TiO2 Nanospheres: A Facile Size‐Tunable Synthesis and Effective Light‐Harvesting Layer for Dye‐Sensitized Solar Cells

A facile route to synthesize amorphous TiO₂ nanospheres by a controlled oxidation and hydrolysis process without any structure‐directing agents or templates is presented. The size of the amorphous TiO₂ nanospheres can be easily turned from 20 to 1500 nm by adjusting either the Ti species or ethanol content in the reaction solution. The phase structure of nanospheres can be controlled by hydrothermal treatment. The TiO₂ nanospheres show excellent size‐dependent light‐scattering effects and can be structured into a light‐harvesting layer for dye‐sensitized solar cells with a quite high power conversion efficiency of 9.25 %.     

Nd‐Doped TiO2 Nanorods: Preparation and Application in Dye‐Sensitized Solar Cells

Monodispersed Nd‐doped TiO₂ nanorods (20 nm×2 nm) were synthesized by solvothermal methods and characterized by TEM, XRD, and EDS. Application of the nanorods for modifying conventional photoanodes in dye‐sensitized solar cells (DSSCs) was investigated. Data show that, after modification, an enhancement of the incident‐photon‐to‐current conversion efficiency (IPCE) in the whole range of visible light was observed and an increase of 33.3 % for overall conversion efficiency was achieved. Our mechanistic proposal is that Nd ions doped on TiO₂ nanorods to some extent enhance the injection of excited electrons and decrease the recombination rate of the injected electrons.     

Mesostructured Dye‐Doped Titanium Dioxide for Micro‐Optoelectronic Applications

Optically transparent, mesostructured titanium dioxide thin films were fabricated using an amphiphilic poly(alkylene oxide) block copolymer template in combination with retarded hydrolysis of a titanium isopropoxide precursor. Prior to calcination, the films displayed a stable hexagonal mesophase and high refractive indices (1.5 to 1.6) relative to mesostructured silica (1.43). After calcination, the hexagonal mesophase was retained with surface areas >300 m² g^?1. The dye Rhodamine 6G (commonly used as a laser dye) was incorporated into the copolymer micelle during the templating process. In this way, novel dye‐doped mesostructured titanium dioxide films were synthesised. The copolymer not only directs the film structure, but also provides a solubilizing environment suitable for sustaining a high monomer‐to‐aggregate ratio at elevated dye concentrations. The dye‐doped films displayed optical thresholdlike behaviour characteristic of amplified spontaneous emission. Soft lithography was successfully applied to micropattern the dye‐doped films. These results pave the way for the fabrication and demonstration of novel microlaser structures and other active optical structures. This new, high‐refractive index, mesostructured, dye‐doped material could also find applications in areas such as optical coatings, displays and integrated photonic devices.     

Hierarchically Structured ZnO Nanorods as an Efficient Photoanode for Dye‐Sensitized Solar Cells

Hierarchical ZnO nanorods composed of interconnected nanoparticles, which were synthesized by controlling precursor concentrations in a solvothermally assisted process, were exploited as photoanodes in dye‐sensitized solar cells (DSCs). The as‐prepared hierarchical nanorods showed greatly enhanced light scattering compared to ZnO nanoparticles for boosting light harvesting while maintaining sufficient dye‐adsorption capability. The charge‐transfer characteristics were studied by electrochemical impedance measurements, and reduced electron recombination and longer electron lifetime were observed for the ZnO nanorods. Photovoltaic characterization demonstrated that DSCs utilizing the hierarchical nanorods significantly improved the overall conversion efficiency by 34 % compared to nanoparticle‐based DSCs.     

Nitrogen‐Doped Carbon Nanotube‐Based Bilayer Thin Film as Transparent Counter Electrode for Dye‐Sensitized Solar Cells (DSSCs)

Carbon nanotubes (CNTs) have been widely considered as one of the promising candidates for replacing fluorine‐doped tin oxide (FTO)/platinum (Pt) electrodes to reduce the fabrication cost of dye‐sensitized solar cells (DSSCs). Here, we report that a bilayer transparent film containing N‐doped CNTs (which are highly catalytic) and normal CNTs (which are highly conductive) as a counter electrode in DSSCs results in efficiencies up to 2.18 %, yet still maintains a good transparency with a transmittance of approximately 57 % at 550 nm.     

