Energy level diagram of HC(NH2)2PbI3 single crystal evaluated by electrical and optical analyses.

Recently, organic-inorganic halide perovskites have received attention for applications in solar cells. Measurements of high-quality single crystals reveal lower defect densities and longer carrier lifetimes than those of conventional thin films, which result in improved electrical and optical properties. However, single crystal surfaces are sensitive to exposure to ambient conditions, and degrade under long-term storage in air. The surface also shows differences from the bulk in terms of its optical and electronic characteristics. For a heterojunction device, the interface at the single crystal is important. Understanding the difference between the surface and bulk properties offers insights into device design. Here, we prepared non-sliced and sliced formamidinium lead iodide (FAPbI3; FA+ = HC(NH2)2+) single crystals with a bandgap of 1.4 eV, which matches well with the requirements for solar cell photoabsorption layers. We evaluate the energy level diagrams of the surface and bulk regions, respectively. Our data indicate that the valence band maximum of the surface region is at a higher energy level than that of the bulk region. We also discuss hypotheses for the well-known and unexplained phenomena (multiple bandgaps and bandgap narrowing) seen in the absorption and photoluminescence spectra of single crystals. We conclude that these effects are likely caused by a combination of the degraded surface, Rashba-splitting in bulk, and self-absorption by the single crystal itself.

Prevention of thermal- and moisture-induced degradation of the photoluminescence properties of the Sr2Si5N8:Eu(2+) red phosphor by thermal post-treatment in N2-H2.

A red phosphor of Sr2Si5N8:Eu(2+) powder was synthesized by a solid state reaction. The synthesized phosphor was thermally post-treated in an inert and reductive N2-H2 mixed-gas atmosphere at 300-1200 °C. The main phase of the resultant phosphor was identified as Sr2Si5N8. A passivation layer of ∼0.2 µm thickness was formed around the phosphor surface via thermal treatment. Moreover, two different luminescence centers of Eu(SrI) and Eu(SrII) in the synthesized Sr2Si5N8:Eu(2+) phosphor were proposed to be responsible for 620 nm and 670 nm emissions, respectively. More interestingly, thermal- and moisture-induced degradation of PL intensity was effectively reduced by the formation of a passivation layer around the phosphor surface, that is, the relative PL intensity recovered 99.8% of the initial intensity even after encountering thermal degradation; both moisture-induced degraded external and internal QEs were merely 1% of the initial QEs. The formed surface layer was concluded to primarily prevent the Eu(2+) activator from being oxidized, based on the systemic analysis of the mechanisms of thermal- and moisture-induced degradation.

Cathodoluminescence and photoconductive characteristics of single-crystal ternary CdS/CdSe/CdS biaxial nanobelts.

The cathodoluminescence and optoelectronic properties based on an individual CdS/CdSe/CdS biaxial nanobelt are revealed in the present study. Both typical CdS and CdSe emissions are detected from as-grown CdS/CdSe/CdS nanobelts. The photodetector based on this nanobelt exhibits high sensitivity and excellent cycle stability. This opens a door to rational design of germanium chalcogenide compounds with unique optical properties.

Synthesis and crystal structures of BaLaSi2 with cis-trans Si chains and Ba5LaSi6 with pentagonal Si rings.

Prismatic single crystals of novel compounds BaLaSi2 and Ba5LaSi6 were synthesized from the elements with or without a Na flux. The crystal structures of the compounds were analyzed by X-ray diffraction. BaLaSi2, containing cis­trans ∞1[Si] chains, crystallizes in an orthorhombic cell (a = 4.6414(2) Å, b = 14.8851(7) Å, c = 6.7519(5) Å; space group, Cmcm (No. 63), Z = 4) and is isotypic with the low-temperature phase of LaSi. The crystal structure of Ba5LaSi6 (a = 17.1447(5) Å, b = 4.8767(1) Å, and c = 17.9102(4) Å; space group Pnma (No. 62), Z = 4) is a new type containing isolated anionic groups (0[Si5­Si]) of a pentagonal Si ring with a Si­Si stem. The electrical resistivities measured for the polycrystalline BaLaSi2 and Ba5LaSi6 sintered samples were 0.31 and 0.48 mΩ·cm, respectively, at 300 K and increased with temperature. The Seebeck coefficients of BaLaSi2 and Ba5LaSi6 were −7.6 and −11 µV·K­1, respectively, at 296 K.

