A maskless synthesis of TiO2-nanofiber-based hierarchical structures for solid-state dye-sensitized solar cells with improved performance

TiO₂ hierarchical nanostructures with secondary growth have been successfully synthesized on electrospun nanofibers via surfactant-free hydrothermal route. The effect of hydrothermal reaction time on the secondary nanostructures has been studied. The synthesized nanostructures comprise electrospun nanofibers which are polycrystalline with anatase phase and have single crystalline, rutile TiO₂ nanorod-like structures growing on them. These secondary nanostructures have a preferential growth direction [110]. UV–vis spectroscopy measurements point to better dye loading capability and incident photon to current conversion efficiency spectra show enhanced light harvesting of the synthesized hierarchical structures. Concomitantly, the dye molecules act as spacers between the conduction band electrons of TiO₂ and holes in the hole transporting medium, i.e., spiro-OMeTAD and thus enhance open circuit voltage. The charge transport and recombination effects are characterized by electrochemical impedance spectroscopy measurements. As a result of improved light harvesting, dye loading, and reduced recombination losses, the hierarchical nanofibers yield 2.14% electrochemical conversion efficiency which is 50% higher than the efficiency obtained by plain nanofibers.     

Improved dye-sensitized solar cell with a ZnO nanotree photoanode by hydrothermal method

This study investigated the influence of ZnO nanostructures on dye adsorption to increase the photovoltaic conversion efficiency of solar cells. ZnO nanostructures were grown in both tree-like and nanorod (NR) arrays on an AZO/FTO film structure by using a hydrothermal method. The results were observed in detail using X-ray diffraction, field-emission scanning electron microscopy (FE-SEM), UV-visible spectrophotometry, electrochemical impedance spectroscopy, and solar simulation. The selective growth of tree-like ZnO was found to exhibit higher dye adsorption loading and conversion efficiency than ZnO NRs. The multiple ‘branches’ of ‘tree-like nanostructures’ increases the surface area for higher light harvesting and dye loading while reducing charge recombination. These improvements result in a 15% enhancement in power conversion. The objective of this study is to facilitate the development of a ZnO-based dye-sensitized solar cell.     

The influence of anatase-rutile mixed phase and ZnO blocking layer on dye-sensitized solar cells based on TiO2nanofiberphotoanodes

High performance is expected in dye-sensitized solar cells (DSSCs) that utilize one-dimensional (1-D) TiO₂ nanostructures owing to the effective electron transport. However, due to the low dye adsorption, mainly because of their smooth surfaces, 1-D TiO₂ DSSCs show relatively lower efficiencies than nanoparticle-based ones. Herein, we demonstrate a very simple approach using thick TiO₂ electrospun nanofiber films as photoanodes to obtain high conversion efficiency. To improve the performance of the DSCCs, anatase-rutile mixed-phase TiO₂ nanofibers are achieved by increasing sintering temperature above 500°C, and very thin ZnO films are deposited by atomic layer deposition (ALD) method as blocking layers. With approximately 40-μm-thick mixed-phase (approximately 15.6?wt.% rutile) TiO₂ nanofiber as photoanode and 15-nm-thick compact ZnO film as a blocking layer in DSSC, the photoelectric conversion efficiency and short-circuit current are measured as 8.01% and 17.3?mA?cm^?2, respectively. Intensity-modulated photocurrent spectroscopy and intensity-modulated photovoltage spectroscopy measurements reveal that extremely large electron diffusion length is the key point to support the usage of thick TiO₂ nanofibers as photoanodes with very thin ZnO blocking layers to obtain high photocurrents and high conversion efficiencies.     

Enhancement of the photoelectric performance of dye-sensitized solar cells using Ag-doped TiO<Subscript>2</Subscript> nanofibers in a TiO<Subscript>2</Subscript> film as electrode

For high solar conversion efficiency of dye-sensitized solar cells [DSSCs], TiO₂ nanofiber [TN] and Ag-doped TiO₂ nanofiber [ATN] have been extended to be included in TiO₂ films to increase the amount of dye loading for a higher short-circuit current. The ATN was used on affected DSSCs to increase the open circuit voltage. This process had enhanced the exit in dye molecules which were rapidly split into electrons, and the DSSCs with ATN stop the recombination of the electronic process. The conversion efficiency of TiO₂ photoelectrode-based DSSCs was 4.74%; it was increased to 6.13% after adding 5 wt.% ATN into TiO₂ films. The electron lifetime of DSSCs with ATN increased from 0.29 to 0.34 s and that electron recombination was reduced.     

