Lanthanide-doped core-shell nanoparticles for

solid state lighting applications

by
Saurabh Singh
Chemical Engineering Department
Indian Institute of Technology Kanpur

A Thesis Submitted in Partial Fulfillment of the

Requirements for the Degree of

Master of Technology

CERTIFICATE

It is certified that the work contained in the thesis entitled Lanthanidedoped core-shell nanoparticles for solid state lighting applications has been
carried out by Saurabh Singh under my supervision and that it has not been
submitted elsewhere for a degree.

Dr. Sri Sivakumar

Assistant Professor
Department of Chemical Engineering
Indian Institute of Technology Kanpur
India, 208016

ABSTRACT
There is a large interest in the production of cheap and efficient white light for the
applications such as liquid crystal display, display devices, general lighting and active
materials in laser. The optical materials that have been developed include mercury vapour
lamps; fluorescent light tubes and the latest to the field are Organic LEDs and Inorganic
LEDs which exploit electricity for the light generation. There are issues of long term
stability of emitters and low efficiency of incandescent light sources which produce light
by heating. To overcome these issues, lanthanide ions are gaining popularity these days
which can produce light by two processes 1) Up-conversion which is based on sequential
absorption of photons followed by energy transfer leading to the conversion of near
infrared photons to visible photons. 2) Down-conversion which is the conversion of UV
into visible light.
This thesis describes the incorporation of luminescent lanthanide ions-doped
nanoparticles into an inorganic matrix to improve the optical properties of lanthanide ions
and these materials can potentially be used in white light devices, optical amplifiers,
lasers, and biolabeling. Bright white light has been generated from luminescent
lanthanide ions doped LaVO4 core-shell nanoparticles through down-conversion of a
single 280 nm light source. The down-conversion mechanisms involved in the generation
of light have been discussed in detail. Preparation of luminescent lanthanide ions-doped
LaVO4 core-shell nanoparticles has been discussed and they show energy transfer from
the semiconductor matrix to the lanthanide ions.
Supervisor:

Dr. Sri Sivakumar (Chemical Engineering Department)

Dedicated to my
family

Acknowledgement

First, I thank my advisor Dr. Sri Sivakumar, for his supervision

and guidance. He was always there to listen and to give advice. He
taught me how to ask questions and express my ideas. He showed me
different ways to approach a research problem and the need to be
persistent to accomplish any goal. I am really thankful to him for being
such a nice friend.

I would like to thank the staff of XRD, TEM, FTIR and NMR labs
for helping me out in the characterization of the nanoparticles I
prepared. My special thanks to Haider, Chote dada (Rupesh), Arun,
Manish and Anurodh with whom I worked during my stay here.
Further my other labmates Pooja, Jaishree, Amritha, Auhin and
Vishal deserve a word of appreciation for their help and maintaining
convivial atmosphere in the lab.

I have been fortunate to have made very good friends at IIT

Kanpur and the times I have spent with them are the best in my life.
Starting with a long list, I am grateful to Tiwari, Ramu, Bhuwan, Raze
da, Piyush, Lala, Gunjan, Rehul, Bajpai, Sugga, Laddu, GMD,
Rupesh and Babbar.

I would like to thank everybody who was important to the

successful completion of my stay at IIT Kanpur.

Last, but not least, I thank my family: my parents, father and

mother for giving me life in the first place, for educating me with
aspects from both arts and sciences, for unconditional support and
encouragement to pursue my interests, my sister Swati for giving her
sort of useful advices, for listening to my complaints and frustrations,
and for believing in me and Priyanka, my soul mate for her dedication,
support and for reminding me that my research should always be useful
and serve good purposes for all humankind.

Table of Contents
Certificate.. .1
Abstract...2
Acknowledgement..4
List of tables8
List of figures..8
1. CHAPTER 1: General Introduction.10
1.1. Introduction..11
1.2. Optical properties of lanthanide ions14
1.2.1. Lanthanides in the Periodic Table..14
1.2.2. Luminescence of trivalent lanthanide ions.15
1.2.3. Phenomena of fluorescence19
1.2.4. Phenomena of phosphorescence.19
1.3. Jablonski Diagram, Lifetime and Quantum Yield20
1.3.1. Jablonski Diagram..20
1.3.2. Quantum yield22
1.3.3. Lifetime..22
1.4. Quenching process.23
1.4.1. Multi-phonon emission23
1.4.2. Energy transfer between lanthanide ions.24
1.4.3. Cross relaxation.......................................................................................25
1.5 Objective.31

2. CHAPTER 2: Synthesis of lanthanide (III)-doped nanoparticles33

2.1. Introduction.34
2.2. Preparation of oleic acid stabilised lanthanide doped nanoparticles ..35
2.3. Characterization...36

3. CHAPTER 3: Results and Discussions39

3.1. Characterization ...40
3.2. Eu3+ emission45
3.3. Tb3+ emission50
3.4. Dy3+ Emission..53
3.5. Tm3+ emission..55
3.6. White light through LaVO4: 0.5% Eu3+, 12.5% Tb3+ & 20% Tm3+ core-shell
nanoparticles....................................................................................57
3.7. White light through LaVO4: 0.125% Dy3+ & 20% Tm3+ core-shell
nanoparticles.59
3.8. Control Experiment..62
CONCLUSION64
REFERENCES66

List of tables and figures

CHAPTER 1
Table 1.1 Important emission lines of some lanthanide ions...18
Figure 1.1 Periodic table showing the position of the elements..14
Figure 1.2 Energy level diagram of Eu3+, Dy3+, Tb3+ & Tm3+ 17
Figure 1.3 Jablonski Diagram showing ...20
Figure 1.4 Energy level diagram showing energy transfer between Tb3+ and Eu3+ ....24
Figure 1.5 Cross-relaxation processes in Eu3+ & Pr3+ .26
Figure 1.6 Scheme showing the generation of white light ..32
CHAPTER 2
Figure 2.1 Schematic for the preparation of Ln3+: LaVO4 core-shell NP..36
CHAPTER 3
Figure 3.1 Structure of oleic acid40
Figure 3.2 XRD scan of the sample.41
Figure 3.3 FTIR spectrum of the sample 42
Figure 3.4 NMR spectrum of the sample 43
Figure 3.5 TEM image of the sample .44
Figure 3.6 a) Emission Spectrum of LaVO4: Eu3+ core nanoparticles.46
Figure 3.6 b) Emission Spectrum of LaVO4: Eu3+ core-shell nanoparticles46
Figure 3.7 a) Excitation Spectrum of LaVO4: Eu3+ core nanoparticles47
Figure 3.7 b) Excitation Spectrum of LaVO4: Eu3+ core-shell nanoparticles...47

