Enhanced efficiency of dye-sensitized solar cells by UV–O3 treatment of TiO2 layer

Solar conversion efficiency of dye-sensitized solar cells was improved by UV–O₃ treatment of TiO₂ before and/or after sintering. The enhancement was resulted from the removal of the residual organics originated from the TiO₂ precursor pastes, increased adsorption of dyes to the TiO₂, surface, and longer diffusion length and shorter electron transit time of electrons through the TiO₂ mesoscopic structure. The power conversion efficiency of the cells reaches to 7.2% with the open circuit voltage of 0.71 V, the short circuit current density of 15.2 mA/cm² and the fill factor of 0.67 under illumination with AM 1.5 (100 mW/cm²) simulated sunlight.     

Improved short-circuit photocurrent densities in dye-sensitized solar cells based on ordered arrays of titania nanotubule electrodes

We report on the synthesis of highly ordered arrays of titania nanotubules and their applications in enhanced photoelectrochemical cells. Ordered arrays of titania nanotubules of ∼120 nm external diameter, ∼100 nm internal diameter, and ∼5 μm length were fabricated on transparent conductive oxide (TCO) glass substrates by sol–gel processes using in-house prepared anodic alumina templates. After thermal bonding and template removal, the resultant nanotubule structures were applied in dye-sensitized solar cells (DSCs). Overall photoconversion efficiency of nearly 4.8% was achieved with Ru-bipyridine dye, N719, and iodolyte liquid electrolyte. This remarkable performance, for electrodes only ∼5 μm thick, is attributed to an unexpectedly high short-circuit photocurrent density of 16 mA/cm² for masked cells and up to 17 mA/cm² for unmasked cells. The enhanced short-circuit photocurrent (J_sc) is attributed to the high surface area (roughness factor ca. 1207) of the nanotubules and thus improved dye adsorption to the electrodes. The improved J_sc is also attributed to the parallel and vertical orientation of the nanostructures and thus to a well-defined electron diffusion path.     

Synthesis of two-dimensional nanowall of Cu-Doped TiO2 and its application as photoanode in DSSCs

Two-dimensional nanowall of Cu-doped TiO₂ (CuTNW) has been prepared in this work to study the role of Cu doping on its photoactivity properties and its photovoltaic performance as photoanode in a dye-sensitized solar cell (DSSC). TiO₂ nanowall with five Cu ion doping, i.e. 6.25, 12.5, 25.0, 50.0 and 100.0 mM, were prepared via a liquid-phase deposition method using ammoniumhexafluorotitanate and hexamethylenetetramine as the reagents with a growth temperature of 90 °C. The X-Ray Diffraction (XRD), X-ray energy dispersion (EDX) and diffuse optical reflectance spectroscopy analysis results confirmed the successfulness of the Cu doping process in the TiO₂ nanowall and effective modification on the photoactivity of the TiO₂ nanowall. We found that the power conversion efficiency of the DSSC utilizing TiO₂ nanowall as photoanode can be enhanced up to 2 times, i.e. from 0.2% to 0.44%, when the TiO₂ nanowall doped with Cu ion. The nanostructure preparation, device fabrication and the mechanism for the device performance enhancement will be discussed.     

Photosensitized growth of TiO2 nanoparticles improved the charge transfer dynamics of a bichromophoric dye

Nanostructured TiO₂ particles utilized in dye-sensitized solar cells (DSSCs) provide a large surface area, which facilitates the adsorption of sensitizing dye and charge recombination due to the high density of surface traps. In this article, a modified surface of TiO₂ nanoparticles was successfully synthesized in the presence of (1-hydroxycyclohexyl)(phenyl)methanone (HCPM) as a sensitizer to control formation in a toluene/ethanol medium via a photolytic process. A particle-size analysis showed that the oxides which had fully oxidized to TiO₂ were 20～35 nm in diameter. The structure of the TiO₂ particles being of an amorphous nature and the nearly defect-free distributions of Ti⁴⁺ and O^2- energy levels imply that the grain boundaries and surface trap sites were effectively suppressed. TiO₂ particles were subsequently blended with the bichromophoric dye, AMIP, to study fluorescence decay dynamics between AMIP/TiO₂ interfaces. Fluorescence lifetime measurements gave the rate constant for the charge-transfer process from the excited singlet of AMIP to the conduction band of TiO₂ as 1.2×10⁹ s^?l. When PL quenching measured as the TiO₂ contents of these composites reached a 2.5 wt% level, the maximum enhanced charge-transfer dynamics occurred. Structural properties and photophysical behaviors of composites of AMIP bound to TiO₂ were extensively demonstrated.     

