Manipulation of light harvesting for efficient dye‐sensitized solar cell by doping an ultraviolet light‐capturing fluorophore

An organic fluorophore is doped into a mesoporous TiO₂ photoelectrode to absorb ultraviolet light and convert it to green light for more efficient light harvesting of N719 dye. This fluorescence conversion enables the absorption of additional green light by dye molecules by means of Förster resonance energy transfer between fluorescent compound donor and N719 dye acceptor. Owing to close fit between the emission peak of fluorophore and the absorption peak of N719 dye, the Förster resonance energy transfer effect enhances the incident photon to current conversion efficiency of the dye‐sensitized solar cells based on fluorophore‐doped TiO₂ photoelectrodes. Improved power conversion efficiency (8.03–8.13%) is also achieved for the fluorophore‐doped (10⁻⁴ M) dye‐sensitized solar cells compared with a cell without the doping of fluorophore (7.63%). Copyright © 2013 John Wiley & Sons, Ltd.     

Transparent conductive oxide‐less back contact dye‐sensitized solar cells using cobalt electrolyte

Transparent conductive oxide‐less (TCO‐less) dye‐sensitized solar cells (DSSCs) have been fabricated and characterized using nanoporous TiO₂‐coated stainless steel metal mesh as flexible photoanode and cobalt bipyridyl complex (Co(bpy))‐based one electron redox shuttle electrolyte. Attempts have been made towards enhancing the efficiency of TCO‐less DSSCs to match with their TCO‐based DSSC counterparts. It has been found that surface protection of metal mesh is highly required for enhancing the efficiency of TCO‐less DSSCs specially using cobalt electrolytes as confirmed by dark current–voltage characteristics. Photocurrent action spectra clearly reveal that TCO‐based DSSCs using (Co(bpy)) electrolyte exhibits photon harvesting (incident photon to current conversion efficiency (IPCE) 52%) in the 370–450 nm wavelength region as compared to photon harvesting at peak absorption of the dye (IPCE 56% at 550 nm), which is almost the same (IPCE 47%) in the 400–610 nm wavelength region for TCO‐less DSSCs. Under similar experimental conditions, replacing indoline dye D‐205 to porphyrin‐based dye YD2‐o‐C8 led to the enhancement in the photoconversion efficiency from 3.33% to 4.84% under simulated solar irradiation. Copyright © 2014 John Wiley & Sons, Ltd.     

Increasing the Efficiency of Organic Dye‐Sensitized Solar Cells over 10.3% Using Locally Ordered Inverse Opal Nanostructures in the Photoelectrode

3D inverse opal (3D‐IO) oxides are very appealing nanostructures to be integrated into the photoelectrodes of dye‐sensitized solar cells (DSSCs). Due to their periodic interconnected pore network with a high pore volume fraction, they facilitate electrolyte infiltration and enhance light scattering. Nonetheless, preparing 3D‐IO structures directly on nonflat DSSC electrodes is challenging. Herein, 3D‐IO TiO₂ structures are prepared by templating with self‐assembled polymethyl methacrylate spheres on glass substrates, impregnation with a mixed TiO₂:SiO₂ precursor and calcination. The specific surface increases from 20.9 to 30.7 m² g^?1 after SiO₂ removal via etching, which leads to the formation of mesopores. The obtained nanostructures are scraped from the substrate, processed as a paste, and deposited on photoelectrodes containing a mesoporous TiO₂ layer. This procedure maintains locally the 3D‐IO order. When sensitized with the novel benzothiadiazole dye YKP‐88, DSSCs containing the modified photoelectrodes exhibit an efficiency of 10.35% versus 9.26% for the same devices with conventional photoelectrodes. Similarly, using the ruthenium dye N719 as sensitizer an efficiency increase from 5.31% to 6.23% is obtained. These improvements originate mainly from an increase in the photocurrent density, which is attributed to an enhanced dye loading obtained with the mesoporous 3D‐IO structures due to SiO₂ removal.     

