Colloidal Synthesis of P-Type Zn3As2 Nanocrystals.

Zinc pnictides, particularly Zn3As2, hold significant promise for optoelectronic applications owing to their intrinsic p-type behavior and appropriate bandgaps. However, despite the outstanding properties of colloidal Zn3As2 nanocrystals, research in this area is lacking because of the absence of suitable precursors, occurrence of surface oxidation, and intricacy of the crystal structures. In this study, a novel and facile solution-based synthetic approach is presented for obtaining highly crystalline p-type Zn3As2 nanocrystals with accurate stoichiometry. By carefully controlling the feed ratio and reaction temperature, colloidal Zn3As2 nanocrystals are successfully obtained. Moreover, the mechanism underlying the conversion of As precursors in the initial phases of Zn3As2 synthesis is elucidated. Furthermore, these nanocrystals are employed as active layers in field-effect transistors that exhibit inherent p-type characteristics with native surface ligands. To enhance the charge transport properties, a dual passivation strategy is introduced via phase-transfer ligand exchange, leading to enhanced hole mobilities as high as 0.089 cm2 V-1 s-1. This study not only contributes to the advancement of nanocrystal synthesis, but also opens up new possibilities for previously underexplored p-type nanocrystal research.

Magnetic quasi-atomic electrons driven reversible structural and magnetic transitions between electride and its hydrides.

In electrides, interstitial anionic electrons (IAEs) in the quantized energy levels at cavities of positively charged lattice framework possess their own magnetic moment and interact with each or surrounding cations, behaving as quasi-atoms and inducing diverse magnetism. Here, we report the reversible structural and magnetic transitions by the substitution of the quasi-atomic IAEs in the ferromagnetic two-dimensional [Gd2C]2+·2e- electride with hydrogens and subsequent dehydrogenation of the canted antiferromagnetic Gd2CHy (y > 2.0). It is demonstrated that structural and magnetic transitions are strongly coupled by the presence or absence of the magnetic quasi-atomic IAEs and non-magnetic hydrogen anions in the interlayer space, which dominate exchange interactions between out-of-plane Gd-Gd atoms. Furthermore, the magnetic quasi-atomic IAEs are inherently conserved by the hydrogen desorption from the P[Formula: see text] 1m structured Gd2CHy, restoring the original ferromagnetic state of the R[Formula: see text]m structured [Gd2C]2+·2e- electride. This variable density of magnetic quasi-atomic IAEs enables the quantum manipulation of floating electron phases on the electride surface.

Room-temperature ammonia gas sensing via Au nanoparticle-decorated TiO2 nanosheets.

A high-performance gas sensor operating at room temperature is always favourable since it simplifies the device fabrication and lowers the operating power by eliminating a heater. Herein, we fabricated the ammonia (NH3) gas sensor by using Au nanoparticle-decorated TiO2 nanosheets, which were synthesized via two distinct processes: (1) preparation of monolayer TiO2 nanosheets through flux growth and a subsequent chemical exfoliation and (2) decoration of Au nanoparticles on the TiO2 nanosheets via hydrothermal method. Based on the morphological, compositional, crystallographic, and surface characteristics of this low-dimensional nano-heterostructured material, its temperature- and concentration-dependent NH3 gas-sensing properties were investigated. A high response of ~ 2.8 was obtained at room temperature under 20 ppm NH3 gas concentration by decorating Au nanoparticles onto the surface of TiO2 nanosheets, which generated oxygen defects and induced spillover effect as well.

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%.

Acceleration of NO2 gas sensitivity in two-dimensional SnSe2 by Br doping.

The authors report a Br doping effect on the NO2 gas sensing properties of a two-dimensional (2D) SnSe2 semiconductor. Single crystalline 2D SnSe2 samples with different Br contents are grown by a simple melt-solidification method. By analyzing the structural, vibrational as well as electrical properties, it can be confirmed that the Br impurity substitutes on the Se-site in SnSe2 serving as an efficient electron donor. When we measure the change of resistance under a 20 ppm NO2 gas flow condition at room temperature, both responsivity and response time are drastically improved by Br doping from 1.02% and 23 s to 3.38% and 15 s, respectively. From these results, it can be concluded that Br doping plays a key role for encouraging the charge transfer efficiency from the SnSe2 surface to the NO2 molecule by elaborating Fermi level in 2D SnSe2.