Figure 3.8 a) Lifetime decay curve of LaVO4: Eu3+ core nanoparticles ..48
Figure 3.8 b) Lifetime decay curve of LaVO4: Eu3+ core-shell nanoparticles 49
Figure 3.9 Emission Spectrum of LaVO4: Tb3+ core-shell nanoparticles ....51
Figure 3.10 Excitation Spectrum of LaVO4: Tb3+ core-shell nanoparticles ........52
Figure 3.11 Luminescence decay curve of Tb3+ emission....52
Figure 3.12 Emission Spectrum of LaVO4: Dy3+ core-shell nanoparticles .....53
Figure 3.13 Excitation Spectrum of LaVO4: Dy3+ core-shell nanoparticles ...54
Figure 3.14 Luminescence decay curve of Dy3+ emission....54
Figure 3.15 Emission Spectrum of LaVO4: Tm3+ core-shell nanoparticles ....55
Figure 3.16 Excitation Spectrum of LaVO4: Tm3+ core-shell nanoparticles .......56
Figure 3.17 Luminescence decay curve of Tm3+ emission.......56
Figure 3.18 Scheme ......57
Figure 3.19 Emission Spectrum of LaVO4: Eu3+/Tb3+/Tm3+core-shell nanoparticles..58
Figure 3.20 Excitation Spectra for all the major emissions......59
Figure 3.21 Emission spectrum of LaVO4: Tm3+, Dy3+ core-shell nanoparticles.....60
Figure 3.22 Excitation Spectra for 474 nm (Tm3+) & 572 nm (Dy3+) emission...61
Figure 3.23 Emission Spectrum of control sample .. ...62

Chapter 1
General Introduction

10

1.1

Introduction

Most of the lanthanide ions were discovered in the early 19 th and some in the 20 th
century,[1] but since this fairly recent discovery the technological importance of the ions
has been growing rapidly. Although they are called rare earth ions, they are not as rare as
the name would suggest the ions are abundant in the earths crust, but they do not have
the tendency to form concentrated ore deposits. [2] A wide variety of minerals, which can
be found on a few places in the world, do contain rare earth elements at relatively high
concentration, in different compositions. [3] The lighter ions have a higher abundance in
these ores and consequently have lower prices. The ions have a wide variety of
technological importance such as in permanent magnets, catalysis, batteries, and optics. [4]
The optical properties of lanthanide ions became important when techniques were
developed to separate the different lanthanide ions to high purity. Cathode ray tubes of
computers and colour televisions use europium as the red phosphor[5] and in fiber optic
telecommunication, erbium ions are used in laser amplifiers to enhance optical signals. [6]

There is a large interest in the production of cheap and efficient white light for the
applications such as liquid crystal display (LCD), display devices, general lighting and
active materials in laser. The optical materials that have been developed include mercury
vapour lamps, fluorescent light tubes and the latest to the field are Organic Light
Emitting Diodes (OLEDs)[7], Inorganic Light Emitting Diodes (ILEDs)[8] and Ploymer
Light Emitting Diodes (PLEDs) which exploit electricity for the light generation. After
being introduced in 1879 by Thomas Alva Edison, incandescent light sources which

11

produce light using electricity have still very low efficiencies (10-12%)[9],[10]. Later on,
mercury vapour lamps and fluorescent light tubes were developed which still in use
having low efficiencies (~28). Source of emission used in fluorescent tubes are
lanthanide ions because of their stable photocycle, increased brightness, and high
quantum yield. To overcome the issues of efficiency, organic light-emitting diodes
(OLEDs) and polymer light-emitting diodes (PLEDs)[11] are being developed. However,
there are issues of long term stability of emitters, high fabrication costs, low
photostability and bias dependent colour variation which limits the use of
OLEDs/PLEDs. To overcome these issues, lanthanide ions are gaining popularity these
days which can produce light by two processes 1) Up-conversion[12] which is based on
sequential absorption of photons followed by energy transfer leading to the conversion of
near infrared photons to visible photons. 2) Down-conversion[13] which is the conversion
of UV into visible light. White light for these uses can also be generated using various
combinations of different lanthanide ions in different concentrations. Generation of white
light by different combinations of various lanthanide ions is the subject of this thesis.

The Ln3+ ions used in the experiments are extremely stable, because no chemical
bonds are involved so degradation does not occur. The solubility of the ions in organic
materials is low due to which they cant be processed further via spin coating technique
and coating it over LED of the required range. One way to solve this problem is by the
synthesis of lanthanide complexes, which are soluble in organic materials. However, a
disadvantage of the use of these complexes is that the good optical properties these
lanthanide ions have in inorganic materials are largely reduced in the organic

12

complexes.[14] The high vibrational energies of the chemical bonds in organic complexes
are efficient quenchers of lanthanide luminescence. In case of an organic matrix,
vibrational energy of the bonds is sufficient enough to quench the luminescence of the
lanthanide ion so the preferred matrix for doping is an inorganic one with the addition of
a ligand to make the product dispersible in organic solutions. In order to use lanthanide
ions in an inorganic matrix, they have to be shielded from the organic environment in
order to have good luminescence properties.
Light can be generated from the lanthanide ions by either by up-conversion or by
down-conversion by incorporating the lanthanide ions into an organic/inorganic matrix
and then exciting the sample with IR/UV light depending on the type of process we are
using for light generation. Luminescent NPs that are soluble in organic solvents attract a
great deal of interest because these materials can be easily processed via spin-coating
techniques to form a uniform film from an organic solution. Among the known
luminescent materials, Ln3+ - doped inorganic materials offer a range of compounds with
unique versatility.

Bright white light has been generated from luminescent lanthanide-doped coreshell LaVO4 nanoparticles through down-conversion of a single 280 nm light source. The
down-conversion mechanisms involved in the generation of light has been discussed.
Preparation of luminescent lanthanide ions-doped LaVO4 core-shell nanoparticles has
been discussed and they show energy transfer from the semiconductor matrix to the
lanthanide ions.

13

1.2 Optical properties of lanthanide ions

1.2.1 Lanthanides in the Periodic Table
Rare Earth Elements: Series of chemical elements of the periodic table. The rare earth
elements (or rare earth metals) include the elements with atomic numbers 57 through 71,
and, named in order, are lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium
(Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb),
dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), and
lutetium (Lu). Yttrium (Y, atomic no. 39) and scandium (Sc, atomic no. 21) are also
included in the group of rare earth elements. The elements cerium (Ce, atomic no. 58)
through lutetium (Lu, atomic no. 71) is commonly known as the lanthanide series.

Fig. 1.1 Periodic table showing the position of the elements

Oxides of the rare earth elements are called rare earths, and are found in minerals
that are actually more abundant than those of some other metals, such as those in the
platinum group. The principal source of rare earths is the mineral monazite. Some other

14

rare minerals that also contain small amounts of rare earths include cerite, gadolinite, and
samarskite.
The lanthanides usually exist as trivalent cations, in which case their electronic
configuration is (Xe) 4f n, with n varying from 1 (Ce3+) to 14 (Lu3+). The transitions of
the f-electrons are responsible for the interesting photo physical properties of the
lanthanide ions, such as long-lived luminescence and sharp absorption and emission
lines. The f-electrons are shielded from external perturbations by filled 5s and 5p orbitals,
thus giving rise to line-like spectra.

The f-f electronic transitions are forbidden, leading to long excited state lifetimes,
in the micro- to millisecond range. The forbidden nature of the f-f transitions is also
reflected in low extinction coefficients, making direct photo-excitation of lanthanide ions
difficult. This can be overcome by using energy transfer from organic chromophores to
lanthanide ions.