Novel Conjugated Organic Dyes for Efficient Dye‐Sensitized Solar Cells

Novel conjugated organic dyes that have N,N‐dimethylaniline (DMA) moieties as the electron donor and a cyanoacetic acid (CAA) moiety as the electron acceptor were developed for use in dye‐sensitized nanocrystalline‐TiO₂ solar cells (DSSCs). We attained a maximum solar‐energy‐to‐electricity conversion efficiency (η) of 6.8 % under AM 1.5 irradiation (100 mW cm^–2) with a DSSC based on 2‐cyano‐7,7‐bis(4‐dimethylamino‐phenyl)hepta‐2,4,6‐trienoic acid (NKX‐2569): short‐circuit photocurrent density (J_sc) = 12.9 mA cm^–2, open‐circuit voltage (V_oc) = 0.71 V, and fill factor (ff) = 0.74. The high performance of the solar cells indicated that highly efficient electron injection from the excited dyes to the conduction band of TiO₂ occurred. The experimental and calculated Fourier‐transform infrared (FT‐IR) absorption spectra clearly showed that these dyes were adsorbed on the TiO₂ surface with the carboxylate coordination form. A molecular‐orbital calculation indicated that the electron distribution moved from the DMA moiety to the CAA moiety by photoexcitation of the dye.     

NIR‐II Light Activated Photosensitizer with Aggregation‐Induced Emission for Precise and Efficient Two‐Photon Photodynamic Cancer Cell Ablation

Near infrared (NIR) light excitable photosensitizers are highly desirable for photodynamic therapy with deep penetration. Herein, a NIR‐II light (1200 nm) activated photosensitizer TQ‐BTPE is designed with aggregation‐induced singlet oxygen (¹O₂) generation for two‐photon photodynamic cancer cell ablation. TQ‐BTPE shows good two‐photon absorption and bright aggregation‐induced NIR‐I emission upon NIR‐II laser excitation. The ¹O₂ produced by TQ‐BTPE in an aqueous medium is much more efficient than that of commercial photosensitizer Ce6 under white light irradiation. Upon NIR‐II excitation, the two‐photon photosensitization of TQ‐BTPE is sevenfold higher than that of Ce6. The TQ‐BTPE molecules internalized by HeLa cells are mostly located in lysosomes as small aggregate dots with homogeneous distribution inside the cells, which favors efficient photodynamic cell ablation. The two‐photon photosensitization of TQ‐BTPE upon NIR‐I and NIR‐II excitation shows higher ¹O₂ generation efficiency than under NIR‐I excitation owing to the larger two‐photon absorption cross section at 920 nm. However, NIR‐II light exhibits better biological tissue penetration capability after passing through a fresh pork tissue, which facilitates stronger two‐photon photosensitization and better cancer cell ablation performance. This work highlights the promise of NIR‐II light excitable photosensitizers for deep‐tissue photodynamic therapy.     

A Near‐Infrared cis‐Configured Squaraine Co‐Sensitizer for High‐Efficiency Dye‐Sensitized Solar Cells

A cis‐configured squaraine dye (HSQ1), synthesized by incorporation of a strongly electron‐withdrawing dicyanovinyl group into the central squaric acid moiety, is employed in dye‐sensitized solar cells (DSCs). In solution, HSQ1 displays an intense absorption in the near‐infrared region with a maximum at 686 nm and when the dye is adsorbed on a TiO₂ surface, the absorption spectrum broadens in both the blue and the near‐infrared regions, which is favorable for efficient light harvesting over a broad wavelength range. A solar cell sensitized with HSQ1 shows a broader incident photon‐to‐current conversion efficiency (IPCE) spectrum (from 400 to 800 nm) and a higher IPCE in the long‐wavelength region (71% at 700 nm) than a cell sensitized with squaraine dye SQ1. Furthermore, a solar cell co‐sensitized with HSQ1 and N3 dye shows remarkably improved short‐circuit current density and open‐circuit voltage compared to those of a DSC based on N3 alone and fabricated under the same conditions. The energy‐conversion efficiency of the co‐sensitized DSC is 8.14%, which is the highest reported efficiency for a squaraine dye–based co‐sensitized DSC without using Al₂O₃ layer.     

