Weakly Conjugated Hybrid Zinc Porphyrin Sensitizers for Solid‐State Dye‐Sensitized Solar Cells

Molecularly engineered weakly conjugated hybrid porphyrin systems are presented as efficient sensitizers for solid‐state dye‐sensitized solar cells. By incorporating the quinolizino acridine and triazatruxene based unit as the secondary light‐harvester as well as electron‐donating group at the meso‐position of the porphyrin core, the power conversion efficiencies of 4.5% and 5.1% are demonstrated in the solid‐state devices containing 2,2′,7,7′‐tetrakis (N,N‐di‐p‐methoxyphenylamine)‐9,9′‐spiro bifluorene as hole transporting material. The photovoltaic performance of the triazatruxene donor based porphyrin sensitizer is better than that of the previously published porphyrin molecules exhibiting strongly conjugated push–pull structure. The effect of molecular structure on the optical and electrochemical properties, the dynamics of charge extraction, as well as the photovoltaic performance are systematically investigated, which offers a new design strategy for further refinement of porphyrin molecules.     

Enhancing the Performance of Solid‐State Dye‐Sensitized Solar Cells Using a Mesoporous Interfacial Titania Layer with a Bragg Stack

High efficiency dye‐sensitized solar cells (DSSCs) are fabricated with a heterostructured photoanode that consists of a 500‐nm‐thick organized mesoporous TiO₂ (om‐TiO₂) interfacial layer (IF layer), a 7 or 10‐μm thick nanocrystalline TiO₂ layer (NC layer), and a 2‐μm‐thick mesoporous Bragg stack (meso‐BS layer) as the bottom, middle and top layers, respectively. An om‐TiO₂ layer with a high porosity, transmittance, and interconnectivity is prepared via a sol‐gel process, in which a poly(vinyl chloride)‐g‐poly(oxyethylene methacrylate) (PVC‐g‐POEM) graft copolymer is used as a structure‐directing agent. The meso‐BS layer with large pores is prepared via alternating deposition of om‐TiO₂ and colloidal SiO₂ (col‐SiO₂) layers. Structure and optical properties (refractive index) of the om‐TiO₂ and meso‐BS layers are studied and the morphology of the heterostructured photoanode is characterized. DSSCs fabricated with the heterostructured IF/NC/BS photoanode and combined with a polymerized ionic liquid (PIL) exhibit an energy conversion efficiencies of 6.6% at 100 mW/cm², one of the highest reported for solid‐state DSSCs and much larger than cells prepared with only a IF/NC layer (6.0%) or a NC layer (4.5%). Improvements in energy conversion efficiency are attributed to the combination of improved light harvesting, decreased resistance at the electrode/electrolyte interface, and excellent electrolyte infiltration.     

A Low Temperature Route toward Hierarchically Structured Titania Films for Thin Hybrid Solar Cells

The requirement of high‐temperature calcination for titanium dioxide in (solid‐state) dye‐sensitized solar cells (DSSCs) implies challenges with respect to reduced energy consumption and the potential for flexible photovoltaic devices. Moreover, the use of dye molecules increases production costs and leads to problems related with dye bleaching. Therefore, fabrication of dye‐free hybrid solar cells at low temperature is a promising alternative for current DSSC technology. In this work the authors fabricate hierarchically structured titania thin films by combining a polystyrene‐block‐polyethylene oxide template assisted sol–gel synthesis with nano‐imprint lithography at low temperatures. The achieved films are filled with poly(3‐hexylthiophene) to form the active layer of hybrid solar cells. The surface morphology is probed via scanning electron microscopy and atomic force microscopy, and the bulk film morphology is examined with grazing incidence X‐ray scattering. Good light absorption by the active layer is proven by UV–vis spectroscopy. An enhancement in light absorption is observed and ascribed to light scattering in mesoporous titania films with imprinted superstructures. Accordingly a better photovoltaic performance is found for nano‐imprinted solar cells at various angles of light incidence.     

