Ambient stable solution-processed organic field effect transistors from electron deficient planar aromatics: effect of end-groups on ambient stability.

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 (NDIFCN2 and EHNDICN2) 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 (NDIFCN2) 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.

Thermally activated delayed fluorescence in a mechanically soft charge-transfer complex: role of the locally excited state.

Molecular design for thermally activated delayed fluorescence (TADF) necessitates precise molecular geometric requirements along with definite electronic states to ensure high intersystem crossing (ISC) rate and photoluminescence quantum yield (PLQY). Achieving all these requirements synchronously while maintaining ease of synthesis and scalability is still challenging. To circumvent this, our strategy of combining a crystal engineering approach with basic molecular quantum mechanical principles appears promising. A holistic, non-covalent approach for achieving efficient TADF in crystalline materials with distinct mechanical properties is highlighted here. Charge transfer (CT) co-crystals of two carbazole-derived donors (ETC and DTBC) with an acceptor (TFDCNB) molecule are elaborated as a proof-of-concept. Using temperature-dependent steady-state and time-resolved photoluminescence techniques, we prove the need for a donor-centric triplet state (3LE) to ensure efficient TADF. Such intermediate states guarantee a naturally forbidden, energetically uphill reverse intersystem crossing (RISC) process, which is paramount for effective TADF. A unique single-crystal packing feature with isolated D-A-D trimeric units ensured minimal non-radiative exciton loss, leading to a high PLQY and displaying interesting mechanical plastic bending behaviour. Thus, a comprehensive approach involving a non-covalent strategy to circumvent the conflicting requirements of a small effective singlet-triplet energy offset and a high oscillator strength for efficient TADF emitters is achieved here.

Covalent Organic Framework Thin-Film Photodetectors from Solution-Processable Porous Nanospheres.

The synthesis of homogeneous covalent organic framework (COF) thin films on a desired substrate with decent crystallinity, porosity, and uniform thickness has great potential for optoelectronic applications. We have used a solution-processable sphere transmutation process to synthesize 300 ± 20 nm uniform COF thin films on a 2 × 2 cm2 TiO2-coated fluorine-doped tin oxide (FTO) surface. This process controls the nucleation of COF crystallites and molecular morphology that helps the nanospheres to arrange periodically to form homogeneous COF thin films. We have synthesized four COF thin films (TpDPP, TpEtBt, TpTab, and TpTta) with different functional backbones. In a close agreement between the experiment and density functional theory, the TpEtBr COF film showed the lowest optical band gap (2.26 eV) and highest excited-state lifetime (8.52 ns) among all four COF films. Hence, the TpEtBr COF film can participate in efficient charge generation and separation. We constructed optoelectronic devices having a glass/FTO/TiO2/COF-film/Au architecture, which serves as a model system to study the optoelectronic charge transport properties of COF thin films under dark and illuminated conditions. Visible light with a calibrated intensity of 100 mW cm-2 was used for the excitation of COF thin films. All of the COF thin films exhibit significant photocurrent after illumination with visible light in comparison to the dark. Hence, all of the COF films behave as good photoactive substrates with minimal pinhole defects. The fabricated out-of-plane photodetector device based on the TpEtBr COF thin film exhibits high photocurrent density (2.65 ± 0.24 mA cm-2 at 0.5 V) and hole mobility (8.15 ± 0.64 ×10-3 cm2 V-1 S-1) compared to other as-synthesized films, indicating the best photoactive characteristics.

Crystallizing Sub 10 nm Covalent Organic Framework Thin Films via Interfacial-Residual Concomitance.

Synthesis of covalent organic framework (COF) thin films on different supports with high crystallinity and porosity is crucial for their potential applications. We have designed a new synchronized methodology, residual crystallization (RC), to synthesize sub 10 nm COF thin films. These residual crystallized COF thin films showcase high surface area, crystallinity, and conductivity at room temperature. We have used interfacial crystallization (IC) as a rate-controlling tool for simultaneous residual crystallization. We have also diversified the methodology of residual crystallization by utilizing two different crystallization pathways: fiber-to-film (F-F) and sphere-to-film (S-F). In both cases, we could obtain continuous COF thin films with high crystallinity and porosity grown on various substrates (the highest surface area of a TpAzo COF thin film being 2093 m2 g-1). Precise control over the crystallization allows the synthesis of macroscopic defect-free sub 10 nm COF thin films with a minimum thickness of ∼1.8 nm. We have synthesized two COF thin films (TpAzo and TpDPP) using F-F and S-F pathways on different supports such as borosilicate glass, FTO, silicon, Cu, metal, and ITO. Also, we have investigated the mechanism of the growth of these thin films on various substrates with different wettability. Further, a hydrophilic support (glass) was used to grow the thin films in situ for four-probe system device fabrication. All residual crystallized COF thin films exhibit outstanding conductivity values. We could obtain a conductivity of 3.7 × 10-2 mS cm-1 for the TpAzo film synthesized by S-F residual crystallization.

