Enhanced charge-collection efficiencies and light scattering in dye-sensitized solar cells using oriented TiO2 nanotubes arrays

We report on the microstructure and dynamics of electron transport and recombination in dye-sensitized solar cells (DSSCs) incorporating oriented TiO2 nanotube (NT) arrays. The morphology of the NT arrays, which were prepared from electrochemically anodized Ti foils, were characterized by scanning and transmission electron microscopies. The arrays were found to consist of closely packed NTs, several micrometers in length, with typical wall thicknesses and intertube spacings of 8-10 nm and pore diameters of about 30 nm. The calcined material was fully crystalline with individual NTs consisting of about 30 nm sized crystallites. The transport and recombination properties of the NT and nanoparticle (NP) films used in DSSCs were studied by frequency-resolved modulated photocurrent/photovoltage spectroscopies. While both morphologies display comparable transport times, recombination was much slower in the NT films, indicating that the NT-based DSSCs have significantly higher charge-collection efficiencies than their NP-based counterparts. Dye molecules were shown to cover both the interior and exterior walls of the NTs. Analysis of photocurrent measurements indicates that the light-harvesting efficiencies of NT-based DSSCs were higher than those found for DSSCs incorporating NPs owing to stronger internal light-scattering effects.     

TiO2 nanotubes infiltrated with nanoparticles for dye sensitized solar cells

We present a detailed study of the infiltration of titanium dioxide (TiO(2)) nanotubes (NTs) with TiO(2) nanoparticles (NPs) for dye sensitized solar cells (DSSCs). The aim is to combine the merits of the NP's high dye loading and high light harvesting capability with the NT's straight carrier transport path and high electron collection efficiency to improve the DSSC performance. On infiltrating NTs with TiCl(4) solution followed by hydrothermal synthesis, 10 nm size NPs were observed to form a conformal and dense layer on the NT walls. Compared with the bare NT structure, dye loading of this mixed NT and NP structure is more than doubled. The overall photon conversion efficiencies of the fabricated DSSCs are improved by 152%, 107%, and 49% for 8, 13, and 20 μm long NTs, respectively. Electron transport and recombination parameters were extracted based on electrochemical impedance spectroscopy measurements. Although a slight reduction of electron lifetime was observed in the mixed structures due to enhanced recombination with a larger surface area, the diffusion length is still significantly longer than the NT length used, suggesting that most electrons are collected. In addition to dye loading and hence photocurrent increment, the photovoltage and filling factor were also improved in the mixed structure due to a low serial resistance, leading to the enhancement of the overall efficiency.     

Effect of the geometry of the anodized titania nanotube array on the performance of dye-sensitized solar cells

Highly ordered TiO2 nanotube arrays are superior photoanodes for dye-sensitized solar cells (DSSCs) due to reduced intertube connections, vectorial electron transport, suppressed electron recombination, and enhanced light scattering. Performance of the cells is greatly affected by tube geometry, such as wall thickness, length, inner diameter and intertube spacing. In this paper, effect of geometry on the photovoltaic characteristics of DSSCs is reviewed. The nanotube wall has to be thick enough for a space charge layer to form for faster electron transportation and reduced recombination. When the tube wall is too thin to support the space charge layer, electron transport in the nanotubes will be hindered and reduced to that similar in a typical nanoparticle photoanode, and recombination will easily take place. Length of the nanotubes also plays a role: longer tube length is desired because of more dye loading, however, tube length longer than the electron diffusion length results in low collecting efficiency, which in turn, results in low short-circuit current density and thus low overall conversion efficiency. The tube inner diameter (pore size) affects the conversion efficiency through effective surface area, i.e., larger pore size gives rise to smaller surface area for dye adsorption, which results in low short-circuit current density under the same light soaking. Another issue that may seriously affect the conversion efficiency is whether each of the tube stands alone (free from connecting to the neighboring tubes) to facilitate infiltration of dye and fully use the outer surface area.     