Overcharge-Induced Phase Heterogeneity and Resultant Twin-Like Layer Deformation in Lithium Cobalt Oxide Cathode for Lithium-Ion Batteries.

Overcharging is expected to be one of the solutions to overcome the current energy density limitation of lithium-ion battery cathodes, which will support the rapid growth of the battery market. However, high-voltage charging often poses a major safety threat including fatal incendiary incidents, limiting further application. Numerous researches are dedicated to the disadvantages of the overcharging process; nonetheless, the urgent demand for addressing failure mechanisms is still unfulfilled. Herein, it is revealed that overcharging induces phase heterogeneity into layered and cobalt oxide phases, and consequent "twin-like deformation" in lithium cobalt oxide. The interplay between the uncommon cobalt(III) oxide and the deformation is investigated by revealing the atomistic formation mechanism. Most importantly, abnormal cracking is discovered in the vicinity of the cobalt oxide where structural instability induces substantial contraction. In addition, surface degradation is widely observed in the crack boundary inside the particle. As unintentional overcharging can occur due to local imbalance in state-of-charge in severe operating conditions such as fast charging, the issues on overcharging should be emphasized to large extent and this study provides fundamental knowledge of overcharge by elucidating the crack development mechanism of layered cathodes, which is expected to broaden the horizon into high voltage operation.

Quantum electron liquid and its possible phase transition.

Purely quantum electron systems exhibit intriguing correlated electronic phases by virtue of quantum fluctuations in addition to electron-electron interactions. To realize such quantum electron systems, a key ingredient is dense electrons decoupled from other degrees of freedom. Here, we report the discovery of a pure quantum electron liquid that spreads up to ~3 Å in a vacuum on the surface of an electride crystal. Its extremely high electron density and weak hybridization with buried atomic orbitals show the quantum and pure nature of the electrons, which exhibit a polarized liquid phase, as demonstrated by our spin-dependent measurement. Furthermore, upon enhancing the electron correlation strength, the dynamics of the quantum electrons change to that of a non-Fermi liquid along with an anomalous band deformation, suggestive of a transition to a hexatic liquid crystal phase. Our findings develop the frontier of quantum electron systems and serve as a platform for exploring correlated electronic phases in a pure fashion.

Atomic Reconstruction and Oxygen Evolution Reaction of Mn3O4 Nanoparticles.

Understanding the chemical states of individual surface atoms and their arrangements is essential for addressing several current issues such as catalysis, energy stroage/conversion, and environmental protection. Here, we exploit a profile imaging technique to understand the correlation between surface atomic structures and the oxygen evolution reaction (OER) in Mn3O4 nanoparticles. We image surface structures of Mn3O4 nanoparticles and observe surface reconstructions in the (110) and (101) planes. Mn3+ ions at the surface, which are commonly considered as the active sites in OER, disappear from the reconstructed planes, whereas Mn3+ ions are still exposed at the edges of nanoparticles. Our observations suggest that surface reconstructions can deactivate low-index surfaces of Mn oxides in OER. These structural and chemical observations are further validated by density functional theory calculations. This work shows why atomic-scale characterization of surface structures is crucial for a molecular-level understanding of a chemical reaction in oxide nanoparticles.

Excellent Crystallinity and Stability Covalent-Organic Frameworks with High Emission and Anions Sensing.

Covalent-organic frameworks (COFs) are a new class of porous crystalline frameworks with high π-conjugation and periodical skeletons. The highly ordered π-conjugation structures in some COFs allow exciton migration and energy transfer over the frameworks, which leads to good fluorescence probing ability. In this work, two COFs (TFHPB-TAPB-COF and TFHPB-TTA-COF) are successfully condensed via the Schiff base condensation reaction. The intramolecular hydrogen bonds between imine bonds and hydroxyl groups form the excited-state intramolecular proton transfer (ESIPT) strategy. Owing to intramolecular hydrogen bonds in the skeleton, the two COFs show high crystallinity, remarkable stability, and excellent luminescence. The COFs represent a good sensitivity and selectivity to fluoride anions via fluorescence turn-off. Other halogen anions (chloride, bromide, and iodine) and acid anions (nitrate and hydrogen carbonate) remain inactive. These results imply that only fluoride anion is capable of opening the hydrogen bond interaction and hence break the ESIPT strategy. The detection limit toward fluoride anion is down to nanomoles level, ranking the best performances among fluoride anion sensors systems.

