Efficient and stable emission of warm-white light from lead-free halide double perovskites.

Lighting accounts for one-fifth of global electricity consumption1. Single materials with efficient and stable white-light emission are ideal for lighting applications, but photon emission covering the entire visible spectrum is difficult to achieve using a single material. Metal halide perovskites have outstanding emission properties2,3; however, the best-performing materials of this type contain lead and have unsatisfactory stability. Here we report a lead-free double perovskite that exhibits efficient and stable white-light emission via self-trapped excitons that originate from the Jahn-Teller distortion of the AgCl6 octahedron in the excited state. By alloying sodium cations into Cs2AgInCl6, we break the dark transition (the inversion-symmetry-induced parity-forbidden transition) by manipulating the parity of the wavefunction of the self-trapped exciton and reduce the electronic dimensionality of the semiconductor4. This leads to an increase in photoluminescence efficiency by three orders of magnitude compared to pure Cs2AgInCl6. The optimally alloyed Cs2(Ag0.60Na0.40)InCl6 with 0.04 per cent bismuth doping emits warm-white light with 86 ± 5 per cent quantum efficiency and works for over 1,000 hours. We anticipate that these results will stimulate research on single-emitter-based white-light-emitting phosphors and diodes for next-generation lighting and display technologies.

Nanoscale Ultrasensitive Temperature Sensing Based on Upconversion Nanoparticles with Lattice Self-Adaptation.

Upconversion nanoparticles have recently received increasing attention due to their outstanding performance in temperature sensing at the nanoscale. Although much effort has been devoted to improve their thermal sensitivity, there is no efficient way for achieving significant enhancement. Here, we show that lattice self-adaptation can unlock a new route for remarkably enhancing the thermal sensitivity of upconversion nanoparticles. The thermally sensitive fluorescence intensity ratio (FIR) of the dopant Er3+ is used for indicating the temperature variation, while a heterojunction of NaGdF4/NaYF4 is prepared as host material to produce a lattice distortion at the interface which is also sensitive to temperature. With the increase of temperature, the FIR of the transitions 2H11/2/4S3/2 → 4I15/2 increases, accompanied by the self-adapted decrease of interface lattice distortion that leads to the additional increase in FIR. Using core/shell upconversion nanoparticles with lattice self-adaptation, we achieve an enhanced thermal sensitivity three times higher than core-only nanoparticles.

Strong Second- and Third-Harmonic Generation in 1D Chiral Hybrid Bismuth Halides.

Breaking the symmetry of a crystal structure can enable even-order nonlinear activities, including second-harmonic generation (SHG). The emerging chiral hybrid organic-inorganic metal halides feature unique optical and electronic properties and flexible crystal structures, making them a class of promising nonlinear optical materials. However, their nonlinear response performances are currently inferior to traditional nonlinear crystals, because of the lack of research on resonant enhancement and third-harmonic generation (THG). Herein, we designed chiral hybrid bismuth halides with naturally nonsymmetrical structure to enable SHG. Simultaneously, these chiral compounds preserve 1D crystal structures to create strong free exciton, broad self-trapped exciton (STE), and discrete band energy levels, which facilitate the resonant enhancement of SHG and THG susceptibilities. These new chiral films showcase superior effective SHG susceptibility (χ(2) ∼ 130.5 pm V-1 at an interesting wavelength of 1550 nm), exceeding that of the reference, a commercial LiNbO3 (χ(2) ∼ 83.4 pm V-1) single-crystal film. Furthermore, their THG intensities are even higher than their SHG intensities, with effective THG susceptibility (χ(3)) being ∼9.0 × 106 pm2 V-2 at 1550 nm (37 times that of the reference monolayer WS2). Their high SHG and THG performances indicate the promising future of these 1D chiral hybrid bismuth halides toward nonlinear optical applications.

Experimental Determination of Magnetic Anisotropy in Exchange-Bias Dysprosium Metallocene Single-Molecule Magnets.

