Nano-scale smooth surface of the compact-TiO2 layer via spray pyrolysis for controlling the grain size of the perovskite layer in perovskite solar cells.

The mechanism of perovskite film growth is critical for the final morphology and, thus, the performance of the perovskite solar cell. The nano-roughness of compact TiO2 (c-TiO2) fabricated via the spray pyrolysis method had a significant effect on the perovskite grain size and perovskite solar cell performance in this work. While spray pyrolysis is a low-cost and straightforward deposition technique suitable for large-scale application, it is influenced by a number of parameters, including (i) alcoholic solvent precursor, (ii) spray temperature, and (iii) annealing temperature. Among alcoholic solvents, 2-propanol and 1-butanol showed a smooth surface without any large TiO2 particles on the surface compared to EtOH. The lowest roughness of the c-TiO2 layer was obtained at 450 °C with an average perovskite grain size of around 300 nm. Increased annealing temperature has a positive effect on the roughness of TiO2. The highest efficiency of the solar cell was achieved by using 1-butanol as the solvent. The decrease in the nano roughness of c-TiO2 promoted larger perovskite grain sizes via a relative decrease in the nucleation rate. Therefore, controlling the spray pyrolysis technique used to deposit the c-TiO2 layer is a promising route to control the surface nanoroughness of c-TiO2, which results in an increase in the MAPbI3 grain size.

A Structure-Based Gaussian Expansion for Quantum Reaction Dynamics in Molecules: Application to Hydrogen Tunneling in Malonaldehyde.

We developed an approximate method for quantum reaction dynamics simulations, namely, a structure-based Gaussian (SBG) expansion approach, where SBG bases for the expansion of the wave function Ψ, expressed by a product of single-atom Cartesian Gaussians centered at the positions of respective nuclei, are mainly placed around critical structures on reaction pathways such as on the intrinsic reaction coordinate (IRC) through a transition state. In the present approach, the "pseudo-lattice points" at which SBGs are deployed are selected in a perturbative manner so as to make moderate the expansion length. We first applied the SBG idea to a two-dimensional quadruple-well model and obtained accurate tunneling splitting values between the lowest four states. We then applied it to hydrogen tunneling in malonaldehyde and achieved a tunneling splitting of 27.1 cm-1 with only 875 SBGs at the MP2/6-31G(d,p) level of theory, in good agreement with 25 cm-1 by the more elaborate multiconfiguration time-dependent Hartree method. Reasonable results were also obtained for singly and doubly deuterated malonaldehyde. We analyzed the tunneling states by utilizing expansion coefficients of individual SBGs and found that 40-45% of the SBGs in Ψ are nonplanar structures and SBGs away from the IRC contribute a little to hydrogen transfer.

Real-time assessment of swallowing sound using an electronic stethoscope and an artificial intelligence system.

OBJECTIVES: Daily assessments of swallowing function and interventions such as rehabilitation and dietary adjustments are necessary to improve dysphagia. Cervical auscultation is convenient for health care providers for assessing swallowing ability. Although this method allows for swallowing sound evaluations, sensory evaluations with this method are difficult. Thus, we aimed to assess swallowing sound by the combined use of an electronic stethoscope and an artificial intelligence (AI) system that incorporates sound recognition. MATERIAL AND METHODS: Herein, 20 fifth-year dentistry student volunteers were included; each participant was drank 10 ml and then 20 ml of water in different positions (sitting and supine). We developed an algorithm for indexing bolus inflow sounds using AI, which compared the swallowing sounds and created a new index. RESULTS: The new index value used for swallowing sound was significantly higher in men than in women and in the sitting position than in the supine position. A software for acoustic analysis confirmed that the swallowing index was significantly higher in men than in women as well as in the sitting position than in the supine position. These results were similar to those obtained using the new index. However, the new index substantially differed between sexes in terms of posture compared with effective sound pressure. CONCLUSIONS: We developed a new algorithm for indexing swallowing sounds using a stethoscope and an AI system, which could identify swallowing sounds. For future research and development, evaluations of patients with dysphagia are necessary to determine the efficacy of the new index for bedside screening of swallowing conditions.

Unravelling the electron injection/transport mechanism in organic light-emitting diodes.

