Unraveling Sodium-Ion Dynamics in Honeycomb-Layered Na2MgxZn2-xTeO6 Solid Electrolytes with Solid-State NMR.

All-solid-state sodium-ion batteries (SIBs) have the potential to offer large-scale, safe, cost-effective, and sustainable energy storage solutions by supplementing the industry-leading lithium-ion batteries. However, for the enhanced bulk properties of SIB components (e.g., solid electrolytes), a comprehensive understanding of their atomic-scale structure and the dynamic behavior of sodium (Na) ions is essential. Here, we utilize a robust multinuclear (23Na, 125Te, 25Mg, and 67Zn) magnetic resonance approach to explore a novel Mg/Zn homogeneously mixed-cation honeycomb-layered oxide Na2MgxZn2-xTeO6 solid solution series. These new intermediate compounds exhibit tailorable bulk Na-ion conductivity (σ) with the highest σ = 0.14 × 10-4 S cm-1 for Na2MgZnTeO6 at room temperature suitable for SIB solid electrolyte applications as observed by powder electrochemical impedance spectroscopy (EIS). A combination of powder X-ray diffraction (XRD), energy-dispersive X-ray (EDX) spectroscopy, and field emission scanning electron microscopy (FESEM) reveals highly crystalline phase-pure compounds in the P6322 space group. We show that the Mg/Zn disorder is random within the honeycomb layers using 125Te nuclear magnetic resonance (NMR) and resolve multiple Na sites using two-dimensional (triple-quantum magic-angle spinning (3QMAS)) 23Na NMR. The medium-range disorder in the honeycomb layer is revealed through the combination of 25Mg and 67Zn NMR, complemented by electronic structure calculations using density functional theory (DFT). Furthermore, we expose very fast local Na-ion hopping processes (hopping rate, 1/τNMR = 0.83 × 109 Hz) by using a laser to achieve variable high-temperature (∼860 K) 23Na NMR, which are sensitive to different Mg/Zn ratios. The Na2MgZnTeO6 with maximum Mg/Zn disorder displays the highest short-range Na-ion dynamics among all of the solid solution members.

Cu1.5SeyTe1-y (y = 0.2-0.7): A Series of Narrow Band Gap Semiconductors with Low Thermal Conductivity at Ambient Temperature.

Coinage metal chalcogenides offer ideal prerequisites for high thermoelectric performance and sensor applications, with their usually low lattice thermal and high electrical conductivity, as well as small band gaps. In the solid solution Cu1.5SeyTe1-y we synthesized phase pure materials with y = 0.2-0.7 and characterized them concerning selected physical properties. X-ray crystal structure determination was performed for two representatives of the solid solution, Cu1.5Se0.3Te0.7 and Cu1.5Se0.5Te0.5. The entire series crystallizes cubically, in space group Pm3̅n. No structural changes are observed between room temperature and the synthesis temperature of 723 K. The conductivity measurements and Seebeck coefficients of Cu1.5Se0.3Te0.7 and Cu1.5Se0.5Te0.5 indicate that the two representatives are narrow band gap semiconductors (Eg 0.06-0.08 eV). Both compounds show positive Seebeck coefficients and reasonably low thermal conductivities at moderate temperatures. Cu1.5Se0.5Te0.5 is characterized by a bulk modulus of 40.9 GPa.

Rare earths stick to rare cyanobacteria: Future potential for bioremediation and recovery of rare earth elements.

