Electron Transfer Enhanced by a Minimal Energetic Driving Force at the Organic-Semiconductor Interface.

Energetic driving force for electron transfer must be minimized to realize efficient optoelectronic devices including organic light-emitting diodes (OLEDs) and organic photovoltaics (OPVs). Exploring dynamics of a charge transfer (CT) state at an interface leads to a comprehension of the relationship between energetics, electron transfer efficiency, and device performance. Here, we investigate the electron transfer from the CT state to the triplet excited state (T1) in upconversion OLEDs with 45 material combinations. By analyzing the CT emission and the singlet excited state emission from triplet-triplet annihilation via dark T1, their energetics and electron transfer efficiencies are extracted. We demonstrate that the CT→T1 electron transfer is enhanced by the stronger CT interaction and a minimal energetic driving force (<0.1 eV), which is explained using the Marcus theory with a small reorganization energy of <0.1 eV. Through our analysis, a novel donor-acceptor combination for the OLED is developed and shows an efficient blue emission with an extremely low turn-on voltage of 1.57 V. This work provides a solution to control interfacial CT state toward efficient optoelectronic devices without energy loss.

Evaporable Fullerene Indanones with Controlled Amorphous Morphology as Electron Transport Layers for Inverted Perovskite Solar Cells.

Fullerenes are among the most commonly used electron-transporting materials (ETMs) in inverted perovskite solar cells (IPSCs). Although versatile functionalized fullerene derivatives have shown excellent performance in IPSCs, pristine [60]fullerene (C60) is still the most widely used in devices mainly because of its uniform morphology by thermal deposition. However, thermally evaporable fullerene derivatives have not yet been achieved. Herein, we developed a series of evaporable fullerene derivatives, referred to as fullerene indanones (FIDOs), affording IPSCs with high power conversion efficiency (PCE) and long-term storage stability. The FIDOs were designed with a unique architecture in which the fullerene moiety and a benzene ring moiety are linked via a five-membered carbon ring in benzene ring plane. This molecular arrangement affords exceptional thermal stability, allowing the FIDOs to withstand harsh thermal deposition conditions. Moreover, by manipulating the steric bulk of the functional groups, we could control the state of the organic film from crystalline to amorphous. Subsequently, we used FIDOs as an electron transport layer (ETL) in IPSCs. Thanks to the suitable energy level and dual-passivation effect of FIDOs compared with a reference ETL using C60, the device using FIDOs achieved an open-circuit voltage of 1.16 V and a fill factor of 0.77. As a result, the PCE reached 22.11%, which is superior to 20.45% of the best-performing reference device. Most importantly, the FIDO-based IPSC devices exhibited exceptional stability in comparison to the reference device due to the stability of the amorphous ETL films.

Influence of N-Substituents on Photovoltaic Properties of Singly Bay-Linked Dimeric Perylene Diimides.

The influence of N-substituents on the photovoltaic properties of singly bay-linked perylene diimides (diPDIs) was systematically investigated to understand the aromatic-aliphatic balance, which is beneficial for achieving high device performance in organic photovoltaic (OPV) systems. The synthesis of various N-substituted diPDIs was successfully achieved using a newly developed one-step procedure, resulting in sufficiently high yields. Detailed investigations of seven variants of diPDIs demonstrated that the primary alkyl substituents, particularly the 2-ethylhexyl group, induce the self-organized growth of thin films with high crystallinity. This is beneficial for enhancing the device performance of bulk heterojunction (BHJ) systems. The results presented herein reveal the important roles of alkyl side chains as hydrophobic solubilizing auxiliaries or primary determinants in the control of the active layer nanomorphology. This offers a valuable guideline that is essential for developing high-performance organic semiconductor materials for future practical applications.

Electrochemical Detection of Circadian Redox Rhythm in Cyanobacterial Cells via Extracellular Electron Transfer.

Recent research on cellular circadian rhythms suggests that the coupling of transcription-translation feedback loops and intracellular redox oscillations is essential for robust circadian timekeeping. For clarification of the molecular mechanism underlying the circadian rhythm, methods that allow for the dynamic and simultaneous detection of transcription/translation and redox oscillations in living cells are needed. Herein, we report that the cyanobacterial circadian redox rhythm can be electrochemically detected based on extracellular electron transfer (EET), a process in which intracellular electrons are exchanged with an extracellular electrode. As the EET-based method is non-destructive, concurrent detection with transcription/translation rhythm using bioluminescent reporter strains becomes possible. An EET pathway that electrochemically connected the intracellular region of cyanobacterial cells with an extracellular electrode was constructed via a newly synthesized electron mediator with cell membrane permeability. In the presence of the mediator, the open circuit potential of the culture medium exhibited temperature-compensated rhythm with approximately 24 h periodicity. Importantly, such circadian rhythm of the open circuit potential was not observed in the absence of the electron mediator, indicating that the EET process conveys the dynamic information regarding the intracellular redox state to the extracellular electrode. These findings represent the first direct demonstration of the intracellular circadian redox rhythm of cyanobacterial cells.