A Europium Complex With Excellent Two‐Photon‐Sensitized Luminescence Properties

We report the synthesis and excellent two‐photon‐sensitized luminescence properties of a new complex [Eu(tta)₃dmbpt] (tta = henoyltrifluoroacetonate; dmbpt = 2‐(N,N‐diethyl‐2,6‐dimethylanilin‐4‐yl)‐4,6‐bis(3,5‐dimethylpyrazol‐1‐yl)‐1,3,5‐triazine) that exhibits the highest efficiency of lanthanide luminescence when excited by near‐infrared (NIR) laser pulses (action cross section of two‐photon‐excited fluorescence δ × Φ_F: 85 GM at 812 nm and 56 GM at 842 nm; 1 GM = 10^–50 cm⁴ s photon^–1 molecule^–1). Compared to a previously reported [Eu(tta)₃dpbt] complex, (dpbt = 2‐(N,N‐diethylanilin‐4‐yl)‐4,6‐bis(3,5‐dimethylpyrazol‐1‐yl)‐1,3,5‐triazine), [Eu(tta)₃dmbpt] has two excess methyl groups at the 2,6‐positions of the phenyl ring. Crystallographic data of dmbpt show that the 2,6‐dimethyl substitutes bring about a significant twist in the conformation of the diethylamino group compared to that in dpbt, which severely influences the conjugation in the ground state between the electron lone pair of N in the –N(CH₂–)₂ moiety and the aromatic electron system in dmbpt. The large two‐photon absorption (TPA) cross section of dmbpt is mainly derived from its large static dipole moment difference between the S₀ and the S₁ states, which is partly responsible for the high capability of two‐photon‐sensitized luminescence of [Eu(tta)₃dmbpt]. The broader two‐ and single‐photon excitation windows and the superior two‐photon‐sensitized luminescent properties in the long‐wavelength NIR region of [Eu(tta)₃dmbpt] compared to [Eu(tta)₃dpbt] are also explained according to the calculated results and twisted structure.     

Effectively Utilizing NIR Light Using Direct Electron Injection from Up‐Conversion Nanoparticles to the TiO2 Photoanode in Dye‐Sensitized Solar Cells

TiO₂/NaYF₄:Yb³⁺,Er³⁺ nano‐heterostructures are prepared in situ on the TiO₂ photoanode of dye‐sensitized solar cells (DSCs). Transmission electron microscopy (TEM) and high‐resolution (HR)‐TEM confirm the formation of TiO₂/NaYF₄:Yb³⁺,Er³⁺ nano‐heterostructures. The up‐converted fluorescence spectrum of the photoanode containing the nano‐heterostructure confirms electron injection from NaYF₄:Yb³⁺,Er³⁺ to the condution band (CB) of TiO₂. When using a photoanode containing the nano‐heterostructure in a DSC, the overall efficiency (η) of the device is 17% higher than that of a device without the up‐conversion nanoparticles (UCNPs) and 13% higher than that of a device containing mixed TiO₂ and UCNPs. Nano‐heterostructures of TiO₂/NaYF₄:Yb³⁺,Tm³⁺ and TiO₂/NaYF₄:Yb³⁺,Ho³⁺ can also be prepared in situ on TiO₂ photoanodes. The overall efficiency of the device containing TiO₂/NaYF₄:Yb³⁺,Ho³⁺ nano‐heterostructures is 15% higher than the control device without UCNPs. When nano‐heterostructures of TiO₂/NaYF₄:Yb³⁺,Tm³⁺ are used, the open‐circuit voltage (V_oc) and the short‐circuit current density (J_sc) are all slightly decreased. The effect of the different UCNPs results from the different energy levels of Er³⁺, Tm³⁺, and Ho³⁺. These results demonstrate that utilizing the UCNPs with the apporpriate energy levels can lead to effective electron injection from the UCNPs to the CB of TiO₂, effectively improving the photocurrent and overall efficiency of DSCs while using NIR light.     

Amorphous Zinc Stannate (Zn2SnO4) Nanofibers Networks as Photoelectrodes for Organic Dye‐Sensitized Solar Cells

A new strategy for developing dye‐sensitised solar cells (DSSCs) by combining thin porous zinc tin oxide (Zn₂SnO₄) fiber‐based photoelectrodes with purely organic sensitizers is presented. The preparation of highly porous Zn₂SnO₄ electrodes, which show high specific surface area up to 124 m²/g using electrospinning techniques, is reported. The synthesis of a new organic donor‐conjugate‐acceptor (D‐π‐A) structured orange organic dye with molar extinction coefficient of 44 600 M^?1 cm^?1 is also presented. This dye and two other reference dyes, one organic and a ruthenium complex, are employed for the fabrication of Zn₂SnO₄ fiber‐based DSSCs. Remarkably, organic dye‐sensitized DSSCs displayed significantly improved performance compared to the ruthenium complex sensitized DSSCs. The devices based on a 3 μm‐thick Zn₂SnO₄ electrode using the new sensitizer in conjunction with a liquid electrolyte show promising photovoltaic conversion up to 3.7% under standard AM 1.5G sunlight (100 mW cm^?2). This result ranks among the highest reported for devices using ternary metal oxide electrodes.     

