Sodium fluoride-assisted modulation of anodized TiO₂ nanotube for dye-sensitized solar cells application

This work reports the use of sodium fluoride (in ethylene glycol electrolyte) as the replacement of hydrofluoric acid and ammonium fluoride to fabricate long and perpendicularly well-aligned TiO? nanotube (TNT) (up to 21 μm) using anodization. Anodizing duration, applied voltage and electrolyte composition influenced the geometry and surface morphologies of TNT. The growth mechanism of TNT is interpreted by analyzing the current transient profile and the total charge density generated during anodization. The system with low water content (2 wt %) yielded a membrane-like mesoporous TiO? film, whereas high anodizing voltage (70 V) resulted in the unstable film of TNT arrays. An optimized condition using 5 wt % water content and 60 V of anodizing voltage gave a stable array of nanotube with controllable length and pore diameter. Upon photoexcitation, TNTs synthesized under this condition exhibited a slower charge recombination rate as nanotube length increased. When made into cis-diisothiocyanato-bis(2,2?-bipyridyl-4,4?-dicarboxylato) ruthenium(II) bis (tetrabutyl-ammonium)(N719) dye-sensitized solar cells, good device efficiency at 3.33 % based on the optimized TNT arrays was achieved with longer electron time compared with most mesoporous TiO? films.     

Electrospray preparation of hierarchically-structured mesoporous TiO₂ spheres for use in highly efficient dye-sensitized solar cells

We report a simple method to prepare hierarchically structured TiO(2) spheres (HS-TiO(2)), using an electrostatic spray technique, that are utilized for photoelectrodes of highly efficient dye-sensitized solar cells (DSSCs). This method has an advantage to remove the synthesis steps in conventional sol-gel method to form nano-sized spheres of TiO(2) nanoclusters. The fine dispersion of commercially available nanocrystalline TiO(2) particles (P25, Degussa) in EtOH without surfactants and additives is electro-sprayed directly onto a fluorine-dopoed tin-oxide (FTO) substrate for DSSC photoelectrodes. The DSSCs of HS-TiO(2) photoelectrodes show high energy conversion efficiency over 10% under illumination of light at 100 mW cm(-2), AM1.5 global. It is concluded from frequency-dependent measurements that the faster electron diffusion coefficient and longer lifetime of HS-TiO(2) than those in nonstructured TiO(2) contribute to the enhanced efficiency in DSSCs.     

CdS/CdSe-cosensitized TiO₂ photoanode for quantum-dot-sensitized solar cells by a microwave-assisted chemical bath deposition method

A CdS/CdSe quantum-dot (QD)-cosensitized TiO(2) film has been fabricated using a microwave-assisted chemical bath deposition technique and used as a photoanode for QD-sensitized solar cells. The technique allows a direct and rapid deposition of QDs and forms a good contact between QDs and TiO(2) films. The photovoltaic performance of the as-prepared cell is investigated. The results show that the performance of the CdS/CdSe-cosensitized cell achieves a short-circuit current density of 16.1 mA cm(-2) and a power conversion efficiency of 3.06% at one sun (AM 1.5 G, 100 mW cm(-2)), which is comparable to the one fabricated using conventional successive ionic layer adsorption and reaction technique.     

High-efficiency, solid-state, dye-sensitized solar cells using hierarchically structured TiO₂ nanofibers

