1.

Introduction

1.1. Nanoscience and Nanotechnology

From the last decades, new directions of modern research have emerged in the most
exciting and fastest growing fields usually goes under the name nanoscience and
technology. Nanoscience and nanotechnology arises from the combination of physics,
chemistry, material science, biology and electronics to create new functional
nanoscale dimensions systems of the order of a billionth of a meter. The research in
this direction has been attracted more by the recent availability of new and high
revolutionary instruments and techniques which are able to improve our investigation
abilities concerning the material properties with a resolution close to atomic scale.
Such technological advances have inspirited new pioneering experiments which have
revealed new physical properties and effects of matter at an intermediate level
between atomic and bulk. Nanotechnology is the engineering of functional system at
the molecular scale.

Originally nanotechnology refers to the ability to project and construct by

using tools and techniques being developed today for the completion of highly
advanced products. Nanotechnology refers to the study, manipulation and utilization
of nano size materials for making different devices. Generally speaking
nanotechnology used to describe materials that are characterized by structural features
ranging in size from 1 to 100 nanometers (nm). The brilliant concept of the nano came
up with the physicist Richard Feynman, Nobel Prize winner for Physics in 1965 when
he said “there is plenty of room at the bottom” during a conference of the American
Physical Society [1]. The first use of the term “nanotechnology” was by Norio
Taniguchi in 1974 at the International Conference on Precision Engineering (ICPE).
His definition referred to “production technology to get extra high accuracy and ultra
fine dimensions, i.e., the preciseness and fineness on the order of 1 nm (nanometer),
10−9 m in length” [2].

Nanostructured materials have indeed become a very active research field in

the area of material science involving organic, inorganic and composite materials
have a significant fraction of grain boundaries with a high degree of disorder of atoms
along the grain boundaries and a large surface area to volume. Chemical composition
of the phases and the interfaces between nanograins and must be controlled as well.

Chapter 1 1
One of the most important characteristics of nanostructured materials is the significant
dependence of certain properties upon the size in the nanoscale region. Earlier people
believed that material properties can be changed only by varying the chemical
composition. But later it has been found that the material properties can be tuned by
varying the size of the material without changing the chemical composition. The
transition from micron sized particles to nanoparticles leads to a number of changes in
their physical properties. The major change is the increase in the surface area to
volume ratio, as the size of the particle moves to a regime where quantum
confinement effects are predominant. These new properties or phenomena will not
only satisfy everlasting human curiosity, but also promise a new advancement in
technology. Another very important aspect of nanotechnology is the miniaturization
of current and new instruments, sensors and machines that will have great impact on
the world we live in. Nanotechnology has an extremely broad range of potential
applications from nanoscale electronics and optics, to nanobiological systems.

For example electronic property, with quantum size effect caused by spatial
confinement of delocalized valence electrons is directly dependent on the particle
size. Small particle size permits conventional restrictions of phase equilibrium and
kinetics to be overcome during the synthesis and processing by the combination of
short diffusion distances and high driving forces of available large surfaces and
interfaces. A wide range of materials, including metals, metal oxides and ceramics in
crystalline, quasi-crystalline or amorphous phases have been synthesized as nanosized
or nanostructured materials. The large surface area gives higher reactivity and
diffusivity. Thus novel property may results from surface defects.

In addition, there are other structural features in the nanostructured materials

that depend on the manner in which these materials are synthesized and processed
such as surface pores, grain boundary junctions, and crystal lattice defects. The
change in lattice parameters can be attributed to changes in surface stress, while
reduction in the melting temperature results from the increase in surface free energy.
This opens the doors for tailoring given properties by careful synthesis of the building
blocks, and their assembly to fabricate functional materials with improved properties.

Further, nanotechnology was also expanded extensively to other fields due to

the novel properties of nanomaterials discovered and to be discovered. For example,
nanowires can be potentially used in nanophotonics, laser [3], nanoelectronics [4],

Chapter 1 2
solar cells [5], resonators [6] and high sensitivity sensors [7]. Nanoparticles can be
potentially used in catalysts [8], functional coatings, nanoelectronics [9], energy
storage [10], drug delivery [11] and biomedicines [12]. Nanostructured thin
films/powders can be used in light emitting devices, displays and high efficiency
photovoltaics.

Nanotechnology has an extremely broad range of potential applications in

nanoscale electronics, optics, nanobiological systems, nanomedicine etc. Therefore it
requires formation and contribution from multidisciplinary of physicists, chemists,
materials scientists, engineers, molecular biologists, pharmacologists and others to
work together on

 synthesis and processing of nanomaterials and nanostructures,

 understanding the physical properties related to the nanometer scale,
 design and fabrication of nano devices or devices with nanomaterials
as building blocks, and
 design and construction of novel tools for characterization of
nanostructures and nanomaterials.

The term nonmaterial cover various types of nanostructure materials which

posses at least one dimension in the nanometer range. Various nanostructures which
include zero dimension nanostructures such as metallic, semiconducting and ceramic
nanoparticles; one dimension nanostructures such nanowires, nanotubes and
nanorods; two dimension nanostructures such as quantum well structures. Besides this
individual nanostructures, ensembles of these nanostructures form high dimension
arrays, assemblies and super lattices. The properties of materials with nanometer
dimensions are significantly different from those of atoms and bulk materials. This is
mainly due to the nanometer size of the materials which render them:

large fraction of surface atoms,

high surface energy,
spatial confinement,
reduced imperfections,

which do not exist in the corresponding bulk materials [13]. Due to their small
dimensions, nanomaterials have extremely large surface area to volume ratio, which
makes a large fraction of atoms of the materials to be on the surface or interfacial

Chapter 1 3
atoms, resulting in more surface dependent material properties. Especially when the
sizes of nanomaterials are comparable to Debye length, the entire material will be
affected by the surface properties of nanomaterials [14, 15]. This in turn may enhance
or modify the properties of the bulk materials. The quantum confinement of
nanomaterials has profound effects on the properties of nanomaterials. The energy
band structure and charge carrier density in the materials can be modified quite
differently from their bulk counterpart and this in turn will modify the electronic and
optical properties of the materials.

The manipulation of material properties by one dimensional, two-dimensional

and three-dimensional confinement will revolutionize the luminescence area with
huge advances in digital memory storage, image processing, optical
telecommunications, photonics, etc [16-19]. Nanomaterials with different size and
shape such as nanoparticles, nanowires, nanotubes, nanorods and nanocomposites are
currently the focus of intense investigations due to their potential for revolutionary
technological applications. Further nano and micro-crystal materials with identical
compositions often possess special properties but common particle size does not have
special properties. Nanotechnology is an interdisciplinary research field in which
many physicists, chemists, biologists, materials scientist and other specialists are
involved. Fig. 1.1 shows the fundamental triads (tree map) of material science.

Fig. 1.1. Tree map of material science

Chapter 1 4
1.2. Properties of nanomaterials

A number of physical phenomena become noticeably pronounced as the size of the

material decreases. The electronic properties of solids are significantly altered with
reduction in particle size. This effect becomes dominant when the nanometer size
range is reached. Additionally, a number of physical properties change when
compared to macroscopic systems. In the following section, mechanical, thermal,
electronic, optical and chemical properties of materials with nanosize dimensions are
discussed.

Mechanical properties: As a primary microstructural parameter, grain size imparts

significant influence on the mechanical behavior of materials. The drive for refining
grain size comes from the demand for increased strength in many applications.
Certainly, the grain size, or average grain diameter, influences the mechanical
properties of a material. It is important to note that properties of the nanostructure
material not only depend on the average grain size, but are also strongly influenced by
the grain size distribution and the grain boundary structure. Due to the nanometer
size, many of the mechanical properties of the nonmaterial are different from the bulk
materials including the hardness, elastic modulus, fracture toughness, scratch
resistance and fatigue strength etc. An enhancement of mechanical properties of
nonmaterial can result due to this modification, which are generally resulting from
structural perfection of the materials [13, 20]. Moreover, the external surfaces of
nanomaterials also have less or free of defects compared to bulk materials, serving to
enhance the mechanical properties of nanomaterials [13]. The enhanced mechanical
properties of the nanomaterials could have many potential applications both in
nanoscale such as mechanical nano resonators, sensors, microscope probe tips and
nanotweezers for nanoscale object manipulation, light weight high strength materials,
flexible conductive coatings, wear resistance coatings, tougher and harder cutting
tools etc.

Thermal properties: By controlling the structures of materials at nanoscale

dimensions, the properties of the nanostructures can be controlled and tailored in a
very predictable manner to meet the needs for a variety of applications. Many
properties of the nanoscale materials have been well studied. However, the thermal
properties of nanomaterials have only shown a slower progress. This is partially due
to the difficulties of experimental measuring and controlling the thermal transport in

Chapter 1 5
nano scale dimensions. Atomic force microscope (AFM) has been introduced to
measure the thermal transport of nanostructures with nanometer-scale high spatial
resolution, providing a promising way to probe the thermal properties with
nanostructures [21]. In nanomaterials systems, several factors such as the small size,
the special shape, the large interfaces modify the thermal properties of the
nanomaterials, rendering them the quite different behavior as compared to the
macroscopic materials. As the dimension goes down to nanoscales, the size of the
nanomaterials is comparable to the wavelength and the mean free path of the phonons,
so that the phonon transport within the materials will be changed significantly due the
phonon confinement and quantization of phonon transport, resulting in modified
thermal properties. The special structure of nanomaterials also affects the thermal
properties. For example, because of the tubular structures of carbon nanotubes, they
have extremely high thermal conductivity in axial directions, leaving high anisotropy
in the heat transport in the materials [22].

