Cobalt Polypyridyl Complexes as Transparent Solution‐Processable Solid‐State Charge Transport Materials

Charge transport materials (CTMs) are traditionally inorganic semiconductors or metals. However, over the past few decades, new classes of solution‐processable CTMs have evolved alongside new concepts for fabricating electronic devices at low cost and with exceptional properties. The vast majority of these novel materials are organic compounds and the use of transition metal complexes in electronic applications remains largely unexplored. Here, a solution‐processable solid‐state charge transport material composed of a blend of [Co(bpyPY4)](OTf)₂ and Co(bpyPY4)](OTf)₃ where bpyPY4 is the hexadentate ligand 6,6′‐bis(1,1‐di(pyridin‐2‐yl)ethyl)‐2,2′‐bipyridine and OTf^? is the trifluoromethanesulfonate anion is reported. Surprisingly, these films exhibit a negative temperature coefficient of conductivity (dσ/dT) and non‐Arrhenius behavior, with respectable solid‐state conductivities of 3.0 S m^?1 at room temperature and 7.4 S m^?1 at 4.5 K. When employed as a CTM in a solid‐state dye‐sensitized solar cell, these largely amorphous, transparent films afford impressive solar energy conversion efficiencies of up to 5.7%. Organic–inorganic hybrid materials with negative temperature coefficients of conductivity generally feature extended flat π‐systems with strong π–π interactions or high crystallinity. The lack of these features promotes [Co(bpyPY4)](OTf)_{2+ x} films as a new class of CTMs with a unique charge transport mechanism that remains to be explored.     

Inverted Semi‐transparent Polymer Solar Cells with Transparency Color Rendering Indices approaching 100

Window‐ or building‐integrated semi‐transparent solar cells are particularly interesting applications for organic photovoltaic devices. In this work, we present an easy‐to‐process inverted device architecture comprising fully solution processable poly(3,4‐ethylenedioxythiophene):polystyrenesulfonate (PEDOT:PSS) bilayer top‐electrodes for efficient semi‐transparent organic solar cells. By incorporating dyes with a complementary absorption to the light harvesting polymer poly[[9‐(1‐octylnonyl)‐9H‐carbazole‐2,7‐diyl]‐2,5‐thiophenediyl‐2,1,3‐benzothiadiazole‐4,7‐diyl‐2,5‐thiophenediyl] (PCDTBT) into the PEDOT:PSS electrode, we achieve fully color neutral transparency perception and a color rendering index approaching 100. This makes the devices suitable for applications such as window shadowing or the integration into overhead glazing.     

Conductive,Solution‐Processed Dioxythiophene Copolymers for Thermoelectric and Transparent Electrode Applications

Conjugated polymers with high electrical conductivities are attractive for applications in capacitors, biosensors, organic thermoelectrics, and transparent electrodes. Here, a series of solution processable dioxythiophene copolymers based on 3,4‐propylenedioxythiophene (ProDOT) and 3,4‐ethylenedioxythiophene (EDOT) is investigated as thermoelectric and transparent electrode materials. Through structural manipulation of the polymer repeat unit, the conductivity of the polymers upon oxidative solution doping is tuned from 1 × 10^?3 to 3 S cm^?1, with a polymer consisting of a solubilizing alkylated ProDOT unit and an electron‐rich biEDOT unit (referred to as PE₂) showing the highest electrical conductivity. Optimization of the film casting method and screening of dopants result in AgPF₆‐doped PE₂ achieving a high electrical conductivity of over 250 S cm^?1 and a thermoelectric power factor of 7 μW m^?1 K^?2. Oxidized spray cast films of PE₂ are also assessed as a transparent electrode material for use with another electrochromic polymer. This bilayer shows reversible electrochemical switching from a colored charge‐neutral state to a highly transmissive color‐neutral, oxidized state. These results demonstrate that dioxythiophene‐based copolymers are a promising class of materials, with ProDOT–biEDOT serving as a soluble analog to the well‐studied PEDOT as a p‐type thermoelectric and electrode material.     