Strong Energy-Transfer-Induced Enhancement of Luminescence Efficiency of Eu(2+)- and Mn(2+)-Codoped Gamma-AlON for Near-UV-LED-Pumped Solid State Lighting.

A series of Eu(2+)- and Mn(2+)-codoped γ-AlON (Al1.7O2.1N0.3) phosphors was synthesized at 1800 °C under 0.5 MPa N2 by using the gas-pressure sintering method (GPS). Eu(2+) and Mn(2+) ions were proved to enter into γ-AlON host lattice by means of XRD, CL, and EDS measurements. Under 365 nm excitation, two emission peaks located at 472 and 517 nm, resulting from 4f(6)5d(1) → 4f(7) and (4)T1(4G) → (6)A1 electron transitions of Eu(2+) and Mn(2+), respectively, can be observed. Energy transfer from Eu(2+) to Mn(2+) was evidenced by directly observing appreciable overlap between the excitation spectrum of Mn(2+) and the emission spectrum of Eu(2+) as well as by the decreased decay time of Eu(2+) with increasing Mn(2+) concentration. The critical energy-transfer distance between Eu(2+) and Mn(2+) and the energy-transfer efficiency were also calculated. The mechanism of energy transfer was identified as a resonant type via a dipole-dipole mechanism. The external quantum efficiency was increased 7 times (from 7% for γ-AlON:Mn(2+) to 49% for γ-AlON:Mn(2+),Eu(2+) under 365 nm excitation), and color-tunable emissions from blue-green to green-yellow were also realized with the Eu(2+) → Mn(2+) energy transfer in γ-AlON.

Active vitamin D analogs, maxacalcitol and alfacalcidol, as maintenance therapy for mild secondary hyperparathyroidism in hemodialysis patients - a randomized study.

BACKGROUND: The present randomized study was designed to compare the efficacy between two active vitamin D analogs, alfacalcidol (ACD) and maxacalcitol (OCT), for the management of mild secondary hyperparathyroidism (SHPT) in dialysis patients. METHODS: SHPT in all 32 patients analyzed in the study was initially treated with OCT. Once patients' intact PTH levels decreased to the target range of 150 - 180 pg/mL, they were randomized either to switch to ACD at 0.5 µg/day (n = 14), or to remain on an effectively unchanged dose of OCT (n = 13). Phosphate, calcium, and intact PTH levels were measured every 2 weeks for 12 weeks and vitamin D doses were changed according to target ranges of phosphate (3.5 - 6.0 mg/dL), calcium (albuminadjusted calcium: 8.4 - 10.0 mg/dL), and intact parathyroid hormone (60 - 180 pg/mL). Achievement rates of the target ranges of the parameters were estimated. RESULTS: Baseline calcium levels in the OCT group were significantly higher than in the ACD group. Changes in achievement rates of target ranges of intact PTH and calcium during the study did not differ significantly between the vitamin D drugs. Changes in calcium levels in the OCT and ACD groups were similar during the study. Achievement rates of the target range of phosphate in both groups were also similar until 8 weeks, although the rate in the OCT group declined at 10 weeks. CONCLUSIONS: The efficacy and safety of OCT for the treatment of mild SHPT are similar to those of ACD in hemodialysis patients.

Triangular ZnO nanosheets: synthesis, crystallography and cathodoluminescence.

ZnO nanosheets with triangular morphology have been synthesized on an Au-coated silicon substrate through a facile thermal evaporation process. The morphologies and microstructures of the nanosheets were studied by a scanning electron microscope (SEM) and a high-resolution transmission electron microscope (HR-TEM). These studies show that a nanosheet is commonly composed of two parts: a triangular ZnO sheet and an Au nanoparticle attached on its tip-end. Detailed crystallography analyses conclude that the formation of the highly crystalline nanostructures can be assigned to a combination of a vapor-liquid-solid (VLS) process that is believed to be responsible for its initial nucleation and subsequent crystallization along the growth direction, and a vapor-solid (VS) process that is responsible for its further radial growth. The spatially-resolved cathodoluminescence (CL) spectra exhibit a sharp strong near-band-edge (NBE) emission in the ultraviolet range and a negligible green emission.

