Control Of Molecular Orientation Research Articles

Hexacarbazolylbenzene: An Excellent Host Molecule Causing Strong Guest Molecular Orientation and the High-Performance OLEDs.

Hexacarbazolylbenzene (6CzPh), which is benzene substituted by six carbazole rings, is a simple and attractive compound. Despite the success of a wide variety of carbazole derivatives in organic light-emitting diodes (OLEDs), 6CzPh has not received attention so far. Here, excellent performances of 6CzPh are revealed as a host material in OLEDs regarding conventional host materials. Various strategies are implemented to improve the performance of OLEDs, e.g., triplet utilization by thermally activated delayed fluorescence (TADF) and phosphorescence emitters for maximizing internal quantum efficiency, and molecular orientation control for increasing outcoupling efficiency. The present host material is suited for both criteria. Robustness of the structure and sufficiently high triplet energy enables a high external quantum efficiency with a long device lifetime. Besides, the host material boosts the horizontal molecular orientations of several guest emitters. It is noteworthy that disk-shaped 4CzIPN marks the complete horizontal molecular orientations (Θh = 100%, S = -0.50). These results provide an effective way of improving efficiencies without sacrificing device durability for future OLEDs.

A–D–A'–D–A type nonfused ring electron acceptors for efficient organic solar cells via synergistic molecular packing and orientation control

AbstractNonfused ring electron acceptors (NFREAs) are promising candidates for future commercialization of organic solar cells (OSCs) due to their simple synthesis. Still, the power conversion efficiencies (PCEs) of NFREA‐based OSCs have large room for improvement. In this work, by merging end group halogenation and side chain engineering, we developed four A–D–A'–D–A type NFREAs, which we refer to as EH‐4F, C4‐4F, EH‐4Cl, and C4‐4Cl. Single crystal X‐ray diffraction revealed that multiple intermolecular S···F interactions between cyclopentadithiophene and 5,6‐difluoro‐3‐(dicyanomethylene)indanone could cause an unfavorable dimer formation, leading to ineffective π–π stackings in EH‐4F and C4‐4F, whereas no such dimer was found in EH‐4Cl and C4‐4Cl after replacing with 5,6‐dichloro‐3‐(dicyanomethylene)indanone. Moreover, although the shorter n‐butyl side chain resulted in a closer molecular packing in C4‐4Cl, EH‐4Cl (2‐ethylhexyl substitution) with proper crystallinity exhibited enhanced face‐on orientation in thin film, which is favorable for vertical charge transport and further reducing charge recombination. As a result, a PCE of 13.0% is obtained for EH‐4Cl‐based OSC with a fill factor of 0.70. This work highlights the importance of molecular packing and orientation control toward future high‐performance A–D–A'–D–A type NFREAs.

Exploring the interplay of liquid crystal orientation and spherical elastic shell deformation in spatial confinement.

The application of liquid crystal technology typically relies on the precise control of molecular orientation at a surface or interface. This control can be achieved through a combination of morphological and chemical methods. Consequently, variations in constrained boundary flexibility can result in a diverse range of phase behaviors. In this study, we delve into the self-assembly of liquid crystals within elastic spatial confinement by using the Gay-Berne model with the aid of molecular dynamics simulations. Our findings reveal that a spherical elastic shell promotes a more regular and orderly alignment of liquid crystals compared to a hard shell. Moreover, during the cooling process, the hard-shell confined system undergoes an isotropic-smectic phase transition. In contrast, the phase behavior within the spherical elastic shell closely mirrors the isotropic-nematic-smectic phase transition observed in bulk systems. This indicates that the orientational arrangement of liquid crystals and the deformations induced by a flexible interface engage in a competitive interplay during the self-assembly process. Importantly, we found that phase behavior could be manipulated by altering the flexibility of the confined boundaries. This insight offers a fresh perspective for the design of innovative materials, particularly in the realm of liquid crystal/polymer composites.