Graphene‐Indanthrone Donor–π–Acceptor Heterojunctions for High‐Performance Flexible Supercapacitors

To overcome the low energy density bottleneck of graphene‐based supercapacitors and to organically endow them with high‐power density, ultralong‐life cycles, etc., one rational strategy that couple graphene sheets with multielectron, redox‐reversible, and structurally‐stable organic compounds. Herein, a graphene‐indanthrone (IDT) donor–π–acceptor heterojunction is conceptualized for efficient and smooth 6H⁺/6e^? transfers from pseudocapacitive IDT molecules to electrochemical double‐layer capacitive graphene scaffolds. To construct this, water‐processable graphene oxide (GO) is employed as a graphene precursor, and to in situ exfoliate IDT industrial dyestuff, followed by a hydrothermally‐induced reduction toward GO and self‐assembly between reduced GO (rGO) donors (D) and IDT acceptors (A), affording rGO‐π‐IDT D–A heterojunctions. Electrochemical tests indicate that rGO‐π‐IDT heterojunctions deliver a gravimetric capacitance of 535.5 F g^?1 and an amplified volumetric capacitance of 685.4 F cm^?3. The assembled flexible all‐solid‐state supercapacitor yields impressive volumetric energy densities of 31.3 and 25.1 W h L^?1, respectively, at low and high power densities of 767 and 38 554 W L^?1, while exhibiting an exceptional rate capability, cycling stability, and enduring mechanically‐challenging bending and distortions. The concept and methodology may open up opportunities for other two‐dimensional materials and other energy‐related devices.     

Anomalous Charge‐Extraction Behavior for Graphene‐Oxide (GO) and Reduced Graphene‐Oxide (rGO) Films as Efficient p‐Contact Layers for High‐Performance Perovskite Solar Cells

Reduced graphene oxides (rGO) are synthesized via reduction of GO with reducing agents as a hole‐extraction layer for high‐performance inverted planar heterojunction perovskite solar cells. The best efficiencies of power conversion (PCE) of these rGO cells exceed 16%, much greater than those made of GO and poly(3,4‐ethenedioxythiophene):poly(styrenesulfonate) films. A flexible rGO device shows PCE 13.8% and maintains 70% of its initial performance over 150 bending cycles. It is found that the hole‐extraction period is much smaller for the GO/methylammonium lead‐iodide perovskite (PSK) film than for the other rGO/PSK films, which contradicts their device performances. Photoluminescence and transient photoelectric decays are measured and control experiments are performed to prove that the reduction of the oxygen‐containing groups in GO significantly decreases the ability of hole extraction from PSK to rGO and also retards the charge recombination at the rGO/PSK interface. When the hole injection from PSK to GO occurs rapidly, hole propagation from GO to the indium‐doped tin oxide (ITO) substrate becomes a bottleneck to overcome, which leads to a rapid charge recombination that decreases the performance of the GO device relative to the rGO device.     

High‐Performance Suspended Particle Devices Based on Copper‐Reduced Graphene Oxide Core–Shell Nanowire Electrodes

Smart windows are one of the key components of so‐called “green” buildings. These windows are based on an actively switchable electro‐optic material that is sandwiched between two transparent electrodes. Although great progress has been made in identifying the optimal materials for such active windows, there is still a great need to improve their key elements, especially the performance of the transparent electrodes. Here, a new suspended particle device (SPD), holding a great potential for smart window applications, which is built upon copper‐reduced graphene oxide (Cu‐rGO) core–shell nanowire (NW) films as a transparent conductive electrode is reported. With the wrapping of rGO, the Cu NW electrodes demonstrate both high optical transparency and electrical conductivity, as well as significantly improved stability under various testing conditions. The novel sandwich‐structured SPDs, based on these electrodes, show a large change in their optical transmittance (42%) between “on” and “off” states, impressively fast switching time and superior stability. These high performances are comparable to those of the SPDs based on indium tin oxide electrodes. These promising results pave the way for the electrodes to be an integral part of a variety of optoelectronic devices, including energy‐friendly and flexible electronics.     