Biosorption of metal ions by phototrophic microorganisms is regarded as a sustainable and alternative method for bioremediation and metal recovery. In this study, 12 cyanobacterial strains, including 7 terrestrial and 5 aquatic cyanobacteria, covering a broad phylogenetic diversity were investigated for their potential application in the enrichment of rare earth elements through biosorption. A screening for the maximum adsorption capacity of cerium, neodymium, terbium, and lanthanum was conducted in which Nostoc sp. 20.02 showed the highest adsorption capacity with 84.2-91.5 mg g-1. Additionally, Synechococcus elongatus UTEX 2973, Calothrix brevissima SAG 34.79, Desmonostoc muscorum 90.03, and Komarekiella sp. 89.12 were promising candidate strains, with maximum adsorption capacities of 69.5-83.4 mg g-1, 68.6-83.5 mg g-1, 44.7-70.6 mg g-1, and 47.2-67.1 mg g-1 respectively. Experiments with cerium on adsorption properties of the five highest metal adsorbing strains displayed fast adsorption kinetics and a strong influence of the pH value on metal uptake, with an optimum at pH 5 to 6. Studies on binding specificity with mixed-metal solutions strongly indicated an ion-exchange mechanism in which Na+, K+, Mg2+, and Ca2+ ions are replaced by other metal cations during the biosorption process. Depending on the cyanobacterial strain, FT-IR analysis indicated the involvement different functional groups like hydroxyl and carboxyl groups during the adsorption process. Overall, the application of cyanobacteria as biosorbent in bioremediation and recovery of rare earth elements is a promising method for the development of an industrial process and has to be further optimized and adjusted regarding metal-containing wastewater and adsorption efficiency by cyanobacterial biomass.

A Switchable One-Compound Diode.

A diode requires the combination of p- and n-type semiconductors or at least the defined formation of such areas within a given compound. This is a prerequisite for any IT application, energy conversion technology, and electronic semiconductor devices. Since the discovery of the pnp-switchable compound Ag10 Te4 Br3 in 2009, it is in principle possible to fabricate a diode from a single material without adjusting the semiconduction type by a defined doping level. Often a structural phase transition accompanied by a dynamic change of charge carriers or a charge density wave within certain substructures are responsible for this effect. Unfortunately, the high pnp-switching temperature between 364 and 580 K hinders the application of this phenomenon in convenient devices. This effect is far removed from a suitable operation temperature at ambient conditions. Ag18 Cu3 Te11 Cl3  is a room temperature pnp-switching material and the first single-material position-independent diode. It shows the highest ever reported Seebeck coefficient drop that takes place within a few Kelvin. Combined with its low thermal conductivity, it offers great application potential within an accessible and applicable temperature window. Ag18 Cu3 Te11 Cl3 and pnp-switching materials have the potential for applications and processes where diodes, transistors, or any defined charge separation with junction formation are utilized.

Stripped: contribution of cyanobacterial extracellular polymeric substances to the adsorption of rare earth elements from aqueous solutions.

The transformation of modern industries towards enhanced sustainability is facilitated by green technologies that rely extensively on rare earth elements (REEs) such as cerium (Ce), neodymium (Nd), terbium (Tb), and lanthanum (La). The occurrence of productive mining sites, e.g., is limited, and production is often costly and environmentally harmful. As a consequence of increased utilization, REEs enter our ecosystem as industrial process water or wastewater and become highly diluted. Once diluted, they can hardly be recovered by conventional techniques, but using cyanobacterial biomass in a biosorption-based process is a promising eco-friendly approach. Cyanobacteria can produce extracellular polymeric substances (EPS) that show high affinity to metal cations. However, the adsorption of REEs by EPS has not been part of extensive research. Thus, we evaluated the role of EPS in the biosorption of Ce, Nd, Tb, and La for three terrestrial, heterocystous cyanobacterial strains. We cultivated them under N-limited and non-limited conditions and extracted their EPS for compositional analyses. Subsequently, we investigated the metal uptake of a) the extracted EPS, b) the biomass extracted from EPS, and c) the intact biomass with EPS by comparing the amount of sorbed REEs. Maximum adsorption capacities for the tested REEs of extracted EPS were 123.9-138.2 mg g-1 for Komarekiella sp. 89.12, 133.1-137.4 mg g-1 for Desmonostoc muscorum 90.03, and 103.5-129.3 mg g-1 for Nostoc sp. 20.02. A comparison of extracted biomass with intact biomass showed that 16% (Komarekiella sp. 89.12), 28% (Desmonostoc muscorum 90.03), and 41% (Nostoc sp. 20.02) of REE adsorption was due to the biosorption of the extracellular EPS. The glucose- rich EPS (15%-43% relative concentration) of all three strains grown under nitrogen-limited conditions showed significantly higher biosorption rates for all REEs. We also found a significantly higher maximum adsorption capacity of all REEs for the extracted EPS compared to cells without EPS and untreated biomass, highlighting the important role of the EPS as a binding site for REEs in the biosorption process. EPS from cyanobacteria could thus be used as efficient biosorbents in future applications for REE recycling, e.g., industrial process water and wastewater streams.

