Dual Chalcogen-Bonding Interaction for High-Performance Filterless Narrowband Organic Photodetectors.

A novel green-absorbing organic molecule featuring dual intramolecular chalcogen bonds is synthesized and characterized. This molecule incorporates two such bonds: one between a tellurium atom and the oxygen atom of a carbonyl moiety, and the other between the tellurium atom and the adjacent nitrogen atom within a pyridine moiety. The molecule, featuring dual intramolecular chalcogen bonds exhibits a narrow absorption spectrum and elevated absorption coefficients, closely aligned with a resonance parameter of approximately 0.5. This behavior is due to its cyanine-like characteristics and favorable electrical properties, which are a direct result of its rigid, planar molecular structure. Therefore, this organic molecule forming dual intramolecular chalcogen bonds achieves superior optoelectronic performance in green-selective photodetectors, boasting an external quantum efficiency of over 65% and a full-width at half maximum of less than 95 nm while maintaining the performance after 1000 h of heating aging at 85 °C. Such organic photodetectors are poised to enhance stacked organic photodetector-on-silicon hybrid image sensors, paving the way for the next-generation of high-resolution and high-sensitivity image sensors.

Octupole moment driven free charge generation in partially chlorinated subphthalocyanine for planar heterojunction organic photodetectors.

In this study, high-performance organic photodetectors are presented which utilize a pristine chlorinated subphthalocyanine photoactive layer. Optical and optoelectronic analyses indicate that the device photocurrent is primarily generated through direct charge generation within the chlorinated subphthalocyanine layer, rather than exciton separation at layer interfaces. Molecular modelling suggests that this direct charge generation is facilitated by chlorinated subphthalocyanine high octupole moment (-80 DÅ2), which generates a 200 meV shift in molecular energetics. Increasing the thickness of chlorinated subphthalocyanine leads to faster response time, correlated with a decrease in trap density. Notably, photodetectors with a 50 nm thick chlorinated subphthalocyanine photoactive layer exhibit detectivities approaching 1013 Jones, with a dark current below 10-7 A cm-2 up to -5 V. Based on these findings, we conclude that high octupole moment molecular semiconductors are promising materials for high-performance organic photodetectors employing single-component photoactive layer.

The State-of-the-Art Solution-Processed Single Component Organic Photodetectors Achieved by Strong Quenching of Intermolecular Emissive State and High Quadrupole Moment in Non-Fullerene Acceptors.

A bulk-heterojunction (BHJ) blend is commonly used as the photoactive layer in organic photodetectors (OPDs) to utilize the donor (D)/acceptor (A) interfacial energetic offset for exciton dissociation. However, this strategy often complicates optimization procedures, raising serious concerns over device processability, reproducibility, and stability. Herein, highly efficient OPDs fabricated with single-component organic semiconductors are demonstrated via solution-processing. The non-fullerene acceptors (NFAs) with strong intrinsic D/A character are used as the photoactive layer, where the emissive intermolecular charge transfer excitonic (CTE) states are formed within <1 ps, and efficient photocurrent generation is achieved via strong quenching of these CTE states by reverse bias. Y6 and IT-4F-based OPDs show excellent OPD performances, low dark current density (≈10-9 A cm-2 ), high responsivity (≥0.15 A W-1 ), high specific detectivity (>1012 Jones), and fast photo-response time (<10 µs), comparable to the state-of-the-art BHJ OPDs. Together with strong CTE state quenching by electric field, these excellent OPD performances are also attributed to the high quadrupole moments of NFA molecules, which can lead to large interfacial energetic offset for efficient CTE dissociation. This work opens a new way to realize efficient OPDs using single-component systems via solution-processing and provides important molecular design rules.

The Effect of Alkyl Chain Length in Organic Semiconductor and Surface Polarity of Polymer Dielectrics in Organic Thin-Film Transistors (OTFTs).

