A Nitroxide Radical Conjugated Polymer as an Additive to Reduce Nonradiative Energy Loss in Organic Solar Cells.

Nonfullerene-acceptor-based organic solar cells (NFA-OSCs) are now set off to the 20% power conversion efficiency milestone. To achieve this, minimizing all loss channels, including nonradiative photovoltage losses, seems a necessity. Nonradiative recombination, to a great extent, is known to be an inherent material property due to vibrationally induced decay of charge-transfer (CT) states or their back electron transfer to the triplet excitons. Herein, it is shown that the use of a new conjugated nitroxide radical polymer with 2,2,6,6-tetramethyl piperidine-1-oxyl side groups (GDTA) as an additive results in an improvement of the photovoltaic performance of NFA-OSCs based on different active layer materials. Upon the addition of GDTA, the open-circuit voltage (VOC ), fill factor (FF), and short-circuit current density (JSC ) improve simultaneously. This approach is applied to several material systems including state-of-the-art donor/acceptor pairs showing improvement from 15.8% to 17.6% (in the case of PM6:Y6) and from 17.5% to 18.3% (for PM6:BTP-eC9). Then, the possible reasons behind the observed improvements are discussed. The results point toward the suppression of the CT state to triplet excitons loss channel. This work presents a facile, promising, and generic approach to further improve the performance of NFA-OSCs.

Regulating Pseudo-Jahn-Teller Effect and Superstructure in Layered Cathode Materials for Reversible Alkali-Ion Intercalation.

The Jahn-Teller effect (JTE) is one of the most important determinators of how much stress layered cathode materials undergo during charge and discharge; however, many reports have shown that traces of superstructure exist in pristine layered materials and irreversible phase transitions occur even after eliminating the JTE. A careful consideration of the energy of cationic distortion using a Taylor expansion indicated that second-order JTE (pseudo-JTE) is more widespread than the aforementioned JTE because of the various bonding states that occur between bonding and antibonding molecular orbitals in transition-metal octahedra. As a model case, a P2-type Mn-rich cathode (Na3/4MnO2) was investigated in detail. MnO6 octahedra are well known to undergo either elongation or contraction in a specific direction due to JTE. Here, the substitution of Li for Mn (Na3/4(Li1/4Mn3/4)O2) helped to oxidize Mn3+ to Mn4+ suppressing JTE; however, the MnO6 octahedra remained asymmetric with a clear trace of the superstructure. With various advanced analyses, we disclose the pseudo-JTE as a general reason for the asymmetric distortions of the MnO6 octahedra. These distortions lead to the significant electrochemical degradation of Na3/4Li1/4Mn3/4O2. The suppression of the pseudo-JTE modulates phase transition behaviors during Na intercalation/deintercalation and thereby improves all of the electrochemical properties. The insight obtained by coupling a theoretical background for the pseudo-JTE with verified layered cathode material lattice changes implies that many previous approaches can be rationalized by regulating pseudo-JTE. This suggests that the pseudo-JTE should be thought more important than the well-known JTE for layered cathode materials.

Closely Packed Polypyrroles via Ionic Cross-Linking: Correlation of Molecular Structure-Morphology-Thermoelectric Properties.

A series of ionically interconnected polypyrrole (PPy) films are fabricated through two-monomer-connected-precursor polymerization by varying diacid linkers, thereby significantly influencing the crystalline morphology and electrical properties. The structure obtained using 1,5-napthalenedisulfonic acid (PPy-Nap) as a fused aromatic linker exhibits a higher electrical conductivity (∼78 S cm-1) than that (6.7 S cm-1) without a linker (PPy-ref). Cryogenic conductivity measurements reveal that the percolation carrier transport barrier of PPy-Nap is significantly smaller than that of PPy-ref, and the calculated carrier mobility of PPy-Nap is ∼5 times higher compared to PPy-ref. The carrier transport characteristics show a good agreement with morphological data by 2D grazing-incidence X-ray scattering. All PPys have similar doped charge carrier concentrations and, thus, similar Seebeck coefficients (5-8 µV K-1) but very different electrical conductivities. Consequently, PPy-Nap exhibits a higher power factor than that of PPy-ref (0.21 vs 0.043 µW m-1 K-2). The results show that the trade-off relationship between the Seebeck coefficient and electrical conductivity can be overcome by improving crystalline morphology and carrier transport. Thus, both the electrical conductivities and thermoelectric power factors can be improved with maintaining the Seebeck coefficients by enhancing the ordered conductive domains and carrier mobility while maintaining the doping level.