Realization of Structural Colors via Capped Cu-based F-P Cavity Structure.

Structural colors with tunable properties have several applications in the beautification of mobile devices, surface decoration, art and color filters. Herein, we propose an asymmetric F-P cavity design to systematically tune structural colors by changing the thickness of the top metal and intermediate insulator. In this study, Cu and Si3N4 were chosen as the top metal and intermediate insulator layers, respectively, various reflection colors being realized on the Cu surface. Various capping layers-that is, SiO2, polymethyl methacrylate (PMMA), and a commercially available clear coat named ProtectaClear-were used to protect the Cu surface from scratching and oxidation. PMMA coatings can protect Cu from corrosive environments without degradation of the color quality. The colors can be tuned by controlling the thickness of either the metal or intermediate insulator layers, and vivid structural colors-including orange, bright orange, red, purple, violet, light blue, green-yellow, and yellow-green-can be printed. The colors obtained can be attributed to thin-film interference.

A supramolecular host-guest interaction-mediated injectable hydrogel system with enhanced stability and sustained protein release.

Injectable hydrogels have been studied as drug delivery systems because of their minimal invasiveness and sustained drug release properties. Pluronic F127, consisting of poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) triblock copolymers, exhibits thermo-responsive properties and hence is injectable due to its rapid sol-gel transition. Unmodified Pluronic F127-based hydrogels, however, have limited long-term stability and controllable release of drugs entrapped within them. In this study, host-guest interactions between adamantane-conjugated Pluronic F127 (F127-Ad) and polymerized ß-cyclodextrin (CDP) were employed to develop a hydrogel-based protein delivery system. Single or multiple adamantane units were successfully introduced at the termini of Pluronic F127 with a 100% conversion yield, and the synthesized F127-Ad polymer produced a physically crosslinked micelle-packing structure when mixed with CDP. As the number of adamantanes at the terminal ends of Pluronic F127 increased, the critical gelation concentration of F127-Ad/CDP hydrogel decreased from 15 to 6% (w/v). The F127/CDP hydrogel was able to maintain its structure even with lower polymer content, and its injectability improved with a reduction of the hydrogel viscosity. The long-term stability of F127/CDP hydrogels was evaluated in vitro and in vivo, and it was demonstrated that the subcutaneously injected hydrogel did not disintegrate for up to 30 d. Throughout the drug release test using gelatin and insulin as model drugs, it was demonstrated that their release rates could be regulated via complexation between the protein drugs and the ß-cyclodextrin molecules inside the hydrogel. In conclusion, the F127-Ad/CDP hydrogel is expected to be a versatile protein delivery system with controllable durability and drug release characteristics. STATEMENT OF SIGNIFICANCE: Pluronic F127 is one of the widely studied polymeric materials for thermo-sensitive injectable hydrogels due to its high biocompatibility and rapid sol-gel transition. Since the Pluronic F127-based hydrogel has some limitations in its long-term stability and mechanical property, it is inevitable to modify its structure for the application to drug delivery. In this study, mono- or multi- adamantane-conjugated Pluronic F127s were synthesized and mixed with ß-cyclodextrin polymers to form hydrogels with host-guest interaction-mediated micelle-packing structures. The host-guest interaction introduced into the hydrogel system endowed it a sustained protein drug release behavior as well as high durability in vitro and in vivo. By increasing the number of adamantane molecules at the end of the Pluronic F127, both the stability and injectability of the hydrogel could be also modulated.

Synthesis of Uniformly Sized Bi0.5Sb1.5Te3.0 Nanoparticles via Mechanochemical Process and Wet-Milling for Reduced Thermal Conductivity.

