New bithiazole-based sensitizers for efficient and stable dye-sensitized solar cells

A series of new push-pull organic dyes (BT-I-VI), incorporating electron-withdrawing bithiazole with a thiophene, furan, benzene, or cyano moiety, as π?spacer have been synthesized, characterized, and used as the sensitizers for dye-sensitized solar cells (DSSCs). In comparison with the model compound T1, these dyes containing a thiophene moiety between triphenylamine and bithiazole display enhanced spectral responses in the red portion of the solar spectrum. Electrochemical measurement data indicate that the HOMO and LUMO energy levels can be tuned by introducing different π?spacers between the bithiazole moiety and cyanoacrylic acid acceptor. The incorporation of bithiazole substituted with two hexyl groups is highly beneficial to prevent close π-π aggregation, thus favorably suppressing charge recombination and intermolecular interaction. The overall conversion efficiencies of DSSCs based on bithiazole dyes are in the range of 3.58 to 7.51?%, in which BT-I-based DSSCs showed the best photovoltaic performance: a maximum monochromatic incident photon-to-current conversion efficiency (IPCE) of 81.1?%, a short-circuit photocurrent density (J(sc)) of 15.69?mA?cm(-2), an open-circuit photovoltage (V(oc)) of 778?mV, and a fill factor (ff) of 0.61, which correspond to an overall conversion efficiency of 7.51?% under standard global AM 1.5 solar light conditions. Most importantly, long-term stability of the BT-I-III-based DSSCs with ionic-liquid electrolytes under 1000?h of light soaking was demonstrated and BT-II with a furan moiety exhibited better photovoltaic performance of up to 5.75?% power conversion efficiency.     

Cubic CeO2 nanoparticles as mirror-like scattering layers for efficient light harvesting in dye-sensitized solar cells

A new type of bilayered photoanodes with cubic CeO(2) nanoparticles as mirror-like scattering thin layers was prepared via a screen-printing technique for dye-sensitized solar cells (DSSCs). The light harvesting efficiency was significantly enhanced due to the mirror-like light scattering effect, resulting in noticeable ～17.8% improvement of light-to-electric conversion efficiency.     

Benzotriazole-Bridged Sensitizers Containing a Furan Moiety for Dye-Sensitized Solar Cells with High Open-Circuit Voltage Performance

Two new benzotriazole-bridged sensitizers are designed and synthesized ( BTA-I and BTA-II ) containing a furan moiety for dye-sensitized solar cells (DSSCs). Two corresponding dyes ( BTA-III and BTA-IV ) with a thiophene spacer were also synthesized for comparison. All of these dyes performed as sensitizers for DSSCs, and the photovoltaic performance data of these benzotriazole-bridged dyes showed a high open-circuit voltage (V_oc: 804–834 mV). Among the four dyes, DSSCs based on BTA-II , with a furan moiety and branched alkyl chain, showed the highest V_oc (834 mV), a photocurrent density (J_sc) of 12.64 mA cm⁻², and a fill factor (FF) of 0.64, corresponding to an overall conversion efficiency (η) of 6.72 %. Most importantly, long-term stability of the BTA-I , BTA-II , BTA-III , BTA-IV -based DSSCs with ionic-liquid electrolytes under 1000 h light-soaking was demonstrated, and BTA-II exhibited better photovoltaic performance of up to 5.06 % power conversion efficiency.     

Organic redox couples and organic counter electrode for efficient organic dye-sensitized solar cells

A series of organic thiolate/disulfide redox couples have been synthesized and have been studied systematically in dye-sensitized solar cells (DSCs) on the basis of an organic dye (TH305). Photophysical, photoelectrochemical, and photovoltaic measurements were performed in order to get insights into the effects of different redox couples on the performance of DSCs. The polymeric, organic poly(3,4-ethylenedioxythiophene) (PEDOT) material has also been introduced as counter electrode in this kind of noniodine-containing DSCs showing a promising conversion efficiency of 6.0% under AM 1.5G, 100 mW·cm(-2) light illumination. Detailed studies using electrochemical impedance spectroscopy and linear-sweep voltammetry reveal that the reduction of disulfide species is more efficient on the PEDOT counter electrode surface than on the commonly used platinized conducting glass electrode. Both pure and solvated ionic-liquid electrolytes based on a thiolate anion have been studied in the DSCs. The pure and solvated ionic-liquid-based electrolytes containing an organic redox couple render efficiencies of 3.4% and 1.2% under 10 mW·cm(-2) light illumination, respectively.     