1.2.2 Luminescence of trivalent lanthanide ions

The lanthanides are the elements following lanthanum in the periodic table. In this
range of elements the 4f shell is successively filled. Since the valence electrons are the
same for all the ions, they all show very similar reactivity and coordination behavior. [4]
Few ions in the series also show luminescence in the divalent state (Eu 2+, Sm2+).[15] Since
luminescence of the trivalent lanthanide ions arises from transitions within the 4f shell
and because this shell is shielded by filled 5s and 5p shells, the absorption and emissions
of the ions are only slightly affected by the environment. The transitions within the 4f

15

state are parity forbidden, but due to mixing with allowed transitions, like the 4f-5d
transitions, they do occur. As a result of the forbidden character, absorption coefficients
are low and luminescence lifetimes are long, ranging from microseconds up to several
milliseconds. Energy level diagram of the four lanthanide ions used in the synthesis for
white light generation is shown here. Three lanthanide ions which do not show any
emission in visible spectrum are La3+, Lu3+ & Ce3+. La3+and Lu3+ have a completely
empty and a completely filled 4f shell, respectively, and therefore have no optical
transitions and Ce3+ has one electron and one 4f level just above the ground state. Ce3+ has
the lowest oxidation potential of the lanthanide ions making the allowed 4f-5d transitions
possible in the UV.
The energy levels are denoted as

(2S+1)

J (Russel-Saunders notation), where S is

the spin multiplicity, the orbital angular momentum, and J the total angular momentum.
Due to the effective shielding of the 4f electrons, the crystal field has almost no effect on
the energy of the levels. For this reason this energy level diagram can be used for
lanthanide ions in all sorts of host materials. In principle this could lead to very similar
emission and absorption spectra for the same lanthanide ion in a range of different hosts,
but symmetry and quenching will have an effect on the emission properties as discussed
further in this chapter. The selection rules for the different transitions are influenced by
the symmetry of the environment. The nature of the transitions varies from pure magnetic
dipole transitions to pure electric dipole transitions and mixtures of the two.

16

Figure 1.2 Energy level diagram of Eu3+, Dy3+, Tb3+ & Tm3+
Y3+ is usually also treated as a lanthanide ion, because of similar reactivity and
coordination behaviour. This ion also has no optical transitions, but luminescent
lanthanide ions are often incorporated in host materials with Y 3+ ions.

The emission spectrum of the Eu3+ ion is strongly influenced by the symmetry of
the surroundings. The main emissions of this ion occur from the 5D0 to the 7FJ (J = 0-6)
levels. The 5D0 7F1 transition is a pure magnetic dipole transition, which is practically
independent of the symmetry of the surroundings and the strength can be calculated
theoretically. The transitions to the 7F0,

3, 5

levels are forbidden both in magnetic and

electric dipole schemes and are usually very weak in the emission spectrum. The

17

remaining transitions to the 7F2, 4, 6 levels are pure electric dipole transitions and they are
strongly dependent on the symmetry of the environment. In a crystal site with inversion
symmetry the electric dipole transitions are strictly forbidden and the 5D0 7F1 transition
is usually the dominant emission line. In a site without inversion symmetry the strength
of the electric dipole transitions is higher. The 5D07F2 transition is usually the strongest
emission line in this case, because transitions with J = 2 are hypersensitive to small
deviations from inversion symmetry.[16] The symmetry around the lanthanide ion can thus
be obtained from the shape of the emission spectrum of the Eu 3+ ion. The other lanthanide
ions have transitions that are usually mixtures of electric and magnetic dipole transitions
and the effects of the symmetry are less pronounced.

Table 1.1: Important emission lines of some lanthanide ions.

Ion

Transition

Pr3+

Nd3+

Wavelength (nm)

Application

G43H5

1300

Optical amplifier

F3/24I11/2

1064

Solid state lasers

Eu3+

D07F2

615

Displays, lighting

Tb3+

D47F5

545

Lighting

F11/2 +6H9/26H15/2

1300

Optical amplifier

1530

Optical amplifier

H43F4

1480

Optical amplifier

F5/22F7/2

980

Sensitizer

Dy3+
Er3+

I13/24I15/2

Tm3+
Yb3+

18

The symmetry also has an influence on the radiative lifetime of the 5D0 level. The
radiative lifetime is the time for the luminescence to drop to 1/e in intensity in absence of
quenching. In the case of a Eu3+ ion without inversion symmetry the rate of the forced
electric dipole transition is higher than in the case of a Eu 3+ ion with inversion symmetry.
This automatically means that the radiative lifetime of a Eu 3+ ion in a site with inversion
symmetry is longer.

1.2.3 Phenomena of fluorescence

Luminescence is the emission of light from excited states of any substance.
Luminescence is divided in to two types fluorescence and phosphorescence, which
depends on the nature of excited states.
Fluorescence emission of light when an electron in excited singlet state returns
to the ground state where it is paired to another electron of opposite spin. Return to the
ground state is spin allowed and occurs rapidly by emission of a photon, thus
fluorescence has a very short lifetime (~ 10 ns).

1.2.4 Phenomena of Phosphorescence

Phosphorescence emission of light from triplet excited state where electrons in
excited and ground state have the same spin and thus transition is spin forbidden leading
to low emission rates and consequently longer lifetimes of the order of seconds.
Phosphorescence is usually not seen in fluid solutions at room temperature because of
many deactivation processes that compete with emission, such as non-radiative decay and
quenching processes. Fluorescence typically occurs from organic molecules, e.g. quinine.

19

1.3 Jablonski Diagram, Lifetime and Quantum Yield

13.1 Jablonski Diagram
The processes that usually occur between the absorption and emission of light are
illustrated by Jablonski diagram.

Fig. 1.3 Jablonski Diagram showing molecular processes involved in excited states

A typical Jablonski diagram is shown in Figure 1.3. The singlet ground, first, and
second electronic states are depicted by S0, S1, and S2, respectively. At each of these
electronic energy levels the fluorophores can exist in a number of vibrational energy
levels, depicted by 0, 1, 2, etc. In this Jablonski diagram a number of interactions such as
quenching, energy transfer, and solvent interactions have been excluded. The transitions

20

between states are depicted as vertical lines to illustrate the instantaneous nature of light
absorption. Transitions occur in about 10-5 s, a time too short for significant displacement
of nuclei. This is the Franck-Condon principle. At room temperature thermal energy is
not adequate to significantly populate the excited vibrational states.

Absorption and emission occur mostly from molecules with the lowest vibrational
energy. The larger energy difference between the S 0 and S1 excited states is too large for
thermal population of S1. For this reason light is used and not heat to induce fluorescence.
Following light absorption, several processes usually occur. A fluorophore is usually
excited to some higher vibrational level of either S 1 or S2. With a few rare exceptions,
molecules in condensed phases rapidly relax to the lowest vibrational level of S 1. This
process is called internal conversion and generally occurs within 10 -12 s or less. Since
fluorescence lifetimes are typically near 10 -8 s, internal conversion is generally completed
prior to emission. Hence, fluorescence emission generally results from a thermally
equilibrated excited state, that is, the lowest energy vibrational state of S 1. Return to the
ground state typically occurs to a higher excited vibrational ground state level, which
then quickly (10-12 s) reaches thermal equilibrium (Figure 1.3). Return to an excited
vibrational state at the level of the S0 state is the reason for the vibrational structure in the
emission spectrum of perylene.
An interesting consequence of emission to higher vibrational ground states is that
the emission spectrum is typically a mirror image of the absorption spectrum of the S 0
S1 transition. This similarity occurs because electronic excitation does not greatly alter
the nuclear geometry. Hence the spacing of the vibrational energy levels of the excited

21

states is similar to that of the ground state. As a result, the vibrational structures seen in
the absorption and the emission spectra are similar. Molecules in the S1 state can also
undergo a spin conversion to the first triplet state T 1. Emission from T1 is termed
phosphorescence, and is generally shifted to longer wavelengths (lower energy) relative
to the fluorescence. Conversion of S1 to T1 is called intersystem crossing. Transition from
T1 to the singlet ground state is forbidden, and as a result the rate constants for triplet
emission are several orders of magnitude smaller than those for fluorescence. Molecules
containing heavy atoms such as bromine and iodine are frequently phosphorescent. The
heavy atoms facilitate intersystem crossing and thus enhance phosphorescence quantum
yields.

