Effects of electrode film modifications on the open-circuit photovoltage in enhanced dye-sensitized solar cells

In this study, the open-circuit photovoltage (V _oc) decay technique was used to investigate the relationship between the electrode film morphology and the open-circuit photovoltage. Results indicate that dye-sensitized solar cells (DSCs) based on ordered arrays of TiO₂ nanostructures (100 nm external diameters and 20–50 nm internal diameters) generally show higher open-circuit photovoltage (V _oc) values than those based on sintered TiO₂ nanoparticles (20–40 nm diameters). In particular, cells based on thick nanotubules (wall thickness ≥ 45 nm in our research) and on nanorods (100 nm diameters) show particularly high V _oc values, indicating slow recombination kinetics under open-circuit conditions. It can be argued that the nanorods and the thick nanotubules act like singles crystals and therefore the injected electrons in the inner TiO₂ molecules are shielded from holes in the electrolyte under open-circuit conditions. The open-circuit recombination time constant of electrons accumulated in the TiO₂ conduction band is therefore prolonged and resulting in high V _oc values.     

Comparison of the performances of dye-sensitized solar cells based on different TiO2 electrode nanostructures

This article reports on the performances of dye-sensitized solar cells based on three different working electrode structures, i.e., (i) sintered TiO₂ nanoparticles (20–40 nm diameters), (ii) ordered arrays of TiO₂ nanotubules (150 nm external diameters and 80 nm internal diameters), and (iii) ordered arrays of TiO₂ nanorods (150 nm diameters). Even though the highest short-circuit current density was achieved with systems based on TiO₂ nanotubules, the most efficient cells were those based on ordered arrays of TiO₂ nanorods. This is probably due to higher open-circuit photovoltage values attained with TiO₂ nanorods than with TiO₂ nanotubules. The nanorods are thicker than the nanotubules and therefore the injected electrons, stored in the trap states of the inner TiO₂ molecules, are shielded from recombination with holes in the redox electrolyte at open circuit. The high short-circuit photocurrent densities seen in the ordered TiO₂ systems can be explained by the fact that, as opposed to the sintered nanoparticles, the parallel and vertical orientation of the ordered nanostructures provide well-defined electrons percolation paths thus significantly reduce the diffusion distance and time constant.     

Rapid microwave-assisted hydrothermal synthesis of Bi12TiO20 hierarchical architecture with enhanced visible-light photocatalytic activities

Flower-like Bi₁₂TiO₂₀ hierarchical nanostructures composed of numerous nanobelts were synthesized at 180 °C within 1 h by a microwave-assisted hydrothermal method in the presence of cetyltrimethylammonium bromide (CTAB) for the first time. The as-prepared products were characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and ultraviolet–visible (UV–vis) absorption spectroscopy. Furthermore, the hierarchical Bi₁₂TiO₂₀ nanostructures exhibited higher photocatalytic activities in the degradation of Rhodamine B under visible-light irradiation than that of the samples prepared without CTAB. In addition, the role of CTAB cationic surfactant has been investigated thoroughly and a possible mechanism is proposed.     

Synthesis and photocatalytic activity of polyaniline–TiO<Subscript>2</Subscript> composites with bionic nanopapilla structure

Polyaniline (PANI)–TiO₂ nanocomposites possessing both nano and microscale structures were prepared through a facile hydrothermal route in the presence of PANI. The nanopapilla particles were characterized by scanning electron microscopy, transmission electron microscopy, energy dispersive X-ray analysis, X-ray photoelectron spectra, X-ray diffraction, FTIR spectra, UV–Vis spectroscopy, and N₂ adsorption analysis, etc. The results show that the composites possess both nano and microscale structures. The TiO₂ nanorods are dispersed on PANI with one end fixed to the surface. The photocatalytic properties of the powders were verified by the photodegradation of gaseous acetone under UV (λ = 254 nm) and visible-light irradiation (λ > 400 nm). In fact, the photocatalytic effects exhibited by the composite particles were superior to that of pure TiO₂ and P25 samples. This excellent behavior is attributed to the structural features of PANI–TiO₂ microspheres and the synergistic effect between PANI and TiO₂ which facilitates a larger amount of surface active sites. This in turn causes a faster charge separation and slower charge recombination which results in a more efficient decomposition of gaseous pollutants.     

