MAJOR PROJECT

ON
DYSPROSIUM
DOPED GLASS
Submitted

by:
(2k12/EP/036)
Agarwal (2k12/EP/051)
Chopra

(2k12/EP/073)

Mayank
Rahul
Tarun

ACKNOWLEDGEMENT
I have taken efforts in this project. However, it would not have been
possible without the kind support and help of many individuals and
organizations. I would like to extend my sincere thanks to all of
them.
I am highly indebted to MR. A.S. RAO for their guidance and
constant supervision as well as for providing necessary information
regarding the project & also for their support in completing the
project.
I would like to express my gratitude towards my parents & member
of Delhi Technological University for their kind co-operation and
encouragement which help me in completion of this project.
I would like to express my special gratitude and thanks to lab staff
for giving me such attention and time.
My thanks and appreciations also go to my fellow batch mates in
developing the project and people who have willingly helped me out
with their abilities.

CERTIFICATE
This is certified to be the bonafide work of the students in the Major Project -2 during the
academic year 2015-2016.

Topic DYSPROSIUM DOPED GLASS

Details of Student 1 NAME MAYANK

ROLL NO. 2K12/EP/36
Details of Student 2 NAME RAHUL KUMAR AGARWAL
ROLL NO. 2K12/EP/51
Details of Student 3 NAME TARUN CHOPRA
ROLL NO. 2K12/EP/73

Mentor Mr. A. S. RAO

(MENTORS SIGNATURE)
ORDINATORS SIGNATURE)

(CO-

TABLE OF CONTENTS
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Content

Introduction
Solid State Lightning
Light Emitting Diodes
Luminescence
Types Of Luminescence
Fluorescence
Phosphorescence
Phosphors
Phosphor Synthesis
Advancements in white
LEDs
Rare-Earth Elements
Manufacturing Of Glass
Results and Discussions
References

Signature

INTRODUCTION
Solid State Lighting (SSL) based devices are predicted to play a crucial role in the coming
years. They offer to save huge amounts of electrical energy and reduce carbon emissions
by almost 28 million metric tons per year, globally. Apart from their signicant roles in
reducing energy consumption and being environment friendly, SSL based devices such as
white LEDs (w-LEDs), liquid-crystal displays, full-color displays, trafc signals, automotive displays, cellular phone illumination etc., are seen to be a signicant
improvement over their predecessors especially in performance, durability and costeffectiveness. W-LEDs have an
edge over traditional lighting sources due to their
compact size, higher reliability, shock resistance, interesting design possibilities, higher
transparency and an extremely long lifetime.
There are two main approaches to produce w-LEDs.
One of them is to use a blue emitting InGaN LED and yellow YAG:Ce3+ phosphor.
Though this method of phosphor converted w-LEDs (pc w-LEDs) has advantages of
low cost and high brightness, but various drawbacks like halo effect, poor color
rendering index.
The other approach of manufacturing w-LEDs makes use of RGB phosphors excited
by a ultraviolet (UV) chip. This method has merits like higher CRI values, but
suffers from low luminescent efciency due to re- absorption of blue light.
Moreover in both of these approaches, phosphors are encapsulated in an epoxy resin,
which holds the powder together in the w-LED package. This epoxy resin adds a lot of
disadvantages such as the problems of cracking or delamination of epoxy encapsulations
and yellowing of the epoxy, which heavily impacts the color output of the w-LEDs.
Glasses doped with rare-earth ions are an alternative to pc w-LEDs due
to their advantages like ease of manufacture, ease in forming any
shape, lower production cost, higher thermal stability, and especially for
epoxy resin free manufacturing process . Trivalent dysprosium ion, with
4f9 electronic conguration, was chosen as the rare earth dopant
because there are many advantages including potential applications in
white light generation as a single phase white emitting source, mercuryfree luminescence lamps, electron trapping materials and as light
conversion materials when used along with a mixture of other rare
earth.

WHAT IS SOLID STATE LIGHTNING?

Lighting applications that uses Light-emitting diodes (LEDs) and Organic
light-emitting diodes (OLEDs) are commonly referred to as solid-state
lighting (SSL).Solid-state lighting consists of semiconductors that convert
electricity into light. Used in a variety of lighting applications because it
offers many benefits, including Long life. LEDs and OLEDs can provide
50,000 hours or more of life, which can reduce maintenance costs.