Ion Dynamics and Polymorphism in Cu20Te11Cl3.

Coinage metal polychalcogenide halides are an intriguing class of materials, and many representatives are solid ion conductors and thermoelectric materials. The materials show high ion mobility, polymorphism, and various attractive interactions in the cation and anion substructures. Especially the latter feature leads to complex electronic structures and the occurrence of charge-density waves (CDWs) and, as a result, the first p-n-p switching materials. During our systematic investigations for new p-n-n switching materials in the Cu-Te-Cl phase diagram, we were able to isolate polymorphic Cu20Te11Cl3, which we characterized structurally and with regard to its electronic and thermoelectric properties. Cu20Te11Cl3 is trimorphic, with phase transitions occurring at 288 and 450 K. The crystal structures of two polymorphs, the α phase, stable above 450 K, and the ß polymorph (288-450 K), are reported, and the complex structure chemistry featuring twinning upon a phase change is illustrated. We identified a dynamic cation substructure and a static anion substructure for all polymorphs, characterizing Cu20Te11Cl3 as a solid Cu-ion conductor. Temperature-dependent measurements of the Seebeck coefficient and total conductivity were performed and substantiated a linear response of the Seebeck coefficient, a lack of CDWs, and no p-n-p switching. Reasons for a lack of CDWs in Cu20Te11Cl3 are discussed and illustrated in the context of existing p-n-p switching materials.

Ultrafast Photoconductivity and Terahertz Vibrational Dynamics in Double-Helix SnIP Nanowires.

Tin iodide phosphide (SnIP), an inorganic double-helix material, is a quasi-1D van der Waals semiconductor that shows promise in photocatalysis and flexible electronics. However, the understanding of the fundamental photophysics and charge transport dynamics of this new material is limited. Here, time-resolved terahertz (THz) spectroscopy is used to probe the transient photoconductivity of SnIP nanowire films and measure the carrier mobility. With insight into the highly anisotropic electronic structure from quantum chemical calculations, an electron mobility as high as 280 cm2 V-1 s-1 along the double-helix axis and a hole mobility of 238 cm2 V-1 s-1 perpendicular to the double-helix axis are detected. Additionally, infrared-active (IR-active) THz vibrational modes are measured, which shows excellent agreement with first-principles calculations, and an ultrafast photoexcitation-induced charge redistribution is observed that reduces the amplitude of a twisting mode of the outer SnI helix on picosecond timescales. Finally, it is shown that the carrier lifetime and mobility are limited by a trap density greater than 1018 cm-3 . The results provide insight into the optical excitation and relaxation pathways of SnIP and demonstrate a remarkably high carrier mobility for such a soft and flexible material, suggesting that it could be ideally suited for flexible electronics applications.

Anisotropic moiré optical transitions in twisted monolayer/bilayer phosphorene heterostructures.

Moiré superlattices of van der Waals heterostructures provide a powerful way to engineer electronic structures of two-dimensional materials. Many novel quantum phenomena have emerged in graphene and transition metal dichalcogenide moiré systems. Twisted phosphorene offers another attractive system to explore moiré physics because phosphorene features an anisotropic rectangular lattice, different from isotropic hexagonal lattices previously reported. Here we report emerging anisotropic moiré optical transitions in twisted monolayer/bilayer phosphorenes. The optical resonances in phosphorene moiré superlattice depend sensitively on twist angle and are completely different from those in the constitute monolayer and bilayer phosphorene even for a twist angle as large as 19°. Our calculations reveal that the Γ-point direct bandgap and the rectangular lattice of phosphorene give rise to the remarkably strong moiré physics in large-twist-angle phosphorene heterostructures. This work highlights fresh opportunities to explore moiré physics in phosphorene and other van der Waals heterostructures with different lattice configurations.