Although significant progress has been made in the development of light-emitting materials for organic light-emitting diodes along with the elucidation of emission mechanisms, the electron injection/transport mechanism remains unclear, and the materials used for electron injection/transport have been basically unchanged for more than 20 years. Here, we unravelled the electron injection/transport mechanism by tuning the work function near the cathode to about 2.0 eV using a superbase. This extremely low-work function cathode allows direct electron injection into various materials, and it was found that organic materials can transport electrons independently of their molecular structure. On the basis of these findings, we have realised a simply structured blue organic light-emitting diode with an operational lifetime of more than 1,000,000 hours. Unravelling the electron injection/transport mechanism, as reported in this paper, not only greatly increases the choice of materials to be used for devices, but also allows simple device structures.

Understanding coordination reaction for producing stable electrode with various low work functions.

The realisation of a cathode with various work functions (WFs) is required to maximise the potential of organic semiconductors that have various electron affinities. However, the barrier-free contact for electrons could only be achieved by using reactive materials, which significantly reduce the environmental stability of organic devices. We show that a stable electrode with various WFs can be produced by utilising the coordination reaction between several phenanthroline derivatives and the electrode. Although the low WF of the electrode realised by using reactive materials is specific to the material, the WF of the phenanthroline-modified electrode is tunable depending on the amount of electron transfer associated with the coordination reaction. A phenanthroline-modified electrode that has a higher electron injection efficiency than lithium fluoride has been demonstrated. The observation of various WFs induced by the coordination reaction affords strategic perspectives on the development of stable cathodes unique to organic electronics.

Universal Strategy for Efficient Electron Injection into Organic Semiconductors Utilizing Hydrogen Bonds.

Molecular n-dopants that can lower the electron injection barrier between organic semiconductors and electrodes are essential in present-day organic electronics. However, the development of stable molecular n-dopants remains difficult owing to their low ionization potential, which generally renders them unstable. It is shown that the stable bases widely used in organic synthesis as catalysts can lower the electron injection barrier similar to that in conventional n-doping in organic optoelectronic devices. In contrast to conventional n-doping, which is based on the electron transfer from dopants with low ionization potential, the reduction of the injection barrier caused by adding bases is determined by the formation of hydrogen bonds between the hosts and the bases, providing energy-level-independent electron injection. The observation of the efficient electron injection induced by hydrogen bonding affords new perspectives on the method for controlling the behavior of electrons unique to organic semiconductors.

Effects of Energy-Level Alignment on Characteristics of Inverted Organic Light-Emitting Diodes.

Inverted organic light-emitting diodes (iOLEDs) without the use of alkali metals have attracted extensive attention owing to the demand for the realization of flexible OLEDs that do not require stringent encapsulation. In this paper, we discuss the correlation between the characteristics of iOLEDs and the energy-level alignment at cathode/organic layer interfaces examined by ultraviolet photoelectron spectroscopy. Two similar electron-transporting materials having different orbital energies, 2,8-bis(diphenylphosphoryl)dibenzo[ b, d]thiophene (PPT) and 2,8-bis(diphenylphosphoryl)dibenzo[ b, d]thiophene sulfone (PPT-S), are inserted between the cathode/polyethyleneimine and the emitting layer in the iOLED. The iOLED employing PPT-S exhibits a lower driving voltage and a higher efficiency than that employing PPT, which is consistent with the orbital energies of the two molecules. Although the stabilities of these two molecules are expected to be similar, the iOLED employing PPT-S exhibits an operational lifetime that is more than 100 times longer than that of the iOLED employing PPT. It was found that the difference in operational lifetime is caused by the difference in the energy-level alignment at the cathode/organic layer interfaces. Our results are expected to promote the development of promising materials and device configurations for fabricating efficient and operationally stable iOLEDs.

Diffractive Imaging of C_{60} Structural Deformations Induced by Intense Femtosecond Midinfrared Laser Fields.