Enhancing the Performance of Dye‐Sensitized Solar Cells with a Gold‐Nanoflowers Box

To improve the electron collection, electron lifetime, and light‐harvesting efficiency of dye‐sensitized solar cells simultaneously, Au nanoflowers were prepared and used to cover the entire TiO₂ film. Deposition of Au nanoflowers around the TiO₂ film formed a light‐scattering “box” that covered the entire TiO₂ film. Compared with a light‐scattering layer that only covers the top surface of TiO₂, the Au‐nanoflowers box exhibited better light‐harvesting efficiency due to omnidirectional light scattering, faster electron transport (attributed to the formation of electron channels between the metallic Au nanoflowers and the electron‐collection electrode), and slower charge recombination. As a consequence, the short‐circuit photocurrent and open‐circuit photovoltage were both enhanced significantly, which improved the power conversion efficiency from 8.12 to 10.91 % (34 %) when an Au‐nanoflowers box was wrapped around the photoanode.     

Guanidinium Iodides-based Ionic Liquids： Synthesis and Application for Dye-sensitized Solar Cells（DSSCs）

A series of guanidinium ionic liquids(GILs) was designed, synthesized, and used as electrolytes for dye-sensitized solar celIs(DSSCs). The effect of electrolytes containing GILs on the photovoltaic performance of DSSCs was investigated. It is demonstrated that these GILs are promising for being used as electrolytes for DSSCs and a conversion efficiency of 4.1% can be obtained under AM 1.5 sun light irradiation.     

High molar extinction coefficient heteroleptic ruthenium complexes for thin film dye-sensitized solar cells

Two novel heteroleptic sensitizers, Ru((4,4-dicarboxylic acid-2,2'-bipyridine)(4,4'-bis(p-hexyloxystyryl)-2,2-bipyridine)(NCS)2 and Ru((4,4-dicarboxylic acid-2,2'-bipyridine)(4,4'-bis(p-methoxystyryl)-2,2'-bipyridine) (NCS)2, coded as K-19 and K-73, respectively, have been synthesized and characterized by 1H NMR, FTIR, UV-vis absorption, and emission spectroscopy and excited-state lifetime and spectroelectrochemical measurements. The introduction of the alkoxystyryl group extends the conjugation of the bipyridine donor ligand increasing markedly their molar extinction coefficient and solar light harvesting capacity. The dynamics of photoinduced charge separation following electronic excitation of the K-19 dye was scrutinized by time-resolved laser spectroscopy. The electron transfer from K-19 to the conduction band of TiO2 is completed within 20 fs while charge recombination has a half-life time of 800 s. The high extinction coefficients of these sensitizers enable realization of a new generation of a thin film dye sensitized solar cell (DSC) yielding high conversion efficiency at full sunlight even with viscous electrolytes based on ionic liquids or nonvolatile solvents. An unprecedented yield of over 9% was obtained under standard reporting conditions (simulated global air mass 1.5 sunlight at 1000 W/m2 intensity) when the K-73 sensitizer was combined with a nonvolatile "robust" electrolyte. The K-19 dye gave a conversion yield of 7.1% when used in conjunction with the binary ionic liquid electrolyte. These devices exhibit excellent stability under light soaking at 60 degrees C. The effect of the mesoscopic TiO2 film thickness on photovoltaic performance has been analyzed by electrochemical impedance spectroscopy (EIS).     