Foldable All‐Solid‐State Supercapacitors Integrated with Photodetectors

Recent development in flexible electronics has promoted the increasing demand for their energy storage systems that will be lightweight, thin, flexible, and even foldable. Although various flexible supercapacitors recently have been successfully developed, the design and assembly of highly foldable supercapacitors have received less attention. Furthermore, foldable supercapacitors are in general operated independently with other electronics, resulting in some space and energy consumption from the external connection system. Therefore, the authors fabricate the foldable all‐solid‐state integrated devices with supercapacitor and photodetector functions in a simplified and compact configuration based on single‐walled carbon nanotube films and TiO₂ nanoparticles. The integrated devices not only retain the intrinsic capacitance behavior but also show excellent sensitivity of detecting white light. More importantly, the capacitance behavior of integrated devices remains almost unchanged and the photodetector behavior is quite stable even folded by 180° due to their unique integrated configuration. Such rational design of all‐solid‐state integrated devices will pave the way for assembling energy storage devices and other electronics into highly flexible and foldable integrated devices.     

Pore Filling of Spiro‐OMeTAD in Solid‐State Dye‐Sensitized Solar Cells Determined Via Optical Reflectometry

A simple strategy is presented to determine the pore‐filling fraction of the hole‐conductor 2,2‐7,7‐tetrakis‐N,N‐di‐pmethoxyphenylamine‐9,9‐spirobifluorene (spiro‐OMeTAD) into mesoporous photoanodes in solid‐state dye‐sensitized solar cells (ss‐DSCs). Based on refractive index determination by the film's reflectance spectra and using effective medium approximations the volume fractions of the constituent materials can be extracted, hence the pore‐filling fraction quantified. This non‐destructive method can be used with complete films and does not require detailed model assumptions. Pore‐filling fractions of up to 80% are estimated for optimized solid‐state DSC photoanodes, which is higher than that previously estimated by indirect methods. Additionally, transport and recombination lifetimes as a function of the pore‐filling fraction are determined using photovoltage and photocurrent decay measurements. While extended electron lifetimes are observed with increasing pore‐filling fractions, no trend is found in the transport kinetics. The data suggest that a pore‐filling fraction of greater than 60% is necessary to achieve optimized performance in ss‐DSCs. This degree of pore‐filling is even achieved in 5 μm thick mesoporous photoanodes. It is concluded that pore‐filling is not a limiting factor in the fabrication of “thick” ss‐DSCs with spiro‐OMeTAD as the hole‐conductor.     

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.     

Parameters Influencing Charge Separation in Solid‐State Dye‐Sensitized Solar Cells Using Novel Hole Conductors

Solid‐state dye‐sensitized solar cells employing a solid organic hole‐transport material (HTM) are currently under intensive investigation, since they offer a number of practical advantages over liquid‐electrolyte junction devices. Of particular importance to the design of such devices is the control of interfacial charge transfer. In this paper, the factors that determine the yield of hole transfer at the dye/HTM interface and its correlation with solid‐state‐cell performance are identified. To this end, a series of novel triarylamine type oligomers, varying in molecular weight and mobility, are studied. Transient absorption spectroscopy is used to determine hole‐transfer yields and pore‐penetration characteristics. No correlation between hole mobility and cell performance is observed. However, it is found that the photocurrent is directly proportional to the hole‐transfer yield. This hole‐transfer yield depends on the extent of pore penetration in the dye‐sensitized film as well as on the thermodynamic driving force ΔG_dye–HTM for interfacial charge transfer. Future design of alternative solid‐state HTMs should focus on the optimization of pore‐filling properties and the control of interfacial energetics rather than on increasing material hole mobilities.     

Compact Inverse‐Opal Electrode Using Non‐Aggregated TiO2 Nanoparticles for Dye‐Sensitized Solar Cells

Compact inverse‐opal structures are constructed using non‐aggregated TiO₂ nanoparticles in a three‐dimensional colloidal array template as the photoelectrode of a dye‐sensitized solar cell. Organic‐layer‐coated titania nanoparticles show an enhanced infiltration and a compact packing within the 3D array. Subsequent thermal decomposition to remove the organic template followed by impregnation with N‐719 dye results in excellent inverse‐opal photoelectrodes with a photo‐conversion efficiency as high as 3.47% under air mass 1.5 illumination. This colloidal‐template approach using non‐aggregated nanoparticles provides a simple and versatile way to produce efficient inverse‐opal structures with the ability to control parameters such as cavity diameter and film thickness.     

