The field-effect hole mobility of rubicene having high ionization energy (∼5.5 eV) is 0.20 cm2 V−1 s−1 and is improved to 0.32 cm2 V−1 s−1 with PFBT SAM treatment which reduces the hole injection barrier and induces an edge-on configuration.

The primary role of substituted side chains in organic semiconductors is to increase their solubility in common organic solvents. In the recent past, many literature reports have suggested that the side chains play a critical role in molecular packing and strongly impact the charge transport properties of conjugated polymers. In this work, we have investigated the influence of side-chains on the charge transport behavior of a novel class of diketopyrrolopyrrole (DPP) based alternating copolymers. To investigate the role of sidechains, we prepared four diketopyrrolopyrrole-diketopyrrolopyrrole (DPP-DPP) conjugated polymers with varied side-chains and carried out a systematic study of thin film microstructure and charge transport properties in polymer thin-film transistors (PTFTs). Combining results obtained from grazing incidence X-ray diffraction (GIXD) and charge transport properties in PTFTs, we conclude side-chains have a strong influence on molecular packing, thin film microstructure, and the charge carrier mobility of DPP-DPP copolymers. However, the influence of side-chains on optical properties was moderate. The preferential ''edge-on'' packing and dominant n-channel behavior with exceptionally high field-effect electron mobility values of 41 cm 2 V À1 s À1 were observed by incorporating hydrophilic (triethylene glycol) and hydrophobic side-chains of alternate DPP units. In contrast, moderate electron and hole mobilities were observed by incorporation of branched hydrophobic side-chains. This work clearly demonstrates that the subtle balance between hydrophobicity and hydrophilicity induced by side-chains is a powerful strategy to alter the molecular packing and improve the ambipolar charge transport properties in DPP-DPP based conjugated polymers. Theoretical analysis supports the conclusion that the side-chains influence polymer properties through morphology changes, as there is no effect on the electronic properties in the gas phase. The exceptional electron mobility is at least partially a result of the strong intramolecular conjugation of the donor and acceptor as evidenced by the unusually wide conduction band of the polymer.

Transport of charge carriers through conjugated polymers is strongly influenced by the presence and distribution of structural disorders. In the present work, structural defects caused by the presence of torsional angle were investigated in a diketopyrrolopyrrole (DPP)-based conjugated polymer. Two new copolymers of DPP were synthesized with varying torsional angles to trace the role of structural disorder. The optical properties of these copolymers in solution and thin film reveal the strong influence of torsional angle on their photophysical properties. A strong influence was observed on carrier transport properties of polymers in organic field-effect transistors (OFET) device geometry. The polymers based on phenyl DPP with higher torsional angle (PPTDPP-OD-TEG) resulted in high threshold voltage with less charge carrier mobility as compared to the polymer based on thiophene DPP (2DPP-OD-TEG) bearing a lower torsional angle. Carrier mobility and the molecular orientation of the conjugated polymers were correlated on the basis of grazing incidence Xray scattering measurements showing the strong role of torsional angle introduced in the form of structural disorder. The results presented in this Article provide a deep insight into the sensitivity of structural disorder and its impact on the device performance of DPP-based conjugated polymers.

Interfacial engineering is essential for the development of highly efficient and stable solar cells through minimizing energetic losses at interfaces. Self-assembled monolayers (SAMs) have been shown as a handle to tune the work function (WF) of indium tin oxide (ITO), improving photovoltaic cell performance and device stability. In this study, we utilize a new class of boronic acid-based fluorine-terminated SAMs to modify ITO surfaces in planar perovskite solar cells. The SAM treatment demonstrates an increase of the WF of ITO, an enhancement of the short-circuit current, and a passivation of trap states at the ITO/[poly(3,4ethylenedioxylenethiophene):poly(styrenesulfonic acid)] interface. Device stability improves upon SAM modification, with efficiency decreasing only 20% after one month. Our work highlights a simple treatment route to achieve hysteresis-free, reproducible, stable, and highly efficient (16%) planar perovskite solar cells.

An all-acceptor napthalenediimide-bithiazole-based copolymer, P(NDI2OD-BiTz), was synthesized and characterized for application in thin-film transistors. Density functional theory calculations point to an optimal perpendicular dihedral angle of 90°between acceptor units along isolated polymer chains; yet optimized transistors yield electron mobility of 0.11 cm 2 /(V s) with the use of a zwitterionic naphthalene diimide interlayer. Grazing incidence X-ray diffraction measurements of annealed films reveal that P(NDI2OD-BiTz) adopts a highly ordered edge-on orientation, exactly opposite to similar bithiophene analogs. This report highlights an NDI and thiazole allacceptor polymer and demonstrates high electron mobility despite its nonplanar backbone conformation.

We report on the graphene-assisted growth, crystallization, and phase transition of zinc phthalocyanine (ZnPc) vertically oriented single crystal nanopillars. Postcrystallization thermal annealing of the nanostructures results in a molecular packing change while maintaining the vertical orientation of the single crystals orthogonal to the underlying substrate. Grazing incidence X-ray diffraction and high-resolution TEM studies characterized this phase transition from a metastable crystal phase to the more stable β-phase commonly observed in bulk crystals. These vertical arrays of crystalline nanopillars exhibit a high-surface-to-volume ratio, which is advantageous for applications such as gas sensors. We fabricated chemiresistor sensors with ZnPc nanopillars grown on graphene and demonstrated its selectivity for ammonia vapors, and improvement in sensitivity in the β-phase crystal packing pillars due to their molecular orientation increasing the exposure of the Zn ion to the ammonia analyte. This work highlights the first morphology-retentive phase transition in organic single crystal nanopillars through simple postprocessing thermal annealing. This study opens up the possibility of molecular packing control without large variations in morphology, a necessity for high-performance devices and establishing structure-property relations.

Alkyl chains of varied length and steric bulk are generally appended to π-conjugated chromophores to increase solubility. These alkyl chains also regulate many aspects of the solid-state packing and, in turn, resultant electronic and optical properties of organic semiconductors, yet there remains little understanding as to how these moieties govern such characteristics. Here, we report on a series of (2,5-bis­(3-alkylthiophen-2-yl) thieno­[3,2-b]­thiophenes) (BTTT) monomers where the single-crystal packing configurations and melting points alternate as a function of whether the alkyl side chains have an even or odd number of carbon atoms. When the alkyl chains contain an even number of carbon atoms, the molecules predominantly crystallize with the BTTT units of the stacked lamellae aligned in the same direction. In contrast, when the number of carbon atoms is odd, alternating lamellae are twisted with respect to their neighbors, i.e. the BTTT moieties in one layer are aligned in an orthogonal-like fashion to those in its neighboring lamellae, and the crystal melting points tend to be higher than those with the even-numbered alkyl chains. With density functional theory calculations and geometric analyses, the variations in crystal structure and thus the differences in physical properties are rationalized by an oscillating interlayer interaction that is a function of alkyl side chain atom count and length. This study characterizes an extreme case of an organic semiconductor crystal packing alternation to highlight the effect of even–odd assembly as an underutilized and under-reported handle for tuning the molecular packing of organic semiconductor materials.

In studying the formation and thermally activated cycloreversion of oxidized rubrene to pristine rubrene, we observed an irreversible, second stage oxidized product. Understanding the formation of the irreversible adduct will help one design more chemically robust rubrene derivatives.