PREVIOUS GENERATION TECHNIQUES

There are two major previous generation lighting techniques:
Incandescent
Fluorescent

Incandescent light bulb:

The incandescent lamp was invented by Thomas Edison in 1879 .The filament
in an incandescent lamp is what heats up. Filaments are made out of double
coils of tungsten, a type of metal. Tungsten has a high electrical resistance,
causing it to glow (incandesce) when an electric current flows through.

Fluorescent lamps:

Fluorescent light, a common form of illumination in offices, has a more

complicated light emission mechanism than incandescent light. Electrons
emitted from the electrode collide with the mercury atoms comprising the
vapor inside the glass tube. This causes the mercury atoms to enter an excited
state, causing them to jump to a higher orbit. Excited mercury atoms
constantly try to return to their ground state. And the energy difference
between two orbital levels is released as light in the form of ultraviolet waves.
Ultraviolet not visible to the human eyes, the inside of the glass tube is coated
with a fluorescent material that converts ultraviolet rays to visible light and to
glow white.

A Light Emitting Diode or LED as it is more commonly called, is

basically just a specialized type of PN junction diode, made from a very thin
layer of fairly heavily doped semiconductor material.
Then we can say that when operated in a forward biased direction Light
Emitting Diodes are semiconductor devices that convert electrical energy
into light energy.

CONSTRUCTION
The construction of a Light Emitting Diode is very different from that
of a normal signal diode. The PN junction of an LED is surrounded by
a transparent, hard plastic epoxy resin hemispherical shaped shell or
body, which protects the LED from both vibration and shock.

 LED junction does not actually emit that much light so the epoxy resin
body is constructed in such a way that the photons of light emitted by
the junction are reflected away from the surrounding substrate base to
which the diode is attached and are focused upwards through the
domed top of the LED, which itself acts like a lens concentrating the
amount of light.
This is why the emitted light appears to be brightest at the top of the
LED.
Because LEDs are solid-state devices, they can be extremely small and
durable and provide much longer lamp life than normal
light sources.

Working of LEDs
The holes are present in the valance band and the free electrons are in
the conduction band.
When a p-n junction is forward biased, the electron from n-type
semiconductor material cross the p-n junction and combine with the
holes in the p-type semiconductor material.
Thus with respect to the holes, the free electrons are at higher energy
level.
When a free electron recombines with hole, the energy level related
with it changes from higher value to the lower value and it falls from
the conduction band to the valance band.
There is an energy release due to the electron travel. In normal diodes,
this energy released is in the form of heat.
But in LED the energy release in the form of photons, which emit the
light energy. The entire process is called electroluminescence and the
diodes are called the light emitting diode.
In LED, energy released in the form of light depends on the forbidden
energy gap. One can determine the wavelength of the light emitted.

Hence the color of the light and also whether the light is visible or not
can be determined from wavelength.
The color and wavelength of the emitted light can be controlled by
doping with various impurities

What determines the color of LED?

The material used in the semiconducting element of an LED determines
its color.
The two main types of LEDs presently used for lighting systems are:
Aluminum gallium indium phosphide (AlGaInP) alloys for red, orange
and yellow LEDs;
Indium gallium nitride (InGaN) alloys for green, blue and white LEDs.
Slight changes in the composition of these alloys changes the color of
the emitted light.

Process in LEDs:
Light output by application of low voltage. There are three Basic Process
involved: Excitation Process:
Most of the commercial LEDs use the process of injection
minority carriers through a forward biased PN junction for
excitation process.
Recombination Process:
Recombination Process
Recombination.

of

e-h

pairs

is

the

radiative

Photon Extraction Process

Photons are generated in LEDs within a few m of the junction.
The emitted light has to pass through the semiconductor for
reaching its surface. Amount of light at the surface is function of
distance measured from the junction and the absorption
coefficient of the material is given.

