Enhancing Optoelectronic Anisotropy in Highly Oriented Thin Films by Fluorine Substitution in Novel Semiconducting Polymers.

The recent past has witnessed remarkable progress in organic electronics, driven by the quest for flexible, lightweight, and cost-effective electronic devices. Semiconducting polymers (SCPs) have emerged as key materials in this field, offering unique electronic and optoelectronic properties along with mechanical flexibility. This study focuses on designing, synthesizing, and utilizing novel donor-acceptor (D-A) copolymer-based SCPs introducing a difluorothiophene moiety in the polymeric backbone.

Naphthalene Diimide-Based Donor-Acceptor-Donor Small Molecules as Metal-Free Organocatalysts for Photocatalytic CO Reaction.

The application of organic small molecules as metal-free photocatalysts for light-driven photoreduction of carbon dioxide (CO) has seldom been explored. This work developed four naphthalene diimide (NDI)-derived donor-acceptor-donor small molecules with different numbers of thiophene units, namely, NDI-2T, NDI-TT, NDI-4T, and NDI-6T, as metal-free photocatalysts to catalyze the reduction of CO under irradiation with an air mass 1.5G solar simulator at one-sun intensity.

Cesium Lead Halide Perovskite Nanocrystals Assembled in Metal-Organic Frameworks for Stable Blue Light Emitting Diodes.

All inorganic cesium lead trihalide nanocrystals are promising light emitters for bright light emitting diodes (LEDs). Here, CsPb(BrCl) nanocrystals in metal-organic frameworks (MOF) thin films are demonstrated to achieve bright and stable blue LEDs. The lead metal nodes in the MOF thin film react with Cs-halide salts, resulting in 10-20 nm nanocrystals.

Quasi-2D Perovskite Crystalline Layers for Printable Direct Conversion X-Ray Imaging.

Polycrystalline perovskite film-based X-ray detector is an appealing technology for assembling large scale imager by printing methods. However, thick crystalline layer without trap and solvent residual is challenging to fabricate. Here, the authors report a solution method to produce high quality quasi-2D perovskite crystalline layers and detectors that are suitable for X-ray imaging.

Chromatic Fulleropyrrolidine as Long-Lived Metal-Free Catalyst for CO Photoreduction Reaction.

Conversion of CO into carbonaceous fuels with the aid of solar energy has been an important research subject for decades. Owing to their excellent electron-accepting capacities, fullerene derivatives have been extensively used as n-type semiconductors. This work reports that the fulleropyrrolidine functionalized with 4,7-di(thiophen-2-yl)benzo[c][1,2,5]thiadiazole, abbreviated as DTBT-C , could efficiently catalyze the photoreduction of CO to CO.

Exohedral Functionalization of Fullerene by Substituents Controlling of Molecular Organization for Spontaneous C Dimerization in Liquid Crystal Solutions and in a Bulk Controlled by a Potential.

A study was carried out on the possibility of orderly and spontaneous dimerization at room temperature of C cages in fullerene liquid crystal fullerene dyads (R-C). For this purpose, dyads with a structural elements feature supporting π-stacking and Van der Waals interactions were tested, due to the presence of terthiophene donors linked through an α-position or dodecyloxy chains. In addition, this possibility was also tested and compared to dyads with shorter substituents and the pristine C.

Facile Fabrication of Self-Assembly Functionalized Polythiophene Hole Transporting Layer for High Performance Perovskite Solar Cells.

Crystallinity and crystal orientation have a predominant impact on a materials' semiconducting properties, thus it is essential to manipulate the microstructure arrangements for desired semiconducting device performance. Here, ultra-uniform hole-transporting material (HTM) by self-assembling COOH-functionalized P3HT (P3HT-COOH) is fabricated, on which near single crystal quality perovskite thin film can be grown. In particular, the self-assembly approach facilitates the P3HT-COOH molecules to form an ordered and homogeneous monolayer on top of the indium tin oxide (ITO) electrode facilitate the perovskite crystalline film growth with high quality and preferred orientations.