The Origin of Higher Open‐Circuit Voltage in Zn‐Doped TiO2 Nanoparticle‐Based Dye‐Sensitized Solar Cells

Zn‐doped anatase TiO₂ nanoparticles are synthesized by a one‐step hydrothermal method. Detailed electrochemical measurements are undertaken to investigate the origin of the effect of Zn doping on the performance of dye‐sensitized solar cells (DSSCs). It is found that incorporation of Zn²⁺ into an anatase lattice elevates the edge of the conduction band (CB) of the photoanodes and the Fermi level is shifted toward the CB edge, which contributes to the improvement in open‐circuit voltage (V_OC). Charge‐density plots across the cell voltage further confirm the increase in the CB edge in DSSCs directly. Photocurrent and transient photovoltage measurements are employed to study transport and recombination dynamics. The electron recombination is accelerated at higher voltages close to the CB edge, thus leading to a negative effect on the V_OC.     

A p‐Type NiO‐Based Dye‐Sensitized Solar Cell with an Open‐Circuit Voltage of 0.35 V

In tandem : Employing a molecular dyad and a cobalt‐based electrolyte gives a threefold‐increase in open‐circuit voltage (V_OC) for a p‐type NiO device (V_OC=0.35 V), and a fourfold better energy conversion efficiency. Incorporating these improvements in a TiO₂/NiO tandem dye‐sensitized solar cell (TDSC), results in a TDSC with a V_OC=0.91 V (see figure; CB=conductance band, VB= valence band).

     

非金属元素掺杂纳米二氧化钛

二氧化钛在光电转化、光催化等众多领域具有重要的应用价值,但较宽的禁带宽度和较低的电子传递效率导致其光利用率较低.离子掺杂和纳米化是改变其能带结构、提高电子传输能力的有效策略,根据掺杂离子的性质,可分为金属离子掺杂和非金属元素掺杂.与传统二氧化钛相比,纳米二氧化钛具有特殊的表面效应和粒度效应,其化学活性、耐热性等都强于传...     

Photoanode Based on Chain‐Shaped Anatase TiO2 Nanorods for High‐Efficiency Dye‐Sensitized Solar Cells

Anatase TiO₂ nanorods with large specific surface areas and high crystallinity have been synthesized by surfactant‐free hydrothermal treatment of water‐soluble peroxotitanium acid (PTA). X‐ray diffraction and TEM analysis showed that all TiO₂ nanorods derived from PTA in different hydrothermal processes were in the anatase phase, and high aspect ratio TiO₂ nanorods with chain‐shaped structures were formed at 150 °C for 24 h by oriented growth. The nanorods were fabricated as photoanodes for high‐efficiency dye‐sensitized solar cells (DSSCs). DSSCs fabricated from the chain‐shaped TiO₂ nanorods gave a highest short‐circuit current density of 14.8 mA cm^?2 and a maximum energy conversion efficiency of 7.28 %, as a result of the presence of far fewer surface defects and grain boundaries than are present in commercial P25 TiO₂ nanoparticles. Electrochemical impedance spectroscopy also confirmed that DSSCs based on the TiO₂ nanorods have enhanced electron transport properties and a long electron lifetime.     

