Defect Engineering of Metal Halide Perovskite Nanocrystals via Spontaneous Diffusion of Ag Nanocrystals.

Perovskite nanocrystals (NCs) have emerged as a promising building block for the fabrication of optic-/optoelectronic-/electronic devices owing to their superior characteristics, such as high absorption coefficient, rapid ion mobilities, and tunable energy levels. However, their low structural stability and poor surface passivation have restricted their application to next-generation devices. Herein, a drug delivery system (DDS)-inspired post-treatment strategy is reported for improving their structural stability by doping of Ag into CsPbBr3 (CPB) perovskite NCs; delivery to damaged sites can promote their structural recovery slowly and uniformly, averting the permanent loss of their intrinsic characteristics. Ag NCs are designed through surface-chemistry tuning and structural engineering to enable their circulation in CPB NC dispersions, followed by their delivery to the CPB NC surface, defect-site recovery, and defect prevention. The perovskite-structure healing process through the DDS-type process (with Ag NCs as the drug) is analyzed by a combination of theoretical calculations (with density functional theory) and experimental analyses. The proposed DDS-inspired healing strategy significantly enhances the optical properties and stability of perovskite NCs, enabling the fabrication of white light-emitting diodes.

Elemental-Migration-Assisted Full-Color-Tunable Upconversion Nanoparticles for Video-Rate Three-Dimensional Volumetric Displays.

Herein, we demonstrate video-rate color three-dimensional (3D) volumetric displays using elemental-migration-assisted full-color-tunable upconversion nanoparticles (UCNPs). In the heavily doped NaErF4:Tm-based core@multishell UCNPs, erbium migration was observed. By tailoring this migration through adjustment of the intermediate shell thickness between the core and the sensitizer-doped second shell, red-green orthogonal upconversion luminescence (UCL) was achieved. Furthermore, highly efficient red-green-blue orthogonal UCL and full-color tunability were achieved in the UCNPs through a combination of elemental-migration-assisted color tuning and selective photon blocking. Finally, 3D volumetric displays were fabricated using a UCNP-polydimethylsiloxane composite. More specifically, 3D color images were created and motion pictures based on the expansion, rotation, and up/down movement of the displayed images were realized in the display matrix. Overall, our study provides new insights into upconversion color tuning and the achievement of motion pictures in the UCNP-polydimethylsiloxane composite is expected to accelerate the further development of solid-state full-color 3D volumetric displays.

Metatarsal sliding osteotomy is effective without altering plantar pressure in Morton's neuroma: Retrospective case series.

BACKGROUND: Various operative methods for the treatment of Morton's neuroma have been discussed, and osteotomy of the metatarsal bone has been reported recently. However, there has been no report of pedobarographic changes after metatarsal osteotomy. Pedobarographic changes of other metatarsal area after the surgery may cause transfer metatarsalgia, and thorough analysis of the pedobarographic data should be performed peri-operatively. The purpose of this study is to investigate the post-operative pedobarographic changes of sliding osteotomy of the 3rd metatarsal bone for treating Morton's neuroma. METHODS: Forty patients (45 feet) who underwent metatarsal sliding osteotomy of the 3rd metatarsal bone for treating Morton's neuroma from November 2013 to December 2021 were retrospectively reviewed. Proximal sliding osteotomy was performed at the proximal 3rd metatarsal bone through dorsal approach. Clinical outcomes were evaluated with American Orthopaedic Foot and Ankle Society Lesser Metatarsophalangeal Interphalangeal Scale (AOFAS LMIS), Foot Function Index (FFI), and Visual Analogue Scale (VAS). Plain radiograph and pedobarogram were performed to evaluate the radiologic and pedobarographic outcomes. RESULTS: AOFAS score was improved from 52.8 ± 9.0 (18-62) to 88.8 ± 9.8 (78-100) and FFI was improved from 61.8 ± 4.9 (50-70) to 32.2 ± 5.1 (23-42) on average. The 3rd metatarsal bone was shortened by 3.1 ± 0.8 mm and dorsally shifted by 1.5 ± 0.4 mm after the surgery. Plantar intermetatarsal distances between 2nd and 3rd and 3rd and 4th metatarsal heads were significantly increased post-operatively. Average forefoot pressure and maximum pressure of the 2nd to 4th metatarsal head were not significantly changed between pre-operatively and post-operatively. CONCLUSION: Proximal metatarsal sliding osteotomy of the 3rd metatarsal bone shows a satisfactory result in both clinical and pedobarographical evaluations. It could be an effective treatment of permanent indirect decompression of Morton's neuroma with avoiding recurred neuroma, adhesion of tissue, paresthesia, and transfer metatarsalgia.

