OPTIMIZATION OF LUMINESCENT FEATURES IN MULTICOLOR EMITTING RARE EARTH DOPED ALKALINE EARTH VANADATE PHOSPHOR FOR SOLID STATE LIGHTING APPLICATIONS

Abstract

Recent advances in solid state lighting (SSL) technology have encouraged its utilization in versatile applications. SSL technology based on phosphor converted light emitting diodes (pc-LEDs) are acting potentially as a substitute for traditional incandescent and fluorescent lamps on an account of their unprecedented luminous efficiency, low energy consumption, less emission of harmful gases, high brightness, compact design, fast switching and long working lifetimes. The pc-LEDs utilize phosphors coated on the LED chip capable of emitting light in desirable spectral regions upon an appropriate excitation. In the light of the above mentioned advantages, pc-LEDs are believed to be the next generation SSL technology and will bring a revolutionary changes in the lighting industry. For example, the white pc-LEDs have been the most preferred lighting devices for general illumination due to effective energy utilization, long lifetime, safety and so on. Moreover, pc-LEDs can be harnessed for indoor agricultural lighting owing to their excellence in controlling the spectral composition and lighting intensity to mimic the changes of sunlight during the day. Therefore, all the above mentioned fascinating features like effective energy saving and desirable light emission have enabled pc-LEDs to become economically feasible choice for general illumination and large scale indoor agricultural lighting applications around the corners of the world. The phosphor based w-LEDs can be developed by (i) coating of appropriate mixture of red, green and blue (RGB) phosphors excited with UV LED chip (ii) single yellow phosphor by a blue LED chip. However, reabsorption of blue color by RG phosphors in the former approach and lack of red component in later approach may lead to shortcomings like low color saturation, deteriorated color rendering index (CRI) and low color temperature stability. To overcome the above mentioned shortcomings, it is necessary to develop single phase phosphor doped with appropriate combination of rare earth ions (such as Dy3+/Eu3+, Tb3+/Eu3+ , Tb3+/Sm3+, Dy3+/Sm3+ etc.) providing white light emission via energy transfer or new red

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phosphor for the improvement of performance factors like luminous efficiency, CRI and correlated color temperature (CCT). Further, for plant growth under controlled environment

fitted with smart pc-LEDs, it is necessary to conduct a widespread research for deep-red, far- red and blue light emitting phosphors that can be utilised to best drive photosynthetic

metabolism and photo-morphogenesis as per the literature survey. Therefore, the ascending demand of energetically efficient lighting devices for general illumination and plant growth applications has led to a significant interest in the development of novel high quality phosphors with superior brightness, multiple emission color and excellent color purity. Besides lighting, the phosphors facilitate their utilization in diverse applications such as solar cells, bio-sensing and other optoelectronic devices due to their versatile physical, chemical and luminescent properties. In general, phosphor consisting of a host matrix (crystalline host) and an activator (luminescent center) have been pondered as a technologically significant components for the development of w-LEDs and agricultural lighting systems. In the past few decades, inorganic phosphors activated with rare earth (RE) ions have remained the prevalent protocol for fabricating pc-LEDs due to unique luminescence properties of RE ions. In such phosphors, the intermixing of oxygen atomic orbitals of host with orbitals of RE ion creates a specific crystal field environment around it such that transitions between incompletely filled 4f energy levels of RE ions deliver distinctive luminescence features. Also, the efficient energy transfer from the host crystal to the RE activators have been investigated to comprehend interesting optical phenomena. Among all the various inorganic oxides, vanadates have attracted acquiescent utilization in the wide-spread of luminescent device applications due to their wide-range of excitation wavelengths with abundant luminous colour, good physical and chemical stability. In addition, the vanadate materials are cost-effective and their preparation methods are energy efficient. The vanadate based phosphors give a broadband emission originating from inherent [VO4] 3- group. The broadband emission in the visible range by vanadate hosts can bring