Gas-Induced Ion-Free Stable Radical Anion Formation of Organic Semiconducting Solids as Highly Gas-Selective Probes.

The formation of stabilized radical anions on organic materials in the solid state is an important issue in radical-based fundamental research and various applications. Herein, for the first time, we report on gas-induced ion-free stable radical anion formation (SRAF) of organic semiconducting solids with high gas selectivities through the use of organic field-effect transistor (OFET) gas sensors and electron spin resonance spectroscopy. In contrast to the previously reported SRAF, which requires either anionic analytes in solution and/or cationic substituents on π-electron-deficient aromatic cores, NDI-EWGs consist of an n-type semiconducting naphthalene diimide (NDI) and various electron-withdrawing groups (EWGs) that exhibit non-ion-involved, gas-selective SRAF in the solid state. In the presence of hard Lewis base gases, NDI-EWG-based OFETs exhibit enhanced conductivity (Current-ON mode) through the formation of an SRAF NDI/gas complex, while in the presence of borderline and soft Lewis base gases, NDI-EWG-based OFETs show decreased conductivity (Current-OFF mode) by the formation of a resistive NDI/gas complex. Organic semiconducting solids with EWGs exhibiting highly gas-selective solid-SRAF constitute a very promising platform for radical-based chemistry and can be used in various applications, such as highly gas-selective probes.

Spontaneous Doping at the Polymer-Polymer Interface for High-Performance Organic Transistors.

Low- k amorphous fluorinated polymers such as poly(perfluoroalkenylvinyl ether) (CYTOP) have widely been used as gate dielectrics for organic field-effect transistors (OFETs) because of their strong hydrophobicity to prevent the penetration of moisture and other contaminants and their perfect solvent orthogonality with organic semiconductors. Here, we report a new functionality of the fluorinated low- k polymer dielectrics, which is spontaneous p doping at the dielectric-semiconductor interface in OFETs. This functionality makes the ambipolar charge transport a unipolar p type. In the OFETs based on indacenodithiophene- co-benzothiadiazole and diketopyrrolopyrrole-thieno[3,2- b]thiophene, the charge transport is obviously ambipolar when paired with common polymer dielectrics such as poly(methyl methacrylate); however, it is perfectly modulated to the unipolar p type by applying the fluorinated dielectrics of CYTOP and poly(tetrafluoroethylene) (Teflon). We propose that this modulation of charge transport results from the rearrangement of C-F bonds at the interface between the fluorine-containing dielectrics and the conjugated polymer semiconductors by proper thermal annealing. These well-aligned dipole moments lead to an abrupt downshift of the Fermi level of the semiconductor toward the highest occupied molecular orbitals near the dielectric-semiconductor interface, which provides a p-doping effect on the channel transport and results in unipolar p-type characteristics in the composed OFETs. This study reveals a new functionality of the fluorinated dielectrics for future organic electronics.

Enhanced Efficiency and Long-Term Stability of Perovskite Solar Cells by Synergistic Effect of Nonhygroscopic Doping in Conjugated Polymer-Based Hole-Transporting Layer.

