Donor and acceptor dynamics of phosphorous doped ZnO nanorods with stable p-type conduction: photoluminescence and junction characteristics

We employed temperature-dependent photoluminescence (PL) to explain the donor and acceptor dynamics in phosphorus doped stable p-type P:ZnO nanorods. The room temperature PL revealed good crystalline and optical quality of P:ZnO nanorods. The 10 K PL spectrum exhibited a dominant acceptor bound exciton (A0X) or donor bound exciton (D0X) emission corresponding to p- and n-type P:ZnO nanorods, respectively. The donor-acceptor-pair (DAP) transitions exhibited different thermal dissociation energies for the p- and n-type P:ZnO nanorods, suggesting their different quenching channels. The quenching of the DAP transitions of the p-type ZnO:P nanorods was associated with the thermal dissociation of the DAP into free excitons, while the DAP transition of the n-type ZnO:P nanorods was quenched through the thermal dissociation of the shallow donor into free electrons. The rectifying behavior of a p-n homojunction diode formed by the p-type P:ZnO nanorods on n-type ZnO film confirmed the p-type conduction of the P:ZnO nanorods.     

Single-Crystal Nanowire Cesium Tin Triiodide Perovskite Solar Cell

This work reports for the first time a highly efficient single-crystal cesium tin triiodide (CsSnI₃) perovskite nanowire solar cell. With a perfect lattice structure, low carrier trap density (≈5 × 10¹⁰ cm⁻³), long carrier lifetime (46.7 ns), and excellent carrier mobility (>600 cm² V⁻¹ s⁻¹), single-crystal CsSnI₃ perovskite nanowires enable a very attractive feature for flexible perovskite photovoltaics to power active micro-scale electronic devices. Using CsSnI₃ single-crystal nanowire in conjunction with highly conductive wide bandgap semiconductors as front-surface-field layers, an unprecedented efficiency of 11.7% under AM 1.5G illumination is achieved. This work demonstrates the feasibility of all-inorganic tin-based perovskite solar cells via crystallinity and device-structure improvement for the high-performance, and thus paves the way for the energy supply to flexible wearable devices in the future.     

Honeycomb RhI3 Flakes with High Environmental Stability for Optoelectronics

The emerging 2D layered transition metal trihalides (MX₃) have attracted extremely high interest given their exceptional structural and physical properties. Continuing to extend the library of 2D MX₃ is essential for exploring new physical phenomena and enabling new functionality. Herein, the optical and electrical properties and the photodetection behavior of atomically thin RhI₃ flakes exfoliated from bulk crystals are reported. This compound exhibits superior air and thermal stability, as well as thickness-dependent bandgap from 1.1 (18L) to 1.4 eV (2L). Field-effect transistors based on the few-layer RhI₃ flakes display n-type semiconducting behavior with competitive mobility of 2.5 cm² V⁻¹ s⁻¹ and ON/OFF current ratio of 4 × 10⁴. Importantly, the outstanding responsivity of 11.5 A W⁻¹ and high specific detectivity of 2 × 10¹⁰ Jones are recorded from the RhI₃ photodetectors under 980 nm illumination at room temperature in air. These findings indicate a variety of potential applications of atomically thin RhI₃ flakes in future 2D-material-based electronic and optoelectronic devices.     

Designing Efficient Energy Funneling Kinetics in Ruddlesden–Popper Perovskites for High‐Performance Light‐Emitting Diodes

Mixed Ruddlesden–Popper (RP) perovskites are of great interest in light‐emitting diodes (LEDs), due to the efficient energy transfer (funneling) from high‐bandgap (donor) domains to low‐bandgap (acceptor) domains, which leads to enhanced photoluminescence (PL) intensity, long PL lifetime, and high‐efficiency LEDs. However, the influence of reduced effective emitter centers in the active emissive film, as well as the implications of electrical injection into the larger bandgap donor material, have not been addressed in the context of an active device. The electrical and optical signatures of the energy cascading mechanisms are critically assessed and modulated in a model RP perovskite series ((C₈H₁₇NH₃)₂(CH(NH₂)₂)_m?1Pb_mBr_3m+1). Optimized devices demonstrate a current efficiency of 22.9 cd A^?1 and 5% external quantum efficiency, more than five times higher than systems where funneling is absent. The signature of nonideal funneling in RP perovskites is revealed by the appearance of donor electroluminescence from the device, followed by a reduction in the LED performance     

2D Ca3Sn2S7 Chalcogenide Perovskite: A Graphene‐Like Semiconductor with Direct Bandgap 0.5 eV and Ultrahigh Carrier Mobility 6.7 × 104 cm2 V−1 s−1