Molecular Orientation Control of Regioisomeric Small-Molecule Acceptors for High-Performance Poly(3-hexylthiophene)-Based Organic Solar Cells with 9.3% Efficiency

Use of poly(3-hexylthiophene) (P3HT) enables low-cost manufacture of organic solar cells (OSCs). However, the power conversion efficiencies (PCEs) of the P3HT-based OSCs should be further enhanced. Herein, we report the development of noncovalently fused nonfullerene acceptors (NFAs) that realize high-performance P3HT-based OSCs (>9%). We synthesize regioisomeric NFAs (C4-In and C4-Out) in which the positions of the methyl substituents of their end groups differ. Interestingly, the molecular orientation of the regioisomers in thin film is found to change from edge-on (C4-Out) to face-on (C4-In) orientation, allowing a model study exploring the impact of the microstructure of NFAs on the performance of P3HT-based OSCs. We find that face-on oriented C4-In facilitates both electron and hole transport in a P3HT-based OSC along the vertical direction. In addition, C4-In shows reduced trap densities and suppressed charge recombination in the P3HT:C4-In OSC due to its lower energetic disorder relative to C4-Out. As a result, the P3HT:C4-In OSC (PCE = 9.35%) outperforms a P3HT:C4-Out OSC (PCE = 8.12%) owing to simultaneous enhancement in open-circuit voltage, short-circuit current density, and fill factor. This study demonstrates the importance of molecular orientation of NFAs for developing high-performance P3HT-based OSCs.

Quantum control of field-free molecular orientation.

Generating field-free (non-stationary) orientation of molecules in space has been a longstanding goal in the field of quantum control of molecular rotation, which has significant applications in physical chemistry, chemical physics, strong-field physics, and quantum information science. In this Perspective, we review and examine several representative control schemes developed in recent years and implemented in theoretical and experimental areas for generating field-free orientation of molecules. By conducting numerical simulations of different control schemes on the same molecular system, we demonstrate that quantum coherent control, specifically targeting a limited number of the lowest-lying rotational levels to achieve an optimal superposition, can result in a high degree of orientation. To this end, we provide an overview of our latest developed analytical method, which enables the precise design of terahertz field parameters through resonant excitation. This design approach facilitates the attainment of desired field-free orientations by optimizing the amplitudes and phases of rotational wave functions for the selected rotational levels. Finally, we outlook the significance of such progress in multiple frontier research fields, highlighting its potential applications in ultracold physics, quantum computation, quantum simulation, and quantum metrology.

F-Center-Mediated Growth of Patterned Organic Semiconductor Films on Alkali Halides

Organic semiconductors combine flexible tailoring of their optoelectronic properties by synthetic means with strong light-matter coupling, which is advantageous for organic electronic device applications. Although spatially selective deposition has been demonstrated, lateral patterning of organic films with simultaneous control of molecular and crystalline orientation is lacking as traditional lithography is not applicable. Here, a new patterning approach based on surface-localized F-centers (halide vacancies) generated by electron irradiation of alkali halides is presented, which allows structural control of molecular adlayers. Combining optical and atomic force microscopy, X-ray diffraction, and density functional theory (DFT) calculations, it is shown that dinaphthothienothiophene (DNTT) molecules adopt an upright orientation on pristine KCl surfaces, while the F-centers stabilize a recumbent orientation, and that these orientations are maintained in thicker films. This specific nucleation results also in different crystallographic morphologies, namely, densely packed islands and jagged fibers, each epitaxially aligned on the KCl surface. Spatially selective surface irradiation can also be used to create patterns of F-centers and thus laterally patterned DNTT films, which can be further transferred to any (including elastomer) substrate due to the water solubility of the alkali halide growth templates.

Control of Molecular Orientation and Carrier Transport of Thiophene-Based Semiconducting Polymer via Superparamagnetic Nanoparticles Fe3O4@C-Assisted Magnetic Alignment Method

Realizing the high molecular orientation and structurally ordered microstructure of organic semiconductor polymer thin films is beneficial for enhancing the charge transport of conjugated polymers and achieving high-performance organic electronic devices. In this work, we successfully developed large-area highly aligned films of a thiophene-based polymer, namely poly(2,5-bis(3-alkylthiophen-2-yl) thieno [3,2-b] thiophene) (PBTTT), using the magnetic alignment method at a low magnetic field (0.12 T), which was assisted by superparamagnetic nanoparticles Fe3O4@C. The aligned microstructure of the composite films is confirmed by systematic analysis that includes polarized optical microscopy, polarized UV–visible absorption spectroscopy, and an atomic force microscope. Organic field effect transistors based on magnetic aligned composite film exhibit a 2.8-fold improvement in carrier mobility compared with the unaligned films. We hold a formation mechanism that the rapid magnetically induced self-assembly property of Fe3O4@C and its intermolecular interaction with polymer chains are key to the new method of preparing oriented thin films.

