Search

Ambient stable solution processed n-channel organic field effect transistors (OFETs) are essential for next-generation low-cost organic electronic devices. Several molecular features, such as suitable orbital energy levels, easy synthetic steps, etc. , must be considered while designing efficient active layer materials. Here, we report a case of improved ambient stability of solution-processed n-type OFETs upon suitable end-groups substitution of the active layer materials. A pair of core-substituted napthalenediimide (NDIFCN 2 and EHNDICN 2 ) derivatives with alkyl and perfluorinated end groups are considered. The transistor devices made out of these two derivatives exhibited largely different ambient stability behavior. The superior device stability (more than 25 days under ambient conditions) of one of the derivatives (NDIFCN 2 ) was ascribed to the presence of fluorinated end groups that function as hydrophobic guard units inhibiting moisture infiltration into the active layer, thereby achieving ambient stability under humid conditions (>65% relative atmospheric humidity). Molecular level optical and electrochemical properties, thermal stability, and the solution-processed (spin coat and drop cast active layers) device characteristics are described in detail. Our findings highlight the requirement of hydrophobic end groups or sidechains for ambient stability of active layer materials, along with deep LUMO levels for ambient stability., Competing Interests: The authors declare no competing financial interest., (This journal is © The Royal Society of Chemistry.)

Despite the rapid rise in the performance of a variety of perovskite optoelectronic devices with vertical charge transport, the effects of ion migration remain a common and longstanding Achilles' heel limiting the long-term operational stability of lead halide perovskite devices. However, there is still limited understanding of the impact of tin (Sn) substitution on the ion dynamics of lead (Pb) halide perovskites. Here, we employ scan-rate-dependent current-voltage measurements on Pb and mixed Pb-Sn perovskite solar cells to show that short circuit current losses at lower scan rates, which can be traced to the presence of mobile ions, are present in both kinds of perovskites. To understand the kinetics of ion migration, we carry out scan-rate-dependent hysteresis analyses and temperature-dependent impedance spectroscopy measurements, which demonstrate suppressed ion migration in Pb-Sn devices compared to their Pb-only analogues. By linking these experimental observations to first-principles calculations on mixed Pb-Sn perovskites, we reveal the key role played by Sn vacancies in increasing the iodide ion migration barrier due to local structural distortions. These results highlight the beneficial effect of Sn substitution in mitigating undesirable ion migration in halide perovskites, with potential implications for future device development., Competing Interests: S. D. S. is a cofounder of Swift Solar. The remaining authors declare no competing interests., (This journal is © The Royal Society of Chemistry.)

The migration of ionic defects and electrochemical reactions with metal electrodes remains one of the most important research challenges for organometal halide perovskite optoelectronic devices. There is still a lack of understanding of how the formation of mobile ionic defects impact charge carrier transport and operational device stability, particularly in perovskite field-effect transistors (FETs), which tend to exhibit anomalous device characteristics. Here, the evolution of the n-type FET characteristics of one of the most widely studied materials, Cs 0.05 FA 0.17 MA 0.78 PbI 3, is investigated during repeated measurement cycles as a function of different metal source-drain contacts and precursor stoichiometry. The channel current increases for high work function metals and decreases for low work function metals when multiple cycles of transfer characteristics are measured. The cycling behavior is also sensitive to the precursor stoichiometry. These metal/stoichiometry-dependent device non-idealities are correlated with the quenching of photoluminescence near the positively biased electrode. Based on elemental analysis using electron microscopy the observations can be understood by an n-type doping effect of metallic ions that are created by an electrochemical interaction at the metal-semiconductor interface and migrate into the channel. The findings improve the understanding of ion migration, contact reactions, and the origin of non-idealities in lead triiodide perovskite FETs., (© 2023 The Authors. Small published by Wiley-VCH GmbH.)