Theoretical studies indicated that C_{60} exposed to linearly polarized intense infrared pulses undergoes periodic cage structural distortions with typical periods around 100 fs (1 fs=10^{-15} s). Here, we use the laser-driven self-imaging electron diffraction technique, previously developed for atoms and small molecules, to measure laser-induced deformation of C_{60} in an intense 3.6 µm laser field. A prolate molecular elongation along the laser polarization axis is determined to be (6.1±1.4)% via both angular- and energy-resolved measurements of electrons that are released, driven back, and diffracted from the molecule within the same laser field. The observed deformation is confirmed by density functional theory simulations of nuclear dynamics on time-dependent adiabatic states and indicates a nonadiabatic excitation of the h_{g}(1) prolate-oblate mode. The results demonstrate the applicability of laser-driven electron diffraction methods for studying macromolecular structural dynamics in four dimensions with atomic time and spatial resolutions.

RNA-seq-based evaluation of bicolor tepal pigmentation in Asiatic hybrid lilies (Lilium spp.).

BACKGROUND: Color patterns in angiosperm flowers are produced by spatially and temporally restricted deposition of pigments. Identifying the mechanisms responsible for restricted pigment deposition is a topic of broad interest. Some dicots species develop bicolor petals, which are often caused by the post-transcriptional gene silencing (PTGS) of chalcone synthase (CHS) genes. An Asiatic hybrid lily (Lilium spp.) cultivar Lollypop develops bicolor tepals with pigmented tips and white bases. Here, we analyzed the global transcription of pigmented and non-pigmented tepal parts from Lollypop, to determine the main transcriptomic differences. RESULTS: De novo assembly of RNA-seq data yielded 49,239 contigs (39,426 unigenes), which included a variety of novel transcripts, such as those involved in flavonoid-glycosylation and sequestration and in regulation of anthocyanin biosynthesis. Additionally, 1258 of the unigenes exhibited significantly differential expression between the tepal parts (false discovery rates <0.05). The pigmented tepal parts accumulated more anthocyanins, and unigenes annotated as anthocyanin biosynthesis genes (e.g., CHS, dihydroflavonol 4-reductase, and anthocyanidin synthase) were expressed 7-30-fold higher than those in non-pigmented parts. These results indicate that the transcriptional regulation of biosynthesis genes is more likely involved in the development of bicolor lily tepals rather than the PTGS of CHS genes. In addition, the expression level of a unigene homologous to LhMYB12, which often regulates full-tepal anthocyanin pigmentation in lilies, was >2-fold higher in the pigmented parts. Thus, LhMYB12 should be involved in the transcriptional regulation of the biosynthesis genes in bicolor tepals. Other factors that potentially suppress or enhance the expression of anthocyanin biosynthesis genes, including a WD40 gene, were identified, and their involvement in bicolor development is discussed. CONCLUSIONS: Our results indicate that the bicolor trait of Lollypop tepals is caused by the transcriptional regulation of anthocyanin biosynthesis genes and that the transcription profile of LhMYB12 provides a clue for elucidating the mechanisms of the trait. The tepal transcriptome constructed in this study will accelerate investigations of the genetic controls of anthocyanin color patterns, including the bicolor patterns, of Lilium spp.

A high-pressure-induced dense CO overlayer on a Pt(111) surface: a chemical analysis using in situ near ambient pressure XPS.

We investigated the high-density CO adsorption phase formed on a Pt(111) surface when exposed to CO gas of pressure ranging from UHV to 100 mTorr using near-ambient-pressure (NAP)-XPS. Combined results from the NAP-XPS measurements and DFT calculations reveal the adsorption structure of CO molecules in the dense CO overlayer, which is stable under realistic conditions.

Active Surface Oxygen for Catalytic CO Oxidation on Pd(100) Proceeding under Near Ambient Pressure Conditions.

Catalytic CO oxidation reaction on a Pd(100) single-crystal surface under several hundred mTorr pressure conditions has been studied by ambient pressure X-ray photoelectron spectroscopy and mass spectroscopy. In-situ observation of the reaction reveals that two reaction pathways switch over alternatively depending on the surface temperature. At lower temperatures, the Pd(100) surface is covered by CO molecules and the CO2 formation rate is low, indicating CO poisoning. At higher temperatures above 190 °C, an O-Pd-O trilayer surface oxide phase is formed on the surface and the CO2 formation rate drastically increases. It is likely that the enhanced rate of CO2 formation is associated with an active oxygen species that is located at the surface of the trilayer oxide.