short circuit current (J_sc) of 1.25 mA/cm², the open circuit voltage (V_oc) of 0.45 V, the fill factor (FF) of 0.65 and the overall energy conversion efficiency (η) of 0.68%.     

Preparation and Visible Light Photocatalytic Activity for Photocatalyst of Permeable Glass Membrane/TiO2 Doped with Co

The photocatalyst of permeable glass membrane/TiO2 doped with Co （permeable glass membrane/TiO2 doped with Co） is prepared by the sol-gel method. The morphology and phase of the samples are determined by the field emission scanning electron microscopy （FESEM） and x-ray diffraction experiment, respectively. The photo- catalytic results show that the photocatalyst is sensitive to the visible light and exhibits excellent photocatalytic activity of photodegradation methylene blue. The photocatalytic mechanism is also discussed.     

A facile low temperature synthesis of TiO2 nanorods for high efficiency dye sensitized solar cells

Titania (TiO₂) nanorods have been synthesized with controlled size for dye-sensitized solar cells (DSSCs) via hydrothermal route at low hydrothermal temperature of 100 °C for 24 h. The titania nanorods were characterized using XRD, SEM, TEM/HRTEM, UV-vis Spectroscopy, FTIR and BET specific surface area (S _BET), as well as pore-size distribution by BJH. The results indicated that the bulk traps and the surface states within the TiO₂ nanorods films have enhanced the efficiency of DSSCs. The size of the titania nanorods was 6.7 nm in width and 22 nm in length. The high surface area can provide more sites for dye adsorption, while the fast photoelectron-transfer channel can enhance the photogenerated electron transfer to complete the circuit. The specific surface area S _BET was 77.14 m²?g^?1 at the synthesis conditions. However, the band gap energy of the obtained titania nanorods was 3.2 eV. The oriented nanorods with appropriate lengths are beneficial in improving the electron transport property and thus leading to the increase of photocurrent, together enhancing the power conversion efficiency. A nearly quantitative absorbed photon-to-electrical current conversion achieved upon excitation at wave length of 550 nm and the power efficiency was enhanced from 5.6 % for commercial TiO₂ nanoparticles Degussa (P25) cells to 7.2 % for TiO₂ nanorods cells under AM 1.5 illumination (100 mW?cm^?2). The TiO₂ cells performance was improved due to their high surface area, hierarchically mesoporous structures and fast electron-transfer rate compared with the Degussa (P25).     

Multiple nano-TiO2 layers to prevent dye/nano-TiO2 from photodegradation under a UV-exposure environment

A device of multiple nano-TiO₂ layers was proposed and fabricated to prevent a dye/nano-TiO₂ region from serious photo-degradation. In this device, the top of the dye/TiO₂ region was designed to be coated using sol-gel nano-TiO₂ thin films to shield UV irradiation from the photo-degradation effect. The sol-gel TiO₂ was prepared in a low temperature (75 °C) and verified as nano-sized particles and an anatase crystalline structure. Different devices of the multi-layer samples fabricated using different compositions of nano-TiO₂ were produced and exposed for UV irradiation tests. Results show that the presence of the sol-gel TiO₂ films coated on top of the dye/TiO₂ region can significantly alleviate the dye photo-degradation under UV irradiation. This multi-layer device can effectively improve the photo-stability of the dye/TiO₂ region in a UV-exposure environment.     

Vacuum Annealing Induced Room-Temperature Ferromagnetism in Co0.1Ti0.9O2-δ Films Prepared by Sol-Gel Method

The Co-doped TiO2 films （Co0.1Ti0.9O2-δ） are prepared on silicon substrates by sol-gel method and post annealing. TheCo0.1Ti0.9O2-δ film annealed in air is non-ferromagnetic at room temperature. After further annealed in a vacuum, the room-temperature ferromagnetism （RTFM） is observed. Experimental evidences show that the RTFM in the Co0.1Ti0.9O2-δ film may come from the Co-doped TiO2 matrix and is related to the oxygen vacancies created by vacuum annealing.     