Graphene, a star 2D material, has attracted much attention because of its unique properties including linear electronic dispersion, massless carriers, and ultrahigh carrier mobility (10⁴–10⁵ cm² V^?1 s^?1). However, its zero bandgap greatly impedes its application in the semiconductor industry. Opening the zero bandgap has become an unresolved worldwide problem. Here, a novel and stable 2D Ruddlesden–Popper‐type layered chalcogenide perovskite semiconductor Ca₃Sn₂S₇ is found based on first‐principles GW calculations, which exhibits excellent electronic, optical, and transport properties, as well as soft and isotropic mechanical characteristics. Surprisingly, it has a graphene‐like linear electronic dispersion, small carrier effective mass (0.04 m₀), ultrahigh room‐temperature carrier mobility (6.7 × 10⁴ cm² V^?1 s^?1), Fermi velocity (3 × 10⁵ m s^?1), and optical absorption coefficient (10⁵ cm^?1). Particularly, it has a direct quasi‐particle bandgap of 0.5 eV, which realizes the dream of opening the graphene bandgap in a new way. These results guarantee its application in infrared optoelectronic and high‐speed electronic devices.     

Ice‐Templated Assembly Strategy to Construct 3D Boron Nitride Nanosheet Networks in Polymer Composites for Thermal Conductivity Improvement

Owing to the growing heat removal issue of modern electronic devices, polymer composites with high thermal conductivity have drawn much attention in the past few years. However, a traditional method to enhance the thermal conductivity of the polymers by addition of inorganic fillers usually creates composite with not only limited thermal conductivity but also other detrimental effects due to large amount of fillers required. Here, novel polymer composites are reported by first constructing 3D boron nitride nanosheets (3D‐BNNS) network using ice‐templated approach and then infiltrating them with epoxy matrix. The obtained polymer composites exhibit a high thermal conductivity (2.85 W m⁻¹ K⁻¹), a low thermal expansion coefficient (24–32 ppm K⁻¹), and an increased glass transition temperature (T_g) at relatively low BNNSs loading (9.29 vol%). These results demonstrate that this approach opens a new avenue for design and preparation of polymer composites with high thermal conductivity. The polymer composites are potentially useful in advanced electronic packaging techniques, namely, thermal interface materials, underfill materials, molding compounds, and organic substrates.     

Phosphonate Metal–Organic Frameworks: A Novel Family of Semiconductors

Herein, the first semiconducting and magnetic phosphonate metal–organic framework (MOF), TUB75, is reported, which contains a 1D inorganic building unit composed of a zigzag chain of corner-sharing copper dimers. The solid-state UV–vis spectrum of TUB75 reveals the existence of a narrow bandgap of 1.4 eV, which agrees well with the density functional theory (DFT)-calculated bandgap of 1.77 eV. Single-crystal conductivity measurements for different orientations of the individual crystals yield a range of conductances from 10⁻³ to 10³ S m⁻¹ at room temperature, pointing to the directional nature of the electrical conductivity in TUB75. Magnetization measurements show that TUB75 is composed of antiferromagnetically coupled copper dimer chains. Due to their rich structural chemistry and exceptionally high thermal/chemical stabilities, phosphonate MOFs like TUB75 may open new vistas in engineerable electrodes for supercapacitors.     

Abnormal Pressure‐Induced Photoluminescence Enhancement and Phase Decomposition in Pyrochlore La2Sn2O7

La₂Sn₂O₇ is a transparent conducting oxide (TCO) material and shows a strong near‐infrared fluorescent at ambient pressure and room temperature. By in situ high‐pressure research, pressure‐induced visible photoluminescence (PL) above 2 GPa near 2 eV is observed. The emergence of unusual visible PL behavior is associated with the seriously trigonal lattice distortion of the SnO₆ octehedra, under which the Sn–O1–Sn exchange angle θ is decreased below 22.1 GPa, thus enhancing the PL quantum yield leading to Sn ³P₁ → ¹S₀ photons transition. Besides, bandgap closing followed by bandgap opening and the visible PL appearing at the point of the gap reversal, which is consistent with high‐pressure phase decomposition, are discovered. The high‐pressure PL results demonstrate a well‐defined pressure window (7–17 GPa) with flat maximum PL yielding and sharp edges at both ends, which may provide a great calibration tool for pressure sensors for operation in the deep sea or at extreme conditions.     