Effect of milling time on the properties of Pb(Mg1/3Nb2/3)O3 ceramics using the starting precursors PbO and MgNb2O6

Lead magnesium niobate, Pb(Mg_1/3Nb_2/3)O₃ (PMN) ceramics were prepared from the columbite method using calcined powders of various milling time (24–96 h). The effects on the grain size and dielectric properties of the ceramics were investigated. The results show that dielectric properties of ceramics are strongly influenced by the milling time of the starting precursors. Higher percentage of perovskite phase was found in the ceramics that was milled longer and thus the dielectric constant was found to increase when compared to the conventional 24 h milled results. Moreover, milling time also affected the particle size of the starting precursors and that of PMN powders. Therefore, milling time did not only affect the particle size of PMN powders but also the resultant grain size and the formation of perovskite phase, consequently affecting the dielectric constant of the ceramics.     

Enhanced photocatalytic performance of TiO2 particles via effect of anatase–rutile ratio

In the present work anatase–rutile transformation temperature and its effect on physical/chemical properties as well as photocatalytic activity of TiO₂ particles were investigated. The characterisation of the synthesised and annealed TiO₂ particles were determined by X-Ray Powder Diffraction (XRD), scanning electron microscope (SEM), dynamic light scattering (DLS) and Brunauer–Emmett–Teller surface area analysis (BET). The refraction in the ultraviolet–visible (UV–vis) range was assessed using a dual-beam spectrophotometer. The photocatalytic performance of the particles was tested on methylene blue solution. The XRD data indicated that the percentage of rutile increased with the annealing temperature and almost 100% of anatase transformed to rutile at 1000 °C. In addition, the phase transformation was a linear function of annealing temperature so phase composition of TiO₂ can be controlled by changing the annealing temperature. The SEM and BET results presented the increase of agglomerate size and the decrease of specific surface area with the increasing annealing temperature. This proved that anatase has smaller particle size and higher surface area than rutile. The photocatalytic activity of the annealed TiO₂ powders reduced with the increase of annealing temperature. The samples annealed at 900 °C and 925 °C with anatase: rutile ratio of 92:8 and 77:23, respectively, showed the best activity. These results suggested that the photocatalytic activity of TiO₂ particles is a function of phase composition. Thus it can be enhanced by changing its phase composition which can be controlled by annealing temperature.     

Natural dye-based photoelectrode for improvement of solar cell performance

In the present paper, photovoltaic studies of dye-sensitized solar cells (DSSCs) based on betacyanin/TiO₂ and betacyanin/WO₃–TiO₂ have been done. The cell performances were compared through I–V curves and wavelength dependant photocurrent measurements for the two new types of DSSCs. The TiO₂-coated DSSC showed the photovoltage and photocurrent of 300 mV and 4.96 mA/cm², whereas the cell employing WO₃–TiO₂ photoelectrode showed the values 435 mV and 9.86 mA/cm², respectively. The conversion efficiency of TiO₂ based dye-sensitized solar cell was found to be 0.69 %, while WO₃–TiO₂-based cell exhibited a higher conversion efficiency of 2.2 %. The better performance of the WO₃–TiO₂ dye-sensitized solar cell photoelectrode is thought to be due to an inherent energy barrier at the electrode/electrolyte interface leading to the reduced recombination of photoinduced electrons.     

Electrochemical properties of TiO2 nanoparticle/nanorod composite photoanode for dye-sensitized solar cells

A unique composite of TiO₂ nanoparticles (NPs) and nanorods (NRs) has been used to fabricate a photoelectrode for developing dye-sensitized solar cells (DSSCs) with higher sensitivity. The TiO₂ nanorods were synthesized using a mechanical process, in which electrospun TiO₂ nanofibers was grinded in a controlled way to obtain uniform size distribution. The characteristics of electron transport, recombination lifetime and charge collection were investigated by intensity-modulated photocurrent spectroscopy (IMPS) and intensity-modulated photovoltage spectroscopy (IMVS). Photoelectrodes prepared with the composites of NRs and NPs showed significant improvements in electron transportation compared to only NP photoelectrodes, which would enhance the photovoltaic performance of DSSCs. IMPS and IMVS measurements show that fast electron transport and slightly decreased recombination lifetime resulted in the improvement of efficiency. The highest energy conversion efficiency obtained from the photoelectrodes fabricated with the as-prepared rutile TiO₂ nanofibers at 5 wt% NR content was up to 6.1% under AM1.5G solar illumination. The results demonstrate that the composite nanostructure can take advantage of both the fast electron transport of the nanorods and the high surface area of the nanoparticles.     