C(OH) and Its Nanocomposite for High-Performance Lithium Storage.

Organic carbon materials, such as graphene and nanotubes, with a high specific capacity show promise in improving the energy density for lithium ion batteries (LiBs). Here, we report on the synthesis and characterization of C(OH) and the C(OH)/graphene oxide (GO) composite and demonstrate their use as anode materials in LiBs. We find that the C(OH)/GO composite forms due to the chemical reactions between the carboxyl and epoxy groups of GO and the hydroxyl of C(OH) nanoparticles and that C(OH) uniformly grows on the surface of GO nanosheets.

Mechanistic Insights into the Effect of Polymer Regioregularity on the Thermal Stability of Polymer Solar Cells.

Thermal stability is a bottleneck toward commercialization of polymer solar cells (PSCs). The effect of PCBM aggregation on a multilength scale on the bulk-heterojunction (BHJ) structure, performance, and thermal stability of PSCs is studied here by grazing-incidence small- and wide-angle X-ray scattering. The evolution of hierarchical BHJ structures of a blend film tuned by regioregularity of polymers from the as-cast state to the thermally unstable state is systematically investigated.

Effect of Fullerene Passivation on the Charging and Discharging Behavior of Perovskite Solar Cells: Reduction of Bound Charges and Ion Accumulation.

Ion accumulation of organometal halide perovskites (OHPs) induced by electrode polarization of perovskite solar cells (PSCs) under illumination has been intensely studied and associated with a widely observed current-voltage hysteresis behavior. This work is dedicated to the investigation of the behavior of charged species at the compact TiO/OHP interface with respect to electrode polarization in PSC devices. By providing a comprehensive discussion of open-circuit voltage ( V) buildup and V decay under illumination and in the dark for the PSCs modified with [6,6]-phenyl-C butyric acid methyl ester (PCBM) at the TiO/OHP interface and their corresponding electrochemical impedance spectroscopies (EISs), a justified mechanism is proposed attempting to elucidate the dynamics of interfacial species with respect to the time and frequency domains.

Novel Two-Dimensional Conjugated Polymer Containing Fluorinated Bithiophene as Donor and Benzoselenodiazole as Acceptor Units with Vinyl-Terthiophene Pendants for Polymer Photovoltaic Cells.

Novel two-dimensional conjugated copolymer, abbreviated as PDTBSeVTT-2TF, containing electron-deficient 4,7-di(thiophen-2-yl)benzo[][1,2,5]selenodiazole (DTBSe) unit, conjugated vinyl-terthiophene (VTT) side chain and 3,3'-difluoro-2,2'-bithiophene (2TF) was designed and synthesized using microwave-assisted Stille cross-coupling polymerization. UV⁻visible absorption and cyclic voltammetry studies revealed that this copolymer possesses a strong and broad absorption in the range of 300⁻800 nm and a narrow optical bandgap () of 1.57 eV with low-lying HOMO and LUMO energy levels.

Amino-Acid-Induced Preferential Orientation of Perovskite Crystals for Enhancing Interfacial Charge Transfer and Photovoltaic Performance.

Interfacial engineering of perovskite solar cells (PSCs) is attracting intensive attention owing to the charge transfer efficiency at an interface, which greatly influences the photovoltaic performance. This study demonstrates the modification of a TiO electron-transporting layer with various amino acids, which affects charge transfer efficiency at the TiO /CH NH PbI interface in PSC, among which the l-alanine-modified cell exhibits the best power conversion efficiency with 30% enhancement. This study also shows that the (110) plane of perovskite crystallites tends to align in the direction perpendicular to the amino-acid-modified TiO as observed in grazing-incidence wide-angle X-ray scattering of thin CH NH PbI perovskite film.

Insights into the Morphological Instability of Bulk Heterojunction PTB7-Th/PCBM Solar Cells upon High-Temperature Aging.

