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A visible-light-enabled photoredox radical cascade cyclization of 2-vinyl benzimidazole derivatives is developed. This chemistry is applicable to a wide range of N -aroyl 2-vinyl benzimidazoles as acceptors, and halo compounds, including alkyl halides, acyl chlorides and sulfonyl chlorides, as radical precursors. The Langlois reagent also serves as an effective partner in this photocatalytic oxidative cascade process. This protocol provides a robust alternative for rendering highly functionalized benzo[4,5]imidazo[1,2- b ]isoquinolin-11(6 H )-ones.

As the research of photonic electronics thrives, the enhanced efficacy from an optic unit cell can considerably improve the performance of an optoelectronic device. In this regard, organic phototransistor memory with a fast programming/readout and a distinguished memory ratio produces an advantageous outlook to fulfill the demand for advanced applications. In this study, a hydrogen-bonded supramolecular electret is introduced into the phototransistor memory, which comprises porphyrin dyes, meso-tetra(4-aminophenyl)porphine, meso-tetra( p -hydroxyphenyl)porphine, and meso-tetra(4-carboxyphenyl)porphine (TCPP), and insulated polymers, poly(4-vinylpyridine) and poly(4-vinylphenol) (PVPh). To combine the optical absorption of porphyrin dyes, dinaphtho[2,3- b :2',3'- f ]thieno[3,2- b ]thiophene (DNTT) is selected as a semiconducting channel. The porphyrin dyes serve as the ambipolar trapping moiety, while the insulated polymers form a barrier to stabilize the trapped charges by forming hydrogen-bonded supramolecules. We find that the hole-trapping capability of the device is determined by the electrostatic potential distribution in the supramolecules, whereas the electron-trapping capability and the surface proton doping originated from hydrogen bonding and interfacial interactions. Among them, PVPh:TCPP with an optimal hydrogen bonding pattern in the supramolecular electret produces the highest memory ratio of 1.12 × 10 8 over 10 4 s, which is the highest performance among the reported achievements. Our results suggest that the hydrogen-bonded supramolecular electret can enhance the memory performance by fine-tuning their bond strength and cast light on a potential pathway to future photonic electronics.

An integrated strategy of molecular design and conjugated polymer doping is proposed to improve the electronic characteristics for organic field effect transistor (OFET) applications. Here, a series of soluble naphthalene diimide ( NDI )-based random donor-acceptor copolymers with selenophene π-conjugated linkers and four acceptors with different electron-withdrawing strengths (named as rNDI-N / S / NN / SS ) are synthesized, characterized, and used for OFETs. N-type doping of NDI -based random copolymers using (12 a ,18 a )-5,6,12,12 a ,13,18,18 a ,19-octahydro-5,6-dimethyl-13,18[1',2']-benzenobisbenzimidazo[1,2- b :2',1'- d ]benzo[ i ][2.5]benzodiazocine potassium triflate adduct ( DMBI-BDZC ) is successfully demonstrated. The undoped rNDI-N , rNDI-NN , and rNDI-SS samples exhibit ambipolar charge transport, while rNDI-S presents only a unipolar n-type characteristic. Doping with DMBI-BDZC significantly modulates the performance of rNDI-N / S OFETs, with a 3- to 6-fold increase in electron mobility (μ e ) for 1 wt % doped device due to simultaneous trap mitigation, lower contact resistance ( R C ), and activation energy ( E A ), and enhanced crystallinity and edge-on orientation for charge transport. However, the doping of intrinsic pro-quinoidal rNDI-NN / SS films exhibits unchanged or even reduced device performance. These findings allow us to manipulate the energy levels by developing conjugated copolymers based on various acceptors and quinoids and to optimize the dopant-polymer semiconductor interactions and their impacts on the film morphology and molecular orientation for enhanced charge transport.

Naphthobisthiadiazole has been known as a promising building unit of π-conjugated polymers for organic photovoltaics (OPVs). Here, we synthesized new NTz-based polymers that were combined with a benzodithiophene (BDT) unit having alkylthienyl substituents in the polymer backbone, named PNTzBDT , and PNTzBDT-F and PNTzBDT-Cl with fluorine and chlorine groups in the substituents, respectively. The polymers had significantly improved solubility than the previously reported NTz-based polymer ( PNTz4T ), most likely due to the torsion of the alkylthienyl substituents with respect to the BDT moiety, which suppresses the intermolecular interaction between the backbones. Despite the lower intermolecular interaction and thereby lower crystallinity, these polymers, in particular PNTzBDT and PNTzBDT-F , exhibited higher photovoltaic performances, with power conversion efficiencies as high as 13.3%, than PNTz4T in the cells that used Y6 as the acceptor material. The improved performance was ascribed to the enhanced miscibility of the polymers with the nonfullerene acceptor due to the increased solubility, which in addition led to the better charge generation and reduced charge recombination. These results indicate that NTz-based π-conjugated polymers have high potential for nonfullerene-based OPVs.