Electrical properties: The changes which occur in electronic properties as the system
length scale is reduced are related mainly to the increasing influence of the wave-like
property of the electrons (quantum mechanical effects) and the scarcity of scattering
centres. As the size of the system becomes comparable with the de Broglie
wavelength of the electrons, the discrete nature of the energy states becomes apparent.
The effects of size on electrical conductivity of nanostructures and nanomaterials are
complex, since they are based on distinct mechanisms. These mechanisms can be
generally grouped into four categories: surface scattering including grain boundary
scattering, quantized conduction including ballistic conduction, Coulomb charging
and tunneling, and widening and discrete of band gap and change of microstructures.
In addition, increased perfection, such as reduced impurity, structural defects and
dislocations, would affect the electrical conductivity of nanostructures and
nanomaterials. Nanomaterials can hold considerably more energy than conventional
ones because of their large grain boundary area. They are materials in which an
optical absorption band can be introduced, or an existing band can be altered by the
passage of current through these materials, or by the application of an electric field.
All these phenomena can be utilized to produce radically different types of
components for electronic, optoelectronic and information processing applications,
such as resonant tunneling transistors and single-electron transistors.

Chapter 1 6
Optical properties: Nanocrystalline systems have attracted much interest for their
novel optical properties, which differ remarkably from bulk crystals. Key contributory
factors include quantum confinement of electrical carriers within nanoparticles,
efficient energy and charge transfer over nanoscale distances and in many systems a
highly enhanced role of interfaces. The linear and nonlinear optical properties of such
materials can be finely tailored by controlling the crystal dimensions, and the
chemistry of their surfaces, fabrication technology becomes a key factor for the
applications. The reduction of materials‟ dimension has pronounced effects on the
optical properties. The size dependence can be generally classified into two groups.
One is due to the increased energy level spacing as the system becomes more
confined, and the other is related to surface plasmon resonance. The quantum size
effect is most pronounced for semiconductor nanoparticles, where the band gap
increases with a decreasing size, resulting in the interband transition shifting to higher
frequencies [23, 24].

In a semiconductor, the energy difference between the completely filled

valence band and the empty conduction band is of the order of a few electron volts
and increases rapidly with a decreasing size [24]. Quantum confinement produces a
blue shift in the band gap as well as appearance of discrete subbands corresponding to
quantization along the direction of confinement. The optical properties of
nanostructured semiconductors are highly size dependent and thus can be modified by
varying the size alone, keeping the chemical composition intact. The luminescent
emission from the semiconductor nanostructures can be tuned by varying the size of
the nanoparticles.

Chemical properties: One of the important factors for the chemical applications of
nanomaterials is the increment of their surface area which increases the chemical
activity of the material. Due to their enhanced chemical activity, nanostructural
materials can be used as catalysts to react with such noxious and toxic gases as carbon
monoxide and nitrogen oxide in automobile catalytic converters and power generation
equipment to prevent environmental pollution arising from burning gasoline and coal.
Catalysis using finely divided nanoscale systems can increase the rate, selectivity and
efficiency of chemical reactions such as combustion or synthesis rate simultaneously,
significantly reducing waste and pollution. Nanoparticles often exhibit new chemistry
as distinct from their larger particulate counterparts; for example, many new

Chapter 1 7
medicines are insoluble in water when in the form of micron sized particles but will
dissolve easily when in a nanostructured form.

Bulk gold is chemically inert and thus considered to be not active or useful as
a catalyst. However, gold nanoparticles can have excellent catalytic properties. For
example, gold nanoparticles with clean surface have demonstrated to be extremely
active in the oxidation of carbon monoxide if deposited on partly reactive oxides, such
as Fe2 O3, NiO and MnO, alumina and titania and were also found to be reactive.
Further gold nanoparticles also exhibit extraordinary high activity for partial oxidation
of hydrocarbons, hydrogenation of unsaturated hydrocarbons and reduction of
nitrogen oxides.
1.3. Phosphors and luminescence mechanism

1.3.1. Fundamentals of Phosphors

The word „phosphor‟ comes from the Greek language and means „light bearer‟, to
describe light-emitting or luminescent materials; barium sulfide is one of the earlier
known naturally occurring phosphors [25]. A German physicist, in 1888, used the
word luminescence (emission of light). This word originates from the Latin word
lumen, which means light. Presently, the word luminescence is defined as a
phenomenon in which the electronic state of a substance is excited by some kind of
external energy and the excitation energy is given off as light. Here, the word light
includes not only electromagnetic waves in the visible region of 400 to 700 nm, but
also those in the neighboring regions on both ends, i.e., the near‐ultraviolet and the
near‐infrared regions.

The excitation of the electron is caused by absorption of energy from an

external source such as another electron, a photon or an electric field. An excited
electron occupies a quantum state whose energy is above the minimum energy ground
state. In semiconductors and insulators, the electronic ground state is commonly
referred to electrons in the valence band, which is completely filled with these
electrons. The excited quantum state often lies in the conduction band, which is empty
and is separated from the valence band by an energy gap called the band gap,
Therefore, unlike metallic materials, small continuous changes in electron energy
within the band are not possible. Instead a minimum energy equal to the band gap is
necessary to excite an electron in a semiconductor or insulator, and the energy

Chapter 1 8
released by de-excitation is often nearly equal to the band gap. The band gap of a
semiconductor material is such that at room temperature very few electrons are
promoted from the valence band to the conduction band leaving holes in the valence
band.

Materials exhibiting luminescence are known as “Luminophors” or

“Phosphors”. Usually, the phosphors are in the form of crystalline powder with size
ranging between 1 μm and 100 μm. Unidimensional materials of less than 100 nm
sizes are termed as nanophosphors. They are characterized by marked absorption and
emission with higher efficiency and lifetime. The remarkable luminescence efficiency
and greatly reduced radiative lifetime have rendered nanophosphor compounds of
considerable interest.

1.3.2. Basic ingredients of phosphors

A phosphor for its complete specification requires three basic ingredients. They are
host material or matrix lattice
an activator and
flux
1.3.2.1. Host material or Matrix lattice

In addition to the relative ionic sizes of the cation and anion [26], the type of
chemical bonding is one of the determinative factors in selecting the base material for
phosphor preparation. Although no general rule could be formulated for finding which
base material and which impurities combine to form efficient phosphor [27]. It is
sufficient to note that crystal with covalent, ionic or mixed ionic covalent bindings are
of utmost importance as base Materials for many types of phosphors like insulators
which tend to have predominantly ionic binding and semiconductors which tend to
have predominantly covalent binding.

Even though luminescence emission is often produced by dopant ions, the

influence of the host lattice cannot be underrated. It is possible to change the optical
properties of the luminescent ion by changing the host lattice. The main factors
responsible for different optical properties of a luminescent ion in different host
matrices are listed below [28].
Covalency: When the covalency between ligands and luminescent ion
increases, the interaction between the electrons of the luminescent ion reduces

Chapter 1 9
 and electrons spread out over wider orbitals. As a result, electronic transition
energy between energy levels shift to lower values and this effect is called the
nephelauxetic effect. [28, 29]. Additionally, at higher covalency the
interaction between luminescent ion and ligands increases, consequently the
charge-transfer transition occurs at lower energy.
Crystal field: While covalence causes a global shift of the energy levels, the
crystal field, which is the electric field of the surroundings on the ion under
consideration, leads to a splitting of the energy levels.

Depending on the application area the required features of the host matrix change.
However, several basic requirements can be outlined.

 The host materials should be transparent at the emission wavelengths of the

luminescent ion. That is the band gap of the host materials should be wider
than the emission energy.
 To facilitate the substitution of dopant ions and host cations, their sizes should
match. Further, the oxidation state of the substituted cation should
preferentially be the same as that of the dopant ion.
 Crystalline materials are preferred [30] for higher luminescence intensity,
since the disordered structure of the host materials can cause a decrease in the
luminescent intensity.

1.3.2.2. Activators

Impurities that provide localized energy levels in the forbidden energy gap of a
semiconductor and an insulator are called activators [31], with some exception
[32,33] most of the inorganic materials have their luminescence due to the presence of
specific activators [34, 35-37]. In other inorganic compounds [33, 38, 39]
luminescence in pure state, either the missing component of lattice or non-
stoichiometry provide the activating energy level and thus the luminescence is
attributed to self activation.

1.3.2.3. Flux

Since long it has been realized that the preparation of phosphor requires the presence
of readily recrystallizing medium known as flux. It consists of readily fusible salt,
mixture of salts such as NaCl, KCl, KBr, LiCl, NH 4Cl, Na2SO4, NaF, CaCl2, CaF2,
MgF2, Li2SO 4, Borax etc. The requirement of an ideal flux is that it should be a

Chapter 1 10
substance which will melt at or below the firing temperature and that the solubility of
the base material in it should be sufficient to effect their rapid crystallization.

The following function gives the clear understanding about complex nature of
flux in luminescence processes

It increases the speed of reactions at relatively lower temperatures [40, 41]

It promotes crystal growth at lower temperatures and facilitates the
incorporation of activators and its homogenous distribution in the host lattice
[40, 42]
It acts as inhibitor of sublimation [39]
Flux promotes the formation of defects or lattice distortion and thus affects the
luminescence efficiency
Some authors also shown in many cases that [43 - 45] flux serves as charge
compensating agent.