We investigate a family of dinuclear dysprosium metallocene single-molecule magnets (SMMs) bridged by methyl and halogen groups [Cp'2 Dy(µ-X)]2 (Cp'=cyclopentadienyltrimethylsilane anion; 1: X=CH3 - ; 2: X=Cl- ; 3: X=Br- ; 4: X=I- ). For the first time, the magnetic easy axes of dysprosium metallocene SMMs are experimentally determined, confirming that the orientation of them are perpendicular to the equatorial plane which is made up of dysprosium and bridging atoms. The orientation of the magnetic easy axis for 1 deviates from the normal direction (by 10.3°) due to the stronger equatorial interactions between DyIII and methyl groups. Moreover, its magnetic axes show a temperature-dependent shifting, which is caused by the competition between exchange interactions and Zeeman interactions. Studies of fluorescence and specific heat as well as ab initio calculations reveal the significant influences of the bridging ligands on their low-lying exchange-based energy levels and, consequently, low-temperature magnetic properties.

Carbon Quantum Dots/TiOx Electron Transport Layer Boosts Efficiency of Planar Heterojunction Perovskite Solar Cells to 19.

In planar n-i-p heterojunction perovskite solar cells, the electron transport layer (ETL) plays important roles in charge extraction and determine the morphology of the perovskite film. Here, we report a solution-processed carbon quantum dots (CQDs)/TiO2 composite that has negligible absorption in the visible spectral range, a very attractive feature for perovskite solar cells. Using this novel CQDs/TiO2 ETL in conjunction with a planar n-i-p heterojunction, we achieved an unprecedented efficiency of ∼19% under standard illumination test conditions. It was found that a CQDs/TiO2 combination increases both the open circuit voltage and short-circuits current density as compared to using TiO2 alone. Various advanced spectroscopic characterizations including ultrafast spectroscopy, ultraviolet photoelectron spectroscopy, and electronic impedance spectroscopy elucidate that the CQDs increases the electronic coupling between the CH3NH3PbI3-xClx and TiO2 ETL interface as well as energy levers that contribute to electron extraction.

Dynamic Magnetic and Optical Insight into a High Performance Pentagonal Bipyramidal DyIII Single-Ion Magnet.

The pentagonal bipyramidal single-ion magnets (SIMs) are among the most attractive prototypes of high-performance single-molecule magnets (SMMs). Here, a fluorescence-active phosphine oxide ligand CyPh2 PO (=cyclohexyl(diphenyl)phosphine oxide) was introduced into [Dy(CyPh2 PO)2 (H2 O)5 ]Br3 ⋅2 (CyPh2 PO)⋅EtOH⋅3 H2 O, and combined dynamic magnetic measurement, optical characterization, ab initio calculation, and magneto-optical correlation of this high-performance pseudo-D5h DyIII SIM with large Ueff (508(2) K) and high magnetic hysteresis temperature (19 K) were performed. This work provides a deeper insight into the rational design of promising molecular magnets.

Magnetic tuning of upconversion luminescence in Au/NaGdF4:Yb3+/Er3+ nanocomposite.

Lanthanide-doped upconversion nanoparticles (UCNPs) NaGdF4:Yb3+/Er3+ have received increasing attention due to their unique optical-magnetic bifunctional properties. Here, we show that the luminescent intensity from NaGdF4:Yb3+/Er3+ nanoparticles decreases monotonously with increasing the applied magnetic field from 0 to 37.1 T, while plasmon-enhanced upconversion luminescence in Au/NaGdF4:Yb3+/Er3+ nanocomposite is independent of a magnetic field lower than 6 T. The surface plasmon resonances could compensate for the energetic mismatching between the excitation light and the energy-level gaps induced by magnetic field and enhance the radiative efficiency, which is the main factor for achieving this stable upconversion emission in this nanocomposite under a magnetic field not higher than 6 T. These findings provide a novel route for exploring the magnetic control of upconversion luminescence in lanthanide-doped bifunctional nanoparticles.