Investigation of benzo(1,2-b:4,5-b′)dithiophene as a spacer in organic dyes for high efficient dye-sensitized solar cell

Two benzo(1,2-b:4,5-b′)dithiophene (denoted as BDT) based organic dyes, Dye 1 and Dye 2, containing triphenylamine and carbazole in the molecular frameworks respectively, were synthesized, characterized and applied in dye-sensitized solar cells (DSSCs). The photo-physical, photovoltaic, and electrochemical properties of the two dyes were analyzed in this work. The two dyes exhibit strong charge transfer absorption bands in the visible region. The dyes were applied in dye sensitized solar cells obtaining 11.34 mA/cm², 0.75 V and 0.74, for the short-circuit photocurrent density (J_sc), open-circuit voltage (V_oc), and fill factor (FF) respectively, corresponding to an overall power conversion efficiency of 6.3%. These results revealed that BDT-based dyes are promising dyes for DSSCs.     

PtCoFe Nanowire Cathodes Boost Short‐Circuit Currents of Ru(II)‐Based Dye‐Sensitized Solar Cells to a Power Conversion Efficiency of 12.29%

PtCoFe nanowires with different alloying compositions are chemically prepared and acted as counter electrodes (CEs) in dye‐sensitized solar cells (DSSCs) with Ru(II)‐based dyes. Due to their superior reduction activity, PtCoFe nanowires with rich (111) facets enhance the performance of DSSCs. Hence, N719 DSSCs with PtCoFe nanowires, respectively, produce better power conversion efficiency (PCE) of 8.10% for Pt₃₃Co₂₄Fe₄₃ nanowire, 8.33% for Pt₇₄Co₁₂Fe₁₄ nanowire, and 9.26% for Pt₄₉Co₂₃Fe₂₈ nanowire in comparison to the PCE of Pt CE (7.32%). Further, the PRT‐22 DSSC with Pt₄₉Co₂₃Fe₂₈ nanowire exhibits a maximum PCE of 12.29% with a certificated value of 12.0%, which surpass the previous PCE record of the DSSCs with Ru(II)‐based dyes. The photovoltaic and electrochemical results reveal the composition‐dependent activity along with a volcano‐shaped trend in the I^?/ redox reaction. Theoretical work on the adsorption energies of I₂, the desorption energies of I^?, and the corresponding absolute energy demonstrates that the reduction activity followed in the order of Pt₄₉Co₂₃Fe₂₈(111) plane > Pt₇₄Co₁₂Fe₁₄(111) plane > Pt₃₃Co₂₄Fe₄₃(111) plane, proving Pt₄₉Co₂₃Fe₂₈ nanowire to be a superior cathode material for DSSCs.     

Enhanced photovoltaic performance of cross‐linked ruthenium dye with functional cross‐linkers for dye‐sensitized solar cell