1.3.3. Preparation parameters of a phosphor

Phosphor characteristics common to all in some deviation from the ideal crystal
structure either because of small quantities of impurities or of structural defects.
Generally key to the preparation of useful phosphors is the combination of particular
host matrix with specific activators and flux. The activator is introduced in the host
lattice by proper heat treatment of the homogeneous mixture of host crystal and
activator together with a specific flux at elevated temperatures.

The choice of a method for the preparation of phosphors depends upon several
characteristics such as the chemical, physical and mechanical qualities desired in the
finished phosphor. Different phosphors thus require different methods of preparation.

The processes of luminescence affected by number of factors which are

closely connected with crystal imperfections [46].

In general, the variables that determine the nature of the resultant phosphor are

* Lattice structure of the host material [47]

* Nature of activator and its concentration [48,49]
* The nature and quantity of flux [50-53]
* Purity of ingredients and of reaction vessels
* Grain size of ingredients

Chapter 1 11
 * Method of mixing the ingredients
* Reaction vessels for firing
* Furnace
* Temperature and time of firing
* Choice of ambient atmosphere during firing
* Cooling of the phosphor
* Grinding and grain size of the finished phosphor and
* Mechanical handling of phosphor

1.3.4. Luminescence Mechanisms

Luminescent materials, also called phosphors, are mostly solid inorganic
materials consisting of a host lattice, usually intentionally doped with impurities [54]
(Fig. 1.2). The impurity concentrations generally are low in view of the fact that at
higher concentrations the efficiency of the luminescence process usually decreases
(concentration quenching). In addition, most of the phosphors have a white body
color. Especially for fluorescent lamps, this is an essential feature to prevent
absorption of visible light by the phosphors used. The absorption of energy, which is
used to excite the luminescence, takes place by either the host lattice or by
intentionally doped impurities. Figure 1.2 Shows the mechanism in which the
luminescent material containing activator ions A (ions showing the desired emission)
and sensitizing ions S (on which UV excitation can take place).

Fig. 1.2. Luminescent mechanism

Chapter 1 12
In most cases, the emission takes places on the impurity ions, when they also generate
the desired emission, are called activator ions. When the activator ions show too weak
an absorption, a second kind of impurities can be added (sensitizers), which absorb
the energy and subsequently transfer the energy to the activators. This process
involves transport of energy through the luminescent materials. Quite frequently, the
emission color can be adjusted by choosing the proper impurity ion, without changing
the host lattice in which the impurity ions are incorporated.

On the other hand, quite a few activator ions show emission spectra with
emission at spectral positions which are hardly influenced by their chemical
environment. This is especially true for many of the rare-earth ions. To avoid the
occurrence of the transient decay processes such as concentration quenching, which
diminish the efficiency of the luminescence process, the impurity concentrations used
are usually low.

1.3.5. Applications of nanophosphors

Persistence luminescence materials, especially those activated with rare earth ions
(nanophosphors), have been extensively investigated during the last decade due to
their potential in various applications such as displays, cathode-ray-tube (CRT) color
television, medical imaging and lighting, fluorescent lamps and x-ray fluorescent
screens, plasma display panels (PDP‟s) and fiber amplifiers. Figure 1.3 shows some
of these applications. Major advances of CRTs and fluorescent lamps resulted from
the improvement of the phosphors. The fluorescent lamp is basically operated with
low pressure mercury discharge lamp connected to a layer of phosphor particles inside
the surface of the glass tube. Phosphors are used to provide the backlighting for liquid
crystal displays (LCDs), which are used in the place of CRTs in products such as
mobile phones and for large flat panel screens. Their main advantages are high
resolution, low scattering, very high contrast ratios with wider viewing angles, high
quality colours and low power consumption [55]. The phosphors will continue to be
used to produce "white" light emitting diode (LED) light sources [56]. LEDs are used
in applications such as video displays, computer and advertising panels, general
lighting and traffic signals. The advantages of LEDs are longer lifetime, compactness,
efficient light output and reduced power consumption (it uses milliwatts of power
compared to watts of power for incandescent and fluorescent lamps [57]).

Chapter 1 13
Field emission display (FEDs) technology: The Field Emission Display technology
is very promising and much research has been conducted to bring them to the market
place to compete with or to replace Cathode Ray Tubes [58, 59]. Such interest arose
due to its potential to provide displays with very high brightness, high contrast ratio,
light weight, and low-power consumption. Both Field Emission Displays and Cathode
Ray Tubes require electron bombardment to produce luminescence. However, these
two technologies differ in a sense that FEDs operate at low voltages (300 V to 10 kV)
and much higher current densities (100 mA) while CRT operates at 25-30 kV and low
current densities [58, 60, 61]. Just like in a CRT, the image in a FED is produced by
impinging electrons which are generated by sharp emitters onto a phosphor coated
screen [58, 59]. Phosphors used in FEDs must not be only efficient at low voltages,
but must also be resistant to Coulombic aging and saturation at high current densities.

Plasma display panels (PDPs): Unlike LCD which is restricted to a small viewing
angle and by a slow response, PDP provides a rapid response and a large viewing
angle [62]. Hence, is regarded as the most promising candidate for large TV displays.
PDP operates similar to fluorescence lamps [63, 64] except that it uses neon or xenon
gasses instead of mercury and argon used in fluorescent lamps. Neon and xenon
gasses generate peak wavelengths at 147 and 173 nm in the vacuum ultraviolet
(VUV) spectral region [63, 65, 66]. The red, green, and blue PDP phosphors absorb
this strong energetic VUV radiation from inert gas plasma and re-radiate the energy as
visible light to produce colours that appear in screen.

In addition, their applications are being expanded to optoelectronics of image

storage and detectors of energy radiation [67, 68, 69]. They can also be used in other
simple applications, such as luminous paints with long persistent phosphorescence
[70], phosphorescence pigments for luminous watches and clocks [71] and emergency
lighting, safe traffic and wall paintings [72].

Chapter 1 14
 Fig. 1.3. Phosphor devices [29]

1.4. Classification of Luminescence

To indicate the means of excitation, the phenomenon of luminescence is grouped into

the fallowing headings [73]. Table 1.1 shows the various types of luminescence,
excitations source and its applications.

Chapter 1 15
 Table 1.1. Types of luminescence, excitations source and its applications.

Source of Excitation Luminescence Applications

Chemical reactions Chemiluminescence Adenosine Triphosphate

(ATP), Lower Limit of
Detection (LLD),
Immunoassay
Mechanical energy Triboluminescence Crash prevension

Sound wave in liquid Sonoluminescence Marine biology

Electric field or current Electroluminescence Electron discharge,

Electrolumiescent (EL)
panels

Heating after prior storage Thermoluminescence Environmental protection

of energy

Electron beam/ Cathode Cathodoluminescence CTR - Cerro Toledo

rays
Photons( UV / visible light)
Rhyolite, FED - Field
emission displays, VFD -
vacuum flourescwnt
displays
Photoluminescence Lamps, Displays,
Diagnosis, Dentistry

Bio chemical reactions Bioluminescence Oxy. Detection, Chem

Assay
Ions (Particles) Ionoluminescence Material analysis, Defect
studies

Ionizing radiations (α, β, γ, Radioluminescence Radiology

X - rays)

Infra Red light Anti-stokes luminescence Authentication, Display,

Medical, Security

1.5. Photoluminescence (PL)

When the phosphor material absorbs a photon (i.e. electromagnetic radiation) an

electron may be excited to a higher energy quantum state. If the excited electron
returns to a lower energy quantum state by emission of a photon, the process is called
photoluminescence (PL). PL in solids is classified in view of the nature of the

Chapter 1 16
electronic transitions producing the luminescence. In the case of photoluminescence a
molecule absorbs light of wavelength λ 1 decays to lower energy excited electronic
state and then emits light of wavelength λ 2 as it radiatively decays to its ground
electronic state. Generally the wavelength of emission λ2 is longer than the excitation
wavelength, but in resonance emission λl=λ2. Luminescence bands can be either
fluorescence or phosphorescence, depending on the average lifetime of the excited
state, which is much longer for phosphorescence than fluorescence. The relative
broadness of the emission band is related to the relative difference in equilibrium
distance between the excited emitting state and the ground electronic state.
Photoluminescence of a molecular species is different from emission from an atomic
species. In the case of atomic emission both the excitation and emission are at the
resonance wavelengths, in contrast excitation of a molecular species usually results in
an emission that has a longer wavelength than the excitation wavelength.
Photoluminescence can occur in gas, liquid and solid phases. An energy level diagram
as in Fig. 1.4 shows the radiative and non-radiative transitions that lead to the
observation of molecular photoluminescence.

The spin multiplicities of a given electronic state can either a paired electron
(singlet) or an unpaired electron (triplet). The ground electronic state is normally a
singlet state and is designated as S0. Excited electronic states are either singlet (S2, S1)
or triplet (T 1) states. When the molecule absorbs light an electron is promoted within
10-14 - 10-15 seconds from the ground electronic state to an excited state that posses the
same spin multiplicity as the ground state. This excludes a triplet-excited state, as the
final state of electronic absorption because the selection rules for electronic transition
dictates the spin state should be maintained upon excitation. A pattern of radiative and
non-radiative processes usually occur following the absorption light to the observation
of molecular luminescence.

1.5.1. Non-radiative relaxation processes

Internal conversion: If the molecule is excited to a higher energy excited singlet

state S2 (Figure 1.4), a rapid non-radiative relaxation usually occurs to the lowest
energy singlet excited state S1 . Relaxation processes between electronic states of like
spin multiplicity such as S1 and S2 are called internal conversion. It is normally occurs
on a time scale of 10 -14 seconds.