Formation Mechanisms for Phosphorene and SnIP.

Phosphorene-the monolayered material of the element allotrope black phosphorus (Pblack )-and SnIP are 2D and 1D semiconductors with intriguing physical properties. Pblack and SnIP have in common that they can be synthesized via short way transport or mineralization using tin, tin(IV) iodide and amorphous red phosphorus. This top-down approach is the most important access route to phosphorene. The two preparation routes are closely connected and differ mainly in reaction temperature and molar ratios of starting materials. Many speculative intermediates or activator side phases have been postulated especially for top-down Pblack /phosphorene synthesis, such as Hittorf's phosphorus or Sn24 P19.3 I8 clathrate. The importance of phosphorus-based 2D and 1D materials for energy conversion, storage, and catalysis inspired us to elucidate the formation mechanisms of these two compounds. Herein, we report on the reaction mechanisms of Pblack /phosphorene and SnIP from P4 and SnI2 via direct gas phase formation.

Red-phosphorus-impregnated carbon nanofibers for sodium-ion batteries and liquefaction of red phosphorus.

Red phosphorus offers a high theoretical sodium capacity and has been considered as a candidate anode for sodium-ion batteries. Similar to silicon anodes for lithium-ion batteries, the electrochemical performance of red phosphorus is plagued by the large volume variation upon sodiation. Here we perform in situ transmission electron microscopy analysis of the synthesized red-phosphorus-impregnated carbon nanofibers with the corresponding chemo-mechanical simulation, revealing that, the sodiated red phosphorus becomes softened with a "liquid-like" mechanical behaviour and gains superior malleability and deformability against pulverization. The encapsulation strategy of the synthesized red-phosphorus-impregnated carbon nanofibers has been proven to be an effective method to minimize the side reactions of red phosphorus in sodium-ion batteries, demonstrating stable electrochemical cycling. Our study provides a valid guide towards high-performance red-phosphorus-based anodes for sodium-ion batteries.

Cu9.1Te4Cl3: A Thermoelectric Compound with Low Thermal and High Electrical Conductivity.

Cu9.1Te4Cl3 is a new polymorphic compound in the class of coinage metal polytelluride halides. Copper is highly mobile, which results in multiple order-disorder phase transitions in a limited temperature interval from 240 to 370 K. Mainly as a consequence of thermal transport properties, the compound's thermoelectric figure of merit reaches values up to ZT = 0.15 in the temperature range between room temperature and 523 K. Its structure is closely related to that of Ag10Te4Br3, another coinage metal polytelluride halide, which represents the first p-n-p-switchable semiconductor approachable by a simple temperature change. The title compound outperforms Ag10Te4Br3 in terms of thermoelectric properties by 1 order of magnitude and therefore acts as a link between the class of p-n-p compounds and thermoelectric materials.

Vapor growth of binary and ternary phosphorus-based semiconductors into TiO2 nanotube arrays and application in visible light driven water splitting.

We report successful synthesis of low band gap inorganic polyphosphide and TiO2 heterostructures with the aid of short-way transport reactions. Binary and ternary polyphosphides (NaP7, SnIP, and (CuI)3P12) were successfully reacted and deposited into electrochemically fabricated TiO2 nanotubes. Employing vapor phase reaction deposition, the cavities of 100 µm long TiO2 nanotubes were infiltrated; approximately 50% of the nanotube arrays were estimated to be infiltrated in the case of NaP7. Intensive characterization of the hybrid materials with techniques including SEM, FIB, HR-TEM, Raman spectroscopy, XRD, and XPS proved the successful vapor phase deposition and synthesis of the substances on and inside the nanotubes. The polyphosphide@TiO2 hybrids exhibited superior water splitting performance compared to pristine materials and were found to be more active at higher wavelengths. SnIP@TiO2 emerged to be the most active among the polyphosphide@TiO2 materials. The improved photocatalytic performance might be due to Fermi level re-alignment and a lower charge transfer resistance which facilitated better charge separation from inorganic phosphides to TiO2.