A face-on oriented and p-doped semicrystalline conjugated polymer, poly[(2,5-bis(2-hexyldecyloxy)phenylene)-alt-(5,6-difluoro-4,7-di(thiophen-2-yl)benzo[c][1,2,5]-thiadiazole)] (PPDT2FBT), was studied as a hole-transport layer (HTL) in methylammonium lead triiodide-based perovskite solar cells (PVSCs). PPDT2FBT exhibits a mid-band gap (1.7 eV), high vertical hole mobility (7.3 × 10-3 cm2/V·s), and well-aligned frontier energy levels with a perovskite layer for efficient charge transfer/transport, showing a maximum power conversion efficiency (PCE) of 16.8%. Upon doping the PPDT2FBT HTL with a nonhygroscopic Lewis acid, tris(pentafluorophenyl)borane (BCF, 2-6 wt %), the vertical conductivity was improved by a factor of approximately 2, and the resulting PCE was further improved up to 17.7%, which is higher than that of standard PVSCs with 2,2',7,7'-tetrakis(N,N-di-p-methoxyphenylamine)-9,9'-spirobifluorene (spiro-OMeTAD) as an HTL. After BCF doping, the clearly enhanced carrier diffusion coefficient, diffusion length, and lifetime were measured using intensity-modulated photocurrent and photovoltage spectroscopy. Furthermore, compared to the standard PVSCs with spiro-OMeTAD, the temporal device stability was remarkably improved, preserving the ∼60% of the original PCE for 500 h without encapsulation under light-soaking condition (1 sun AM 1.5G) at 85 °C and 85% humidity, which is mainly due to the highly crystalline conjugated backbone of PPDT2FBT and nonhygroscopic nature of BCF. In addition, formamidinium lead iodide/bromide (FAPbI3-xBrx)-based PVSCs with the BCF-doped PPDT2FBT as an HTL was also prepared to show 18.8% PCE, suggesting a wide applicability of PPDT2FBT HTL for different types of PVSCs.

Superparamagnetic Gold Nanoparticles Synthesized on Protein Particle Scaffolds for Cancer Theragnosis.

Cancer theragnosis using a single multimodality agent is the next mainstay of modern cancer diagnosis, treatment, and management, but a clinically feasible agent with in vivo cancer targeting and theragnostic efficacy has not yet been developed. A new type of cancer theragnostic agent is reported, based on gold magnetism that is induced on a cancer-targeting protein particle carrier. Superparamagnetic gold-nanoparticle clusters (named SPAuNCs) are synthesized on a viral capsid particle that is engineered to present peptide ligands targeting a tumor cell receptor (TCR). The potent multimodality of the SPAuNCs is observed, which enables TCR-specific targeting, T2 -weighted magnetic resonance imaging, and magnetic hyperthermia therapy of both subcutaneous and deep-tissue tumors in live mice under an alternating magnetic field. Furthermore, it is analytically elucidated how the magnetism of the SPAuNCs is sufficiently induced between localized and delocalized spins of Au atoms. In particular, the SPAuNCs show excellent biocompatibility without the problem of in vivo accumulation and holds promising potential as a clinically effective agent for cancer theragnosis.

Singly and Doubly Occupied Higher Quantum States in Nanocrystals.

Filling the lowest quantum state of the conduction band of colloidal nanocrystals with a single electron, which is analogous to the filling the lowest unoccupied molecular orbital in a molecule with a single electron, has attracted much attention due to the possibility of harnessing the electron spin for potential spin-based applications. The quantized energy levels of the artificial atom, in principle, make it possible for a nanocrystal to be filled with an electron if the Fermi-energy level is optimally tuned during the nanocrystal growth. Here, we report the singly occupied quantum state (SOQS) and doubly occupied quantum state (DOQS) of a colloidal nanocrystal in steady state under ambient conditions. The number of electrons occupying the lowest quantum state can be controlled to be zero, one (unpaired), and two (paired) depending on the nanocrystal growth time via changing the stoichiometry of the nanocrystal. Electron paramagnetic resonance spectroscopy proved the nanocrystals with single electron to show superparamagnetic behavior, which is a direct evidence of the SOQS, whereas the DOQS of the two- or zero-electron occupied nanocrystals in the 1Se exhibit diamagnetic behavior. In combination with the superconducting quantum interference device measurement, it turns out that the SOQS of the HgSe colloidal quantum dots has superparamagnetic property. The appearance and change of the steady-state mid-IR intraband absorption spectrum reflect the sequential occupation of the 1Se state with electrons. The magnetic property of the colloidal quantum dot, initially determined by the chemical synthesis, can be tuned from diamagnetic to superparamagnetic and vice versa by varying the number of electrons through postchemical treatment. The switchable magnetic property will be very useful for further applications such as colloidal nanocrystal based spintronics, nonvolatile memory, infrared optoelectronics, catalyst, imaging, and quantum computing.