Chapter 1 17
 Fig. 1.4. Energy diagram for electronic transition

Vibrational relaxation: Generally excitation occurs to higher vibrational level of the

target-excited state. The excited molecules normally relax rapidly to the lowest
vibrational level of the excited electronic state. These non-radiative processes are
called vibrational relaxation. It occurs within 10-14 to 10-12 seconds, a time much
shorter than the typical luminescence lifetime. So such processes occur prior to
luminescence.

Intersystem crossing: Non-radiative relaxation processes can also occur between

excited states of different spin multiplicity. Such relaxation process is known as
intersystem crossing. The relaxation from S I to T 1 in Figure 1.4 is an example of
intersystem crossing.

Non-radiative de-excitation: The above mentioned non-radiative processes occur

very rapidly and release small amount of energy .The rest of the energy is dissipated
either radiatively, by emission of photons, or non-radiatively by the release of thermal
energy. The non-radiative decay of excitation energy which leads to the decay of

Chapter 1 18
excited molecule to the ground electronic state is called nonradiative de-excitation.
The amount of energy released in the form of heat is very small and cannot be
measured experimentally. The evidence for non-radiative de-excitation process is the
quenching of luminescence. In solid-state luminescent materials the crystal vibrations
(phonons) provide the mechanism for non-radiative de-excitation.

1.5.2. Radiative processes – Fluorescence and Phosphorescence

In luminescent materials, fluorescence and phosphorescence are distinguished by

whether the transition to emit light is allowed or forbidden by spin selection rules.
Fluorescence refers to the emission of longer wavelength light associated with a
radiative transition from an excited electronic state that has the same spin multiplicity
as the ground electronic state. The radiative transition S 1 - S2 in Figure 1.4 represents
fluorescence. Since fluorescence transitions are spin allowed they occur very rapidly
and average lifetimes of the excited states responsible for are typically less than 10 -5
seconds. Electronic transitions between states of different spin multiplicity are spin
forbidden, however it becomes more probable when spin orbit coupling increases.
The result of spin orbit coupling is the mixing of excited singlet and triplet states. This
mixing removes the spin forbidden nature of the transitions between pure singlet and
pure triplet states. Therefore if intersystem crossing populates the triplet-excited state
then luminescence might occur from the triplet state to the ground state.

Phosphorescence refers to the emission of light associated with a radiative

transition from an electronic state that has a different spin multiplicity from that of
ground electronic state. The radiative transition T 1 - S0 in Figure 1.4 represents the
phosphorescence. Since phosphorescence transitions are spin forbidden they occur
slowly and so the average lifetime for such emission typically ranges from 10 -5 to
several seconds. Phosphorescence is also known as 'delayed fluorescence.

1.5.3. Lanthanides

In this study, different rare earth ions were used to prepare the phosphor powders. The
lanthanide elements (or rare earth elements) correspond to a series of elements with a
related electronic structure. These ions play an important role in modern technology
as the active constituents of many optical materials. There are a vast number of
applications for these rare-earth-activated materials and much of today's cutting-edge
optical technology and emerging innovations are enabled by their unique properties.

Chapter 1 19
The „rare-earths‟ is the traditional name for the lanthanides. The lanthanides are the
elements in the periodic table from La (Z = 57) to Lu (Z = 71) as given in Table 1.2.

Table 1.2. Electronic ground state and ion size of lanthanide elements

Electronic configuration
Atomic
Element Valence
number Neutral atom Trivalent ion
57 Lanthanum 3 4f06s2 5d 4f0

58 Cerium 3,4 4f16s2 5d 4f1

59 Praseodymium 3 4f36s2 4f2

60 Neodymium 3 4f46s2 4f3

61 Promethium 3 4f56s2 4f4

62 Samarium 2,3 4f66s2 4f5

63 Europium 2,3 4f76s2 4f6

64 Gadolinium 3 4f76s2 5d 4f7

65 Terbium 3,4 4f96s2 4f8

66 Dysprosium 3,4 4f106s2 4f9

67 Holmium 3 4f116s2 4f10

68 Erbium 3 4f126s2 4f11

69 Thulium 3 4f136s2 4f12

70 Ytterbium 2,3 4f146s2 4f13

71 Lutetium 3 4f146s2 5d 4f14

Chapter 1 20
Lanthanide ions are formed by ionization of a number of atoms located in a periodic
table after lanthanum. Trivalent lanthanides ions have an outer electronic
configuration 5s2 5p6 4fn, where n varies from 1 (Ce3+) to 13 (Yb3+) and indicates the
number of electrons in the incomplete 4f shell [74, 75]. The 4fn electrons are primarily
responsible for the optical properties of the rare earths. Fig. 1.5 represents a
substantial part of the energy levels of the trivalent ions of lanthanides that originate
from the 4fn configuration as a function of the atomic number.

Fig. 1.5. Dieke diagram showing the energy levels of the trivalent lanthanides [16].

Chapter 1 21
1.5.4. Some luminescent centres

Trivalent europium ion (Eu3+): The outer electronic configuration in trivalent

lanthanide ions is 5s25p64f n, where n indicates the number of electrons in the unfilled
n
4f shell while the 4f electrons are the valence electrons that are responsible for the
optical transitions [77]. The luminescence from Eu 3+ usually consists of narrow lines
in the red spectral range and has been extensively used as phosphors in many fields,
such as display applications, and the material shows typical f-f transitions of Eu3+ ions
[78]. The transitions are 5D0→7 FJ, the most common of which have J=0, 1, 2, 3 and 4.
Eu3+ emission is characterized by quenching, magnetic, and electric dipole transitions,
respectively. The 5D0 →7F2 peak (612 nm) is highly sensitive to the structure and
environment effects. The intensity of electric dipole transitions strongly depends on
the site symmetry whereas the magnetic dipole transitions do not depend on the site
symmetry as they are parity allowed. If Eu3+ occupies an inversion symmetry site in
the crystal site, the orange red emission, magnetic dipole transition 5D0→7 F1 which is
about 590 nm is dominant. If the Eu 3+ does not occupy an inversion symmetry site,
the red emission, electric dipole transition 5 D0→7 F2 (around 612 nm) is the dominant
peak. In addition to 5D0, the emission from 5D1 and 5D2 can also be observed in the
green and blue region for some hosts [79].

Trivalent cerium ion (Ce3+): There has been a wide investigation of the optical
properties of cerium doped compounds. There is great interest in Ce3+ doped
compounds or crystals for applications as phosphors, white LEDs, scintillators and
tuneable lasers [80, 81]. Most Ce3+ activated phosphors show broad band emission
range in the UV to visible due to the 4f05d1–4f1 transition of Ce3+ [82]. In 4f-5d
transitions, one of the 4f electrons is excited to a 5d orbital of higher energy [83]. This
n n-1
type of excitation absorption is usually denoted 4f → 4f 5d and is typically
observed in Ce3+ ions (4f 1 configuration). Since empty, half filled or completely filled
electron shell configurations are the most stable ones, the excess 4f electron of Ce3+ is
easily transferred to the 5d orbital. Unlike 4f-4f transitions, 4f-5d transitions are
allowed, which results in strong and broad absorption cross-sections.

Usually, the trivalent cerium ion Ce3+ with the electronic configuration 4f1
yields two levels 2 F7/2 and 2F5/2 as the ground states separated by ~2000 cm-1 due to
spin-orbit coupling [84]. The lower manifold 2F5/2 is populated and the manifold 2 F7/2
is almost empty at room temperature. The excited 5d 1 configuration is split by the

Chapter 1 22
crystal field in 2 to 5 components. The total splitting amounts to some 15000 cm -1. As
the positions of the energy levels of 5d excited states of Ce3+ are not only affected by
the crystal field but also by the degree of covalent bonding, it causes variations in the
absorption and emission from UV to long wavelength by varying the host lattice [85].
In some hosts there is problem that the Ce 3+ is converted to Ce4+ which is non-
luminescent because the 4f levels are unoccupied. To convert non-luminescent Ce4+
ions to the luminescent Ce3+ charge state requires annealing in a reducing atmosphere
e.g. H2 [86, 87].

Trivalent terbium ion (Tb3+): The trivalent terbium ion (Tb3+) has been extensively
studied due to its dark green emission under ultraviolet (UV) excitation. The green
emission is attributed to transitions of the type 5D4→ 7FJ, consisting of 5D4 →7F6 (489
nm), 5D4→ 7F5 (543 nm), 5D4→7 F4 (588 nm) and 5D4→ 7F3 (625 nm). Among these
transitions the most intense is the 5D4→7 F5 which is situated around 543 nm. Also,
there can be considerable blue emission from the 5D3 level. The intensity ratio of the
green emission from 5D4 to the blue emission from 5D3 depends mainly on the Tb3+
concentration. For high concentration the electrons from 5D3 level are nonradiatively
dissipated through cross relaxation to the lower energy level of 5D4 decreasing the
blue emission. The 4f-4f transitions are forbidden by the parity selection rule [88, 89],
which states that electronic transitions between energy levels with the same parity
cannot occur. In reality, this transition can occur because the parity rule is relaxed due
to perturbation such as electron vibration coupling and uneven crystal field term from
host lattice.

The 4f electrons are well shielded from the surrounding external fields by the
5s and 5p electrons. The influence of the crystal field on the optical transitions within
the 4fn configuration is very small. Therefore the emission is independent on the host.
The excitation of Tb3+ is divided into two regions, the first from f-d excitation and the
other from f-f excitation. The range for the f-d excitation is below 300 nm while the f-
f excitation band is between 300 and 500 nm. The f-f excitation is weak because it is
not allowed. The 4f-5d transitions are dipole allowed unlike the f-f transitions, and the
5d states are diffuse and overlap with ligand orbitals. For this reason the 4f-5d
excitation strongly depends on the crystal field of the host and therefore varies over
the spectral range of the deep UV region.