Ultrathin Layered SnSe Nanoplates for Low Voltage,High‐Rate,and Long‐Life Alkali–Ion Batteries

2D electrode materials with layered structures have shown huge potential in the fields of lithium‐ and sodium‐ion batteries. However, their poor conductivity limits the rate performance and cycle stability of batteries. Herein a new colloid chemistry strategy is reported for making 2D ultrathin layered SnSe nanoplates (SnSe NPs) for achieving more efficient alkali‐ion batteries. Due to the effect of weak Van der Waals forces, each semiconductive SnSe nanoplate stacks on top of each other, which can facilitate the ion transfer and accommodate volume expansion during the charge and discharge process. This unique structure as well as the narrow‐bandgap semiconductor property of SnSe simultaneously meets the requirements of achieving fast ionic and electronic conductivities for alkali‐ion batteries. They exhibit high capacity of 463.6 mAh g⁻¹ at 0.05 A g⁻¹ for Na‐ion batteries and 787.9 mAh g⁻¹ at 0.2 A g⁻¹ for Li‐ion batteries over 300 cycles, and also high stability for alkali‐ion batteries.     

Mechanical and thermal properties of RE4Hf3O12 (RE=Ho,Er, Tm) ceramics with defect fluorite structure

The thermal and environmental barrier coatings (T/EBC) are technologically important for advanced propulsion engine system. In this study, RE₄Hf₃O₁₂ (RE=Ho, Er, Tm) with defect fluorite structure was investigated for potential use as top TBC layer. Dense pellets were fabricated via a hot pressing method and the mechanical and thermal properties were characterized. RE₄Hf₃O₁₂ (RE=Ho, Er, Tm) possessed a high Vickers hardness of 11 GPa. The material retained high elastic modulus at elevated temperatures up to 1773 K, which made it attractive for high temperature application. The coefficient of thermal expansion (CTE) of RE₄Hf₃O₁₂ (RE = Ho, Er, Tm) laid in the range between 7 × 10⁻⁶ K⁻¹ to 10 × 10⁻⁶ K⁻¹ from 473 K to 1673 K. In addition, the rare earth hafnates exhibited lower thermal conductivity which rendered it a good candidate material for thermal barrier applications.     

Stacking-Order-Driven Optical Properties and Carrier Dynamics in ReS2

Two distinct stacking orders in ReS₂ are identified without ambiguity and their influence on vibrational, optical properties and carrier dynamics are investigated. With atomic resolution scanning transmission electron microscopy (STEM), two stacking orders are determined as AA stacking with negligible displacement across layers, and AB stacking with about a one-unit cell displacement along the a axis. First-principles calculations confirm that these two stacking orders correspond to two local energy minima. Raman spectra inform a consistent difference of modes I & III, about 13 cm⁻¹ for AA stacking, and 20 cm⁻¹ for AB stacking, making a simple tool for determining the stacking orders in ReS₂. Polarized photoluminescence (PL) reveals that AB stacking possesses blueshifted PL peak positions, and broader peak widths, compared with AA stacking, indicating stronger interlayer interaction. Transient transmission measured with femtosecond pump–probe spectroscopy suggests exciton dynamics being more anisotropic in AB stacking, where excited state absorption related to Exc. III mode disappears when probe polarization aligns perpendicular to b axis. The findings underscore the stacking-order driven optical properties and carrier dynamics of ReS₂, mediate many seemingly contradictory results in the literature, and open up an opportunity to engineer electronic devices with new functionalities by manipulating the stacking order.     

Dy<Superscript>3+</Superscript>-activated M<Subscript>2</Subscript>SiO<Subscript>4</Subscript> (M = Ba,Mg, Sr)-type phosphors

The alkaline orthosilicates of M₂SiO₄ (M = Ba, Mg, Sr) activated with Dy³⁺ and co-doped with Ho³⁺ are prepared through conventional solid-state method, i.e., mixing and grinding of solid form precursors followed by high-temperature heat treatments of several hours in furnaces, generally under open atmosphere and investigated by X-ray diffraction (XRD) to get phase properties and photoluminescence (PL) analysis to get luminescence properties. The thermal behaviours of well-mixed samples were determined by differential thermal analysis (DTA)/thermogravimetry (TG). The PL spectra show that the 478 and 572 nm maximum emission bands are attributed, respectively, to ⁴F_9/2 → ⁶H_15/2 and ⁴F_9/2 → ⁶H_13/2 transitions of Dy³⁺ ions.     

