Ultrafast Optically Induced Perturbation of Oxygen Octahedral Rotations in Multiferroic BiFeO3 Thin Films.

The functional properties of complex oxides, including magnetism and ferroelectricity, are closely linked to subtle structural distortions. Ultrafast optical excitations provide the means to manipulate structural features and ultimately to affect the functional properties of complex oxides with picosecond-scale precision. We report that the lattice expansion of multiferroic BiFeO3 following above-bandgap optical excitation leads to distortion of the oxygen octahedral rotation (OOR) pattern. The continuous coupling between OOR and strain was probed using time-resolved X-ray free-electron laser diffraction with femtosecond time resolution. Density functional theory calculations predict a relationship between the OOR and the elastic strain consistent with the experiment, demonstrating a route to employing this approach in a wider range of systems. Ultrafast control of the functional properties of BiFeO3 thin films is enabled by this approach because the OOR phenomena are related to ferroelectricity, and via the Fe-O-Fe bond angles, the superexchange interaction between Fe atoms.

Subpicosecond Optical Stress Generation in Multiferroic BiFeO3.

Optical excitation leads to ultrafast stress generation in the prototypical multiferroic BiFeO3. The time scales of stress generation are set by the dynamics of the population of excited electronic states and the coupling of the electronic configuration to the structure. X-ray free-electron laser diffraction reveals high-wavevector subpicosecond-time scale stress generation following ultraviolet excitation of a BiFeO3 thin film. Stress generation includes a fast component with a 1/e rise time with an upper limit of 300 fs and longer-rise time components extending to 1.5 ps. The contributions of the fast and delayed components vary as a function of optical fluence, with a reduced a fast-component contribution at high fluence. The results provide insight into stress-generation mechanisms linked to the population of excited electrons and point to new directions in the application of nanoscale multiferroics and related ferroic complex oxides. The fast component of the stress indicates that structural parameters and properties of ferroelectric thin film materials can be optically modulated with 3 dB bandwidths of at least 0.5 THz.

A zero-thermal-quenching phosphor.

Phosphor-converted white light-emitting diodes (pc-WLEDs) are efficient light sources used in lighting, high-tech displays, and electronic devices. One of the most significant challenges of pc-WLEDs is the thermal quenching, in which the phosphor suffers from emission loss with increasing temperature during high-power LED operation. Here, we report a blue-emitting Na3-2xSc2(PO4)3:xEu2+ phosphor (λem = 453 nm) that does not exhibit thermal quenching even up to 200 °C. This phenomenon of zero thermal quenching originates from the ability of the phosphor to compensate the emission losses and therefore sustain the luminescence with increasing temperature. The findings are explained by polymorphic modification and possible energy transfer from electron-hole pairs at the thermally activated defect levels to the Eu2+ 5d-band with increasing temperature. Our results could initiate the exploration of phosphors with zero thermal quenching for high-power LED applications.

A Phosphosilicate Compound, NaCa3PSiO8: Structure Solution and Luminescence Properties.

NaCa3PSiO8 was synthesized in a microwave-assisted solid-state reaction. The crystal structure of the synthesized compound was solved using a least-squares method, followed by simulated annealing. The compound was crystallized in the orthorhombic space group Pna21, belonging to Laue class mmm. The structure consisted of two layers of cation planes, each of which contained three cation channels. The cation channels in each of the layers ran antiparallel to that of the adjacent layer. All the major cations together constituted four distinct crystallographic sites. The Rietveld refinement of the powder X-ray diffraction data, followed by the maximum-entropy method analysis, confirmed the obtained structure solutions. The electronic band structure of the compound was analyzed through density function theory calculations. Luminescence properties of the compound, upon activating with Eu2+ ions, were analyzed through photoluminescence measurements and decay profile analysis. The compound was found to exhibit green luminescence centered at ∼502 nm, with a typical broadband emission due to the transition from the crystal-field split 4f65d to 4f7 levels.

Engineering the Lattice Site Occupancy of Apatite-Structure Phosphors for Effective Broad-Band Emission through Cation Pairing.