Surface functionalization of organic semiconductor films by segregated monolayers.

Fullerene-based surfactants with semifluoroalkyl chains bearing one of five different functional groups at the end were synthesized and used for the facile surface modification of organic semiconductor films. Surface analysis showed that the modifiers were segregated and the functional groups were exposed at the surface.

Efficient Spin Interconversion by Molecular Conformation Dynamics of a Triplet Pair for Photon Up-Conversion in an Amorphous Solid.

Solid-state materials with improved light-to-energy conversions in organic photovoltaics and in optoelectronics are expected to be developed by realizing efficient triplet-triplet annihilation (TTA) by manipulating the spin conversion processes to the singlet state. In this study, we elucidate the spin conversion mechanism for delayed fluorescence by TTA from a microscopic view of the molecular conformations. We examine the time evolution of the electron spin polarization of the triplet-pair state (TT state) in an amorphous solid-state system exhibiting highly efficient up-conversion emission by using time-resolved electron paramagnetic resonance. We clarified that the spin-state population of the singlet TT increased through the spin interconversion from triplet and quintet TT states during exciton diffusion with random orientation dynamics between the two triplets for the modulation of the exchange interaction, achieving a high quantum yield of up-conversion emission. This understanding provides us with a guide for the development of efficient light-to-energy conversion devices utilizing TTA.

Wavily Curved Perylene Diimides: Synthesis, Characterization, and Photovoltaic Properties.

Solubility enhancement is a key issue for developing the perylene diimide-based functional materials. Introduction of curved structure proved an effective solubilizing method without employing steric repulsion. In this work, wavily curved perylene diimides were developed as a new family of highly soluble curved perylene diimides. Moreover, their conformational dynamics, aggregating properties, electronic properties, and photovoltaic performances were thoroughly examined in comparison to the previously reported isomer exhibiting an arched curvature. The waved isomer demonstrated heightened rigidity and a greater propensity for aggregation compared to the arched isomer, likely attributed to its more planar structure. Each benzoxepin unit played a role in cancelling out the curvature on the opposite side. While the difference in the molecular curvature did not cause significant alterations in the photophysical and electron-accepting properties, we identified that the modulation of the curved structure is effective in controlling the morphology of the photoelectric conversion layer.

Bottom Contact 100 nm Channel-Length α-In2 Se3 In-Plane Ferroelectric Memory.

Owing to the emerging trend of non-volatile memory and data-centric computing, the demand for more functional materials and efficient device architecture at the nanoscale is becoming stringent. To date, 2D ferroelectrics are cultivated as channel materials in field-effect transistors for their retentive and switchable dipoles and flexibility to be compacted into diverse structures and integration for intensive production. This study demonstrates the in-plane (IP) ferroelectric memory effect of a 100 nm channel-length 2D ferroelectric semiconductor α-In2 Se3 stamped onto nanogap electrodes on Si/SiO2 under a lateral electric field. As α-In2 Se3 forms the bottom contact of the nanogap electrodes, a large memory window of 13 V at drain voltage between ±6.5 V and the on/off ratio reaching 103 can be explained by controlled IP polarization. Furthermore, the memory effect is modulated by the bottom gate voltage of the Si substrate due to the intercorrelation between IP and out-of-plane (OOP) polarization. The non-volatile memory characteristics including stable retention lasting 17 h, and endurance over 1200 cycles suggest a wide range of memory applications utilizing the lateral bottom contact structure.

Blue organic light-emitting diode with a turn-on voltage of 1.47 V.

Among the three primary colors, blue emission in organic light-emitting diodes (OLEDs) are highly important but very difficult to develop. OLEDs have already been commercialized; however, blue OLEDs have the problem of requiring a high applied voltage due to the high-energy of blue emission. Herein, an ultralow voltage turn-on at 1.47 V for blue emission with a peak wavelength at 462 nm (2.68 eV) is demonstrated in an OLED device with a typical blue-fluorescent emitter that is widely utilized in a commercial display. This OLED reaches 100 cd/m2, which is equivalent to the luminance of a typical commercial display, at 1.97 V. Blue emission from the OLED is achieved by the selective excitation of the low-energy triplet states at a low applied voltage by using the charge transfer (CT) state as a precursor and triplet-triplet annihilation, which forms one emissive singlet from two triplet excitons.

