xiii

ABSTRACT

Nanomaterials are cornerstones of nanoscience and

nanotechnology. Nanotechnology is an interdisciplinary area of

research found major contributions to Science and Technology in the

past few years. This field revolutionized the methods of preparation of

materials and functionality of devices. It has already shown a

significant influence in the fields like medicinal, technological,

biological etc. The reasons for selecting nano scale are the increased

surface to volume ratio and quantum confinement (QC) effect. The

increased surface to volume ratio increases the chemical reactivity

and changes the physical strength of the materials. Further, QC

effect can become much more significant in deciding the materials

properties leading to unusual behaviors.

Recently, the use of nanomaterials in the field of luminescene

has been vastly increased due to its unique optical, electronic, and

structural properties. Recent advancement in optical equipments

namely display systems, lasers, emergency lighting systems,

detection of harmful radiations, multidimensional optical data and

image storage units, has inspired to performa lot of work on nano-

structured luminescent materials also known as nanophosphors.

Nano-structured phosphors can be applied in various fields due to

decreased particle size nearer to atomic level, which considerably

changes the optical and electronic properties. Hence, the

 xiv

preparation of nanomaterials with controlled dimensionality,

chemical composition, morphology and desired properties has

become one of the most thrust areas of research.

Calcium titanate (CaTiO3) is a perovskite structured material

known for stable chemical and thermal properties with excellent

mechanical resistance. Because of these properties, this compound

is considered as a candidate for a new phosphor or even a new host

for powder lasers. The refractive index and melting point of CaTiO3

are 2.4 (at 632 nm) and 2220 K respectively. Also CaTiO3 is used in

sensors, electroluminescent devices, and host material for

luminescence of rare earth ions. Further, CaTiO3 is a promising,

multipurpose luminescent host material due to the capability of

obtaining multi-colors from various guest ions. In this host matrix,

the octahedral (TiO6) ion offers excellent mechanical resistance and

stability to the phosphor material. Moreover, in the literature,

titanate-based host lattices have been reported for their efficient

luminescence yielding. In view of the practical importance and

immense potential applications, we have chosen nano CaTiO 3 for the

present work.

Nanoparticles of undoped and RE3+ (Eu, Sm and Tb)

doped CaTiO3 were prepared using low temperature solution

combustion method with metal nitrates and urea as precursors and

fuel respectively. The powder X-ray diffraction patterns of the

product shows orthorhombic phase. The crystallite size estimated

 xv

was found to be in the range 40-65 nm. Thermoluminescence (TL)

of the gamma irradiated samples with different dose ranging from

100-500 Gy was recorded. This result shows two well resolved glow

peaks at 164C and 214C along with shouldered peak at 186C. TL

intensity increases in the beginning and after 300 Gy, it decreases

with further increase of dose. The kinetic parameters were estimated

and results were discussed in detail. The effect of rare earth ions as

a dopant to CaTiO3 was studied and the luminescence properties

were discussed in detail. The Europium doped CaTiO3 exhibit bright

red emission upon 398 nm excitation. The magnetic dipole transition

corresponding to 5D0→7F1 of Eu3+ ions (596 nm) was weaker than the

electronic transition corresponding to 5D0→7F2 of Eu3+ ions (615 nm).

The emission spectra of Sm3+ doped CaTiO3 consists of intra 4f

transitions of Sm3+, such as 4G5/2→ 6H5/2, 4G5/2→ 6H7/2, 4G5/2→ 6H9/2

and 4G5/2→ 6H11/2 respectively. Further, the emission at 601-611 nm

shows strong orange-red emission.

The emission spectra of CaTiO3:Tb3+ corresponds to 5D4 →7FJ

(J = 6, 5, 4, 3 ) transitions. The most intense emission of Tb3+ is for

the transition (5D4 →7F5) at 541 nm. Further, the estimated CIE

chromaticity co-ordinates of RE3+ doped CaTiO3 are very close to

NTSC standard values of this phosphor. Hence, the CaTiO3:RE3+

nanophosphors are promising materials in display applications.