The interface between dielectric and organic semiconductor is critically important in determining organic thin-film transistor (OTFT) performance. Surface polarity of the dielectric layer can hinder charge transport characteristics, which has restricted utilization of polymeric dielectric materials containing polar functional groups. Herein, the electrical characteristics of OTFTs are analyzed depending on the alkyl chain length of organic semiconductors and surface polarity of polymer dielectrics. High-performance dibenzothiopheno[6,5-b:6',5'-f]thieno[3,2-b]thiophene (DBTTT) and newly synthesized its alkylated derivatives (C6-DBTTT and C10-DBTTT) are utilized as organic semiconductors. As dielectric layers, non-polar poly(1,3,5-trimethyl-1,3,5-trivinylcyclitrisiloxane) (pV3D3) and poly(2-cyanoethyl acrylate-co-diethylene glycol divinyl ether) [p(CEA-co-DEGDVE)] with polar cyanide functionality are utilized. The fabricated OTFTs with pV3D3 commonly exhibit the excellent charge transport characteristics. In addition, the OTFT performance is improved with lengthening the alkyl chain in organic semiconductors, which can be attributed to the molecular orientation of semiconductors. On the other hand, non-alkylated DBTTT OTFTs with polar p(CEA-co-DEGDVE) show relatively poor electrical characteristics, while their performance is drastically enhanced with the alkylated DBTTTs. The ultraviolet photoelectron spectroscopy (UPS) reveals that surface polarity of the dielectric layer can be abated with alkyl chain in organic semiconductors. It is believed that this study can provide a useful insight to optimize dielectric/semiconductor interface to achieve high-performance OTFTs.

Small Molecule Based Organic Photo Signal Receiver for High-Speed Optical Wireless Communications.

The present work describes the development of an organic photodiode (OPD) receiver for high-speed optical wireless communication. To determine the optimal communication design, two different types of photoelectric conversion layers, bulk heterojunction (BHJ) and planar heterojunction (PHJ), are compared. The BHJ-OPD device has a -3 dB bandwidth of 0.65 MHz (at zero bias) and a maximum of 1.4 MHz (at -4 V bias). A 150 Mbps single-channel visible light communication (VLC) data rate using this device by combining preequalization and machine learning (ML)-based digital signal processing (DSP) is demonstrated. To the best of the authors' knowledge, this is the highest data rate ever achieved on an OPD-based VLC system by a factor of 40 over the previous fastest reported. Additionally, the proposed OPD receiver achieves orders of magnitude higher spectral efficiency than the previously reported organic photovoltaic (OPV)-based receivers.

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.

In-Depth Investigation of the Correlation between Organic Semiconductor Orientation and Energy-Level Alignment Using In Situ Photoelectron Spectroscopy.

Organic semiconductors (OSCs) are of interest for replacing traditional Si-based semiconductors as their flexibility and transparency enable new applications. The properties of OSC materials greatly depend on their orientation and molecular arrangement, which are strongly dependent on the underlying substrate material. Hence, in this study, in situ ultraviolet photoelectron spectroscopy (UPS) is used to elucidate the effect of the substrate on OSC orientation. Two types of OSCs, namely those with shape anisotropy (pentacene, dinaphtho[2,3-b:2',3'-f]thieno[3,2-b]thiophene, and dibenzothiopheno[6,5-b:6',5'-f]thieno[3,2-b]thiophene) and those with shape isotropy (N,N'-di(1-naphthyl)-N,N'-diphenyl-(1,1'-biphenyl)-4,4'-diamine, tris(4-carbazoyl-9-ylphenyl)amine, and [6,6]-phenyl C71 butyric acid methyl ester), are deposited on different electrode materials. The differences in the UPS spectra of these materials are observed directly. In general, the orientation of anisotropic OSC molecules significantly depends on the substrate properties, while that of the isotropic ones do not. All the anisotropic OSC molecules grown on poly(3,4-ethylenedioxythiophene)-polystyrenesulfonate (PEDOT:PSS) electrodes show a greater degree of molecular ordering than those grown on Au and multiwalled carbon nanotube/PEDOT:PSS electrodes. The molecular arrangements within the OSC/electrode structures are reflected in the energy-level shifts in the corresponding UPS spectra and hence in the electronic configurations. The results of this study should aid the design and synthesis of OSC materials with configurations suitable for organic electronic devices.

