SPECTROSCOPIC STUDY OF Pr3+ CO-DOPED WITH ALUMINIUM IN SOL-GEL

SILICA GLASS

A PROJECT REPORT SUBMITTED IN PARTIAL FULFILLMENT OF THE

REQUIREMENT FOR THE DEGREE OF MASTER OF SCIENCE IN PHYSICS

BY

BABIE LALLAWMZUALI
ROLL NO. – 22/PHY/012
REGISTRATION NO. – 2300029

UNDER THE SUPERVISION OF

PROF. SUMAN RAI

DEPARTMENT OF PHYSICS
MIZORAM UNIVERSITY
TANHRIL, AIZAWL

MIZORAM – 796004
JUNE 2024
 Mizoram University
(A Central University with NAAC ‘A’ Grade)
Tanhril-796004, Aizawl, Mizoram
Department of Physics
Prof. Suman Rai Post Box No.:190
Phone: +91-8732853277 Phone: 0389-2330435, 230522

Certificate
Certify that Mrs. Babie Lallawmzuali bearing Roll No – 22/PHY/012 with
Registration No. – 2300029 has carried out project dissertation work under my Supervision
and guidance in the Department of Physics, Mizoram University. The results of the project
dissertation work by Mrs. Babie Lallawmzuali entitled ‘Spectroscopic study of Pr3+ co-doped
with aluminium in sol-gel silica glass’ has been submitted to the Mizoram University,
Aizawl, Mizoram, for the degree of Master of Science.

Mrs. Babie Lallawmzuali has fulfilled all the requirements and regulation for the
degree of Master of Science under Mizoram University. To the best of my knowledge, this
project dissertation as a whole or any part thereof has not been submitted to this University
or any other institution for any degree.

Countersigned by:

(Prof. Zaithanzauva Pachuau) (Prof. Suman Rai)

Head of Department Supervisor
Department of Physics

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 Declaration of the Candidate
Mizoram University
June 2024

I, Babie Lallawmzuali hereby declare that the subject matter of this dissertation is the
record of work done by me, that the contents of this dissertation did not form basis of the
award of any previous degree to me, or to the best of my knowledge to anybody else, and that
the dissertation has not been submitted by me for any degree in any other
University/Institute.

This is being submitted to the Mizoram University for the degree of Master of Science
in Physics.

(BABIE LALLAWMZUALI)
Candidate

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 ACKNOWLEDGEMENT

First and foremost, I thank my supervisor, Prof. Suman Rai, Department of Physics,
Mizoram University, for his careful planning and guidance in the fulfillment of this project
work and always having time for my doubts regarding this project work. Without his
invaluable help, supervision and advice this project would not have been possible.

Secondly, I would like to thank Mr. C.Zothansanga, for his help and assistance, for
his immense knowledge in this field I am able to carry out his project work. I give thanks to
all the teaching and non-teaching staff of the Department of Physics, Mizoram University, for
all the help, assistance and care they have given me throughout the year.

Additionally, I would like to give special thanks to my parents and my friends

because, without their special suggestions , it was not easy to complete this project.

Above all, I thank God Almighty for giving me opportunity, guidance, and good health
to be able to complete this project work.

Date: 5th June, 2024 BABIE LALLAWMZUALI

Mizoram University 22/PHY/012
Aizawl, 796004

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 CONTENTS
Title Page No
Certificate of Supervisor i
Declaration ii
Acknowledgement iii
Content iv

Chapter 1: Introduction 1

Chapter 2: Review of literature 3

Chapter 3: Objectives 4

Chapter 4: Methodology 5

Chapter 5: Theory 5

Chapter 3: Results and Discussions

3.1 Absorption spectra 8
3.2 PL spectra 9

Chapter 4: Conclusions 11
REFERENCES

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INTRODUCTION

Rare earth (RE) ions have numerous applications as a result of their unique
spectroscopic properties which is due to the various transitions among the 4f energy states. A
excited RE ion in a certain host material may relax to the lower states radiatively or non-
radiatively depending on a number of factors. One such factor is multi-phonon relaxation
where the energy of an excited ion is lost to the vibration of the host lattice i.e. as phonons
rather than photons. The probability of multi-phonon relaxation is higher for the energy levels
with smaller gaps from the immediate next lower level due to the lower number of phonons
required to bridge the gap. Hence, in general radiative relaxation or luminescence is more
probable from levels with larger energy gaps and strong luminescence have been observed
from levels like 4F3/2 of Nd3+, 4I13/2 of Er3+, 5D4 of Tb3+ etc. which have relatively large energy
gaps. The 1D2 and 3P0 states of Pr3+ ion have adequate energy gaps for radiative relaxation
and can produce luminescence in the visible region of the spectrum through relaxation to the
lower energy levels. This makes Pr3+ an interesting dopant offering laser transition in the
blue, green, orange and red regions using the same pumping scheme. Silica glass has many
favorable properties as a host for RE ions as it has high optical transparency in the visible and
ultra-violet region, good chemical and thermal stability, low thermal expansion and good
mechanical strength. The downside is that it has high melting point making the production
through traditional melt quenching impractical.