Influence of pH on the preparation of dispersed Ag–TiO<Subscript>2</Subscript> nanocomposite

In this paper, data concerning the effect of pH on the morphology of Ag–TiO₂ nanocomposite during photodeposition of Ag on TiO₂ nanoparticles is reported. TiO₂ nanoparticles prepared by sol–gel method were coated with Ag by photodeposition from an aqueous solution of AgNO₃ at various pH levels ranging from 1 to 10 in a titania sol, under UV light. The as-prepared nanocomposite particles were characterized by UV–vis absorption spectroscopy, transmission electron microscopy (TEM), X-ray diffraction (XRD), and N₂ adsorption/desorption method at liquid nitrogen temperature (−196 °C) from Brunauer–Emmett–Teller (BET) measurements. It is shown that at a Ag loading of 1.25 wt.% on TiO₂, a high-surface area nanocomposite morphology corresponding to an average of one Ag nanoparticle per titania nanoparticle was achieved. The diameter of the titania crystallites/particles were in the range of 10–20 nm while the size of Ag particles attached to the larger titania particles were 3 ± 1 nm as deduced from crystallite size by XRD and particle size by TEM. Ag recovery by photo harvesting from the solution was nearly 100%. TEM micrographs revealed that Ag-coated TiO₂ nanoparticles showed a sharp increase in the degree of agglomeration for nanocomposites prepared at basic pH values, with a corresponding sharp decrease in BET surface area especially at pH > 9. The BET surface area of the Ag–TiO₂ nanoparticles was nearly constant at around a value of 140 m² g⁻¹ at all pH from 1–8 with an anomalous maximum of 164 m² g⁻¹ when prepared from a sol at pH of 4, and a sharp decrease to 78 m² g⁻¹ at pH of 10.     

Dispersion of electro-optic coefficients in sillenite crystals

The photorefractive crystals of the sillenite family (Bi₁₂SiO₂₀ or BSO, Bi₁₂GeO₂₀ or BGO, and Bi₁₂TiO₂₀ or BTO) that belong to the cubic 23 point group are optically active, and exhibit the piezoelectric, elasto-optic, electro-optic and electrogyration effect. In this paper we measure the dispersion of the electro-optic coefficient for all the crystals of the sillenite family in the visible spectral range (500–800 nm). For this we measure by ellipsometry the polarization properties of a beam transmitted in the transverse configuration under the action of an externally applied field. The experimental data are fitted with an analytical expression of the beam polarization to find the electro-optic coefficient. The results show a normal dispersion of the electro-optic coefficient in all three sillenite crystals, similarly to other electro-optic crystals.     

A new one-step synthesis method for coating multi-walled carbon nanotubes with iron oxide nanorods

A facile solution-chemical method has been developed to be capable of covering a multiwalled carbon nanotube (MWNTs) with iron oxide nanorods without using any bridging species. MWNTs in this composite were decorated randomly by α-Fe₂O₃ nanorods with diameters in the range of 3–5 nm and lengths of 15–30 nm. The formation route to anchor α-Fe₂O₃ nanorods onto MWNTs was proposed as the intercalation and adsorption of iron ions onto the wall of MWNTs, followed by the nucleation and growth of α-Fe₂O₃ nanorods. α-Fe₂O₃/MWNTs nanocomposites show specific high Brunauer–Emmett–Teller surface areas. The photocatalytic activity experiment indicated that the prepared α-Fe₂O₃/MWNTs nanocomposites exhibited a higher photocatalytic activity for the photocatalytic decolorization of rhodamine B aqueous solution under the visible-light illumination than the single phase α-Fe₂O₃ samples. This methodology made the synthesis of MWNTs-nanorods composites possible and may be further extended to prepare more complicated nanocomposites based on MWNTs for technological applications.     

Linear photogalvanic current excited in sillenite crystals by femtosecond laser pulses

We observe electric pulses generated in sillenite crystals (Bi₁₂SiO₂₀ and Bi₁₂TiO₂₀) by 100-fs laser pulses at the wavelength of 400 nm (below the band gaps of both crystals). The peak value of the current pulses scales linearly with the intensity of laser pulses up to ∼45 GW/cm². The direction of the induced current depends on the polarization state of the laser pulse. This polarization dependence and features of the current detection via charge accumulation at the sample electrodes allow us to conclude that the electric pulses are generated due to the linear photogalvanic effect.     