Comparison of TiO2 and ZrO2 Films Deposited by Electron-Beam Evaporation and by Sol-Gel Process

TiO2 and ZrO2 films are deposited by electron-beam （EB） evaporation and by sol-gel process. The film properties are characterized by visible and Fourier-transform infrared spectrometry, x-ray diffraction analysis, surface roughness measure, absorption and laser-induced damage threshold （LIDT） test. It is found that the sol-gel films have lower refractive index, packing density and roughness than EB deposited films due to their amorphous structure and high OH group concentration in the film. The high LIDT of sol-gel films is mainly due to their amorphous and porous structure, and low absorption. LIDT of EB deposited film is considerably affected by defects in the film, and LIDT of sol-gel deposited film is mainly effected by residual organic impurities and solvent trapped in the film.     

40% Efficiency enhancement in solar cells using ZnO nanorods as shell prepared via novel hydrothermal synthesis

Herein, rod-like ZnO nanostructures were synthesized via a novel hydrothermal route using Zn(OAc)₂, ethylenediamine and hydrazine as a new set of starting reagents. The as-synthesized products were characterized by techniques including XRD, EDS, SEM, XPS, Pl and FTIR. The prepared ZnO nanostructures were utilized as shell on TiO₂ film in DSSCs. Effect of precursor type, morphology and thickness of ZnO shell (number of electrophoresis cycle) on solar cells efficiency were well studied. Our results showed that ethylenediamine has crucial effect on morphology of synthesized ZnO nanostructures and using ZnO nanostructures leads to an increase in DSSCs efficiency compared to bare TiO₂ from 4.66 to 7.13% (~40% improvement). Moreover, highest amount of solar cell efficiency (7.13%) was obtained by using ZnO nanorods with two cycle of electrophoresis for deposition.     

Structural and Magnetic Properties of Codoped ZnO based Diluted Magnetic Semiconductors

Zn1-xCoxO （x = 0.01, 0.02, 0.05, 0.10 and 0.20） diluted magnetic semiconductors are prepared by the sol-gel method. The structural and magnetic properties of the samples are studied using x-ray diffraction （XRD）, extended x-ray absorption fine structure （EXAFS） and superconducting quantum interference device （SQUID）. The XRD patterns does not show any signal of precipitates that are different from wurtzite type ZnO when Co content is lower than x = 0.10. An EXAFS technique for the Co K-edge has been employed to probe the local structures around Co atoms doped in ZnO powders by fluorescence mode. The simulation results for the first shell EXAFS signals indicate that Zn sites can be substituted by Co atoms when Co content is lower than x = 0.05. The SQUID results show that the samples （x 〈 0.05） exhibit clear hysteresis loops at 300K, and magnetization versus temperature from 5 K to 350K at H = 100 Oe for the sample x = 0.02 shows that the samples have ferromagnetism above room temperature. A double-exchange mechanism is proposed to explain the ferromagnetic properties of the samples.     

Study on the properties and charge generation in dye-sensitized n-TiO2|dye|p-CuI solid state photovoltaic solar cells

Transparent semiconducting copper iodide (CuI) films were prepared by XeCl Excimer laser and their characteristics are investigated. These films exhibited optical transmittance over 80% in the wavelength range from 400 to 900 nm and minimum resistivity of about 2 kΩ cm⁻¹. The optical absorption of the these films shows a remarkable blue shift compared to that of polycrystalline of CuI, which can be explained from the viewpoint formation of ultra fine of CuI grains. The titanium dioxide (TiO₂) films have been prepared by sol-gel method. The properties of pulsed laser deposited CuI and TiO₂ films in power output of n-TiO₂|dye|p-CuI cells is studied. An efficient charge generation is observed through the illumination of TiO₂ layer of the fabricated n-TiO₂|dye|p-CuI solid state photovoltaic solar cells. From the current-voltage characteristics, the fill factor and power conversion efficiency were about of 45 and 3%, respectively. The maximum photo-current of about 12.5 mA/cm² and photo-voltage of 475 mV under AM 1.5 conditions were obtained for the n-TiO₂|dye|p-CuI solid states photovoltaic solar cells with good reproducibility. Adsorbed dye molecules to the TiO₂ surface act as a relay, especially under illumination through TiO₂ layer in the wave range region of 300-400 nm.     

Structural and Magnetic Properties of Fe-Doped Anatase TiO2 Films Annealed in Vacuum

Structural and magnetic properties of Fe-doped anatase TiO2 films fabricated by sol-gel spin coating are investigated. X-ray diffraction measurements reveal that Fe^3＋ ions are incorporated into the TiO2 lattice. No ferromagnetism-related secondary phases and magnetic nanopaxticles are observed in the films. The presence of electron paramagnetic resonance signals at 9- 2.0 supports oxygen vacancies and/or defects generated in the films after annealing in vacuum. Magnetic measurements indicate that Fe-doped anatase TiO2 films are ferromagnetic at room temperature. These observations suggest that oxygen vacancies and/or defects axe energetically favorable for the long range Fe^3＋-Fe^3＋ ferromagnetic coupling in Fe-doped anatase TiO2 films.     