Orthogonal R/G/B Upconversion Luminescence-based Full-Color Tunable Upconversion Nanophosphors for Transparent Displays.

Here, excitation orthogonalized red/green/blue upconversion luminescence (UCL)-based full-color tunable rare-earth (RE) ion-doped upconversion nanophosphors (UCNPs) are reported. The LiREF4-based core/sextuple-shell (C/6S) UCNPs are synthesized, and they consist of a blue-emitting core, green-emitting inner shell, and red-emitting outer shell, with inert intermediate and outermost shells. The synthesized C/6S UCNPs emit blue, green, and red light under 980, 800, and 1532 nm, respectively. Importantly, by combining incident near-infrared (NIR) light with various wavelengths (800, 980, and 1532 nm), full-color UCL including blue, cyan, green, yellow, orange, red, purple, and white UCL is achieved from the single C/6S UCNP composition. The color gamut obtained from the C/6S UCNPs shows 101.6% of the sRGB standard color gamut. Furthermore, transparent C/6S UCNP-polydimethylsiloxane (PDMS) composite is prepared. Full-color display realized in the transparent C/6S UCNP-PDMS composite indicates the feasibility of constructing the C/6S UCNP-based three-dimensional volumetric displays with wide color gamut.

Iatrogenic second transfer metatarsalgia and the first metatarsal shortening and elevation after Scarf osteotomy.

BACKGROUND: Transfer metatarsalgia is a potential complication of hallux valgus surgery. This study aimed to investigate the shortened first metatarsal length and elevation and to compare groups with and without second transfer metatarsalgia after Scarf osteotomy. METHODS: The first metatarsal length of 123 feet was measured via the Maestro's method using the metatarsal axial length and the relative second metatarsal protrusion to the first metatarsal. Metatarsal elevation was measured using the first metatarsal angle. RESULTS: Second transfer metatarsalgia occurred after Scarf osteotomy in 11 (8.9%) feet. When baseline characteristics were considered in propensity score matching, the 11 feet were compared with the 33 feet in the control group. The group with transfer metatarsalgia showed a more shortened first metatarsal axial length (-4.1 ± 1.8 mm vs. -2.5 ± 2.2 mm, p = 0.032), a significantly longer relative second metatarsal protrusion (+5.8 ± 2.6 mm vs. +1.2 ± 2.6 mm, p < 0.001), and a significantly lower first metatarsal angle (18.1 ± 4.3° vs. 21.5 ± 4.0°, p = 0.012) than the control group postoperatively. CONCLUSIONS: To avoid iatrogenic transfer metatarsalgia, first metatarsal length shortening should be minimized to at least less than 4.0 mm. Furthermore, the metatarsal parabola should be retained.

Comparison of outcomes of osteosynthesis in type II accessory navicular by variable fixation methods.

BACKGROUND: To compare the outcomes of fixation methods for osteosynthesis of a type II symptomatic accessory navicular between screw and tension band wiring. METHODS: Forty-four patients (mean age, 29.2 years; range, 13-54 years; 21 males and 23 females) who had undergone operative treatment after failed conservative treatment were chosen for the study between 2007 and 2014. The patients were divided into two groups by the method of osteosynthesis: group 1 (screw) and group 2 (tension band wiring). Pre and postoperative evaluations were performed, using the midfoot scale from the American Orthopaedic Foot and Ankle Society (AOFAS), a visual analog scale, time to return to social activities, and plain radiography. RESULTS: The AOFAS midfoot and visual analog scale scores of both groups were improved at the last postoperative follow-up. The time to return to social activities was 12.3 weeks in the screw group and 11.9 weeks in the tension band wiring group (p=0.394). A broken screw was observed in one case in the screw group and a broken k-wire was detected in two cases in the tension band wiring group. Nonunion was observed in two cases in each group. CONCLUSION: The tension band wiring technique could be another treatment choice of osteosynthesis for fixation of the accessory navicular bone. LEVEL OF EVIDENCE: Level III, Retrospective Case Control Study.