Spin-exciton interaction and related micro-photoluminescence spectra of ZnSe:Mn DMS nanoribbon.

For their spintronic applications the magnetic and optical properties of diluted magnetic semiconductors (DMS) have been studied widely. However, the exact relationships between the magnetic interactions and optical emission behaviors in DMS are not well understood yet due to their complicated microstructural and compositional characters from different growth and preparation techniques. Manganese (Mn) doped ZnSe nanoribbons with high quality were obtained by using the chemical vapor deposition (CVD) method. Successful Mn ion doping in a single ZnSe nanoribbon was identified by elemental energy-dispersive x-ray spectroscopy mapping and micro-photoluminescence (PL) mapping of intrinsic d-d optical transition at 580 nm, i.e. the transition of 4 T 1(4 G) â†’ 6 A 1(6 s),. Besides the d-d transition PL peak at 580 nm, two other PL peaks related to Mn ion aggregates in the ZnSe lattice were detected at 664 nm and 530 nm, which were assigned to the d-d transitions from the Mn2+-Mn2+ pairs with ferromagnetic (FM) coupling and antiferromagnetic (AFM) coupling, respectively. Moreover, AFM pair formation goes along with strong coupling with acoustic phonon or structural defects. These arguments were supported by temperature-dependent PL spectra, power-dependent PL lifetimes, and first-principle calculations. Due to the ferromagnetic pair existence, an exciton magnetic polaron (EMP) is formed and emits at 460 nm. Defect existence favors the AFM pair, which also can account for its giant enhancement of spin-orbital coupling and the spin Hall effect observed in PRL 97, 126603(2006) and PRL 96, 196404(2006). These emission results of DMS reflect their relation to local sp-d hybridization, spin-spin magnetic coupling, exciton-spin or phonon interactions covering structural relaxations. This kind of material can be used to study the exciton-spin interaction and may find applications in spin-related photonic devices besides spintronics.

UV-free red electroluminescence from the cross-connected p-ZnO:Cu nanobushes/n-GaN light emitting diode.

A p-ZnO:Cu/n-GaN heterojunction light emitting diode (LED) is fabricated by growing cross-connected p-ZnO:Cu nanobushes on n-GaN film using chemical vapor deposition under oxygen-rich condition. This LED emits stable UV-free red light of 677 nm and 745 nm. The electroluminescence (EL) light of this LED is tuned from ultraviolet (UV) of ZnO/GaN to UV-free red by the electronic interfacial transition from the conduction band of n-GaN to the deep acceptor levels of p-ZnO:Cu. Both room temperature and low temperature (5K) photoluminescence spectra of ZnO:Cu indicate that the UV emission of ZnO is suppressed and the green emission is enhanced, which implies the formation of Cu-related deep levels introduced by intentionally doping Cu in ZnO. These deep levels help the EL red emission in the LED device.

Near-UV-enhanced broad-band large third-order optical nonlinearity in aluminum nanorod array film with sub-10 nm gaps.

Plasmonic nanostructures with sub-10 nm gaps possess intense electric field enhancements, leading to their high reputation for exploring various functional applications at nanoscale. Till now, although large amounts of efforts have been devoted into investigation of such structures, few works were emphased on the nonlinear optical properties in near-ultraviolet (UV) region. Here, by combining sputtering technique and an optimized anodic aluminum oxide (AAO) template growing method, we obtain aluminum (Al) nanorod array film (NRAF) with average rod diameter and gap size of 50 and 7 nm, respectively. The Al-NRAF exhibits large third-order optical nonlinear susceptibility (χ(3)) and high figure of merit (χ(3)/α) over a broad wavelength range from 360 to 900 nm, and reaches their maximums at the shortest measured wavelength. In addition, comparisons with Au-NRAF and Ag-NRAF samples further confirm that Al-NRAF has better nonlinear optical properties in the blue and near-UV wavelength regions. These results indicate that Al nanostructures are promising candidates for nonlinear plasmonic applications at blue and near-UV wavelengths.

