Suppressed Lattice Disorder for Large Emission Enhancement and Structural Robustness in Hybrid Lead Iodide Perovskite Discovered by High-Pressure Isotope Effect

The soft nature of organic–inorganic halide perovskites renders their lattice particularly tunable to external stimuli such as pressure, undoubtedly offering an effective way to modify their structure for extraordinary optoelectronic properties. Here, using the methylammonium lead iodide as a representative exploratory platform, it is observed that the pressure-driven lattice disorder can be significantly suppressed via hydrogen isotope effect, which is crucial for better optical and mechanical properties previously unattainable. By a comprehensive in situ neutron/synchrotron-based analysis and optical characterizations, a remarkable photoluminescence (PL) enhancement by threefold is convinced in deuterated CD₃ND₃PbI₃, which also shows much greater structural robustness with retainable PL after high peak-pressure compression–decompression cycle. With the first-principles calculations, an atomic level understanding of the strong correlation among the organic sublattice and lead iodide octahedral framework and structural photonics is proposed, where the less dynamic CD₃ND₃⁺ cations are vital to maintain the long-range crystalline order through steric and Coulombic interactions. These results also show that CD₃ND₃PbI₃-based solar cell has comparable photovoltaic performance as CH₃NH₃PbI₃-based device but exhibits considerably slower degradation behavior, thus representing a paradigm by suggesting isotope-functionalized perovskite materials for better materials-by-design and more stable photovoltaic application.     

Dielectric–Semiconductor Interface Limits Charge Carrier Motion at Elevated Temperatures and Large Carrier Densities in a High‐Mobility Organic Semiconductor

The fundamental nature of charge transport in highly ordered organic semiconductors is under constant debate. At cryogenic temperatures, effects within the semiconductor such as traps or the interaction of charge carriers with the insulating substrate (dipolar disorder or Fröhlich polarons) are known to limit carrier motion. In comparison, at elevated temperatures, where charge carrier mobility often also decreases as function of temperature, phonon scattering or dynamic disorder are frequently discussed mechanisms, but the exact microscopic cause that limits carrier motion is debated. Here, the mobility in the temperature range between 200 and 420 K as function of carrier density is explored in highly ordered perylene‐diimide from 3 to 9 nm thin films. It is observed that above room temperature increasing the gate electric field or decreasing the semiconducting film thickness leads to a suppression of the charge carrier mobility. Via X‐ray diffraction measurements at various temperatures and electric fields, changes of the thin film structure are excluded as cause for the observed mobility decrease. The experimental findings point toward scattering sites or traps at the semiconductor–dielectric interface, or in the dielectric as limiting factor for carrier mobility, whose role is usually neglected at elevated temperatures.     

A Roadmap for Controlled and Efficient n‐Type Doping of Self‐Assisted GaAs Nanowires Grown by Molecular Beam Epitaxy

N‐type doping of GaAs nanowires has proven to be difficult because the amphoteric character of silicon impurities is enhanced by the nanowire growth mechanism and growth conditions. The controllable growth of n‐type GaAs nanowires with carrier density as high as 10²⁰ electron cm^?3 by self‐assisted molecular beam epitaxy using Te donors is demonstrated here. Carrier density and electron mobility of highly doped nanowires are extracted through a combination of transport measurement and Kelvin probe force microscopy analysis in single‐wire field‐effect devices. Low‐temperature photoluminescence is used to characterize the Te‐doped nanowires over several orders of magnitude of the impurity concentration. The combined use of those techniques allows the precise definition of the growth conditions required for effective Te incorporation.     

PNET “ONDM 2019” special issue

Photonic Network Communications -     

Modification of physicochemical properties of actin filaments suppresses cell fragmentation in the execution phase of staurosporine-induced apoptotic processes

Effects of jasplakinolide (JSP), a stabilizer of F-actin, and latrunculin A (LTA), a destabilizer of F-actin, on a series of events occurring in the execution phase of staurosporine (STS)-induced apoptotic processes were studied using human osteosarcoma 143B cells. Time-dependent apparent increases of the population of cells with collapsed membrane potential of mitochondria (Delta Psi(m)) caused by STS treatment were not due to actual decreases in the Delta Psi(m) per cell, but due to the fragmentation of cells resulting in decreases in the number of active mitochondria per cell. Decreases in the Delta Psi(m) in fragmented cells occurred late in the execution phase. Both JSP and LAT failed to prevent STS-induced release of cytochrome c from mitochondria followed by the activation of caspases 3 and 9, the cleavage of poly (ADP-ribose) polymerase (PARP) and apoptotic nuclear fragmentation. However, both drugs prevented STS-induced apoptotic cell fragmentation and decreases in the Delta Psi(m). These results indicate that physicochemical states of actin filaments play a certain role in the execution phase of STS-induced apoptotic processes.     