Solid‐State Plastic Crystal Electrolytes: Effective Protection Interlayers for Sulfide‐Based All‐Solid‐State Lithium Metal Batteries

All‐solid‐state lithium metal batteries (ASSLMBs) have attracted significant attention due to their superior safety and high energy density. However, little success has been made in adopting Li metal anodes in sulfide electrolyte (SE)‐based ASSLMBs. The main challenges are the remarkable interfacial reactions and Li dendrite formation between Li metal and SEs. In this work, a solid‐state plastic crystal electrolyte (PCE) is engineered as an interlayer in SE‐based ASSLMBs. It is demonstrated that the PCE interlayer can prevent the interfacial reactions and lithium dendrite formation between SEs and Li metal. As a result, ASSLMBs with LiFePO₄ exhibit a high initial capacity of 148 mAh g^?1 at 0.1 C and 131 mAh g^?1 at 0.5 C (1 C = 170 mA g^?1), which remains at 122 mAh g^?1 after 120 cycles at 0.5 C. All‐solid‐state Li‐S batteries based on the polyacrylonitrile‐sulfur composite are also demonstrated, showing an initial capacity of 1682 mAh g^?1. The second discharge capacity of 890 mAh g^?1 keeps at 775 mAh g^?1 after 100 cycles. This work provides a new avenue to address the interfacial challenges between Li metal and SEs, enabling the successful adoption of Li metal in SE‐based ASSLMBs with high energy density.     

Enhanced‐Light‐Harvesting Amphiphilic Ruthenium Dye for Efficient Solid‐State Dye‐Sensitized Solar Cells

A ruthenium sensitizer (coded C101, NaRu (4,4′‐bis(5‐hexylthiophen‐2‐yl)‐2,2′‐bipyridine) (4‐carboxylic acid‐4′‐caboxylate‐2,2′‐bipyridine) (NCS)₂) containing a hexylthiophene‐conjugated bipyridyl group as an ancillary ligand is presented for use in solid‐state dye‐sensitized solar cells (SSDSCs). The high molar‐extinction coefficient of this dye is advantageous compared to the widely used Z907 dye, (NaRu (4‐carboxylic acid‐4′‐carboxylate) (4,4′‐dinonyl‐2,2′‐bipyridine) (NCS)₂). In combination with an organic hole‐transporting material (spiro‐MeOTAD, 2,2′,7,7′‐tetrakis‐(N,N‐di‐p‐methoxyphenylamine) 9, 9′‐spirobifluorene), the C101 sensitizer exhibits an excellent power‐conversion efficiency of 4.5% under AM 1.5 solar (100 mW cm^?2) irradiation in a SSDSC. From electronic‐absorption, transient‐photovoltage‐decay, and impedance measurements it is inferred that extending the π‐conjugation of spectator ligands induces an enhanced light harvesting and retards the charge recombination, thus favoring the photovoltaic performance of a SSDSC.     

High Efficiency Solid‐State Dye‐Sensitized Solar Cells Assembled with Hierarchical Anatase Pine Tree‐like TiO2 Nanotubes

A facile and effective method to prepare hierarchical pine tree‐like TiO₂ nanotube (PTT) arrays with an anatase phase directly grown on a transparent conducting oxide substrate via a one‐step hydrothermal reaction. The PTT arrays consist of a vertically oriented long nanotube (NT) stem and a large number of short nanorod (NR) branches. Various PTT morphologies are obtained by adjusting the water/diethylene glycol ratio. The diameter of the NTs and the size of the NR branches decreases from 300 to100 nm and from 430 to 230 nm, respectively, with increasing water content. The length of the PTT arrays could be increased up to 19 μm to significantly improve the charge transport and specific surface area. The solid‐state dye‐sensitized solar cells (ssDSSC) assembled with the 19 μm long PTT arrays exhibit an outstanding energy‐conversion efficiency of 8.0% at 100 mW/cm², which is two‐fold higher than that of commercially available paste (4.0%) and one of the highest values obtained for N719 dye‐based ssDSSCs. The high performance is attributed to the larger surface area, improved electron transport, and reduced electrolyte/electrode interfacial resistance, resulting from the one‐dimensional, well‐aligned structure with a high porosity and large pores.     