Transparent Metal Selenide Alloy Counter Electrodes for High‐Efficiency Bifacial Dye‐Sensitized Solar Cells

The exploration of cost‐effective and transparent counter electrodes (CEs) is a persistent objective in the development of bifacial dye‐sensitized solar cells (DSSCs). Transparent counter electrodes based on binary‐alloy metal selenides (M‐Se; M=Co, Ni, Cu, Fe, Ru) are now obtained by a mild, solution‐based method and employed in efficient bifacial DSSCs. Owing to superior charge‐transfer ability for the I^?/I₃^? redox couple, electrocatalytic activity toward I₃^? reduction, and optical transparency, the bifacial DSSCs with CEs consisting of a metal selenide alloy yield front and rear efficiencies of 8.30 % and 4.63 % for Co_0.85Se, 7.85 % and 4.37 % for Ni_0.85Se, 6.43 % and 4.24 % for Cu_0.50Se, 7.64 % and 5.05 % for FeSe, and 9.22 % and 5.90 % for Ru_0.33Se in comparison with 6.18 % and 3.56 % for a cell with an electrode based on pristine platinum, respectively. Moreover, fast activity onset, high multiple start/stop capability, and relatively good stability demonstrate that these new electrodes should find applications in solar panels.     

Molecular Design Principle of All‐organic Dyes for Dye‐Sensitized Solar Cells

All‐organic dyes have shown promising potential as an effective sensitizer in dye‐sensitized solar cells (DSSCs). The design concept of all‐organic dyes to improve light‐to‐electric‐energy conversion is discussed based on the absorption, electron injection, dye regeneration, and recombination. How the electron‐donor–acceptor‐type framework can provide better light harvesting through bandgap‐tuning and why proper arrangement of acceptor/anchoring groups within a conjugated dye frame is important in suppressing improper charge recombination in DSSCs are discussed. Separating the electron acceptor from the anchoring unit in the donor–acceptor‐type organic dye would be a promising strategy to reduce recombination and improve photocurrent generation.     

Effects of Dye‐Adsorption Solvent on the Performances of the Dye‐Sensitized Solar Cells Based on Black Dye

The effects of the dye‐adsorption solvent on the performances of the dye‐sensitized solar cells (DSSCs) based on black dye have been investigated. The highest conversion efficiency (10.6 %) was obtained in the cases for which 1‐PrOH and the mixed solvent of EtOH and tBuOH (3:1 v/v) were employed as dye‐adsorption solvents. The optimized value for the dielectric constant of the dye‐adsorption solvent was found to be around 20. The DSSCs that used MeOH as a dye‐adsorption solvent showed inferior solar‐cell performance relative to the DSSCs that used EtOH, 1‐PrOH, 2‐PrOH, and 1‐BuOH. Photo‐ and electrochemical measurements of black dye both in solution and adsorbed onto the TiO₂ surface revealed that black dye aggregates at the TiO₂ surface during the adsorption process in the case for MeOH. Both the shorter electron lifetime in the TiO₂ photoelectrode and the greater resistance in the TiO₂–dye–elecrolyte interface, attributed to the dye aggregation at the TiO₂ surface, cause the decrease in the solar‐cell performance of the DSSC that used MeOH as a dye adsorption solvent.     

Structural Control of Hierarchically‐Ordered TiO2 Films by Water for Dye‐Sensitized Solar Cells

A facile way of controlling the structure of TiO₂ by changing the amount of water to improve the efficiency of dye‐sensitized solar cells (DSSCs) is reported. Hierarchically ordered TiO₂ films with high porosity and good interconnectivity are synthesized in a well‐defined morphological confinement arising from a one‐step self‐assembly of preformed TiO₂ (pre‐TiO₂) nanocrystals and a graft copolymer, namely poly(vinyl chloride)‐g‐poly(oxyethylene methacrylate). The polymer–solvent interactions in solution, which are tuned by the amount of water, are shown to be a decisive factor in determining TiO₂ morphology and device performance. Systematic control of wall and pore size is achieved and enables the bifunctionality of excellent light scattering properties and easy electron transport through the film. These properties are characterized by reflectance spectroscopy, incident photon‐to‐electron conversion efficiency, and electrochemical impedance spectroscopy analyses. The TiO₂ photoanode that is prepared with a higher water ratio, [pre‐TiO₂]:[H₂O]=1:0.3, shows a larger surface area, greater light scattering, and better electron transport, which result in a high efficiency (7.7 %) DSSC with a solid polymerized ionic liquid. This efficiency is much greater than that of commercially available TiO₂ paste (4.0 %).