Efficient visible light-induced photoelectrocatalytic degradation of rhodamine B by polyaniline-sensitized TiO<Subscript>2</Subscript> nanotube arrays

Self-organized anodic TiO₂ nanotube arrays were sensitized with polyaniline by a simple electrodeposite method. The morphological and structural properties studied by scanning electron microscopy and fourier transform infrared spectroscopy reveal the successful deposition of polyaniline on the nanotube arrays. The polyaniline-sensitized TiO₂ nanotube arrays exhibit a distinguishable red shift on the absorption spectrum. Electrochemical impedance investigation attested to a significant improvement of the interfacial electron-transfer kinetics for promoted electron–hole effective separation. The as-prepared samples showed a high efficiency for the photoelectrocatalytic degradation of rhodamine B under visible-light irradiation (λ > 400 nm). The enhanced photoelectrocatalytic activity could be attributed to the extended absorption in the visible-light region by the polyaniline and the effective separation of photogenerated carriers driven by the photoinduced potential difference generated at the polyaniline/TiO₂ nanotube arrays interface.     

Polarization effects associated with two-wave interaction in bismuth titanate and bismuth silicate crystals

Polarization effects associated with two-wave interaction in Bi₁₂TiO₂₀ and Bi₁₂SiO₂₀ crystals are investigated. The experimental data are subjected to the required theoretical analysis. A new procedure is proposed for determining the density of acceptor centers (N _A) in photorefractive crystals. The values of N _A obtained by this procedure are in good agreement with published data. Fiz. Tverd. Tela (St. Petersburg) 39, 1990–1994 (November 1997)     

TiO<Subscript>2</Subscript> Nanorod Arrays Sensitized with CdS Quantum Dots for Solar Cell Applications: Effects of Rod Geometry on Photoelectrochemical Performance

CdS quantum dot (QD) sensitized TiO₂ nanorod array (NRA) film electrodes with different rod geometries were fabricated via a solvothermal route followed by a sequentialchemical bath deposition (S-CBD) process. By controlling the solution growth conditions, the rod geometries, especially the tip structures, of the TiO₂ NRAs were tuned. The results indicated that the vertically aligned hierarchical NRAs possessed conically shaped tip geometry, which was favorable for film electrodes due to the reduced reflectance, enhanced light harvesting, fast charge-carrier separation and transfer, suppression of carrier recombination, sufficient electrolyte penetration and subsequent efficient QD assembly. CdS QD sensitized TiO₂ NRA film electrodes with tapered tips exhibited an enhanced photoelectrochemical (PEC) performance, a photocurrent intensity of 5.13 mA/cm² at a potential of 0 V vs. saturated calomel electrode, an open-circuit potential of −0.68 V vs. saturated calomel electrode and an incident photon to current conversion efficiency (IPCE) of 22% in the visible-light region from 400 to 500 nm. The effects of rod geometry on the optical absorption, reflectance, hydrophilic properties and PEC performance of bare TiO₂ and CdS QD sensitized TiO₂ NRA film electrodes were investigated. The mechanism of charge-carrier generation and transfer in these CdS QD sensitized solar cells based on vertically aligned TiO₂ nanorods is discussed.     

Structure, ferroelectric and piezoelectric properties of?(Bi0.98?xLa0.02Na1?x)0.5BaxTiO3 lead-free ceramics

Lead-free (Bi_0.98−x La_0.02Na_1−x )_0.5Ba _x TiO₃ ceramics have been prepared by an ordinary sintering technique and their structure, ferroelectric and piezoelectric properties have been studied. The results of X-ray diffraction show that La²⁺ and Ba²⁺ diffuse into the Bi_0.5Na_0.5TiO₃ lattices to form a new solid solution with a pure perovskite structure, and a morphotropic phase boundary (MPB) exists at 0.04<x<0.10. Compared with pure Bi_0.5Na_0.5TiO₃ ceramics, the (Bi_0.98−x La_0.02Na_1−x )_0.5Ba _x TiO₃ ceramics possess much smaller coercive field E _c and larger remanent polarization P _r. Because of the low E _c (3.38 kV/mm), large P _r (46.2 μC/cm²) and the formation of the MPB of rhombohedral and tetragonal phases, the piezoelectric properties of the ceramics are significantly enhanced at x=0.06: d ₃₃=181 pC/N and k _p=36.3%. The depolarization temperature T _d reaches a minimum value near the MPB. The ceramics exhibit relaxor characteristic, which is probably a result from the cation disordering in the 12-fold coordination sites. The temperature dependences of the ferroelectric and dielectric properties suggest that the ceramics may contain both polar and non-polar regions at the temperatures above T _d.     

