Co-sedimentation of TiO2 nanoparticles and polymer beads to fabricate macroporous TiO2 photoelectrodes

Dye-sensitized solar cells based on highly porous nanocrystalline TiO2 films have drawn considerable attention due to their high conversion efficiency and low production cost. TiO2 nanocrystalline electrodes have been investigated extensively as a key material. In this study, we discuss dye-sensitized solar cells based on macroporous TiO2 films using a highly-dispersed aqueous solution of TiO2 nanoparticles and polymeric particles. After drying this solution on the conducting glass substrate, the sacrificial polymer particles were removed selectively by thermal sintering at high temperatures over 400 degrees C or chemical treatment at the low temperature of 150 degrees C. This method provides the flexible control of TiO2 fractions or pore size or fabrication temperature. Also highly-dispersed TiO2 particles with a high crystallinity would provide a promising solution on low-temperature process for flexible DSSCs.     

Synthesis of SnS nanoparticles by SILAR method for quantum dot-sensitized solar cells

SnS-sensitized TiO2 electrodes were applied in quantum dot-sensitized solar cells (QDSSCs) which are environmentally more favorable than conventional Cd or Pb-chalcogenide-sensitized electrodes. SnS nanoparticles were well-distributed over the surface of TiO2 nanoparticles by the successive ionic layer adsorption and reaction (SILAR) method. Deposited SnS nanoparticles had diameter about 3 nm. Under AM1.5 irradiation with 100 mW/cm2 light intensity (at 1 sun), the energy conversion efficiency of obtained cells reached a value of 0.21% (0.25 cm2) at SILAR coating cycles of 5. In addition, the photovoltaic performance was improved by additional ZnS coating on the surface of SnS-sensitized TiO2 electrodes.     

Expanding the spectral response of a dye-sensitized solar cell by applying a selective positioning method

We have developed a facile method to position different dyes (N719 and N749) sequentially in a mesoporous TiO(2) layer through selective desorption and adsorption processes. From the selective removal of the only upper part of the first adsorbed dye, double-layered dye-sensitized solar cells have been successfully achieved without any damage to the dye. From the incident photon-to-current conversion efficiency (IPCE) measurement, the multi-layered dye-sensitized solar cell (MDSSC) was found to exhibit an expanded spectral response for the solar spectrum while maintaining the maximum IPCE value of each single-layered cell. The highest photocurrent density, 19.3 mA cm( - 2), was obtained from the MDSSC utilizing an N719/N749 bi-layered mesoporous TiO(2) film. The power conversion efficiency of 9.8% was achieved from the MDSSC, which is higher than that of single N719-or N749-based cells and cocktail-dyed (a mixture of N719 and N749) cells.     

Organized mesoporous TiO2 films exhibiting greatly enhanced performance in dye-sensitized solar cells

The Pluronic P123 templated mesoporous TiO2 film was grown via layer-by-layer deposition and characterized by a novel methodology based on the adsorption of n-pentane. Multiple-layer depositions did not perturb the mesoporous structure significantly. Our TiO2 film was sensitized by a newly developed Ru-bipyridine dye (N945) and was applied as a photoanode in dye-sensitized solar cell. The 1-microm-thick mesoporous film, made by the superposition of three layers, showed enhanced solar conversion efficiency by about 50% compared to that of traditional films of the same thickness made from randomly oriented anatase nanocrystals.     

Fabrication and properties of meso-macroporous electrodes screen-printed from mesoporous titania nanoparticles for dye-sensitized solar cells

A meso-macroporous TiO₂ film electrode was fabricated by using mesoporous TiO₂ (m-TiO₂) nanoparticles through a screen-printing technique in order to efficiently control the main fabrication step of dye-sensitized solar cells (DSSCs). The qualities of the screen-printed m-TiO₂ films were characterized by means of spectroscopy, electron microscopy, nitrogen adsorption–desorption and photoelectrochemical measurements. Under the optimal paste composition and printing conditions, the DSSC based on the meso-macroporous m-TiO₂ film electrode exhibits an energy conversion efficiency of 4.14%, which is improved by 1.70% in comparison with DSSC made with commercially available nonporous TiO₂ nanoparticles (P25, Degussa) electrode printed with a similar paste composition. The meso-macroporous structure within the m-TiO₂ film is of great benefit to the dye adsorption, light absorption and the electrolyte transportation, and then to the improvement of the overall energy conversion efficiency of DSSC.     

Direct assembly of preformed nanoparticles and graft copolymer for the fabrication of micrometer-thick, organized TiO2 films: high efficiency solid-state dye-sensitized solar cells

Solid-state dye-sensitized solar cell with 7.1% efficiency at 100 mW/cm(2) is reported, one of the highest observed for N719 dye. Excellent performance was achieved via a graft copolymer-templated, organized mesoporous TiO(2) film with a large surface area using spindle-shaped, preformed TiO(2) nanoparticles and solid polymer electrolyte.     