Sol-gel technique offers a low temperature alternative as it involves chemical reaction

of liquid precursors to form solid glass matrix rather than melting of components. One
advantage of sol-gel technique is the high purity attainable. This is in part due to the
precursors being in the liquid state that can be easily purified by repeated distillation. Also
since the process does not require melting of the constituents in crucibles, the contamination
from the containing crucibles is avoided. It also allows superior homogeneity as the
constituents can be thoroughly stirred and mixed owing to the liquid state of the precursors.
Unwanted impurities and inhomogeneities present in glasses can have adverse effect and can
reduce the transparency and cause scattering loss. Silica glass however has low solubility of
RE ions which causes clustering. This clustering of RE ions result in concentration
quenching, which can diminish the luminescence efficiently drastically. Further, the energy
level structure of Pr3+ ion also presents possible channels for cross-relaxation when the ions
are in close proximities which can greatly decrease luminescence . Al3+ had been used to

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increase the solubility of RE ions and many studies and the previous works have shown that
codoping with Aluminum can significantly improve the luminescence. Recent work by
Bhargavi et al. has also shown the declustering effect of Al3+ on Pr3+ ions in PbO-SiO2
glasses. This work aims to further clarify the effect of Al3+ co-doping from the study of Pr3+
and Al3+ co-doped in SiO2 glass prepared by sol-gel technique.

With few exceptions, no single idea is conceived without bringing together the work
of previous ideas and forming a complete picture. So it was in August 1962 when there
appeared in the literature, simultaneously and independently, two identical formulations of a
theory. One by Brian R. Judd at the University of California at Berkeley and the other by a
Ph.D. student, George S. Ofelt, at the Johns Hopkins University in Baltimore. Judd and Ofelt
had never met personally, and were not aware of each other’s interest in the intensities of rare
earth ions in solids. While there are some differences in the two formulations, the approach
and the assumptions used to arrive at the final result are remarkably similar. The titles of the
two articles reflect a thought along similar lines. Judd referred to Optical Absorption, while
Ofelt referred to Crystal Spectra, and each to Intensities of Rare-Earth Ions. The formulations
as originally published by Judd and Ofelt came to be known as the Judd-Ofelt theory of the
intensities of rare earth ions. Regarding these publications, the late Professor Brian G.
Wybourne has said, “I suggest that the coincidence of discovery was indicative that the time
was right for the solution of the problem”.

In the light of the advancement in the understanding of complex atomic spectra in the
quarter century preceding the 1962 publications of Judd and Ofelt, this suggestion of
Wybourne is based on very sound reasoning. The rare earths comprise Y, Sc, La, Ce, Pr, Nd,
Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu. The last 15 make up the lanthanide series.
Most of these elements were discovered over a period of time stretching from the late 18th
century to the early 20th century. Promethium (Pm) was the last to be discovered in 1947 at
Oak Ridge National Laboratory. So, with the exception of Promethium, all the rare earths
were discovered in the span of a little more than a century. Part of the reason why they are
called rare earths is two-fold. First, they are very difficult to chemically extract from the
earth. Second, they do not exist in nature in high abundance. In the universe, the rare earths
are approximately 106 times less abundant than the more common element silicon. In spite of
their scarcity and difficulty in obtaining, the rare earths are highly valued for their unique
properties, especially as optically active elements in their ionized state for lasers .

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REVIEW OF LITERATURE

These kind of topics has been extensively studied by Dawngliana, et al. (2023)
studied that the Sol-Gel method was used to successfully synthesis the Eu3+ (0.75, 2.0, and
4.0 mol%) doped in the alumino-silicate glass. The transparent glass samples are of good
optical quality. The XRD spectra confirmed that the glass samples were amorphous. The
FTIR spectra analysis confirms the removal of the OH-group along with the formation of
NBO. The PL spectral is confirmation of the utility of prepared materials in optoelectronic
devices. The chromaticity diagram is evidence of color tunability at different Eu3+ ion
concentrations. Additionally, the high optical quality of the glass as well as its excellent third-
order non-linear behaviour are confirmed by the physical and non-linear properties, such as
the relatively high Abbe number (υAb),low non-linear refractive index (n2), co-efficient (γce)
and susceptibility (χ e(3)) values.