In the current work, biomaterial composed of Xanthan gum and Diethylene glycol dimethacrylate with impregnation of graphite nanopowder filler in their matrices was fabricated successfully for their potential usage in the engineering of bone defects. Various physicochemical properties associated with the biomaterial were characterized using FTIR, XRD, TGA, SEM etc. The biomaterial rheological studies imparted the better notable properties associated with the inclusion of graphite nanopowder. The biomaterial synthesized exhibited a controlled drug release. Adhesion and proliferation of different secondary cell lines do not generate ROS on the current biomaterial and thus show its biocompatibility and non-toxic nature. The synthesized biomaterial's osteogenic potential on SaOS-2 cells was supported by increased ALP activity, enhanced differentiation and biomineralization under osteoinductive circumstances. The current biomaterial demonstrates that in addition to the drug-delivery applications, it can also be a cost-effective substrate for cellular activities and has all the necessary properties to be considered as a promising alternative material suitable for repairing and restoring bone tissues. We propose that this biomaterial may have commercial importance in the biomedical field., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

Development of new n-type semiconductors with tunable band gap and dielectric constant has significant implication in dissociating bound charge carrier relevant for demonstrating high performance optoelectronic devices. Boron-β-thioketonates (MTDKB), analogues to boron-β-diketonates containing a sulfur atom in the framework of β-diketones were synthesized. Bulk transport measurement exhibited an outstanding bulk electron mobility of ≈0.003 cm 2  V -1  s -1 , which is among the best values reported till date in these class of semiconducting materials and correspondingly a single junction photo responsivity of upto 6 mA W -1 was obtained. This new family of O,S-chelated boron compounds exhibited luminescence in the far red/near-infrared region. The remarkable red shift of 89 nm (fluorescence) observed for 4 a in comparison with analogues boron-β-diketonate signifies the importance of sulfur in these molecules. MTDKBs with amine functionality have also been investigated as an ON/OFF fluorescent sensor., (© 2023 Wiley-VCH GmbH.)

Investigation of the inherent field-driven charge transport behaviour of three-dimensional lead halide perovskites has largely remained challenging, owing to undesirable ionic migration effects near room temperature and dipolar disorder instabilities prevalent specifically in methylammonium-and-lead-based high-performing three-dimensional perovskite compositions. Here, we address both these challenges and demonstrate that field-effect transistors based on methylammonium-free, mixed metal (Pb/Sn) perovskite compositions do not suffer from ion migration effects as notably as their pure-Pb counterparts and reliably exhibit hysteresis-free p-type transport with a mobility reaching 5.4 cm 2  V -1  s -1 . The reduced ion migration is visualized through photoluminescence microscopy under bias and is manifested as an activated temperature dependence of the field-effect mobility with a low activation energy (~48 meV) consistent with the presence of the shallow defects present in these materials. An understanding of the long-range electronic charge transport in these inherently doped mixed metal halide perovskites will contribute immensely towards high-performance optoelectronic devices., (© 2023. The Author(s), under exclusive licence to Springer Nature Limited.)