Photovoltaic performance of cross‐linkable Ru(2,2′‐bipyridine‐4,4′‐bicarboxylic acid)(4,4′‐bis((4‐vinyl benzyloxy)methyl)‐2,2′‐bipyridine)(NCS)₂ (denoted as RuS dye) adsorbing on TiO₂ mesoporous film was enhanced by polymerizing with either ionic liquid monomer, 1‐(2‐acryloyloxy‐ethyl)‐3‐methyl‐imidazol‐1‐ium iodide (AMImI), to form RuS‐cross‐AMImI or di‐functional acrylic monomer with ether linkage, triethyleneglycodimethacrylate (TGDMA), to form RuS‐cross‐TGDMA. Their cross‐linking properties were investigated by UV–vis spectroscopy by rinsing with 0.1 N NaOH aqueous solution. The power conversion efficiencies (PCEs) of dye‐sensitized solar cells (DSSCs) with RuS‐cross‐AMImI and RuS‐cross‐TGDMA both reached over 8% under standard global air mass 1.5 full sunlight. The increased PCE for DSSCs with RuS‐cross‐AMImI comparing with cross‐linked RuS was attributed to the I⁻ counterion of AMImI increasing the charge regeneration rate of RuS dye, whereas that with RuS‐cross‐TGDMA was attributed to the Li⁺ coordination property of TGDMA. The photovoltaic performance of RuS‐cross‐TGDMA was also slightly better than that of RuS‐cross‐AMImI because of higher open‐circuit photovoltage (V_oc) and short‐circuit photocurrent (J_sc). Its higher V_oc was supported by the Bode plot of impedance under illumination and Nyquist plots at dark, whereas higher J_sc was supported by the incident monochromatic photon‐to‐current conversion efficiency spectra and charge extraction experiments. Copyright © 2013 John Wiley & Sons, Ltd.     

Electrospinning Preparation and Drug‐Delivery Properties of an Up‐conversion Luminescent Porous NaYF4:Yb3+, Er3+@Silica Fiber Nanocomposite

Up‐conversion (UC) luminescent porous silica fibers decorated with NaYF₄:Yb³⁺, Er³⁺ nanocrystals (NCs) (denoted as NaYF₄:Yb³⁺, Er³⁺@silica fiber) are prepared by the electrospinning process using cationic surfactant P123 as a template. Monodisperse and hydrophobic oleic acid capped β‐NaYF₄: Yb³⁺, Er³⁺ NCs are prepared by thermal decomposition methodology. Then, these NCs are transferred into aqueous solution by employing cetyltrimethylammonium bromide (CTAB) as secondary surfactant. The water‐dispersible β‐NaYF₄:Yb³⁺, Er³⁺ NCs are dispersed into precursor electrospinning solution containing P123 and tetraethyl orthosilicate (TEOS), followed by preparation of precursor fibers via electrospinning. Finally, porous α‐NaYF₄:Yb³⁺, Er³⁺@silica fiber nanocomposites are obtained after annealing the precursor fibers containing β‐NaYF₄:Yb³⁺, Er³⁺ at 550 °C. The as‐prepared α‐NaYF₄:Yb³⁺, Er³⁺@silica fiber possesses porous structure and UC luminescence properties simultaneously. Furthermore, the obtained nanocomposites can be used as a drug delivery host carrier and drug storage/release properties are investigated, using ibuprofen (IBU) as a model drug. The results indicate that the IBU–loaded α‐NaYF₄:Yb³⁺, Er³⁺@silica fiber nanocomposites show UC emission of Er³⁺ under 980 nm NIR laser excitation and a controlled release property for IBU. Meanwhile, the UC emission intensity of IBU–α‐NaYF₄:Yb³⁺, Er³⁺@silica fiber system varies with the released amount of IBU.     

Honeycomb‐Like Organized TiO2 Photoanodes with Dual Pores for Solid‐State Dye‐Sensitized Solar Cells

A solid‐state dye‐sensitized solar cell (ssDSSC) with 7.4% efficiency at 100 mW/cm² is reported. This efficiency is one of the highest observed for N719 dye. High performance is achieved via a honeycomb‐like, organized mesoporous TiO₂ photoanode with dual pores, high porosity, good interconnectivity, and excellent light scattering properties. The TiO₂ photoanodes are prepared without any TiCl₄ treatment via a one‐step, direct self‐assembly of hydrophilically preformed TiO₂ nanocrystals and poly(vinyl chloride)‐g‐poly(oxyethylene methacrylate) (PVC‐g‐POEM) graft copolymer as a titania source and a structure‐directing agent, respectively. Upon controlling the secondary forces between the polymer/TiO₂ hybrid and the solvent by varying the amounts of HCl/H₂O mixture or toluene, honeycomb‐like structures are generated to improve light scattering properties. Such multifunctional nanostructures with dual pores provide good pore‐filling of solid polymer electrolyte with large volume, enhanced light harvesting and reduced charge recombination, as confirmed by reflectance spectroscopy, incident photon‐to‐electron conversion efficiency (IPCE), and electrochemical impedance spectroscopy (EIS) analysis.     