Effect of TiO2 rutile nanorods on the photoelectrodes of dye-sensitized solar cells

In order to enhance the electron transport on the photoelectrodes of dye-sensitized solar cells, one-dimensional rutile nanorods were prepared using electrospun TiO₂ nanofibers. The grain size of the nanorods increased with increasing temperature. Electrochemical impedance spectroscopy measurements revealed reduced interface resistance of the cells with the one-dimensional rutile nanorods due to the improved electron transport and the enhanced electrolyte penetration. Intensity-modulated photocurrent/photovoltage spectroscopy showed that the one-dimensional rutile nanorods provided the electrons with a moving pathway and suppressed the recombination of photogenerated electrons. However, an excessive quantity of rutile nanorods created an obstacle to the electrons moving in the TiO₂ thin film. The photoelectrode with 7 wt.% rutile nanorods optimized the performance of the dye-sensitized solar cells.     

Anatase TiO2 spheres with high surface area and mesoporous structure via a hydrothermal process for dye-sensitized solar cells

Spherical pure anatase TiO₂ spheres with a mesoporous structure and high surface area of up to 116.5 m² g⁻¹ were prepared by a simple urea-assisted hydrothermal process and investigated as dye-sensitized solar-cell electrodes. Although the particle diameters of the prepared TiO₂ spheres ranged from 0.4 to 1.3 μm, due to the high specific surface area, mesoporous TiO₂ sphere electrode was obtained with enhanced light harvesting and a larger amount of dye loading. An overall light conversion efficiency of 7.54% under illumination of simulated AM 1.5G solar light (100 mW cm⁻²) was achieved using the mesoporous TiO₂ spheres electrode, which was significantly higher than a commercial Degussa P25 TiO₂ nanocrystals electrode (5.69%).     

Enhanced electron collection efficiency of nanostructured dye‐sensitized solar cells by incorporating TiO2 cubes

Herein, enhancement of dye‐sensitized solar cell (DSC) performance is reported by combining the merits of the dye loading of TiO₂ nanoparticles and light scattering, straight carrier transport path, and efficient electron collection efficiency of TiO₂ cubes. We fabricate DSC devices with various arrangement styles and compositions of the electrodes in the forms of monolayer and double layer films. For this purpose, the solvothermal synthesized TiO₂ cubic particles (100‐600 nm) are employed as the scattering layer, whereas TiO₂ nanoparticles (15‐30 nm) synthesized via a combination of solvothermal and sol‐gel routes are used as the active layer of devices. We improve the photovoltaic characteristics of DSCs by two mechanisms. First, the light harvesting of DSC devices made of nanoparticles is improved by controlling the thickness of monolayer films, reaching the highest efficiency of 7.0%. Second, the light scattering and electron collection efficiency are enhanced by controlling the composition of double layer films composed of mixtures of TiO₂ nanoparticles and cubes, obtaining the maximum efficiency of 8.21%. The enhancements are attributed to balance between charge transfer resistance and charge recombination of photo‐generated electrons as well as dye loading and light scattering.     

Effect of TiO2 nanotubes with TiCl4 treatment on the photoelectrode of dye-sensitized solar cells

In this study, we used the electrochemical anodization to prepare TiO₂ nanotube arrays and applied them on the photoelectrode of dye-sensitized solar cells. In the field emission scanning electron microscopy analysis, the lengths of TiO₂ nanotube arrays prepared by electrochemical anodization can be obtained with approximately 10 to 30 μm. After titanium tetrachloride (TiCl₄) treatment, the walls of TiO₂ nanotubes were coated with TiO₂ nanoparticles. XRD patterns showed that the oxygen-annealed TiO₂ nanotubes have a better anatase phase. The conversion efficiency with different lengths of TiO₂ nanotube photoelectrodes is 3.21%, 4.35%, and 4.34% with 10, 20, and 30 μm, respectively. After TiCl₄ treatment, the efficiency of TiO₂ nanotube photoelectrode for dye-sensitized solar cell can be improved up to 6.58%. In the analysis of electrochemical impedance spectroscopy, the value of R_k (charge transfer resistance related to recombination of electrons) decreases from 26.1 to 17.4 Ω when TiO₂ nanotubes were treated with TiCl₄. These results indicate that TiO₂ nanotubes treated with TiCl₄ can increase the surface area of TiO₂ nanotubes, resulting in the increase of dye adsorption and have great help for the increase of the conversion efficiency of DSSCs.     