Chapter 1 23
Trivalent Dysprosium ion (Dy3+): Dy3+ emits in two spectral regions: (A) 470 to 500
nm region due to the 4 F9/2 → 6 H15/2 transition. (B) 570 to 600 nm region due to the
6
F15/2→ 6F11/2 transition [90]. However, the direct UV excitation of this ion is not
effective due to the relatively large energy of both the charge transfer as well as the
4f85d1 , states. Excitation by means of host complex ions may be achievable by an
energy transfer process [91].

Trivalent bismuth ion (Bi3+): Metallic impurities with an outer ns2 configuration
ground state such as Ti +, Pb2+, Bi3+ and Sb3+ ions may also be excellent luminescence
activators [80]. Bi atoms are the heaviest member with an electronic configuration
[Xe] 4f145d106s2p3 and Bi3+ ions, with outermost 6s2 electrons, have been widely used
as activators for various host materials including oxides, phosphates, aluminates and
borates [92]. The 6s2 ground state has a single energy level 1 S0 while the 6s16p1
excited configuration has energy levels 3P0 , 3 P1, 3P2 and 1P1 in order of increasing
energy. Electron transitions between the 1S0 ground state and the 3 PJ levels are spin
forbidden, but optical absorption can occur to the high energy 1 P1 level [85].

However, spin-orbit coupling between the 1 P1 and 3 P1 levels makes the lower
energy transitions 1 S0 ↔ 3P1 possible and the luminescence from Bi3+ activated
phosphors is usually attributed to this transition. In some materials the 1P1 ↔ 1 S0
emission is also observed [93]. The outer electron orbitals of Bi3+ are not shielded as
in the case of the 4f energy levels of trivalent lanthanide ions, so the broad
luminescence band shows a strong dependence on the composition and crystal
structure of the host lattice and the emission wavelength is tuneable from the UV,
through blue to green [94].

1.5.5. Energy transfer process in phosphors

The enhanced luminescence intensity (efficiency) from the phosphor can be achieved
via energy transfer between the donor (sensitizer) and the acceptor. The study of
energy transfer between a pair of identical or non identical rare earth ions has been
done by several researchers [95-97].

Consider the case of a non-radiative energy transfer between a donor (e.g. a

sensitizer S) and an acceptor (e.g. an activator A). Upon excitation with an
electromagnetic radiation, the sensitizer S absorbs an incoming photon and is raised to
an excited state S*. It then returns to the ground state by transferring its energy to the

Chapter 1 24
activator A (without photon emission), which is then excited to its excited state A*
the energy transfer can be denoted as:
S* + A → S + A* (1.0)
Where the asterisk (*) indicates an excited state.

The energy transfer can be governed by electrostatic multipolar interactions or

by exchange interactions. In the case of an energy transfer by electrostatic interaction,
there is no physical contact between the interacting sensitizer and activator, and no
electron is exchanged between them. It is sufficient that S* induces a dipole
oscillation on A. This type of interaction occurs when the interacting sensitizer and
activator are far from each other. Exchange interactions only occur if the donor and
acceptor ions are close enough for direct overlap of their electronic wave functions.
Consequently, energy transfer due to quantum mechanical exchange interactions
between the S* and A ions is only important at very short distances (nearest neighbor
positions).

The theory of energy transfer resonance derived by Dexter has revealed that
two luminescence centers, a Donor and an Acceptor within a certain distance, R with
a certain interaction (i.e. exchange or multipole-multipole interaction) may be in
resonance and transfer excitation energy from one (donor) to another (acceptor). The
distance R between the two must be shorter than the critical distance which is
approximately twice the radius of a sphere. can be practically calculated using the
relation given by:

Where,
Xc represent the critical concentration at which the quenching occurs,
V is the volume of the sphere,
N is the Z ions in the unit cell [98, 99].

When an energy donor S and an acceptor A are close enough that their
electronic wave functions overlap each other, the excitation energy of the sensitizer S
can be transferred to an acceptor A via exchange interactions.

Chapter 1 25
1.5.6. Luminescence quenching

Concentration quenching: The efficiency of luminescence as a function of activator

concentration in singly activated phosphors increases at low concentrations reaches a
maximum and decreases again at higher concentrations. This is known as
concentration quenching [100]. Some researchers [101-103] have explained the
concentration quenching on the assumption that the proximity of a given activator to
another activator or certain types of lattice defect increases the probability of
radiationless transitions. According to Dexter and Schulmann [104] resonance transfer
of energy from one activator to another activator takes place until the energy reaches
near one of the quenching sites. These quenching sites may be another activator or
lattice defects.

Thermal quenching: The decrease of luminescence intensity with increasing

temperature called as a thermal quenching [105, 106, 107]. This is may be due to the
local heating by energetic electrons or photons. This process is known to occur at high
temperatures when thermal vibrations of atoms surrounding luminescent center
transfer energy away from the center leading to a non-radiative recombination, and a
subsequent dissipation of the excess energy as phonons in the host lattice [108].

When the system is thermally excited, it undergoes a vertical transition from

ground state to the excited state. In a short space of time the system may then
undergo a radiative transition from higher state to lower state with excess energy
dissipated as heat. Since non-radiative processes can now also take place, the
observed luminescence intensity from a large quantity of excited ions will diminish.

1.5.7. Color coordinates

Color characterization of a spectral distribution is done to gauge the quality of its

chromaticity. This is accomplished using color coordinates [109]. In 1931, the
commission Intemationale de I'Eclairage (CIE) established an international standard
for quantifying all visible colors, known as CIE color coordinates. The CIE has
defined a system that classifies color according to the the human visual system
(HVS). Using this system we can specify any color in terms of its CIE coordinates.
The CIE coordinates are obtained from the three CIE tristimulus values, X, Y and Z.
These tristimulus values are computed by integrating the product of the spectrum of

Chapter 1 26
the light source, P(λ), and standard observer functions called the CIE color matching
functions, xλ(λ), yλ(λ) and zλ(λ) (Figure 1.6) over the entire visible spectrum [110].

Since the spectra are measured as discrete values, integration is replaced by

sum given as,

Once X, Y, Z is known, the ClE is calculated using the equations:

Being constrained by the relation (x + y + z) = 1, any two of the three CIE

color coordinates are independent. Hence only x and y values are reported. Plotting of
the CIE y color coordinates versus the CIE x color coordinate over the visual range of
light leads to a horseshoe shaped diagram known as the CIE chromaticity diagram
represented in Fig. 1.7.

The dot at the center represents white light. The dominant wavelength of the
color is the intersection of the line connecting these CIE coordinates and those of
white light with the upper arc of the diagram. Further, when the light emission from

Chapter 1 27
phosphors of two colors is mixed, the range of colors that it is possible to produce by
mixing these colors is given by the line that ties the CIE coordinates of these two
colors together [111]. The CIE coordinates, therefore, is an extremely powerful
concept because it allows the representation of an entire luminescent spectrum on a
two dimensional plane.

Fig. 1.6. Plot of the CIE tristimulus (x, y, and z) functions [110]

Fig. 1.7. The CIE chromaticity diagram.

Chapter 1 28
1.6. Thermoluminescence (TL)

Thermoluminescence is the name given to thermally stimulated emission of light from

insulator or semiconductor following previous exposed ionizing radiation energy
absorption (α, β, γ, UV and X-rays) under the conditions of increasing temperature.
Unlike other luminescence process such as chemiluminescence, electroluminescence,
here heat is not an exciting agent, but it acts only as a stimulant. Hence, it is better
known as thermally stimulated luminescence (TSL). TSL is exhibited by a host of
materials, glasses, ceramics, plastics and some organic solids. By far insulating solids
doped with suitable chemical impurities, termed as activator, are the most sensitive
TL materials. The fundamental principles which govern the production of TL are
essentially is the same as those which govern all luminescence processes and
hence TL is one member of a large family of luminescence.

1.6.1. Thermoluminescence mechanism

The process of thermoluminescence can be understood in terms of the band structure

model of insulators, in which the forbidden gap between the valence band and
conduction band is of the order of few eV. According to this model the trace of
impurities and lattice defects may create new localized energy levels in the forbidden
band gap responsible for the luminescence in solids. The positions of the energy
levels depend on the nature of the defects and the host lattice. Some of these defects
are capable to trap an electron or a hole. Therefore the centers are referred to as
electron or hole traps and after trapping an electron or hole the new defects are called
trapped electron or trapped hole centers, respectively.

The traps described represent 'different energy levels, which lie between the
valence and conduction bands on an energy level diagram. The steps involved in
thermoluminescence are shown in Figures 1.8 and 1.9. A trap is characterized by the
energy E that a trapped electron or trapped hole must acquire from lattice vibrations to
escape to the conduction band or valence band. Figure 1.8 illustrates the energy
storage mechanism. Electrons in the conduction band can move freely in the crystal.
Holes which were removed from traps are free to move in the crystal, when they are
excited to energy levels in the valence band. There is a characteristic temperature at
which the thermal vibrations of the crystal lattice are sufficient to cause the release of
trapped electrons. Some of the released electrons reach luminescence centers, which

Chapter 1 29
are filled with holes, and light is emitted in the recombination process (Figure 1.9)
[112].

