Sanjith Unithrattil

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.

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.

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.

Facile one-step fabrication of 2-layered and 4-quadrant type phosphor-in-glass plates for white LEDs: an insight into angle dependent luminescence

Phosphor-in-glass (PiG) when used in combination with a blue light emitting diode (LED) chip in a remote phosphor configuration offers precise tuning and yields higher luminous efficiencies at elevated temperatures, compared to the conventional conformal LED packaging. However, drawbacks such as spectral overlapping of the constituent phosphors and resultant reabsorption remain unresolved in multi phosphor color conversion plates. These issues were solved up to a desired extent by arranging different color-emitting PiGs, via cutting and reassembly. However, the interface of the multicolored plates acted as a dissipative layer. In this work, a novel fabrication technique was proposed to overcome this drawback by eliminating the interfacial layer through a one-step process. PiGs were fabricated using glass frits at a low softening temperature of 600 °C. As a result, a higher efficacy of the studied prototypes, i.e., a horizontal 2-layered PiG and a 4-quadrant PiG, was obtained as compared with their counterparts. The angular dependency of the luminescence of the segmented 4-quadrant type PiG was studied, and the results were discussed.

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.

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.

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.

New melilite (Ca,Sr,Ba)4MgAl2Si3O14:Eu2+ phosphor: structural and spectroscopic analysis for application in white LEDs

A series of new Eu2+-activated melilite-structured phosphor compounds was developed through solid-state reactions. The structural and spectroscopic properties of the phosphors were analyzed; all phosphors showed emissions in the blue to green regions of visible light. All developed compounds showed asymmetric broad-bands with shoulders on the lower-energy sides. The spectroscopic parameters of Eu2+ emission in the host compound were estimated and their correlation with the chemical composition of the phosphor was verified. The luminescence mechanism in the phosphors was analyzed through luminescence decay measurements. The broad emission band in the developed compound, due to transitions in the 4f65d–4f7 levels of Eu2+, was found to be ideal for application in solid-state lighting devices. The feasibility of the compound as a potential white LED phosphor was demonstrated by fabricating a white LED with excellent emission properties.

Synergic coating and doping effects of Ti-modified integrated layered–spinel Li1.2Mn0.75Ni0.25O2+δ as a high capacity and long lifetime cathode material for Li-ion batteries

An integrated layered–spinel material with a nominal composition of (1 − x)Li1.2Mn0.6Ni0.2O2·xLiMn1.5Ni0.5O4 (0.15 < x < 0.3) and crystal defects has been found to be a promising cathode material with a high capacity of 280 mA h g−1. However, capacity fading arising from Mn2+ dissolution occurred at low voltages and long cycling times. To improve the cycling stability while preserving the advantages of this cathode material, a synergic coating and doping approach was studied. This method yields a coating with a similar, but more stable, structure to that of the pristine sample. This coating is achieved by the bulk doping of the surface while maintaining the ratio of layered to spinel phases. The coating layer had a thickness of 12 to 18 nm, which increased with increasing Ti doping, and protected the sample at low voltages while maintaining the ion and charge transport channels on the surface. The Ti-doped sample enhanced the capacity retention by up to 97% after 100 cycles at C/10 and 89% after 200 cycles at 1C compared to 75% and 74% of the pristine sample, respectively. The optimized sample delivered a stable capacity of 270, 250, and 145 mA h g−1 at C/20, C/10, and 1C respectively. This study provides an effective approach to improve the cycling performance of integrated spinel-layered cathode materials.