KAUR, SUMANDEEP. "STRUCTURAL AND LUMINESCENT PROPERTIES OF RARE EARTH ACTIVATED CALCIUM ALUMINOZINCATE PHOSPHOR FOR SOLID STATE LIGHTING APPLICATIONS". Thesis, 2019. http://dspace.dtu.ac.in:8080/jspui/handle/repository/16612.
Streszczenie:
Recently, the increasing requirement for energetically efficient, high resolution
displays and lighting devices necessitate the development of such devices with enhanced
brightness and good color purity. Solid state lighting (SSL) technology involves white Light
Emitting Diodes (wLEDs) which are globally used for wide-spread applications in consumer
electronics and general illumination. It offers many scientific and technological patronages
such as environmental friendliness, lower operating temperature and effective energy
utilization by saving 80% of energy consumption over conventional lighting devices. In the
light of the aforementioned advantages, wLEDs are considered to be the next generation
lighting technology. Generally, there are three different approaches which can be used for
generating white light based on solid state lighting LEDs: (1) by mixing red, green, blue (RGB)
LEDs, (2) by using an ultraviolet (UV) LED to stimulate RGB phosphors, and (3) by using a
blue-emitting GaN LED chip that excites a yellow-emitting phosphor (YAG: Ce) embedded in
an organic material; the combination of blue and yellow light makes a white-emitting LED
(pc-wLEDs). However, pc-wLEDs made by means of blue-LED + YAG: Ce yellow phosphors
suffer some weaknesses, such as poor color rendering index (CRI) and low stability of color
temperature. Since the white light is generated by the combination of blue light emitted by an
LED chip and yellow light emitted by YAG: Ce phosphors, deterioration of the chip or
YAG: Ce phosphors would cause some significant color changes. The instability of color
temperature also exists for RGB LEDs as the degradation of different color LEDs or variations
of driving current which also complicate its fabrication. In tricolor (RGB) phosphors, the
excitation is achieved by n-UV/UV LEDs. Moreover, in tricolor pc-wLED the efficiency of
red phosphors is low in comparison with green and blue phosphors and the rate of degradation
of tricolor phosphors is different. Therefore, it is necessary to develop single phase phosphor
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with tunable emission containing white emission or new red phosphor such that luminous
efficiency, CRI and correlated color temperature (CCT) can be improved.
Phosphors have been considered as key and technologically important components of
the functionality and success of many lighting and display systems over the past several years.
Versatile physical properties of the phosphors facilitate their usage in many areas, both
scientific research and practical applications. Inorganic compound incorporated with the
rare earth (RE) elements is the most prevalent protocol to synthesize brilliant luminescence
phosphor in visible region. Among different inorganic oxides, zincates have been long studied
because of its high chemical stability, high brightness, high melting point, and long persistence
time without radioactive radiations. Moreover, zincate-based compounds in suitable
composition could be potential candidates for white light emitting phosphors. When excited
with LED emission in UV or n-UV region, these novel materials have the capability to convert
the ultraviolet emission of a UV-LED into visible emission. Therefore, the work done for the
thesis is based on novel ternary calcium aluminozincate (Ca3Al4ZnO10,) as a host material for
SSL application. By incorporating suitable RE ions, the present host can be tuned for different
emissions in visible region of the electromagnetic spectrum for SSL applications. The present
thesis embraces seven chapters to accomplish the research objectives. The brief summary of
each chapter is as follows:
Chapter1 emphasize on the brief history and technological advancements of white light
generation, their advantages, related issues. Spectroscopy of RE ions and theoretical models
adopted for the analysis of observed spectral data, ionic interaction and energy transfer between
RE ions. The Judd-Ofelt (J-O) theory that elucidates radiative transition probability (AR),
branching ratio (β) and radiative lifetime (τR). The emission spectral data enables to evaluate
the CIE coordinates, color purity and correlated color temperature (CCT).
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Chapter 2 describes the methods to prepare calcium aluminozincate (Ca3Al4ZnO10: CAZ)
phosphors activated with different RE ions (Eu3+, Sm3+, and Dy3+) with varying concentrations.
It also explains the experimental tools/equipment’s used to analyse structural, morphological
and optical properties of the CAZ phosphors. The thermal, structural and vibrational properties
determined from thermal gravimetric analysis (TGA), X-ray Diffractometer, Fourier transform
infrared (FT-IR) spectroscopy, Diffuse reflectance absorbance (DRA) have also been
discussed. The morphology of the as-prepared phosphors investigated from scanning electron
microscopy and the photoluminescence properties of the CAZ phosphors doped with different
RE ions were also discussed in this chapter.
