Dibenzo[ f,h]furazano[3,4- b]quinoxalines: Synthesis by Intramolecular Cyclization through Direct Transition Metal-Free C-H Functionalization and Electrochemical, Photophysical, and Charge Mobility Characterization

Herein, we describe the synthesis of unsymmetrically substituted dibenzo[f,h]furazano[3,4-b]quinoxalines by intramolecular cyclization through direct transition metal-free C-H functionalization. The electrochemical and photophysical properties for several polycycles have been measured. In thin films of the dibenzo[f,h]furazano[3,4-b]quinoxalines, hole mobility is in the order of 10-4 cm2 V-1 s-1. The results show that the HOMO and LUMO energy levels are appropriate for using the compounds as hole-transport materials in thin-film devices, in particular, organic and perovskite solar cells. Copyright © 2020 American Chemical Society.Russian Foundation for Basic Research, RFBR: 18-33-00103-mol_aRussian Science Foundation, RSF: 18-13-00409The research was financially supported by the Russian Science Foundation (project no. 18-13-00409). Y.A.K would like to acknowledge the financial support for the part of the synthetic section from the Russian Foundation for Basic Research (research project no. 18-33-00103-mol_a). The authors are grateful to Grigory A. Kim for carrying out the DFT calculations, which were performed by using “Uran” supercomputer of the Institute of Mathematics and Mechanics of the Ural Branch of the Russian Academy of Sciences. NMR experiments were carried out by using equipment of the Center for Joint Use “Spectroscopy and Analysis of Organic Compounds” at the Postovsky Institute of Organic Synthesis of the Ural Branch of the Russian Academy of Sciences

Ion-beam sputtering of NiO hole transporting layers for p-i-n halide perovskite solar cells

Ion-beam sputtering offers significant benefits in terms of deposition uniformity and pinhole-free thin-films without limiting the scalability of the process. In this work, the reactive ion-beam sputtering of nickel oxide has been developed for the hole transporting layer of a p-i-n perovskite solar cells (PCSs). The process is carried out by oxidation of the scattered Ni particles with additional post-treatment annealing regimes. Using deposition rate of 1.2 nm/min allowed growth of very uniform NiO coating with the roughness below 0.5 nm on polished Si wafer (15x15 cm2). We performed a complex investigation of structural, optical, surface and electrical properties of the NiO thin-films. The post-treatment annealing (150-300C) was considered as an essential process for improvement of the optical transparency, decrease of defects concentration and gain of the charge carrier mobility. As result, the annealed ion-beam sputtered NiO films delivered a power conversion efficiency (PCE) up to 20.14%, while device without post-treatment reached the value of 11.84%. The improvement of the output performance originated from an increase of the short-circuit current density (Jsc), open circuit voltage (Voc), shunt and contact properties in the devices. We also demonstrate that the ion-beam sputtering of NiO can be successfully implemented for the fabrication of large area modules (54.5 cm2) and PSCs on a flexible plastic substrate (125 microns)

Benzo[ b]selenophene/thieno[3,2- b]indole-Based N,S,Se-Heteroacenes for Hole-Transporting Layers

Two series of new N,S,Se-heteroacenes, namely, 6H-benzo[4′,5′]selenopheno[2′,3′:4,5]thieno[3,2-b]indoles and 12H-benzo[4″,5″]selenopheno[2″,3″:4′,5′]thieno[2′,3′4,5]thieno[3,2-b]indoles, were successfully obtained using an effective strategy based on Fiesselmann thiophene and Fischer indole synthesis. The new molecules exhibit a large optical band gap (2.82 eV < Egopt < 3.23 eV) and their highest occupied molecular orbital (HOMO) energy formed by the plane π-core ranges between -5.2 and -5.6 eV, with the narrower optical band gap and lower HOMO level corresponding to selenated heteroacenes. In thin solid films of the heteroacenes, hole mobility measured using the conventional CELIV technique ranges between 10-5 and 10-4 cm2·V-1·s-1. All these make the proposed condensed-ring compounds a promising platform for the development of hole-transporting materials applicable in organic electronics. Copyright © 2020 American Chemical Society.The research (synthesis of new heteroacenes and investigation of their semiconductor properties) was financially supported by the Russian Science Foundation (project no. 18-13-00409). N.S.D. and N.A.R. would like to acknowledge the financial support for the analytical studies of synthesized compounds from the Ministry of Education and Science of the Russian Federation within the framework of the State Assignment for Research (project no. AAAA-A19-119012490006-1). The authors are grateful to Grigory A. Kim for carrying out the DFT calculations which were performed using ⟨⟨Uran⟩⟩ supercomputer of the Institute of Mathematic and Mechanics of the Ural Branch of the Russian Academy of Sciences. The XRD measurements were performed using the equipment of CKP FMI IPCE RAS