In this study, Bi0.5Sb1.5Te3.0 (BST) nanoparticles (NPs) with high crystallinities were synthesized via a mechanochemical process (MCP). X-ray diffraction (XRD), and Raman and X-ray photoelectron spectroscopy (XPS) spectra of the BST NPs showed that the Bi, Sb, and Te powders successfully formed BiSbTe phase and transmission electron microscopy (TEM) images, verifying the high crystallinity and smaller size, albeit agglomerated. The as-synthesized BST NPs with agglomerated clusters were ground into smaller sizes of approximately 41.8 nm with uniform distribution through a simple wet-milling process during 7 days. The thermal conduction behaviors of bulk alloys fabricated by spark plasma sintering (SPS) of the BST NPs were studied by comparing those of samples fabricated from as-synthesized BST NPs and a BST ingot. The thermal conductivities (κ) of the BST nanocomposites were significantly reduced by introducing BST NPs with smaller grain sizes and finer distributions in the temperature range from 300 to 500 K. The BST nanocomposites fabricated from wet-milled BST NPs offered ultralow κ values of 0.84 W m-1 K-1 at approximately 398 K.

The impact of the COVID-19 pandemic on current tertiary aviation education and future careers: Students' perspective.

This study investigates Australian undergraduate tertiary aviation students' perceptions of the aviation industry and skills required to succeed following the COVID-19 pandemic. By developing an understanding of the skills students perceive to be necessary for their careers following the COVID-19 pandemic, comparisons can be drawn with industry perspectives to determine whether these perspectives align and, more importantly, support students' successful development of skills as sought by the industry. An online survey of current undergraduate tertiary aviation students at Australian universities was conducted to determine the perceived impediments, additional skills required, post-graduation plans and how university courses should evolve post-COVID-19. The results show that students are cognisant of the current oversupply of aviation professionals due to the downturn in the industry and are seeking further support with the development of non-technical skills to better prepare themselves to be competitive following graduation. These findings have implications for both undergraduate aviation students and universities offering an undergraduate aviation program. By considering these findings universities can adapt their programs to better prepare students and support the development of skilled aviation professionals, equipped to deal with challenges of the post-COVID-19 aviation industry.

Centrifugal microfluidic device for the high-throughput synthesis of Pd@AuPt core-shell nanoparticles to evaluate the performance of hydrogen peroxide generation.

We propose a novel high-throughput screening platform using a centrifugal microfluidic device for producing combinatorial tri-metallic catalysts. The centrifugal device was designed to perform 60 reactions under different conditions on a single device. As a model to search for an optimal tri-metallic catalyst, we synthesized a variety of Pd@AuPt nanoparticles (NPs), in which Pd nanocubes served as a core, and Au and Pt atoms formed a shell. The centrifugal microfluidic device was etched on the top and bottom sides, in which two zigzag-shaped microchannels were patterned on the top side, and 60 reaction chambers were fabricated on the bottom side. Through the sophisticated zigzag-shaped microchannels, Pt2+ ion and Pd nanocube solutions were injected into the channel in one shot, and the centrifugal force equally and automatically divided the injected solutions into 60 aliquots during the rotation. By controlling the sophisticated channel dimensions and designing the passive valve structure, the Pt2+ ion, Pd nanocube, and Au3+ solutions were loaded into the reaction chamber in sequential order depending on the programmed rotational direction and speed. Therefore, the ratio of Au to Pt to synthesize Pd@AuPt core-shell NPs was changed from 0.028 : 1 to 12 : 1, and accordingly, the resultant 60 types of Pd@AuPt catalysts presented with different ratios of metal atom compositions. Then, we screened the catalytic activity of the Pd@AuPt NPs for generating H2O2 according to the degree of coating of Au and Pt, and the Pd@AuPt catalyst with the Au/Pt ratio at 0.5 turned out to be the most effective.

Author Correction: Ferromagnetic quasi-atomic electrons in two-dimensional electride.

An amendment to this paper has been published and can be accessed via a link at the top of the paper.

Sodium-assisted passivation of grain boundaries and defects in Cu2ZnSnSe4 thin films.