Mapping the Density of States Distribution of Organic Semiconductors by Employing Energy Resolved–Electrochemical Impedance Spectroscopy

Although the density of states (DOS) distribution of charge transporting states in an organic semiconductor is vital for device operation, its experimental assessment is not at all straightforward. In this work, the technique of energy resolved–electrochemical impedance spectroscopy (ER-EIS) is employed to determine the DOS distributions of valence (highest occupied molecular orbital (HOMO)) as well as electron (lowest unoccupied molecular orbital (LUMO)) states in several organic semiconductors in the form of neat and blended films. In all cases, the core of the inferred DOS distributions are Gaussians that sometimes carry low energy tails. A comparison of the HOMO and LUMO DOS of P3HT inferred from ER-EIS and photoemission (PE) or inverse PE (IPE) spectroscopy indicates that the PE/IPE spectra are by a factor of 2–3 broader than the ER-EIS spectra, implying that they overestimate the width of the distributions. A comparison of neat films of MeLPPP and SF-PDI₂ or PC(61)BM with corresponding blends reveals an increased width of the DOS in the blends. The results demonstrate that this technique does not only allow mapping the DOS distributions over five orders of magnitude and over a wide energy window of 7 eV, but can also delineate changes that occur upon blending.     

The Effect of Gradual Fluorination on the Properties of FnZnPc Thin Films and FnZnPc/C60 Bilayer Photovoltaic Cells

Motivated by the possibility of modifying energy levels of a molecule without substantially changing its band gap, the impact of gradual fluorination on the optical and structural properties of zinc phthalocyanine (F_nZnPc) thin films and the electronic characteristics of F_nZnPc/C₆₀ (n = 0, 4, 8, 16) bilayer cells is investigated. UV–vis measurements reveal similar Q‐ and B‐band absorption of F_nZnPc thin films with n = 0, 4, 8, whereas for F₁₆ZnPc a different absorption pattern is detected. A correlation between structure and electronic transport is deduced. For F₄ZnPc/C₆₀ cells, the enhanced long range order supports fill factors of 55% and an increase of the short circuit current density by 18%, compared to ZnPc/C₆₀. As a parameter being sensitive to the organic/organic interface energetics, the open circuit voltage is analyzed. An enhancement of this quantity by 27% and 50% is detected for F₄ZnPc‐ and F₈ZnPc‐based devices, respectively, and is attributed to an increase of the quasi‐Fermi level splitting at the donor/acceptor interface. In contrast, for F₁₆ZnPc/C₆₀ a decrease of the open circuit voltage is observed. Complementary photoelectron spectroscopy, external quantum efficiency, and photoluminescence measurements reveal a different working principle, which is ascribed to the particular energy level alignment at the interface of the photoactive materials.     

Characterization and exploitation of heterogeneous OFDM primary users in cognitive radio networks

The fundamental features of cognitive radio (CR) systems are their ability to adapt to the wireless environment where they operate and their opportunistic occupation of the licensed spectrum bands assigned to the primary network. CR users in CR systems should not cause any interference to primary users (PUs) of the primary network. For this purpose, CR users need to accurately estimate the features and activities of the primary users. In this paper, a novel characterization of heterogeneous PUs and a novel reconfigurability solution in CR networks are introduced. The characterization of PUs consists of a detector and classifier that distinguishes between heterogenous PUs. The PU characteristics stored in radio environmental maps are utilized by an interference/throughput adapter for the optimization of CR parameters. The performance of the proposed solutions is evaluated by showing false alarm and missed detection probabilities of the detector/classifier in a multipath fading channel with additive white Gaussian noise. Moreover, the impact of the PU characteristics on the CR throughput is analyzed.     

Hierarchically Structured Magnetic Nanoconstructs with Enhanced Relaxivity and Cooperative Tumor Accumulation

Iron oxide nanoparticles are formidable multifunctional systems capable of contrast enhancement in magnetic resonance imaging, guidance under remote fields, heat generation, and biodegradation. Yet, this potential is underutilized in that each function manifests at different nanoparticle sizes. Here, sub‐micrometer discoidal magnetic nanoconstructs are realized by confining 5 nm ultra‐small super‐paramagnetic iron oxide nanoparticles (USPIOs) within two different mesoporous structures, made out of silicon and polymers. These nanoconstructs exhibit transversal relaxivities up to ≈10 times (r ₂ ≈ 835 mm ^?1 s^?1) higher than conventional USPIOs and, under external magnetic fields, collectively cooperate to amplify tumor accumulation. The boost in r ₂ relaxivity arises from the formation of mesoscopic USPIO clusters within the porous matrix, inducing a local reduction in water molecule mobility as demonstrated via molecular dynamics simulations. The cooperative accumulation under static magnetic field derives from the large amount of iron that can be loaded per nanoconstuct (up to ≈65 fg) and the consequential generation of significant inter‐particle magnetic dipole interactions. In tumor bearing mice, the silicon‐based nanoconstructs provide MRI contrast enhancement at much smaller doses of iron (≈0.5 mg of Fe kg^?1 animal) as compared to current practice.     

Ultra-Robust Flexible Electronics by Laser-Driven Polymer-Nanomaterials Integration

Polyethylene terephthalate (PET) is the most widely used polymer in the world. For the first time, the laser-driven integration of aluminum nanoparticles (Al NPs) into PET to realize a laser-induced graphene/Al NPs/polymer composite, which demonstrates excellent toughness and high electrical conductivity with the formation of aluminum carbide into the polymer is shown. The conductive structures show an impressive mechanical resistance against >10000 bending cycles, projectile impact, hammering, abrasion, and structural and chemical stability when in contact with different solvents (ethanol, water, and aqueous electrolytes). Devices including thermal heaters, carbon electrodes for energy storage, electrochemical and bending sensors show this technology's practical application for ultra-robust polymer electronics. This laser-based technology can be extended to integrating other nanomaterials and create hybrid graphene-based structures with excellent properties in a wide range of flexible electronics’ applications.