Chapter 3 explains single phase CAZ phosphor doped with Sm3+ ions with varying
concentrations prepared at 1300°C by conventional solid-state reaction (SSR) method. The
crystal structure and phase analysis of the as-prepared phosphor has been carried out by XRD
studies. Morphology and functional groups present in the phosphor have been investigated
thoroughly by using SEM and FT-IR spectral measurements respectively. Under 401nm
excitation, the as-prepared phosphor exhibits intense visible orange emission at 601nm. The
Sm3+ ions concentration is optimized to 1.0 mol% to achieve intense visible orange emission.
The PL analysis reveals that the dipole-dipole interaction is primarily responsible for the
concentration quenching observed beyond 1.0 mol% of Sm3+ ions. The PL decay study reveals
bi-exponential behaviour of decay curves with an average lifetime of the order of
microseconds. The CIE coordinates (x= 0.574 and y= 0.424) measured for the optimized
phosphor are very close to the intense orange emission coordinates specified by Nichia
Corporation developed Amber LED NSPAR 70BS (0.57, 0.42). The Spectroscopic, PL and PL
decay studies suggest the potential use of Sm3+ doped CAZ phosphors for display and white
light emitting devices.
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Chapter 4 describes about the Eu3+ ions doped CAZ phosphors without flux and blended
with various fluxes (NaF, NaCl and Na2B4O7) synthesized by using conventional SSR method
and characterized by employing XRD, SEM, DRA and Spectrofluorophotometer to study the
structural, morphological and PL properties. The Judd-Ofelt (J-O) analysis has been carried
out to get insights of optical properties. All the XRD peaks are matching well with the standard
ICDD card confirms that all the prepared phosphors consist of single phase with orthorhombic
structure. The band gap has been calculated from DRA spectra. The PL spectra recorded under
near-UV/blue excitations demonstrate a very distinct and intense red emission from all the
phosphors. The intensity of emission in these phosphors increases up to 2.0 mol% of Eu3+ ions
concentration and beyond concentration quenching is observed. The PL studies exhibit
significant enhancement in the red emission for Eu3+ doped CAZ phosphor with the
incorporation of Na2B4O7. The emission intensity has been found to increase approximately
1.5 times using NaCl and 2.5 times for Na2B4O7 in Eu3+ doped CAZ phosphor as compared to
the phosphor without any flux. The energy transfer mechanism has also been studied in detail.
The CIE chromaticity coordinates measured from the PL spectra of the prepared samples lies
in the red region of the visible spectrum. From the measured PL and CIE chromaticity co
ordinates, it was found that Eu3+ doped CAZ phosphors with optimized concentration of Eu3+
ions as 2.0 mol% and optimized flux (Na2B4O7) could be used as red phosphor in the
development of white LEDs.
Chapter 5 described about the Eu3+ doped CAZ phosphors synthesized via solid-state
reaction (SSR), combustion (CS) and Pechini sol-gel (SG) methods for better luminescent
properties and optimization of the synthesis method. The XRD, SEM, PL and PL decay curve
measurements have been recorded for the detailed investigation of the luminescence properties
of the as-synthesized phosphor. The XRD peaks indicate the complete matching of the
diffraction peaks of the as-synthesized sample with the standard data for Ca3Al4ZnO10. The
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morphology of the sample synthesized via SG method shows homogeneous distribution of
agglomerated particles with smaller particle size than those obtained from CS and SSR
methods. The detail investigation shows significant red emission enhancement in Eu3+ doped
CAZ phosphors synthesized via SG method. The obtained results suggest that the Eu3+ doped
CAZ phosphor synthesized via SG method could be a great choice as red emitter for SSL
applications.
Chapter 6 describes the preparation and characterization of a series of Dy3+ doped and
Dy3+/Eu3+ co-doped CAZ phosphors using Pechini sol-gel method. The crystal structure was
analysed by recording XRD patterns and further it was confirmed from Rietveld refinement
using Fullprof suite software. The morphology of the as-prepared phosphors was studied by
recording SEM images. The PL properties were analysed from excitation and emission spectra.
The colorimetric properties were studied by evaluating CIE coordinates and CCT. The decay
curves were recorded, and energy transfer mechanism was analysed using I-H model, Dexter
theory and Reisfeld’s approximation. The obtained results indicate that the white light from
warm to neutral to cool emission can be achieved and color tunability can also be achieved in
Dy3+/Eu3+ co-activated CAZ phosphor by varying the excitation or activator concentration in
the host lattice.
Chapter 7 summarizes the results obtained from the content presented in chapters 3 to 6.
The futuristic scope of the thesis work has also been elaborated with respect to the expected
applications of these phosphors in versatile fields.