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improvement in CRI and CCT values. Recent investigations have been established the possibility of achieving tunable visible emissions in RE activated vanadate phosphors via controlling [VO4] 3- to RE ions energy transfer. To harness the above mentioned precedencies, an investigation on a new ternary vanadate (CaBiVO5) phosphor doped with RE ions has been done for general and agricultural lighting applications. By incorporating suitable RE ions, the present host (CaBiVO5) can be tuned to emit different colors in the visible region suitable for pc-LEDs used in general illumination and agricultural lighting applications. Based on the extensive structural, morphological and photoluminescence characterizations, the outcome of the research work for accomplishing the research objectives has been organized in seven chapters. The brief summary of each chapter is as follows: Chapter 1 highlights the brief history, motivation, an outlook on the recent developments, potential challenges and great opportunities in white light generation and agricultural lighting. This chapter explains the basic concepts related to luminescence, spectroscopic features of RE ions, theoretical models implemented for examining the observed spectral data, and possible energy transfer processes. This chapter also present a brief viewpoint on the various characteristics and indices such as chromaticity coordinates, color purity, CCT and activation energy describing the color quality, thermal stability and performance of pc-LEDs. The importance of the present work and selected vanadate host have been discussed briefly in this chapter. At the last, the objectives of the thesis based on literature review have been included. Chapter 2 makes a thorough discussion about the different synthesis methods opted for the synthesis of single phase calcium bismuth vanadate (CaBiVO5: CBV) phosphors activated with different RE ions (Eu3+, Sm3+, Pr3+ and Dy3+). It also explicates the basic principle and working of experimental techniques employed to explore structural, morphological, optical and luminescent properties of CBV phosphors. The thermal and structural properties are studied by thermogravimetric analysis (TGA) and X-ray Diffraction (XRD) method, respectively. The

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scanning electron microscopy (SEM) reveals the morphology of the as synthesized phosphors. The optical properties are determined from diffuse-reflectance (DR) spectral measurements, while photoluminescence properties, thermal stability and decay kinetics of the CBV phosphors doped with different RE ions were investigated using spectrofluorophotometer. All these characterization techniques have been discussed in this chapter. Chapter 3 describes about the synthesis of single phase Eu3+ activated calcium bismuth vanadate (CaBiVO5) phosphors using solid state reaction method. X-ray diffraction (XRD) analysis confirms the pure phase formation and scanning electron microscope (SEM) micrographs exhibit inhomogeneous particle formation with irregular morphology of Eu3+ doped CaBiVO5 (CBV) phosphor. The photoluminescence excitation (PLE) spectrum indicates significant absorption in the ultraviolet (UV) and near ultraviolet (n-UV) spectral regions for un-doped CBV sample, whereas Eu

3+ doped CBV phosphors reveal various sharp absorption bands in n-UV and blue region along with host absorption bands. Trivalent europium activated CBV phosphors under 342 nm excitation exhibit dominant red emission peak at 613 nm wavelength accompanied by weak broadband originating from VO4 groups, whereas the phosphors under 464 nm excitation, exhibit similar emission profile with most intense one centered at 613 nm by excluding host emission bands. The energy transfer mechanism and the probable cause for concentration quenching beyond 4.0 mol% of Eu3+ ions concentration have been discussed in detail. The CIE chromaticity coordinates for the optimized phosphor, (0.551, 0.398) and (0.639, 0.358), situated in the reddish-orange and red region under 342 and 464 nm excitations, respectively. The CIE coordinates calculated based on the emission spectra measured under 464 nm excitation are close to the commercial phosphor Y2O2S: Eu3+ (0.622, 0.351). All the above mentioned results support the utilization of Eu3+ doped CBV phosphor as a potential red emitting component for luminescent devices.