Simultaneous enhancement of upconversion and downshifting luminescence via plasmonic structure.

We describe a metal nanodisk-insulator-metal (MIM) structure that enhances lanthanide-based upconversion (UC) and downshifting (DS) simultaneously. The structure was fabricated using a nanotransfer printing method that facilitates large-area applications of nanostructures for optoelectronic devices. The proposed MIM structure is a promising way to harness the entire solar spectrum by converting both ultraviolet and near-infrared to visible light concurrently through resonant-mode excitation. The overall photoluminescence enhancements of the UC and DS were 174- and 29-fold, respectively.

Core/shell-structured upconversion nanophosphor and cadmium-free quantum-dot bilayer-based near-infrared photodetectors.

The core/shell-structured upconversion nanophosphors (UCNPs) and Cd-free CuInS(2)/ZnS quantum dots (QDs) were synthesized via coprecipitation and hot-injection methods, respectively, and they were applied to near infrared (NIR) photodetectors. The ß-NaYF(4):Yb,Er/ß-NaYF(4) UCNPs emitted intense visible light peaking at 522, 542, and 656 nm via (2)H(11/2), (4)S(3/2), and (4)F(9/2)→(4)I(15/2) transitions under excitation with 980 nm NIR light. The core/shell UCNPs showed 6.4 times higher emission intensity than core UCNPs. Charge carriers can be generated from CuInS(2)/ZnS QDs in the QD-UCNP mixture due to their broad absorption in the visible spectral region shorter than 600 nm. The photodetector devices were fabricated by spin-coating CuInS(2)/ZnS QDs on a SiO(2)/Si substrate with patterned gold electrodes followed by spin-coating UCNPs on the QD layer. The fabricated QD-UCNP-bilayer-based device showed a drastically increased photocurrent (128 µA) compared with the QD-layer-based device under 980 nm NIR light illumination. Additionally, the fabricated device showed stable ON-OFF switching properties against on and off NIR light.

Electrostatic Stabilized InP Colloidal Quantum Dots with High Photoluminescence Efficiency.

Electrostatically stabilized InP quantum dots (QDs) showing a high luminescence yield of 16% without any long alkyl chain coordinating ligands on their surface are demonstrated. This is achieved by UV-etching the QDs in the presence of fluoric and sulfuric acids. Fluoric acid plays a critical role in selectively etching nonradiative sites during the ligand-exchange process and in relieving the acidity of the solution to prevent destruction of the QDs. Given that the InP QDs show high luminescence without any electrical barriers, such as long alkyl ligands or inorganic shells, this method can be applied for QD treatment for application to highly efficient QD-based optoelectronic devices.

Correlation of clinical symptoms and function with fatty degeneration of infraspinatus in rotator cuff tear.

PURPOSE: The aim of this study was to analyse the correlation of clinical symptoms and function with the fatty degeneration of the infraspinatus in rotator cuff tears. METHODS: A total of 152 patients who had rotator cuff tears was enroled retrospectively. The infraspinatus muscle was divided into two compartments according to the bundle of fibres, and the patients were divided into four groups that reflected fatty degeneration. The muscle strength of the shoulder and clinical symptoms was investigated. RESULTS: The severity of the rotator cuff tear and retraction increased with fatty degeneration of both the superior and inferior parts in the infraspinatus muscles. Because of the increasing fatty degeneration of the superior part of the infraspinatus, the shoulder strength index (SSI) of abduction had poor results. Additionally, as the fatty degeneration of the inferior part of the infraspinatus increased, the SSI of abduction and external rotation had worse results. CONCLUSIONS: Fatty degeneration of the superior part of the infraspinatus has no correlation with the power of external rotation but has a negative correlation with the power of abduction. Moreover, fatty degeneration of the inferior part of the infraspinatus has a negative correlation with both the power of abduction and external rotation. LEVEL OF EVIDENCE: Retrospective study, Level IV.

Quantum-dot-based white lighting planar source through downconversion by blue electroluminescence.