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.     

Ultrasonic assisted synthesis of TiO2–reduced graphene oxide nanocomposites with superior photovoltaic and photocatalytic activities

In this work, TiO₂–reduced graphene oxide (RGO) nanocomposites were successfully produced by an ultrasonication-assisted reduction process. The reduction of graphene oxide (GO) and the formation TiO₂ crystals occurred simultaneously. The synthesized nanocomposite was characterized by SEM, EDX, Raman spectroscopy, FTIR, XRD, XPS, UV–vis spectroscopy, photoluminescence spectrometer and electrochemical impedance spectroscopy. As a result of the introduction of RGO, the light absorption of octahedral TiO₂ was markedly improved. The photocatalytic results revealed that weight percent of RGO has substantial influence on degradation of Rhodamine B under visible light irradiation. The enhancement of the photocatalytic activity can be attributed to the enhancement of the visible-light irradiation harvesting and efficiently separation of the photogenerated charge carriers. Meanwhile, upon the RGO loading, the photoelectric conversion efficiency of TiO₂–RGO nanocomposite modified electrode was also highly improved.     

The effect of dye-sensitized solar cell based on the composite layer by anodic TiO2 nanotubes

TiO₂ nanotube arrays are very attractive for dye-sensitized solar cells (DSSCs) owing to their superior charge percolation and slower charge recombination. Highly ordered, vertically aligned TiO₂ nanotube arrays have been fabricated by a three-step anodization process. Although the use of a one-dimensional structure provides an enhanced photoelectrical performance, the smaller surface area reduces the adsorption of dye on the TiO₂ surface. To overcome this problem, we investigated the effect of DSSCs constructed with a multilayer photoelectrode made of TiO₂ nanoparticles and TiO₂ nanotube arrays. We fabricated the novel multilayer photoelectrode via a layer-by-layer assembly process and thoroughly investigated the effect of various structures on the sample efficiency. The DSSC with a four-layer photoelectrode exhibited a maximum conversion efficiency of 7.22% because of effective electron transport and enhanced adsorption of dye on the TiO₂ surface.     

Hydrothermal synthesis of Ag2CO3-TiO2 loaded reduced graphene oxide nanocomposites with highly efficient photocatalytic activity

Abstract

In this work, a growth of Ag₂CO₃-TiO₂ NPs over GO sheets and reduction of GO were simultaneously achieved by the hydrothermal process at 130 °C for 4?h. The photocatalytic activity of the as-prepared Ag₂CO₃-TiO₂ NPs decorated reduced graphene oxide (Ag₂CO₃-TiO₂/rGO) composite was studied by the degradation of methylene blue (MB) solution under visible light irradiation. A remarkable enhancement in the photocatalytic activity of the TiO₂ was achieved after sensitizing with Ag₂CO₃ and loading in rGO sheets which is attributed to the reduced charge recombination, enhanced dye adsorption, and the improvement in the light harvesting capacity of the composite.     

Synergetic effect of graphene sheet and three‐dimensional crumpled graphene on the performance of dye‐sensitized solar cells

Herein, an improved structure of the dye‐sensitized solar cell (DSSC) is demonstrated which is composed of surface modified fluorine‐doped tin oxide (FTO) glass with graphene (GR) sheets and TiO₂ films incorporated with three‐dimensional crumped graphene (3‐D CGR)/GR sheets. The morphologies of the as‐prepared GR sheets on FTO glasses and 3‐D CGR/GR sheets/TiO₂ films were observed by field‐emission scanning electron microscopy. Light harvesting and charge recombination kinetics were investigated with a solar simulator and electrochemical impedance spectroscopy analysis. In addition to the reduced charge resistance by the GR modified FTO, the enhanced dye loading capability of the 3‐D CGR, and the rapid charge transport by the 2‐D GR sheets, the power conversion efficiency was 7.2%, which was an increase of 56% compared to a “conventional” structured DSSC. © 2015 American Institute of Chemical Engineers AIChE J, 62: 574–579, 2016     