1.3.2 Quantum Yield

Quantum yield of a fluorophore can be defined as the ratio of the number of photons
emitted to the number of photons absorbed.

1.3.3 Lifetime
Lifetime of an excited state is defined by average time the molecule spends in excited
state prior to return to the ground state. Generally fluorescence lifetimes are near 10 ns.
Lifetime of a fluorophore is given by the equation:

where, is the emissive rate of the fluorophore and Knr is the rate of non-radiative decay

22

The lifetime of a fluorophore in the absence of non-radiative processes is called the

intrinsic lifetime.

1.4 Quenching processes

1.4.1 Multi-phonon quenching

Non-radiative processes can also play an important role. The energy of the excited
state can be taken up by the surroundings in the form of vibrational energy, often referred
to as phonon emission. The effectiveness of this process depends on the availability of
high-energy vibrations in the surroundings and the energy difference between the energy
levels of the lanthanide ion. The fundamental vibrations of the chemical bonds in the
surroundings and the energy of the vibration are determined by the reduced mass of a
bond. Especially bonds with hydrogen have a small reduced-mass and therefore high
vibrational energies. These bonds are therefore able to take up large amounts of energy
and effectively quench lanthanide ions with large separations between the energy levels.
The visible emitting ions Eu3+ and Tb3+ have large gaps between the emissive 5D0 and 5D4
level of 12,000 and 15,000 cm-1, respectively, but still these ions and especially Eu 3+ are
quenched substantially when the ions are dissolved in water (vibrational energy: max
3500 cm-1). The quenching efficiency is strongly dependent on the number of vibrational
quanta that are needed to bridge the gap between the lowest emitting level and the highest
non-emitting level of the lanthanide ion. The observation of luminescence of a lanthanide
ion in solvents with high vibrational energies (water) is dependent on the energy
difference between the lowest radiative level and the highest non-radiative level. For

23

example, Tb3+ in water shows reasonable luminescence but Eu3+ luminescence is almost
completely quenched. The Eu3+ ion is quenched by energy transfer to the 4th overtone of
the OH bonds, while the Tb3+ ion is quenched by energy transfer to the 5th overtone of the
OH bond. Another important factor governing the efficiency of quenching is the distance
between the lanthanide ion and the quencher group. Quenching occurs through a dipoledipole interaction in a Frster-type mechanism.[17] In this Frster mechanism the
interaction between the lanthanide ion (donor) and the quenching site (acceptor) only
occurs when the energy levels of the donor and acceptor are resonant. The donor and
acceptor do not have to have overlap of their wave functions, but the process is strongly
distance dependent. For dipole-dipole interactions the rate of quenching has a distance
dependence of r-6.[18]

1.4.2 Energy transfer between lanthanide ions

Fig. 1.4 Energy level diagram showing energy transfer between Tb3+ and Eu3+.

24

Another factor in the quenching of lanthanide ions is the interaction between the
lanthanide ions, of the same or different type. Two different lanthanide ions can transfer
energy when they have similar separations between the energy levels. The small
mismatch in energy can be compensated for by the emission or uptake of a phonon.
Energy transfer of one lanthanide ion can be used to enhance luminescence of the other
lanthanide ion. For example, the lanthanide couple Tb3+- Eu3+, when excited at <375 nm
or at 480 nm, which in this case is chosen since that will be sufficiently blue to enable a
white light spectrum when combined with the Eu 3+ red and Tb3+ green, the Tb3+ ion
transfers its energy to the Eu3+ ion, 5D4(Tb)
Tb3+ emissions (5D4

D1(Eu), resulting in a greatly diminished

FJ) and an increase in the Eu3+ emissions (5D0

FJ). [19]

1.4.3 Cross-relaxation

In a cross-relaxation process two ions that are closely together interact and
exchange energy. Examples of these processes are given in Figure 1.4 for Eu3+ and Pr3+.
A Eu3+ ion in the D1 excited state can transfer its energy to a neighbouring Eu 3+ ion
promoting it to the 7F3 level. This leads to one ion in the 5D0 excited state and one in the
7

F3 level. In the case of Pr3+, the 3P0 level can be quenched by cross-relaxation leading to

an ion in the 3H6 and an ion in the 1D2 level. The 1D2 level can be quenched again by
cross-relaxation leading to an ion in the 1G4 state and an ion in the 3F3 level.

25

Fig. 1.5 Cross-relaxation processes in Eu3+ & Pr3+

Energy migration is another form of cross-relaxation between two ions of the
same sort. The excited state energy levels of two identical ions are resonant, so the
energy can be transferred to the neighbouring ion by cross-relaxation and travel through
the material hopping from one ion to the other. An increase in the doping concentration
leads to a faster energy migration through the material, making the chance of meeting a
quenching site higher. For reasons of cross-relaxation and energy migration, high doping
concentrations often lead to a decrease in luminescence intensity and luminescence
lifetime.

It is known that the luminescent spectra of Ln3+-doped nanocrystals (and Ln3+doped materials in general) vary little from host to host. [20] However, the crystal field

26

exerted on the Ln3+ dopant ions by the host (nano) matrix plays a pivotal role in
determining transition probabilities, lifetimes of the excited states, luminescence
efficiency, as well as energy transfer efficiency. [21]

In this thesis, we focus mainly on lanthanide-doped LaVO4 nanoparticles and

study their optical properties. Many research groups have investigated the optical
properties of lanthanide ions in detail in various nanoparticles matrices such as
oxides[22],[23],

fluorides[24],[25],

phosphates[26],

vanadates[27],[28]

and

semiconductor

nanoparticles[29],[30].

Capobianco and his co-workers have investigated the effect co-doping of Yb3+ ion
with Tm3+ and Er3+ ions in up-conversion of Lu3Ga5O12 nanocrystals[31]. They prepared
the nanocrystals by a simple sol-gel method exhibiting bright white light following
excitation with lower energy near-infrared light (exc) 980 nm) via an upconversion
process. The combination of upconverted blue (from Tm3+), green, and red (from Er3+)
emissions resulted in the white luminescence, which is intense and visible to the naked
eye at a laser power less than 30 mW (3.4 W/cm2). The calculated CIE colour coordinates
fell within the white region and changed only very little with the incident pump power.
These two significant characteristics in combination with the thermal stability of the
lutetium garnets made this material an ideal candidate for the development of white light
based lasers and LEDs.

27

They have also studied the up-conversion properties of effect of doping of Er 3+

ions in Gd3Ga5O12[32] at different concentration (1% and 5%). Green emission from the
(2H11/2, 4S3/2)

I15/2 and red emission from the 4 F9/2

I15/2 transitions were observed

following excitation with 800 nm into the 4I9/2 state. They determined that up-conversion
occurred via excited-state absorption in the 1% sample while energy transfer upconversion took over as the dominant mechanism as the concentration was increased to
5%. An enhancement of the red (4F9/2

I15/2) emission was observed and hypothesized

to occur via the concentration dependent ( 4I9/2, 4I11/2)

(4I13/2, 4F9/2) ion pair process,

which directly populated the 4F9/2 state.