Although many examples of mechanically flexible crystals are currently known, their utility in all-flexible devices is not yet adequately demonstrated, despite their immense potential for fabricating high performance flexible devices. Here, we report two alkylated diketopyrrolopyrrole (DPP) semiconducting single crystals, one of which displays impressive elastic mechanical flexibility whilst the other is brittle. Using the single crystal structures and density functional theory (DFT) calculations, we show that the methylated diketopyrrolopyrrole (DPP-diMe) crystals, with dominant π-stacking interactions and large contributions from dispersive interactions, are superior in terms of their stress tolerance and field-effect mobility ( μ FET ) when compared to the brittle crystals of the ethylated diketopyrrolopyrrole derivative (DPP-diEt). Periodic dispersion-corrected DFT calculations revealed that upon the application of 3% uniaxial strain along the crystal growth ( a )-axis, the elastically flexible DPP-diMe crystal displays a soft energy barrier of only 0.23 kJ mol -1 while the brittle DPP-diEt crystal displays a significantly larger energy barrier of 3.42 kJ mol -1 , in both cases relative to the energy of the strain-free crystal. Such energy-structure-function correlations are currently lacking in the growing literature on mechanically compliant molecular crystals and have the potential to support a deeper understanding of the mechanism of mechanical bending. The field effect transistors (FETs) made of flexible substrates using elastic microcrystals of DPP-diMe retained μ FET (from 0.019 cm 2 V -1 s -1 to 0.014 cm 2 V -1 s -1 ) more efficiently even after 40 bending cycles when compared to the brittle microcrystals of DPP-diEt which showed a significant drop in μ FET just after 10 bending cycles. Our results not only provide valuable insights into the bending mechanism, but also demonstrate the untapped potential of mechanically flexible semiconducting crystals for designing all flexible durable field-effect transistor devices., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Herein, we describe the synthesis, characterization, and optoelectronic investigation of a stable 4nπ dihydrotetraazapentacene derivative. The neutral dihydrotetraazapentacene contains a 24π-conjugated N -heteroacene core with two phenyl pendants appended thereof. The exceptional stability of this formally antiaromatic π-system is attributed to the fused dihydropyrazine ring, which has ethenamine (enamine) conjugations, and hence, the π-electrons delocalize over the nearly planar azapentacene core to endow with a global aromatic characteristic. The embedded dihydropyrazine also offers an additional Clar's sextet with enhanced aromaticity. The present dihydrotetraazapentacene can be considered as a multitasking N -heteroacene, which showed photoresponsive nature under visible light illumination, acidochromism in solution, and p-type charge transport with an appreciable field-effect hole mobility of 0.02 cm 2 V -1 s -1 and a bulk p-type mobility of 0.98 × 10 -4 cm 2 V -1 s -1 in the space charge-limited regime of operation measured in the hole-only device. Nucleus-independent chemical shift calculation, anisotropy of the induced current density plot, and anisotropic mobility calculation were performed to support the experimental findings.

Controlling the flow of electrical current at the nanoscale typically requires complex top-down approaches. Here, a bottom-up approach is employed to demonstrate resistive switching within molecular wires that consist of double-helical metallopolymers and are constructed by self-assembly. When the material is exposed to an electric field, it is determined that ≈25% of the copper atoms oxidize from Cu I to Cu II , without rupture of the polymer chain. The ability to sustain such a high level of oxidation is unprecedented in a copper-based molecule: it is made possible here by the double helix compressing in order to satisfy the new coordination geometry required by Cu II . This mixed-valence structure exhibits a 10 4 -fold increase in conductivity, which is projected to last on the order of years. The increase in conductivity is explained as being promoted by the creation, upon oxidation, of partly filled d z 2 orbitals aligned along the mixed-valence copper array; the long-lasting nature of the change in conductivity is due to the structural rearrangement of the double-helix, which poses an energetic barrier to re-reduction. This work establishes helical metallopolymers as a new platform for controlling currents at the nanoscale., (© 2021 The Authors. Advanced Materials published by Wiley-VCH GmbH.)

We investigate the charge transport physics of a previously unidentified class of electron-deficient conjugated polymers that do not contain any single bonds linking monomer units along the backbone but only double-bond linkages. Such polymers would be expected to behave as rigid rods, but little is known about their actual chain conformations and electronic structure. Here, we present a detailed study of the structural and charge transport properties of a family of four such polymers. By adopting a copolymer design, we achieve high electron mobilities up to 0.5 cm 2 V -1 s -1 Field-induced electron spin resonance measurements of charge dynamics provide evidence for relatively slow hopping over, however, long distances. Our work provides important insights into the factors that limit charge transport in this unique class of polymers and allows us to identify molecular design strategies for achieving even higher levels of performance., (Copyright © 2021 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works. Distributed under a Creative Commons Attribution NonCommercial License 4.0 (CC BY-NC).)