Mesocrystalline TiO<Subscript>2</Subscript> nanosheet arrays with exposed {001} facets: Synthesis via topotactic transformation and applications in dye-sensitized solar cells

A facile,fluorine-free approach for synthesizing vertically aligned arrays of mesocrystalline anatase TiO2 nanosheets with highly exposed {001} facets was developed through topotactic transformation.Unique mesocrystalline {001}-faceted TiO2 nanosheet arrays vertically aligned on conductive fluorine-doped tin oxide glass were realized through topotactic conversion from single-crystalline precursor nanosheet arrays based on lattice matching between the precursor and the anatase crystals.The morphology and microstructure of the {001}-faceted TiO2 nanosheets could be readily modulated by changing the reactant concentration and annealing temperature.Owing to enhanced dye adsorption,reduced charge recombination,and enhanced light scattering arising from the exposed {001} facets,in addition to the advantageous features of low-dimensional structure arrays (e.g.,fast electron transport and efficient charge collection),the obtained TiO2 nanosheet arrays exhibited superior performance when they were used as anodes for dye-sensitized solar cells (DSSCs).Particularly,{001}-faceted TiO2 nanosheet arrays ～15 μm long annealed at 500 ℃ showed a power conversion efficiency of 7.51％.Furthermore,a remarkable efficiency of 8.85％ was achieved for a DSSC based on double-layered TiO2 nanosheet arrays ～35 μm long,which were prepared by conversion from the precursor nanoarrays produced via secondary hydrothermal growth.     

Effect of highly ordered single-crystalline TiO2 nanowire length on the photovoltaic performance of dye-sensitized solar cells

One-dimensional semiconductor nanostructures grown directly onto transparent conducting oxide substrates with a high internal surface area are most desirable for high-efficiency dye-sensitized solar cells (DSSCs). Herein, we present a multicycle hydrothermal synthesis process to produce vertically aligned, single crystal rutile TiO(2) nanowires with different lengths between 1 and 8 μm for application as the working electrode in DSSCs. Optimum performance was obtained with a TiO(2) nanowire length of 2.0 μm, which may be ascribed to a smaller nanowire diameter with a high internal surface area and better optical transmittance with an increase in the incident light intensity on the N719 dye; as well as a firm connection at the FTO/TiO(2) nanowire interface.     

Photoelectrochemical detection of pentachlorophenol with a multiple hybrid CdSe(x)Te(1-x)/TiO2 nanotube structure-based label-free immunosensor

Driven by the urgent demand of detecting trace amounts of pentachlorophenol (PCP) in contaminative water, a label-free immunosensor with ultra sensitivity and high selectivity was constructed based on a hybrid CdSe(x)Te(1-x) (0 ≤ x ≤ 1) nanocrystal (NCs)-modified TiO(2) nanotube (NT) arrays for the first time. The CdSe(x)Te(1-x) NCs were photoelectrodeposited on inner and outer space of the TiO(2) NTs, leading to high photoelectrical conversion efficiency in the visible region. PCP antibodies are covalently conjugated on the TiO(2) NTs due to the large surface area and good biocompatibility. Since the photocurrent is highly dependent on the TiO(2) surface properties, the specific interaction between PCP and the antibodies results in a sensitive change in the photocurrent, with a limit of detection (LOD) of 1 pM. High sensor-to-sensor reproducibility is achieved. The sensor was applied for the direct analysis of river water samples.     