Sivakumar et al. have demonstrated the generation of white light through Upconversion of a Single NIR Source from Sol-Gel-Derived Thin Film Made with Ln3+Doped LaF3 Nanoparticles.[33] White light was generated from SiO2, ZrO2 sol-gel thin
film made with Ln3+-doped nanoparticles co-doped with Yb3+ ions. They also prepared
the core-shell samples to increase the lifetime values by surrounding a doped LaF3 core
with an undoped LaF3 shell.[34]
Patra et al. have reported the bright white light emission from Eu 3+ doped In2S3
nanoparticles by single wavelength light excitation (350 nm). [35] They found that the
Energy Transfer efficiency from In2S3 nanoparticles to Eu3+ increases from 0.27% to
0.42% with increasing dopant concentration with quantum efficiency 24.2% for 1.0
mol% Eu doped In2S3 nanoparticle and the CIE coordinates 0.27 and 0.29, which fall
within the white region of the 1931 CIE diagram.
A highly efficient blue-green-emitting cationic iridium complex [Ir(dfppz)2(tppyim)]PF6, which contains a bulky side group in the ancillary ligand, has been

28

synthesized and fully characterized. LECs based on [Ir(dfppz) 2(tppyim)] PF6 showed
highly efficient blue-green electroluminescence. White LECs based on [Ir(dfppz)2(tppyim)]PF6 showed warm white light, with CIE coordinates of (0.37, 0.41).[36]
Herland et al. demonstrated the use of self-assembled bionanostructures in
polymer light-emitting diodes. Amyloid fibrils formed by protein misfolding were
decorated with a soluble luminescent conjugated polymer. [37] This conjugated polymer
complex with amyloid fibrils was used as the active layer in a light emitting diode,
resulting in a 10-fold increase in external quantum efficiency compared with pristine
polymer, because of improved carrier injection.
They have also shown that a negatively charged conjugated polyelectrolyte can be
used as a novel optical probe for the detection of the formation of amyloid fibrils. The
formation of amyloid fibrils reflected as an alteration of the geometry and the electronic
structure of the bound polyelectrolyte chains has so far been detected by absorption and
emission, but electrical detection of these transitions will most likely be possible. Their
method is fast and simple and is based on noncovalent assembly between the anionic
polyelectrolyte and the protein. They suggested that their method may be used for a wide
range of proteins, biosensors, and bioelectronic devices.[38]
Chung Hsu et al. developed a novel series of blue and yellowish-green lightemitting single polymers by end-capping of low contents of 4-bromo-7H-benzo
[de]naphtha[2,3:4,5]

imidazo[2,1-a]isoquinolin-7-one

into

polyfluorene.

Electroluminescence (EL) spectra of these polymers exhibit blue emission (max =

430/460 nm) from the fluorene segments and yellowish-green emission (max = 510/530
nm) from the 4-bromo-7H-benzo [de]naphtha [2,3:4,5] imidazo[2,1-a]isoquinolin-7-one

29

units. For the polymer (PFNAP-0.06) with the 4-bromo-7H-benzo [de]naphtha [2,3:4,5]
imidazo[2,1-a]isoquinolin-7-one unit content of 0.06 mol%, its EL spectrum shows
balanced intensities of blue emission and yellowish-green emission with Commission
Internationale de lEclairage (CIE) coordinates of (0.25, 0.34).
A new white polymer-light-emitting-diode (WPLED) can be developed from the
single polymer (PFNAP-0.06) system blended with a red phosphorescent iridium
complex [Bis(2-[20-benzothienyl)-pyridinato-N,C30] iridium (acetylacetonate) (BtpIr)].
They were able to obtain a white-light-emission device by adjusting the molar ratio of
BtpIr to PFNAP-0.06 with a structure of indium tin oxide (ITO)/poly(3,4ethylenedioxythiophene): poly(styrene sulfonic acid) [PEDOT:PSS]/PVK/emission
layer/Ca/Ag. The brightness in such a device configuration is 4030 cd/m2 at 9 V with CIE
coordinates of (0.32, 0.34).[39]
Hung Lu et al. demonstrated a high-efficiency white polymer light-emitting diode
(WPLED) based on carbazolegrafted poly(para-phenylene) (CzPPP) doped with greenand red-emitting Ir complexes as the emitting layer. The device exhibits pure white light
yet with stable sharp blue (430 nm), green (512 nm), and red (613 nm) emissions and has
the aximum current and external quantum efficiencies of 16.8 cd/A and 8.65%,
respectively. The overall performance is resulted from the excellent shielding effect of
CzPPP host to prevent back transfer of triplet energy especially from the green
phosphor.[40]
Dong Ba and his co-workers demonstrated upconversion (UC) white light hybrid
thin films containing Ln3+-tridoped (Yb3+, Er3+ and Tm3+) NaYF4 nanoparticles and
poly(vinyl pyrrolidone) (PVP, M(w) approximately 1300000) prepared by a spin-coating

30

method and characterized by X-ray diffraction (XRD), field emission scanning electron
micrograph (FE-SEM) and Fourier transform infrared spectra (FT-IR).[41] They generated
white light by two different lanthanide ions, Er 3+ (red and green) and Tm3+ (blue) under
excitation by a 980-nm laser diode. They modified PVP to the UC populating processes,
the color stability of the white light in the hybrid films was remarkably improved.
They also demonstrated white light-emitting thin films containing Ln3+-doped
NaYF4 nanoparticles prepared by a simple spin-coating method. They generated white
light by using two different lanthanide ions, Er3+ (red and green) and Tm3+ (blue), by
upconversion process under the excitation of a 980-nm laser diode.[42] The ratio of the
intensity of the three main emissions was tuned by controlling the concentration of the
nanoparticles in the thin film and the concentration of the lanthanide ions in the
nanoparticles. The color coordinates corresponding to emissions of different nanoparticle
concentrations and with the different pump powers were investigated. When the pump
power was fixed at 900 mW, the thin film with a concentration ratio of 2.5:1 emitted pure
white light with coordinates of (0.333, 0.339).

1.5 Objective
The goal of this thesis was to prepare bright white light emitting nanoparticles via
down-conversion of UV-light prepared by doping LaVO4 with various luminescent
lanthanide ions and are dispersible in organic solvents like chloroform, etc. Core-shell
approach was used as shown in the figure 1.6, to separate the various lanthanide ions
from each other as well as outer environment so as to prevent different types of

31

quenching processes described earlier in this chapter. We successfully prepared such

nanoparticles followed by their characterization using various techniques.

Fig. 1.6 Scheme showing the generation of white light

32

Chapter 2
Synthesis of lanthanide(III)-doped nanoparticles

33

2.1 Introduction
The luminescence of lanthanide ions has found important commercial
applications in displays,[43] optical amplifiers,[44] and lasers,[45] as described in chapter 1.
There is a growing interest to use this luminescence in polymer-based materials, because
of the easy processing of polymers and ease of integrating different optical components.
The luminescence of these lanthanide ions arises from transitions within the 4f electron
shell. These transitions are parity forbidden, leading to low absorption cross-sections and
long luminescence lifetimes. However, this long-lived excited state can be quenched very
efficiently in the presence of the high-energy vibrations of organic solvents, polymers, or
ligands, thus hampering the application in polymer-based devices. Therefore, to use
lanthanide luminescence in an organic environment it is important to shield the
lanthanide ion from the organic surroundings. Shielding of the lanthanide ion can be
achieved by doping it in the inorganic part of nanoparticles that should still be soluble in
organic solvents.