A Bottom‐Up Approach toward All‐Solution‐Processed High‐Efficiency Cu(In,Ga)S2 Photocathodes for Solar Water Splitting

The development of solution‐processable routes to prepare efficient photoelectrodes for water splitting is highly desirable to reduce manufacturing costs. Recently, sulfide chalcopyrites (Cu(In,Ga)S₂) have attracted attention as photocathodes for hydrogen evolution owing to their outstanding optoelectronic properties and their band gap—wider than their selenide counterparts—which can potentially increase the attainable photovoltage. A straightforward and all‐solution‐processable approach for the fabrication of highly efficient photocathodes based on Cu(In,Ga)S₂ is reported for the first time. It is demonstrated that semiconductor nanocrystals can be successfully employed as building blocks to prepare phase‐pure microcrystalline thin films by incorporating different additives (Sb, Bi, Mg) that promote the coalescence of the nanocrystals during annealing. Importantly, the grain size is directly correlated to improved charge transport for Sb and Bi additives, but it is shown that secondary effects can be detrimental to performance even with large grains (for Mg). For optimized electrodes, the sequential deposition of thin layers of n‐type CdS and TiO₂ by solution‐based methods, and platinum as an electrocatalyst, leads to stable photocurrents saturating at 8.0 mA cm^–2 and onsetting at ≈0.6 V versus RHE under AM 1.5G illumination for CuInS₂ films. Electrodes prepared by our method rival the state‐of‐the‐art performance for these materials.     

Investigation on the pH‐independent photoluminescence emission from carbon dots impregnated on polymer matrix

Highly luminescent, polymer nanocomposite films based on poly(vinyl alcohol) (PVA), and monodispersed carbon dots (C‐dots) derived from multiwalled carbon nanotubes (MWCNTs), as coatings on substrates as well as free standing ones are obtained via solution‐based techniques. The synthesized films exhibit pH‐independent photoluminescence (PL) emission, which is an advantageous property compared with the pH‐dependent photoluminescence intensity variations, generally observed for the C‐dots dispersed in aqueous solution. The synthesized C‐dots and the nanocomposite films are characterized by transmission electron microscopy (TEM), scanning electron microscopy (SEM), X‐ray diffraction (XRD), Fourier transform infra‐red spectroscopy ( FTIR), ultraviolet (UV) ? visible spectroscopy and photoluminescence spectroscopy (PL) techniques. The TEM image provides clear evidence for the formation of C‐dots of almost uniform shape and average size of about 8 nm, homogeneously dispersed in aqueous medium. The strong anchoring of C‐dots within the polymer matrix can be confirmed from the XRD results. The FTIR spectral studies conclusively establish the presence of oxygen functional groups on the surfaces of the C‐dots. The photoluminescence (PL) emission spectra of the nanocomposite films are broad, covering most part of the visible region. The PL spectra do not show any luminescence intensity variations, when the pH of the medium is changed from 1 to 11. The pH‐independent luminescence, shown by these films offers ample scope for using them as coatings for designing diagnostic and imaging tools in bio medical applications. The non‐toxic nature of these nanocomposite films has been established on the basis of cytotoxicity studies.     

High‐Performance Ta2O5/Al‐Doped Ag Electrode for Resonant Light Harvesting in Efficient Organic Solar Cells

A efficient indium tin oxide (ITO)‐free transparent electrode based on an improved Ag film is designed by introducing small amount of Al during co‐deposition, producing ultrathin and smooth Ag film with low loss. A transparent electrode as thin as 4 nm is achieved by depositing the film on top of Ta₂O₅ layer, and organic solar cells based on such ultrathin electrode are built, producing power conversion efficiency over 7%. The device efficiency can be optimized by simply tuning Ta₂O₅ layer thickness external to the organic photovoltaic (OPV) structure to create an optical cavity resonance inside the photoactive layer. Therefore Ta₂O₅/Al‐doped Ag films function as a high‐performance electrode with high transparency, low resistance, improved photon management capability and mechanical flexibility.     