基于TiO2纳米管阵列的高效正面透光型染料敏化太阳能电池的制备及其光电性能

报道了一种基于TiO2纳米管(TNT)阵列正面透光型光阳极的高效染料敏化太阳能电池.将TNTs在450°C烧结后能避免其有序结构在HF处理过程中被破坏,使膜内高速电子传输通道被保留,有利于染料敏化太阳能电池(DSSC)实现高速电荷传输.再用HF、TiCl4、HF和TiCl4混合等溶剂对TNTs进行处理,提高其表面粗糙度以吸附更多染料.染料吸附量的增加能提高光阳极在300-570 nm波段光子捕获效率,该波段是染料吸收光子的主要区域.然而,在染料吸收光子较弱的长波段区域(570-800 nm)光子捕获效率的增加主要源于光阳极光散射率的提高.光阳极光子捕获效率的提高使DSSC的内外量子效率在全波段(300-800 nm)均有所增加,从而使短路电流明显提高.从电化学阻抗数据可知,与电子传输性能密切相关的电化学参数如电荷传输电阻、界面电荷复合电阻、电容、电子寿命、电子扩散长度和电子收集效率等在含处理过的TNTs光阳极DSSC中均有所改善,从而提高电池光电转换效率.含HF和TiCl4混合溶剂处理TNTs光阳极的DSSC最高光电转换效率能达到7.30%,比未处理的DSSC(5.38%)提高35.69%.     

New Bithiazole‐Based Sensitizers for Efficient and Stable Dye‐Sensitized Solar Cells

A series of new push–pull organic dyes ( BT‐I – VI ), incorporating electron‐withdrawing bithiazole with a thiophene, furan, benzene, or cyano moiety, as π spacer have been synthesized, characterized, and used as the sensitizers for dye‐sensitized solar cells (DSSCs). In comparison with the model compound T1 , these dyes containing a thiophene moiety between triphenylamine and bithiazole display enhanced spectral responses in the red portion of the solar spectrum. Electrochemical measurement data indicate that the HOMO and LUMO energy levels can be tuned by introducing different π spacers between the bithiazole moiety and cyanoacrylic acid acceptor. The incorporation of bithiazole substituted with two hexyl groups is highly beneficial to prevent close π–π aggregation, thus favorably suppressing charge recombination and intermolecular interaction. The overall conversion efficiencies of DSSCs based on bithiazole dyes are in the range of 3.58 to 7.51 %, in which BT‐I ‐based DSSCs showed the best photovoltaic performance: a maximum monochromatic incident photon‐to‐current conversion efficiency (IPCE) of 81.1 %, a short‐circuit photocurrent density (J_sc) of 15.69 mA cm^?2, an open‐circuit photovoltage (V_oc) of 778 mV, and a fill factor (ff) of 0.61, which correspond to an overall conversion efficiency of 7.51 % under standard global AM 1.5 solar light conditions. Most importantly, long‐term stability of the BT‐I – III ‐based DSSCs with ionic‐liquid electrolytes under 1000 h of light soaking was demonstrated and BT‐II with a furan moiety exhibited better photovoltaic performance of up to 5.75 % power conversion efficiency.     

Increasing the conversion efficiency of dye-sensitized TiO2 photoelectrochemical cells by coupling to photonic crystals

The mechanism of enhancing the light harvesting efficiency of dye-sensitized TiO(2) solar cells by coupling TiO(2) inverse opals or disordered scattering layers to conventional nanocrystalline TiO(2) films has been investigated. Monochromatic incident photon-to-current conversion efficiency (IPCE) at dye-sensitized TiO(2) inverse opals of varying stop band wavelengths and at disordered titania films was compared to the IPCE at bilayers of these structures coupled to nanocrystalline TiO(2) films and to the IPCE at nanocrystalline TiO(2) electrodes. The results showed that the bilayer architecture, rather than enhanced light harvesting within the inverse opal structures, is responsible for the bulk of the gain in IPCE. Several mechanisms of light interaction in these structures, including localization of heavy photons near the edges of a photonic gap, Bragg diffraction in the periodic lattice, and multiple scattering events at disordered regions in the photonic crystal or at disordered films, lead ultimately to enhanced backscattering. This largely accounts for the enhanced light conversion efficiency in the red spectral range (600-750 nm), where the sensitizer is a poor absorber.     