Dawngliana et al. (2022) observed that enhanced PL intensity of Sm3+ can be

attributed to the presence of Al co -dopant and annealing conditions. Al co -doping prevents
RE clustering, RE ions are subjected to a modified vibrational coupling, and RE are located
in the aluminum rich regions because there is a greater quantity of non - bringing Al - O
groups with which to coordinate . Al---O---Si bonds vibrate with lower phonon energy than
Si---O---Si bonds. The amorphous nature of the prepared sample is confirmed by XRD
spectra. In AT R -FTIR spectra, it is confirmed that NBO on the low phonon energy side
evolves for the sample annealed at higher temperatures along with the removal of the OH
group. The intensity parameters were estimated. From the result , it can be concluded that the
rise in the concentration of Al positively influences the enhancement of PL property . From
the chromaticity diagram , it is evident that the color of emission is tunable with different
aluminum concentrations.

Dihinjia et al, (2011)Studied that transparent nanostructured TiO2 thin films in

polymer and glass matrix with enhanced optical properties have been prepared via sol–gel
route. Absorption, emission and upconversion luminescence studies have been performed on
different Nd3þ-doped TiO2–SiO2 samples for photonic applications. The J–O intensity
parameters and the radiative transition rate have been calculated. We have also carried out a
detail analysis on the violet-blue upconversion emissions of Nd3þ-doped TiO2–SiO2 at
temperatures ranging from 100oC – 700oC to verify the luminescence performance. The

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proposed upconversion mechanism was based on two-photon absorption. The evaluation of
radiative properties showed that it has potential to be a laser material at 380, 399 and 420 nm.

Rai et al. (2015) found that heat treatment greatly affects the local environment of the
Nd3+ ions in solgel silica glass, as is evident from the observed nephelauxetic effect and
drastic change in the Ω2 value. This is due the removal of residual organic and hydroxyl
content with heating and the incorporation of Nd3+ ions in the covalent glass network.
Exponential increase in luminescence intensity is observed with increasing annealing
temperature which is attributed to the removal of residual hydroxyls. Annealing to 1050°C
not only enhance the PL emission but also prevent reabsorption of moisture and retains
luminescence. The PL intensities were also remarkably enhanced with increasing the Al3+
content. The modification of structure around Nd3+ ions is thought to be the cause of change
in optical properties. Increasing the Al content also appears to cause the Nd3+ ions to
experience more diverse environments. The high branching ratio and stimulated emission
crosssection of the 1060nm emission shows that Nd3+ : Al3+ co-doped sol-gel silica glass may
be useful in four level laser applications.

OBJECTIVES

The aim of this dissertation is to successfully synthesize Pr doped Al in silica glass

matrix using sol-gel technique . Al is added as dispersion effect so as to enhanced the
absorption of light by the Pr3+ ions ,thereby increasing their luminescent efficiency.
Additionally, aluminium can modify the local environment around the Pr3+ ions ,leading to
improvements in luminescence properties .The sample is annealed at 1000°C to remove
unwanted impurities like organic residues, moisture or volatile compounds that may have
been introduced during synthesis or handling. This high temperature is effective at driving off
suvh impurities, leaving behind a purer sample with improved properties for luminescence
studies or other applications .The luminescent property like absorption and emission are
studied using spectroscopic techniques such as UV-Vis spectroscopy for absorption
measurements and fluorescence spectroscopy for emission measurements .These technique
allow researchers to characterize the behaviour of the luminescent material and understand its
optical properties ,including how it absorbs and emits light at different wavelengths.

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METHODOLOGY

The glass containing Pr3+ in ( 96-x) (SiO2 + 4Al + x Pr) (where x = 0.4 , 0.6 , 0.8)
were made using a sol-gel technique where methanol is used as solvent, Nitric acid (HNO3)
as a catalyst , and Tetraethyl orthosilicate (TEOS) is used as a precursors.