Incorporating a redox active entity to attain electrical bistability in a polymer semiconductor.

Owing to the advantages of 3-D printable stack, scalability and low cost solution state production, polymer-based resistive memory devices have been identified as the promising alternative for conventional oxide technology. Resistive memory devices based on the redox switch mechanism is particularly found to yield high precision with respect to the operational voltages. Reversible non-volatile resistive state switching was realized with high device yield (>80%), with a redox-active chemical entity conjugated to the polymeric semiconductor, and the control experiments with the model compound confirmed the imperative role of the redox-active anthraquinone center in the polymeric backbone. Highly uniform nanodomains and the trap free layers excluded the possibilities of other known switching mechanisms. Optical studies and the molecular modelling data assert the presence of strong charge transfer characteristics upon optical excitation due to the insertion of the anthraquinone unit, which was detrimental in exhibiting bistable conductive states in electrical bias as well.

Irreversible Resistive State Switching in Devices with a Homoleptic Cobalt(II) Complex Active Layer.

Molecules with bi-stable electronic transport behaviour have been in upfront research topics of the molecular semiconductor devices in the past few decades due to the use of such materials in resistive data storage devices. Transition metal complexes (TMC) are expected to be potential candidates in regard to the tunable and manifold redox behaviour expecting multiple bulk transport states. Finding alternate mechanisms in such devices with TMC as the active layer materials would revoke the multifaceted approach to the functional gain. We have succeeded in demonstrating write once-read many (WORM) type of resistive memory device using a homoleptic Cobalt(II) (Co(II)) complex with large on/off current ratio ensuring the easy readout process at lower voltage. The advantage of this device was the turn on voltage was found to be the low (<2.7 V) operational voltage and the success ratio of the devices were more than 83%. The durability of the stored data was found to be more than 35,000 seconds which ensures the stability of the bistable state in the fabricated devices. Such ambient stable, solution processable devices are important for the large-scale printable devices. The manuscript describes the preparation, optical and electrochemical characterisation of the metal complex used along with a detailed mechanistic investigations and electrical characterisation of memory device obtained from a stable cobalt complex.

Influence of non-covalent interactions in dictating the polarity and mobility of charge carriers in a series of crystalline NDIs: a computational case study.

Polycyclic aromatic compounds and their derivatives have emerged as potential molecular entities for air-stable n-type organic semiconductors. In particular, naphthalene diimide (NDI)-derived compounds stand out as one of the most promising classes of molecules that have been studied extensively. There have been a lot of debatable experimental reports on the OFET performance characteristics of some of these materials, which have not yet been resolved completely. Hence, the critical intrinsic aspect of the molecular materials during charge transport in a bulk crystalline state would be essential to categorise the potential candidates. As a case study, in this comprehensive computational approach, we investigated the structural and supramolecular organization in single crystals and the role of those aspects in the bulk carrier transport of a group of selected end-substituted NDI derivatives. A subtle alteration of the end group was observed to result in the modulation of the polarity of charge transport and the charge carrier mobility in the single crystalline state. The disparity is addressed by considering the electronic coupling of the transport states, symmetry of the frontier molecular orbitals and various non-covalent intermolecular interactions. We expect that the present study would benefit towards the rational designing of air-stable n-type organic molecular semiconductors for efficient electronic devices.

Directed Self-Organization Ensured Enhancement of Charge Carrier Mobilities in a Star-Shaped Organic Semiconductor.

Controlled self-organization of organic semiconductor molecules into specifically desired architectures on substrates of interest is one of the most imperative challenges faced in the fabrication of high-performance organic electronic devices. Herein, we report the self-organization of a star-shaped molecule FDT-8 into a highly favored structure, namely, a vertical stack. Thermal annealing of films of FDT-8 deposited on PEDOT: PSS coated ITO substrates was observed to assist the organization of the molecules into columnar stacks. A significant enhancement in the hole (≈50-fold) and the electron (≈13-fold) carrier mobility was observed in single-carrier devices upon thermal annealing that could be attributed to the aforementioned self-organization. The ability of these molecules to spontaneously self-organize was utilized to fabricate bilayer light-emitting devices.

Non-Equilibrium Polymerization of Cross-ß Amyloid Peptides for Temporal Control of Electronic Properties.

Hydrophobic collapse plays crucial roles in protein functions, from accessing the complex three-dimensional structures of native enzymes to the dynamic polymerization of non-equilibrium microtubules. However, hydrophobic collapse can also lead to the thermodynamically downhill aggregation of aberrant proteins, which has interestingly led to the development of a unique class of soft nanomaterials. There remain critical gaps in the understanding of the mechanisms of how hydrophobic collapse can regulate such aggregation. Demonstrated herein is a methodology for non-equilibrium amyloid polymerization through mutations of the core sequence of Aß peptides by a thermodynamically activated moiety. An out of equilibrium state is realized because of the negative feedback from the transiently formed cross-ß amyloid networks. Such non-equilibrium amyloid nanostructures were utilized to access temporal control over its electronic properties.