A series of britholite compounds were synthesized by simultaneous introduction of trivalent La3+ and Si4+ ions into an apatite structure. The variations in the average structure, electronic band structure, and microstructural properties resulting from the introduction of cation pairs were analyzed as a function of their concentration. The effects of the structural variance and microstructural properties on the broad-band-emitting activator ions were studied by introducing Eu2+ ions as activators. For the resulting compound, which had dual emission bands in the blue and yellow regions of the spectrum, the emission peak position and strength were dependent upon the concentration of La3+-Si4+ pairs. By engineering the relative sizes of the two possible activator sites in the structure, 4f and 6h, through the introduction of a combination of trivalent La3+ and a polyanion, the preferential site occupancy of the activator ions was favorably altered. Additionally, the activator ions responsible for the lower-Stokes-shifted blue component of the emission functioned as a sensitizer of the larger-Stokes-shifted yellow-emitting activators, and predominantly yellow-emitting phosphors were achieved. The feasibility of developing a white light-emitting solid-state device using the developed phosphor was also demonstrated.

Robust moisture and thermally stable phosphor glass plate for highly unstable sulfide phosphors in high-power white light-emitting diodes.

Potential white light-emitting diode (LED) phosphor SrGa2S4, which remains superfluous due to its unstable nature in the presence of moisture, was successfully integrated in a high-power white LED system by developing a glass-based phosphor plate. A glass system with softening temperature at around 600°C, which lies far below the possible decomposition temperature of the sulfide phosphor, provides a stable shield. Physical properties such as thermal stability, transparency, and lower porosity along with chemical stability under operating conditions of the LEDs ensure long-term operability. H2S emission due to the decomposition of sulfide phosphors, which leads to corrosion of LED electrodes, was contained using the developed plate. Higher thermal resistivity of the developed glass system in comparison with conventional resins ensures lower thermal quenching of the luminescence and better color purity.

Preparation of electrospun pyrochlore-structure KGdTa2O7:Eu3+ phosphor: the optical and structural properties for white light emitting diode applications.

Red emitting nanofibers, KGdTa2O7:Eu3+ were synthesized by electrospinning technique followed by heat treatment. As-prepared uniform fiber precursor with diameter ranging from about 700 nm to about 900 nm were calcined after removing organic species by calcination. The fiber surface become rough and diameter decreased to about 250-340 nm range due to decomposition of organic species and formation of inorganic phase. Morphology, structural and photoluminescent properties of fibers were analyzed using thermogravimetric and differential thermal analysis (TG-DTA), X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), and photoluminescence (PL). TG-DTA analysis indicates that KGdTa2O7:Eu3+ began to crystalize at 520 degrees C. Fibers annealed at 900 degrees C formed well crystallized uniform fibers. Under ultraviolet excitation KGdTa2O7:Eu3+ exhibits red emission due to transitions in 4f states of Eu3+. The excitation band is dominated by the Eu(3+)--O2-charge transfer band peaked at 289 nm. The emission peak is in the region that is ideal for red light emission.

Stabilization of Ferroelectric Phase in Highly Oriented Quinuclidinium Perrhenate (HQReO4) Thin Films.

The low-temperature processability of molecular ferroelectric (FE) crystals makes them a potential alternative for perovskite oxide-based ferroelectric thin films. Quinuclidinium perrhenate (HQReO4) is one such molecular FE crystal that exhibits ferroelectricity when crystallized in an intermediate temperature phase (ITP). However, bulk HQReO4 crystals exhibit ferroelectricity only for a narrow temperature window (22 K), above and below which the polar phase transforms to a non-FE phase. The FE phase or ITP of HQReO4 should be stabilized in a much wider temperature range for practical applications. Here, to stabilize the FE phase (ITP) in a wider temperature range, highly oriented thin films of HQReO4 were prepared using a simple solution process. A slow evaporation method was adapted for drying the HQReO4 thin films to control the morphology and the temperature window. The temperature window of the intermediate temperature FE phase was successfully widened up to 35 K by merely varying the film drying temperature between 333 and 353 K. The strategy of stabilizing the FE phase in a wider temperature range can be adapted to other molecular FE materials to realize flexible electronic devices.

Narrow-Band SrMgAl10O17:Eu2+, Mn2+ Green Phosphors for Wide-Color-Gamut Backlight for LCD Displays.