Morphological stability of organic solar cells based upon an oligo(p-phenylenevinylene)-C70 dyad.

An oligo(p-phenylenevinylene)-C(70) dyad achieves the highest power conversion efficiency (1.92%) in dyad-based organic solar cells to date. Covalent attachment in the dyad prevents large phase separation, resulting in good morphological and device stability at high temperatures as compared with mixed bulk heterojunction devices.

Synthesis of neutral Li-endohedral PCBM: an n-dopant for fullerene derivatives.

Li@PCBM, the first neutral Li@C60 derivative, was synthesized. The Li@PCBM exists in a monomer-dimer equilibrium in solution but as a monomer in the PCBM matrix. The fully dispersed Li@PCBM n-doped the surrounding empty PCBM, raising the Fermi level by 0.13 eV compared with the undoped PCBM film. The hybrid films were utilized as an ETL for PSCs, promoting the efficiency of the device.

Curved Perylene Diimides Fused with Seven-Membered Rings.

Curved perylene diimides fused with seven-membered rings have been synthesized using a regioselective bay-functionalization method and Pd-catalyzed intramolecular C-H/C-Br coupling reaction. X-Ray analysis and temperature-dependent NMR spectroscopy revealed the curved molecular structure with a certain degree of conformational flexibility. The curved and expanded π-conjugation altered the electronic properties while retaining the intrinsic properties of the parent perylene diimide. Despite the absence of solubilizing N-substituents, the curved perylene diimides showed sufficient solubility for application in solution-processed organic photovoltaic devices. The devices showed superior performance with a power conversion efficiency of up to 2.76% due to suppressed charge recombination. Our detailed investigations suggest that the introduction of a curved structure enables the removal of the bulky N-substituents, which is an effective way to achieve a thin-film morphology suitable for photoelectric conversion.

Quasi-Homoepitaxial Junction of Organic Semiconductors: A Structurally Seamless but Electronically Abrupt Interface between Rubrene and Bis(trifluoromethyl)dimethylrubrene.

Single-crystalline organic semiconductors exhibiting band transport have opened new possibilities for the utilization of efficient charge carrier conduction in organic electronic devices. The epitaxial growth of molecular materials is a promising route for the realization of well-crystallized organic semiconductor p-n junctions for optoelectronic applications enhanced by the improved charge carrier mobility. In this study, the formation of a high-quality crystalline interface upon "quasi-homoepitaxial" growth of bis(trifluoromethyl)dimethylrubrene (fmRub) on the single-crystal surface of rubrene was revealed by using out-of-plane and grazing-incidence X-ray diffraction techniques. Ultraviolet photoelectron spectroscopy results indicated abrupt electronic energy levels and the occurrence of band bending across this quasi-homoepitaxial interface. This study verifies that the minimization of the lattice mismatch enhances the crystalline qualities at the heterojunctions even for van der Waals molecular condensates, potentially opening an untested route for the realization of high-mobility organic semiconductor optoelectronics.

Donor/Acceptor Photovoltaic Cells Fabricated on p-Doped Organic Single-Crystal Substrates.

In this study, the operation of donor/acceptor photovoltaic cells fabricated on homoepitaxially grown p-doped rubrene single-crystal substrates is demonstrated. The photocurrent density is dominated by the sheet conductivity (σ□) of the p-type single-crystal layer doped to 100 ppm with an iron chloride (Fe2Cl6) acceptor. A 65 mm thick p-type rubrene single-crystal substrate is expected to be required for a photocurrent density of 20 mA·cm-2. An entire bulk doping technique for rubrene single crystals is indispensable for the fabrication of practical organic single-crystal solar cells.

Development of Perylene-Based Non-Fullerene Acceptors through Bay-Functionalization Strategy.

Perylene has had a tremendous impact in the history of material research for the molecular semiconductors. Among numerous derivatives of this polyaromatic hydrocarbon, perylene diimide (PDI) represents a promising class of organic materials envisioned as non-fullerene acceptors (NFAs) for the practical organic photovoltaic (OPV) applications due to their enhanced photo- and thermal stability and remarkably high electron affinity, some of which realize band-like transport properties. The present review guides some of the representative achievements in the development of rationally designed PDI systems, highlighting synthetic methodologies based on bay-functionalization strategies for creating well-designed molecular nanostructures and structure-performance relationship of perylene-based small molecular acceptors (SMAs) for the photovoltaic outcomes.