High-performance, room-temperature (RT), solid-state dye-sensitized solar cells (DSSCs) were fabricated using hierarchically structured TiO? nanofiber (HS-NF) electrodes and plastic crystal (PC)-based solid-state electrolytes. The electrospun HS-NF photoelectrodes possessed a unique morphology in which submicrometer-scale core fibers are interconnected and the nanorods are dendrited onto the fibers. This nanorod-in-nanofiber morphology yielded porosity at both the mesopore and macropore level. The macropores, steming from the interfiber space, afforded high pore volumes to facilitate the infiltration of the PC electrolytes, whereas the mesoporous nanorod dendrites offered high surface area for enhanced dye loading. The solid-state DSSCs using HS-NFs (DSSC-NF) demonstrated improved power conversion efficiency (PCE) compared to conventional TiO? nanoparticle (NP) based DSSCs (DSSC-NP). The improved performance (>2-fold) of the DSSC-NFs was due to the reduced internal series resistance (R(s)) and the enhanced charge recombination lifetime (τ(r)) determined by electrochemical impedance spectroscopy and intensity modulated photocurrent/photovoltage spectroscopy. The easy penetration of the PC electrolytes into HS-NF layers via the macropores reduces R(s) significantly, improving the fill factor (FF) of the resulting DSSC-NFs. The τ(r) difference between the DSSC-NF and DSSC-NP in the PC electrolytes was extraordinary (~14 times) compared to reported results in conventional organic liquid electrolytes. The optimized PCE of DSSC-NF using the PC electrolytes was 6.54, 7.69, and 7.93% at the light intensity of 100, 50, and 30 mW cm?2, respectively, with increased charge collection efficiency (>40%). This is the best performing RT solid-state DSSC using a PC electrolyte. Considering the fact that most reported quasi-solid state or nonvolatile electrolytes require higher iodine contents for efficient ion transport, our HS-NFs are a promising morphology for such electrolytes that have limited ion mass transport.     

Low-temperature UV processing of nanoporous SnO₂ layers for dye-sensitized solar cells

Connection of SnO? particles by simple UV irradiation in air yielded cassiterite SnO? porous films at low temperature. XPS, FTIR, and TGA-MS data revealed that the UV treatment has actually removed most of the organics present in the precursor SnO? colloid and gave more hydroxylated materials than calcination at high temperature. As electrodes for dye-sensitized solar cells (DSCs), the N3-modified 1-5 μm thick SnO? films showed excellent photovoltaic responses with overall power conversion efficiency reaching 2.27% under AM1.5G illumination (100 mW cm?2). These performances outperformed those of similar layers calcined at 450 °C mostly due to higher V(oc) and FF. These findings were rationalized in terms of slower recombination rates for the UV-processed films on the basis of dark current analysis, photovoltage decay, and electrical impedance spectroscopy studies.     

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.     

Simple indoline based donor–acceptor dye for high efficiency dye-sensitized solar cells

A simple metal-free donor–acceptor type sensitizer U01, bearing strong electron donor indoline-triphenylamine was synthesized for panchromatic sensitization of TiO₂ nanocrystalline film. Photovoltaic properties of U01 showed remarkably enhanced light harvesting due to the presence of strong electron donor and robust structure. The new U01 sensitized solar cell exhibited a photovoltaic performance: a short-circuit photocurrent density (J_sc) of 10.70 mA cm⁻², an open-circuit photovoltage (V_oc) of 0.758 V and a fill factor (FF) of 0.74, corresponding to an overall conversion efficiency of 6.01% under standard global AM 1.5 solar light condition. Our results suggest that indoline-triphenylamine based robust D–A molecular architecture is a highly promising class of panchromatic sensitizers for improvement of the performance of dye-sensitized solar cells (DSCs).     

Spectrally selective reflector surfaces for heat reduction in concentrator solar cells: modeling and applications of TiO₂:Nb-based thin films

The energy conversion efficiency of a conventional pn junction solar cell decreases as the temperature increases, and this may eventually lead to failures in the photovoltaic system, especially if it uses concentrated solar radiation. In this work, we show that spectrally selective reflector (SSR) surfaces can be important for reducing the heat buildup on passively cooled solar cells. We outline a computational scheme for optimizing DC magnetron-sputtered TiO?:Nb-based SSRs tailored for silicon solar cells and find good agreement of the reflectance with an experimental realization of the optimal SSR. A figure of merit for SSRs has also been derived and applied to the experimental data.     

High-efficiency ferroelectric-film solar cells with an n-type Cu₂O cathode buffer layer

Because of the existence of interface Schottky barriers and depolarization electric field, ferroelectric films sandwiched between top and bottom electrodes are strongly expected to be used as a new kind of solar cells. However, the photocurrent with a typical order of μA/cm(2) is too low to be practical. Here we demonstrate that the insertion of an n-type cuprous oxide (Cu(2)O) layer between the Pb(Zr,Ti)O(3) (PZT) film and the cathode Pt contact in a ITO/PZT/Pt cell leads to the short-circuit photocurrent increasing 120-fold to 4.80 mA/cm(2) and power conversion efficiency increasing of 72-fold to 0.57% under AM1.5G (100 mW/cm(2)) illumination. Ultraviolet photoemission spectroscopy and dark J-V characteristic show an ohmic contact on Pt/Cu(2)O, an n(+)-n heterojunction on Cu(2)O/PZT and a Schottky barrier on PZT/ITO, which provide a favorable energy level alignment for efficient electron-extraction on the cathode. Our work opens up a promising new method that has the potential for fulfilling cost-effective ferroelectric-film photovoltaic.     