Microfluidic‐Assisted Blade Coating of Compositional Libraries for Combinatorial Applications: The Case of Organic Photovoltaics

Microfluidic technologies are highly adept at generating controllable compositional gradients in fluids, a feature that has accelerated the understanding of the importance of chemical gradients in biological processes. That said, the development of versatile methods to generate controllable compositional gradients in the solid‐state has been far more elusive. The ability to produce such gradients would provide access to extensive compositional libraries, thus enabling the high‐throughput exploration of the parametric landscape of functional solids and devices in a resource‐, time‐, and cost‐efficient manner. Herein, the synergic integration of microfluidic technologies is reported with blade coating to enable the controlled formation of compositional lateral gradients in solution. Subsequently, the transformation of liquid‐based compositional gradients into solid‐state thin films using this method is demonstrated. To demonstrate efficacy of the approach, microfluidic‐assisted blade coating is used to optimize blending ratios in organic solar cells. Importantly, this novel technology can be easily extended to other solution processable systems that require the formation of solid‐state compositional lateral gradients.     

ITO‐Free and Fully Solution‐Processed Semitransparent Organic Solar Cells with High Fill Factors

Organic photovoltaic (OPV) solar cells that can be simply processed from solution are in the focus of the academic and industrial community because of their enormous potential to reduce cost. One big challenge in developing a fully solution‐processed OPV technology is the design of a well‐performing electrode system, allowing the replacement of ITO. Several solution‐processed electrode systems were already discussed, but none of them could match the performance of ITO. Here, we report efficient ITO‐free and fully solution‐processed semitransparent inverted organic solar cells based on silver nanowire (AgNW) electrodes. To demonstrate the potential of these AgNW electrodes, they were employed as both the bottom and top electrodes. Record devices achieved fill factors as high as 63.0%, which is comparable to ITO based reference devices. These results provide important progress for fully printed organic solar cells and indicate that ITO‐free, transparent as well as non‐transparent organic solar cells can indeed be fully solution‐processed without losses.     

A Solution‐Processable Polymer Photocatalyst for Hydrogen Evolution from Water

Direct photocatalytic water splitting is an attractive strategy for clean energy production, but multicomponent nanostructured systems that mimic natural photosynthesis can be difficult to fabricate because of the insolubility of most photocatalysts. Here, a solution‐processable organic polymer is reported that is a good photocatalyst for hydrogen evolution from water, either as a powder or as a thin film, suggesting future applications for soluble conjugated organic polymers in multicomponent photocatalysts for overall water splitting.     

Effects of Shortened Alkyl Chains on Solution‐Processable Small Molecules with Oxo‐Alkylated Nitrile End‐Capped Acceptors for High‐Performance Organic Solar Cells

Solution‐processable small molecules are significant for producing high‐performance bulk heterojunction organic solar cells (OSCs). Shortening alkyl chains, while ensuring proper miscibility with fullerene, enables modulation of molecular stacking, which is an effective method for improving device performance. Here, the design and synthesis of two solution‐processable small molecules based on a conjugated backbone with a novel end‐capped acceptor (oxo–alkylated nitrile) using octyl and hexyl chains attached to π–bridge, and octyl and pentyl chains attached to the acceptor is reported. Shortening the length of the widely used octyl chains improves self‐assembly and device performance. Differential scanning calorimetry and grazing incidence X‐ray diffraction results demonstrated that the molecule substituted by shorter chains shows tighter molecular stacking and higher crystallinity in the mixture with 6,6‐phenyl‐C₇₁‐butyric acid methyl ester (PC₇₁BM) and that the power conversion efficiency (PCE) of the OSC is as high as 5.6% with an open circuit voltage (V_oc) of 0.87 V, a current density (J_sc) of 9.94 mA cm^‐2, and an impressive filled factor (FF) of 65% in optimized devices. These findings provide valuable insights into the production of highly efficient solution‐processable small molecules for OSCs.     

