A highly efficient deep red-emitting Mn4+-powered oxyfluoride nanophosphor developed for plant growth and optical thermometric applications.

This research mainly highlighted an intense deep red-emitting and Mn4+-powered oxyfluoride nanophosphor, Mg14Ge4.99O16F8:0.01Mn4+ (MGOF:Mn), which was synthesized via adopting a scalable synthesis route for commercial temperature sensing and artificial plant growth applications. The electron microscopic analysis confirmed the formation of nanosized particles without any defined shape or size distribution. The obtained nanophosphor exhibited sharp emission peaks at 659 nm and 631 nm under UV (317 nm) and blue excitation (417 nm) owing to Mn4+:2Eg → 4A2g and Mn4+:2T1g → 4A2g transitions, respectively. The emission spectrum is situated in the deep red region of the CIE color diagram where the red color purity approached 100% under both the excitations. The absorption efficiency and the internal and external quantum efficiencies of this red-emitting system were calculated to be 53%, ∼77%, and ∼41%, respectively, under blue excitation of 417 nm, which indicated its potential for indoor plant cultivation. A prototype red LED was fabricated by pasting the red-emitting MGOF:Mn4+ nanophosphor powder on a 410 nm blue LED chip. The resulting electroluminescence spectrum overlapped with those of the important organic pigments of normal plants. Importantly, the thermometric properties of the nanophosphor were evaluated in detail for FIR and lifetime-based thermometry applications. The examined nanophosphor showed an extreme absolute sensitivity of 0.00326 K-1 at 373 K with excellent reproducibility and temperature resolution. Because of the small particle size and high luminescence efficiency, the nanophosphor could be implemented in various nano-devices where non-contact optical thermometry is necessary for high performance.

Coconut husk-lignin derived carbon dots incorporated carrageenan based functional film for intelligent food packaging.

Carbon dots (CDs) derived from sustainable natural feed-stocks like lignin have gained wide acceptance by virtue of their renewability and promising potential in intelligent sensing applications. The precursor lignin is isolated from agro-biomass waste, coconut husk through sodium hydroxide based extraction process. CDs are synthesised from amine functionalized lignin through solvothermal process and integrated into carrageenan biopolymer matrix (1, 2 and 3 wt%). The composite film with 2 wt% CDs (CARR2CD) showed optimum fluorescent emission intensity, excellent pH dependent fluorescent color change in the food pH range, reasonable tensile strength (46.50 ± 1.32 MPa) and 27 % increase in elongation at break. CDs imparted UV-light blocking properties (70 % UV-light) and enhanced hydrophobicity of the carrageenan matrix. CARR2CD film showed 84 % visible light transparency, 79 % reduction in oxygen transmittance rate (OTR), 81 % reduction in CO2 gas permeability and excellent antioxidant and antibacterial properties (against E. coli and S. aureus). As a practical application, the developed responsive packaging material is used to track pH change associated with milk spoilage via noticeable color change in fluorescent emission of the composite film. Thus, the developed responsive composite film paves a way for use as green and sustainable transparent intelligent food packaging material.

Microwave-assisted synthesis of GdOF: Eu3+/Tb3+ ultrafine phosphor powders suitable for advanced forensic and security ink applications.

The rare-earth-doped inorganic ultrafine oxyfluoride host matrices in forensic science, especially in latent fingerprint detection and anti-counterfeiting applications, were still unexplored and may replace the existing technology owing to its high sensitivity. Herein, GdOF: Eu3+/Tb3+ ultrafine red and green phosphors were synthesized via a rapid, green microwave-assisted hydrothermal method at 150 °C. The phosphors synthesized by this novel method possess good luminescent intensity for the hypersensitive 5D0→7F2 transition of Eu3+ and 5D4→7F5 transition of Tb3+ ions as compared to the phosphors prepared via other conventional methods such as co-precipitation synthesis, sol-gel synthesis, and microwave-assisted co-precipitation synthesis. Further, an enhancement in the luminescent intensity of the ultrafine phosphor was noticed when the microwave parameters and pH values were tuned. The optimized red and green phosphors having high luminescence intensity, good color purity, and high quantum yields of 89.3%, and 71.2%, respectively, were used for the visualization of latent fingerprints on various substrates. These promising phosphors exhibited excellent visualization regardless of the background interference and limit the risk of duplication and are highly reliable. The security inks developed using these phosphors are highly efficient for anti-counterfeiting applications. These multifunctional properties of investigated phosphors can be explored for security applications.

Enriching the Deep-Red Emission in (Mg, Ba)3M2GeO8: Mn4+ (M = Al, Ga) Compositions for Light-Emitting Diodes.