Plasmon-Enhanced Second-Harmonic Generation Nanorulers with Ultrahigh Sensitivities.

Attainment of spatial resolutions far below diffraction limits by means of optical methods constitutes a challenging task. Here, we design nonlinear nanorulers that are capable of accomplishing approximately 1 nm resolutions by utilizing the mechanism of plasmon-enhanced second-harmonic generation (PESHG). Through introducing Au@SiO2 (core@shell) shell-isolated nanoparticles, we strive to maneuver electric-field-related gap modes such that a reliable relationship between PESHG responses and gap sizes, represented by "PESHG nanoruler equation", can be obtained. Additionally validated by both experiments and simulations, we have transferred "hot spots" to the film-nanoparticle-gap region, ensuring that retrieved PESHG emissions nearly exclusively originate from this region and are significantly amplified. The PESHG nanoruler can be potentially developed as an ultrasensitive optical method for measuring nanoscale distances with higher spectral accuracies and signal-to-noise ratios.

Intrinsic Defect-Driven Synergistic Synaptic Heterostructures for Gate-Free Neuromorphic Phototransistors.

The optoelectronic synaptic devices based on two-dimensional (2D) materials offer great advances for future neuromorphic visual systems with dramatically improved integration density and power efficiency. The effective charge capture and retention are considered as one vital prerequisite to realizing the synaptic memory function. However, the current 2D synaptic devices are predominantly relied on materials with artificially-engineered defects or intricate gate-controlled architectures to realize the charge trapping process. These approaches, unfortunately, suffer from the degradation of pristine materials, rapid device failure, and unnecessary complication of device structures. To address these challenges, an innovative gate-free heterostructure paradigm is introduced herein. The heterostructure presents a distinctive dome-like morphology wherein a defect-rich Fe7S8 core is enveloped snugly by a curved MoS2 dome shell (Fe7S8@MoS2), allowing the realization of effective photocarrier trapping through the intrinsic defects in the adjacent Fe7S8 core. The resultant neuromorphic devices exhibit remarkable light-tunable synaptic behaviors with memory time up to ≈800 s under single optical pulse, thus demonstrating great advances in simulating visual recognition system with significantly improved image recognition efficiency. The emergence of such heterostructures foreshadows a promising trajectory for underpinning future synaptic devices, catalyzing the realization of high-efficiency and intricate visual processing applications.

Dipole plasmon resonance induced large third-order optical nonlinearity of Au triangular nanoprism in infrared region.

Au triangular nanoprisms with strong dipole plasmon absorption peak at 1240 nm were prepared by wet chemical methods. Both numerical calculations and experiments were carried out to investigate the optical properties of the samples. Finite difference time domain (FDTD) and Local Density of States (LDOS) calculations demonstrate that strong electric field enhancement and large LDOS can be obtained at tip areas of the Au triangular nanoprisms. Z scan techniques were used to characterize the nonlinear absorption, nonlinear refraction, as well as one- and two-photon figures of merit (W and T, respectively) of the sample. The results show that maximum nonlinear refractive index can be obtained around the resonance absorption wavelength of 1240 nm, detuning the wavelength from the absorption peak will lead to the decrease of the nonlinear refractive index n(2), while the nonlinear absorption coefficient ß doesn't change much with the wavelength. This large wavelength dependence of n(2) and small change of ß enable the sample to satisfy the all-optical switching demand of W> 1 and T< 1 easily in a large wavelength range of 1200-1300 nm. These significant nonlinear properties of the sample imply that Au triangular nanoprism is a good candidate for future optical switches in infrared optical communication wavelength region.