The impact of the morphological stability of the donor/acceptor mixture under thermal stress on the photovoltaic properties of bulk heterojunction (BHJ) solar cells based on the poly[4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)benzo[1,2-b;4,5-b']-dithiophene-2,6-diyl-alt-(4-(2-ethylhexyl)-3-fluorothieno[3,4-b]-thiophene)-2-carboxylate-2,6-diyl]/phenyl-C-butyric acid methyl ester (PTB7-Th/PCBM) blend is extensively investigated. Both optical microscopy and transmission electron microscopy micrographs show that long-term high-temperature aging stimulates the formation of microscale clusters, the size of which, however, is about 1 order of magnitude smaller than those observed in thermally annealed poly(3-hexylthiophene)/PCBM composite film. The multilength-scale evolution of the morphology of PTB7-Th/PCBM film from the scattering profiles of grazing incidence small-angle and wide-angle X-ray scattering indicates the PCBM molecules spatially confine the self-organization of polymer chains into large domains during cast drying and upon thermal activation.

Development of Conjugated Polymers for Memory Device Applications.

This review summarizes the most widely used mechanisms in memory devices based on conjugated polymers, such as charge transfer, space charge traps, and filament conduction. In addition, recent studies of conjugated polymers for memory device applications are also reviewed, discussed, and differentiated based on the mechanisms and structural design. Moreover, the electrical conditions of conjugated polymers can be further fine-tuned by careful design and synthesis based on the switching mechanisms.

Near-Infrared-Absorbing and Dopant-Free Heterocyclic Quinoid-Based Hole-Transporting Materials for Efficient Perovskite Solar Cells.

New heterocyclic quinoid-based hole transporting materials (HTMs) with a rigid quinoid core [3,6-di(2H-imidazol-2-ylidene)cyclohexa-1,4-diene] have been synthesized. The new HTMs have good hole mobility (>10  cm  V  s ) and very intense absorption in the near-infrared region extending to >800 nm. High performance perovskite solar cells can be fabricated using these HTMs without dopant.

Synthesis and Characterization of Two-Dimensional Conjugated Polymers Incorporating Electron-Deficient Moieties for Application in Organic Photovoltaics.

A series of novel p-type conjugated copolymers, PTTVBDT, PTTVBDT-TPD, and PTTVBDT-DPP, cooperating benzo[1,2-b:4,5-b']dithiophene (BDT) and terthiophene-vinylene (TTV) units with/without thieno[3,4-]pyrrole-4,6-dione (TPD) or pyrrolo[3,4-]pyrrole-1,4-dione (DPP) via Stille polymerization were synthesized and characterized. Copolymer PTTVBDT shows a low-lying HOMO energy level and ordered molecular-packing behavior. Furthermore, two terpolymers, PTTVBDT-TPD and PTTVBDT-DPP, display stronger absorption ability, alower-lying HOMO energy level, and preferred molecular orientation, due to the replacement TTV-monomer units with electron-deficient groups.

Coexistence of Two Electronic Nano-Phases on a CHNHPbICl Surface Observed in STM Measurements.

Scanning tunneling microscopy is utilized to investigate the local density of states of a CHNHPbICl perovskite in cross-sectional geometry. Two electronic phases, 10-20 nm in size, with different electronic properties inside the CHNHPbICl perovskite layer are observed by the dI/dV mapping and point spectra. A power law dependence of the dI/dV point spectra is revealed.

Bifunctional Polymer Nanocomposites as Hole-Transport Layers for Efficient Light Harvesting: Application to Perovskite Solar Cells.

A new approach to largely enhancing light harvesting of solar cells by employing bifunctional polymer nanocomposites as hole-transport layers (HTLs) is proposed. To illustrate our working principle, CH3NH3PbI3-xClx perovskite solar cells are used as examples. Gold nanoparticles (Au-NPs) are added into a conjugated poly(3-hexylthiophene-2,5-diyl) (P3HT) matrix, resulting in a ∼4-fold enhancement in the electrical conductivity and carrier mobility of the native P3HT film.

Impact of constitution of the terthiophene-vinylene conjugated side chain on the optical and photovoltaic properties of two-dimensional polythiophenes.