Photoconversion Mechanism at the pn-Homojunction Interface in Single Organic Semiconductor.

Clarifying critical differences in free charge generation and recombination processes between inorganic and organic semiconductors is important for developing efficient organic photoconversion devices such as solar cells (SCs) and photodetector. In this study, we analyzed the dependence of doping concentration on the photoconversion process at the organic pn-homojunction interface in a single organic semiconductor using the temperature dependence of J-V characteristics and energy structure measurements. Even though the organic pn-homojunction SC devices were fabricated using a single host material and the doping technique resembling an inorganic pn-homojunction, the charge generation and recombination mechanisms are similar to that of conventional donor/acceptor (D/A) type organic SCs; that is, the charge separation happens from localized exciton and charge transfer (CT) state being separated by the energy offset between adjacent molecules, and the recombination happens from localized charge carrier at two adjacent molecules. The determining factor for photoconversion processes is the localized nature of charges in organic semiconductors. The results demonstrated that controlling the delocalization of the charges is important to realize efficient organic photoconversion devices.

Regioselective Bay-Functionalization of Perylenes Toward Tailor-Made Synthesis of Acceptor Materials for Organic Photovoltaics.

The development of an efficient synthetic protocol for multiply bay-functionalized perylenes and application of these products to photovoltaics are reported. Tetrabenzyl 1-(4-tert-butylphenoxy)perylene-3,4,9,10-tetracarboxylate underwent a regioselective bromination at the 7-position followed by a further bromination at the 12-position to provide a 7,12-dibromide in high 84% yield. This compound was transformed into a tetrasubstituted C2h -symmetric dibromide by a controlled monoetherification and a final bromination. The synthetic versatility of the new brominated precursors was demonstrated by their application to cross-coupling reactions, cyanation, and derivatization to the corresponding perylene diimide (PDI). Owing to the high solubility and the raised LUMO level, the obtained tetrasubstituted PDI showed significant advantages as an acceptor material for photovoltaic applications, exhibiting a remarkably high open-circuit voltage (VOC ) reaching 1.00 V. The observed high VOC could be understood by reduction of energy offset for charge separation and non-radiative recombination loss.

Electronic and Crystallographic Examinations of the Homoepitaxially Grown Rubrene Single Crystals.

Homoepitaxial growth of organic semiconductor single crystals is a promising methodology toward the establishment of doping technology for organic opto-electronic applications. In this study, both electronic and crystallographic properties of homoepitaxially grown single crystals of rubrene were accurately examined. Undistorted lattice structures of homoepitaxial rubrene were confirmed by high-resolution analyses of grazing-incidence X-ray diffraction (GIXD) using synchrotron radiation. Upon bulk doping of acceptor molecules into the homoepitaxial single crystals of rubrene, highly sensitive photoelectron yield spectroscopy (PYS) measurements unveiled a transition of the electronic states, from induction of hole states at the valence band maximum at an adequate doping ratio (10 ppm), to disturbance of the valence band itself for excessive ratios (≥ 1000 ppm), probably due to the lattice distortion.

Parts-per-Million-Level Doping Effects in Organic Semiconductor Films and Organic Single Crystals.

Controlling the pn-type behavior of a semiconductor such as silicon by adding an extremely small quantity of an impurity (doping) is a central part of inorganic semiconductor electronics since the 20th century. Recent progress in the doping of organic semiconductors strongly suggests the advent of a new era of doped organic semiconductors. Here, the principles and effects of doping at the level of parts per million (ppm) in organic semiconductor films and single crystals are described, including descriptions of complete pn-control, doping sensitization, ppm doping using an extremely low-speed deposition technique reaching 10-9 nm s-1 , and emerging ppm-level doping effects, such as trap filling, majority carriers, homojunction formation, and decreased mobility, as well as ppm-level doping effects in organic single crystals measured by the Hall effect, which shows a doping efficiency of 24%. The Wannier excitonic doping of organic single crystals possessing band conduction and the defect science of organic single crystals related to carrier trapping and scattering are introduced as a new scientific field. The dawn of organic single-crystal electronics is also discussed.

Li@C60 endohedral fullerene as a supraatomic dopant for C60 electron-transporting layers promoting the efficiency of perovskite solar cells.

C60:Li@C60 hybrid n-type semiconducting films were first fabricated. The Fermi level of 1% Li@C60-added C60 films was determined to be -4.52 eV, which was 0.12 eV higher than that of pristine C60 films. A fraction of Li@C60 is distributed uniformly within the C60 film. Its application in PSCs was demonstrated, in which the addition of Li@C60 into a C60 film improved the device performance.