Molecular Alignment Research Articles

Performance-enhanced intrinsic polarization-sensitive organic photodetectors by molecular interaction modulation

Polarization-sensitive organic photodetectors (OPDs) are increasingly paid attention for their broad application prospect. However, it is extremely difficult to achieve highly sensitive detection of polarized light for most organic semiconductor polymers with intrinsic isotropic amorphous behavior. In this study, the performance-enhanced intrinsic anisotropic all-polymer bulk heterojunctions (BHJs) are obtained by constructing molecular fluorination engineering in the fused-ring backbone of the acceptor polymer. The molecular orientation, alignment, and packing can be effectively optimized during the floating-film formation process without using any additives and post-treatments. The outstanding intrinsic polarization-sensitive photodetection performance with a very high photocurrent dichroic ratio of 3.73, a specific detectivity of 1.3 × 1011 Jones at 0 V, and a broad linear dynamic range of 120 dB is achieved for the optimum-fluorine-content self-assembly all-polymer organic BHJ film. The superiorities of self-powered capability, fast response, and high-contrast imaging demonstrate that the backbone fluorination for acceptor polymers is conducive to achieving excellent structural regularity and can endow the intrinsic polarization-sensitive all-polymer OPDs with more demanding polarized-light detection ability.

Quantum chemical study of symmetricalnon-fullerene acceptor chromophores for organic photovoltaics

It is well reported that the fused ring acceptor modification can be an effective method for improving the optoelectronic and photovoltaic properties of organic materials. The addition of acceptor groups to a core can enhance its electron-withdrawing ability, resulting in improved charge transport and higher power conversion efficiencies in organic solar cells (OSCs). Thieno[3,2-b]thiophene, and diketopyrrolopyrrole are commonly used groups in OSCs due to their powerful electron-withdrawing capabilities and well-established synthetic protocols. Their incorporation into donor–acceptor systems has been shown to enhance the materials absorption spectra, increase the open-circuit voltage (VOC), and improve device performance. Following integrating several acceptor groups onto the recently synthesized core based on thieno[3,2-b]thiophene, and diketopyrrolopyrrole, we have created six novel electron donors (BDPTM1-BDPTM6) with interesting optoelectronic and photovoltaic properties. It is indeed common practice to use computational methods such as density functional theory (DFT) and time-dependent density functional theory (TD-DFT) to investigate the optoelectronic and photovoltaic properties of newly created molecules. These methods allow researchers to obtain crucial parameters such as the HOMO and LUMO energies, energy gap (Egap), frontier molecular orbital alignment, density of states, molecular electrostatic potential, absorption maxima (λmax), excitation energy (Eex), binding energy and transition density matrix…… Among all the designed compounds, BDPTM3 exhibited the lowest energy bandgap (1.63 eV) with bathochromic shift of 921.610 nm in Dichloro-methane and 852.242 nm in gaseous phase. BDPTM2 displayed the highest dipole moment (µtot) at 7.557 eV, BDPTM5, and BDPTM6 demonstrated consistent linear polarizability〈α〉 at 191.612 × 10−22 esu and 196.2823 × 10−22 esu respectively. Notably, BDPTM6 calculated the highest frst hyperpolarizability βtot at 583.849 × 10–30. Based on the results obtained from the theoretical investigation of the optoelectronic and photovoltaic properties of the developed molecules, it may be possible to recommend them as better candidates for use in organic solar cells (OSCs).

Enhancing Performance and Stability of Sn-Pb Perovskite Solar Cells with Oriented Phenyl-C61-Butyric Acid Methyl Ester Layer via High-Temperature Annealing.

Phenyl-C61-butyric acid methyl ester (PCBM) can be used as a passivation material in perovskite solar cells (PeSCs) in order to reduce the trap site of the perovskite. Here, we show that a thick PCBM layer can form a smoother surface on the SnO2 substrate, improving the grain size and reducing the microstrain of the perovskite. High-temperature annealing treatment of PCBM layer not only increases its solvent resistance to perovskite precursor or antisolvent, but also enhances its molecular alignment, resulting in improved conductivity as an electron transport layer. High-temperature annealed PCBM (HT-PCBM) effectively minimizes trap-assisted nonradiative recombination by reducing trap density in perovskite and improving the electrical properties at the interface between SnO2 and perovskite layers. This HT-PCBM process significantly enhances the performance of the PeSCs, including the open-circuit voltage (VOC) from 0.39 to 0.77 V, fill factor from 52% to 65%, and power conversion efficiency (PCE) from 6.03% to 15.50%, representing substantial improvements compared to devices without PCBM. This PCE is the highest efficiency among conventional (n-i-p) Sn-Pb PeSCs reported to date. Moreover, passivating the trap sites of SnO2 and separating the interface between the Sn-containing perovskite and the substrate effectively have improved the stability of the Sn-Pb perovskite in the n-i-p structure. The optimized best device with HT-PCBM has maintained an efficiency of over 90% for more than 300 h at 85 °C and 5000 h at room temperature in a glovebox atmosphere.