Advantages, Disadvantages and Applications of LEDs:

Advantages:
i. Small in size and light in weight, Cheap and compatible with ICs
ii. Mechanically rugged and longer life than lamps
iii. Switch-on time is very small and higher speed
iv. Low operating temperature
v. No complex driver circuitry required
Disadvantages:
i. Quantum efficiency is low
ii. Damages due to over voltage and over current.
iii. Temperature dependent
Applications:

i. Used in various displays.

ii. Used as indicator lamps.
iii. Used as indicators in measuring equipments
iv. Used as sources in opto-couplers.
v. Used in IR remote controls

Luminescence
Luminescence is emission of light by a substance not resulting from heat; it is
thus a form of cold bodyradiation. It can be caused by chemical
reactions, electrical energy, subatomic motions, or stress on a crystal. This
distinguishes luminescence from incandescence, which is light emitted by a
substance as a result of heating. Historically, radioactivity was thought of as a
form of "radio-luminescence", although it is today considered to be separate
since it involves more than electromagnetic radiation. The term 'luminescence'
was introduced in 1888 by Eilhard Wiedemann.[1][2]
The dials, hands, scales and signs of aviation and navigational instruments
and markings are often coated with luminescent materials in a process known
as 'luminising'
The name luminescence has been accepted for all light phenomena not caused
solely by a rise of temperature, but the distinction between the
terms phosphorescence and fluorescence is still open to discussion. With
respect to organic molecules, the term phosphorescence means light emission
caused by electronic transitions between levels of different multiplicity
(explained more fully below), whereas the term fluorescence is used for light
emission connected with electronic transitions between levels of like
multiplicity. The situation is far more complicated in the case of inorganic
phosphors.

TYPES OF LUMINESCENCE
Bioluminescence, i.e. luminescence generated by a living organism.

The light generating molecules become excited by a chemical

reaction; bioluminescence is thus related to chemiluminescence.
Some biological entities like bugs, e.g. fireflies, denizens of the
deep like anglerfish, some mushrooms and even bacteria can
control this reaction. They produce the chemicals luciferin (a

pigment) and luciferase (an enzyme). The luciferin reacts with

oxygen to create light. The luciferase acts as a catalyst to speed up
the reaction.

Firefly attracting females

with
lit
up
behind
(Source Wikipedia)

Mushroom; glowing just for

fun?
(Source amazingdata.com)

Chemiluminescence (or "chemoluminescence") results from some

(actually amazingly few) chemical or electrochemical reactions.
The energy needed comes from the reaction enthalpy. The reaction
produces some new molecule that can have its electrons in an
exited state right after it was formed. Decay to a ground state may
then produce visible light (the exception) or release the energy in
some other way (the rule).
The flash of light you see when some dynamite explodes is not
chemiluminescence even so the energy comes from a chemical
reaction but simply black body radiation or incandescence from
things getting very hot very quickly.
Crystalloluminescence is occasionally produced during crystallization
It's another variant of chemiluminescence because the energy
comes essentially from bonding between atoms.

Electroluminescence generates light in response to an electric current

passing through some material
In essence, electroluminescence results radiative recombination of
electrons and holes; typically (but not exclusively) in
semiconductors. We have treated that extensively before. It is the
basis for LED's and semiconductor Lasers and thus of prime
importance in the context of light sources.
Recently electroluminescence is also used for characterizing solar
cell. Feed a large current into a good solar cell in the dark and
your IR camera will see (weak) electroluminescence even so Si is
an indirect semiconductor. The reason is simple: Good solar cells,
by definition, are Si devices where all regular recombination
channels have been "closed off", i.e. made inefficient, otherwise
the solar cell cannot be good. Radiant recombination then "wins"
and is raised to a level where it can be detected The following
picture shows an example.

Electroluminescence
solar cell

from

Photoluminescence
solar cell

from

Colors code intensity. The pictures look almost identical but

differences
not
only
exist
but contain a lot of specific information about this solar cell.

Cathodoluminescence occurs when an electron beam impacts on a

luminescent material such as a "phosphor"

For almost 100 years cathodoluminescence was used for making

displays, your classical cathode ray tube or TV tube that was
recently replaced by flat screen displays like LCD's.
We still need cathodoluminescence for electron microscope
(TEM type) screens for obvious reasons. But we can also look at
the cathodoluminescence that specimen produce in the electron
beam of an SEM; then we use it as an analytical tool. The
"phosphors" tend to be large bandgap semiconductors line ZnO,
again for (hopefully) obvious reasons; if color is needed like for
an (old fashioned) TV, more involved different materials emitting
red, green, and blue are necessary.
Mechanoluminescence, resulting from any mechanical action on a
solid, can be subdivided into:
Triboluminescence (one of my favorites). Take a lump of sugar,
go into a dark room, wait a while so your eyes adapt, and than
violently crush that sugar between your teeth (keeping your lips
open, so you can see your teeth and the sugar in a mirror). Blue
flashes of light will be generated! Triboluminescence happens
quite a lot, it is just not seen at daylight conditions because it is
typically weak. It happens when bonds in a material are broken
because that material is scratched, crushed, or rubbed. The effect
is not really understood; separation and reunification of electrical
charges seems to play a role; and there might simply be sparking
in large electric fields.
Fractoluminescence,
triboluminescence.