The strength of the photoluminescence excitation (PLE) spectrum of SrMgAl10O17:Eu2+, Mn2+ (SAM:Eu2+, Mn2+) phosphor increased at deep blue (∼430 nm) and red-shifted from violet to deep blue with increasing concentrations of both Eu2+ ions Mn2+ ions. Eu2+-Mn2+ energy transfer between Eu2+ ions in Sr-O layer and Mn2+ ions at Al-O tetrahedral sites was maximized, and the photoluminescence (PL) intensity of the narrow-band Mn2+ emission was improved by optimizing the concentrations of Eu2+ and Mn2+ ions. The PL emission spectrum of the (Sr0.6Eu0.4)(Mg0.4Mn0.6)Al10O17 (SAM:Eu2+, Mn2+) phosphor peaks was optimized at 518 nm at a full width at half-maximum (FWHM) of 26 nm under light-emitting diode (LED) excitation at 432 nm LED. The color gamut area of a color-filtered RGB triangle of down-converted white LEDs (DC-WLEDs) incorporated with optimum SAM:Eu2+, Mn2+ green and K2SiF6:Mn4+ (KSF:Mn4+) red phosphors is enlarged by 114% relative to that of the NTSC standard system in the CIE 1931 color space. The luminous efficacy of our DC-WLED was measured and found to be ∼92 lm/W at 20 mA. Increased energy transfers between dual activators and red-shifted band-edge and enhanced intensity of PLE spectrum indicate the possibility of developing dual-activated narrow-band green phosphors for wide-color gamut in an LCD backlighting system.

Publisher Correction: Probing molecule-like isolated octahedra via phase stabilization of zero-dimensional cesium lead halide nanocrystals.

The original version of this Article contained an error in the title, which incorrectly read 'Probing molecule-like isolated octahedra via-phase stabilization of zero-dimensional cesium lead halide nanocrystals.' The correct version states 'via phase stabilization' in place of 'via-phase stabilization'. This has been corrected in both the PDF and HTML versions of the Article.

Probing molecule-like isolated octahedra via-phase stabilization of zero-dimensional cesium lead halide nanocrystals.

Zero-dimensional (0D) inorganic perovskites have recently emerged as an interesting class of material owing to their intrinsic Pb2+ emission, polaron formation, and large exciton binding energy. They have a unique quantum-confined structure, originating from the complete isolation of octahedra exhibiting single-molecule behavior. Herein, we probe the optical behavior of single-molecule-like isolated octahedra in 0D Cesium lead halide (Cs4PbX6, X = Cl, Br/Cl, Br) nanocrystals through isovalent manganese doping at lead sites. The incorporation of manganese induced phase stabilization of 0D Cs4PbX6 over CsPbX3 by lowering the symmetry of PbX6 via enhanced octahedral distortion. This approach enables the synthesis of CsPbX3 free Cs4PbX6 nanocrystals. A high photoluminescence quantum yield for manganese emission was obtained in colloidal (29%) and solid (21%, powder) forms. These performances can be attributed to structure-induced confinement effects, which enhance the energy transfer from localized host exciton states to Mn2+ dopant within the isolated octahedra.

Colloidal Organolead Halide Perovskite with a High Mn Solubility Limit: A Step Toward Pb-Free Luminescent Quantum Dots.

Organolead halide perovskites have emerged as a promising optoelectronic material for lighting due to its high quantum yield, color-tunable, and narrow emission. Despite their unique properties, toxicity has intensified the search for ecofriendly alternatives through partial or complete replacement of lead. Herein, we report a room-temperature synthesized Mn2+-substituted 3D-organolead perovskite displacing ∼90% of lead, simultaneously retaining its unique excitonic emission, with an additional orange emission of Mn2+ via energy transfer. A high Mn solubility limit of 90% was attained for the first time in lead halide perovskites, facilitated by the flexible organic cation (CH3NH3)+ network, preserving the perovskite structure. The emission intensities of the exciton and Mn were influenced by the halide identity that regulates the energy transfer to Mn. Homogeneous emission and electron spin resonance characteristics of Mn2+ indicate a uniform distribution of Mn. These results suggest that low-toxicity 3D-CH3NH3Pb1-xMnxBr3-(2x+1)Cl2x+1 nanocrystals may be exploited as magnetically doped quantum dots with unique optoelectronic properties.

Hydrophobic Organic Skin as a Protective Shield for Moisture-Sensitive Phosphor-Based Optoelectronic Devices.