Red emission from Mn4+-containing oxides inspired the development of high color rendering and cost-effective white-light-emitting diodes (WLEDs). Aiming at this fact, a series of new crystallographic site modified (Mg, Ba)3M2GeO8: Mn4+ (M = Al, Ga) compositions were developed with strong deep-red emission in the reaction to UV and blue lights. The Mg3Al2GeO8 host is composed of three phases: orthorhombic-Mg3Ga2GeO8, orthorhombic-Mg2GeO4, and cubic-MgAl2O4. However, Mg3Ga2GeO8 secured an orthorhombic crystal structure. Interestingly, Mg3Al2GeO8: Mn4+ showed a 13-fold more intense emission than Mg3Ga2GeO8: Mn4+ since Mn4+ occupancy was preferable to [AlO6] sites compared to [GaO6]. The coexisting phases of MgAl2O4 and Mg2GeO4 in Mg3Al2GeO8: Mn4+ contributed to Mn4+ luminescence by providing additional [AlO6] and [MgO6] octahedrons for Mn4+ occupancy. Further, these sites reduced the natural reduction probability of Mn4+ to Mn2+ in [AlO4] tetrahedrons, which was confirmed using cathodoluminescence analysis for the first time. A cationic substitution strategy was employed on Mg3M2GeO8: Mn4+ to improve the luminescence, and Mg3-xBaxM2GeO8: Mn4+ (M = Al, Ga) phosphors were synthesized. Partial substitution of larger Ba2+ ions in Mg2+ sites caused structural distortions and generated a new Ba impurity phase, which improved the photoluminescence. Compositionally tuned Mg2.73Ba0.27Al1.993GeO8: 0.005Mn4+ exhibited a 35-fold higher emission than that of Mg3Ga1.993GeO8: 0.005Mn4+. Additionally, this could retain 70% of its ambient emission intensity at 453 K. A warm WLED with a correlated color temperature (CCT) of 3730 K and a CRI of 89 was fabricated by combining the optimized red component with Y3Al5O12: Ce3+ and 410 nm blue LED. By tuning the ratio of blue (BaMgAl10O17: Eu2+), green (Ce0.63Tb0.37MgAl11O19), and red (Mg2.73Ba0.27Al2GeO8: 0.005Mn4+) phosphors, another WLED was developed using a 280 nm UV-LED chip. This showed natural white emission with a CRI of 79 and a CCT of 5306 K. Meanwhile, three red LEDs were also fabricated using the Mg2.73Ba0.27Al1.993GeO8: 0.005Mn4+ phosphor with commercial sources. These could be potential pc-LEDs for plant growth applications.

The elevated colour rendering of white-LEDs by microwave-synthesized red-emitting (Li, Mg)3RbGe8O18:Mn4+ nanophosphors.

The bright red emissive nature of low-cost Mn4+ ions can replace the commercially available Eu2+-doped nitrides/oxynitrides for application in white light-emitting diodes (W-LED). Herein, the Mn4+-doped Li3RbGe8O18 (LRGO) phosphor was synthesized via the solid-state reaction (SSR), microwave-assisted diffusion (MWD), and microwave-assisted sol-gel (MWS) techniques. The MWS-derived crystalline nanoparticles having sizes less than 200 nm exhibited higher red emission intensity at around 668 nm as compared to that of the micron-sized particles obtained with other approaches, owing to the improved compositional homogeneity provided by the MWS technique. The effect of microwaves was studied to gain the optimized morphology with enhanced red emission brightness. Obtained samples showed narrow red emission maxima at 668 nm under UV (300 nm) and blue (455 nm) excitations owing to 2Eg → 4A2g: Mn4+ transitions with the possibility of degeneracy. The existence of doubly degenerate forms and the splitting of 2E2g and 4A2g levels were further confirmed via low-temperature photoluminescence (PL) analysis. The emission intensity was also enhanced by the Mg2+ co-doping of MWS-derived LRGO:Mn4+ nanophosphors. Comparative photoluminescence analysis indicated that the optimized MWS route and the Mg2+ co-doping enhanced the red emission intensity by 182% as compared to the solid-state-derived LRGO:Mn4+. The optimized Mg2+ co-doped nanophosphor showed ∼99% red colour purity under UV and blue excitations. Finally, several W-LEDs were fabricated by combining the mixture of yellow-emitting YAG:Ce3+ phosphor and the optimized red-emitting LRGO:Mn4+,Mg2+ nanophosphor on a 460 nm blue-LED chip. The chromaticity of W-LEDs was tuned from bluish-white with the correlated color temperature of 6952 K, to pure white with the CCT of 5025 K. The color rendering index was also improved from 71 to 92, which could be suitable for indoor lighting applications.