One-step synthesis of CdS sensitized TiO₂ photoanodes for quantum dot-sensitized solar cells by microwave assisted chemical bath deposition method

Sensitized-type solar cells based on TiO? photoanodes and CdS quantum dots (QDs) as sensitizers have been studied. CdS QDs are grown on TiO? films, utilizing one-step microwave assisted chemical bath deposition (MACBD) method. This method allows a facile and rapid deposition and integration between CdS QDs and TiO? films. The photovoltaic performances of the cells fabricated using CdS precursor solutions with different concentrations are investigated. The results show that the cell based on MACBD deposited TiO?/CdS electrode achieves a maximum short circuit current density of 7.20 mAcm?2 and power conversion efficiency of 1.18 % at one sun (AM 1.5G, 100 mW cm?2), which is comparable to the ones prepared using conventional techniques.     

Front-side illuminated CdS/CdSe quantum dots co-sensitized solar cells based on TiO₂ nanotube arrays

We fabricated a front-side illuminated CdS/CdSe quantum dots co-sensitized solar cell based on TiO(2) nanotube arrays. The freestanding TiO(2) nanotube arrays were first detached from anodic oxidized Ti foils and then transferred to the fluorine-doped tin oxide to form photoanodes. An opaque Cu(2)S with high electrochemical activity was used as the counter electrode. A photovoltaic conversion efficiency as high as 3.01% under one sun illumination has been achieved after optimizing the deposition time of CdSe quantum dots and the length of the TiO(2) nanotube arrays. It is observed that the power conversion efficiency of quantum dots sensitized solar cells from the front-side illumination mode (3.01%) is much higher than that of the back-side illumination mode (1.32%) owing to the poor catalytic activity of Pt to polysulfide electrolytes and light absorption by the electrolytes for the latter.     

Effect of different concentration Li-doping on the morphology,defect and photovoltaic performance of Li–ZnO nanofibers in the dye-sensitized solar cells

Low concentrations of Li in Li-doped ZnO nanofibers prepared using hydrothermal method at low temperature can introduce oxygen vacancies and intrinsic Zn ions into the structure. Photo-luminance (PL) was used to investigate oxygen vacancies in the structure of ZnO nanofibers prepared by lower annealing temperature, and the XPS technique was also employed to satisfy the PL analysis results. PL analysis showed that oxygen vacancies increase in conjunction with Li concentrations. A shift in the lower angle of XRD patterns also demonstrates the defect in ZnO structure related to Li doping. Higher-efficiency DSSCs were obtained from the lower Li concentration of 0.01 M in ZnO nanofibers. Higher concentrations of Li tended to produce large amounts of cross-like nanofibers, which increase the open circuit voltage of the DSSCs. The highest open circuit voltage (V_oc) obtained was 750 mV, which was higher than the best reported ZnO nanofibers-based DSSCs. Intensity modulation photocurrent spectroscopy (IMPS) and intensity modulation photo-voltage spectroscopy (IMVS) analysis showed that low amounts of Li-doping improved the electron injection efficiency of ZnO nanofibers in DSSCs. Lower recombination rates with higher electron transfer efficiency for 0.01 M Li-doped DSSCs exhibited higher efficiency of 0.59% than non-doped ZnO nanofibers DSSCs.     