Good solubility is generally achieved by having organic groups on the outside of

the nanoparticles. Most nanoparticles doped with lanthanide ions are made in high
temperature procedures leading to nanoparticles without organic groups on the surface
and, therefore, they have no solubility in solvents. [46] Only very few examples of these
lanthanide-doped nanoparticles are there that have a good solubility in organic solvents
have been reported.[47] Nanoparticles with dimensions of a few nanometers are small
enough to minimize scattering in polymer films. [48] The largest contribution to scattering
in polymer films originates from particles with a size comparable to the wavelength of

34

light, or bigger (Mie scattering). Nanoparticles have a size much smaller than the
wavelength of light and when clustering of the nanoparticles in a polymer film is
prevented, scattering should be minimal.

All the lanthanide salts were obtained from Sigma-Aldrich. Ethanol was obtained
from Mercks chemicals and chloroform, oleic acid and tri-ethyl amine were obtained
from Qualigens. We used all the chemicals and salts without any further purification.
Distilled water was applied for all synthesis and treatment processes.

2.2 Preparation of oleic acid stabilised lanthanide doped core-shell

nanoparticles
A solution of distilled water ethanol (1:1) mixture (70 ml) with Oleic acid (2 ml)
was prepared and was allowed to heat to 750C with the pH of the solution was adjusted to
6 by the addition of (CH3)3N (30% w/v). Stoichiometric amount of Na3VO4 was added to
the solution, followed by the addition of stoichiometric amounts of the nitrate salts of
lanthanide ions (99.99%) dissolved in 2 ml of water and added drop wise. For Tm3+, Tb3+
& Eu3+ doped LaVO4 core-shell nanoparticles, Tm3+ doped La(NO3)3 makes the core,
followed by the addition of undoped La(NO3)3 shell which will protect Tm3+ from the
interaction with other lanthanide ions. Then Tb3+ doped La(NO3)3 shell is added followed
by undoped La(NO3)3 shell with the subsequent addition of Eu(NO3)3 doped La(NO3)3
and undoped La(NO3)3 shell.

35

Fig. 2.1 Scheme for the preparation of white light emitting Ln3+: LaVO4 core-shell NP
Formation of precipitate indicates the completion of reaction after two hours of
stirring and heating at 750C. The solution was then cooled to room temperature for
another two hours then precipitate formed was collected by centrifuge at 5000 rpm,
washed with water and ethanol, and dried under ambient conditions. After drying the
particles were dispersible in chloroform.

2.3 Characterization
The down conversion fluorescence analysis was done using FLSP920 Edinburgh
Instrument. The excitation source used was 450W Xe arc lamp and the detector was a

36

Red-sensitive Peltier element cooled Hamamatsu R928-P PMT. For recording decay
curves F-flash lamp was used. Sample was prepared by dissolving the precipitate
obtained earlier in to chloroform (CHCl3) followed by the excitation with 280 nm UV
light.
The formation of core-shell structure was visualized from Transmission Electron
Microscope (TEM) images obtained using FEI Technai Twin microscope with high
contrast and resolution at 20kV to 120kV. Sample for TEM was prepared by dissolving
the precipitate in CHCl3, followed by the sonication of the solution. The sonicated
solution was then loaded on the copper coated TEM grid which was further used.

NMR: The NMR graph was recorded using Bruker AC 300 instrument. The basic
frequency for 1H nucleus is 500 MHz. Sample was prepared by dissolving the precipitate
in CDCl3 not in CHCl3 to prevent C-H peak in the NMR spectrum.

XRD analysis: Approximately 20-25 mg of the sample was powdered in an

alumina mortar to break up lumps. The powder was smeared on to a zero-diffraction
quartz plate using ethanol. Step-scan X-ray powder-diffraction data were collected over
the 2 range 3 - 100 with CuK (40 kV, 40 mA) radiation on a Siemens D5000 BraggBrentano -2 diffractometer equipped with a diffracted-beam graphite monochromator
crystal, 2 mm (1) divergence and anti-scatter slits, 0.6 mm receiving slit, and incident
beam Soller slit. The scanning step size was 0.042 with a counting time of 1.5 s/step. Xray powder diffraction data for different phases were refined with the Rietveld program
Topas 2.1 from Bruker using the fundamental parameters approach.

37

FTIR: The Fourier Transform Infra Red (FTIR) spectra were obtained from Vertex
70V spectrometer using KBr pellet technique. Sample preparation was similar to that
done for fluorescence characterization.

38

Chapter 3
Results and Discussions

39

3.1 Characterization

LaVO4 nanoparticles were synthesized using a procedure described in chapter 2.

Oleic Acid is depicted in Figure 3.1 was used as a ligand for the synthesis of the
lanthanide-doped luminescent nanoparticles. To a solution of Na3VO4 in a water/ethanol
mixture was added drop wise a solution of the La(NO3)3 salts in water. The oleate headgroup of the ligand coordinates weakly to the lanthanide ions allowing the growth of the
nanoparticles, but coordinates strongly enough to prevent the nanoparticles from
aggregating. The 1H NMR spectrum of the nanoparticles obtained after the synthesis
shows broadened signals of the ligand due to the co-ordination of the ligand to the
nanoparticle surface. This broadening can be ascribed to the inhomogeneous distribution
of the magnetic environment around the nanoparticle and a reduction in rotational degree
of the ligand. No free ligand is present because no sharp signals are observed for unbound
ligand in the solution. Peak of oleate at 5.2 ppm of the protons on the double bond is
observed.

Fig. 3.1 Structure of oleic acid used as a ligand for the synthesis of LaVO4 nanoparticles

40

The X-ray powder diffraction pattern of LaVO4 was refined in space group D194h with the
Rietveld refinement method using the fundamental parameters approach.

Figure 3.2 Rietveld refinement plot of LaVO4: Eu, Tm & Tb nanoparticles

The pattern fits well with the xenotime structure of LaVO4, in contrast to the
monazite structure that is generally observed for bulk LaVO 4. The sharp peaks in XRD
pattern indicate the good crystallinity of the sample. The difference in crystal structure of

41

this nano crystalline LaVO4 and bulk LaVO4 is most likely a result of the increased
amount of surface ions in these materials.

FTIR Spectrum

Figure 3.3 FTIR spectrum of the sample dissolved in CHCl3

FTIR spectrum of the sample was carried to prove the presence of oleic acid
molecules. Absorbance peak at 789.40 cm-1 is the characteristic peak of the tetrahedral
VO43- (range is 780 920 cm-1). Due to La O vibration, there is a small peak at 442.11
cm-1. For m-LaVO4, absorbance peak are split in to 3 peaks while for that of t-LaVO4

42

phase there is only one peak near 800 cm-1 which indicates that the sample prepared is in
t-LaVO4 phase. Peaks at 2924 cm-1 and 2853 cm-1 are assigned to anti-symmetric and
symmetric methylene stretches (Vas(CH2)), (Vs(CH2)) of the oleic acid molecule.
Sharpness of the peaks indicates that the hydrocarbon chains are well arranged. Peak at
3006 cm-1 is due to V(C-H) made of the C-H bond adjacent to the C=C bond. 2500 cm-1
3500 cm-1 is assigned to (O-H) stretch which is visible at 3414 cm-1. It also imply that
CH=CH group of oleic acid does not interact with oleic acid surface thus, the oleic acid
molecules are adsorbed on the LaVO4 nanoparticles.