pretty

much

the

same

thing

as

Piezoluminescence, is produced by the action of pressure on,

well, piezoelectric materials. It's different from the above because
you do not need to break bonds but just some elastic deformation.
Photoluminescence is caused by moving electrons to energetically
higher levels through the absorption of photons.
It's easily done in semiconductors with photons of energy larger
than the bandgap, radiating recombination channels than produce
bandgap light. The solar cell picture above gives an example. It

was irradiated with very intense red light; the luminescence occurs
in the IR.
Radioluminescence is generated when some materials are exposed to
ionizing radiation like , or rays.
It was used, even so that is hard to believe nowadays, to make
watch dials glow in the around 1960. A mixture of radium and
copper-doped zinc sulfide was used to paint the dials, giving a
greenish glow. Radioluminescence is also used for detecting
ionizing radiation, especially rays, by analyzing the light
flashed generated when a quant is absorbed in certain crystals.
Thermoluminescence, describes the phenomenon that certain
crystalline materials emit light when heated that is not black body
radiation or incandescence
What happens is that previously absorbed energy from, e.g.,
electromagnetic or ionizing radiation was stored (meaning the
excited electrons just stay on upper energy levels), typically at
defects. It is released in the form of light if some thermal energy
allows the excited electrons to overcome the energy barrier that
kept then "up".
Thermoluminescence is an important method for dating some
archeological artifacts. Ceramic parts being buried receive some
ionizing dose from radioactive elements in the soil or from cosmic
rays that is proportional to their age - and so is the intensity of the
luminescence produced upon heating.

FLOURESCENCE

The fluorescence process is governed by three important events, all of which

occur on timescales that are separated by several orders of magnitude.
Excitation of a susceptible molecule by an incoming photon happens in
femtoseconds (10E-15 seconds), while vibrational relaxation of excited state
electrons to the lowest energy level is much slower and can be measured in
picoseconds (10E-12 seconds). The final process, emission of a longer
wavelength photon and return of the molecule to the ground state, occurs in
the relatively long time period of nanoseconds (10E-9 seconds). Although the
entire molecular fluorescence lifetime, from excitation to emission, is
measured in only billionths of a second, the phenomenon is a stunning
manifestation of the interaction between light and matter that forms the basis
for the expansive fields of steady state and time-resolved fluorescence
spectroscopy and microscopy. Because of the tremendously sensitive emission
profiles, spatial resolution, and high specificity of fluorescence investigations,
the technique is rapidly becoming an important tool in genetics and cell
biology.
The electronic state of a molecule determines the distribution of negative
charge and the overall molecular geometry. For any particular molecule,
several different electronic states exist (illustrated as S(0), S(1), and S(2) in
Figure 1), depending on the total electron energy and the symmetry of various
electron spin states. Each electronic state is further subdivided into a number
of vibrational and rotational energy levels associated with the atomic nuclei
and bonding orbitals. The ground state for most organic molecules is an
electronic singlet in which all electrons are spin-paired (have opposite spins).
At room temperature, very few molecules have enough internal energy to
exist in any state other than the lowest vibrational level of the ground state,
and thus, excitation processes usually originate from this energy level.

Transition

Process

Rate Constant

S(0) => S(1) or S(n)

Absorption (Excitation)

Instantaneous

Timescale
(Seconds)
10-15
-14

to 10-10

S(n) => S(1)

Internal Conversion

k(ic)

10

S(1) => S(1)

Vibrational Relaxation

k(vr)

10-12 to 10-10

S(1) => S(0)

Fluorescence

k(f) or

10-9 to 10-7

S(1) => T(1)

Intersystem Crossing

k(pT)

10-10 to 10-8

S(1) => S(0)

Non-Radiative Relaxation
Quenching

k(nr), k(q)

10-7 to 10-5

T(1) => S(0)

Phosphorescence

k(p)

10-3 to 100

T(1) => S(0)

Non-Radiative Relaxation
Quenching

k(nr), k(qT)