Self-assembled TiO₂ with increased photoelectron production, and improved conduction and transfer: enhancing photovoltaic performance of dye-sensitized solar cells

Highly crystalline mesoporous anatase TiO(2) is prepared through supramolecular self-assembly and by utilizing cetyltrimethylammonium bromide (CTAB) as templating material. Photoanodes of dye-sensitized solar cells (DSSCs) made from these TiO(2) nanoparticles are found to have a high specific surface area of 153 m(2)/g and high surface roughness. Optical absorption spectroscopy studies reveal that the photoanode films adsorb four times more dye than films made of commercial P25 TiO(2). Mercury porosimetry and field emission scanning electron microscope (FESEM) studies show hierarchical macro- and meso-porosity of the photoanode films leading to better dye and electrolyte percolation, combined with improved electron conduction pathways compared to P25 films. Electrochemical impedance studies confirm lower impedance and higher electron lifetime in the synthesized mesoporous TiO(2) films compared to P25 films. Higher photovoltaic efficiency was recorded of cells made from the synthesized mesoporous TiO(2) in comparison to the corresponding cells made from P25. Incident-photon-to-current efficiency data provided critical understanding of recombination kinetics, and provided proof of Mie scattering by the self-assembled submicrometer sized TiO(2) aggregates and the macropores in their structure. The scattering phenomenon was further corroborated by diffused reflectance studies. An in-depth analysis of CTAB-templated mesoporous TiO(2) has been conducted to show how it can be a good candidate photoanode material for enhancing the performance of DSSCs.     

High efficiency dye-sensitized solar cells based on hierarchically structured nanotubes

Dye-sensitized solar cells (DSSCs) based on hierarchically structured TiO(2) nanotubes prepared by a facile combination of two-step electrochemical anodization with a hydrothermal process exhibited remarkable performance. Vertically oriented, smooth TiO(2) nanotube arrays fabricated by a two-step anodic oxidation were subjected to hydrothermal treatment, thereby creating advantageous roughness on the TiO(2) nanotube surface (i.e., forming hierarchically structured nanotube arrays-nanoscopic tubes composed of a large number of nanoparticles on the surface) that led to an increased dye loading. Subsequently, these nanotubes were exploited to produce DSSCs in a backside illumination mode, yielding a significantly high power conversion efficiency, of 7.12%, which was further increased to 7.75% upon exposure to O(2) plasma.     

Enhanced electron transport in mesoporous TiO2 films modified by sol-gel necking for dye-sensitized solar cells

Mesoporous TiO2 films modified via sol-gel necking were fabricated by dispersing Ti tetra-isopropoxide (TTIP; 8 to 16 wt% over TiO2) with TiO2 nanoparticles in isopropyl alcohol. The dye-sensitized solar cells (DSSCs) with 13 wt% TTIP-modified TiO2 film exhibited significantly improved overall energy conversion efficiency, despite having less adsorbed dye when compared with DSSCs with untreated and TiCl4 post-treated TiO2 films. The improvement can be attributed to the sol-gel necking (or interconnection) between the nanoparticles which leads to a much faster electron transport and a suppression of the recombination (or back electron transfer) between the TiO2 and electrolyte.     

Improvement in performances of dye-sensitized solar cell with SiO2-coated TiO2 photoelectrode

The pure TiO2 and the nano-porous SiO2-coated TiO2 (STO) films were deposited on the FTO substrates by spray technique for the application of dye-sensitized solar cells (DSSCs). XRD pattern shows the pure TiO2 and STO films exhibits the same structure. We found that there is no much difference in dye absorption between the STO and the pure TiO2 films. The electrochemical impedance spectra reveal that insulating nature of the porous SiO2 increases surface resistance of the TiO2 film and supresses back transfer of the photogenerated electrons to the electrolyte. The field-emission scanning electron microscopy (FE-SEM) and energy dispersion X-ray spectroscopy (EDS) reveal that the surface morphology and the existence of SiO2 layer on the surface of the TiO2 films, respectively. The photoelectrochemical results show that the short-circuit photocurrent (J(SC)) increased from 16.73 mA cm(-2) to 18.31 mA cm(-2) and the open-circuit voltage (V(OC)) value changed from 0.71 V to 0.74 V for the STO films. The efficiency of cell has been greatly improved from 8.25 to 9.3%.