Since the invention of field effect transistors (FETs) in the mid-20th century, nanosheet (NS) transistors have been considered the future toward fulfilling Moore's law of scaling. Moving beyond conventional semiconductors, thickness tunable orthorhombic CsPbBr 3 NSs are achieved by a perfect control in which the lateral dimension can be extended close to 1 μm. While 18-carbon-chain ligands produce ∼4.5 nm thick NSs, the strongly adsorbed less dynamic 8-carbon-chain ligands result in ∼9.2 nm NSs. Equipped with a minimum trap state density, a lower effective mass of charge carriers, and better carrier transport, the NSs enable an order of magnitude increase in the field effect mobility as compared to that of CsPbBr 3 nanocubes, thus revealing the efficacy of designing the two-dimensional morphology. The p -type field effect mobility (μ FET ) of the photoexcited NSs reaches 10 -5 cm 2 V -1 s -1 at 200 K upon mitigation of the challenges of ionic screening and constrained tunneling probability across organic ligands.

Using circularly polarized broadband transient absorption, time-resolved circular photoluminescence, and transient Faraday rotation spectroscopy, we report that spin-dependent interactions have a significant impact on exciton energies and spin depolarization times in layered Ruddlesden-Popper hybrid metal-halide perovskites. In BA 2 FAPb 2 I 7 , we report that room-temperature spin lifetimes are largest (3.2 ps) at a carrier density of ∼10 17 cm -3 with increasing depolarization rates at higher exciton densities. This indicates that many-body interactions reduce spin-lifetimes and outcompete the effect of D'yakonov-Perel precessional relaxation that has been previously reported at lower carrier densities. We further observe a dynamic circular dichroism that arises from a photoinduced polarization in the exciton distribution between total angular momentum states. Our findings provide fundamental and application relevant insights into the spin-dependent exciton-exciton interactions in layered hybrid perovskites.

Precise control of the microstructure in organic semiconductors (OSCs) is essential for developing high-performance organic electronic devices. Here, a comprehensive charge transport characterization of two recently reported rigid-rod conjugated polymers that do not contain single bonds in the main chain is reported. It is demonstrated that the molecular design of the polymer makes it possible to achieve an extended linear backbone structure, which can be directly visualized by high-resolution scanning tunneling microscopy (STM). The rigid structure of the polymers allows the formation of thin films with uniaxially aligned polymer chains by using a simple one-step solution-shear/bar coating technique. These aligned films show a high optical anisotropy with a dichroic ratio of up to a factor of 6. Transport measurements performed using top-gate bottom-contact field-effect transistors exhibit a high saturation electron mobility of 0.2 cm 2 V -1 s -1 along the alignment direction, which is more than six times higher than the value reported in the previous work. This work demonstrates that this new class of polymers is able to achieve mobility values comparable to state-of-the-art n-type polymers and identifies an effective processing strategy for this class of rigid-rod polymer system to optimize their charge transport properties., (© 2020 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Despite sustained research, application of lead halide perovskites in field-effect transistors (FETs) has substantial concerns in terms of operational instabilities and hysteresis effects which are linked to its ionic nature. Here, we investigate the mechanism behind these instabilities and demonstrate an effective route to suppress them to realize high-performance perovskite FETs with low hysteresis, high threshold voltage stability (ΔV t < 2 V over 10 hours of continuous operation), and high mobility values >1 cm 2 /V·s at room temperature. We show that multiple cation incorporation using strain-relieving cations like Cs and cations such as Rb, which act as passivation/crystallization modifying agents, is an effective strategy for reducing vacancy concentration and ion migration in perovskite FETs. Furthermore, we demonstrate that treatment of perovskite films with positive azeotrope solvents that act as Lewis bases (acids) enables a further reduction in defect density and substantial improvement in performance and stability of n-type (p-type) perovskite devices., (Copyright © 2020 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works. Distributed under a Creative Commons Attribution NonCommercial License 4.0 (CC BY-NC).)