Photocurrent enhancement by surface plasmon resonance of silver nanoparticles in highly porous dye-sensitized solar cells

Localized surface plasmon resonance (LSPR) by silver nanoparticles that are photochemically incorporated into an electrode-supported TiO(2) nanoparticulate framework enhances the extinction of a subsequently adsorbed dye (the ruthenium-containing molecule, N719). The enhancement arises from both an increase in the dye's effective absorption cross section and a modest increase in the framework surface area. Deployment of the silver-modified assembly as a photoanode in dye-sensitized solar cells leads to light-to-electrical energy conversion with an overall efficiency of 8.9%. This represents a 25% improvement over the performance of otherwise identical solar cells lacking corrosion-protected silver nanoparticles. As one would expect based on increased dye loading and electromagnetic field enhanced (LSPR-enhanced) absorption, the improvement is manifested chiefly as an increase in photocurrent density ascribable to improved light harvesting.     

Enhanced performance of the dye-sensitized solar cells with phenothiazine-based dyes containing double D-A branches

Double donor-acceptor (D-A) branched dyes (DBD) with a phenothiazine unit as electron donor and a 2-cyanoacrylic acid unit as electron acceptor were synthesized and used as sensitizers for solar cells (DSSCs). The conversion efficiency of the DSSCs amounts up to 4.22% (2.91% for the single D-A branched dye) under AM 1.5 G irradiation. The results show that the performance of DSSCs can be effectively enhanced by the cooperation of two donor-acceptor containing branches in one molecule of the dyes.     

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.     

Photoinduced Betaine Generation for Efficient Photothermal Energy Conversion

The conversion of solar energy to thermal, chemical, or electrical energy attracts great attention in chemistry and physics. There has been a considerable effort for the efficient extraction of photons throughout the entire solar spectrum. In this work light energy was efficiently harvested by using a long-lived betaine photogenerated from an acridinium-based electron donor–acceptor dyad. The photothermal energy-conversion efficiency of the dyad is significantly enhanced by simultaneous illumination with blue (420–440 nm) and yellow (>480 nm) light in comparison with the sum of the conversion efficiencies for individual illumination with blue or yellow light. The enhanced photothermal effect is due to the photogenerated betaine, which absorbs longer-wavelength light than the dyad, and thus the dyad–betaine combination is promising for efficient photothermal energy conversion. The mechanisms of betaine generation and energy conversion are discussed on the basis of steady-state and transient spectral measurements.     

A novel composite polymer electrolyte containing room-temperature ionic liquids and heteropolyacids for dye-sensitized solar cells

A novel composite polymeric gel comprising room-temperature ionic liquids (1-butyl-3-methyl-imidazolium-hexafluorophosphate, BMImPF₆) and heteropolyacids (phosphotungstic acid, PWA) in poly(2-hydroxyethyl methacrylate) matrix was successfully prepared and employed as a quasi-solid state electrolyte in dye-sensitized solar cells (DSSCs). These composite polymer electrolytes offered specific benefits over the ionic liquids and heteropolyacids, which effectively enhanced the ionic conductivity of the composite polymer electrolyte. Unsealed devices employing the composite polymer electrolyte with the 3% content of PWA achieved the solar to electrical energy conversion efficiency of 1.68% under irradiation of 50 mW cm⁻² light intensity, increasing by a factor of more than three compared to a DSSC with the blank BMImPF₆-based polymer electrolyte without PWA. It is expected that these composite polymer electrolytes are an attractive alternative to previously reported hole transporting materials for the fabrication of the long-term stable quasi-solid state or solid state DSSCs.     

A Two-dimensional Amorphous Plasmonic Heterostructure of Pd/MoO3-x for Enhanced Photoelectrochemical Water Splitting Performance

Two-dimensional (2D) heterostructures based on localized surface plasmon resonance (LSPR) have a great potential for solar energy harvesting applications. Exploring 2D amorphous plasmonic heterostructures with high light absorption and catalytic activity is desirable yet challenging. Herein, 2D Pd/MoO_3-x amorphous heterostructures can be obtained by immobilizing Pd single atoms in unsaturated coordination sites of amorphous MoO_3-x, because of strong metal-support interactions, and it reaches a current density of 50 μA cm⁻² for photoelectrochemical response with good durability, and exhibits a high incident-photon-to-current-conversion efficiency (IPCE) of 14.8% at 460 nm. Such an enhanced catalytic effects are contributed to the enhanced light absorption in visible region and change of electronic structure owing to enhanced electron transfer through dominant Pd−O bonds, which facilitate water splitting. This work moves a step closer to the expansion of photovoltaic device with the high conversion efficiency for visible light for amorphous heterostructures.     