Air-Stable Room-Temperature Mid-Infrared Photodetectors Based on hBN/Black Arsenic Phosphorus/hBN Heterostructures.

Layered black phosphorus (BP) has attracted wide attention for mid-infrared photonics and high-speed electronics, due to its moderate band gap and high carrier mobility. However, its intrinsic band gap of around 0.33 electronvolt limits the operational wavelength range of BP photonic devices based on direct interband transitions to around 3.7 µm. In this work, we demonstrate that black arsenic phosphorus alloy (b-As xP1- x) formed by introducing arsenic into BP can significantly extend the operational wavelength range of photonic devices. The as-fabricated b-As0.83P0.17 photodetector sandwiched within hexagonal boron nitride (hBN) shows peak extrinsic responsivity of 190, 16, and 1.2 mA/W at 3.4, 5.0, and 7.7 µm at room temperature, respectively. Moreover, the intrinsic photoconductive effect dominates the photocurrent generation mechanism due to the preservation of pristine properties of b-As0.83P0.17 by complete hBN encapsulation, and these b-As0.83P0.17 photodetectors exhibit negligible transport hysteresis. The broad and large photoresponsivity within mid-infrared resulting from the intrinsic photoconduction, together with the excellent long-term air stability, makes b-As0.83P0.17 alloy a promising alternative material for mid-infrared applications, such as free-space communication, infrared imaging, and biomedical sensing.

A Chemical, High-Temperature Way to Ag1.9Te via Quasi-Topotactic Reaction of Stuetzite-type Ag1.54Te: Structural and Thermoelectric Properties.

Semiconducting silver tellurides gained reasonable interest in the past years due to its thermoelectric, magneto-caloric, and nonlinear optic properties. Nanostructuring has been frequently used to address quantum-confinement effects of minerals and synthetic compounds in the Ag-Te system. Here, we report on the structural, thermal, and thermoelectric properties of stuetzite-like Ag1.54Te (or Ag4.63Te3) and Ag1.9Te. By a quasi-topotactic reaction upon tellurium evaporation Ag1.54Te can be transferred to Ag1.9Te after heat treatment. Crystal structures, thermal and thermoelectric properties of stuetzite-like Ag1.54Te (or Ag4.63Te3) and Ag1.9Te were determined by ex situ and in situ experiments. This method represents an elegant chemical way to Ag1.9Te, which was so far only accessible electrochemically via electrochemical removal of silver from the mineral hessite (Ag2Te). The mixed conductors show reasonable high total electric conductivities, very low thermal conductivities, and large Seebeck coefficients, which result in a significant high thermoelectric figure of 0.57 at 680 K.

Co11Li[(OH)5O][(PO3OH)(PO4)5], a Lithium-Stabilized, Mixed-Valent Cobalt(II,III) Hydroxide Phosphate Framework.

A new metastable phase, featuring a lithium-stabilized mixed-valence cobalt(II,III) hydroxide phosphate framework, Co11.0(1)Li1.0(2)[(OH)5O][(PO3OH)(PO4)5], corresponding to the simplified composition Co1.84(2)Li0.16(3)(OH)PO4, is prepared by hydrothermal synthesis. Because the pH-dependent formation of other phases such as Co3(OH)2(PO3OH)2 and olivine-type LiCoPO4 competes in the process, a pH value of 5.0 is crucial for obtaining a single-phase material. The crystals with dimensions of 15 µm × 30 µm exhibit a unique elongated triangular pyramid morphology with a lamellar fine structure. Powder X-ray diffraction experiments reveal that the phase is isostructural with the natural phosphate minerals holtedahlite and satterlyite, and crystallizes in the trigonal space group P31m (a = 11.2533(4) Å, c = 4.9940(2) Å, V = 547.70(3) Å3, Z = 1). The three-dimensional network structure is characterized by partially Li-substituted, octahedral [M2O8(OH)] (M = Co, Li) dimer units which form double chains that run along the [001] direction and are connected by [PO4] and [PO3(OH)] tetrahedra. Because no Li-free P31m-type Co2(OH)PO4 phase could be prepared, it can be assumed that the Li ions are crucial for the stabilization of the framework. Co L-edge X-ray absorption spectroscopy demonstrates that the cobalt ions adopt the oxidation states +2 and +3 and hence provides further evidence for the incorporation of Li in the charge-balanced framework. The presence of three independent hydroxyl groups is further confirmed by infrared spectroscopy. Magnetization measurements imply a paramagnetic to antiferromagnetic transition at around T = 25 K as well as a second transition at around 9-12 K with a ferromagnetic component below this temperature. The metastable character of the phase is demonstrated by thermogravimetric analysis and differential scanning calorimetry, which above 558 °C reveal a two-step decomposition to CoO, Co3(PO4)2, and olivine-type LiCoPO4 with release of water and oxygen.