A Thermoplastic Gel Electrolyte for Stable Quasi‐Solid‐State Dye‐Sensitized Solar Cells

Dye‐sensitized solar cells (DSSCs) are receiving considerable attention as low‐cost alternatives to conventional solar cells. In DSSCs based on liquid electrolytes, a photoelectric efficiency of 11 % has been achieved, but potential problems in sealing the cells and the low long‐term stability of these systems have impeded their practical use. Here, we present a thermoplastic gel electrolyte (TPGE) as an alternative to the liquid electrolytes used in DSSCs. The TPGE exhibits a thermoplastic character, high conductivity, long‐term stability, and can be prepared by a simple and convenient protocol. The viscosity, conductivity, and phase state of the TPGE can be controlled by tuning the composition. Using 40 wt % poly(ethylene glycol) (PEG) as the polymeric host, 60 wt % propylene carbonate (PC) as the solvent, and 0.65 M KI and 0.065 M I₂ as the ionic conductors, a TPGE with a conductivity of 2.61 mS cm^–2 is prepared. Based on this TPGE, a DSSC is fabricated with an overall light‐to‐electrical‐energy conversion efficiency of 7.22 % under 100 mW cm^–2 irradiation. The present findings should accelerate the widespread use of DSSCs.     

Dependence of Dye Regeneration and Charge Collection on the Pore‐Filling Fraction in Solid‐State Dye‐Sensitized Solar Cells

Solid‐state dye‐sensitized solar cells rely on effective infiltration of a solid‐state hole‐transporting material into the pores of a nanoporous TiO₂ network to allow for dye regeneration and hole extraction. Using microsecond transient absorption spectroscopy and femtosecond photoluminescence upconversion spectroscopy, the hole‐transfer yield from the dye to the hole‐transporting material 2,2′,7,7′‐tetrakis(N,N‐di‐p‐methoxyphenylamine)‐9,9'‐spirobifluorene (spiro‐OMeTAD) is shown to rise rapidly with higher pore‐filling fractions as the dye‐coated pore surface is increasingly covered with hole‐transporting material. Once a pore‐filling fraction of ≈30% is reached, further increases do not significantly change the hole‐transfer yield. Using simple models of infiltration of spiro‐OMeTAD into the TiO₂ porous network, it is shown that this pore‐filling fraction is less than the amount required to cover the dye surface with at least a single layer of hole‐transporting material, suggesting that charge diffusion through the dye monolayer network precedes transfer to the hole‐transporting material. Comparison of these results with device parameters shows that improvements of the power‐conversion efficiency beyond ≈30% pore filling are not caused by a higher hole‐transfer yield, but by a higher charge‐collection efficiency, which is found to occur in steps. The observed sharp onsets in photocurrent and power‐conversion efficiencies with increasing pore‐filling fraction correlate well with percolation theory, predicting the points of cohesive pathway formation in successive spiro‐OMeTAD layers adhered to the pore walls. From percolation theory it is predicted that, for standard mesoporous TiO₂ with 20 nm pore size, the photocurrent should show no further improvement beyond an ≈83% pore‐filling fraction.     

Band‐Edge Engineered Hybrid Structures for Dye‐Sensitized Solar Cells Based on SnO2 Nanowires

In this report, we show for the first time that SnO₂ nanowire based dye sensitized solar cells exhibit an open circuit voltage of 560 mV, which is 200 mV higher than that using SnO₂ nanoparticle based cells. This is attributed to the more negative flat band potential of nanowires compared to the nanoparticles as determined by open circuit photo voltage measurements made at high light intensities. The nanowires were employed in hybrid structures consisting of highly interconnected SnO₂ nanowire matrix coated with TiO₂ nanoparticles, which showed an open circuit voltage of 720 mV and an efficiency of 4.1% compared to 2.1% obtained with pure SnO₂ nanowire matrix. The electron transport time constants for SnO₂ nanowire matrix were an order of magnitude lower and the recombination time constants are about 100 times higher than that of TiO₂ nanoparticles. The higher efficiency observed for DSSCs based on hybrid structure is attributed to the band edge positions of SnO₂ relative to that of TiO₂ and faster electron transport in SnO₂ nanowires.     