Electrical properties of nanofibers and structural characterization of DNA-Au(III) complexes.

In order to realize deoxyribonucleic acid (DNA)-based molecular electronics, chemical modifications of DNA are needed to improve electrical conductivity. We developed a novel method utilizing the incorporation of Au(III) ions into DNA bases to alter their electronic properties. When Au(III) ions were incorporated proportionally into DNA bases, conductance increased up to an Au(III) content of 0.42 Au(III) ion/nucleotide. Surprisingly, electron paramagnetic resonance signals of Au(II) ions were detected at g ∼1.98, and the calculated spin number of Au(II) ions ranged from ∼10(13) to ∼10(15). The structural deformation of the DNA helix occurred when complexed with Au(III); simultaneously, the conductance of DNA-Au(III) complexes decreased when the content of Au(III) was higher than 0.42 atom/nucleotide. This observation implies that the maintenance of helical structure in the Au(III) doped state of DNA molecules is very important to the enhancement of the carrier mobility of DNA.

Optical and structural properties of nanobiomaterials.

In this review, the optical and structural properties of biomaterials are discussed. First, we demonstrate the optical and structural properties of natural and plasma-treated DNA, using UV-visible absorption, circular dichroism (CD), and Raman spectroscopy. Fluorescence and lasing action in the dye-doped DNA-surfactant complex are also explained. Additionally, nanomaterial-based DNA detection and DNA-templated nanomaterial growth are described. Next, we discuss protein folding studies utilizing fluorescence, CD, and nuclear magnetic resonance (NMR) spectroscopy. From the CD spectra of alpha-chymotrypsin (CT), we estimate the composition of a-helices and the beta-sheets, and random coils in the CT. 1H NMR spectroscopy is used to investigate the thermal effect on the refolding of CT in the presence of an ionic liquid. Finally, we explain the numerical simulation method used for studying the optical properties of biomaterials. Applications of the Monte-Carlo method in photodynamic therapy, skin tissue optics, and bioimaging are described.

Designed cyanide- and phenoxide-bridged Fe(III)Mn(III) single-molecule magnet constructed by highly blocked paramagnetic precursors.

A tetranuclear Fe(III)(2)Mn(III)(2) compound was prepared using highly blocked precursors. The well-isolated molecular entity associated with appropriate magnetic anisotropy allows for single-molecule magnet behavior.

DNA-templated preparation of gold nanoparticles.

DNA-mediated gold nanoparticles were prepared by chemical reduction of DNA-Au(III) complex. The DNA-Au(III) was first formed by reacting DNA with HAuCl4 at a pH of 5.6. The complex in solution was reacted with hydrazine reducing Au(III) to Au. The reduced Au formed nanodimensional aggregates. The particle distributions were obtained by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). This method resulted in a rather uniform dispersion of Au nanoparticles of near-spherical shape and 45~80 nm in diameter. Gold nanoparticles were embedded and stabilized by DNA.

High-temperature ferromagnetism of a discotic liquid crystal dilutely intercalated with iron(III) phthalocyanine.

Room-temperature ferromagnetism of an organic discotic liquid crystalline compound (DLC) is achieved by intercalation at low levels with paramagnetic iron(III) phthalocyanine (see figure). These ferromagnetic DLCs are very similar to the so-called dilute magnetic semiconductors of inorganic nature. It is expected that this novel approach will open up a new way of preparing the high-temperature organic ferromagnetic compounds needed for molecular spintronics.