10-3 to 100

PHOSPHORESENCE
Phosphorescence, emission of light from a substance exposed to radiation and
persisting as an afterglow after the exciting radiation has been removed.
Unlike fluorescence, in which the absorbed light is spontaneously emitted
about
10-8 second after excitation, phosphorescence requires additional
excitation to produce radiation and may last from about 10 -3 second to days or
years, depending on the circumstances.
In fluorescence, an electron is raised from a certain baseline energy known as
the ground level to an excited level by a light photon or other radiation.
Transition of the electron back to the ground level can occur spontaneously
with radiation of the same energy as that which was absorbed. According to
electromagnetic theory, the return is almost coincident, occurring within 108
second or so. The case for phosphorescence is different. In phosphorescence,
interposed between the ground level and the excited level is a level of
intermediate energy, called a metastable level, or electron trap, because a
transition between the metastable level and other levels is forbidden (highly
improbable). Once an electron has fallen from the excited level to the
metastable level (by radiation or by energy transfer to the system), it remains
there until it makes a forbidden transition or until it is further excited back to
the transition level. This excitation may come about through thermal agitation
of the neighboring atoms or molecules (called thermo luminescence) or
through optical (e.g., infrared) stimulation. The time spent in the metastable
level, or electron trap, determines the length of time that phosphorescence

PHOSPHORS
A phosphor is a chemical material that, when stimulated by absorption of
energy often in the form of photons will emit photons usually at lower
energy (longer wavelength) than the stimulating source.
In appearance, a phosphor is usually a fine white or pastel- colored powder.
There are two general types of phosphors: organic and inorganic. This
presentation deals with inorganic. The majority of thermometry applications
in our experience have used inorganic phosphors. Organic fluorescing
materials may have advantages in certain situations.
Inorganic phosphors consist of:
o Host material: e.g., oxide, garnet, sulfide, oxysulfide, vanadate,
germanate, etc.
o Activator material (aka dopant or impurity): usually rare-earth or
transition metal elements.
An advantage of these dopants is that, typically, the emission consists of
narrow bands.

History of phosphors
Phosphors became technologically and industrially important with the
introduction of fluorescent lamps in 1938.
Thermometry use suggested in German patent in 1938. First peerreviewed article, to our knowledge, appeared in 1949.
Between approximately 1950 to 1980, it was not widely used. Its most
common use was for aerodynamics applications.
Advances in lasers, microelectronics, and other supporting technologies
enabled additional commercial as well as scientific uses.
CRT phosphors were standardized beginning around World War II and
designated by the letter P followed by a number.

Characteristics of phosphors

 Must survive hazardous chemical environments.

Cannot be water soluble
Durable
Easy to apply
Not easily detected or noticed without specialized equipment
There are a wide variety of ceramic phosphors, which fit these
characteristics.

Phosphors Synthesis
A Physicists approach: Top down: 1. Laser ablation, 2. Vacuum evaporation,
3. High-energy ball milling, 3. Inert gas condensation, 4.Sputtering
A Chemists approach: Bottom up: 1. Combustion, 2.Hydrothermal, 3.Solgel, 4. Precipitation, 5. Sono-chemical route

ADVANCEMENTS IN WHITE LEDs

First method to produce w-LEDs from phosphors comprises of :

Blue emitting InGaN LED.
Yellow YAG:Ce3+ phosphor.
Advantages:
Low cost and high brightness.
Drawbacks:
halo effect.
poor color rendering index (with Ra 7080).
high CCT (7750 K).
The second method of manufacturing w-LEDs:
Makes use of RGB phosphors excited by a ultraviolet (UV) chip.

Merits:
Higher CRI values.
Demerits:
Suffers from low luminescent efciency due to re- absorption of blue
light.

DRAWBACKS OF USING PHOSPHORS

Phosphors are encapsulated in an epoxy resin, which holds the powder
together in the w-LED package. This epoxy resin adds a lot of
disadvantages such as the problems of cracking or delamination of
epoxy encapsulations and yellowing of the epoxy, which heavily impacts
the color output of the w-LEDs. Recently, silicone-based materials with
high thermal resistance have been used for making an epoxy. They
add problems like declining performance of w-LEDs and deviation
from originally required shape due to thermal shrinking. Hence, the
manufacturing process becomes difcult, lengthy and costly which
decreases the manufacturing productivity of w-LEDs encapsulants.