Influence of structural defects on the thermal conductivity of polycrystalline and single-crystal PbTe

We have measured the thermal conductivity of unannealed and annealed (800 K, 120 h) polycrystalline and single-crystal PbTe samples at temperatures from 80 to 303 K, evaluated the electronic and lattice components of their thermal conductivity, and determined the thermal resistivity due to structural defects, whose concentration in the unannealed single-crystal samples reaches ∼10¹⁷ cm⁻³. The results demonstrate that the thermal resistivity of the unannealed polycrystalline and single-crystal samples is 9.4 and 1.7 cm K/W, respectively. Annealing eliminates the defects, thereby increasing the lattice thermal conductivity of the material.     

Energy Storage Application of Conducting Polymers Featuring Dual Acceptors: Exploring Conjugation and Flexible Chain Length Effects

Solution-processable conducting polymers (CPs) are a compelling alternative to inorganic counterparts because of their potential for tuning chemical properties and creating flexible organic electronics. CPs, which typically comprise either only an electron donor (D) or its alternative combinations with an electron acceptor (A), exhibit charge transfer behavior between the units, resulting in an electrical conductivity suitable for utilization in electronic devices and for energy storage applications. However, the energy storage behavior of CPs with a sequence of electron acceptors (A–A), has rarely been investigated, despite their promising lower band gap and higher charge carrier mobility. Utilizing the aforesaid concept herein, four CPs featuring benzodithiophenedione (BDD), and diketopyrrolepyrrole (DPP) are synthesized. Among them, the BDDTH-DPPEH polymer exhibited the highest specific capacitance of 126.5 F g⁻¹ at a current density of 0.5 A g⁻¹ in an organic electrolyte over a wide potential window of −0.6–1.4 V. Notably, the supercapacitor properties of the polymeric electrode materials improved with increasing conjugation length by adding thiophene donor units and shortening the alkyl chain lengths. Furthermore, a symmetric supercapacitor device fabricated using BDDTH-DPPEH exhibited a high-power density of 4000 W kg⁻¹ and an energy density of 31.66 Wh kg⁻¹.     

Synthesis of Ultrathin Topological Insulator β-Ag2Te and Ag2Te/WSe2-Based High-Performance Photodetector

β-Ag₂Te has attracted considerable attention in the application of electronics and optoelectronics due to its narrow bandgap, high mobility, and topological insulator properties. However, it remains a significant challenge to synthesize 2D Ag₂Te because of the non-layered structure of Ag₂Te. Herein, the synthesis of large-size, ultrathin single crystal topological insulator 2D Ag₂Te via the van der Waals epitaxial method for the first time is reported. The 2D Ag₂Te crystal exhibits p-type conduction behavior with high carrier mobility of 3336 cm² V⁻¹ s⁻¹ at room temperature. Taking advantage of the high mobility and perfect electron structure of Ag₂Te, the Ag₂Te/WSe₂ heterojunctions are fabricated via mechanical stacking and show an ultrahigh rectification ratio of 2 × 10⁵. Ag₂Te/WSe₂ photodetector also exhibits self-driven properties with a fast response speed (40 µs/60 µs) in the near-infrared region. High responsivity (219 mA W⁻¹) and light ON/OFF ratio of 6 × 10⁵ are obtained under the photovoltaic mode. The overall performance of the Ag₂Te/WSe₂ photodetector is significantly competitive among all reported 2D photodetectors. These results indicate that 2D Ag₂Te is a promising candidate for future electronic and optoelectronic applications.     

Stable and High-Efficiency Methylammonium-Free Perovskite Solar Cells

Organic–inorganic metal halide perovskite solar cells (PSCs) have achieved certified power conversion efficiency (PCE) of 25.2% with complex compositional and bandgap engineering. However, the thermal instability of methylammonium (MA) cation can cause the degradation of the perovskite film, remaining a risk for the long-term stability of the devices. Herein, a unique method is demonstrated to fabricate highly phase-stable perovskite film without MA by introducing cesium chloride (CsCl) in the double cation (Cs, formamidinium) perovskite precursor. Moreover, due to the suboptimal bandgap of bromide (Br⁻), the amount of Br⁻ is regulated, leading to high power conversion efficiency. As a result, MA-free perovskite solar cells achieve remarkable long-term stability and a PCE of 20.50%, which is one of the best results for MA-free PSCs. Moreover, the unencapsulated device retains about 80% of the original efficiencies after a 1000 h aging study. These results provide a feasible approach to enhance solar cell stability and performance simultaneously, paving the way for commercializing PSCs.     