Low Substrate Temperature Encapsulation for Flexible Electrodes and Organic Photovoltaics

Encapsulation is of key importance to improve the stability and lifetime of organic conductors and devices, mainly in applications such as flexible electrodes or organic photovoltaics (OPV). Here, a single‐layer conformal encapsulation method is demonstrated via initiated chemical vapor deposition (iCVD) for organic conductor, poly (3,4‐ethylenedioxythiophene) (PEDOT). The accelerated degradation tests at 100 °C show that the conductivity of encapsulated PEDOT can be retained up to 17 times longer than that of the unencapsulated counterpart. PEDOT degradation and encapsulation mechanisms are also discussed. Furthermore, the versatility of the iCVD encapsulation on a top‐illuminated OPV architecture that can be used to produce low‐cost photovoltaics devices on various unconventional substrates (e.g., paper) is demonstrated. Unlike previous approaches of using solely water/oxygen barriers, the encapsulation effect of polymer films on OPV devices is improved by a thin layer capping of evaporated UV‐screening material, Cerium(IV) oxide (CeO₂) over the iCVD polymer layer. This bilayer encapsulation strategy efficiently slows the degradation of OPVs and represents a new method to encapsulate OPV and other organic devices.     

Composite thin film and electrospun biomaterials for urologic tissue reconstruction

A replacement material for autologous grafts for urinary tract reconstruction would dramatically reduce the complications of surgery for these procedures. However, acellular materials have not proven to work sufficiently well, and cell‐seeded materials are technically challenging and time consuming to generate. An important function of the urinary tract is to prevent urine leakage into the surrounding tissue—a function usually performed by the urothelium. We hypothesize that by providing an impermeable barrier in the acellular graft material, urine leakage would be minimized, as the urothelium forms in vivo. However, since urothelial cells require access to nutrients from the supporting vasculature, the impermeable barrier must degrade over time. Here we present the development of a novel biomaterial composed of the common degradable polymers, poly(ε‐caprolactone) and poly(L ‐lactic acid) and generated by electrospinning directly onto spin‐coated thin films. The composite scaffolds with thin films on the luminal surface were compared to their electrospun counterparts and commercially available small intestinal submucosa by surface analysis using scanning electron microscopy and by analysis of permeability to small molecules. In addition, the materials were examined for their ability to support urothelial cell adhesion, proliferation, and multilayered urothelium formation. We provide evidence that these unique composite scaffolds provide significant benefit over commonly used acellular materials in vitro and suggest that they be further examined in vivo. Biotechnol. Bioeng. 2011; 108:207–215. © 2010 Wiley Periodicals, Inc.     

Self‐Assembly Atomic Stacking Transport Layer of 2D Layered Titania for Perovskite Solar Cells with Extended UV Stability

A novel atomic stacking transporting layer (ASTL) based on 2D atomic sheets of titania (Ti_1?δO₂) is demonstrated in organic–inorganic lead halide perovskite solar cells. The atomically thin ASTL of 2D titania, which is fabricated using a solution‐processed self‐assembly atomic layer‐by‐layer deposition technique, exhibits the unique features of high UV transparency and negligible (or very low) oxygen vacancies, making it a promising electron transporting material in the development of stable and high‐performance perovskite solar cells. In particular, the solution‐processable atomically thin ASTL of 2D titania atomic sheets shows superior inhibition of UV degradation of perovskite solar cell devices, compared to the conventional high‐temperature sintered TiO₂ counterpart, which usually causes the notorious instability of devices under UV irradiation. The discovery opens up a new dimension to utilize the 2D layered materials with a great variety of homostructrual or heterostructural atomic stacking architectures to be integrated with the fabrication of large‐area photovoltaic or optoelectronic devices based on the solution processes.     