Organic-inorganic hybrid perovskite solar cells are on the brink of a breakthrough in photovoltaic technology. Scale-up and large-area processing have become the focal points that must be resolved before commercialization. In this study, the scalable ultrasonic spray deposition method for high-throughput coating of the perovskite photoactive layer with a large active area of up to 3 cm 2 is implemented by precisely controlling the concentration of the precursor solution and spray passes. CH 3 NH 3 PbI 3 films with large crystallites and a suitable thickness of ∼350 nm are facilely developed through one-step direct ultrasonic spraying. Less hysteresis and highly reproducible power conversion efficiencies (PCEs) of up to 12.30% (11.43 ± 0.43% on average for 20 devices) are achieved by an optimized single-junction device with an active area of 1 cm 2 , along with good ambient stability. The device retained ∼80 and ∼65% of the initial PCE after 60 and 105 days in ambient, respectively. The ultrasonic spray-coated perovskite solar cells can be further scaled to larger areas of 2 and 3 cm 2 and exhibit PCEs of 10.18 and 7.01%, respectively. The reliable scale-up process for manufacturing the atmospheric wet-coated perovskite film is available in cost-effective and easily operated bench-top variants to bridge the interconnection between applied research and industry.

A novel aggregation enhanced emission (AEE)-active polyamide TPA-CN-TPE with a high photoluminesence characteristic was successfully synthesized by the direct polymerization of 4-cyanotriphenyl diamine (TPA-CN) and tetraphenylethene (TPE)-containing dicarboxylic acid. The obtained luminescent polyamide plays a significant role as the polymer electret layer in organic field-effect transistors (OFETs)-type memory. The strong green emission of TPA-CN-TPE under ultraviolet (UV) irradiation can be directly absorbed by the pentacene channel, displaying a light-induced programming and voltage-driven erasing organic phototransistor-based nonvolatile memory. Memory window can be effectively manipulated between the programming and erasing states by applying UV light illumination and electrical field, respectively. The photoinduced memory behavior can be maintained for over 10 4 s between these two states with an on/off ratio of 10 4 , and the memory switching can be steadily operated for many cycles. With high photoresponsivity ( R) and photosensitivity ( S), this organic phototransistor integrated with AEE-active polyamide electret layer could serve as an excellent candidate for UV photodetectors in optical applications. For comparison, an AEE-inactive aromatic polyimide TPA-PIS electret with much weaker solid-state emission was also applied in the same OFETs device architecture, but this device did not show any UV-sensitive and UV-induced memory characteristics, which further confirmed the significance of the light-emitting capability of the electret layer.

Here, two diketopyrrolopyrrole (DPP)-based oligomers, DPP-4T and DPP-6T, are studied to reveal the influences of conjugation length on thin-film morphology and organic field-effect transistor (OFET) performances. PDMS-assisted crystallization in a solvent-annealing chamber is applied to prepare crystal arrays of DPP-4T and DPP-6T to optimize the quality of charge channels for OFET characterizations. To deliver insights into microstructure and morphology of thin films, a characterization procedure for determining molecular packing in thin film and crystallinity of the crystal arrays is presented via grazing incidence wide-angle X-ray scattering, electron diffraction, and lattice simulation software package (Cerius2). With the lattice parameters derived from analyses of grazing incidence wide-angle X-ray scattering (GIWAXS) and electron diffraction (ED), the lattice modeling results indicate that the inferior organic field-effect transistor (OFET) performances of DPP-6T are attributed to longer π-stacking distance. Also, less-ordered molecular arrangement and lower continuity of crystalline domains, both of which are revealed from crystallinity results, lead to lower mobility of DPP-6T. In this case, longer conjugated backbones with more conformational degrees of freedom thus cause inherent crystal defects during the crystal growth process, despite the potential to enhance intermolecular π-orbital overlap. Therefore, to achieve better OFET performance, suitable backbone length makes conjugated oligomers give high intermolecular π-orbital overlap and low density of structural disorder, which are the priorities for constructing good charge channel.

Organic field-effect transistors (OFETs) memory devices based on hybrid nanocomposite electret were fabricated by cooperative supramolecular polystyrene-block-poly(4-vinylpyridine) (PS-b-P4VP) with two different block compositions (asymmetric L1 and symmetric L2) that contain hydroxyl-functionalized ferrocene small molecules (FMs). Because of the selective hydrogen interaction between the hydroxyl groups of FM and pyridine groups in P4VP block, the small FMs can preferentially disperse in the P4VP nanodomain, which can be used as nanostructured charge-trapping nanocomposite electret (L1-FMX and L2-FMX) under solvent-annealing process. The charge-storage functionalities can be easily tailored by morphologies of the hybrid nanocomposite thin film and spatial distribution of the FM molecules in which the relative molecular mass of block copolymers and the FM loading ratio can further control both of them. These block copolymer nanocomposite thin film electrets with charge-controlling guest FM for OFETs memory devices exhibit significant features including the ternary bits storage, high-density trapping sites, charge-carrier trapping of both polarities (ambipolar trapping), and solution processing that can make important progress for future advanced storage and memory technology.