We report the unprecedented fabrication of a planar white lighting quantum dot light-emitting diode (QD-LED) through integrating a CdZnS QD-based blue electroluminescence (EL) device with a free-standing polymethyl methacrylate (PMMA) composite film embedded with orange-emitting Cu-In-S (CIS) green-greenish yellow-emitting Cu-In-Ga-S (CIGS) QDs. The hybrid device successfully generates bicolored white emission that comprises blue EL and downconverted QD photoluminescence. The hybrid QD-LEDs loaded with the composite film embedded with one type of QDs exhibit a limited white spectral coverage, consequently producing low values (<65) in color rendering index (CRI). Thus, the QD-PMMA film consisting of a blend of green CIGS and orange CIS QD downconverters is applied for obtaining a higher-CRI white light through the spectral extension, resulting in a much improved CRI of 75-77. Various EL performances of the hybrid planar white device versus the reference blue QD-LED are also characterized in details.

Strategy to Achieve a Pure Red/Green/Blue-Emitting Upconversion Luminescence for Full-Color Displays.

Multicolor tunable upconversion nanoparticles (UCNPs) have garnered attention owing to their diverse applications such as displays, imaging, and security. Typically, achieving multicolor emission from UCNPs requires complicated core/multishell nanostructures comprising a core with at least five shells. Here, we propose a strategy to achieve bright and orthogonal red (R), green (G), and blue (B) upconversion (UC) luminescence without synthesizing complicated core/quintuple-shell or core/sextuple-shell nanostructures. For achieving bright and orthogonal RGB triprimary color UC luminescence, orthogonal bicolor-emitting core/shell-structured UCNPs are synthesized and blended. Orthogonal RB, RG, and GB luminescence are achieved through photon blocking. The combination of two orthogonal bicolor-emitting UCNPs exhibits pure RGB UC luminescence and full-color tunability via manipulation of excitation laser conditions. Furthermore, we present color displays achieved with transparent UCNP-polymer composites utilizing three distinct near-infrared light wavelengths, implying that the proposed strategy for attaining RGB UC luminescence may facilitate advancements in the development of full-color volumetric displays.

Photonic control of ligand nanospacing in self-assembly regulates stem cell fate.

Extracellular matrix (ECM) undergoes dynamic inflation that dynamically changes ligand nanospacing but has not been explored. Here we utilize ECM-mimicking photocontrolled supramolecular ligand-tunable Azo+ self-assembly composed of azobenzene derivatives (Azo+) stacked via cation-π interactions and stabilized with RGD ligand-bearing poly(acrylic acid). Near-infrared-upconverted-ultraviolet light induces cis-Azo+-mediated inflation that suppresses cation-π interactions, thereby inflating liganded self-assembly. This inflation increases nanospacing of "closely nanospaced" ligands from 1.8 nm to 2.6 nm and the surface area of liganded self-assembly that facilitate stem cell adhesion, mechanosensing, and differentiation both in vitro and in vivo, including the release of loaded molecules by destabilizing water bridges and hydrogen bonds between the Azo+ molecules and loaded molecules. Conversely, visible light induces trans-Azo+ formation that facilitates cation-π interactions, thereby deflating self-assembly with "closely nanospaced" ligands that inhibits stem cell adhesion, mechanosensing, and differentiation. In stark contrast, when ligand nanospacing increases from 8.7 nm to 12.2 nm via the inflation of self-assembly, the surface area of "distantly nanospaced" ligands increases, thereby suppressing stem cell adhesion, mechanosensing, and differentiation. Long-term in vivo stability of self-assembly via real-time tracking and upconversion are verified. This tuning of ligand nanospacing can unravel dynamic ligand-cell interactions for stem cell-regulated tissue regeneration.

Intense Near-Infrared Light-Emitting NaYF4:Nd,Yb-Based Nanophosphors for Luminescent Solar Concentrators.