Dissociative ionization and post-ionization alignment of aligned O2 in an intense femtosecond laser field.

We examined dissociative ionization of O2 in an intense femtosecond laser field (782 nm, 120 fs, 4 × 1014 W cm-2) by recording the kinetic energy distribution of O+ emitted along the laser polarization direction as a function of the delay time between the pump pulse (9 × 1013 W cm-2) for the molecular alignment and the probe pulse for the dissociative ionization. We found the two distinct rotational revival patterns which are out-of-phase by π with each other in the kinetic energy distribution of O+. One of the patterns shows the dissociative ionization is enhanced when the O2 axis is parallel to the laser polarization direction, suggesting that the ionization is induced by the electron emission from the 3σg orbital. On the other hand, the other pattern shows that the dissociative ionization is enhanced when the O2 axis is perpendicular to the laser polarization direction, suggesting that the ionization is induced by the electron emission from the 1πu orbital. Because of the collection efficiency of the time-of-flight mass spectrometer, the enhancement of the O+ yield at the anti-alignment time delay indicates that the electron emission from the 1πu orbital is followed by the molecular alignment of O2+ in the course of the dissociation. We performed classical trajectory Monte-Carlo simulation of O2+ with the dissociation and rotational coordinates in the light-dressed potential to evaluate the effect of the post-ionization alignment by the probe pulse.

Supramolecular complexation of C60 with branched polyethylene.

Fullerene C60 is a ubiquitous material for application in organic electronics and nanotechnology, due to its desirable optoelectronic properties including good molecular orbital alignment with electron-rich donor materials, as well as high and isotropic charge carrier mobility. However, C60 possesses two limitations that hinder its integration into large-scale devices: (1) poor solubility in common organic solvents leading to expensive device processing, and (2) poor optical absorbance in the visible portion of the spectrum. Covalent functionalization has long been the standard for introducing structural tunability into molecular design, but non-covalent interactions have emerged as an alternative strategy to tailor C60-based materials, offering a versatile and tuneable alternative to novel functional materials and applications. In this work, we report a straightforward non-covalent functionalization of C60 with a branched polyethylene (BPE), which occurs spontaneously in dilute chloroform solution under ambient conditions. A detailed characterization strategy, based on UV-vis spectroscopy and size-exclusion chromatography was performed to verify and investigate the structure of the C60+BPE complex. Among others, our work reveals that the supramolecular complex has an order of magnitude higher molecular weight than its C60 and BPE constituents and points towards oxidation as the driving force behind complexation. The C60+BPE complex also possesses significantly broadened optical absorbance compared to unfunctionalized C60, extending further into the visible portion of the spectrum. This non-covalent approach presents an inexpensive route to address the shortcomings of C60 for electronic applications, situating the C60+BPE complex as a promising candidate for further investigation in organic electronic devices.

Local changes in protein filament properties drive large-scale membrane transformations involved in endosome tethering and fusion.

Large-scale cellular transformations are triggered by subtle physical and structural changes to individual biomacromolecular and membrane components. A prototypical example of such an event is the orchestrated fusion of membranes within an endosome that enables transport of cargo and processing of biochemical moieties. In this work, we demonstrate how protein filaments on the endosomal membrane surface can leverage a rigid-to-flexible transformation to elicit a large-scale change in membrane flexibility to enable membrane fusion. We develop a polymer field-theoretic model that captures molecular alignment arising from nematic interactions with varying surface density and fraction of flexible filaments, which are biologically controlled within the endosomal membrane. We then predict the collective elasticity of the filament brush in response to changes in the filament alignment, predicting a greater than 20-fold increase of the effective membrane elasticity over the bare membrane elasticity that is triggered by filament alignment. These results show that the endosome can modulate the filament properties to orchestrate membrane fluidization that facilitates vesicle fusion, providing an example of how active processes that modulate local molecular properties can result in large-scale transformations that are essential to cellular survival.