Photoelectrochromic properties of NiO film deposited on an N-doped TiO2 photocatalytical layer

N-doped TiO₂ film was synthesized on indium–tin oxide (ITO) conducting glass substrate by the hydrolysis method and characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). Then high porous NiO was deposited onto the TiO_2?xN_x layer by chemical bath deposition (CBD) to prepare a double-layer TiO_2?xN_x/NiO electrode. The photoelectrochromic properties of the TiO_2?xN_x/NiO electrode were discussed through the results of UV–vis transmittance spectra, cyclic voltammogram and photocurrent transient measurements. It was found that the TiO_2?xN_x/NiO electrode was sensitive to light and exhibited a noticeable photoelectrochromism. The NiO film changed its color from colorless to brown, and the transmittance varied from 86.8% to 14.5% at 500 nm after 1 h irradiation.     

Microstructure and optical characterizations of mechanosynthesized nanocrystalline semiconducting ZrTiO4 compound

A ZrO₂–TiO₂ solid solution is obtained by high energy ball milling of equimolar mixture of monoclinic (m) ZrO₂ and anatase (a) TiO₂. Nanocrystalline orthorhombic ZrTiO₄ compound is initiated from the nucleation of TiO₂–ZrO₂ solid solution with isostructural s-TiO₂ (srilankite) base after 30 min of milling. After 12 h of milling, 95 mol% non-stoichiometric ZrTiO₄ phase is formed. Post-annealing of 12 h ball-milled powder mixture at 1073 K for 1 h in open air results in complete formation of stoichiometric ZrTiO₄ compound. Microstructures of all powder mixtures milled for different durations have been characterized by Rietveld's structure and microstructure refinement method using X-ray powder diffraction data. HRTEM images of 12 h milled and annealed samples provide direct evidence of the results obtained from the Rietveld analysis. Optical bandgaps of ball milled and annealed ZrTiO₄ compounds lie within the semiconducting region (~2.0 eV) and increases with increase in milling time.     

Ionic conductivities of various GeS2-based oxy-sulfide amorphous materials prepared by melt-quenching and mechanical milling methods

We have previously explored the Li₂S + GeS₂ + GeO₂ system to determine the specific effect of added GeO₂ to a base 0.5Li₂S + 0.5GeS₂ glass composition. In this new study, we report the conductivities of these Li₂S + GeS₂ + GeO₂ glasses over their full glass forming range to more fully optimize the ionic conductivity. In addition to this study of bulk glasses, we have also studied the effect of creating powders of the bulk glasses and compared the conductivities of the bulk glasses to those of compacted powders. This latter study is relevant due to the fact that in most battery applications powders are the form of choice in forming battery stacks. Since we used the mechanical milling technique to produce the powders, we further extended this study to determine the extent to which the amorphous range could be expanded using the mechanical milling technique. Having access to these extended compositional range materials, we were able to extend all examinations of the role of composition, powder size, and compaction of the sample on the conductivity and we compared these results to those of the bulk glass samples.     

Simple one-step ultrasonic synthesis of anatase titania/polypyrrole nanocomposites

In this work, hybrid nanocomposites based on anatase titania:polypyrrole (TiO₂:PPy) were directly obtained from a simple, one-step, ultrasonic (UT)-assisted synthesis. The properties of these crystalline nanocomposites were compared with those of others fabricated using cold (Cold)-assisted synthesis without any UT assistance, which required a hydrothermal treatment (HT) to yield crystalline anatase titania in the nanocomposite (TiO₂:PPy) at low temperature (130 °C) and in a short time (3 h). The SEM results demonstrated that the UT-assisted synthesis is a feasible method to obtain anatase TiO₂:PPy nanocomposites with controlled morphology using low energy. The Fourier transform infrared (FT-IR) bands of the crystalline nanocomposites exhibited a shift with respect to neat components, which was attributed to the strong interaction between the secondary amine groups (N–H) of PPy and the oxygen from TiO₂. The acceptable absorption in the visible region (λ_max = 670 nm) indicates that these nanocomposites are good candidates for harvesting energy in solar cells. Devices based on these nanocomposites were built to evaluate their electrical properties. An increase in the photocurrent was observed for the devices prepared with the nanocomposites from the UT-assisted synthesis.     

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.     