Magnetic field induced great photoluminescence enhancement in an Er3+:YVO4 single crystal used for high magnetic field calibration.

An optical technique is proposed for the accurate calibration of pulsed high magnetic fields utilizing the magnetic field dependent photoluminescence (PL) properties in an Er(3+):YVO(4) single crystal at 80 K. Bright green PL emissions are excited by a 487.5 nm laser line and can be enhanced greatly by a magnetic field at certain field values (B(c)). Since the B(c)'s under 10 T are extremely stable for a given sample at a certain temperature, and the FWHM of the enhancement peaks are less than 0.9 T, an Er(3+):YVO(4) single crystal is proven to be a good candidate for pulsed high magnetic field calibration. The detailed processes and numerous advantages of the technique are presented in this work.

Manipulation and Optical Detection of Artificial Topological Phenomena in 2D Van der Waals Fe5 GeTe2 /MnPS3 Heterostructures.

2D ferromagnet is a good platform to investigate topological effects and spintronic devices owing to its rich spin structures and excellent external-field tunability. The appearance of the topological Hall Effect (THE) is often regarded as an important sign of the generation of chiral spin textures, like magnetic vortexes or skyrmions. Here, interface engineering and an in-plane current are used to modulate the magnetic properties of the nearly room-temperature 2D ferromagnet Fe5 GeTe2 . An artificial topology phenomenon is observed in the Fe5 GeTe2 /MnPS3 heterostructure by using both anomalous Hall Effect and reflective magnetic circular dichroism (RMCD) measurements. Through tuning the applied current and the RMCD laser wavelength, the amplitude of the humps and dips observed in the hysteresis loops can be modulated accordingly. Magnetic field-dependent hysteresis loops demonstrate that the observed artificial topological phenomena are induced by the generation and annihilation of the magnetic domains. This work provides an optical method for investigating the topological-like effects in magnetic structures and proposes an effective way to modulate the magnetic properties of magnetic materials, which is important for developing magnetic and spintronic devices in van der Waals magnetic materials.

Manipulating exchange bias in 2D magnetic heterojunction for high-performance robust memory applications.

The exchange bias (EB) effect plays an undisputed role in the development of highly sensitive, robust, and high-density spintronic devices in magnetic data storage. However, the weak EB field, low blocking temperature, as well as the lack of modulation methods, seriously limit the application of EB in van der Waals (vdW) spintronic devices. Here, we utilized pressure engineering to tune the vdW spacing of the two-dimensional (2D) FePSe3/Fe3GeTe2 heterostructures. The EB field (HEB, from 29.2 mT to 111.2 mT) and blocking temperature (Tb, from 20 K to 110 K) are significantly enhanced, and a highly sensitive and robust spin valve is demonstrated. Interestingly, this enhancement of the EB effect was extended to exposed Fe3GeTe2, due to the single-domain nature of Fe3GeTe2. Our findings provide opportunities for the producing, exploring, and tuning of magnetic vdW heterostructures with strong interlayer coupling, thereby enabling customized 2D spintronic devices in the future.

Nonlocal Manipulation of Magnetism in an Itinerant Two-Dimensional Ferromagnet.

Two-dimensional (2D) magnets are crucial in the construction of 2D magnetic and spintronic devices. Many devices, including spin valves and multiple tunneling junctions, have been developed by vertically stacking 2D magnets with other functional blocks. However, owing to limited local interactions at the interfaces, the device structures are typically extremely complex. To solve this problem, the nonlocal manipulation of magnetism may be a good solution. In this study, we use the magneto-optical Kerr effect technique to demonstrate the nonlocal manipulation of magnetism in an itinerant 2D ferromagnet, Fe3GeTe2 (FGT), whose magnetism can be manipulated via an antiferromagnet/ferromagnet interface or a current-induced spin-orbital torque placed distant from the local site. It is discovered that the coupling of a small piece of MnPS3 (∼40 µm2) with FGT can significantly enhance the coercive field and emergence of exchange bias in the entire FGT flake (∼2000 µm2). Moreover, FGT flakes with different thicknesses have the same coercive field at low temperatures if they are coupled together. Our study provides an understanding of the basic magnetism of 2D itinerant ferromagnets as well as opportunities for engineering magnetism with an additional degree of freedom.