TiO2–BaTiO3 nanocomposite for electron capture in dye‐sensitized solar cells

Different compositions of TiO₂–BaTiO₃ nanocomposites are synthesized with various weight ratios for dye‐sensitized solar cell (DSSC) applications. TiO₂ and BaTiO₃ nanoparticles (NPs) are synthesized by sol‐gel and solvothermal methods, respectively and are employed as the photoanode electrodes. BaTiO₃ NPs have pure cubic perovskite crystal structure with an average size of 20‐40 nm, while TiO₂ NPs show pure anatase phase with 15‐30 nm size. The power conversion efficiency (PCE) enhancement of the cells is first attained by controlling the thickness of the films for light harvesting improvement. The fabricated DSSC composed of pure BaTiO₃ NPs with an optimal thickness of 25 μm shows efficiency of 6.83%, whereas that made of pure TiO₂ NPs with 14 μm thickness has cell efficiency of 7.24%. Further improvement of cell efficiency is achieved by preparation of binary oxide nanocomposites using TiO₂ and BaTiO₃ NPs with various weight ratios. The highest PCE of 9.40% is obtained for the nanocomposite with TiO₂:BaTiO₃=85:15 (wt%). The enhancement is assigned to less recombination of photo‐generated electrons and higher incident photon to current conversion yield as a result of rapid charge collection and higher dye sensitization.     

The improvement of electron transport rate of TiO2 dye-sensitized solar cells using mixed nanostructures with different phase compositions

Dye-sensitized solar cells (DSCCs) in the form of mixed nanostructures containing TiO₂ nanoparticles and nanowires with different weight ratios and phase compositions are reported. X-ray diffraction and field emission scanning electron microscopy analyses revealed that the synthesized TiO₂ nanoparticles had average crystallite size in the range 21–39 nm, whereas TiO₂ nanowires showed diameter in the range 20–50 nm. The indirect optical band gap energy of TiO₂ nanowires, anatase- and rutile-TiO₂ nanoparticles was calculated to be 3.35, 3.28 and 3.17 eV, respectively. The power conversion efficiency of the solar cells changed with nanowire to nanoparticle weight ratio, reaching a maximum at a specific value. An increase of 4.3% in cell efficiency was achieved by introducing 10 wt% nanowire into the as-synthesized TiO₂ nanoparticles (WP1 cell). Furthermore, an increase of 27.6% in cell efficiency was achieved by using crystalline anatase-TiO₂ nanoparticles rather than as-synthesized TiO₂ nanoparticles in WP1 solar cell. It was found that the power conversion efficiency and short circuit current of WP1 cell were decreased down to around 30.8% and 39.1%, respectively using rutile nanoparticles rather than anatase nanoparticles. The improvement of cell efficiency was related to rapid electron transport and less recombination of photogenerated electrons, as confirmed by electrochemical impedance spectroscopy.     

TiO2‐Modified Flower‐Like Bi2WO6 Nanostructures with Enhanced UV‐Vis Photocatalytic Activity

Anatase TiO₂‐modified flower‐like Bi₂WO₆ nanostructures were prepared by a simple hydrothermal reaction followed by layer‐by‐layer deposition and calcination. The photocatalytic activity was evaluated using Brilliant Red X3B, an anionic azo dye, as the target organic pollutant under UV‐Vis light irradiation. The experiment results showed that the photocatalytic activity of the hybrid increases first and then decreases with increasing loading amount of TiO₂. The hybrid coated with four layers of TiO₂ (containing 20 wt‐% TiO₂) showed the highest photocatalytic activity, which is 10.45 and 3.20 times higher than that of pure Bi₂WO₆ and TiO₂, respectively. The improved photocatalytic performance of TiO₂‐modified Bi₂WO₆ nanostructures could be ascribed to the improved light‐harvesting ability, efficient photo‐generated electron‐hole separation, and enhanced adsorption of the dye. This work may shed light on the design of complex architectures and the exploitation of their potential applications.     

