Paulraj Arunkumar

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.

Smart design to resolve spectral overlapping of phosphor-in-glass for high-powered remote-type white light-emitting devices

The white light-emitting diode (WLED) is a state-of-the-art solid state technology, which has replaced conventional lighting systems due to its reduced energy consumption, its reliability, and long life. However, the WLED presents acute challenges in device engineering, due to its lack of color purity, efficacy, and thermal stability of the lighting devices. The prime cause for inadequacies in color purity and luminous efficiency is the spectral overlapping of red components with yellow/green emissions when generating white light by pumping a blue InGaN chip with yellow YAG:Ce³⁺ phosphor, where red phosphor is included, to compensate for deficiencies in the red region. An innovative strategy was formulated to resolve this spectral overlapping by alternatively arranging phosphor-in-glass (PiG) through cutting and reassembling the commercial red CaAlSiN₃:Eu²⁺ and green Lu₃Al₅O₁₂:Ce³⁺ PiG. PiGs were fabricated using glass frits with a low softening temperature of 600°C, which exhibited excellent thermal stability and high transparency, improving life time even at an operating temperature of 200°C. This strategy overcomes the spectral overlapping issue more efficiently than the randomly mixed and patented stacking design of multiple phosphors for a remote-type WLED. The protocol for the current design of PiG possesses excellent thermal and chemical stability with high luminous efficiency and color purity is an attempt to make smarter solid state lighting for high-powered remote-type white light-emitting devices.

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.

Influence of Ti4+ on the Electrochemical Performance of Li-Rich Layered Oxides - High Power and Long Cycle Life of Li2Ru1–xTixO3 Cathodes

Li-rich layered oxides are the most attractive cathodes for lithium-ion batteries due to their high capacity (>250 mAh g(-1)). However, their application in electric vehicles is hampered by low power density and poor cycle life. To address these, layered Li2Ru0.75Ti0.25O3 (LRTO) was synthesized and the influence of electroinactive Ti(4+) on the electrochemical performance of Li2RuO3 was investigated. LRTO exhibited a reversible capacity of 240 mAh g(-1) under 14.3 mA g(-1) with 0.11 mol of Li loss after 100 cycles compared to 0.22 mol of Li for Li2Ru0.75Sn0.25O3. More Li(+) can be extracted from LRTO (0.96 mol of Li) even after 250 cycles at 143 mA g(-1) than Li2RuO3 (0.79 mol of Li). High reversible Li extraction and long cycle life were attributed to structural stability of the LiM2 layer in the presence of Ti(4+), facilitating the lithium diffusion kinetics. The versatility of the Li2MO3 structure may initiate exploration of Ti-based Li-rich layered oxides for vehicular applications.

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.

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.

High-performance spinel-rich Li 1.5 MnTiO 4+ δ ultralong nanofibers as cathode materials for Li-ion batteries

Recently, composite materials based on Li-Mn-Ti-O system were developed to target low cost and environmentally benign cathodes for Li-ion batteries. The spinel-layered Li1.5MnTiO4+δ bulk particles showed excellent cycle stability but poor rate performance. To address this drawback, ultralong nanofibers of a Li1.5MnTiO4+δ spinel-layered heterostructure were synthesized by electrospinning. Uniform nanofibers with diameters of about 80 nm were formed of tiny octahedral particles wrapped together into 30 μm long fibers. The Li1.5MnTiO4+δ nanofibers exhibited an improved rate capability compared to both Li1.5MnTiO4+δ nanoparticles and bulk particles. The uniform one-dimensional nanostructure of the composite cathode exhibited enhanced capacities of 235 and 170 mAh g−1 at C/5 and 1 C rates, respectively. Its unique structure provided a large effective contact area for Li+ diffusion, and low charge transfer resistance. Moreover, the layered phase contributed to its capacity in over 3 V region, which increased specific energy (726 Wh kg−1) compared to the bulk particles (534 Wh kg−1).

Effect of synthesis temperature on the structural defects of integrated spinel-layered Li1.2Mn0.75Ni0.25O2+δ: a strategy to develop high-capacity cathode materials for Li-ion batteries

An integrated layered-spinel with a nominal composition of (1 − x)Li1.2Mn0.6Ni0.2O2·xLiMn1.5Ni0.5O4 (0.15 < x < 0.3) was synthesized by a hydrothermal reaction followed by firing at different temperatures. The effects of firing temperature on the phase components, cation disorder, and crystal defects, and their relationship with the electrochemical performance of the cathode material were studied. The sample fired at 650 °C showed the highest capacity of up to 320 mA h g−1 and highest initial coulombic efficiency (98%, 2–4.9 V), but the capacity decreased dramatically to only 55% after 50 cycles. The sample fired at 850 °C showed the slowest activation of the layered phase, requiring up to several dozen cycles. The intermediate firing temperature of 750 °C showed a balance between the activation rate, capacity, initial coulombic efficiency, and cycling stability, with 270 mA h g−1 after 10 cycles and a 99% capacity retention after 50 cycles. All samples showed different rates of the layered-to-spinel phase transformation, which depends on the activation rate. This study reports the relationships between synthesis conditions, structure, and electrochemical performance, providing a strategy to develop high-capacity cathode materials based on the (1 − x)Li1.2Mn0.6Ni0.2O2·xLiMn1.5Ni0.5O4 system.

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.