Figure 1.8. Energy-level diagram of the energy storage stage for

thermoluminescence Processes

Figure 1.9. Energy-level diagram of the energy release stage for

thermoluminescence processes

Chapter 1 30
1.6.2. Theory (Mathematical Description)

For a material to exhibit thermoluminescence, it must actually contain traps for

electrons and holes, and recombination centres where the electrons and holes
recombine, with the emission of light. These traps and centres are associated with
various kinds of defects in the material. Most thermoluminescent materials are
crystalline solids. Different assumptions about electron trapping lead to different
mathematical theories of thermoluminescence, namely first, second and general order
kinetics. These are then related to different experimental methods of determining trap
parameters.

1.6.2.1. First-Order-Kinetics.

There are several forms of the equations describing the thermoluminescence process
and the shape of the glow-peak. These correspond to different sets of underlying
assumptions. The theory of first order kinetics was first described by Randall and
Wilkins (1945). It is based on the assumption that there is no re-trapping of electrons
after they are released from traps. i.e., if an electron is liberated from a trap it always
goes straight to a luminescence centre. Three additional simplifying assumptions are
also made:

Only the trapping and release of electrons is considered. (The treatment of

holes would be exactly similar).
Only one kind of trap and one kind of recombination centre are involved.
The temperature increases at a constant rate during readout. Since the
electrons In the traps have a Maxwell distribution of thermal energies, the
probability per unit time of an electron escaping from a trap of depth E below
the conduction band is

(-E/kT) (1.8)

Where k is Boltzmann's constant, T is the absolute temperature, and s is a constant

(which may, however, vary slowly with temperature, according to Randall and
Wilkins, 1945).

Following Mott and Gurney (1940), s is interpreted by regarding the trap as a

potential box; then s is the product of the frequency with which the electron strikes

Chapter 1 31
the sides of the box, and the reflection coefficient. s has units seconds-1 and is called
the frequency factor. Its value is expected to be somewhat less than the vibrational
frequency of the crystal, typically 1012 S-1 . If there are n electrons in the traps at time t
then from equation 1.8,
(1.9)
The thermoluminescence emission intensity (I) is proportional to the number
of electrons recombining with holes per second, i.e. to dn/dt. If the units are chosen
such that the constant of proportionality is 1, then

(1.10)

Rearranging terms gives

(1.11)

The heating rate β = dT/dt is constant, thus

dt = (1/β) dT

Substituting this in equation 1.11 and integrating gives

where there are no trapped electrons at temperature T o.

Thus
(1.12)

and then from equation 1.10, the intensity of the glow peak is

o (1.13)

An important feature is that intensity (I) is proportional to the Initial

concentration of trapped electrons, no . Thus for first-order kinetics the peak shape
remains the same when n o is varied, i.e. when the phosphor is irradiated to different
levels of absorbed dose. Equation 1.13 also shows that the area under the glow-peak is
proportional to no.

At the low-temperature side of the curve, where T is close to T 0, the term in

square brackets is close to zero and intensity (I) varies approximately as exp (-E/kT).
At higher temperatures, the term in square brackets decreases rapidly and tends to
zero, so that intensity (I) decreases to zero on the high-temperature side.

Chapter 1 32
The temperature of the peak maximum, T max, can be found from equation 1.13 by
differentiating and putting dI/dT = 0 at T= T max, from the form of equation 1.13, it is
easier to differentiate ln I than I., and this would be equivalent since

Thus from equation 1.13,

2
max Tmax

which gives
2
max max (1.14)
This does not contain no , so the position of the maximum does not depend on
the absorbed radiation dose. The equation shows that T max does depend on β, the
heating rate; it can be shown that as β increases, T max also increases.

1.6.2.2. Second order kinetics

If it is assumed that electrons released from traps have an equal probability of

combining with holes in recombination centres and of being re-trapped., the theory
known as second-order kinetics is developed. This was first given by Garlick and
Gibson (1948), although the suggestion that the two probabilities might be
approximately equal was taken from Randall and Wilkins (1945).

If there are a total of N electron traps in the phosphor, and n are filled by
electrons at some instant, then N-n are empty. There are also n holes in luminescence
centres, since equal numbers of electrons and holes were originally produced by
Irradiation. Then the probability of an electron recombining with a hole at a
luminescence centre, rather than being re-trapped, is
(1.15)

Combining equation 1.18 with equation 1.13 then gives the second-order equation
2
(1.16)

It is usual to express S/N as a constant s', this pre-exponential factor does not exactly
correspond to the frequency factor s of first-order kinetics, as it has units m3s-1. Using
s', equation 1.16 becomes
2
(1.17)

Chapter 1 33
If, as before, the heating rate β = dT/dt is constant, the equation of the glow-peak
becomes
2 -2
o 0 (1.18)

The Intensity (I) is not simply proportional to n0, as it was in the case of first-order
kinetics. This means that the shape of the peak depends on n o, and therefore on the
absorbed dose received by the phosphor.

On the low-temperature side of the peak where T is close to T o, the term in

square brackets is practically equal to 1, thus I varies approximately as exp(-E/kT).
This is the same result as for first-order kinetics; similarly, at higher temperatures, the
second function becomes more important, and approaches zero. Conveniently for
dosimetric use, however, the total area under the glow-peak is proportional to the
absorbed radiation dose. This is shown in a simple way by Chen (1984).

Since I= -dn/dt from equation 1.17, integrating with respect to time from zero to
infinity gives

(1.19)

But ∞ = 0 since the traps are all empty at very high temperatures, so that the integral
is equal to n0 (or proportional to n0 If some different choice of units had been made).
The temperature of the peak maximum can be found by differentiating I from
equation 1.18, and setting dI/dT = 0. Chen (1969) has shown that this gives

= max (1.20)

Here it is obvious that T max depends on no (unlike the first-order case). If no increases,
Tmax decreases.

1.6.2.3. Evaluation of „S‟

Several workers have proposed different methods for evaluating S [113, 114]. In
general these methods are tedious and it is difficult to apply them in practice.
Therefore, to calculate activation energy from glow curve measurements, a value of S
is generally assumed [115]. However some workers [116-120] have shown that the
value of S can be calculated by measuring the glow curves at two different warming
rates.

Chapter 1 34
Let T1 and T 2 be the peak temperatures corresponding to heating rates β 1 and β2 . If β1
> β2, then T 1 >T2. Using expression 1 and eliminating S we get,

(1.21)

For S, we can get

Thus equations 1.22 and 1.23 can be used to determine the value of S.

1.6.2.4. Evaluation of trap depth „E‟

Several workers in the field of luminescence have developed methods for calculating
trap depths on the assumptions of uniform heating rate, separate trap levels and
absence of retrapping. Garlic and Gibson [121] have proposed a simple method for
calculating the trap depth from the initial rise of glow curve. With increase in
temperature, the first exponential term in expression 4 increases whereas the second
exponential term may still unity.

Where,

I; the glow intensity,

no; the number of filled traps at the beginning of heating,

β; the Warming rate,

dT; the rise in temperature in time dt,

C; the constant involving luminescence efficiency

The intensity may be written as

(1.25)

Chapter 1 35
F can be taken as constant for the initial part of the glow peak. Hence

(1.26)

Thus a plot of I verses 1/T results in a straight line with a slope equal to –E/K. The
trap depth is thus obtained without knowing the frequency of escape constant S, This
value E can be used to calculate S from equation 1.27,

(1.27)

Here S depends strongly on the selected value of E, the activation energy can be
calculated much more accurately than the frequency factor S.

1.6.3. Applications of TL

The applications of the phenomenon of thermally stimulated luminescence to the

measurement of radiation dose have progressed a great deal since the initial work by
Daniels and Colleagues (1953). Several thermo luminescent phosphors are now used
routinely in many dosimetric applications, in that extensively used for dosimetry of
ionizing radiation [122], as a potential tool for identifying the nature of defects
formed. TL is also, widely used in various fields such as, Forensic science, for
monitoring integrated radiation exposure, archeology and geological dating.
environmental monitoring, personnel dosimetry and medical applications. For
dosimetric applications, it is always desirable to use TLD phosphors in various
physical forms, as routine measurements with loose powder are quite manageable due
to associated weighing of individual powder samples.

A large number of dosimetry phosphors are now available in various physical

forms such as single crystals, microrods, sintered pellets and as thin substrates for
beta and charged particle dosimetry. TL technique successfully be used to study the
electron and hole process associated with some point defects such as color centers.
Thus TL is a very sensitive experimental tool to investigate defects in materials [123].
Below figure 1.10 shows the scheamatic representation of applications of TL.

Chapter 1 36
 Fig. 1.10. Applications of TL used in various disciplines

1.7. Preparation methods of phosphors

One of the largest activities in this field over the past a few decades and till date
remained the synthesis of high quality nanocrystals (NC) of desired size and shape.
High quality generally refers to better monodispersity of particles size, good
crystallinity, electronically and chemically passivated NC surface and so on.
Nanostructures can be made in numerous ways. There are two different approaches to
synthesize nanocrystals: “top-down” approach and “bottom-up” approach [124-127].
The broad classification divides methods into either those which build from the
bottom up, atom by atom, or those which construct from the top down using processes
that involve the removal or reformation of atoms to create the desired structure. In the
bottom-up approach, atoms, molecules and even nanoparticles themselves can be used
as the building blocks for the creation of complex nanostructures; the useful size of

Chapter 1 37
the building blocks depends on the properties to be engineered. By altering the size of
the building blocks, controlling their surface and internal chemistry, and then
controlling their organization and assembly, it is possible to engineer properties and
functionalities of the overall nanostructured solid or system.

These processes are essentially highly controlled, complex chemical synthesis.