Synthesis and photocatalytic property of N-doped TiO2 nanorods and nanotubes with high nitrogen content

Nano N-doped TiO₂ nanotubes were fabricated by hydrothermally treating N-doped TiO₂ nanorods in a 8 M NaOH solution at 110 °C for 20 h. The N-doped TiO₂ nanorods were synthesized by a solvothermal process with precursor solution containing titanium sulfate, urea, and dichloroethane. The N-doped TiO₂ nanorods and nanotubes were characterized with X-ray diffraction, transmission electron microscopy, and UV-vis spectrophotometry. The nitrogen contents of the N-doped TiO₂ nanorods and nanotubes were reached to high values of 36.9 at.% and 25.7 at.%, respectively. The nitrogen doping narrowed the band gap of the N-doped TiO₂ nanorods and nanotubes and introduced indirect band gap to the powders, which respectively extended the absorption edge to visible light and infrared region. The nanotubes showed larger specific surface area and greater degradation efficiency to methyl orange than the nanorods.     

Hydroxyethyl cellulose-assisted hydrothermal synthesis of Bi2S3 urchin-like colonies

Orthorhombic Bi₂S₃ with different morphologies was successfully synthesized by the acid-catalyst hydrothermal reactions of bismuth nitrate (Bi(NO₃)₃) and thiourea (NH₂CSNH₂) solutions containing different amounts of hydroxyethyl cellulose (HEC). Phase, morphologies, and optical properties were characterized by X-ray diffraction, selected area electron diffraction, scanning and transmission electron microscopy, and ultraviolet-visible spectroscopy. The products, hydrothermally synthesized in the HEC-free, 0.25 g HEC-added, 0.5 g HEC-added and 1.00 g HEC-added solutions, were respectively proved to be orthorhombic Bi₂S₃ irregular nanorods, complete urchin-like colonies of regular nanorods, incomplete urchin-like colonies of regular nanorods, and highly crystalline regular nanorods growing along the [001] direction. Tauc band gaps of the orthorhombic Bi₂S₃ nanorods, synthesized in the HEC-free, 0.25 g HEC-added, and 1.00 g HEC-added solutions were determined to be 3.0, 1.75 and 1.8 eV, respectively. Formation mechanism of orthorhombic Bi₂S₃ nanorods, synthesized in the HEC-free and HEC-added solutions, was also discussed at great detail.     

Structure and electrical properties of Bi0.5(Na, K)0.5TiO3−BiGaO3 lead-free piezoelectric ceramics

Lead-free piezoelectric ceramics (1 − x − y)Bi_0.5Na_0.5TiO₃−xBi_0.5K_0.5TiO₃− yBiGaO₃ have been fabricated by an ordinary sintering technique, and their structure and electrical properties and depolarization temperature have been studied. The results of X-ray diffraction reveal that Bi_0.5K_0.5TiO₃ and BiGaO₃ diffuse into the Bi_0.5Na_0.5TiO₃ lattices to form a new solid solution with a pure perovskite structure. An obvious change in microstructure with increasing concentration of Bi_0.5K_0.5TiO₃ and BiGaO₃ was observed. The piezoelectric constant d₃₃ and the electromechanical coupling factor k_p of the ceramics attain maximum values of 165 pC/N and 0.346 at y = 0.01(x = 0.18) and x = 0.21(y = 0.01), respectively. The temperature dependence of dielectric constant indicates an obvious relaxor characteristic with strong frequency dependence of dielectric constant. The depolarization temperature decreased with increasing content of BiGaO₃ and first decreases and then increases with increasing amount of Bi_0.5K_0.5TiO₃.     

Synthesis and nanostructural investigation of TiO<Subscript>2</Subscript> nanorods doped by SiO<Subscript>2</Subscript>

TiO₂ Nano rods can be used as dye-sensitized solar cells, various sensors and photocatalysts. These nanorods are synthesized by a hydrothermal corrosion process in NaOH solution at 200°C using TiO₂ powder as the source material. In the present work, the synthesis of TiO₂ nanorods in anatase, rutile and Ti₇O₁₃ phases and synthesis of TiO₂ nanorods by incorporating SiO₂ dopant, using the sol–gel method and alkaline corrosion are reported. The morphologies and crystal structures of the TiO₂ nanorods are characterized using field emission scanning electron microscopy (FE-SEM), atomic force microscopy (AFM) and X-ray diffraction (XRD) study. The obtained results show not only an aggregation structure at high calcination temperatures with spherical particles but also Ti–O–Si bonds having four-fold coordination with oxygen in SiO^4 −.     