Air-Stable 2D Cr5 Te8 Nanosheets with Thickness-Tunable Ferromagnetism.

2D magnetic materials have aroused widespread research interest owing to their promising application in spintronic devices. However, exploring new kinds of 2D magnetic materials with better stability and realizing their batch synthesis remain challenging. Herein, the synthesis of air-stable 2D Cr5 Te8 ultrathin crystals with tunable thickness via tube-in-tube chemical vapor deposition (CVD) growth technology is reported. The importance of tube-in-tube CVD growth, which can significantly suppress the equilibrium shift to the decomposition direction and facilitate that to the synthesis reaction direction, for the synthesis of high-quality Cr5 Te8 with accurate composition, is highlighted. By precisely adjusting the growth temperature, the thickness of Cr5 Te8 nanosheets is tuned from ≈1.2 nm to tens of nanometers, with the morphology changing from triangles to hexagons. Furthermore, magneto-optical Kerr effect measurements reveal that the Cr5 Te8 nanosheet is ferromagnetic with strong out-of-plane spin polarization. The Curie temperature exhibits a monotonic increase from 100 to 160 K as the Cr5 Te8 thickness increases from 10 to 30 nm and no apparent variation in surface roughness or magnetic properties after months of exposure to air. This study provides a robust method for the controllable synthesis of high-quality 2D ferromagnetic materials, which will facilitate research progress in spintronics.

Spin mapping of intralayer antiferromagnetism and field-induced spin reorientation in monolayer CrTe2.

Intrinsic antiferromagnetism in van der Waals (vdW) monolayer (ML) crystals enriches our understanding of two-dimensional (2D) magnetic orders and presents several advantages over ferromagnetism in spintronic applications. However, studies of 2D intrinsic antiferromagnetism are sparse, owing to the lack of net magnetisation. Here, by combining spin-polarised scanning tunnelling microscopy and first-principles calculations, we investigate the magnetism of vdW ML CrTe2, which has been successfully grown through molecular-beam epitaxy. We observe a stable antiferromagnetic (AFM) order at the atomic scale in the ML crystal, whose bulk is ferromagnetic, and correlate its imaged zigzag spin texture with the atomic lattice structure. The AFM order exhibits an intriguing noncollinear spin reorientation under magnetic fields, consistent with its calculated moderate magnetic anisotropy. The findings of this study demonstrate the intricacy of 2D vdW magnetic materials and pave the way for their in-depth analysis.

Band gap shift and the optical nonlinear absorption of sputtered ZnO-TiO2 films.

ZnO-TiO2 composite films with different Zn/Ti atomic ratios were prepared with radio frequency reactive sputtering method. The Zn percentage composition (f(Zn)) dependent optical band gap and optical nonlinear absorption were investigated using the transmittance spectrum and the Z-scan technique, respectively. The results showed that composite films with f(Zn) in the range of 23.5%-88.3% are poor crystallized and their optical properties are anomalous which exhibit adjustable optical band gap and large optical nonlinear absorption. The optical absorption edge shifted to the blue wavelength direction with the increasing of f(Zn) and reached the minimum value of 285 nm for the sample with f(Zn) = 70.5%, which has the largest direct band gap of 4.30 eV. Further increasing of f(Zn) resulted in the red-shift of the optical absorption edge. The maximum optical nonlinear absorption coefficient of 1.5 x 10(3) cm/GW was also obtained for the same sample with f(Zn) = 70.5%, which is more than 40 times larger than those of pure TiO2 and ZnO films.