On the other hand, top down approaches are inherently simpler and rely either on the
removal or division of bulk material, or on the miniaturization of bulk to produce the
desired structure with the appropriate properties. When controlled, both top-down and
bottom-up methods may be viewed as essentially different forms of nanostructural
engineering. Biological processes are essentially intermediate between top-down and
bottom-up processes; however in reality they usually constitute complex bottom-up
processes. Bottom-up processes effectively encompass chemical synthesis and/or the
highly controlled deposition and growth of materials. Chemical synthesis may be
carried out in either the solid, liquid or gaseous states are bottom up methods.

Listed below are a few examples for top-down and bottom-up approaches:

Top-Down approach

 Lithography processes
 Ball milling
 Machining, etc

Bottom-Up approach

 Chemical synthesis
 Self assembly
 Chemical vapor deposition
 Physical vapor deposition
 Plasma-assisted deposition processes
 Metal organic vapour phase epitaxy (MOVPE)
 Colloidal methods, sol gel methods etc.

There are advantages and disadvantages in both approaches. The biggest problem
with top down approach is the imperfection of surface structure and significant
crystallographic damage to the processed patterns. These imperfections in turn lead to
extra challenges in the device design and fabrication. But this approach enables the
bulk production of nanostructures. On the other hand, bottom up approach promises a

Chapter 1 38
better chance to obtain nanostructures with less defects, more homogeneous chemical
composition. This approach includes many widely used chemical methods for the
synthesis of metal oxide semiconductors.

Recently, there have been improvements in ways of synthesizing phosphor

materials using bottom-up approach, which can control the particle size and shape.
The commonly used synthesis methods are: combustion synthesis [128, 129], sol-gel
processing [130], the microwave process [131], spray pyrolysis [132], precipitation
[133], solid-state reactions [131, 134] and hydrothermal synthesis [135].In the present
study commonly used methods based on the bottom up approach are briefly described
below.

Rare-earth doped phosphors synthesized by solid state reaction method have

played a significant role in determining the microstructure, luminescence properties
and quantum efficiency of phosphors. Luminescent materials were synthesized
conventionally via a solid-state reaction process, using powdered raw materials as the
starting materials. Due to their relatively rough grains, the solid-state reaction method
requires high reaction temperature for a long time period. Therefore it is difficult to
prepare phosphor particles with controlled shape and fine size by this method. And it
could be mitigated by alternate routes offered by wet-chemistry.

Sol-gel methods have also been employed to synthesize nanophosphors by

many researchers [136-139]. However, the as-prepared powders obtained from the
sol-gel method have low crystallinity and often require post-treatment at high
temperature, which results in severe agglomerations. The required stoichiometry can
be lost during the filtering steps when there is a large difference of solubility among
the precipitates. Also, as the number of components increases, it becomes more
difficult in finding a suitable precipitating agent.

1.7.1. Co-precipitation method

Co-precipitation method involves simultaneous precipitation of more than one type of

ions from a solution. All the co-precipitation techniques involve two steps, namely the
nucleation and growth. Nucleation involves the formation of nuclei, which is defined
as the smallest solid phase formed by combination/ aggregation of minimum number
of atoms/ ions/ molecules. The nuclei are susceptible for spontaneous growth to
bigger particles.

Chapter 1 39
Many researchers used co-precipitation method to synthesize more homogeneous
powder than that conventional mixed-oxide method. However, the required
stoichiometry can be lost during the filtering steps when there is a large difference of
solubility among the precipitates. In addition, as the number of components increases,
it becomes more difficult to find a suitable precipitating agent. These limitations, to
greater extent, can be controlled by aqueous organic-gel method, which is an alternate
way to produce inorganic powder, using poly-functional hydroxyl acids and metal
salts to form soluble complexes in aqueous solution. The clean solution is dehydrated
to yield the amorphous solid precursor, which can form the desired compound after
firing at elevated temperatures.

1.7.2. Solvo / hydrothermal method

The solvo / hydrothermal method provide a means of using solvents at temperatures

well above their boiling points, by carrying out the reaction in a sealed vessel. The
pressure generated in the vessel due to solvent vapours elevates the boiling point of
the solvent. Typically, solvothermal methods make use of solvents such as ethanol,
toluene, water, etc. During the synthesis of nanocrystals, parameters such as water
pressure, temperature, reaction time, precursors, etc. can be modified to maintain a
high nucleation rate leading to the formation particles with uniform size distribution
[140]. The main disadvantages of this method are the high temperature, high pressure
developed during the reaction and lack of flexibility for controlling the nucleation and
growth processes. The obtained product has to carry out calcinations to get required
phase of the material for some compounds.

1.7.3. Combustion method

Combustion synthesis is an important powder processing technique generally used for

the synthesis and processing of advanced ceramics (structural and functional),
catalysts, composites, alloys, intermetallics and specially nanomaterials. The method
produces rapid, exothermic, self-sustaining reactions resulting from the appropriate
combination of salts such as nitrates or acetates (oxidizers) and a suitable organic fuel
like urea, carbohydrazide, glycine, etc. (reductant). A composition of metal nitrates
and fuel in which the fuel reacts completely with all of the metal nitrates in the
mixture so that no residues remain in the product material is known as a
stoichiometric ratio. In general, good fuels should react non-violently, produce

Chapter 1 40
nontoxic gases, and act as chelating agents for metal cations. For any combustion
reaction to take place, a fuel and an oxidizer are necessary. Different fuels may be
used but they all serve two purposes [141]:
 They are the source of C and H, which on combustion form CO 2 and H2O
and liberate heat.
 They form complexes with the metal ions, facilitating homogeneous
mixing of the cations in solution.

The combustion reaction is initiated in a muffle furnace or on a hot plate at

temperatures of the order of 500°C or less. In a typical reaction, the precursor
(mixture of water, metal nitrates and fuel) on heating decomposes, dehydrates and
ruptures into a flame. The resultant product is a voluminous, foamy powder, which
occupies the entire volume of the reaction vessel. The chemical energy released from
the exothermic reaction between the metal nitrates and fuel can rapidly heat the
system to high temperatures without an external heat source.

Nanomaterials synthesized by combustion route are generally homogeneous,

contain very fewer impurities, and have higher surface areas than powders prepared
by conventional solid-state methods. The parameters that influence the reaction are
the nature of fuel, fuel to oxidizer ratio, ignition temperature and water content of the
precursor mixture.

Equation 1.28 is a general stoichiometric combustion reaction of metal nitrate

M(NO3)2(3).6H2O, and urea (CH4N2O) to form MAl2O4.

Metal nitrates (aq) + Fuel (aq) → Combustion product (s) + Heat + Gases. (1.28)

When the complete reaction occurs, only the gaseous products N 2, CO 2 and H 2O are
released and no residuals are left in the synthesized MAl 2O 4 material.

Phosphors prepared by the combustion method have low density and appear
fluffy. Ultra fine particles are produced through this process due to the evolution of
gases. As more gases are released the agglomerates are either not formed or they are
disintegrated into fine particles. Combustion synthesis processes are characterized by
high-temperatures, fast heating rates, and short reaction times. These features make
combustion synthesis an attractive method for the manufacture of technologically
useful materials at lower costs compared to conventional ceramic processes. The

Chapter 1 41
major advantage of this method is that large-scale production can be made at
relatively at low temperatures and some other advantages of this method are [142],

inexpensive processing equipment,

formation of high-purity products,
stabilization of metastable phases and,
formation of products of virtually any size and shape.
production of final product in one step using the chemical energy of
the reactants.
liberation of volatile impurities and thus higher purity products.

1.8. Review of literature

Sample/ Structural
Method Characterisation Outcome Authors
/ Properties
ZnAl2 O4: PXRD, TEM, PL The PL intensity of the green line Tshabalala, et al.
emission from Tb3+ at 544 nm [143]
Ce3+,Tb3+
increased as a result of Ce3+ co-
/CM doping. When the sample was
excited at 230 nm.
ZnAl2 O4: PXRD, SEM, PL Mn2+-doped ZnAl 2O4 showed two Xiaojun Wang, et
Mn2+ /Co- green emission bands centred at al. [144]
M 508 and 517 nm. PL intensity
reached the maximum at 0.5 at.%
Mn2+ under the low-voltage
excitation, it exhibits the bright
green emission
ZnAl2 O4: PXRD, SEM, PL, The TSL glow peak at 430 K is Mithlesh Kumar,
Eu3+ /SG TSL attributed to the electron hole et al. [145]
recombination at Eu3+ site
resulting in its characteristic
emission at 600 nm.

PL spectra showed peaks

corresponding to the 5 D0→7 Fj
(j=0, 1, 2, 3 and 4) transitions of
Eu3+ with λex=230 nm excitation.
ZnAl2 O4: PXRD, PL Photoluminescence studies Dong Zhang, et
Mn /SG showed green and red emissions. al. [146]
The red emission became weaker,
and vanished at last with sintering
temperature increasing from 600
to 900 °C in reducing atmosphere,
while the intensity of green

Chapter 1 42
 emission peak increased. Further
when the phosphor was sintered
at 900 °C in air, the intensity of
red and green emissions
decreased, but the value of
intensity ratio increased. It
suggested that the green emission
resulted from Mn2+ and the red
emission resulted from Mn4+
ZnAl2 O4: PXRD, SEM, PL Photoluminescence (PL) spectra Mu-Tsun Tsai, et
Mn /SG exhibited a strong green emission al. [147]
band centered at 510 nm. The
most intense PL emission was
obtained by exciting at 458 nm.
ZnAl2 O4: PXRD, PL, TSL PL emission spectrum of Ce3+- Mithlesh Kumar,
Ce /SG doped ZnAl2O4 phosphor with et al. [148]
λex=300 nm exhibited an intense
asymmetric broad emission band
ranging from 320–400 nm and
peaking at ~360 nm in the blue–
violet region.