Control over Kinetic and Thermodynamically Driven Pathways of Crystallization to Yield Cofacial and Slipped-Stack Dimers in Single Crystals.

Control over the molecular packing in the solid state is of utmost importance in regulating the bulk optical properties of organic semiconductors. The electronic coupling between the molecules makes it possible to improve the properties of the bulk materials. This work reports an example of control over the selective formation of polymorphic single crystals of donor-acceptor-type small-molecule compound 25TR by 1) kinetic or 2) thermodynamic course of crystallisation to yield slipped stack (S) and cofacial (C) dimers in the single crystals. The distinct optical characteristics of the C-dimer and S-dimer are summarised. Both forms show significant excitonic interactions in the solid state, and the S-dimeric form has strong yellowish orange fluorescence, whereas the C-dimeric form is non-fluorescent in the crystalline state. DFT calculations and differential scanning calorimetric experiments revealed that the C-dimer polymorph is the thermodynamically stable form with a free energy offset of 0.43 eV in comparison with the S-dimer. Interestingly, the thermodynamically driven non-fluorescent single crystal was found to be convertible to its fluorescent form irreversibly by thermal trigger. The charge-carrier-transport characteristics of these two polymorphs were computed by using the Marcus-Hush formalism. The computations of the charge-carrier-transport behaviour revealed that the S-dimer (25TR(R) ) is ambipolar, whereas the C-dimer (25TR(Y) ) is predominantly n-type.

Pyrene-affixed triazoles: a new class of molecular semiconductors for robust, non-volatile resistive memory devices.

Molecular semiconductors that possess electric field induced switching of resistivity have been of great interest as they are excellent candidates for bi-stable resistive memory devices. The supremacy of such devices lies in the reversibility and non-volatile nature of the recorded information. Herein, we have demonstrated a new class of semiconductors that execute reversible non-volatile memory in the fabricated flexible devices with low switching threshold voltages, high ON/OFF ratios and good ambient stability.

Optical modulation of nano-gap tunnelling junctions comprising self-assembled monolayers of hemicyanine dyes.

Light-driven conductance switching in molecular tunnelling junctions that relies on photoisomerization is constrained by the limitations of kinetic traps and either by the sterics of rearranging atoms in a densely packed monolayer or the small absorbance of individual molecules. Here we demonstrate light-driven conductance gating; devices comprising monolayers of hemicyanine dyes trapped between two metallic nanowires exhibit higher conductance under irradiation than in the dark. The modulation of the tunnelling current occurs faster than the timescale of the measurement (∼1 min). We propose a mechanism in which a fraction of molecules enters an excited state that brings the conjugated portion of the monolayer into resonance with the electrodes. This mechanism is supported by calculations showing the delocalization of molecular orbitals near the Fermi energy in the excited and cationic states, but not the ground state and a reasonable change in conductance with respect to the effective barrier width.

Bulk photovoltaic effect in an organic polar crystal.

Organic polar crystals from the donor-acceptor substituted 1,4-diphenybutadiene 1 can generate a short-circuit photocurrent and a photovoltage upon illumination with near UV light. The photocurrent and photovoltage are attributed to a bulk photovoltaic effect. The bulk photovoltaic effect has been known for inorganic polar crystals for decades and can now also be demonstrated for organic polar crystals.

Light induced generation of stable blue phase in photoresponsive diphenylbutadiene based mesogen.

Light induced isothermal phase transition leading from smectic A* phase to a stable blue phase was achieved via photoisomerization of a chiral diphenylbutadiene based mesogen.

Tuning microstructures in organogels: gelation and spectroscopic properties of mono- and bis-cholesterol-linked diphenylbutadiene derivatives.

The gelation and photophysical properties of mono- and bis-cholesterol derivatives linked to diphenylbutadiene have been investigated. Scanning electron microscopy of xerogels of the monocholesterol derivatives indicated that these molecules self-assemble into 3D networks consisting of helically twisted fibers. In contrast, the morphology of xerogels of the bis-cholesterol derivatives indicated agglomerated spheres. In concentrated solutions (> 10(-4) M), the self-assembled superstructure of the monocholesterol derivatives consists of helically twisted fibers whereas that of the bis-cholesterol derivatives indicated clustered spheres. An investigation of spectroscopic properties suggests that the morphology of the superstructures formed in these systems may be correlated to the nature of the molecular aggregates formed. Absorption and emission spectral studies as a function of concentration and temperature suggested the formation of predominantly J-type aggregates in the monocholesterol and H-type aggregates in the bis-cholesterol derivatives. It is proposed that the slipped stack arrangement within the J aggregates of the monocholesterol derivatives resulted in the formation of helically twisted fibers, whereas the cofacial arrangement in the H aggregates of the bis-cholesterol derivatives could prevent such fiber formation, resulting in the formation of the agglomerated spheres.