Effects of annealing temperature on the structures,ferroelectric and magnetic properties of Aurivillius Bi5Ti3FeO15 polycrystalline films

The effects of annealing temperature on the structures, ferroelectric and magnetic properties of Aurivillius layer-structured Bi₅Ti₃FeO₁₅ (BTF) films were investigated. It was found that an annealing temperature above 625 °C can lead to the appearance of Bi₄Ti₃O₁₂ (BiT) secondary phase on Pt substrates. The reduction of the grain sizes was simultaneously confirmed by X-ray diffraction and atomic force microscopy with the introduction of the BiT phase. Moreover, the remanent polarization and coercive field of the BTF films were dramatically enhanced with the introduction of the BiT phase. Improved ferromagnetism for the BTF films was demonstrated upon increasing annealing temperature. Our data indicated that the ferroelectricity strongly correlated with the growth orientation of the BTF films. Finally, the possible factors for the obvious increase of the remanent polarization and coercive field, and the possible reasons for the enhanced ferromagnetic properties were discussed with increasing annealing temperature.     

Ferroelectric properties of Bi3.25−x/3La0.75Ti3−xNbxO12 films prepared by pulsed laser deposition

Bi₄Ti₃O₁₂ (BiT), Bi_3.25La_0.75Ti₃O₁₂ (BLT), Bi_4−x/3Ti_3−xNb_xO₁₂ (BTN) and Bi_3.25−x/3La_0.75Ti_3−xNb_xO₁₂ (BLTN) thin films have been prepared by pulsed laser deposition. BTN and BLTN films exhibit a maximum in the remanent polarization P_r at a Nb content x=0.018. At this Nb content, the BLTN film has a P_r value (25 μC/cm²) that is much higher than that of BiT and a coercive field similar to that of BiT. The polarization of this BLTN film is fatigue-free up to 10⁹ switching cycles. The high fatigue resistance is mainly due to the substitution of Bi³⁺ ions by La³⁺ ions at the A site and the enhanced P_r arises largely from the replacement of Ti⁴⁺ ions by Nb⁵⁺ ions at the B site. The mechanisms behind the effects of the substitution at the two sites are discussed.     

Influence of the optical activity on hologram formation in photorefractive crystals

It is shown that dynamical hologram formation in photorefractive, optically active crystals is accompanied by polarization and energy exchange. These effects may be used like new effective holographic methods for determinations of crystal parameters and optical signal processing in real time. In self-diffraction a polarization rotation the order of degrees/cm for Bi₁₂TiO₂₀ and Bi₁₂SiO₂₀ is predicted.     

Stability of Zn–Ni–TiO<Subscript>2</Subscript> and Zn–TiO<Subscript>2</Subscript> nanocomposite coatings in near-neutral sulphate solutions

Zn–Ni–TiO₂ and Zn–TiO₂ nanocomposites were prepared by galvanostatic cathodic square wave deposition. X-ray diffraction analysis and scanning electron microscopy revealed that the occlusion of TiO₂ nanoparticles (spherical shaped with diameter between 19.5 and 24.2 nm) promotes the formation of the γ-Ni₅Zn₂₁ phase, changes the preferred crystallographic orientation of Zn from (101) and (102) planes to (002), and decreases the particle size of the metallic matrices. The stability of the nanocomposites immersed in near-neutral 0.05 mold m⁻³ Na₂SO₄ solution (pH 6.2) was investigated over 24 h. The initial open circuit potential for the Zn–Ni–TiO₂ and Zn–TiO₂ coatings were −1.32 and −1.51 V (vs. Hg/Hg₂SO₄), respectively, and changed to −1.10 and –1.49 V (vs. Hg/Hg₂SO₄) after 24 h of immersion. Data extracted from the steady state polarization curves demonstrated that the metal–TiO₂ nanocomposites have, with respect to the metal coatings, a higher corrosion potential in the case of the Zn–Ni alloy composite; a lower corrosion potential in the case of Zn-based nanocomposite albeit the predominant (002) crystallographic orientation; and a lower initial corrosion resistance due to the smaller grain size and higher porosity in the Zn–Ni–TiO₂ and Zn–TiO₂ nanocomposites. Morphological and chemical analyses showed that a thicker passive layer is formed on the surface of the Zn–Ni–TiO₂ and Zn–TiO₂ deposits. After 24 h of immersion in the sulphate solution, the Zn–Ni–TiO₂ coating has the highest corrosion stability due to the double-protective action created by the deposit’s surface enrichment in Ni plus the higher amount of corrosion products.