Hierarchical structured TiO2 photoanodes for dye-sensitized solar cells

A novel approach has been developed to fabricate hills-like hierarchical structured TiO2 photoanodes for dye-sensitized solar cells (DSSCs). The appropriately aggregated TiO2 clusters in the photoanode layer could cause stronger light scattering and higher dye loading that increases the efficiency of photovoltaic device. For detailed light-harvesting study, different molecular weights of polyvinyl alcohol (PVA) were used as binders for TiO2 nanoparticles (P-25 Degussa) aggregation. A series of TiO2 films with dissimilar morphology, the reflection of TiO2 films, absorbance of attached dye, amount of dye loading, and performance of fabricated DSSC devices, were measured and investigated. An optimized device had energy conversion efficiency of 4.47% having a higher dye loading and good light harvesting, achieving a 23% increase of short-circuit current J(sc) in DSSCs.     

Highly active nanocrystalline TiO(2) photoelectrodes

A simple method for the fabrication of highly photoactive nanocrystalline two-layer TiO(2) electrodes for solar cell applications is presented. Diluted titanium acetylacetonate has been used as a precursor for covering SnO(2):F (FTO) films with dense packed TiO(2) nanocrystallites. The nanoporous thick TiO(2) film follows the dense packed thin TiO(2) film as a second layer. For the latter, amorphous TiO(2) nanoparticles have been successfully synthesized by a sol-gel technique in an acidic environment with pH<1 and hydrothermal growth at a temperature of 200?°C. The acidic nanoparticle gel was neutralized by basic ammonia and a TiO(2) gel of pH?5 was obtained; this pH value is higher than the recently reported value of 3.1 (Park et al 2005 Adv. Mater. 17 2349-53). Highly interconnected, nanoporous, transparent and active TiO(2) films have been fabricated from the pH?5 gel. SEM, AFM and XRD analyses have been carried out for investigation of the crystal structure and the size of nanoparticles as well as the surface morphology of the films. Investigation of the photocurrent-voltage characteristics has shown improvement in cell performance along with the modification of the surface morphology, depending on pH of the TiO(2) gel. Increasing the pH of the gel from 2.1 to 5 enhanced the overall conversion efficiency of the dye-sensitized solar cells by approximately 30%. An energy conversion efficiency of 8.83% has been achieved for the cell (AM1.5, 100 mWcm(-2) simulated sunlight) compared to 6.61% efficiency in the absence of ammonia in the TiO(2) gel.     

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.     

Ultrafast Flame Annealing of TiO2 Paste for Fabricating Dye‐Sensitized and Perovskite Solar Cells with Enhanced Efficiency

Mesoporous TiO₂ nanoparticle (NP) films are broadly used as electrodes in photoelectrochemical cells, dye‐sensitized solar cells (DSSCs), and perovskite solar cells (PSCs). State‐of‐the‐art mesoporous TiO₂ NP films for these solar cells are fabricated by annealing TiO₂ paste‐coated fluorine‐doped tin oxide glass in a box furnace at 500 °C for ≈30 min. Here, the use of a nontraditional reactor, i.e., flame, is reported for the high throughput and ultrafast annealing of TiO₂ paste (≈1 min). This flame‐annealing method, compared to conventional furnace annealing, exhibits three distinct benefits. First, flame removes polymeric binders in the initial TiO₂ paste more completely because of its high temperature (≈1000 °C). Second, flame induces strong interconnections between TiO₂ nanoparticles without affecting the underlying transparent conducting oxide substrate. Third, the flame‐induced carbothermic reduction on the TiO₂ surface facilitates charge injection from the dye/perovskite to TiO₂. Consequently, when the flame‐annealed mesoporous TiO₂ film is used to fabricate DSSCs and PSCs, both exhibit enhanced charge transport and higher power conversion efficiencies than those fabricated using furnace‐annealed TiO₂ films. Finally, when the ultrafast flame‐annealing method is combined with a fast dye‐coating method to fabricate DSSC devices, its total fabrication time is reduced from over 3 h to ≈10 min.     