Electronic energy alignment at the PbSe quantum dots/ZnO(101̅0) interface

A number of solar energy conversion strategies depend on exciton dissociation across interfaces between semiconductor quantum dots (QDs) and other electron or hole conducting materials. A critical factor governing exciton dissociation and charge transfer in these systems is the alignment of electronic energy levels across the interface. We probe interfacial electronic energy alignment in a model system, sub-monolayer films of PbSe QDs adsorbed on single crystal ZnO(101?0) surfaces using ultraviolet photoemission spectroscopy. We establish electronic energy alignment as a function of quantum dot size and surface chemistry. We find that replacing insulating oleic-acid capping molecules on the QDs by the short hydrazine or ethanedithiol molecules results in pinning of the valence band maximum (VBM) of QDs to ZnO substrate states, independent of QD size. This is in contrast to similar measurements on TiO₂(110) where the alignment of the PbSe QD VBM to that of the TiO₂ substrate depends on QD size. We interpret these findings as indicative of strong electronic coupling of QDs with the ZnO surface but less with the TiO₂ surface. Based on the measured energy alignment, we predict that electron injection from the 1s_e level in photo-excited PbSe QDs to ZnO can occur with small QDs (diameter ? = 3.4 nm), but energetically unfavorably for larger dots (? = 6.7 nm). In the latter, hot electrons above the 1s_e level are necessary for interfacial electron injection.     

One step ultrafast mechanosynthesis of nanocrystalline cubic Ti0.9Al0.1B and its microstructure evolution

Nanocrystalline single phase cubic Ti_0.9Al_0.1B has been prepared at room temperature in a minimum duration of 4 h by mechanical alloying the stoichiometric mixture of Ti, Al and B powders in a high energy planetary ball mill under argon atmosphere. The Rietveld's structure refinement of X-ray diffraction data reveals that cubic Ti–Al–B phase is initiated just after 1 h of milling and at the same time α-Ti (hcp) phase partially transforms to metastable β-Ti (bcc) phase. In the course of milling, ordered Ti–Al–B lattice gradually transforms to a distorted state and the degree of distortion increases with milling time up to 15 h. The formation of cubic Ti_0.9Al_0.1B is also confirmed from the selected area electron diffraction (SAED) pattern. Microstructure characterization by high resolution transmission electron microscopy (HRTEM) reveals that Ti–Al–B nanoparticles are isotropic in nature with average particle size ~4.5 nm and is in good agreement with the value obtained from the Rietveld analysis of X-ray diffraction data.     

Effect of ball milling time on the substitution of carbon in glucose doped MgB2 superconductors: Dispersion behavior of glucose

The effect of the ball milling time (BMT) on the substitution of the carbon in the glucose doped MgB₂ samples is investigated here. Using in situ solid state reaction, four different doped samples of Mg(B_.98C_.02)₂ were prepared by mixing powders of Mg, boron and glucose for 2 h, 4 h, 8 h and 12 h using planetary ball milling. A reference sample of un-doped MgB₂ was also prepared under same conditions. The particle size distribution of the un-reacted samples show a decrease in the particle size as the BMT is increased. Both the average particle size as well as the standard deviation show a substantial decrease with the increase in the milling time up to 8 h. After 8 h, the size reduction is rather insignificant. From the XRD data, the crystallite size of the doped MgB₂ computed using the Scherrer formula was found to decrease with the increasing BMT, showing a saturation level after 8 h of the milling time. TEM images also confirm the crystallite size obtained from the XRD data. The substitution of the C in the MgB₂ lattice, measured from the change in the c/a ratio, increases with increasing BMT. The maximum carbon substitution is achieved at approximately 8 h of BMT. Moreover, a systematic enhancement of the residual resistivity and a decrease in T_C with an increasing BMT further confirms a progressive substitution of the carbon in the MgB₂. These results suggest that a minimum ball milling time is necessary to disperse the glucose uniformly for a maximum substitution of nano C in the B plane of MgB₂ lattice. The optimum BMT is found to be 8 h. Thus, the decrease in the particle size due to the ball milling enhances the dispersion of the constituent materials thereby favoring a greater substitution of the dopant in the MgB₂ during the solid-state reaction.     

Microstructure characterization of mechanosynthesized nanocrystalline NiFe2O4 by Rietveld's analysis

Nanocrystalline nickel ferrite (NiFe₂O₄) is synthesized at room temperature by high-energy ball milling the stoichiometric mixture of (1:1 mol%) of NiO and α-Fe₂O₃ powders. The structural and microstructural evolution of NiFe₂O₄ caused by milling is investigated by X-ray powder diffraction. The relative phase abundance, particle size, r.m.s. strain, lattice parameter changes of different phases have been estimated employing Rietveld structure refinement analysis of X-ray powder diffraction data. Particle size and content (wt%) of both NiO and α-Fe₂O₃ phases reduce rapidly with increasing milling time and a significant amount of nanocrystalline NiFe₂O₄ is formed within 1 h of ball milling. Particle sizes of all the phases reduce to ∼10 nm within 5 h of milling and remain almost unchanged with increasing milling time up to 20 h. Lattice parameter of cubic NiO decreases linearly with increasing milling time, following the Vegard's law of solid-solution alloy. A continuous decrease in lattice parameter of cubic NiFe₂O₄ phase clearly suggests that smaller Ni atoms have occupied some of the vacant oxygen sites of ferrite lattice. Cation distribution both in octahedral and tetrahedral sites changes continuously with milling time and the normal spinel lattice formed at early stage of milling, transforms to inverse spinel lattice in the course of milling. High-resolution transmission electron microscope (HRTEM) micrographs of 11 h milled sample corroborates the findings of X-ray profile analysis.     