NEW TECHNOLOGY
Glasses doped with rare-earth ions are an alternative to pc w-LEDs due to their
advantages like:
ease of manufacture
ease in forming any shape
lower production cost
higher thermal stability and
epoxy resin free manufacturing process.
PLB:Dy3+ (Lead Lithium Borate doped with dysprosium) glass system was chosen for the
present study.

RARE-EARTH ELEMENTS
The Japanese call them the seeds of technology. The US Department of Energy
calls them technology metals.
They have become irreplaceable in world of technology owing to their unique
magnetic, phosphorescent, and catalytic properties.
They are set of 17 chemical elements in the periodic table, specifically 15
lanthanides plus scandium and yttrium.
Scandium and yttrium are considered rare earth elements since they occur in the
same ore deposits as the lanthanides and exhibit similar chemical properties.

 USAGE OF REs IN TODAYS TECHNOLOGY :

iPhone uses eight rare earths for everything i.e. for its colored
screen, its speakers for the miniaturization of the phones
circuitry.

WHERE DO THEY COME FROM?

China became the world's dominant producer of rare earths in the
1990s because China sold rare earths at very low prices.
China is also the dominant consumer of rare earths, which they
use mainly in the manufacture of electronics products for
domestic use as well as export.
Japan and the United States are the worlds second and third
largest consumers of rare earths.

MANUFACTURING OF GLASS
Various glass samples were prepared using reagent grade high purity oxides: B 2O3,
PbO, Li2O and Dy2O3.
The glass samples had the composition of :
60B2O3 + 30PbO + (10-x) Li2O + xDy2O3
(where x = 0.1, 0.5, 1.0 ,1.5 , 2.0)
The samples were designated as PLB01, PLB05, PLB10 PLB15 and PLB20 in
accordance with the x values.
Steps involved in preparation of glass sample are depicted in a flow chart.

PLB:Dy3+ GLASS SYSTEM

PLB:Dy3+ was chosen as glass system due to:
high chemical stability from borates.
high RE ion solubility from borates.
Low coefcient of thermal expansion.
impressive absorption of gamma and X-rays for application in radiation
shielding glasses.
PLB glass matrix has lower phonon energy (less than 1300 cm -1) which is
much lower than that of visible light (14,285 25,000 cm-1).
Thus, its resultant effect on visible light emission is consequently negligible.

DYSPROSIUM (Dy3+)
Trivalent dysprosium ion, with 4f9 electronic conguration, was chosen as the rare
earth dopant in the PLB matrix.
Advantages of using Dy3+ ion are:
Helps in producing mercury-free luminescence lamps.
It could act as a light conversion materials when used along with a mixture
of other rare earth ions.
Dy3+ ion is one of the most preferred activator ions to be used for
estimating the local environment inside the luminescent materials.
Dy3+ doped glasses and have been extensively studied for various applications such as
white light generation.

LEAD OXIDE
PbO is used extensively in making glass. Depending on the glass, the benefit of using PbO
in glass can be one or more:

increasing the refractive index of the glass.

decreasing the viscosity of the glass.
increasing the electrical resistivity of the glass.
increasing the ability of the glass to absorb X-rays.
Adding PbO to industrial ceramics (as well as glass) makes the materials more
magnetically and electrically inert (raises the Curie temperature) and is often used
for this purpose.
The attractive optical properties of lead glass result from the high content of
the heavy metal lead. The high atomic number of lead also raises the density of the
material.

BORIC ACID
Boric acid (B2O3) is one of the best glass formers known and can form glass alone
at lower melting point with good transparency, high chemical durability, thermal
stability and good rare earth ion solubility.
Normally, glass with B2O3 alone possesses high phonon energies(1300 cm-1) and
cannot suppress non-radiative decay process hence rare earth ion emissions are
strongly reduced.
Thus, heavy metal oxide (PbO) has been added to B 2O3 to suppress the phonon
energies.