TiO2 nanotube membranes on transparent conducting glass for high efficiency dye-sensitized solar cells

Crack-free TiO(2) nanotube (NT) membranes were obtained by short time re-anodization of a sintered TiO(2) NT array on Ti foil, followed by dilute HF etching at room temperature. The resulting freestanding TiO(2) membranes were opaque with a slight yellow color having one end open and another end closed. The membranes were then fixed on transparent fluorine-tin-oxide glass using a thin layer of screen-printed TiO(2) nanoparticles (NPs) as a binding medium. It was found that low temperature treatment of the resulting NT/NP film under appropriate pressure before sintering at 450?°C was critical for successful fixation of the NT membrane on the NP layer. The resulting films with open-ends of NT membranes facing the NP layer (open-ends down, OED, configuration) exhibited better interfacial contact between NTs and NPs than those with closed-ends facing the NP layer (closed-ends down, CED, configuration). The cells with an OED configuration exhibit higher external quantum efficiency, greater charge transfer resistance from FTO/TiO(2) to electrolyte, and better dye loading compared to CED configurations. The solar cells with the OED configuration gave 6.1% energy conversion efficiency under AM1.5G condition when the commercial N719 was used as a dye and I(-)/I(3)(-) as a redox couple, showing the promise of this method for high efficiency solar cells.     

一维二氧化钛光阳极的制备及在染料敏化太阳能电池中的应用综述

二氧化钛由于具有合适的禁带宽度、良好的光电性能、制作工艺简单等特点,目前广泛应用于染料敏化太阳能电池中。其中,大部分光阳极主要是由纳米颗粒组成,但纳米颗粒不利于电子和空穴的分离及传输、染料敏化太阳能电池的光电转化效率的提升。因此,可采用一维纳米结构光阳极替换纳米颗粒,这有利于提升染料敏化太阳能电池的光电转化效率。一维纳米材料具有较少的晶界,可为电荷提供通道、加速电子的传输,且能有效减少空穴/电子的复合,减少电子与染料的复合,从而提高效率。同时一维二氧化钛其较大的比表面积,不仅有利于染料吸附量增加,而且能有效提高电流密度。综述了几种一维二氧化钛制备方法的最新研究进展,分析了不同制备方法对二氧化钛光阳极的能带结构、光吸收特性、染料吸附量和电子传输过程的影响,介绍了近几年一维二氧化钛在染料敏化太阳能中的应用。最后,对一维二氧化钛在染料敏化太阳能电池中的应用进行了展望。     

Wet chemical synthesis and self-assembly of SnS2 nanoparticles on TiO2 for quantum dot-sensitized solar cells

SnS2 nanoparticles were synthesized through a simple wet chemical process at room temperature. The SnS2 nanoparticles were approximately spherical in shape and had diameter about 3-4 nm. SnS2-sensitized TiO2 electrodes were fabricated by the immersion of chemically modified TiO2 to well-dispersed SnS2 solution for 72 h (i.e., self-assembly method.) SnS2-sensitized TiO2 electrodes were applied in quantum dot-sensitized solar cells (QDSSCs). Under AM1.5 irradiation with 100 mW/cm2 light intensity (at 1 sun), the short-circuit current density (J(sc)), the open-circuit voltage (V(oc)), the fill factor (FF), and the energy conversion efficiency (eta) were 0.47 mA/cm2, 0.29 V, 0.58 and 0.081%, respectively.     

Time-resolved indirect nanoplasmonic sensing spectroscopy of dye molecule interactions with dense and mesoporous TiO2 films

Indirect nanoplasmonic sensing (INPS) is an experimental platform exploiting localized surface plasmon resonance (LSPR) detection of processes in nanomaterials, molecular assemblies, and films at the nanoscale. Here we have for the first time applied INPS to study dye molecule adsorption/impregnation of two types of TiO(2) materials: thick (10 μm) mesoporous films of the kind used as photoanode in dye-sensitized solar cells (DSCs), with particle/pore size in the range of 20 nm, and thin (12-70 nm), dense, and flat films. For the thick-film experiments plasmonic Au nanoparticles were placed at the hidden, internal interface between the sensor surface and the mesoporous TiO(2). This approach provides a unique opportunity to selectively follow dye adsorption locally in the hidden interface region inside the material and inspires a generic and new type of nanoplasmonic hidden interface spectroscopy. The specific DSC measurement revealed a time constant of thousands of seconds before the dye impregnation front (the diffusion front) reaches the hidden interface. In contrast, dye adsorption on the dense, thin TiO(2) films exhibited much faster, Langmuir-like monolayer formation kinetics with saturation on a time scale of order 100 s. This new type of INPS measurement provides a powerful tool to measure and optimize dye impregnation kinetics of DSCs and, from a more general point of view, offers a generic experimental platform to measure adsorption/desorption and diffusion phenomena in solid and mesoporous systems and at internal hidden interfaces.     