Precise orientation control of a liquid crystal organic semiconductor via anisotropic surface treatment

We report a three-dimensional (3D) molecular orientation control of a liquid crystal organic semiconductor (LC-OSC) based on the long-range ordering characteristic of an LC material. To this end, a synthetic LC-OSC molecule, MeOPh-BTBT-C8, with a fluidic nematic (N) phase that is essential for alignment control over a large area and a smectic E (SmE) phase showing high ordering, was prepared. A simple flipping of a sandwich cell made of the LC-OSC material between the top and bottom substrates that have uniaxial–planar degenerated alignment as well as crossed rubbing directions responds to the given surface anchoring condition and temperature gradient. Optical observation of the alignment-controlled LC-OSC was carried out by polarized optical microscopy (POM), and the corresponding charge carrier mobility was also measured by fabricating organic field-effect transistors (OFETs). Our platform offers a facile approach for multidirectional and multifunctional organic electronic devices using the stimulus–response characteristics of LC materials.

Enhancing the photochemical reversibility of coumarin-containing polymers by molecular orientation control

With the use of an intramolecular approach and restrictions in the mobility, the reversibility of photoresponsive coumarin dimer-containing polymers was enhanced.

Enhanced Light–Matter Interaction and Polariton Relaxation by the Control of Molecular Orientation

AbstractExciton‐polaritons, in which the electronic state of an excited organic molecule and a photonic state are strongly coupled, can form a Bose–Einstein condensate (BEC) at room temperature. However, so far, the reported thresholds of organic polariton BECs under optical excitation are as high asPth = 11–500 μJ cm–2. One route toward lowering the condensation threshold is to increase the Rabi energy by aligning the molecular transition dipole moments. In this report, it is demonstrated that control of the orientation of a perylene‐based discotic dye, which is able to self‐organize in mesogenic columnar structures, can significantly enhance exciton–photon interaction and polariton relaxation rate in optical cavities. These results show the importance of the molecular orientation for strong light–matter interactions and provide a promising strategy toward the realization of an organic low threshold polariton BEC system and electrically driven organic polariton BEC.

Molecular Orientation Control of Liquid Crystal Organic Semiconductor for High-Performance Organic Field-Effect Transistors.

The control of molecular orientation and ordering of liquid crystal (LC) organic semiconductor (OSC) for high-performance and thermally stable organic thin-film transistors is investigated. A liquid crystalline molecule, 2-(4-dodecyl thiophenyl)[1]dibenzothiopheno[6,5-b:6',5'-f]-thieno[3,2-b]thiophene (C12-Th-DBTTT) is synthesized, showing the highly ordered smectic X (SmX) phase, demonstrating molecular reorganization via thermal annealing. The resulting thermally evaporated polycrystalline film and solution-sheared thin film show high charge carrier mobilities of 9.08 and 27.34 cm2 V-1 s-1, respectively. Atomic force microscopy and grazing-incidence X-ray diffraction analyses prove that the random SmA1-like structure (smectic monolayer) is reorganized to the highly ordered SmA2-like structure (smectic bilayer) of C12-Ph-DBTTT at the crystal-SmX transition temperature region. Because of the strong intermolecular interactions between rigid DBTTT cores, the thin film devices of C12-Th-DBTTT show excellent thermal stability up to 300 °C, indicating that LC characterization of conventional OSC materials can obtain high electrical performance as well as superior thermal durability.

Control of Molecular Orientation in Organic Semiconductors Using Weak Iodine-Iodine Interactions.