A Hybrid Poly(ethylene oxide)/ Poly(vinylidene fluoride)/TiO2 Nanoparticle Solid‐State Redox Electrolyte for Dye‐Sensitized Nanocrystalline Solar Cells

High‐efficiency all‐solid‐state dye‐sensitized nanocrystalline solar cells have been fabricated using a poly(ethylene oxide)/poly(vinylidene fluoride) (PEO/PVDF)/TiO₂‐nanoparticle polymer redox electrolyte, which yields an overall energy‐conversion efficiency of about 4.8 % under irradiation by white light (65.2 mW cm^–2). The introduction of PVDF (which contains the highly electronegative element fluorine) and TiO₂ nanoparticles into the PEO electrolyte increases the ionic conductivity (by about two orders of magnitude) and effectively reduces the recombination rate at the interface of the TiO₂ and the solid‐state electrolyte, thus enhancing the performance of the solar cell.     

High Electroactive Material Loading on a Carbon Nanotube@3D Graphene Aerogel for High‐Performance Flexible All‐Solid‐State Asymmetric Supercapacitors

Freestanding carbon‐based hybrids, specifically carbon nanotube@3D graphene (CNTs@3DG) hybrid, are of great interest in electrochemical energy storage. However, the large holes (about 400 µm) in the commonly used 3D graphene foams (3DGF) constitute as high as 90% of the electrode volume, resulting in a very low loading of electroactive materials that is electrically connected to the carbon, which makes it difficult for flexible supercapacitors to achieve high gravimetric and volumetric energy density. Here, a hierarchically porous carbon hybrid is fabricated by growing 1D CNTs on 3D graphene aerogel (CNTs@3DGA) using a facile one‐step chemical vapor deposition process. In this architecture, the 3DGA with ample interconnected micrometer‐sized pores (about 5 µm) dramatically enhances mass loading of electroactive materials comparing with 3DGF. An optimized all‐solid‐state asymmetric supercapacitor (AASC) based on MnO₂@CNTs@3DGA and Ppy@CNTs@3DGA electrodes exhibits high volumetric energy density of 3.85 mW h cm^?3 and superior long‐term cycle stability with 84.6% retention after 20 000 cycles, which are among the best reported for AASCs with both electrodes made of pseudocapacitive electroactive materials.     

Charge Generation and Photovoltaic Operation of Solid‐State Dye‐Sensitized Solar Cells Incorporating a High Extinction Coefficient Indolene‐Based Sensitizer

An investigation of the function of an indolene‐based organic dye, termed D149, incorporated in to solid‐state dye‐sensitized solar cells using 2,2′,7,7′‐tetrakis(N,N‐di‐p‐methoxypheny‐amine)‐9,9′‐spirobifluorene (spiro‐OMeTAD) as the hole transport material is reported. Solar cell performance characteristics are unprecedented under low light levels, with the solar cells delivering up to 70% incident photon‐to‐current efficiency (IPCE) and over 6% power conversion efficiency, as measured under simulated air mass (AM) 1.5 sun light at 1 and 10 mW cm^?2. However, a considerable nonlinearity in the photocurrent as intensities approach “full sun” conditions is observed and the devices deliver up to 4.2% power conversion efficiency under simulated sun light of 100 mW cm^?2. The influence of dye‐loading upon solar cell operation is investigated and the thin films are probed via photoinduced absorption (PIA) spectroscopy, time‐correlated single‐photon counting (TCSPC), and photoluminescence quantum efficiency (PLQE) measurements in order to deduce the cause for the non ideal solar cell performance. The data suggest that electron transfer from the photoexcited sensitizer into the TiO₂ is only between 10 to 50% efficient and that ionization of the photo excited dye via hole transfer directly to spiro‐OMeTAD dominates the charge generation process. A persistent dye bleaching signal is also observed, and assigned to a remarkably high density of electrons “trapped” within the dye phase, equivalent to 1.8 × 10¹⁷ cm^?3 under full sun illumination. it is believed that this localized space charge build‐up upon the sensitizer is responsible for the non‐linearity of photocurrent with intensity and nonoptimum solar cell performance under full sun conditions.