Hydrothermal synthesis of pseudocubic BaTiO3 nanoparticles using TiO2 nanofibers: Study on photocatalytic and dielectric properties

In this study, TiO₂ nanofibers were fabricated via the electrospinning method followed by air annealing. Then, Ti-requirement in the conventional hydrothermal synthesis of BaTiO₃ stoichiometry was supplied by using these nanofibers. The microstructural and compositional properties of BaTiO₃ nanoparticles were studied using SEM, TEM, XRD, XPS, and Raman spectroscopy. The structural analysis showed that the cubic symmetry was the dominant one in the BaTiO₃ nanoparticles, whereas Raman spectroscopy indicated the coexistence of cubic symmetry with the tetragonal polymorph. The nanoparticles displayed higher photocatalytic reactivity under UV-A light compared to visible irradiation during decomposition of methylene blue dye and reached 24.2% and 18.8% degradation, respectively, after 1 hour. Furthermore, the dielectric properties were investigated using sintered compacts of these nanoparticles. Among the employed temperatures for sintering, the highest relative density (90%) and dielectric constant (2165 at 1 MHz) were obtained at 1250°C and 5 hours. This study revealed that the electrospun TiO₂ nanofiber precursor can successfully be used for the production of nanoscale barium titanate particles suitable for various applications.     

In situ transformation of TiO2 hierarchical nanostructures toward efficient photoelectrochemical water splitting

TiO₂ hierarchical nanomaterials have been intensively investigated as a very promising photoanode in photoelectrochemical water splitting due to its combined effects of large surface area and fast electron transfer. However, the TiO₂ hierarchical nanostructures prepared by most prevailing synthesis methods currently are at distinct disadvantages such as complicated process, poor controllability, poor interfacial contact, excessive impurities and so on. Here we report a facile route to construct a well-defined TiO₂ hierarchical nanostructure via in-situ transformation of TiO₂ nanoparticles with highly exposed {001} facets in the tube wall of the pristine TiO₂ nanotube arrays. The resulted TiO₂ hierarchical nanostructures exhibit enhanced light harvesting, lowe recombination rate of photo-generated charger carrier. Upon these synergistic effects, the target hierarchical nanostructure shows significantly improved PEC performance and excellent photo-switching response with good reproducibility and stability. Corresponding photocurrent density and photon-to-current efficiency achieve 0.76 mA cm⁻² and 0.50%, respectively, which show an enhancement of 1.70 and 1.32 times to those of the control one. This work provides a possible route for fabrication of TiO₂ starting materials with decent efficiencies.     

Optimization of the dye-sensitized solar cell performance by mechanical compression

In this study, the P25 titanium dioxide (TiO₂) nanoparticle (NP) thin film was coated on the fluorine-doped tin oxide (FTO) glass substrate by a doctor blade method. The film then compressed mechanically to be the photoanode of dye-sensitized solar cells (DSSCs). Various compression pressures on TiO₂ NP film were tested to optimize the performance of DSSCs. The mechanical compression reduces TiO₂ inter-particle distance improving the electron transport efficiency. The UV–vis spectrophotometer and electrochemical impedance spectroscopy (EIS) were employed to quantify the light-harvesting efficiency and the charge transport impedance at various interfaces in DSSC, respectively. The incident photon-to-current conversion efficiency was also monitored. The results show that when the DSSC fabricated by the TiO₂ NP thin film compressed at pressure of 279 kg/cm², the minimum resistance of 9.38 Ω at dye/TiO₂ NP/electrolyte interfaces, the maximum short-circuit photocurrent density of 15.11 mA/cm², and the photoelectric conversion efficiency of 5.94% were observed. Compared to the DSSC fabricated by the non-compression of TiO₂ NP thin film, the overall conversion efficiency is improved over 19.5%. The study proves that under suitable compression pressure the performance of DSSC can be optimized.     

TiO2-B narrow nanobelt/TiO2 nanoparticle composite photoelectrode for dye-sensitized solar cells

In order to possess the merits of both building blocks, i.e. the rapid interfacial electron transport of TiO₂-B narrow nanobelts (NBs) and the high surface area of TiO₂ nanoparticles (NPs), the TiO₂-B NBs and TiO₂ NPs composites photoelectrodes were prepared with different weight ratios. The dye-sensitized solar cell prototypes were fabricated based on the composite photoelectrodes and the photoelectrical properties have been systematically studied. Although the amount of adsorption dye of composite solar cells decreased, the composite cells could obtain higher power conversion efficiency compared to pure TiO₂ NP solar cell by rational tuning the weight ratio of TiO₂-B NBs and TiO₂ NPs, which was due to the faster electron transfer rate. The dye adsorption amount and interfacial electron transport, which together determined the overall photoelectrical conversion efficiency, were investigated by the UV–vis spectra, the electrochemical impedance spectra (EIS), intensity-modulated photocurrent spectroscopy (IMPS) and intensity-modulated photovoltage spectroscopy (IMVS).