Controlling the molecular orientation of materials is a key issue for improving the performance of organic semiconductor devices. Herein, we demonstrate the structure-property relationships of iodinated and noniodinated molecules based on an asymmetric thienoacene framework. The noniodinated molecule formed an antiparallel slip-stack structure with small orbital overlap between molecules. In contrast, the iodinated molecule formed a head-to-head layered-herringbone structure, and as a result, the transfer integrals became larger and the hole mobility increased significantly compared with the noniodinated material. The iodinated molecule was made into a stable and solution-processable p-type organic semiconductor with a mobility of 2.2 cm2 V-1 s-1, which was 2 orders of magnitude higher than that of the noniodinated molecule. This study reveals that controlling molecular orientations using iodine-iodine interactions is a promising strategy for accelerating the development of organic semiconductor materials.

Efficient Organic Solar Cells from Molecular Orientation Control of M-Series Acceptors

<h2>Summary</h2> A "face-on" molecular orientation is essential for photovoltaic materials with efficient vertical carrier transport, but understanding how the molecular structures control their orientations remains challenging. Based on a ladder-type fused-ring core without <i>sp</i>³-hybridized bridging atoms, novel acceptor-donor-acceptor (A-D-A or ADA)-type nonfullerene acceptors (M3 and M32) are developed, and their molecular orientation behaviors are successfully controlled by the neighboring side chains. With linear n-cetyl chains on the nitrogen atoms, the acceptor (M32) tends to adopt an "edge-on" molecular orientation, whereas with bulky branched 2-hexyldecyl chains, the acceptor (M3) has a preferred "face-on" orientation. Blended with a donor polymer of PM6, M3 shows optimal phase separation and dramatically improved electron transport, consequently leading to a much higher device performance than M32. Further optimization of the M3-based devices yields an outstanding efficiency of 16.66%. The strategy of molecular orientation control proposed here will inspire many other innovative designs and syntheses of high-performance nonfullerene acceptors.

Close-Packed Arrangements of Flat-On Free-Base Porphyrins Driven by van der Waals Epitaxy

The functionality of low dimensional phases of porphyrins in optical, chemical, electrical, and multimodal combinational devices is strictly related to the control of molecular orientation within the produced solid layers. A promising strategy to drive the growth of adlayers with predictable structural properties relies on the template effect exerted by the substrate. Tetraphenyl porphyrins, being disc-shaped objects, can be adsorbed on a crystal surface by taking on different geometries. An edge-on configuration is adopted when the interactions among molecules overtake those between molecules and substrate, whereas a flat-on configuration is adopted when molecule-substrate interaction is dominant, with the weaker intermolecular interaction driving a close-packed geometry in the adlayer. For this latter reason, square and/or hexagonal lattice symmetries of physisorbed porphyrin layers are disclosed on highly interacting metal substrates such as Au(111). Unfortunately, metal substrates modify the intrinsic properties of porphyrins by suppressing many of their functionalities. To overcome this drawback, here we report the selective growth of porphyrins in a flat-on arrangement on the chiral (110) cleavage surface of the mixed molecular organic crystal formed by 2,5-diketopiperazine and fumaric acid in a 1:1 mole ratio. The energetic advantage ensured by the interaction with the insulating substrate drives the prevalent formation of domains with a square symmetry, which is retained from monolayer to multilayers. However, rare domains with a hexagonal symmetry are revealed and analyzed by high-resolution scanning probe microscopic techniques. The experimental structural analysis performed at the nanoscale, combined with ab initio calculations, allowed us to demonstrate that the molecular architectures we found arise from the simultaneous fulfillment of site adsorption energy maximization driven by peculiar molecular motifs of the selected substrate, close-packing criteria, and epitaxial locking to the substrate surface by weak van der Waals interactions.

Control of Molecular Orientation of Spiro-OMeTAD on Substrates

2,2',7,7'-Tetrakis(N,N-di-p-methoxyphenylamino)-9,9'-spirobifluorene (spiro-OMeTAD) is utilized as a p-type semiconductor layer in perovskite solar cells and solid-state dye-sensitized solar cells. Spiro-OMeTAD has been known to have a spiro center, leading to a random orientation. Although the molecular orientation of organic semiconductor materials influences the conductivity, which is directly related to semiconductor device characteristics, the molecular orientation of spiro-OMeTAD has not been fully discussed. In this study, we prepared spiro-OMeTAD layers on various substrates and investigated their orientation by grazing-incidence wide-angle X-ray scattering (GIWAXS) and near-edge X-ray absorption fine structure (NEXAFS). Additionally, we demonstrated that the molecular orientation of spiro-OMeTAD could be controlled by changing their surface energies by changing the substrate materials. Consequently, we could improve the electrical conductivity by improving its molecular orientation. The results of this study provide a guideline for the preparation of organic semiconductor material layers using the wet-coating method.