Mixed lead-tin halide perovskites have sufficiently low bandgaps (∼1.2 eV) to be promising absorbers for perovskite-perovskite tandem solar cells. Previous reports on lead-tin perovskites have typically shown poor optoelectronic properties compared to neat lead counterparts: short photoluminescence lifetimes (<100 ns) and low photoluminescence quantum efficiencies (<1%). Here, we obtain films with carrier lifetimes exceeding 1 μs and, through addition of small quantities of zinc iodide to the precursor solutions, photoluminescence quantum efficiencies under solar illumination intensities of 2.5%. The zinc additives also substantially enhance the film stability in air, and we use cross-sectional chemical mapping to show that this enhanced stability is because of a reduction in tin-rich clusters. By fabricating field-effect transistors, we observe that the introduction of zinc results in controlled p-doping. Finally, we show that zinc additives also enhance power conversion efficiencies and the stability of solar cells. Our results demonstrate substantially improved low-bandgap perovskites for solar cells and versatile electronic applications., Competing Interests: The authors declare the following competing financial interest(s): Dr. Samuel D. Stranks is a co-founder of Swift Solar Inc. Prof. Henry J. Snaith FRS is a co-founder of Oxford PV.

Optoelectronic devices based on metal halide perovskites, including solar cells and light-emitting diodes, have attracted tremendous research attention globally in the last decade. Due to their potential to achieve high carrier mobilities, organic-inorganic hybrid perovskite materials can enable high-performance, solution-processed field-effect transistors (FETs) for next-generation, low-cost, flexible electronic circuits and displays. However, the performance of perovskite FETs is hampered predominantly by device instabilities, whose origin remains poorly understood. Here, perovskite single-crystal FETs based on methylammonium lead bromide are studied and device instabilities due to electrochemical reactions at the interface between the perovskite and gold source-drain top contacts are investigated. Despite forming the contacts by a gentle, soft lamination method, evidence is found that even at such "ideal" interfaces, a defective, intermixed layer is formed at the interface upon biasing of the device. Using a bottom-contact, bottom-gate architecture, it is shown that it is possible to minimize such a reaction through a chemical modification of the electrodes, and this enables fabrication of perovskite single-crystal FETs with high mobility of up to ≈15 cm 2 V -1 s -1 at 80 K. This work addresses one of the key challenges toward the realization of high-performance solution-processed perovskite FETs., (© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

One source of instability in perovskite solar cells (PSCs) is interfacial defects, particularly those that exist between the perovskite and the hole transport layer (HTL). We demonstrate that thermally evaporated dopant-free tetracene (120 nm) on top of the perovskite layer, capped with a lithium-doped Spiro-OMeTAD layer (200 nm) and top gold electrode, offers an excellent hole-extracting stack with minimal interfacial defect levels. For a perovskite layer interfaced between these graded HTLs and a mesoporous TiO 2 electron-extracting layer, its photoluminescence yield reaches 15% compared to 5% for the perovskite layer interfaced between TiO 2 and Spiro-OMeTAD alone. For PSCs with graded HTL structure, we demonstrate efficiency of up to 21.6% and an extended power output of over 550 hours of continuous illumination at AM1.5G, retaining more than 90% of the initial performance and thus validating our approach. Our findings represent a breakthrough in the construction of stable PSCs with minimized nonradiative losses.

Ferromagnetic ordering in a topological insulator can break time-reversal symmetry, realizing dissipationless electronic states in the absence of a magnetic field. The control of the magnetic state is of great importance for future device applications. We provide a detailed systematic study of the magnetic state in highly doped Cr x Sb 2-x Te 3 thin films using electrical transport, magneto-optic Kerr effect measurements and terahertz time domain spectroscopy, and also report an efficient electric gating of ferromagnetic order using the electrolyte ionic liquid [DEME][TFSI]. Upon increasing the Cr concentration from x = 0.15 to 0.76, the Curie temperature (T c ) was observed to increase by ~5 times to 176 K. In addition, it was possible to modify the magnetic moment by up to 50% with a gate bias variation of just ±3 V, which corresponds to an increase in carrier density by 50%. Further analysis on a sample with x = 0.76 exhibits a clear insulator-metal transition at T c , indicating the consistency between the electrical and optical measurements. The direct correlation obtained between the carrier density and ferromagnetism - in both electrostatic and chemical doping - using optical and electrical means strongly suggests a carrier-mediated Ruderman-Kittel-Kasuya-Yoshida (RKKY) coupling scenario. Our low-voltage means of manipulating ferromagnetism, and consistency in optical and electrical measurements provides a way to realize exotic quantum states for spintronic and low energy magneto-electronic device applications.