Unipolar assembly of zinc oxide rods manifesting polarity-driven collective luminescence.

Oriented assemblies of small crystals forming larger structures are common in nature and crucial for forthcoming technologies as they circumvent the difficulties of structural manipulation at microscopic scale. We have discovered two distinctive concentric assemblies of zinc oxide rods, wherein each rod has an intrinsically positive and a negative polar end induced by the noncentrosymmetric arrangement of Zn and O atoms. All the rods in a single assembly emanate out of a central core maintaining a single polar direction. Due to growth along the two polar surfaces with different atomic arrangements, these assemblies are distinct in their intrinsic properties and exhibit strong UV luminescence in the exterior of Zn-polar assemblies, unlike the O-polar assemblies. Although novel applications can be envisioned, these observations suggest that hierarchical organization with respect to internal asymmetry might be widespread in natural crystal assemblies.

Local analysis of Eu2+ emission in CaAlSiN3.

We have investigated the local luminescence properties of Eu-doped CaAlSiN3 by using low-energy electron beam (e-beam) techniques. The particles yield broad emission centered at 655 nm with a shoulder at higher wavelength under light excitation, and a broad band around 643 nm with a tail at 540 nm under e-beam excitation. Using cathodoluminescence (CL) in a scanning electron microscope (SEM), we have observed small and large particles, which, although with different compositions, exhibit Eu2+-related emissions at 645 and 635 nm, respectively. Local CL measurements reveal that the Eu2+ emission may actually consist of several bands. In addition to the red broad band, regularly spaced sharp peaks have been occasionally observed. These luminescence variations may originate from a variation in the composition inside CaAlSiN3.

Abnormal carnitine metabolism in hemodialysis patients on different anticoagulants.

INTRODUCTION: We aimed to determine whether unfractionated heparin (UH) and low molecular weight heparin (LH) contribute to aberrant carnitine metabolism in patients receiving hemodialysis. METHODS: The rate of increase in serum free fatty acids (FFAs) and the ratio of acylcarnitine to free carnitine (AC/FC) from before to after hemodialysis were determined in patients receiving UH and LH. Additionally, the effect of switching patients to UH from LH was examined. RESULTS: AC/FC was significantly higher in the UH group. In addition, serum FFAs in that group increased to 0.825 ± 0.270 after dialysis from 0.172 ± 0.160 before dialysis, showing a positive correlation with AC/FC. Furthermore, AC/FC was observed to be significantly higher in patients who were switched to UH from LH at 3 months after the change. CONCLUSION: Compared with UH, LH has a lesser effect on lipid metabolism, suggesting that it also has a lesser effect on carnitine metabolism.

Segregation behaviors and radial distribution of dopant atoms in silicon nanowires.

Gaining an understanding the dynamic behaviors of dopant atoms in silicon nanowires (SiNWs) is the key to achieving low-power and high-speed transistor devices using SiNWs. The segregation behavior of boron (B) and phosphorus (P) atoms in B- and P-doped SiNWs during thermal oxidation was closely observed using B local vibrational peaks and Fano broadening in optical phonon peaks of B-doped SiNWs by micro-Raman scattering. Electron spin resonance (ESR) signals from conduction electrons were used for P-doped SiNWs. Our results showed that B atoms preferentially segregate in the surface oxide layer, whereas P atoms tend to accumulate in the Si region around the interface of SiNWs. The radial distribution of P atoms in SiNWs was also investigated to prove the difference segregation behaviors between of P and B atoms.

Bulk synthesis, growth mechanism and properties of highly pure ultrafine boron nitride nanotubes with diameters of sub-10 nm.