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The research work described in this chapter has been published in “Ceramics International 45 (2019) 15385-15393” (Impact factor =4.527) Chapter 4 describes the optimization of synthesis procedure for Sm3+ doped CaBiVO5 phosphor by preparing through it via three different synthesis methods, solid-state reaction (SR), combustion (CB) and citrate sol-gel (SG) method to enhance the luminescent properties. The pure phase formation of CBV: Sm3+ phosphors via diverse routes (SR, CB and SG) is confirmed as diffraction peaks for all prepared phosphors correspond to the standard data (JCPDS card no: 81-1775). The SEM results reveal that CBV: Sm3+ phosphors are synthesized with improved homogeneity and shape regularity at lower reaction temperature via SG method. The excitation spectra measured by monitoring the emission at 649 nm for CBV: Sm3+ phosphors reveal significant absorption in ultraviolet (UV), near (n)-UV and blue spectral regions. The comparative photoluminescence (PL) spectra measured under 343 nm excitation for differently synthesized CBV: Sm3+ phosphors, which exhibit significantly enhanced emission intensity for SG derived phosphor than other adopted methods. The PL spectra for SG derived 1.0 mol% Sm3+ doped CBV phosphor at λex = 275 and 343 nm exhibit sharp peaks located at 566, 606 and 649 nm along with weak host emission broadband and for λex = 406 nm, similar sharp peaks of Sm3+ transitions are observed without any host emission. Unlike mostly explored Sm3+ doped phosphors, emission peak in red spectral region (649 nm) is more intense as compared to the emission peak in orange region (599 nm) in the present work. The energy transfer mechanism responsible for concentration quenching in CBV phosphors is

discussed in detail. The CBV: Sm3+ phosphors manifest color tunability from orange to orange- red region by modulating excitation from 275 nm (0.567, 0.404) to 343 nm (0.591, 0.399) and

finally to 406 nm (0.620, 0.376). The temperature-dependent PL studies indicate appreciable thermal stability of as-prepared phosphor. Above mentioned results suggest that CBV: Sm3+ phosphor has great potential for use in white light-emitting diode (w-LED) applications.

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The research work described in this chapter has been published in “Optical Materials 107 (2020) 110119” (Impact factor =3.080). Chapter 5 describes the citrate sol-gel synthesis of Dy3+ activated and Dy3+/Eu3+ bi-activated

calcium bismuth vanadate (CBV) phosphor to achieve white light emission and color- tunability. The phase purity and quasi-spherical particle with few agglomerations of the as- prepared CBV phosphors are indicated by structural and morphological characterizations,

respectively. The emission spectral properties and energy transfer in Dy3+ doped and Dy3+/Eu3+ co-doped CBV phosphors have been examined extensively. The Dexter and Reisfeld’s approximation applied to emission spectra specifies electric dipolar-dipolar interaction to be accountable for Dy3+ to Eu3+ energy transfer. In CBV: Dy3+ phosphors, co-doping with Eu3+ ion facilitates red component that ensues warm white light emission as well as flexible color tunability with increasing Eu3+ ion concentration under different excitations. The significant

findings like warm white light emission and controllable spectral composition in Dy3+/Eu3+ co- doped CBV phosphor by altering the excitation energy and co-dopant (Eu3+) concentration

potentiate it as a suitable candidate in the domain of lighting and display devices. The research work described in this chapter is communicated to an Internationally reputed Journal “Solid State Sciences (2021)” (Impact factor = 3.059) Chapter 6 describes about orthorhombic Pr3+

-doped calcium bismuth vanadate (CBV: Pr3+) phosphors synthesized via citrate-gel method. The single-phase formation of CBV: Pr3+ phosphor has been endorsed by XRD analysis. The SEM image reveals dense-particle packaging with the quasi-spherical shape for the prepared CBV: Pr3+ phosphors. Under blue light excitation, CBV: Pr3+ phosphors exhibit intense red emission bands located at 608 and 656 nm wavelengths, overlapping with the absorption spectrum of PR phytochrome, which is present in plants. To achieve the maximum red intensity, the Pr3+ ion concentration is optimized

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to be 1.25 mol% in the CBV host, after which the emission intensity ceases due to the concentration quenching. Dexter's theory disclosed the possibility of d-d multipolar interaction among Pr3+ ions at higher concentrations of Pr3+ ions in the CBV host. The CIE coordinates are found to be positioned in the pure red region for CBV: Pr3+ phosphor and in the proximity of red-emitting commercial phosphor. The temperature dependent spectral studies manifest substantial thermal stability of the as-synthesized phosphor. All the studies mentioned above specify the tremendous potentiality of thermally stable CBV: Pr3+ phosphor in agricultural lighting and w-LED applications. The research work described in this chapter has been accepted to publish in “Journal of the American Ceramic Society 104 (2021) 5764-5775” (Impact factor =3.784). Chapter 7 summarizes the research outcomes of the work described in chapters 3 to 6 and outline the future scope of the thesis work for the expected applications.