The development of high-performance multifunctional polymer-based electronic circuits is a major step toward future flexible electronics. Here, we demonstrate a tunable approach to fabricate such devices based on rationally designed dielectric super-lattice structures with photochromic azobenzene molecules. These nanodielectrics possessing ionic, molecular, and atomic polarization are utilized in polymer thin-film transistors (TFTs) to realize high-performance electronics with a p-type field-effect mobility (μ FET ) exceeding 2 cm 2 V -1 s -1 . A crossover in the transport mechanism from electrostatic dipolar disorder to ionic-induced disorder is observed in the transistor characteristics over a range of temperatures. The facile supramolecular design allows the possibility to optically control the extent of molecular and ionic polarization in the ultrathin nanodielectric. Thus, we demonstrate a 3-fold increase in the capacitance from 0.1 to 0.34 μF/cm 2 , which results in a 200% increase in TFT channel current.

Here, we demonstrate the incorporation of monovalent cation additives into CH3NH3PbI3 perovskite in order to adjust the optical, excitonic, and electrical properties. The possibility of doping was investigated by adding monovalent cation halides with similar ionic radii to Pb 2+ , including Cu + , Na + , and Ag + . A shift in the Fermi level and a remarkable decrease of sub-bandgap optical absorption, along with a lower energetic disorder in the perovskite, was achieved. An order-of-magnitude enhancement in the bulk hole mobility and a significant reduction of transport activation energy within an additive-based perovskite device was attained. The confluence of the aforementioned improved properties in the presence of these cations led to an enhancement in the photovoltaic parameters of the perovskite solar cell. An increase of 70 mV in open circuit voltage for AgI and a 2 mA/cm 2 improvement in photocurrent density for NaI- and CuBr-based solar cells were achieved compared to the pristine device. Our work paves the way for further improvements in the optoelectronic quality of CH3NH3PbI3 perovskite and subsequent devices. It highlights a new avenue for investigations on the role of dopant impurities in crystallization and controls the electronic defect density in perovskite structures.

Fundamental understanding of the charge transport physics of hybrid lead halide perovskite semiconductors is important for advancing their use in high-performance optoelectronics. We use field-effect transistors (FETs) to probe the charge transport mechanism in thin films of methylammonium lead iodide (MAPbI 3 ). We show that through optimization of thin-film microstructure and source-drain contact modifications, it is possible to significantly minimize instability and hysteresis in FET characteristics and demonstrate an electron field-effect mobility (μ FET ) of 0.5 cm 2 /Vs at room temperature. Temperature-dependent transport studies revealed a negative coefficient of mobility with three different temperature regimes. On the basis of electrical and spectroscopic studies, we attribute the three different regimes to transport limited by ion migration due to point defects associated with grain boundaries, polarization disorder of the MA + cations, and thermal vibrations of the lead halide inorganic cages.

Reliable and ultrasensitive detection of mercury ions is of paramount importance for toxicology assessment, environmental protection, and human health. Herein, we present a novel optoelectronic approach based on nanoarchitectonics of small-molecule templated DNA system that consists of an adenine (A)-conjugated small organic semiconductor (BNA) and deoxyribo-oligothymidine (dT n ). This mutually templated dynamic chiral coassembly system (BNAn-dT n ) with tunable chiroptical, morphological, and electrical properties is tapped in to enable ultrasensitive and selective detection of inorganic and organometallic mercury in water. We observe a rapid transformation of the BNA n -dT n coassembly into a metallo-DNA duplex [dT-Hg-dT] n in the presence of mercury, which is utilized for a chiro-optical and conductivity-based rapid and subnanomolar sensitivity (≥0.1 nM, 0.02 ppb) to mercury ions in water (∼100 times lower than United States Environmental Protection Agency tolerance limit). This ultrasensitive detection of inorganic and organometallic mercury is driven by a novel chemical design principle that allows strong mercury thymine interaction. This study is anticipated to inspire the development of future templated DNA nanotechnology-based optoelectronic devices for the rapid and ultrasensitive detection of numerous other toxic analytes.