New Approach to Unsymmetrical 1,3- and 1,4-Diazatriphenylene Derivatives Through Intramolecular Oxidative Cyclodehydrogenation

The research was financially supported by the Russian Science Foundation (Project № 16-13-10435). NMR spectra and elemental analyses were covered by Program of the Ural Branch of the Russian Academy of Sciences (Рroject № 18-3-3-12)

Fast photorefractive polymer composites based on nanocrystalline J-aggregates of the

The hole and electron drift mobility, photoelectric properties as well as influence of temperature, dark current and also relative position of oxidation potentials of the interacting components on photorefractive characteristics of the composites from aromatic polyimide doped with nanocrystalline J-aggregates of a cyanine dye are presented. The nanocrystalline J-aggregates were used as the photosensitizers and also as nonlinear optical chromophores. The experimental electric field dependence of the charge carrier photogeneration efficiency is well fitted by Onsager equation when the quantum yield of the bound thermalized electron-hole pairs φ0=1 and the initial separation of the charges in the pair r0=14.1\uc5. The charge photogeneration time constant determines the response time of the photorefractive grating formation. The polymer composites exhibit gain coefficient Γ=218cm-1 and response time shorter than 20ms at applied electric field 50V/μm and a intensity of each writing beam 30mW/cm2. The net gain coefficient Γ-α=143cm -1

Photoconductivity of Low-Bandgap Polymer and Polymer: Fullerene Bulk Heterojunction Studied by Constant Photocurrent Method

Optical and photoelectric properties of modern photosensitive polymers are of great interest due to their prospects for photovoltaic applications. In particular, an investigation of absorption and photoconductivity edge of these materials could provide valuable information. For these purpose we applied the constant photocurrent method which has proved its efficiency for inorganic materials. PCDTBT and PTB7 polymers were used as objects for the study as well as their blends with a fullerene derivative PC71BM. The measurements by constant photocurrent method (CPM) show that formation of bulk heterojunction (BHJ) in the blends increases photoconductivity and results in a redshift of the photocurrent edge in the doped polymers compared with that in the neat polymers. Obtained from CPM data, spectral dependences of absorption coefficient were approximated using Gaussian distribution of density-of-states within HOMO (highest occupied molecular orbital) and LUMO (lowest unoccupied molecular orbital) bands. The approximation procedure allowed us to evaluate rather optical than electrical bandgaps for the studied materials. Moreover, spectra of polymer:PC71BM blends were fitted well by the sum of two Gaussian peaks which reveal both the transitions within the polymer and the transitions involving charge transfer states at the donor-acceptor interface in the BHJ

Fast photorefractive polymer composites based on nanocrystalline J-aggregates of the

The hole and electron drift mobility, photoelectric properties as well as influence of temperature, dark current and also relative position of oxidation potentials of the interacting components on photorefractive characteristics of the composites from aromatic polyimide doped with nanocrystalline J-aggregates of a cyanine dye are presented. The nanocrystalline J-aggregates were used as the photosensitizers and also as nonlinear optical chromophores. The experimental electric field dependence of the charge carrier photogeneration efficiency is well fitted by Onsager equation when the quantum yield of the bound thermalized electron-hole pairs φ0=1 and the initial separation of the charges in the pair r0=14.1\uc5. The charge photogeneration time constant determines the response time of the photorefractive grating formation. The polymer composites exhibit gain coefficient Γ=218cm-1 and response time shorter than 20ms at applied electric field 50V/μm and a intensity of each writing beam 30mW/cm2. The net gain coefficient Γ-α=143cm -1

Photoconduction and Electroluminescence of Copper (II) Protoporphyrin and Chlorin Cu-C-e6

Cu (II) protoporphyrin Cu-PP-IX and chlorin Cu-C-e6 were found to have both thin solid film formation and charge carrier transport abilities. In the layers deposited by resistive thermal evaporation, the mobilities of holes and electrons are on the order of 10−5 cm2 V−1 s−1. Organic light-emitting diodes incorporating the dye molecules as emitting dopants demonstrate electroluminescence in the UV and near-IR ranges