A moisture-stable, red-emitting fluoride phosphor with an organic hydrophobic skin is reported. A simple strategy was employed to form a metal-free, organic, passivating skin using oleic acid (OA) as a hydrophobic encapsulant via solvothermal treatment. Unlike other phosphor coatings that suffer from initial efficiency loss, the OA-passivated K2SiF6:Mn4+ (KSF-OA) phosphor exhibited the unique property of stable emission efficiency. Control of thickness and a highly transparent passivating layer helped to retain the emission efficiency of the material after encapsulation. A moisture-stable KSF-OA phosphor could be synthesized because of the exceptionally hydrophobic nature of OA and the formation of hydrogen bonds (F···H) resulting from the strong interactions between the fluorine in KSF and hydrogen in OA. The KSF-OA phosphor exhibited excellent moisture stability and maintained 85% of its emission intensity even after 450 h at high temperature (85 °C) and humidity (85%). As a proof-of-concept, this strategy was used for another moisture-sensitive SrSi2O2N2:Eu2+ phosphor which showed enhanced moisture stability, retaining 85% of emission intensity after 500 h under the same conditions. White light-emitting devices were fabricated using surface-passivated KSF and Y3Al5O12:Ce3+ which exhibited excellent color rendering index of 86, under blue LED excitation.

Effective Heat Dissipation from Color-Converting Plates in High-Power White Light Emitting Diodes by Transparent Graphene Wrapping.

We have developed a hybrid phosphor-in-glass plate (PGP) for application in a remote phosphor configuration of high-power white light emitting diodes (WLEDs), in which single-layer graphene was used to modulate the thermal characteristics of the PGP. The degradation of luminescence in the PGP following an increase in temperature could be prevented by applying single-layer graphene. First, it was observed that the emission intensity of the PGP was enhanced by about 20% with graphene wrapping. Notably, the surface temperature of the graphene-wrapped PGP (G-PGP) was found to be higher than that of the bare PGP, implying that the graphene layer effectively acted as a heat dissipation medium on the PGP surface to reduce the thermal quenching of the constituent phosphors. Moreover, these experimental observations were clearly verified through a two-dimensional cellular automata simulation technique and the underlying mechanisms were analyzed. As a result, the proposed G-PGP was found to be efficient in maintaining the luminescence properties of the WLED, and is a promising development in high power WLED applications. This research could be further extended to generate a new class of optical or optoelectronic materials with possible uses in a variety of applications.

A morphology, porosity and surface conductive layer optimized MnCo2O4 microsphere for compatible superior Li(+) ion/air rechargeable battery electrode materials.

Uniform surface conductive layers with porous morphology-conserved MnCo2O4 microspheres are successfully synthesized, and their electrochemical performances are thoroughly investigated. It is found that the microwave-assisted hydrothermally grown MnCo2O4 using citric acid as the carbon source shows a maximum Li(+) ion lithiation/delithiation capacity of 501 mA h g(-1) at 500 mA g(-1) with stable capacity retention. Besides, the given microsphere compounds are effectively activated as air cathode catalysts in Li-O2 batteries with reduced charge overpotentials and improved cycling performance. We believe that such an affordable enhanced performance results from the appropriate quasi-hollow nature of MnCo2O4 microspheres, which can effectively mitigate the large volume change of electrodes during Li(+) migration and/or enhance the surface transport of the LiOx species in Li-air batteries. Thus, the rationally designed porous media for the improved Li(+) electrochemical reaction highlight the importance of the 3D macropores, the high specific area and uniformly overcoated conductive layer for the promising Li(+) redox reaction platforms.

Stacked quantum dot embedded silica film on a phosphor plate for superior performance of white light-emitting diodes.

Application of quantum dots as a color converter in white light-emitting diodes (WLEDs) has been highly restrained because of its lower stability under the operating conditions of LEDs. The feasibility of using quantum dots in WLEDs has been studied and demonstrated by developing a non-conventional packing technique. Multiple core shell CuInS2/ZnS quantum dots were coated by silica, and the silica-coated quantum dots were dispersed in ethoxylated trimethylolpropane triacrylate to form a color conversion film. This along with phosphor in a glass plate made of Y3Al5O12:Ce(3+) phosphor was stacked in different configurations, and its effect on color rendering of WLEDs was studied. In addition, the configuration developed here protects the color converter from thermal strain and moisture.