TSL showed a single glow peak at

468 K. The order of the TSL glow
kinetics was estimated from the
peak shape and the trap
parameters were determined using
different heating rate method.
ZnAl2 O4: PXRD, TEM, PL The effects of the terbium Fernandez-
Tb3+ /Co- concentration and particle size of Osorio, et al.
M the samples on their luminescence [149]
properties were studied. The
photoluminescence spectra
exhibited a green emission band,
with an excitation wavelength of
230 nm.
ZnAl2 O4: PXRD, SEM, A series of sharp bands at 576, Xiang Ying Chen
Eu3+ /HT TEM, PL 589, 613, 650 and 699 nm can be , et al. [150]
assigned to the characteristic
transitions of Eu3+ from 5 D0→7 Fj
(j = 0, 1, 2, 3, and 4). Among
them, the most intense emission
peak at 613 nm corresponds to
5
D0→7F2 , usually occurring
through the forced electric dipole
ZnAl2 O4: PXRD, PL PL results confirmed the Motloung, et al.
Ce3+, Eu3+ existence of the radiative energy [151]
/SG transfer from Ce3+→Eu3+. CIE
colour chromaticity showed that
the colour can be tuned from

Chapter 1 43
 bluish to reddish by changing the
Eu3+ concentration.

ZnAl2 O4: PXRD, SEM, PL emission spectrum of Mithlesh Kumar,

Tb3+ /SG TSL, PL ZnAl2 O4:Tb3+ phosphor showed et al. [152]
bands at 487, 542, 586 and
622 nm corresponding to the
4
D5→6Fj (j=6-3) transitions
respectively due to Tb3+ ions.

TSL investigations revealed the

formation of Tb3+, electron / hole
trapped centers and luminescent
centre. The TSL results, glow
peak at 414 K is associated with
recombination of electron and
hole centers through Tb3+
SrAl2O4 : PXRD, SEM, PL When the calcination temperature Yanbin SUN, et
Eu2+,Dy3+ reached 1150 °C, the fine crystal al. [153]
/Co-M of SrAl2O4 was formed and the
long afterglow luminescence
could be obviously observed.
ZnAl2 O4: PXRD, SEM, The photoluminescence (PL) Motloung, et al.
Cr3+ /SG TEM, PL results showed that the host and [154]
the Cr3+-doped nanoparticles
exhibit violet emission slightly at
different peak positions. Slight
peak shifts suggests that the
luminescence can originate from
both the host and Cr3+ ion.
ZnAl2 O4: PXRD,TEM, PL The emission spectra were Zawadzki, et al.
Tb3+ /HT normalized to the highest [155]
emission peak associated with the
green emission of Tb arising from
the dominant 5D4 →7F5 transition
with the peak maximum at 542
nm.
ZnAl2 O4: PXRD, SEM, PL The higher PL emission intensity Hernandez-Pe
Pr3+ / under 257 nm excitation indicates rez, et al. [156]
Co-M more efficient energy transfer
from the aluminate group toward
the Pr3+ ions into the matrix. PL
emission intensity quenching was
induced by increasing the doping
concentration above its optimum
value
ZnAl2 O4: PXRD, TEM, PL The PL properties are investigated Shu Fen Wang,
Dy3+ /CS in detail. Three emission bands in Feng Gu, et al.
blue, yellow, and green region are [157]

Chapter 1 44
 observed, originating from two
different origins. The blue and
yellow emissions are ascribed to
the typical emission of Dy3+,
while the green one is associated
to the host lattice.
YAlO 3:Er3 PXRD, PL The upconversion mechanism Szachowicz, et al.
+
/ SSR responsible to the green [158]
luminescence is mainly a
sequential two-photon absorption
SrAl2O4 : PXRD,TEM, PL, The PL emission and ML spectra Ravi Sharma, et
Eu2+/CS ML showed broad band at 515 nm. al. [159]
The variation in fluxing agent
H3BO3 influenced the PL and ML
intensity and the maximum PL
and ML intensity was observed
for 7.5 % H3 BO3.
(Ce,Tb)M PXRD,SEM, PL Photoluminescence efficiency of Zongyu FENG, et
gAl11O19 phosphor was improved al. [160]
/SSR significantly. However, when the
content of flux was higher than
the critical concentration, the
impurity ions of residual flux
increased largely, which reduced
the photoluminescence efficiency.

Y3Al5O12: PXRD, SEM, PL The effect of NaF concentration Shiqing XU, et al.
Ce3+ / SG on the emission intensity of [161]
YAG:Ce was also investigated.
The value of emission intensity
reached the maximum when the
concentration of NaF was 0.5 %
YAlO 3: PXRD, PL Under 754 nm excitation a strong Osiac, et al. [162]
Ho3+ /Co- green upconverted emission
M occurs in YAlO3:Ho
SrAl2O4 : PXRD, SEM, PL The strongest photoluminescence Wang, et al. [163]
Eu2+, appears in the samples containing
Dy3+/ H3BO3 flux.
microwav
e-assisted
method
YAlO 3: PXRD, SEM, PL Under 754 and 840 nm excitation Osiac, et al. [164]
Ho3+, Yb3+ schemes for green up-converted
/SG emission were proposed
CaAl2 O4: PXRD, SEM, PL Phosphorescent characteristics are Haranath, et al.
Eu2+/ SG significantly influenced by the [165]
addition of small quantities of

Chapter 1 45
 H3BO3 (as low as 1 mol %) in the
starting mixture and maximum PL
is observed for ∼10 mol %
CaAl2 O4: PXRD, PL, SEM The incorporation of alkali metal Guanghuan LI, et
Eu3+, R+ ions greatly enhanced the al. [166]
(R=Li+, luminescence intensity probably
Na+, K+) due to the influence of charge
/SSR compensation of alkali metal ions.
Eu-doped PXRD, PL, SEM The luminescent characteristics Yun Jin Park, et
CaAl2 O4: are significantly influenced by the al. [167]
Eu3+/ SSR addition of small quantities of
H3BO3 in the starting mixture

SrAl2O4 : PXRD, PL, The green emission was enhanced Tshabalala, et al.
Ce3+, HRSEM by energy transferred from Ce3+ [168]
Tb3+/CS toTb3+
YAG XRD, Raman Raman spectra and XRD patterns Iida, et al. [169]
studies of the powders
YAlO3:Pr PXRD, SEM, PL The two cases of YAlO3:Pr and Zen, et al. [170]
Y3Al5O12: YAG:Pr are two classical
Pr/ CZ examples of systems in which
upconversion takes place via ET
(YAlO3) or via ESA (YAG)
YAG /CS PXRD, PL The emission intensity increased McKittrick, et al.
with the measured flame [171]
temperature of the reaction.
Carbohydrazide produced the
highest flame temperature and
also the highest PL emission
intensity.
Present work
ZnAl2 O4: PXRD, SEM, The glow peak intensity at 212 Ravikumar, et al.
Cr3+ / TEM, PL, TL
o
C increases linearly with γ-dose [172]
Green which suggest ZnAl2O4:Cr3+
combusti suitable for radiation dosimetric
on applications.
synthesis
The PL spectrum shows an
intense peak at 688 and 699 nm
assigned to spin forbidden
transition of Cr3+ ions.
ZnAl2 O4: PXRD, SEM, A single TL glow peak was Ravikumar, et al.
Dy3+ / TEM, PL, TL recorded at 172 oC at a warming [173]
Green rate of 2.5 Cs-1. The intensity at
combusti 172 oC peak increases linearly
on up to 1 kGy.
synthesis
The characteristic emission

Chapter 1 46
 peaks at 476 and 573 nm were
observed from PL. The
optimized Dy3+ concentration
was found to be 7 mol%. PL
intensity increases with increase
of plant latex.

ZnAl2 O4: PXRD, SEM, PL results indicated that the Ravikumar, et al.
Ce3+ /CS TEM, PL, TL prepared phosphors showed two [174]
peaks at 363 and 480 nm due to
5d–4f transitions of Ce3+ ions.

Two TL glow peaks were

recorded at 145 and 215 oC
respectively. TL intensity at 145
o
C peak increase linearly upto 1
kGy and after that it decreases.
SSR: Solid-State Reaction, SG: Sol-gel, ST/HT: Solvo / Hydrothermal, CS:
Combustion Synthesis, CZ: Czochralski method, Co-M: Co-precipitation Method
PL: Photo Luminescence, CL: Cathodo Luminescence, TSL: Thermally Stimulated
Luminescence, TL: Thermo Luminescence
1.9. Objectives of the present work

To investigate the effect of Ce3+ rare earth ions on the structural and
luminescent properties of ZnAl2O4:Ce3+ phosphor powders prepared by
combustion method.
Prepare nanophase ZnAl2O4 :Dy3+ phosphor powders by means of a
combustion technique using plant latex as a fuel at a relatively low
temperature and to study the morphological, structural and
photoluminescent properties of the powder products.
The morphological, structural and enhanced photoluminescent properties
of flux assisted red emitting, ZnAl2O4 :Cr3+ phosphor powder.
Synthesis, characterization, dosimetric and enhanced photoluminescence
properties of γ -irradiated ZnAl2O4 :Tb3+ (0.25–5 mol %).
Role of fluxes (metal ions) on enhanced photoluminescence properties of
Bi3+ co-doped ZnAl2O4 :Eu3+ nanophosphors.

Chapter 1 47
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