Thiophene-Thiazole-Based Semiconducting Copolymers for High-Performance Polymer Field-Effect Transistors.

We report a newly synthesized donor (D)-acceptor (A)type semiconducting copolymer, consisting of thiophene as an electron-donating unit and thiazole as an electron-accepting unit (PQTBTz-TT-C8) for the active layer of the organic field-effect transistors (OFETs). Specifically, this study investigates the structure and electrical property relationships of PQTBTz-TT-C8 with comprehensive analyses on the charge-transporting properties corresponding to the spin rate of the spin coater during the formation of the PQTBTz-TT-C8 film. The crystallinity of PQTBTz-TT-C8 films is examined with grazing incidence X-ray diffraction. Temperature-dependent transfer measurements of the OFETs are conducted to extract the density of states (DOS) and characterize the charge-transport properties. Comparative analyses on charge transports within the framework of the physical model, based on polaron hopping and Gaussian DOS, reveal that the prefactors of both physical charge-transport models are independent of the spin-coating condition for the films. For staggered structural transistors, however, the thickness of the PQTBTz-TT-C8 films, which strongly affect the series resistance along the charge-transfer path in a vertical direction, is changed in accordance with the spin-coating rate. In other words, the spin-coating rate of the PQTBTz-TT-C8 films influences the thickness of the polymer films, yet any significant changes in the crystallinity of the film or electronic coupling between the neighboring molecules upon the spin-coating condition were barely noticeable. Because the PQTBTz-TT-C8 backbone chains inside the thin film are stacked up with the edge-on, the series resistances are changed according to the thickness of the film and thus the performance of the device varies depending on the thickness.

The prediction of hole mobility in organic semiconductors and its calibration based on the grain-boundary effect.

A new reliable computational model to predict the hole mobility of poly-crystalline organic semiconductors in thin films was developed. Site energy differences and transfer integrals in crystalline morphologies of organic molecules were obtained from quantum chemical calculations, in which periodic boundary conditions were efficiently applied to capture the interactions with the surrounding molecules in the crystalline organic layer. Then the parameters were employed in kinetic Monte Carlo (kMC) simulations to estimate the carrier mobility. Carrier transport in multiple directions has been considered in the kMC simulation to mimic poly-crystalline characteristics under thin-film conditions. Furthermore, the calculated mobility was corrected using a calibration equation based on microscopy images of the thin films to take the effect of grain boundaries into account. As a result, good agreement was observed between the predicted and measured hole mobility values for 21 molecular species: the coefficient of determination (R(2)) was estimated to be 0.83 and the mean absolute error was 1.32 cm(2) V(-1) s(-1). This numerical approach can be applied to any molecules for which crystal structures are available and will provide a rapid and precise way of predicting device performance.

Thin Films of Highly Planar Semiconductor Polymers Exhibiting Band-like Transport at Room Temperature.

We report the observation of band-like transport from printed polymer thin films at room temperature. This was achieved from donor-acceptor type thiophene-thiazole copolymer that was carefully designed to enhance the planarity of the backbone and the resulting transfer integral between the macromolecules. Due to the strong molecular interaction, the printed polymer film exhibited extremely low trap density comparable to that of molecular single crystals. Moreover, the energy barrier height for charge transport could be readily reduced with the aid of electric field, which led formation of extended electron states for band-like charge transport at room temperature.

Dibenzothiopheno[6,5-b:6',5'-f]thieno[3,2-b]thiophene (DBTTT): high-performance small-molecule organic semiconductor for field-effect transistors.