Room temperature high-detectivity mid-infrared photodetectors based on black arsenic phosphorus.

The mid-infrared (MIR) spectral range, pertaining to important applications, such as molecular "fingerprint" imaging, remote sensing, free space telecommunication, and optical radar, is of particular scientific interest and technological importance. However, state-of-the-art materials for MIR detection are limited by intrinsic noise and inconvenient fabrication processes, resulting in high-cost photodetectors requiring cryogenic operation. We report black arsenic phosphorus-based long-wavelength IR photodetectors, with room temperature operation up to 8.2 µm, entering the second MIR atmospheric transmission window. Combined with a van der Waals heterojunction, room temperature-specific detectivity higher than 4.9 × 109 Jones was obtained in the 3- to 5-µm range. The photodetector works in a zero-bias photovoltaic mode, enabling fast photoresponse and low dark noise. Our van der Waals heterojunction photodetectors not only exemplify black arsenic phosphorus as a promising candidate for MIR optoelectronic applications but also pave the way for a general strategy to suppress 1/f noise in photonic devices.

Black Phosphorus Field-Effect Transistors with Work Function Tunable Contacts.

Black phosphorus (BP) has been recently rediscovered as an elemental two-dimensional (2D) material that shows promising results for next generation electronics and optoelectronics because of its intrinsically superior carrier mobility and small direct band gap. In various 2D field-effect transistors (FETs), the choice of metal contacts is vital to the device performance, and it is a major challenge to reach ultralow contact resistances for highly scaled 2D FETs. Here, we experimentally show the effect of a work function tunable metal contact on the device performance of BP FETs. Using palladium (Pd) as the contact material, we employed the reaction between Pd and H2 to form a Pd-H alloy that effectively increased the work function of Pd and reduced the Schottky barrier height (ΦB) in a BP FET. When the Pd-contacted BP FET was exposed to 5% hydrogen concentrated Ar, the contact resistance (Rc) improved between the Pd electrodes and BP from ∼7.10 to ∼1.05 Ω·mm, surpassing all previously reported contact resistances in the literature for BP FETs. Additionally, with exposure to 5% hydrogen, the transconductance of the Pd-contacted BP FET was doubled. The results shown in this study illustrate the significance of choosing the right contact material for high-performance BP FETs in order to realize the real prospect of BP in electronic applications.

Synthesis, Characterization, and Device Application of Antimony-Substituted Violet Phosphorus: A Layered Material.

Two-dimensional (2D) nanoflakes have emerged as a class of materials that may impact electronic technologies in the near future. A challenging but rewarding work is to experimentally identify 2D materials and explore their properties. Here, we report the synthesis of a layered material, P20.56(1)Sb0.44(1), with a systematic study on characterizations and device applications. This material demonstrates a direct band gap of around 1.67 eV. Using a laser-cutting method, the thin flakes of this material can be separated into multiple segments. We have also fabricated field effect transistors based on few-layer P20.56(1)Sb0.44(1) flakes with a thickness down to a few nanometers. Interestingly, these field effect transistors show strong photoresponse within the wavelength range of visible light. At room temperature, we have achieved good mobility values (up to 58.96 cm2/V·s), a reasonably high on/off current ratio (∼103), and intrinsic responsivity up to 10 µA/W. Our results demonstrate the potential of P20.56(1)Sb0.44(1) thin flakes as a two-dimensional material for applications in visible light detectors.