Synthesis and characterization of Y-shape electron donor–acceptor type organic dyes for dye-sensitized solar cells

Three Y-shape organic dyes, (Z)-3-(5-(3,5-bis(4-(9H-carbazol-9-yl)styryl)-4-methoxyphenyl)thiophen-2-yl)-2-cyanoacrylic acid (OD-1), (Z)-3-(5′-(3,5-bis(4-(9H-carbazol-9-yl)styryl)-4-methoxyphenyl)-2,2′-bithiophen-5-yl)-2-cyanoacrylic acid (OD-2) and (Z)-3-(5′-(3,5-bis(4-(9H-carbazol-9-yl)styryl)-4-methoxyphenyl)-3,4′-4″-trithiophenyl-5-yl)-2-cyanoacrylic acid (OD-3) were synthesized and used as sensitizers in nanocrystalline dye-sensitized solar cells (DSSCs). The introduction of the bis(carbazolylstyryl) units as an electron donor group and oligothiophene units as a both electron donors and π-spacers increased the conjugation length of the sensitizers and thus improved their molar absorption coefficient and light harvesting efficiency. DSSCs with the configuration of SnO₂:F/TiO₂/organic dye/liquid electrolyte/Pt devices were fabricated using these OD-1, OD-2 and OD-3 as a sensitizers. Among the devices, the DSSC composed of OD-3 exhibited highest power conversion efficiency of 3.03% under AM1.5G (100 mW cm⁻²).     

Photovoltaic performance of dye-sensitized solar cells fabricated with polyvinylidene fluoride–polyacrylonitrile–silicondioxide hybrid composite membrane

Electrospun fibrous membranes of hybrid composites of polyvinylidene fluoride (PVdF), polyacrylonitrile (PAN) and silicon dioxide (SiO₂) (PVdF–PAN–SiO₂) are prepared with different proportions of SiO₂ (3, 5 and 7% w/w). The field emission scanning electron microscopy (FE-SEM) reveals that these membranes have three-dimensional, fully interconnected network structures, which are combined with micropores of fine SiO₂ distribution. The surface roughness of the membranes increases with increasing the SiO₂ content. It is found that 7 wt% SiO₂/PVdF–PAN electrolyte membrane has the highest ionic conductivity (6.96 × 10⁻² S cm⁻¹) due to the large liquid electrolyte uptake (about 570%). As the concentration of SiO₂ nanoparticles increase, the contact angle value also increases, ranging from 135.70° to 140.60° which indicates that the membrane has higher hydrophobicity. The dye sensitized solar cells (DSSCs) are fabricated using the hybrid composite membrane with PVdF–PAN with 7 wt % SiO₂. Its photovoltaic performance exhibits an open circuit voltage (V_oc) of 0.79 V and a short circuit current 11.6 mA cm⁻² at an incident light intensity of 100 mW cm⁻², producing an efficiency of 5.61%. DSSC, using the hybrid composite electrospun membrane which shows more stable photovoltaic performance than other assembled DSSCs.     

Enhanced light harvesting from Först-type resonance energy transfer in the quasi-solid state dye-sensitized solar cells

The demonstrated F?rst-type resonance energy transfer (FRET) is demonstrated in quasi-solid type dye-sensitized solar cells between organic fluorescence materials as an energy donor doped in polymeric gel electrolyte and a ruthenium complex as an energy acceptor on the surface of TiO2. Strong spectral overlap of emission/absorption of the energy donor and acceptor is required to obtain high FRET efficiency. The judicious choice of the energy donor allows the enhancement of the light harvesting characters of the energy acceptor (N3) in quasi-solid dye sensitized solar cells which increases the power conversion efficiency by 25% compare to that of a pristine cell. The optimized cell architecture fabricated with the quasi-solid type electrolyte containing fluorescence materials shows a maximum efficiency of 5.08% with a short-circuit current density (J(sc)) of 12.63 mA/cm2, and an open-circuit voltage (V(oc)) of 0.70 V under illumination of simulated solar light (AM 1.5, 100 mW/cm2).     

Design and development of novel linker for PbS quantum dots/TiO₂ mesoscopic solar cell

A novel bifunctional linker molecule, bis(4-mercaptophenyl)phosphinic acid, is designed to be used in a QDs solar cells. The linker anchors to TiO(2) mesoporous film through the phosphinic acid functional group and to the PbS QDs through the two thiol groups. The way of attachment of this new linker molecule in a photovoltaic PbS QDs/TiO(2) mesoporous device was studied by FTIR measurements. The photovoltaic performance of this new linker in a heterojunction PbS QDs solar cell show high V(oc) relative to QDs based solar cells, which will allow to receive high power conversion efficiency using this novel designed linker. This novel bifunctional linker molecule should pave the way for enhancing binding strength, and efficiency of QDs solar cells compared to the state-of-the-art linkers.