We report the facile fabrication and characteristics of organic thin film transistor (OTFT)-based nonvolatile memory devices using the hybrid nanocomposites of semiconducting poly(9,9-dioctylfluorene-alt-bithiophene) (F8T2) and ligand-capped Au nanoparticles (NPs), thereby serving as a charge storage medium. Electrical bias sweep/excitation effectively modulates the current response of hybrid memory devices through the charge transfer between F8T2 channel and functionalized Au NPs trapping sites. The electrical performance of the hybrid memory devices can be effectively controlled though the loading concentrations (0-9 %) of Au NPs and organic thiolate ligands on Au NP surfaces with different carbon chain lengths (Au-L6, Au-L10, and Au-L18). The memory window induced by voltage sweep is considerably increased by the high content of Au NPs or short carbon chain on the ligand. The hybrid nanocomposite of F8T2:9% Au-L6 provides the OTFT memories with a memory window of ~41 V operated at ± 30 V and memory ratio of ~1 × 10(3) maintained for 1 × 10(4) s. The experimental results suggest that the hybrid materials of the functionalized Au NPs in F8T2 matrix have the potential applications for low voltage-driven high performance nonvolatile memory devices.

Resistance switching memory devices with the configuration of poly(ethylene naphthalate)(PEN)/Al/polyimide (PI) blend/Al are reported. The active layers of the PI blend films were prepared from different compositions of poly[4,4'-diamino-4″-methyltriphenylamine-hexafluoroisopropylidenediphthalimide] (PI(AMTPA)) and polycyclic aromatic compounds (coronene or N,N-bis[4-(2-octyldodecyloxy)phenyl]-3,4,9,10-perylenetetracarboxylic diimide (PDI-DO)). The additives of large π-conjugated polycyclic compounds can stabilize the charge transfer complex induced by the applied electric field. Thus, the memory device characteristic changes from the volatile to nonvolatile behavior of flash and write-once-read-many times (WORM) as the additive contents increase in both blend systems. The main differences between these two blend systems are the threshold voltage values and the additive content to change the memory behavior. Due to the stronger accepting ability and higher electron affinity of PDI-DO than those of coronene, the PI(AMTPA):PDI-DO blend based memory devices show a smaller threshold voltage and change the memory behavior in a smaller additive content. Besides, the memory devices fabricated on a flexible PEN substrate exhibit an excellent durability upon the bending conditions. These tunable memory performances of the developed PI/polycyclic aromatic compound blends are advantageous for future advanced memory device applications.

We report the fabrication and characterization of polymer resistive switching memory devices fabricated from conjugated rod-coil poly[2,7-(9,9-dihexylfluorene)]-block-poly(2-vinylpyridine) diblock copolymers (PF-b-P2VP) and their hybrids with [6,6]-phenyl-C(61)-butyric acid methyl ester (PCBM). PF(10)-b-P2VP(37) and PF(10)-b-P2VP(68)-based devices exhibited the volatile static random access memory (SRAM) characteristic with an ON/OFF current ratio up to 1 × 10(7), which was explained by the trapping/back transferring of charge carrier. PF(10)-b-P2VP(68) had a longer holding time in the ON state than PF(10)-b-P2VP(37) because of the delayed back transfer of trapping carriers originally from the longer P2VP blocks. The PCBM aggregated size in the composite thin films were effectively reduced by PF-b-P2VP compared to the homopolymer of PF or P2VP, because of the supramolecular charge transfer interaction, as evidenced by absorption and photoluminescence spectra. Their PCBM/PF-b-P2VP composite devices changed from the nonvolatile write-once-read-many-times (WORM) memory to the conductor behavior as the PCBM composition was increased. The electric-field induced charge transfer effect enabled the electrical bistable states for the applications in digital WORM memory device. The tunable memory characteristics through the block length ratio of block copolymers or PCBM composition provided the solution-processable charge storage nanomaterials for programmable high density memory device with a reducing bit cell size.

We report bistable non-volatile memory devices based on polystyrene derivatives containing pendent electron-donating mono-, di-, and tri(9,9-dihexylfluorene), which are denoted as poly(St-Fl), poly(St-Fl(2)), and poly(St-Fl(3)), respectively. The effects of the oligofluorene chain lengths and polymer surface structures on the memory characteristics were explored. Poly(St-Fl)-, poly(St-Fl(2))-, and poly(St-Fl(3))-based devices exhibited a flash memory characteristic with different turn-on threshold voltages of 2.8, 2.0, and 1.8 V, respectively, which was on the reverse trend with the highest occupied molecular orbital levels of -5.86, -5.80, and -5.77 eV. Moreover, the memory device showed a high ON/OFF current ratio of 2.5 x 10(4) and a long retention time of 10(4) s. The possible mechanism of the switching behavior was explained by the space-charge-limited-current theory and filamentary conduction. The larger aggregation domain size of the polymer thin film processed from the mixed solvent of chlorobenzene/N,N-dimethylformamide probably promoted the diffusion of the Al atoms into the polymer film and formed the conduction channel. Thus, it significantly reduced the turn-on threshold voltage on the studied polymer memory devices. The present study suggested that the polymer memory characteristics could be efficiently tuned through the pendent conjugated chain length and surface structures.