In this study, we synthesized NaYF4-based downshifting nanophosphors (DSNPs), and fabricated DSNP-polydimethylsiloxane (PDMS) composites. Nd3+ ions were doped into the core and shell to increase absorbance at 800 nm. Yb3+ ions were co-doped into the core to achieve intense near-infrared (NIR) luminescence. To further enhance the NIR luminescence, NaYF4:Nd,Yb/NaYF4:Nd/NaYF4 core/shell/shell (C/S/S) DSNPs were synthesized. The C/S/S DSNPs showed a 3.0-fold enhanced NIR emission at 978 nm compared with core DSNPs under 800 nm NIR light. The synthesized C/S/S DSNPs showed high thermal stability and photostability against the irradiation with ultraviolet light and NIR light. Moreover, for application as luminescent solar concentrators (LSCs), C/S/S DSNPs were incorporated into the PDMS polymer, and the DSNP-PDMS composite containing 0.25 wt% of C/S/S DSNP was fabricated. The DSNP-PDMS composite showed high transparency (average transmittance = 79.4% for the visible spectral range of 380-750 nm). This result demonstrates the applicability of the DSNP-PDMS composite in transparent photovoltaic modules.

Performance Enhancement in Powder-Fabricated Cu2(ZnSn)Se4 Solar Cell by Roll Compression.

Despite the improved conversion efficiency of Cu2(ZnSn)Se4 (CZTSe) solar cells, their roll-to-roll fabrication nonetheless leads to low performance. The selenization time and temperature are typically considered major parameters for a powder-based CZTSe film; meanwhile, the importance of the densification during the roll-to-roll process is often overlooked. The densification process is related to the porosity of the light-absorbing layer, where high porosity lowers cell performance. In this study, we fabricated a dense CZTSe absorber layer as a method of controlling the compression of a powder precursor (Cu1.7(Zn1.2Sn1.0)S4.0 (CZTS)) during the roll-press process. The increased particle packing density of the CZTS layer was crucial in sintering the powder layer into a dense film and preventing severe selenization of the Mo back electrode. The pressed absorber layer of the CZTSe solar cell exhibited a more uniform chemical composition determined using dynamic secondary ion mass spectrometry (SIMS). Under the AM 1.5G illumination condition, the power conversion efficiency of the pressed solar cell was 6.82%, while the unpressed one was 4.90%.

Yellow-emitting γ-Ca2SiO4:Ce3+, Li+ phosphor for solid-state lighting: luminescent properties, electronic structure, and white light-emitting diode application.

A new yellow-emitting γ-Ca2SiO4:Ce3+,Li+ phosphor was synthesized via a solid-state reaction. The phosphor showed a strong yellow emission with a wide bandwidth of 135.4 nm under blue light excitation. Absorption and photoluminescence measurements and density functional theory calculations suggest that the luminescence of the phosphor can be attributed primarily to the transitions of 5d→4f (2F(7/2) and 2F(5/2)) of Ce3+ ions occupying Ca(1) sites in the host crystal. White light-emitting diodes (LEDs) were fabricated by combining this phosphor with a blue LED, and excellent white light with a high color rendering index of 86 was created owing to the wide emission bandwidth of the phosphor.

Synthesis of blue emitting InP/ZnS quantum dots through control of competition between etching and growth.

Blue (<480 nm) emitting Cd-free quantum dots (QDs) are in great demand for various applications. However, their synthesis has been challenging. Here we present blue emitting InP/ZnS core/shell QDs with a band edge emission of 475 nm and a full width at half maximum of 39 nm (215 meV) from their quantum confined states. The drastic temperature drop immediately after mixing of the precursors and holding them at a temperature below 150 °C was the critical factor for the synthesis of blue emitting QDs, because the blue QDs are formed by the etching of ultra-small InP cores by residual acetic acid below 150 °C. Etching was dominant at temperatures below 150 °C, whereas growth was dominant at temperatures above 150 °C. ZnS shells were formed successfully at 150 °C, yielding blue emitting InP/ZnS QDs. The colour of the InP/ZnS QDs depicted on the CIE 1931 chromaticity diagram is located close to the edge, indicating a pure blue colour compared to other InP-based QDs.

Environmentally friendly, highly efficient, and large stokes shift-emitting ZnSe:Mn2+/ZnS core/shell quantum dots for luminescent solar concentrators.