Hydrothermal synthesis of TiO2 nanocrystals in different basic pHs and their applications in dye sensitized solar cells

In this research TiO₂ nanocrystals with sizes about 11–70 nm were grown by hydrothermal method. The process was performed in basic autoclaving pH in the range of 8.0–12.0. The synthesized anatase phase TiO₂ nanocrystals were then applied in the phtoanode of the dye sensitized solar cells. It was shown that the final average size of the nanocrystals was larger when the growth was carried out in higher autoclaving pHs. The photoanodes made of TiO₂ nanocrystals prepared in the pHs of 8.0 and 9.0 represented low amounts of dye adsorption and light scattering. The performance of the corresponding dye sensitized solar cells was also not acceptable. Nevertheless, the energy conversion efficiency was better for the state of pH of 9.0. For the photoanodes made of TiO₂ nanocrystals prepared at autoclaving pH of 10.0, the dye adsorption and light scattering were quite higher. The photovoltaic characteristics of the best cell in this state were 15.25 mA/cm², 740 mV, 0.6 and 6.8% for the short-circuit current density, open-circuit voltage, fill factor and efficiency, respectively. The photoanodes composed of TiO₂ nanocrystals prepared in autoclaving pHs of 11.0 and 12.0 demonstrated lower amount of dye adsorption and higher light scattering. This was quite considerable for the state of pH of 12.0. The energy conversion efficiencies were consequently decreased compared to that of the pH of 10.0. The optimum situation was finally discussed based on the nanocrystals size and its influence on the sensitization and light harvesting efficiency.     

Optimal ablation of fluorine-doped tin oxide (FTO) thin film layers adopting a simple pulsed Nd:YAG laser with TEM00 mode

In material processing, a laser system with optimal laser parameters has been considered to be significant. Especially, the laser ablation technology is thought to be very important for fabricating a dye-sensitized solar cell (DSSC) module with good quality. Moreover, the TEM₀₀ mode laser beam is the most dominant factor to decide the incident photon to current conversion efficiency (IPCE) characteristics. In order to get the TEM₀₀ mode, a pin-hole is inserted within a simple pulsed Nd:YAG laser resonator. And the spatial field distribution is measured by using three pin-hole diameters of 1.6, 2.0 and 4.0 mm, respectively. At that moment, each case has the same laser beam energy by adjusting the discharge voltage and pulse per second (pps). From those results, it is known that the pin-hole size of 1.6 mm has the perfect TEM₀₀ mode. In addition, at the charging voltage of 1000 V, 10 pps, the feeding speed of 6.08 mm/s and the overlapping rate (OL) of 62%, the scanning electron microscope (SEM) photograph of fluorine-doped tin oxide (FTO) thin film layers shows the best ablation trace.     

Preparation of silver nanowires coated with TiO2 using chemical binder and their applications as photoanodes in dye sensitized solar cell

In this study, the core–shell structured Ag@TiO₂ wire was prepared for application to dye-sensitized solar cell (DSSC). The Ag nanowire, having an excellent electrical conductivity, was synthesized by using the facile microwave-assisted polyol reduction process. The diameter and length of Ag wires were 40–50 nm and 20–30 μm, respectively, and the face-centered cubic silver crystal structure was obtained. In the presence of 2-mercaptoethanol as a chemical binder, the entire surface of Ag wire was coated with the TiO₂ shell, which has thickness of 20 nm, through solvothermal method. The crystalline structure of TiO₂ shell was the anatase phase possessing an advantage to achieve the high efficiency in DSSC. The core–shell structured Ag@TiO₂ wire exhibited the high thermal stability. The high conversion efficiency (5.56%) in fabricated device with Ag@TiO₂ electrode, which is about 10% higher than reference cell, was achieved by enhancement of short-current density (J_sc) value. The core–shell structured Ag@TiO₂ wire could effectively reduce the charge recombination through the contribution to electron shortcut for improvement in the electron transfer rate and lifetime.