As a structural analogue of the carbon nanotube (CNT), the boron nitride nanotube (BNNT) has become one of the most intriguing non-carbon nanostructures. However, up to now the pre-existing restrictions/limitations of BNNT syntheses have made the progress in their research rather modest. This work presents a new route toward the synthesis of highly pure ultrafine BNNTs based on a modified boron oxide (BO) CVD method. A new effective precursor--a mixture of Li2O and B--has been proposed for the growth of thin, few-layer BNNTs in bulk amounts. The Li2O utilized as the precursor plays the crucial role for the present nanotube growth. The prepared BNNTs have average external diameters of sub-10 nm and lengths of up to tens of µm. Electron energy loss spectrometry and Raman spectroscopy demonstrate the ultimate phase purity of the ultrafine BNNTs. Property studies indicate that the ultrafine nanotubes are perfect electrical insulators exhibiting superb resistance to oxidation and strong UV emission. Moreover, their reduced diameters lead to a dramatically decreased population of defects within the tube walls and result in the observation of near-band-edge (NBE) emission at room temperature.

Damage-less observation of polymers by electron dose control in scanning electron microscope.

Methodology for quantitative evaluation of electron radiation damage and calculation of tolerable electron dose was developed to achieve damage-less scanning electron microscope (SEM) observation of beam-sensitive polymer film. The radiation damage is typically evaluated with visual impressions of SEM images; however, this method may be unreliable because observer's subjectivity may affect the results. Evaluation with quantitative value is crucial to improve reliability. In this study, the radiation damage was evaluated by using normalized correlative coefficient (RNCC) between an initial frame and latter frames of the multiple SEM images that were taken consecutively. Tolerable dose was obtained by defining a threshold point of RNCC where rapid reduction of RNCC started. A SEM image with less damage and acceptable signal-to-noise ratio was obtained by integrating the images from the initial frame to the tolerable frame.

Stable single atomic silver wires assembling into a circuitry-connectable nanoarray.

Atomic metal wires have great promise for practical applications in devices due to their unique electronic properties. Unfortunately, such atomic wires are extremely unstable. Here we fabricate stable atomic silver wires (ASWs) with appreciably unoccupied states inside the parallel tunnels of α-MnO2 nanorods. These unoccupied Ag 4d orbitals strengthen the Ag-Ag bonds, greatly enhancing the stability of ASWs while the presence of delocalized 5s electrons makes the ASWs conducting. These stable ASWs form a coherently oriented three-dimensional wire array of over 10 nm in width and up to 1 µm in length allowing us to connect it to nano-electrodes. Current-voltage characteristics of ASWs show a temperature-dependent insulator-to-metal transition, suggesting that the atomic wires could be used as thermal electrical devices.

352 nm ultraviolet emission from high-quality crystalline AlN whiskers.

High-quality, crystalline AlN whiskers with large yield have been synthesized through the direct nitridation of Al vapor at high temperature. The AlN whiskers exhibited a strong and uniform ultraviolet emission at approximately 352 nm, which is notably shorter compared with the wavelength of previously reported one-dimensional AlN nanostructures. Energy filtered transmission electron microscope (TEM) analyses indicated that nitrogen deficiency and rather lower oxygen content in the AlN lattice might be responsible for the strong 352 nm ultraviolet emission.

Enhancement of the core near-band-edge emission induced by an amorphous shell in coaxial one-dimensional nanostructure: the case of SiC/SiO2 core/shell self-organized nanowires.

We report the influence of the native amorphous SiO(2) shell on the cathodoluminescence emission of 3C-SiC/SiO(2) core/shell nanowires. A shell-induced enhancement of the SiC near-band-edge emission is observed and studied as a function of the silicon dioxide thickness. Since the diameter of the investigated SiC cores rules out any direct bandgap optical transitions due to confinement effects, this enhancement is ascribed to a carrier diffusion from the shell to the core, promoted by the alignment of the SiO(2) and SiC bands in a type I quantum well. An accurate correlation between the optical emission and structural and SiO(2)-SiC interface properties is also reported.

Paraneoplastic neurological syndrome in a patient with gastric cancer.