The long stagnation of the photo-conversion efficiency of kesterites below 13% is a source of frustration in the scientific community. In this study, we investigated the effects of sodium on the passivation of grain boundaries and defects in Cu2ZnSnSe4 (CZTSe) grown on a soda-lime glass (SLG) and borosilicate (BS) glass. Because BS glass does not inherently contain sodium, we placed a thin layer of NaF between CZTSe and Mo. The composition of the samples is Cu-poor and Zn-rich. The distribution of sodium and its contributions to phase formation and defects were examined by cross-sectional energy-dispersive X-ray profiling, Raman scattering spectroscopy and imaging, surface potential and photoluminescence. From the experimental results, it can be strongly claimed that sodium ions segregate predominantly near the grain boundaries and reduce CuZn-related defects. These local surface imaging analyses provided the exact locations of the secondary phases. In particular, the photo-assisted scanning probe method enabled us to observe the changes in the optoelectrical properties of the thin films and the carrier behavior within the materials. Further studies with distinct alkali ions and optimal processing conditions will pave a way to improve the performance of kesterite solar cells.

Ferromagnetic quasi-atomic electrons in two-dimensional electride.

An electride, a generalized form of cavity-trapped interstitial anionic electrons (IAEs) in a positively charged lattice framework, shows exotic properties according to the size and geometry of the cavities. Here, we report that the IAEs in layer structured [Gd2C]2+·2e- electride behave as ferromagnetic elements in two-dimensional interlayer space and possess their own magnetic moments of ~0.52 µB per quasi-atomic IAE, which facilitate the exchange interactions between interlayer gadolinium atoms across IAEs, inducing the ferromagnetism in [Gd2C]2+·2e- electride. The substitution of paramagnetic chlorine atoms for IAEs proves the magnetic nature of quasi-atomic IAEs through a transition from ferromagnetic [Gd2C]2+·2e- to antiferromagnetic Gd2CCl caused by attenuating interatomic exchange interactions, consistent with theoretical calculations. These results confirm that quasi-atomic IAEs act as ferromagnetic elements and trigger ferromagnetic spin alignments within the antiferromagnetic [Gd2C]2+ lattice framework. These results present a broad opportunity to tailor intriguing ferromagnetism originating from quasi-atomic interstitial electrons in low-dimensional materials.

Performance Differences of Hexavalent Chromium Adsorbents Caused by Graphene Oxide Drying Process.

In this study, the influence of drying conditions on amine (-NH3) functionalization of graphene oxide (GO) was evaluated, and the hexavalent chromium (Cr(VI)) adsorption efficiency of the prepared materials was compared. 3-[2-(2-aminoehtylamino) ethylamino]propyl-trimethoxysilane (3N) was used for amine functionalization. The synthesized materials were analyzed by SEM, BET, TGA, XPS, and EA. TGA results showed that the solution-GO (SGO) was functionalized by more 3N molecules than freeze-dried GO (FDGO) and oven-dried GO (ODGO). Additionally, XPS analysis also showed that the ratio of N/C and Si/C was relatively high in SGO than FDGO and ODGO. The maximum adsorption capacity of SGO, FDGO, and ODGO for Cr(VI) was 258.48, 212.46, and 173.45 mg g-1, respectively. These results indicate that it is better to use SGO without drying processes for efficient amine functionalization and Cr(VI) removal. However, when the drying process is required, freeze-drying is better than oven-drying.

Most suitable amino silane molecules for surface functionalization of graphene oxide toward hexavalent chromium adsorption.

Adsorption is a simple and effective method for the removal of hexavalent chromium (Cr(VI)) from contaminated water. Several amino silane-graphene oxide (GO) composites with different species of amino groups (pN-GO, psN-GO, and pssN-GO; p: primary, s: secondary, N: amine) were evaluated to investigate their adsorption capacity and the effects of primary and secondary amines on Cr(VI) adsorption. We conducted a quantitative analysis to reveal the difference between primary and secondary amines in terms of Cr(VI) removal efficiency. A synergic effect was observed between the neighboring secondary amines in pssN-GO. From the Langmuir model prediction, we found that the composite with pssN-GO exhibited the highest maximum adsorption capacity (260.74 mg/g), followed by those with psN-GO (208.22 mg/g) and pN-GO (189.47 mg/g). Monolayer adsorption was more dominant when using pssN-GO, with the pseudo-second-order model best fitting the kinetic experiment results, whereas multilayer adsorption was dominant when using psN-GO and pN-GO.