Europium incorporated barium titanate thin films for optical applications

BaTiO₃:Eu (BT:Eu) thin films were deposited onto quartz substrates by RF magnetron sputtering. The effect on structural, morphological, optical and photoluminescence (PL) properties in the films with different Eu concentrations (0–5 wt%) were investigated. The X-ray diffraction (XRD) pattern of the undoped BT thin film revealed a tetragonal (T) phase with orientations along (101) plane. From XRD pattern, the crystallinity of the films increased with increase in Eu concentration. The SEM images revealed that the films exhibited tetragonal shape, crack free and good adherence to the substrate. Atomic force microscopy studies showed an increase of grain growth with doping concentration. The rms roughness value increased with increase in Eu concentration and the film surface revealed positive skewness and high value of kurtosis which make them suitable for tribological applications. X-ray photoelectron spectroscopy revealed the presence of barium, titanium, europium and oxygen in BT:Eu film. An average transmittance of >80 % (in visible region) was observed for all the films. Optical band gap of Eu doped BT films decreased from 3.86 to 3.53 eV. Such films with optical properties such as high transparency, decrease in band gap and high refractive index are suitable for optoelectronic applications. PL properties showed a sharp line at 625 nm and a broad line at 552 nm due to europium (Eu³⁺) transitions. PL phenomena were observed, owing to the electronic structure of Eu³⁺ ions as well as BT nanocrystallites in the films. The sharp and intense red luminescence is useful for photoelectric devices and optical communications.     

High Efficiency Nonfullerene Polymer Solar Cells with Thick Active Layer and Large Area

In this work, high‐efficiency nonfullerene polymer solar cells (PSCs) are developed based on a thiazolothiazole‐containing wide bandgap polymer PTZ1 as donor and a planar IDT‐based narrow bandgap small molecule with four side chains (IDIC) as acceptor. Through thermal annealing treatment, a power conversion efficiency (PCE) of up to 11.5% with an open circuit voltage (V _oc) of 0.92 V, a short‐circuit current density (J _sc) of 16.4 mA cm^?2, and a fill factor of 76.2% is achieved. Furthermore, the PSCs based on PTZ1:IDIC still exhibit a relatively high PCE of 9.6% with the active layer thickness of 210 nm and a superior PCE of 10.5% with the device area of up to 0.81 cm². These results indicate that PTZ1 is a promising polymer donor material for highly efficient fullerene‐free PSCs and large‐scale devices fabrication.     

Thermal and Mechanical Properties Optimization of ABO4 Type EuNbO4 By the B-Site Substitution of Ta

Ferroelastic ABO₄ type RETaO₄ and RENbO₄ ceramics (where RE stands for rare earth) are being investigated as promising thermal barrier coatings (TBCs), and the mechanical properties of RETaO₄ have been found to be better than those of RENbO₄. In this work, B-site substitution of tantalum (Ta) is used to optimize the thermal and mechanical properties of EuNbO₄ fabricated through a solid-state reaction (SSR). The crystal structure is clarified by means of X-ray diffraction (XRD) and Raman spectroscopy; and the surface microstructure is surveyed via scanning electronic microscope (SEM). The Young’s modulus and the thermal expansion coefficient (TEC) of EuNbO₄ are effectively increased; with respective maximum values of 169 GPa and 11.2 × 10⁻⁶ K⁻¹ (at 1200 °C). The thermal conductivity is reduced to 1.52 W·K⁻¹·m⁻¹ (at 700 °C), and the thermal radiation resistance is improved. The relationship between the phonon thermal diffusivity and temperature was established in order to determine the intrinsic phonon thermal conductivity by eliminating the thermal radiation effects. The results indicate that the thermal and mechanical properties of EuNbO₄ can be effectually optimized via the B-site substitution of Ta, and that this proposed material can be applied as a high-temperature structural ceramic in future.     

Bandgap Tuning with Thermal Residual Stresses Induced in a Quantum Dot

Lattice distortion induced by residual stresses can alter electronic and mechanical properties of materials significantly. Herein, a novel way of the bandgap tuning in a quantum dot (QD) by lattice distortion is presented using 4‐nm‐sized CdS QDs grown on a TiO₂ particle as an application example. The bandgap tuning (from 2.74 eV to 2.49 eV) of a CdS QD is achieved by suitably adjusting the degree of lattice distortion in a QD via the tensile residual stresses which arise from the difference in thermal expansion coefficients between CdS and TiO₂. The idea of bandgap tuning is then applied to QD‐sensitized solar cells, achieving ≈60% increase in the power conversion efficiency by controlling the degree of thermal residual stress. Since the present methodology is not limited to a specific QD system, it will potentially pave a way to unexplored quantum effects in various QD‐based applications.