LITHIUM OXIDE
Adding lithium to a glass batch can reduce energy requirements while also providing a
range of other benefits:

Lithium oxide (Li2O), as well as lithium-bearing ores decreases the melting point,
viscosity and thermal expansion of the glass, leading to increased melting
efficiencies and/or larger effective furnace capacities.
Li2O can lower the required processing temperature by as much as 25C (77F), it
provides a 5-10% reduction in energy use and can also decrease NOx emissions.
Additional benefits include improved glass quality and an increased melt-to-pack
ratio as a result of fewer checks and tears, as well as a potential increase in
refractory life due to lower operating temperatures.
Lithium is the lightest, smallest, and most reactive flux. Adding small amounts by
weight introduces disproportionately large amounts to the glaze formula (because
of its low molecular weight).
Together with boron and sodium, it acts as a melter at lower temperatures. Together
with sodium and potassium oxides, it is classified as one of the Alkaline group.

Results & Discussions

After synthesis of Dy3+ doped PLB glasses, their structural and photoluminescent (PL)
properties are studied. Subsequent results and discussions are included on X-Ray
Diffraction (XRD), Fourier
Transform Infrared Spectroscopy (FTIR) studies, which
describe the structural, morphological, and chemical nature of the as prepared glass.
Further, photoluminescent properties are discussed with the help of excitation and
emission spectra. Colorimetric parameters are calculated from the emission spectra, which
identify the applic- ability of the as prepared glass in various applications like SSL,
electronics displays etc.

XRD SPECTRAL MEASUREMENT

The XRD pattern of the optimized Dy3+ doped PLB glass sample clearly indicates the
amorphous nature and the broad diffuse pattern conrms the absence of any long range
structural order.

PHOTOLUMINESCENCE
Photoluminescence spectrum exhibited characteristic emission bands at em = 484 nm
(blue) and em = 575 nm (yellow) which are ascribed to the 4F9/2 6H15/2 and 4F9/26H13/2
transitions of Dy3+ ion, respectively.

EMISSION SPECTRA
PL emission spectra measured for Dy3+ doped PLB glasses by varying Dy3+ ion
concentration under ex=348 nm. Each spectrum consists of two dominant emission
bands which are prominently characteristic of Dy3+ ions. The two bands, centered at

em = 484 nm (blue) and em 575 nm (yellow), originate, when the electrons make a
radiative transition from the 4F9/2 energy level to the lower lying levels (i.e. 6H15/2 and
6
H13/2, respectively).

The 4F9/2 6H15/2 (blue) transition is a magnetic dipole allowed transition,

hence its intensity does not depend on the local crystal eld of the
constituent atoms in the glassy matrix. Whereas, the emission due to
the transition 4F9/26H13/2 (L=2, J= 2) is an electric dipole transition
band. This
transition is a hyper- sensitive transition wherein the
inuence of the host's local environment on this yellow emission band
is much more pronounced.
The reasons for observing radiative transitions from 4F9/2 level are
three-fold. Firstly, the energy difference between energy states lying
above 4F9/2 level is very small, thus the 4F9/2 level must be receiving
many electrons via non-radiative relaxation and would be highly
populated. Secondly, the energy separation between 4F9/2 level and

its lower lying level is quite large (approximately 7000 cm-1), and
nally, as mentioned earlier, the phonon energy of the borate
amorphous matrix is almost 1100 cm 1, which is not enough to
induce a phonon mediated relaxation from the excited state.

CONCENTRATION QUENCHING
The emission intensity enhanced rapidly with increasing Dy 3+ ion
concentration upto 1.0 mol%. After
which, the emission intensity
declined. The highest emission intensity was observed for
glass
sample with a critical Dy3+ ion
concentration of
1.0mol%.
Concentration quenching occurs when energy is transferred from one
donor to another until the energy reaches a sink or an acceptor in the
amorphous matrix .

EXCITATION SPECTRUM

The PL excitation spectra PLB glasses doped with 1.0 mol% of Dy 3+ ion
is shown. This spectra was measured while keeping the monitoring
wavelength at em = 484 nm,( as it corresponded to the most intense
peak in PL emission spectra). In the excitation spectra, sharp peaks are
observed due to the 4f4f transitions of Dy 3+ ion. They originate from
the ground level (6H15/2) to higher excited levels.

CIE CHROMATICITY

The chromaticity coordinates calculated for Dy3+ doped

PLB under ex = 347 nm is (x = 0.31, y= 0.35), which lies very
close to the CIE standard D65 illuminant (x = 0.31, y = 0.33)
and also standard equal energy white illuminant (x = 0.33, y
=0.33).
Hence, it is suggested that Dy3+ doped PLB glass
under ex= 347 nm excitation is very suitable for the
generation of white light (average daylight illuminant) by
using commercial UV LED chip.

FTIR

References

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