One-pot,large-scale synthesis silica-encapsulated NIR alloy quantum dots CdSeTe within short time

Hydrothermal process has been employed to synthesize titanium oxide (TiO₂) bottle brush. The nanostructured bottle brushes with tetragonal nanorods of ~75 nm diameter have been synthesized by changing the nature of the precursors and hydrothermal processing parameters. The morphological features and structural properties of TiO₂ films were investigated by field emission scanning electron microscopy, X-ray diffraction, high-resolution transmission electron spectroscopy, Fourier transform Raman spectroscopy, and X-ray photoelectron spectroscopy. The influence of such nanostructures on the performance of dye-sensitized solar cells (DSSCs) is investigated in detail. The interface and transient properties of these nanorods and bottle brush-based photoanodes in DSSCs were analyzed by electrochemical impedance spectroscopic measurements in order to understand the critical factors contributing to such high power conversion efficiency. Surface area of sample was recorded using Brunauer–Emmett–Teller measurements. It is found that bottle brush provides effective large surface area 89.34 m² g^?1 which is much higher than TiO₂ nanorods 63.7 m² g^?1. Such effective surface area can facilitate the effective light harvesting, and hence improves the dye adsorption and the photovoltaic performance of DSSCs, typically in short-circuit photocurrent and power conversion efficiency. A best power conversion efficiency of 6.63 % has been achieved. We believe that the present device performance would have wide interests in dye-sensitized solar cell research.     

Effect of Annealing Temperature on Structural and Optical Properties of N-Doped ZnO Films

Nitrogen-doped ZnO （ZnO：N） films are prepared by thermal oxidation of sputtered Zn3N2 layers on A1203 substrates. The correlation between the structural and optical properties of ZnO：N films and annealing temperatures is investigated. X-ray diffraction result demonstrates that the as-sputtered Zn3N2 films are transformed into ZnO：N films after annealing above 600℃. X-ray photoelectron spectroscopy reveals that nitrogen has two chemical states in the ZnO：N films： the No acceptor and the double donor （N2）o. Due to the No acceptor, the hole concentration in the film annealed at 700℃ is predicted to be highest, which is also confirmed by Hall effect measurement. In addition, the temperature dependent photoluminescence spectra allow to calculate the nitrogen acceptor binding energy.     

Influence of annealing temperature on the photoluminescence property of ZnO thin film covered by TiO2 nanoparticles

In this work, ZnO thin films covered by TiO₂ nanoparticles (labeled as TiO₂-ZnO thin films) were prepared by electron beam evaporation. The influence of annealing temperature on the photoluminescence property of the samples was studied. The structures and surface morphologies of the samples were analyzed by X-ray diffraction (XRD) and atomic force microscope, respectively. The photoluminescence was used to investigate the fluorescent properties of the samples. The measurement results show that the ultraviolet emission of ZnO thin films is largely enhanced after they are covered by TiO₂ nanoparticles, while the green emission is suppressed. However, when the annealing temperature is relatively high (≥500 °C), the intensity of ultraviolet emission drops off and a violet emission peak along with a blue emission peak appears. This is probably connected with the atomic interdiffusion between TiO₂ nanoparticles and ZnO thin film. Therefore, selecting a suitable annealing temperature is a key factor for obtaining the most efficient ultraviolet emission from TiO₂-ZnO thin films.     

Temperature Dependence of the Fluorescence Emission Intensity of Eu/TiO2 Nanocrystals

The samples of europium ions doped titanium dioxide （Eu^3＋/TiO2） nanocrystals are synthesized by a modified sol-gel method with hydrothermal treatment. The x-ray diffraction and scanning electron microscopy are used to characterize the sample. The temperature-dependent fluorescence emission effect of Eu^3＋-doped samples is investigated. It is found that under the excitation of 514.5nm light, the emission intensity of Eu^3＋ reaches a maximum value at 450K among various Eu^3＋ dopant concentrations in Eu^3＋ /TiO2 nanocrystals. The variation of the emission intensity may be attributed to the photon-assist absorption and the temperature-quenching effect.