Paraneoplastic neurological syndromes (PNSs) are a heterogeneous group of neurological disorders caused by immune-mediated mechanisms. The incidence of PNS is much less than 1% for solid tumors, except for small-cell lung cancer and thymoma. We report a rare case of gastric cancer that presented with primary clinical findings of PNS. The patient was a 63-year-old woman who was admitted for worsening neuropathy. Laboratory and neurological tests excluded a nutritional deficit, diabetes mellitus, and connective tissue disease as causes of her neuropathy. Computed tomography (CT) of the abdomen, positron emission tomography (PET)-CT, and endoscopy of the stomach revealed gastric cancer with lymph node swelling. Distal gastrectomy was performed and pathological and immunohistochemical examinations indicated endocrine cell carcinoma. The gastrectomy stopped the exacerbation of her symptoms and recurrence was not observed, but the neurological disorders were irreversible. This case suggests that early diagnosis of the primary tumor is required to improve the outcome in patients with PNS.

Low-energy cathodoluminescence microscopy for the characterization of nanostructures.

Spatially and spectrally resolved low-energy cathodoluminescence (CL) microscopy was applied to the characterization of nanostructures. CL has the advantage of revealing not only the presence of luminescence centers but also their spatial distribution. The use of electrons as an excitation source allows a direct comparison with other electron-beam techniques. Thus, CL is a powerful method to correlate luminescence with the sample structure and to clarify the origin of the luminescence. However, caution is needed in the quantitative analysis of CL measurements. In this review, the advantages of cathodoluminescence for qualitative analysis and disadvantages for quantitative analysis are presented on the example of nanostructures.

Improving the Open-Circuit Voltage of Sn-Based Perovskite Solar Cells by Band Alignment at the Electron Transport Layer/Perovskite Layer Interface.

Organic-inorganic lead halide perovskites are promising materials for realization of low-cost and high-efficiency solar cells. Because of the toxicity of lead, Sn-based perovskite materials have been developed as alternatives to enable fabrication of Pb-free perovskite solar cells. However, the solar cell performance of Sn-based perovskite solar cells (Sn-PSCs) remains poor because of their large open-circuit voltage (VOC) loss. Sn-based perovskite materials have lower electron affinities than Pb-based perovskite materials, which result in larger conduction band offset (CBO) values at the interface between the Sn-based perovskite and a conventional electron transport layer (ETL) material such as TiO2. Herein, the relationship between the VOC and the CBO in these devices was studied to improve the solar cell performances of Sn-PSCs. It was found that the band offset at the ETL/perovskite layer interface affects the VOC of the Sn-PSCs significantly but does not affect that of the Pb-PSCs because the Sn-based perovskite material is a p-type semiconductor, unlike the Pb-based perovskite. It was also found that Nb2O5 has the CBO that is closest to zero for Sn-based perovskite materials, and the VOC values of Sn-PSCs that use Nb2O5 as their ETL are higher than those of Sn-PSCs using TiO2 or SnO2 ETLs. This study indicates that control of the energy alignment at the ETL/perovskite layer interface is an important factor in improving the VOC values of Sn-PSCs.

Thin-walled boron nitride microtubes exhibiting intense band-edge UV emission at room temperature.

Boron nitride (BN) microtubes were synthesized in a vertical induction furnace using Li(2)CO(3) and B reactants. Their structures and morphologies were investigated using x-ray diffraction, scanning and transmission electron microscopy, and energy-dispersive x-ray spectroscopy. The microtubes have diameters of 1-3 microm, lengths of up to hundreds of micrometers, and well-structured ultrathin walls only approximately 50 nm thick. A mechanism combining the vapor-liquid-solid (VLS) and template self-sacrificing processes is proposed to explain the formation of these novel one-dimensional microstructures, in which the Li(2)O-B(2)O(3) eutectic reaction plays an important role. Cathodoluminescence studies show that even at room temperature the thin-walled BN microtubes can possess an intense band-edge emission at approximately 216.5 nm, which is distinct compared with other BN nanostructures. The study suggests that the thin-walled BN microtubes should be promising for constructing compact deep UV devices and find potential applications in microreactors and microfluidic and drug delivery systems.