Mesoporous TiO2 microspheres synthesized with assistance of different structural controlling reagents and their photovoltaic properties

In this paper, hierarchical mesoporous TiO₂ microspheres composing of connected nanoparticles were synthesized by the aids of aniline, lauryl alcohol and nonanoic acid. The dye sensitized solar cells (DSSCs) based on the mesoporous TiO₂ microspheres demonstrated photoelectric conversion efficiencies of 3.9–6.5%, which are dramatically higher than that based on commercial P25 (3.26%). Mediated by different structural controlling reagents, the as-formed mesoporous TiO₂ microspheres exhibited obvious difference in photovoltaic properties. Mainly due to the higher dye adsorption capacity, higher light scattering capability, as well as better inter- and intra-sphere connection, the microspheres synthesized with the assistance of aniline offered the highest photovoltaic efficiency.     

Assembly of CdS quantum dots onto mesoscopic TiO(2) films for quantum dot-sensitized solar cell applications

Colloidal cadmium sulfide (CdS) quantum dots (QDs) were prepared and surface modified by mercaptosuccinic acid (MSA) to render a surface with carboxylic acid groups (MSA-CdS). The MSA-CdS QDs were then assembled onto bare TiO(2) mesoporous films using the carboxylic groups/TiO(2) interaction. The TiO(2) film was also surface modified by 3-mercaptopropyl trimethoxysilane (MPTMS) or 3-aminopropyl-methyl diethoxysilane (APMDS) to prepare, respectively, a thiol (-SH) or amino (-NH(2)) terminated surface for binding with the CdS QDs. The experimental results showed that the MPTMS-modified film has the highest adsorption rate and adsorption amount to the CdS QDs, attributable to the strong thiol/CdS interaction. In contrast, the adsorption rate and incorporated amount of the QDs on the bare TiO(2) film are much lower than for the silane-modified films. The incident photon-to-current conversion efficiency (IPCE) obtained for the CdS-sensitized TiO(2) electrode was about 20% (at 400?nm) for the bare TiO(2), 13% for the MPTMS-TiO(2), and 6% for APMDS-TiO(2). The current-voltage measurement under dark conditions reveals a higher dark current on the MPTMS-?and APMDS-modified electrodes, indicating a lower coverage ratio of CdS on these TiO(2) films. This result is attributed to the fast adsorption rate of CdS QDs on the bottleneck of a mesopore which inhibits the transport of the QDs deep into the inner region of a pore. For the bare TiO(2) film, the lower incorporated amount of CdS but higher energy conversion efficiency indicates the formation of a better-covered CdS QDs monolayer. The moderate adsorption rate of MSA-CdS QDs using the carboxylic acid/TiO(2) interaction is responsible for the efficient assembly of QDs onto the mesoporous TiO(2) films.     

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.     

Effect of coadsorbent on the photovoltaic performance of squaraine sensitized nanocrystalline solar cells

The effect of chenodeoxycholic acid as the coadsorbent with a squaraine sensitizer on TiO(2) nanocrystalline solar cells was investigated, and it was found that the coadsorbent prevents the squaraine sensitizer from aggregating on the TiO(2) nanoparticles but reduces dye loading leading to an interdependent photovoltaic performance. Analysis of the absorption spectra, and incident monochromatic photon-to-current conversion efficiency data showed that the load of squaraine sensitizer as well as the appearance of H-aggregates is strongly dependent on the molar concentration of chenodeoxycholic acid coadsorbent. The open circuit voltage of the solar cells with chenodeoxycholic acid increases due to the enhanced electron lifetime in the TiO(2) nanoparticles coupled with the band edge shift of TiO(2) to negative potentials.     

介孔TiO2微球水热法合成及在染料敏化太阳能电池中的应用

以Ti(SO4)2为钛源,采用尿素辅助水热法合成了介孔TiO2微球,利用XRD、FESEM和比表面积分析仪对样品的晶型、形貌和比表面积进行分析,探讨了尿素加入量对TiO2微球的颗粒尺寸、比表面积、孔径和孔容的影响。采用刮涂法,用所合成的介孔TiO2微球制备了染料敏化太阳能电池(DSSC)的光阳极,结果表明,尿素用量为1.2g合成的介孔TiO2微球所组装的电池在模拟太阳光的照射下(100mW/cm2,AM1.5),光电转换效率为6.2%,明显高于商用P25纳晶所组装的电池光电转换效率(4.24%)。     

方酸菁功能材料修饰纳米晶TiO2薄膜电极的光电转换性能研究

考察了三种方酸菁染料修饰的米晶ＴｉＯ２薄膜电极表面应用于光电化学太阳能电池进行光电转换的情况,发现它们的光电化学性能参数按照Ｓｑ３〉Ｓｑ２〉Ｓｑ１的顺序,随着染料在纳米晶ＴｉＯ２上吸附力的增强而提高,其中,Ｓｑ３的光电转换效率为２．１７％,它在６５０ｎｍ处的最高单色光光电流效率ＩＰＣＥ值达到６．２％,表明方酸菁是一类优良的光电转换功能材料。