n-channel organic semiconductors are prone to oxidation upon exposed to ambient conditions. Herein, we report design and synthesis of diketopyrrolopyrrole (DPP)-based oligomers for ambipolar organic thin-film transistors (OFETs) with excellent air and bias stability at ambient conditions. The cyclic voltammetry measurements reveal exceptional electrochemical stability during the redox cycle of oligomers. Structural properties including aggregation, crystallinity, and morphology in thin film were investigated by UV-visible spectroscopy, atomic force microscopy (AFM), thin-film X-ray diffraction (XRD), and grazing incidence small-angle X-ray scattering (GISAXS) measurements. AFM reveals morphological changes induced by different processing conditions whereas GISAXS measurements show an increase in the population of face-on oriented crystallites in films subjected to a combination of solvent and thermal treatments. These measurements also highlight the significance of chalcogen atom from sulfur to selenium on the photophysical, optical, electronic, and solid-state properties of DPP-DPP oligomers. Charge carrier mobilities of the oligomers were investigated by fabricating top-gate bottom-contact (TG-BC) thin-film transistors by annealing the thin films under various conditions. Combined solvent and thermal annealing of DPP-DPP oligomer thin films results in consistent electron mobilities as high as ∼0.2 cm(2) V(-1) s(-1) with an on/off ratio exceeding 10(4). Field-effect behavior was retained for up to ∼4 weeks, which illustrates remarkable air and bias stability. This work paves the way toward the development of n-channel DPP-DPP-based oligomers exhibiting retention of field-effect behavior with superior stability at ambient conditions.

We report on the optimization of the interfacial properties of titania in mesoscopic CH3NH3PbI3 solar cells. Modification of the mesoporous TiO2 film by TiCl4 treatment substantially reduced the surface traps, as is evident from the sharpness of the absorption edge with a significant reduction in Urbach energy (from 320 to 140 meV) determined from photothermal deflection spectroscopy, and led to an order of magnitude enhancement in the bulk electron mobility and corresponding decrease in the transport activation energy (from 170 to 90 meV) within a device. After optimization of the photoanode-perovskite interface using various sizes of TiO2 nanoparticles, the best photovoltaic efficiency of 16.3% was achieved with the mesoporous TiO2 composed of 36 nm sized nanoparticles. The improvement in device performance can be attributed to the enhanced charge collection efficiency that is driven by improved charge transport in the mesoporous TiO2 layer. Also, the decreased recombination at the TiO2-perovskite interface and better perovskite coverage play important roles.

The possibility of designing programmable thin-film supramolecular structures with spontaneous polarization widens the utility of facile supramolecular chemistry. Although a range of low molecular mass molecular single crystals has been shown to exhibit ferroelectric polarization, demonstration of stimuli-responsive, thin-film, solution-processable supramolecular ferroelectric materials is rare. We introduce aromatic π-electron donor-acceptor molecular systems responsive to multiple stimuli that undergo supramolecular chiral mixed-stack charge-transfer (CT) coassembly through the tweezer-inclusion-sandwich process supported by hydrogen-bonding interactions. The structural synergy originating from hydrogen-bonding and chiral CT interactions resulted in the development of spontaneous unidirectional macroscopic polarization in the crystalline nanofibrous hydrogel network, under ambient conditions. Moreover, the tunability of these interactions with optical, mechanical, thermal, and electrical stimuli allowed the design of multistate thin-film memory devices. Our design strategy of the supramolecular motif is expected to help the development of new molecular engineering strategies for designing potentially useful smart multicomponent organic electronics.