Ultrafast pulses Serrodyne nonlinear broadening and frequency shift in molecular alignment system

Ultrafast pulses Serrodyne nonlinear broadening and frequency shift in molecular alignment system

Topological mechanism in the nonlinear power-law relaxation of cell cortex.

Different types of cells exhibit a universal power-law rheology, but the mechanism underneath is still unclear. Based on the exponential distribution of actin filament length, we treat the cell cortex as a collection of chains of crosslinkers with exponentially distributed binding energy, and show that the power-law exponent of its stress relaxation should scale with the chain length. Through this model, we are able to explain how the exponent can be regulated by the crosslinker number and imposed strain during cortex relaxation. Network statistics show that the average length of filament-crosslinker chains decreases with the crosslinker number, which endows a denser network with lower exponent. Due to gradual molecular alignment with the stretch direction, the number of effectively stretched crosslinkers in the network is found to increase with the imposed strain. This effective growth in network density diminishes the exponent under large strain. By incorporating the inclined angle of crosslinkers into the model without in-series structure, we show that the exponent cannot be altered by crosslinker rotation directly, refining our previous conjectures. This work may help to understand cellular mechanics from the molecular perspective.

Retrieval of the molecular alignment distribution from THz generation

Retrieval of the molecular alignment distribution from THz generation

The importance of molecular axis alignment and symmetry-breaking in photoelectron elliptical dichroism.

Photoelectron angular distributions (PADs) produced from the photoionization of chiral molecules using elliptically polarized light exhibit a forward/backward asymmetry with respect to the optical propagation direction. By recording these distributions using the velocity-map imaging (VMI) technique, the resulting photoelectron elliptical dichroism (PEELD) has previously been demonstrated as a promising spectroscopic tool for studying chiral molecules in the gas phase. The use of elliptically polarized laser pulses, however, produces PADs (and consequently, PEELD distributions) that do not exhibit cylindrical symmetry about the propagation axis. This leads to significant limitations and challenges when employing conventional VMI acquisition and data processing strategies. Using novel photoelectron image analysis methods based around Hankel transform reconstruction tomography and machine learning, however, we have quantified-for the first time-significant symmetry-breaking contributions to PEELD signals that are of a comparable magnitude to the symmetric terms in the multiphoton ionization of (1R,4R)-(+)- and (1S,4S)-(-)-camphor. This contradicts any assumptions that symmetry-breaking can be ignored when reconstructing VMI data. Furthermore, these same symmetry-breaking terms are expected to appear in any experiment where circular and linear laser fields are used together. This ionization scheme is particularly relevant for investigating dynamics in chiral molecules, but it is not limited to them. Developing a full understanding of these terms and the role they play in the photoionization of chiral molecules is of clear importance if the potential of PEELD and related effects for future practical applications is to be fully realized.

Field-Free Molecular Alignment by the Optimized Two-Color Laser Fields

Field-Free Molecular Alignment by the Optimized Two-Color Laser Fields

Molecular alignment-assisted spectral broadening and shifting in the near-infrared with a recycled depleted pump from an optical parametric amplifier

We demonstrate how the depleted pump of an optical parametric amplifier can be recycled for impulsive alignment of a molecular gas inside a hollow-core fiber and use such alignment for the broadening and frequency shift of the signal pulse at a center wavelength of ∼1300 nm. Our results combine non-adiabatic molecular alignment, self-phase modulation, and Raman non-linearities. We demonstrate spectral shifts of up to 204 nm and a spectral broadening of more than one octave. We also report on the time delays at which broadening occurs, which do not coincide with any of the molecular rotational constants. Further, we encounter that maximum frequency shifts occur when the signal and pump have perpendicular polarization instead of parallel.

Biosynthesis of 3-Hydroxyphloretin Using Rational Design of 4-Hydroxyphenylacetate 3-Monooxygenase.

The compound 3-hydroxyphloretin is a typical dihydrochalcone that can be obtained in plants by the 3-hydroxylation of phloretin. Here, the flavin-dependent two-component monooxygenase (HpaBC) derived from Pseudomonas aeruginosa was used to convert phloretin into 3-hydroxyphloretin. Following molecular docking and sequence alignment, modifications to the substrate pocket and loop of PaHpaBC were rationally designed, and mutant residues were selected. The results showed that the mutant Q212G/F292A/Q376N gave the best yield of 3-hydroxyphloretin and showed improved catalytic efficiency. Under optimal reaction condition, 2.03 g/L of 3-hydroxyphloretin was produced in the whole-cell catalysis experiment. Molecular docking and molecular dynamics simulations were used to analyze mutants and elucidate the potential mechanism. It was found that the increase in 3-hydroxyphloretin yield was due to the improvement in the flexibility of the loop and the expansion of its substrate pocket. This strategy based on loop and substrate pocket modification has significance in the engineering of PaHpaB.