Co-sensitization of N719 and RhCL dyes on carboxylic acid treated TiO2 for enhancement of light harvesting and reduced recombination

We report herein the findings from a systematic study conducted on the effect of co-sensitization of two dyes i.e. N719 and rhodamine 19 perchlorate (RhCL) onto TiO₂ electrodes (thickness: 4 μm), which were treated by three different carboxylic acids namely, formic acid (FA), oxalic acid (OA) and citric acid (CA). Co-sensitization was carried out by first loading the carboxylic acid treated TiO₂ electrodes with RhCL dye followed by N719. The amount of dye loading was estimated from the UV/vis spectroscopy and the results show that: (i) the amount of individual dye loading (RhCL or N719) onto carboxylic acid treated TiO₂ electrodes is, in general, higher than that onto untreated TiO₂ electrodes; (ii) the amount of individual dye loading is highest for OA-treated and lowest for CA-treated TiO₂ electrodes; and (iii) the co-sensitization leads to highest loading of N719 onto FA-treated and lowest on CA-treated TiO₂ electrodes. The results of dye sensitized solar cells fabricated using these acid treated TiO₂ electrodes revealed that the efficiency (η) is higher for electrodes having higher loading of N719 dye. For single N719 dye loading, the highest η of 4.5% is observed for OA-treated TiO₂; while upon co-sensitization the highest η of ∼5.3% is observed for FA treated TiO₂. A detailed analyses of Fourier transform infrared spectroscopy (FTIR), UV–Visible, impendence, incident photon to current efficiency (IPCE) results show that η enhancement occurs due to the following factors: (i) increased short circuit current density (J_SC) owing to high N719 dye loading which enhances light harvesting; (ii) improved IPCE; (iii) increased open circuit voltage (V_OC) due to an upward shift of the conduction band edge (CBE) and quasi Fermi level; and (iv) suppressed back electron transfer.     

Characterization of two new (A–π)2–D–A type dyes with different central D unit and their application for dye sensitized solar cells

We report the photophysical, electrochemical and theoretical properties of two dyes with same acceptor, π-linker and anchoring acceptor unit and different TPA (D1) and pyran (D2) donor central unit. The change in the central unit resulted in corresponding different photophysical and electrochemical properties. The dye sensitized solar cell fabricated using dye D1 showed the higher incident photon to current efficiency of 54%, a short circuit current (J_sc) of 11.86 mA/cm², an open circuit voltage of 0.64 V, and fill factor (FF) of 0.68, corresponding an overall power conversion efficiency of 5.16% which is higher than that for D2 based DSSCs (4.42%). The difference in the PCE of DSSCs based on D1 and D2 is partly, due to the smaller amount of dye loading, higher dark current and charge recombination rate of D1 based DSSC. The electrochemical spectra of DSSCs demonstrated longer electron life time and charge recombination resistance and small charge transport resistance for D1 sensitized DSSC, results the higher PCE.     

Precise Molecular Engineering of Photosensitizers with Aggregation‐Induced Emission over 800 nm for Photodynamic Therapy

Owing to efficient singlet oxygen (¹O₂) generation in aggregate state, photosensitizers (PSs) with aggregation‐induced emission (AIE) have attracted much research interests in photodynamic therapy (PDT). In addition to high ¹O₂ generation efficiency, strong molar absorption in long‐wavelength range and near‐infrared (NIR) emission are also highly desirable, but difficult to achieve for AIE PSs since the twisted structures in AIE moieties usually lead to absorption and emission in short‐wavelength range. In this contribution, through acceptor engineering, a new AIE PS of TBT is designed to show aggregation‐induced NIR emission centered at 810 nm, broad absorption in the range between 300 and 700 nm with a large molar absorption coefficient and a high ¹O₂ generation efficiency under white light irradiation. Further, donor engineering by attaching two branched flexible chains to TBT yielded TBTC8 , which circumvented the strong intermolecular interactions of TBT in nanoparticles (NPs), yielding TBTC8 NPs with optimized overall performance in ¹O₂ generation, absorption, and emission. Subsequent PDT results in both in vitro and in vivo studies indicate that TBTC8 NPs are promising candidates in practical application.     