Molecular Orientations of Delayed Fluorescent Emitters in a Series of Carbazole-Based Host Materials.

Molecular orientation is one of the most crucial factors to boost the efficiency of organic light-emitting devices. However, active control of molecular orientation of the emitter molecule by the host molecule is rarely realized so far, and the underlying mechanism is under discussion. Here, we systematically investigated the molecular orientations of thermally activated delayed fluorescence (TADF) emitters in a series of carbazole-based host materials. Enhanced horizontal orientation of the TADF emitters was achieved. The degree of enhancement observed was dependent on the host material used. Consequently, our results indicate that π-π stacking, CH/n (n = O, N) weak hydrogen bonds, and multiple CH/π contacts greatly induce horizontal orientation of the TADF emitters in addition to the molecular shape anisotropy. Finally, we fabricated TADF-based organic light-emitting devices with an external quantum efficiency (ηext) of 26% using an emission layer with horizontal orientation ratio (Θ) of 79%, which is higher than that of an almost randomly oriented emission layer with Θ of 62% (ηext = 22%).

Nucleophilic substitution vs elimination reaction of bisulfide ions with substituted methanes: exploration of chiral selectivity by stereodirectional first-principles dynamics and transition state theory.

Control of molecular orientation is emerging as crucial for the characterization of the stereodynamics of kinetics processes beyond structural stereochemistry. The special role played in chiral discrimination phenomena has been particularly emphasized by Aquilanti and collaborators after their extensive probes of experimental control of molecular alignment and orientation. In this work, the manifestation of the Aquilanti mechanism has been demonstrated for the first time in first-principles molecular dynamics simulations: stationary points characterized on potential energy surfaces have been calculated for the study of chemical reactions occurring between the bisulfide anion HS- and oriented prototypical chiral molecules CHFXY (where X = CH3 or CN and Y = Cl or I). The important reaction channels are those corresponding to bimolecular nucleophilic substitution (SN2) and to bimolecular elimination (E2): their relative role has been assessed and alternative pathways due to the mirror forms of the oriented chiral molecule are revealed by the different reactivity of the two enantiomers of CHFCNI in SN2 reaction.

Molecular Orientation of Polymer Acceptor Dominates Open-Circuit Voltage Losses in All-Polymer Solar Cells

Low open-circuit voltage (Voc) induced by energy loss in organic solar cells is considered to be one of the most influencing factors limiting device performance, in which morphology of the active layer plays a crucial role in determining energy loss. By employing a bilayer structure of the P3HT:N2200 all-polymer system, we have identified the isolated impact of a molecular packing structure on device Voc with analysis of energy loss processes. Thermal annealing and various solvents were used to control molecular orientation in P3HT:N2200 bilayer devices, in which different Voc spanning from 0.45 to 0.54 V could be obtained. It was found that energy of charge-transfer state (Ect) differed in these bilayer devices. Besides, increased charge recombination could be observed in bilayer devices when N2200 layers exhibited face-on orientation, which caused an additional energy loss and decreased Voc. Our results suggest that rational control of polymer molecular orientation is essential to reduce the energy loss...

Two-dimensional self-assembly and electrical properties of the donor-acceptor tetrathiafulvalene-polychlorotriphenylmethyl radical on graphite substrates

The electron donor-acceptor tetrathiafulvalene-polychlorotriphenylmethyl (PTM) radical dyad, which shows a strong interplay between intra- and intermolecular charge transfer processes in solution, has been deposited by drop-casting on highly oriented pyrolytic graphite substrates, and its self-assembled structure has been investigated. Conducting atomic force microscopy revealed that the presence of a PTM radical in the molecules enhances the electrical conduction by almost two orders of magnitude and that this enhancement occurs in spite of the poor molecular orientation control achieved with drop-casting. Moreover, the study also reveals that the presence of a tetrathiafulvalene subunit in the deposited molecules can result in slightly asymmetric I-V curves.

Polydiacetylene ribbons formed using the controlled evaporative self-assembly (CESA) method

Abstract