NMR Spectrum.

Figure 3.4 NMR spectrum of the sample dissolved in CDCl3

43

The 1H NMR spectrum of the nanoparticles obtained after the synthesis shows
broadened signals of the ligand due to the co-ordination of the ligand to the nanoparticle
surface. This broadening can be ascribed to the inhomogeneous distribution of the
magnetic environment around the nanoparticle and a reduction in rotational degree of the
ligand. No free ligand is present because no sharp signals are observed for unbound
ligand in the solution. Peak of oleate at 5.2 ppm of the protons on the double bond is
observed.

TEM Image

Fig. 3.5 TEM image of the sample

44

TEM image of the sample shows the agglomeration of the nanoparticles with typical size
around 20 nm.

3.2 Eu3+ emission

5% Eu3+: LaVO4 core and core-shell nanoparticles were prepared following the
method discussed in chapter 2. The Eu3+ emission originating from the 5D0, and 5D1
levels was observed after excitation at 280 nm for LaVO 4: Eu. The LaVO4: Eu
nanoparticles can be excited in a charge transfer band. In the LaVO 4 nanoparticles the
charge transfer is in the V-O bond. Deactivation of the charge transfer state leads to an
excited Eu3+ ion. The LaVO4 nanoparticles have the advantage that the charge transfer
band of the VO4 group is independent of the doping ion, making it possible to excite
almost all lanthanide ions using the charge transfer band of the VO 4 group. The ratio of
the different peaks of the 5D07Fj (J = 1, 2) transitions in the Eu3+ emission spectrum
gives information about the symmetry of the crystal site in which the ion is located. In the
LaVO4 nanoparticles the Eu3+ ion has no inversion symmetry, so the 5D07F2 transition
is clearly the dominating emission band.

In LaVO4: Eu nanoparticles the 5D1 emission could be observed, but due to multiphonon relaxation the emissions were very weak. The emission of the 5D1 level is
however strongly concentration dependent. A cross-relaxation process as described in
chapter 1 is responsible for quenching of the 5D1 emission at higher concentrations of
Eu3+. Difference in the emission and excitation spectra of core and core-shell samples can
be seen easily.

45

Fig. 3.6 a) Emission Spectrum of LaVO4: Eu3+ (5%) core nanoparticles with 280 nm UV excitation and 395 nm filter

3.6 b) Emission Spectrum of LaVO4: Eu3+ (5%) core-shell nanoparticles with 280 nm UV excitation and 395 nm filter

46

Fig. 3.7 a) Excitation Spectrum of LaVO4: Eu3+ (5%) core nanoparticles for 612nm emission using 395 nm filter

3.7 b) Excitation Spectrum of LaVO4: Eu3+ (5%) core-shell nanoparticles for 612nm emission using 395 nm filter

47

As can be seen from the excitation spectra for the two nanoparticles, there is an energy
transfer band from LaVO4 from 250 nm to 350 nm along with a small peak at 395 nm
which is due to self excitation of Eu3+. As can be seen energy transfer is more effective in
case of core-shell sample as compared to core sample as well as charge transfer from CT
VO4 is more efficient as compared to the self excitation of Eu 3+ ions.

Luminescence lifetime: The luminescence lifetime is an important parameter indicative

of the efficiency of the luminescence of the lanthanide ion. The observed luminescence
lifetime is the same as the radiative lifetime when quenching does not play a role.

Fig. 3.8 a) Lifetime decay curve of LaVO4: Eu3+ core nanoparticles

48

3.8 b) Lifetime decay curve of LaVO4: Eu3+ core-shell nanoparticles

Figure 3.8 shows the luminescence decays of the 5D0 level of the Eu3+ ion doped in the
two nanoparticles.
av(ms)

Nanoparticle
3+

LaVO4 : Eu (5%) core NP

0.98

LaVO4 : Eu3+ (5% )core-shell NP

1.20

We can see the increase in the lifetime of the particular level because of the
reduced quenching from the surrounding environment which is because of the formation

49

of an inert layer. The luminescence lifetimes were fitted using a bi-exponential decay. In
the LaVO4 nanoparticles the Eu3+ the ion is in a crystal site that has no inversion
symmetry as was concluded from the emission spectrum. As a result the radiative lifetime
of the Eu3+ ion in LaVO4 is much shorter than in the other matrices. The radiative
lifetime of the Eu3+ ion is strongly dependent on the symmetry of the crystal site.

3.3 Tb3+ emission:

The emission and excitation spectra of nanoparticles doped with Tb3+ ions are
shown in Figure 3.9 and 3.10. The excitation occurs through the charge transfer band of
the VO4 groups, the excitation spectra all show the broad vanadate absorption band. Four
emission peaks are observed of the 5D47FJ (J = 3 - 6) transitions after excitation at 280
nm. The positions of the major peaks are the same, because of the good shielding of the
4f electrons from the environment. Small differences can occur in the peak splitting and
the intensity ratio between the peaks. These small differences are a result of the
difference in symmetry of the doping site.

50

Fig. 3.9 Emission Spectrum of LaVO4: Tb3+ (5%) core-shell nanoparticles with 280 nm UV excitation and 395 nm filter

In the excitation spectrum monitoring the emission at 545 nm, the 4f absorption
bands are clearly visible, together with the allowed 4f-5d absorption. Charge Transfer
from VO4 group can be seen clearly, which shows the efficient energy transfer from
LaVO4 to Tb3+ ions.

51

Fig. 3.10 Excitation Spectrum of LaVO4: Tb3+ (5%) core-shell nanoparticles for 545nm emission using 395 nm filter

Figure 3.11 Luminescence decay of the 5D4 level of the LaVO4: Tb3+ core-shell nanoparticles

52

3.4 Dy3+ Emission:

Figure 3.12 demonstrated the emission spectrum of 5% Dy3+ doped LaVO4 coreshell nanoparticles. Dy3+ shows three emission bands in the visible from the 4F9/2 level to
the 6H15/2 (475 nm), 6H13/2 (570 nm), and the 6H11/2 (655 nm) levels, after excitation at 280
nm. The charge transfer band of the VO4 group is observed in the excitation spectrum for
the LaVO4 nanoparticles alongwith very small self excitation peaks of Dy3+ near 370 nm
which shows efficient energy transfer from VO4 to Dy3+.

Fig. 3.12 Emission Spectrum of LaVO4: Dy3+ (5%) core-shell nanoparticles with 280 nm UV excitation & 395 nm filter

53

Fig. 3.13 Excitation Spectrum of LaVO4: Dy3+ (5%) core-shell nanoparticles for 572nm emission using 395 nm filter

Figure 3.14 Luminescence decay of the 4F9/2 level of the LaVO4: Dy3+ (5%) core-shell nanoparticles

54

3.5 Tm3+ emission:

Tm3+ emission was effectively observed in the doped LaVO4 nanoparticles. The
Tm3+ ion shows a broad absorption band around 360 nm. Luminescence occurs from the
1

G4 level at 475 nm, and 650 nm from transitions to the 3H6, 3H4 levels, respectively, after

excitation in the broad absorption band of the LaVO4:Tm3+ nanoparticles. The excitation
spectrum of the LaVO4 nanoparticles shows the charge transfer band of the VO4 groups.

