New fluorene-based bipolar charge transporting materials.

Air-stable and solution-processable fluorene-based bipolar charge transporting materials (CTMs) were designed, synthesized, and analyzed. These CTMs feature anthraquinone, 9-fluorenone, and 9-dicyanofluorenylidine groups and exhibit good film formation properties for solvent processing. Quantum chemistry simulations and optical absorption measurements proved that several stable conformers and charge transfer complexes form inside the molecules. Hole mobilities in CTMs were around 10-4 to 10-5 cm2 V-1 s-1, while electron mobility in compounds with anthraquinone and 9-dicyanofluorenylidine groups was approximately one order of magnitude lower.

Cross-linkable carbazole-based hole transporting materials for perovskite solar cells.

Carbazole-based molecules V1205 and V1206 capable of cross-linking via three vinyl groups were synthesized by a simple process and applied as hole-transporting materials (HTMs) in inverted perovskite solar cells (PSC). Novel HTMs were thermally polymerized to provide films resistant to organic solvents. A PSC with V1205 exhibited a photovoltaic conversion efficiency of 16.9% with good stability.

Temporal Dynamics of Solid-State Thermally Activated Delayed Fluorescence: Disorder or Ultraslow Solvation?

Time-resolved emission spectra of thermally activated delayed fluorescence (TADF) compounds in solid hosts demonstrate significant temporal shifts. To explain the shifts, two possible mechanisms were suggested, namely, slow solid-state solvation and conformational disorder. Here we employ solid hosts with controllable polarity for analysis of the temporal dynamics of TADF. We show that temporal fluorescence shifts are independent of the dielectric constant of the solid film; however, these shifts evidently depend on the structural parameters of both the host and the TADF dopant. A ≤50% smaller emission peak shift was observed in more rigid polymer host polystyrene than in poly(methyl methacrylate). The obtained results imply that both the host and the dopant should be as rigid as possible to minimize fluorescence instability.

Oxidized Spiro-OMeTAD: Investigation of Stability in Contact with Various Perovskite Compositions.

The power conversion efficiency of perovskite solar cells (PSCs) has risen steadily in recent years; however, one important aspect of the puzzle remains to be solved-the long-term stability of the devices. We believe that understanding the underlying reasons for the observed instability and finding means to circumvent it is crucial for the future of this technology. Not only the perovskite itself but also other device components are susceptible to thermal degradation, including the materials comprising the hole-transporting layer. In particular, the performance-enhancing oxidized hole-transporting materials have attracted our attention as a potential weak component in the system. Therefore, we performed a series of experiments with oxidized spiro-OMeTAD to determine the stability of the material interfaced with five most popular perovskite compositions under thermal stress. It was found that oxidized spiro-OMeTAD is readily reduced to the neutral molecule upon interaction with all five perovskite compositions. Diffusion of iodide ions from the perovskite layer is the main cause for the reduction reaction which is greatly enhanced at elevated temperatures. The observed sensitivity of the oxidized spiro-OMeTAD to ion diffusion, especially at elevated temperatures, causes a decrease in the conductivity observed in the doped films of spiro-OMeTAD, and it also contributes significantly to a drop in the performance of PSCs operated under prolonged thermal stress.

Sterically controlled azomethine ylide cycloaddition polymerization of phenyl-C61-butyric acid methyl ester.

Phenyl-C61-butyric acid methyl ester (PCBM) is polymerized simply using a one-pot reaction to yield soluble, high molecular weight polymers. The sterically controlled azomethine ylide cycloaddition polymerization (SACAP) is demonstrated to be highly adaptable and yields polymers with probable Mn≈ 24 600 g mol(-1) and Mw≈ 73 800 g mol(-1). Products are metal-free and of possible benefit to organic and hybrid photovoltaics and electronics as they form thin films from solution and have raised LUMOs. The promising electronic properties of this new polymer are discussed.

Designing solution-processable air-stable liquid crystalline crosslinkable semiconductors.

Organic electronics technology, in which at least the semiconducting component of the integrated circuit is an organic material, offers the potential for fabrication of electronic products by low-cost printing technologies, such as ink jet, gravure offset lithography and flexography. The products will typically be of lower performance than those using the present state of the art single crystal or polysilicon transistors, but comparable to amorphous silicon. A range of prototypes are under development, including rollable electrophoretic displays, active matrix liquid crystal (LC) displays, flexible organic light emitting diode displays, low frequency radio frequency identification tag and other low performance electronics. Organic semiconductors that offer both electrical performance and stability with respect to storage and operation under ambient conditions are required. This work describes the development of reactive mesogen semiconductors, which form large crosslinked LC domains on polymerization within mesophases. These crosslinked domains offer mechanical stability and are inert to solvent exposure in further processing steps. Reactive mesogens containing conjugated aromatic cores, designed to facilitate charge transport and provide good oxidative stability, were prepared and their liquid crystalline properties evaluated. The organization and alignment of the mesogens, both before and after crosslinking, were probed by grazing incidence wide-angle X-ray scattering of thin films. Both time-of-flight and field effect transistor devices were prepared and their electrical characterization reported.

Liquid-crystalline semiconducting polymers with high charge-carrier mobility.

Organic semiconductors that can be fabricated by simple processing techniques and possess excellent electrical performance, are key requirements in the progress of organic electronics. Both high semiconductor charge-carrier mobility, optimized through understanding and control of the semiconductor microstructure, and stability of the semiconductor to ambient electrochemical oxidative processes are required. We report on new semiconducting liquid-crystalline thieno[3,2-b ]thiophene polymers, the enhancement in charge-carrier mobility achieved through highly organized morphology from processing in the mesophase, and the effects of exposure to both ambient and low-humidity air on the performance of transistor devices. Relatively large crystalline domain sizes on the length scale of lithographically accessible channel lengths ( approximately 200 nm) were exhibited in thin films, thus offering the potential for fabrication of single-crystal polymer transistors. Good transistor stability under static storage and operation in a low-humidity air environment was demonstrated, with charge-carrier field-effect mobilities of 0.2-0.6 cm(2) V(-1) s(-1) achieved under nitrogen.

Stable polythiophene semiconductors incorporating thieno[2,3-b]thiophene.

This work describes a new design methodology that allows the preparation of air stable, semiconducting thiophene polymers with high charge carrier mobilities. The incorporation of thieno[2,3-b]thiophene into a polythiophene backbone introduces cross-conjugated double bonds that disfavor full delocalization, leading to high ionization potential in comparison to a fully conjugated polythiophene, with no reduction in charge carrier mobility. The resulting solution processable polymers exhibit charge carrier mobilities up to 0.15 cm2/V s and on/off ratios greater than 105 when measured in air. Transistors exhibit lifetimes of several months in air with no encapsulation necessary.