Generation of Orbital Angular Momentum Light by Patterning Azopolymer Thin Films

Orbital angular momentum (OAM) encoding is a promising technique to boost data transmission capacity in optical communications. Most recently, azobenzene films have gained attention as a versatile tool for creating and altering OAM-carrying beams. Unique features of azobenzene films make it possible to control molecular alignment through light-induced isomerization about the azo bond. This feature enables the fabrication of diffractive optical devices such as spiral phase plates and holograms by accurately imprinting a phase profile on the incident light. By forming azobenzene sheets into diffractive optical elements, such as spiral phase plates, one can selectively create OAM-carrying beams. Due to the helical wavefront and phase variation shown by these beams, multiple distinct channels can be encoded within a single optical beam. This can significantly increase the data transmission capacity of optical communication systems with this OAM multiplexing technique. Additionally, holographic optical components made from azobenzene films can be used to build and reconstruct intricate wavefronts. It is possible to create OAM-based holograms by imprinting holographic designs on azobenzene films, which makes it simpler to control and shape optical beams for specific communication requirements. In addition, azobenzene-based materials can then be suitable for integration into optical communication devices because of their reconfigurability, compactness, and infrastructure compatibility, which are the main future perspectives for achieving OAM-based technologies for the next generation, among other factors. In this paper, we see the possible use of azobenzene films in the generation and modification of OAM beams for optical communications through light-induced isomerization. In addition, the potential role of azobenzene films in the development of novel OAM-based devices that paves the way for the realization of high-capacity, OAM-enabled optical communication networks are discussed.

Synthesis and Characterization of Side-Chain Liquid-Crystalline Block Copolymers Containing Cyano-Terminated Phenyl Benzoate Moieties

Block copolymers, known for their capacity to undergo microphase separation, spontaneously yield various periodic nanostructures. These precisely controlled nanostructures have attracted considerable interest due to their potential applications in microfabrication templates, conducting films, filter membranes, and other areas. However, it is crucial to acknowledge that microphase-separated structures typically exhibit random alignment, making alignment control a pivotal factor in functional material development. To address this challenge, researchers have explored the use of block copolymers containing liquid-crystalline (LC) polymers, which offer a promising technique for alignment control. The molecular structure and LC behavior of these polymers significantly impact the morphology and alignment of microphase-separated structures. In this study, we synthesized LC diblock copolymers with cyano-terminated phenyl benzoate moieties and evaluated the microphase-separated structures and molecular alignment behaviors. The LC diblock copolymers with a narrow molecular weight distribution were synthesized by atom transfer radical polymerization. Small angle X-ray scattering measurements revealed that the block copolymers exhibit smectic LC phases and form cylinder structures with a lattice period of about 18 nm by microphase separation. The examination of block copolymer films using polarized optical microscopy and polarized UV-visible absorption spectroscopy corroborated that the LC moieties were uniaxially aligned along the alignment treatment direction.

Tuneable Anisotropic Plasmonics with Shape-Symmetric Conducting Polymer Nanoantennas.

A wide range of nanophotonic applications rely on polarization-dependent plasmonic resonances, which usually requires metallic nanostructures that have anisotropic shape. This work demonstrates polarization-dependent plasmonic resonances instead by breaking symmetry via material permittivity. The study shows that molecular alignment of a conducting polymer can lead to a material with polarization-dependent plasma frequency and corresponding in-plane hyperbolic permittivity region. This result is not expected based only on anisotropic charge mobility but implies that also the effective mass of the charge carriers becomes anisotropic upon polymer alignment. This unique feature is used to demonstrate circularly symmetric nanoantennas that provide different plasmonic resonances parallel and perpendicular to the alignment direction. The nanoantennas are further tuneable via the redox state of the polymer. Importantly, polymer alignment could blueshift the plasma wavelength and resonances by several hundreds of nanometers, forming a novel approach toward reaching the ultimate goal of redox-tunable conducting polymer nanoantennas for visible light.

Polyfluorinated Naphthalene-bis-hydrazimide for Solution-Grown n-Type Semiconducting Films.