High-performance silicon nanowire array photoelectrochemical solar cells through surface passivation and modification

Nanowire solar cells: Pt nanoparticle (PtNP) decorated C/Si core/shell nanowire photoelectrochemical solar cells show high conversion efficiency of 10.86 % and excellent stability in aggressive electrolytes under 1-sun AM 1.5 G illumination. Superior device performance is achieved by improved surface passivation of the nanowires by carbon coating and enhanced interfacial charge transfer by PtNPs.     

Synthesis of copolymer electrolytes based on polysiloxane and their high temperature durability analysis for solvent-free dye-sensitized solar cells

The present work develops a new type of solvent-free copolymer electrolyte based on polysiloxane for dye-sensitized solar cells (DSSCs). The electrolyte is characterized by conductivity measurements, hydrogen-1 nuclear magnetic resonance spectroscopy, rheology, and DSSC performance. Repeated units of the ethylene oxide on methylhydrosiloxane show plasticizing effects and enhanced durability of the DSSCs. DSSC employing the polysiloxane electrolytes show no energy conversion efficiency decay after 16 days test at room temperature and yields a conversion efficiency of 1.5% during long-term stability measurement at 90 °C under white light irradiation of 100 mW cm⁻². The new solvent-free polysiloxane copolymer electrolyte can be good candidate for next generation DSSC.     

Quantum dot-sensitized solar cells incorporating nanomaterials

Quantum dot-sensitized solar cells (QDSSCs) are interesting energy devices because of their (i) impressive ability to harvest sunlight and generate multiple electron/hole pairs, (ii) ease of fabrication, and (iii) low cost. The power conversion efficiencies (η) of most QDSSCs (typically <4%) are, however, less than those (up to 12%) of dye-sensitized solar cells, mainly because of narrow absorption ranges and charge recombination occurring at the QD-electrolyte and TiO(2)-electrolyte interfaces. To further increase the values of η of QDSSCs, it will be necessary to develop new types of working electrodes, sensitizers, counter electrodes and electrolytes. This Feature Article describes the nanomaterials that have been used recently as electronic conductors, sensitizers and counter electrodes in QDSSCs. The nature, size, morphology and quantity of these nanomaterials all play important roles affecting the efficiencies of electron injection and light harvesting. We discuss the behavior of several important types of semiconductor nanomaterials (sensitizers, including CdS, Ag(2)S, CdSe, CdTe, CdHgTe, InAs and PbS) and nanomaterials (notably TiO(2), ZnO and carbon-based species) that have been developed to improve the electron transport efficiency of QDSSCs. We point out the preparation of new generations of nanomaterials for QDSSCs and the types of electrolytes, particularly iodide/triiodide electrolytes (I(-)/I(3)(-)), polysulfide electrolytes (S(2-)/S(x)(2-)), and cobalt redox couples ([Co(o-phen)(3)(2+)/(3+)]), that improve their lifetimes. With advances in nanotechnology, we foresee significant improvements in the efficiency (η > 6%) and durability (>3000 h) of QDSSCs.     

Enhancing the device performance of Sb2S3-sensitized heterojunction solar cells by embedding Au nanoparticles in the hole-conducting polymer layer

Performance of Sb(2)S(3)-sensitized heterojunction solar cells is enhanced by embedding Au nanoparticles in the poly-3-hexylthiophene (P3HT) hole-conducting polymer layer. The improved charge transfer/transport at the Sb(2)S(3)/P3HT/Au interface by extended interface area of the P3HT/Au counter electrode and the re-absorption of the backscattering light from the embedded Au nanoparticles enhanced the device performance: J(sc) 11.0 to 12.8 mA cm(-2), V(oc) 606 to 626 mV, fill factor (FF) 60.5 to 61.2%, and power conversion efficiency (η) 4.0 to 4.9%. Simultaneous enhancement of V(oc), J(sc), and FF in Au nanoparticle-embedded systems is mainly attributed to the improved charge collection efficiency and light harvesting efficiency of Sb(2)S(3) due to the improved charge transfer/transport in the Sb(2)S(3)/P3HT/Au interface.