Fig. 3.15 Emission Spectrum of LaVO4: Tm3+ for 280 nm excitation

55

Fig. 3.16 Excitation spectrum of LaVO4: Tm3+ for 475 nm emission

Fig. 3.17 Lifetime decay curve of LaVO4: Tm3+ for 475 nm emission

56

3.6 Scheme 1: White light through LaVO4: 0.5% Eu3+, 12.5% Tb3+ & 20%
Tm3+ core-shell nanoparticles
For getting the white light by doping red, blue and green light emitting lanthanide
ions in to LaVO4 matrix, core-shell nanoparticles stabilized by oleic acid were prepared.
After several experiments using trial and error method, above composition of Ln 3+ ions
was obtained. For the LaVO4 nanoparticles the quenching seems to have a longer range,
going deeper into the nanoparticle. Therefore Tm3+ which is a very weak emitter and is
easily quenched is placed in the core followed by an inert shell then Tb3+ doped LaVO4
shell which is again covered with an inert shell. Eu3+ being the strongest emitter is placed
in the penultimate shell over which another inert shell is placed.

Fig. 3.18 Scheme for the preparation of white light emitting Ln3+: LaVO4 core-shell NP
All shells are under the influence of quenching for the LaVO4 nanoparticles,
because the first shell in the core of the nanoparticle has a lifetime that is substantially
lower than the radiative lifetime. Quenching from the surface is stronger in the LaVO 4

57

nanoparticles because in the LaVO4 nanoparticles, more shells are influenced by surface
quenching. As the absorption coefficient of the vanadate charge-transfer transition is
higher than that of the lanthanide 4f transitions, this property can be exploited to excite
all the lanthanide Ln3+ ions present in the matrix simultaneously using a single excitation
source so 280 nm UV source was used to excite all the Ln3+ ions simultaneously for
getting the white light.

Fig. 3.19 Emission Spectrum for LaVO4: Eu3+, Tb3+ & Tm3+core-shell nanoparticles using 280
nm UV source and 395 nm filter

As can be seen from the above emission spectrum, all the characteristic peaks of
the three Ln3+ ions are there. CIE co-ordinates of the white light obtained were (0.35,
0.35) as compared to that of the pure white light (0.33, 0.33).

58

Fig. 3.20 Excitation Spectra for all the major emissions

Excitation spectra for all the three major emissions show the broad absorption
range from 260 330 nm which is the typical absorption range for LaVO 4. As all the
spectra are of similar shape it means that the energy transfer from LaVO 4 is the main
source of all the Ln3+ emission also the energy transfer is efficient.

3.7 Scheme 2: White light through LaVO4: 0.125% Dy3+ & 20% Tm3+
core-shell nanoparticles
For this type of nanoparticles, number of shells was reduced to three with Tm3+
again at core, followed by an inert/undoped LaVO4 shell surrounded by Dy3+ doped
LaVO4 which is finally covered by an inert/undoped LaVO4 shell. On excitation with 280

59

nm UV source, emission spectrum showed all the characteristic emission peaks of Ln3+
ions doped into the LaVO4 matrix.

Fig. 3.21 Emission spectrum of LaVO4: Tm3+, Dy3+ core-shell nanoparticles

For the above spectrum, CIE co-ordinates obtained were (0.34, 0.35) as compared
to that of pure white light (0.33, 0.33) with the major emission peaks of 474 nm (Tm3+)
and 572 nm (Dy3+). Background emission in the spectrum is possibly due to LaVO 4
emission which is reported to emit in visible region when excited with 280 nm UV light.

60

Fig. 3.22 Excitation Spectra for 474 nm (Tm3+) & 572 nm (Dy3+) emission

Excitation spectra for both the major emissions showed the broad absorption band
of LaVO4 which is the main cause for these emissions. Also the energy transfer is highly
efficient as can be seen from the excitation spectrum for 474 nm (Tm3+) emission where
there is a narrow absorption peak at 350 nm due to its self excitation. In case of 572 nm
(Dy3+) emission, emission occurs solely from the charge transfer from VO4 group.

61

3.8 Control Experiment: Preparation of 12.5% Tb3+, 20% Tm3+ & 0.5%
Eu3+ doped core LaVO4 nanoparticles

Control sample was prepared by doping all the lanthanide ions in the above
composition into LaVO4 to prepare LaVO4: Ln3+ core nanoparticles.

Fig. 3.23 Emission spectrum of the LaVO4: Eu3+, Tm3+ & Tb3+ core nanoparticles using 280 nm
UV source and 395 nm filter

For the above spectrum, CIE co-ordinates obtained were (0.30, 0.37) as compared
to (0.34, 0.35), obtained for core-shell nanoparticles of the same composition. Here, Tm3+

62

emission is not present because Tm3+ emission is quenched due to the presence of other
Ln3+ ions in the same vicinity without any separation. It shows the need of core-shell
structure where all the Ln3+ ions are separated from each other using an inert shell.

63

Conclusion
Generally, the generation of white light can be done by mixing red, green and
blue emission together and this can also be achieved by simply adding blue and yellow
light. We successfully prepared. Bright white light emitting Tm3+, Tb3+ & Eu3+: LaVO4
and Tm3+ & Dy3+: LaVO4 core-shell nanoparticles using oleic acid as a stabilizing agent
to control the size of the nanoparticles and making them dispersible in organic solvents
like chloroform so that they can be further processed via spin coating technique to coat
over UV LED having emission range in the absorption range of LaVO 4, i.e. (260 320
nm) to get white light. CIE co-ordinates of the light obtained from the two nanoparticles,
i.e. LaVO4: Eu3+, Tb3+ & Tm3+ and LaVO4: Tm3+ & Dy3+ were (0.35, 0.35) & (0.34,
0.35) respectively which is very close to that of the pure white light (0.33, 0.33). Control
experiments showed the need of core-shell structure. The use of strongly coordinating
group to the surface of the nanoparticles decreases the non-radiative effects and high
quantum yields can be obtained under certain circumstances. The quantum yield of the
nanoparticles could be improved significantly when the surface is coated with an
inorganic shell. These core-shell particles consist of a core of small band-gap
semiconductor surrounded by a shell of larger band-gap semiconductor.[49] In these coreshell nanoparticles, the hole is confined to the core of the particles while the electron can
travel over the whole particle.

64

Stability of nanoparticles was an issue which tends to agglomerate after some

time of preparation, even after dissolving them in chloroform. This problem has to work
out in future before coating the nanoparticles dispersed solution on a UV LED.

65

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Jones, A.P.a.W., F. , Rare earth minerals: chemistry, origin, and ore

deposites. 1996, London: Chapman and Hall.

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www.molycorp.com. [cited.

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Cotton, S., Lanthanides and Actinides. 1991, Basingstoke: Macmillan

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Feldmann, C.J., T.; Ronda, C. R.; Schmidt, P., J. Adv. Funct. Mater.,
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Becker, P.C.O., N. A.; Simpson, J. R. , Erbium doped amplifiers:

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