Naphthalene tetracarboxylic diimides (NDIs), possessing low-lying and tunable LUMO levels, are of wide interest for their aptitude to provide cost-effective, flexible, and environmentally stable n-type organic semiconductors through simple solution processing. NDI-based aromatic hydrazidimides are herein studied in relation to their chemical and environmental stability and as spin-coated stable thin films. In the case of the pentafluorinated residue, these were found to be crystalline, highly oriented, and molecularly flat (roughness = 0.3 nm), based on optical and atomic force microscopy, X-ray diffraction in specular and grazing incidence geometry, and X-ray reflectivity measurements. A new polymorph, previously undetected during the isolation of bulk powders or in their controlled thermal treatments, is found in the thin film and was metrically and structurally characterized from 2D GIWAXS patterns (monoclinic, P2/c, a = 17.50; b = 4.56; c = 14.24 Å; β = 84.8°). This new thin-film phase, TF-F5, is formed no matter whether silicon, glass, or polymethylmethacrylate substrates are used, thus opening the way to the preparation of solution-grown flexible semiconducting films. The TF-F5 films exhibit a systematic and rigorous molecular alignment with both orientation and packing favorable to electron mobility (μ = 0.02 cm2 V-1 s-1). Structural and morphological differences are deemed responsible for the absence of measurable conductivity in thin films of polyfluorinated analogues bearing -CF3 residues on the hydrazidimide aromatic rings.

Unraveling the serial glycosylation in the biosynthesis of steroidal saponins in the medicinal plant Paris polyphylla and their antifungal action.

Sugar-sugar glycosyltransferases play important roles in constructing complex and bioactive saponins. Here, we characterized a series of UDP-glycosyltransferases responsible for biosynthesizing the branched sugar chain of bioactive steroidal saponins from a widely known medicinal plant Paris polyphylla var. yunnanensis. Among them, a 2'-O-rhamnosyltransferase and three 6'-O-glucosyltrasferases catalyzed a cascade of glycosylation to produce steroidal diglycosides and triglycosides, respectively. These UDP-glycosyltransferases showed astonishing substrate promiscuity, resulting in the generation of a panel of 24 terpenoid glycosides including 15 previously undescribed compounds. A mutant library containing 44 variants was constructed based on the identification of critical residues by molecular docking simulations and protein model alignments, and a mutant UGT91AH1Y187A with increased catalytic efficiency was obtained. The steroidal saponins exhibited remarkable antifungal activity against four widespread strains of human pathogenic fungi attributed to ergosterol-dependent damage of fungal cell membranes, and 2'-O-rhamnosylation appeared to correlate with strong antifungal effects. The findings elucidated the biosynthetic machinery for their production of steroidal saponins and revealed their potential as new antifungal agents.

Putting the F into FBD analysis: tree constraints or morphological data?

AbstractThe fossilized birth–death (FBD) process provides an ideal model for inferring phylogenies from both extant and fossil taxa. Using this approach, fossils are directly integrated into the tree, leading to a statistically coherent prior on divergence times. Since fossils are typically not associated with molecular sequences, additional information is required to place fossils in the tree. We use simulations to evaluate two different approaches to handling fossil placement in FBD analyses: using topological constraints, where the user specifies monophyletic clades based on established taxonomy, or using total‐evidence analyses, which use a morphological data matrix in addition to the molecular alignment. We also explore how rate variation in fossil recovery or diversification rates impacts these approaches. We find that the extant topology is well recovered under all methods of fossil placement. Divergence times are similarly well recovered across all methods, with the exception of constraints which contain errors. We see similar patterns in datasets which include rate variation, however, relative errors in extant divergence times increase when more variation is included in the dataset, for all approaches using topological constraints, and particularly for constraints with errors. Finally, we show that trees recovered under the FBD model are more accurate than those estimated using non‐time calibrated inference. Overall, we show that both fossil placement approaches are reliable even when including uncertainty. Our results underscore the importance of core taxonomic research, including morphological data collection and species descriptions, irrespective of the approach to handling phylogenetic uncertainty using the FBD process.

Evolution of the characterization of horizontally aligned organic light‐emitting molecules and their recent progress of molecular design

AbstractThis review article surveys the organic small molecular materials, light‐emitting for most of them, being studied for the molecular alignment or orientation in thin films. Following a chronicle order, three practical characterization techniques, variable angle spectroscopic ellipsometry (VASE), angle‐dependent photoluminescence (ADPL), and grazing incidence wide‐angle x‐ray scattering (GIWAXS) have been used to probe phosphorescence, thermally activated delayed fluorescence (TADF) materials, as well as those of non‐phosphorescence and non‐TADF materials.