While the mechanism of self-assembly of π-conjugated molecules has been well studied to gain control over the structure and functionality of supramolecular polymers, the intermolecular interactions underpinning it are poorly understood. Here, we study the mechanism of self-assembly of perylene bisimide derivatives possessing dipolar carbonate groups as linkers. It was observed that the combination of carbonate linkers and cholesterol/dihydrocholesterol self-assembling moieties led to a cooperative mechanism of self-assembly. Atomistic molecular dynamics simulations of an assembly in explicit solvent strongly suggest that the dipole-dipole interaction between the carbonate groups imparts a macro-dipolar character to the assembly. This is confirmed experimentally through the observation of a significant polarization in the bulk phase for molecules following a cooperative mechanism. The cooperativity is attributed to the presence of dipole-dipole interaction in the assembly. Thus, anisotropic long-range intermolecular interactions such as dipole-dipole interaction can serve as a way to obtain cooperative self-assembly and aid in rationalizing and predicting the mechanisms in various synthetic supramolecular polymers.

A new thiophene-based salphen-type ligand, 1, and its Cu(II) and Zn(II) complexes, 1·Cu and 1·Zn·MeOH, were designed and synthesized. These metal organic complexes (MOCs), with ultra-close π-stacking interactions were explored as a novel class of active materials for organic field effect transistors (OFETs). The top-contact bottom gated OFETs fabricated from solution-processed thin films of 1·Cu and 1·Zn·MeOH exhibited excellent p-type mobilities (up to 0.7 and 1.5 cm(2) V(-1) s(-1), respectively).

We present here the physicochemical characterization of a series of D-A-D type molecules which comprise benzooxadiazole (BDO) and benzothiadiazole (BDT) core symmetrically linked to two aromatic-heterols (furan (F), thiophene (T) and selenophene (Se)) at 4 and 7-positions. The molecular structures of four compounds 2 (T-BDO-T), 3 (Se-BDO-Se), 5 (T-BDT-T), and 6 (Se-BDT-Se) were determined by single-crystal X-ray diffraction. The combination of chalcogen atoms of benzochalcogenadiazole and chalcogenophene in D-A-D molecules has significant impact on their molecular packing in crystal structures. Structural analyses and theoretical calculations showed that all the molecules are nearly planar. Crystal structures of 2, 3, 5, and 6 showed significant short range interactions such as π···π, CH···π, S···π, Se···π, N···H, O···H, S···H, Se···H, S···O, and Se···N interactions, which influence crystal packing and orientation of the capped aromatic-heterol rings with respect to the central BDO or BDT unit. The π-stacking interactions have been observed via intermolecular overlap of the donor with acceptor units of the adjacent molecules which facilitate the charge transport process. Good thermal stability and solubility in common organic solvents make them good candidate for flexible electronics. Interestingly, the molecules 2, 3, and 6 have the propensity to form ordered crystallites when sheared during the drying process in the thin films. Devices based on these solution processable all organic FETs demonstrated hole mobility as high as 0.08 cm(2) V(-1) s(-1) and Ion/Ioff ratio of 10(4).

The synthesis, characterization, and device studies of poly(benzobisoxazole imide)s containing perylene or naphthalene units in an alternating fashion with the oxazole unit are described. Photoinduced energy transfer and charge separation were studied in methanesulfonic acid (MSA) solution via absorption, excitation, and steady-state fluorescence studies. Excitation of the bisoxazole moiety resulted in enhanced emission from the perylene bisimide unit as a result of FRET (Förster resonance energy transfer). The influence of the imide substitution into the linear chain of poly(benzobisoxazole) (PBO) on its solid-state packing was examined by wide-angle X-ray diffraction (WXRD) analysis. Bottom contact field effect transistors (FET) based on thermally annealed polymer films were fabricated and studied. The polymers showed n-type charge transport and current modulation with an on/off ratio greater than 10(2). It was observed that the FETs consisting of the random copolymer of bisoxazole containing both perylene as well as naphthalene bisimide units had higher performance parameters such as better mobility (μ(e)) and I(on)/I(off) ratio compared to those of the pristine systems.