The effects of the spatial arrangement of the conjugated side chains of two-dimensional polymers on their optical, electrochemical, molecular-packing, and photovoltaic characteristics were investigated. Accordingly, novel polythiophenes with horizontally (PBTTTV-h) and vertically (PBTTTV-v) grafted terthiophene–vinylene (TTV) conjugated side chains were synthesized that display two and one UV-vis peaks, respectively; the difference is due to the different constitutions of the conjugated side-chains. Because the spatial arrangement affects the molecular self-assembly, PBTTTV-h shows stronger crystallinity than PBTTTV-v, which enhances the charge mobility in devices.

Colorimetric detection of fluoride ion by 5-arylidenebarbituric acids: dual interaction mode for fluoride ion with single receptor.

Two 5-arylidenebarbituric acid derivatives (IH and IM) have been synthesized by the Knoevenagel condensation of barbituric acid with 4-N,N-dimethylamino benzaldehyde and studied for anion sensing activities. Both receptors sense fluoride ion with high selectivity and sensitivity and the sensing action has been demonstrated by naked eye detection, UV-visible absorption, and fluorescence spectral changes in the presence of F(-). Indeed, the F(-) sensing mechanism for receptor IH depends on F(-) ion concentration.

Self-assembled all-conjugated block copolymer as an effective hole conductor for solid-state dye-sensitized solar cells.

An all-conjugated diblock copolymer, poly(2,5-dihexyloxy-p-phenylene)-b-poly(3-hexylthiophene) (PPP-b-P3HT), was synthesized and applied as a hole transport material (HTM) for the fabrication of solid-state dye-sensitized solar cells (ss-DSCs). This copolymer is characterized by an enhanced crystallinity, enabling its P3HT component to self-organize into interpenetrated and long-range-ordered crystalline fibrils upon spin-drying and ultimately endowing itself to have a faster hole mobility than that of the parent P3HT homopolymer. Transient photovoltage measurements indicate that the photovoltaic cell based on PPP-b-P3HT as the HTM has a longer electron lifetime than that of the reference device based on P3HT homopolymer.

Benzoselenadiazole fluorescent probes--near-IR optical and ratiometric fluorescence sensor for fluoride ion.

A highly selective and sensitive near-IR optical sensor, benzoselenadiazole based diarylamine (TBS-HN), for fluoride (F(-)) has been designed and synthesized. TBS-HN also shows turn-on ratiometric fluorescence signaling in the presence of F(-) by inhibiting the excited state intramolecular proton transfer (ESIPT) processes.

Mechanism and control of the structural evolution of a polymer solar cell from a bulk heterojunction to a thermally unstable hierarchical structure.

We simultaneously employed grazing incidence small-angle and wide-angle X-ray scattering (GISAXS and GIWAXS) techniques to quantitatively study the structural evolution and kinetic behavior of poly(3-hexylthiophene) (P3HT) crystallization, [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) aggregation and amorphous P3HT/PCBM domains from a bulk heterojunction (BHJ) to a thermally unstable structure. The independent phase separation regimes on the nanoscale (∼10 nm), mesoscale (∼100 nm) and macroscale (∼μm) are revealed for the first time. Bis-PCBM molecules as inhibitors incorporated into the P3HT/PCBM blend films were adopted as a case study of a control strategy for improving the thermal stability of P3HT/PCBM solar cell.

[60]Fulleropyrrolidines bearing π-conjugated moiety for polymer solar cells: contribution of the chromophoric substituent on C₆₀ to the photocurrent.

Two fullerene-terthiophene dyads without hexyl chains (3T-C₆₀) and with hexyl chains (3TH-C₆₀) on the terthiophene substituent are synthesized by 1,3-dipolar cycloaddition of corresponding azomethine ylides to C₆₀. The cyclic voltammetry studies indicate no apparent electronic communication between the terthiophene pendent group and the fulleropyrrolidine core in the ground state. However, a significant florescence quenching is observed for 3T-C₆₀ and 3TH-C₆₀, compared to their fluorescent terthiophene (3T) and 3TH precursors, respectively, suggesting the occurrence of strong intramolecular electron/energy transfers in the photoexcited state.