We present the synthesis, characterization, and structural analysis of a thiophene-rich heteroacene, dibenzothiopheno[6,5-b:6',5'-f]thieno[3,2-b]thiophene (DBTTT) as well as its application in field-effect transistors. The design of DBTTT is based on the enhancement of intermolecular charge transfer through strong S-S interactions. Crystal structure analysis showed that the intermolecular π-π distance is shortened and that the packing density is higher than those of the electronically equivalent benzene analogue, dinaphtho-[2,3-b:2',3'-f]thieno[3,2-b]thiophene (DNTT). The highest hole mobility we obtained in polycrystalline DBTTT thin-film transistors was 19.3 cm(2)·V(-1)·s(-1), six times higher than that of DNTT-based transistors. The observed isotropic angular mobilities and thermal stabilities at temperatures up to 140 °C indicate the great potential of DBTTT for attaining device uniformity and processability.

Reliable and uniform thin-film transistor arrays based on inkjet-printed polymer semiconductors for full color reflective displays.

Stable uniform performance inkjet-printed polymer transistor arrays, which allow demonstration of flexible full-color displays, were achieved by new ambient processable conjugated copolymer semiconductor, and OTFT devices incorporating this material showed high mobility values>1.0 cm2 V(-1) s(-1). Bias-stress stability of the devices was improved with a channel-passivation layer, which suppresses the density of trap states at the channel interface.

Liquid-crystalline semiconducting copolymers with intramolecular donor-acceptor building blocks for high-stability polymer transistors.

The ability to control the molecular organization of electronically active liquid-crystalline polymer semiconductors on surfaces provides opportunities to develop easy-to-process yet highly ordered supramolecular systems and, in particular, to optimize their electrical and environmental reliability in applications in the field of large-area printed electronics and photovoltaics. Understanding the relationship between liquid-crystalline nanostructure and electrical stability on appropriate molecular surfaces is the key to enhancing the performance of organic field-effect transistors (OFETs) to a degree comparable to that of amorphous silicon (a-Si). Here, we report a novel donor-acceptor type liquid-crystalline semiconducting copolymer, poly(didodecylquaterthiophene-alt-didodecylbithiazole), which contains both electron-donating quaterthiophene and electron-accepting 5,5'-bithiazole units. This copolymer exhibits excellent electrical characteristics such as field-effect mobilities as high as 0.33 cm(2)/V.s and good bias-stress stability comparable to that of amorphous silicon (a-Si). Liquid-crystalline thin films with structural anisotropy form spontaneously through self-organization of individual polymer chains as a result of intermolecular interactions in the liquid-crystalline mesophase. These thin films adopt preferential well-ordered intermolecular pi-pi stacking parallel to the substrate surface. This bottom-up assembly of the liquid-crystalline semiconducting copolymer enables facile fabrication of highly ordered channel layers with remarkable electrical stability.

Cleavage of beta-lactone ring by serine protease. Mechanistic implications.

Both enantiomers of 3-benzyl-2-oxetanone (1) were found to be slowly hydrolyzed substrates of alpha-chymotrypsin having k(cat) values of 0.134+/-0.008 and 0.105+/-0.004 min(-1) for (R)-1 and (S)-1, respectively, revealing that alpha-CT is virtually unable to differentiate the enantiomers in the hydrolysis of 1. The initial step to form the acyl-enzyme intermediate by the attack of Ser-195 hydroxyl on the beta-lactone ring at the 2-position in the hydrolysis reaction may not be enzymatically driven, but the relief of high ring strain energy of beta-lactone may constitute a major driving force. The deacylation step is also attenuated, which is possibly due to the hydrogen bond that would be formed between the imidazole nitrogen of His-57 and the hydroxyl group generated during the acylation in the case of (R)-1, but in the alpha-CT catalyzed hydrolysis of (S)-1 the imidazole nitrogen may form a hydrogen bond with the ester carbonyl oxygen.