In this study, heavy-metal-free orange light-emitting ZnSe:Mn2+/ZnS doped-core/shell (d-C/S) quantum dots (QDs) were synthesized using a nucleation doping strategy. To synthesize high quality d-C/S QDs with high photoluminescence (PL) quantum yield (QY), the Mn2+ concentration was optimized. The resulting ZnSe:Mn2+(5%)/ZnS d-C/S QDs showed a high PL QY of 83.3%. The optical properties of the synthesized QDs were characterized by absorption and PL spectroscopy. Their structural and compositional properties were studied by X-ray diffraction, transmission electron microscopy, and energy dispersive X-ray spectroscopy. After doping Mn2+ into a ZnSe core, the ZnSe:Mn2+/ZnS d-C/S QDs showed a large Stokes shift of 170 nm. The ZnSe:Mn2+/ZnS d-C/S QDs were embedded in a poly(lauryl methacrylate) (PLMA) polymer matrix and the ZnSe:Mn2+/ZnS-based polymer film was fabricated. The fabricated ZnSe:Mn2+/ZnS-PLMA film was highly transparent in the visible spectral region (transmittance > 83.8% for λ ≥ 450 nm) and it exhibited bright orange light under air mass (AM) 1.5G illumination using a solar simulator. The optical path-dependent PL measurement of the ZnSe:Mn2+/ZnS-PLMA film showed no PL band shift and minimal PL decrease under variation of excitation position. These results indicate that the highly efficient and large Stokes shift-emitting ZnSe:Mn2+/ZnS QDs are promising for application to luminescent solar concentrators.

A Super-Boosted Hybrid Plasmonic Upconversion Process for Photodetection at 1550 nm Wavelength.

A super-boosted hybrid plasmonic upconversion (UC) architecture comprising a hierarchical plasmonic upconversion (HPU) film and a polymeric microlens array (MLA) film is proposed for efficient photodetection at a wavelength of 1550 nm. Plasmonic metasurfaces and Au core-satellite nanoassembly (CSNA) films can strongly induce a more effective plasmonic effect by providing numerous hot spots in an intense local electromagnetic field up to wavelengths exceeding 1550 nm. Hence, significant UC emission enhancement is realized via the amplified plasmonic coupling of an HPU film comprising an Au CSNA and UC nanoparticles. Furthermore, an MLA polymer film is synergistically coupled with the HPU film, thereby focusing the incident near-infrared light in the micrometer region, including the plasmonic nanostructure area. Consequently, the plasmonic effect super-boosted by microfocusing the incident light, significantly lowers the detectable power limit of a device, resulting in superior sensitivity and responsivity at weak excitation powers. Finally, a triple-cation perovskite-based photodetector coupled with the hybrid plasmonic UC film exhibits the excellent values of responsivity and detectivity of 9.80 A W-1 and 8.22 × 1012 Jones at a weak power density of ≈0.03 mW cm-2 , respectively, demonstrating that the device performance is enhanced by more than 104 magnitudes over a reference sample.

Photoswitchable Microgels for Dynamic Macrophage Modulation.

Dynamic manipulation of supramolecular self-assembled structures is achieved irreversibly or under non-physiological conditions, thereby limiting their biomedical, environmental, and catalysis applicability. In this study, microgels composed of azobenzene derivatives stacked via π-cation and π-π interactions are developed that are electrostatically stabilized with Arg-Gly-Asp (RGD)-bearing anionic polymers. Lateral swelling of RGD-bearing microgels occurs via cis-azobenzene formation mediated by near-infrared-light-upconverted ultraviolet light, which disrupts intermolecular interactions on the visible-light-absorbing upconversion-nanoparticle-coated materials. Real-time imaging and molecular dynamics simulations demonstrate the deswelling of RGD-bearing microgels via visible-light-mediated trans-azobenzene formation. Near-infrared light can induce in situ swelling of RGD-bearing microgels to increase RGD availability and trigger release of loaded interleukin-4, which facilitates the adhesion structure assembly linked with pro-regenerative polarization of host macrophages. In contrast, visible light can induce deswelling of RGD-bearing microgels to decrease RGD availability that suppresses macrophage adhesion that yields pro-inflammatory polarization. These microgels exhibit high stability and non-toxicity. Versatile use of ligands and protein delivery can offer cytocompatible and photoswitchable manipulability of diverse host cells.