Hierarchical Double‐Shell Nanostructures of TiO2 Nanosheets on SnO2 Hollow Spheres for High‐Efficiency,Solid‐State,Dye‐Sensitized Solar Cells

A high‐energy conversion efficiency of 8.2% at 100 mW cm^?2 is reported, one of the highest values for N719‐based, solid‐state, dye‐sensitized solar cells (ssDSSCs). The solar cells are based on hierarchical double‐shell nanostructures consisting of inner SnO₂ hollow spheres (SHS) surrounded by outer TiO₂ nanosheets (TNSs). Deposition of the TNS on the SHS outer surface is performed via solvothermal reactions in order to generate a double‐shell SHS@TNS nanostructure that provides a large surface area and suppresses recombination of photogenerated electrons. An organized mesoporous (OM)‐TiO₂ film with high porosity, large pores, and good interconnectivity is also prepared via a sol‐gel process using a poly(vinyl chloride)‐g‐poly(oxyethylene methacrylate) (PVC‐g‐POEM) graft copolymer template. This film is utilized as a matrix to disperse the double‐shell nanostructures. Such nanostructures provide good pore‐filling for solid polymer electrolytes, faster electron transfer, and enhanced light scattering, as confirmed by reflectance spectroscopy, incident photon‐to‐electron conversion efficiency (IPCE), and intensity‐modulated photocurrent spectroscopy (IMPS)/intensity‐modulated photovoltage spectroscopy (IMVS).     

Significant Improvement of Dye‐Sensitized Solar Cell Performance by Small Structural Modification in π‐Conjugated Donor–Acceptor Dyes

Two donor‐π‐acceptor (D‐π‐A) dyes are synthesized for application in dye‐sensitized solar cells (DSSC). These D‐π‐A sensitizers use triphenylamine as donor, oligothiophene as both donor and π‐bridge, and benzothiadiazole (BTDA)/cyanoacrylic acid as acceptor that can be anchored to the TiO₂ surface. Tuning of the optical and electrochemical properties is observed by the insertion of a phenyl ring between the BTDA and cyanoacrylic acid acceptor units. Density functional theory (DFT) calculations of these sensitizers provide further insight into the molecular geometry and the impact of the additional phenyl group on the photophysical and photovoltaic performance. These dyes are investigated as sensitizers in liquid‐electrolyte‐based dye‐sensitized solar cells. The insertion of an additional phenyl ring shows significant influence on the solar cells' performance leading to an over 6.5 times higher efficiency (η = 8.21%) in DSSCs compared to the sensitizer without phenyl unit (η = 1.24%). Photophysical investigations reveal that the insertion of the phenyl ring blocks the back electron transfer of the charge separated state, thus slowing down recombination processes by over 5 times, while maintaining efficient electron injection from the excited dye into the TiO₂‐photoanode.     

New Family of Ruthenium‐Dye‐ Sensitized Nanocrystalline TiO2 Solar Cells with a High Solar‐Energy‐Conversion Efficiency

A new type of ruthenium complexes 6 – 8 with tridentate bipyridine–pyrazolate ancillary ligands has been synthesized in an attempt to elongate the π‐conjugated system as well as to increase the optical extinction coefficient, possible dye uptake on TiO₂, and photostability. Structural characterization, photophysical studies, and corresponding theoretical approaches have been made to ensure their fundamental basis. As for dye‐sensitized solar cell applications, it was found that 6 – 8 possess a larger dye uptake of 2.4 × 10^–7 mol cm^–2, 1.5 × 10^–7 mol cm^–2, and 1.3 × 10^–7 mol cm^–2, respectively, on TiO₂ than that of the commercial N3 dye (1.1 × 10^–7 mol cm^–2). Compound 8 works as a highly efficient photosensitizer for the dye‐sensitized nanocrystalline TiO₂ solar cell, producing a 5.65 % solar‐light‐to‐electricity conversion efficiency (compare with 6.01 % for N3 in this study), a short‐circuit current density of 15.6 mA cm^–2, an open‐circuit photovoltage of 0.64 V, and a fill factor of 0.57 under standard AM 1.5 irradiation (100 mW cm^–2). These, in combination with its superior thermal and light‐soaking stability, lead to the conclusion that the concomitant tridentate binding properties offered by the bipyridine‐pyrazolate ligand render a more stable complexation, such that extended life spans of DSSCs may be expected.