Strontium Diffusion in Magnetron Sputtered Gadolinia‐Doped Ceria Thin Film Barrier Coatings for Solid Oxide Fuel Cells

Strontium (Sr) diffusion in magnetron sputtered gadolinia‐doped ceria (CGO) thin films is investigated. For this purpose, a model system consisting of a screen printed (La,Sr)(Co,Fe)O_3?δ (LSCF) layer, and thin films of CGO and yttria‐stabilized zirconia (YSZ) is prepared to simulate a solid oxide fuel cell. This setup allows observation of Sr diffusion by observing SrZrO₃ formation using X‐ray diffraction while annealing. Subsequent electron microscopy confirms the results. This approach presents a simple method for assessing the quality of CGO barriers without the need for a complete fuel cell test setup. CGO films with thicknesses ranging from 250 nm to 1.2 μm are tested at temperatures from 850 °C to 1000 °C which yields an in‐depth understanding of Sr diffusion through CGO thin films that may be of high scientific and technical interest for implementation of novel fuel cell materials. Sr is found to diffuse along column/grain boundaries in the CGO films but by modifying the film thickness and microstructure the breaking temperature of the barrier can be increased.     

Effect of pressure‐assisted thermal annealing on the optical properties of ZnO thin films

ZnO thin films were prepared by the polymeric precursor method. The films were deposited on silicon substrates using the spin‐coating technique, and were annealed at 330 °C for 32 h under pressure‐assisted thermal annealing and under ambient pressure. Their structural and optical properties were characterized, and the phases formed were identified by X‐ray diffraction. No secondary phase was detected. The ZnO thin films were also characterized by field‐emission scanning electron microscopy, Fourier transform infrared spectroscopy, photoluminescence and ultraviolet emission intensity measurements. The effect of pressure on these thin films modifies the active defects that cause the recombination of deep level states located inside the band gap that emit yellow–green (575 nm) and orange (645 nm) photoluminescence. Copyright © 2012 John Wiley & Sons, Ltd.     

Efficient Perovskite Solar Cells Based on a Solution Processable Nickel(II) Phthalocyanine and Vanadium Oxide Integrated Hole Transport Layer

An organic–inorganic integrated hole transport layer (HTL) composed of the solution‐processable nickel phthalocyanine (NiPc) abbreviated NiPc‐(OBu)₈ and vanadium(V) oxide (V₂O₅) is successfully incorporated into structured mesoporous perovskite solar cells (PSCs). The optimized PSCs show the highest stabilized power conversion efficiency of up to 16.8% and good stability under dark ambient conditions. These results highlight the potential application of organic–inorganic integrated HTLs in PSCs.     

π‐Extended Narrow‐Bandgap Diketopyrrolopyrrole‐Based Oligomers for Solution‐Processed Inverted Organic Solar Cells

A series of narrow‐bandgap π‐conjugated oligomers based on diketopyrrolopyrrole chromophoric units coupled with benzodithiophene, indacenodithiophene, thiophene, and isoindigo cores are designed and synthesized for application as donor materials in solution‐processed small‐molecule organic solar cells. The impacts of these different central cores on the optoelectronic and morphological properties, carrier mobility, and photovoltaic performance are investigated. These π‐extended oligomers possess broad and intense optical absorption covering the range from 550 to 750 nm, narrow optical bandgaps of 1.52–1.69 eV, and relatively low‐lying highest occupied molecular orbital (HOMO) energy levels ranging from ?5.24 to ?5.46 eV in their thin films. A high power conversion efficiency of 5.9% under simulated AM 1.5G illumination is achieved for inverted organic solar cells based on a small‐molecule bulk‐heterojunction system consisting of a benzodithiophene‐diketopyrrolopyrrole‐containing oligomer as a donor and [6,6]‐phenyl‐C₇₁‐butyric acid methyl ester (PC₇₁BM) as an acceptor. Transmission electron microscopy and energy‐dispersive X‐ray spectroscopy reveal that interpenetrating and interconnected donor/acceptor domains with pronounced mesoscopic phase segregation are formed within the photoactive binary blends, which is ideal for efficient exciton dissociation and charge transport in the bulk‐heterojunction devices.