The sol-gel technique for the preparation of the samples relies on the hydrolysis and
condensation of tetraethyl orthosilicate (TEOS), in the presence of H2O to form the SiO2
network. Pr(NO3)3.6H2O and Al (NO3)3.9H2O are used as the Pr3+ and Al3+ sources . The
mixture is stirred for 1hr using a magnetic stirrer to form a sol. The sol is then poured in
small plastic container and then sealed to prevent evaporation. The sol is left sealed at room
temperature for few days during which it forms a solid gel. Pin holes are then made in the
cover of the plastic container to allow slow evaporation and then left for two weeks, after
which the gels shrunk to only a fraction of the initial volume of the sol. The samples were
heated slowly from room temperature upto 1000 °C to remove residual hydroxyls. Densified
disc shaped glass samples were obtained after annealing to 1000 °C, having density 2.2 g/
cm3.

Absorption and photoluminescence (PL) spectra of the prepared samples were

recorded using iHR320 imaging spectrometer using Syner JY™ software from Horiba
Scientific. The set-up has resolution of 0.5 nm and calibrated using mercury lines. Averaging
of several accumulations were done in the recording of each spectrum to minimize noise and
random errors. The absorption spectra were recorded in the wavelength range of 400 nm –
650nm . The PL spectra were recorded in the spectral range of 475nm - 770nm at room
temperature. A 450 nm diode laser (MDL-III-450, CNI Optoelectronics Tech. Co. Ltd.,
China) operated at 50 mW was used to excite the samples for PL studies.

THEORY

The rare earths presented a puzzle in trying to understand their spectral properties in
the context of the quantum theory that blossomed in 1920’s and 1930’s. In 1937 J.H. Van
Vleck published an article titled “The Puzzle of Rare-Earth Spectra in Solids”. He called it a
puzzle because it was well known that rare earths exhibited sharp spectral lines, which would

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be expected if the transitions occurred between levels inside the 4ƒ electronic shell. Such
transitions were known to be forbidden by the Laporte selection rule, which says that states
with even parity can be connected by electric dipole (E1) transitions only with states of odd
parity, and odd states only with even ones. Another way of saying this is that the algebraic
sum of the angular momenta of the electrons in the initial and final state must change by an
odd integer. For transitions within the 4ƒ shell, ED transitions are forbidden, but allowed for
magnetic dipole (M1) or electric quadrupole (E2) radiation. The terms forbidden and allowed
are not strictly accurate. The term forbidden means a transition may occur in principle, but
with low probability. Given the relatively strong intensities and sharp spectral features of rare
earth spectra, this picture presented a puzzle with the following possibilities: 1. 4ƒ to 5d
transitions. 2. Magnetic dipole or electric quadrupole radiation. 3. Electric dipole radiation.
The operators for E1, M1 and E2 transitions are shown in figure 1 along with their selection
rules. It will be seen later that these selection rules will need to be modified under the Judd
Ofelt theory.

Electric dipole operator (E1) (odd operator)

⃗ = ∑

Magnetic dipole operator (M1) (even operator)

⃗⃗ = ∑ ⃗

Quadrupole operator (E2) (even operator)

⃗ ∑ ⃗

S L J (No 0 ↔ 0) Parity
Electric Dipole ∆S = 0 ∆L = 0, ±1 ∆J = 0, ±1 opposite
Magnetic Dipole ∆S = 0 ∆L = 0 ∆J = 0, ±1 same
Electric ∆S = 0 ∆L = 0,±1 , ±2 ∆J = 0, ±1, ±2 same
quadrupole

The solution to this puzzle was proposed by Van Vleck in 1937 and further resolved
by Broer, et al. in 1945. The first possibility would be indicative of broad spectral lines

6
incontrast to the sharp lines that were observed. Magnetic dipole radiation could account for
some transitions, but not all transitions, and represents a special case. Quadrupole radiation
could account for all the transitions, but was too weak to account for the observed intensities.
Only ED radiation was a reasonable solution, but it is forbidden by the Laporte selection rule.
The solution considered a distortion of the electronic motion by crystalline fields in solids, so
that the selection rules for free atoms no longer applied. Not all crystalline fields are capable
of producing this effect. The crystal field must be noncentrosymmetric, that is, lacking a
center of symmetry at the equilibrium position, otherwise the wavefunctions would retain an
even or odd parity with regards to reflection about the origin. If the wavefunctions retained
their even or odd parity, then Laporte’s rule (even states can connect to odd states and odd to
even) would remain rigorous, and electric dipole radiation would be strictly forbidden. In
other words, In order to have a change of parity, the odd-order terms of the crystalline field,
expressed as a power series in the displacement from equilibrium, must be present. These
terms vanish for a central field, and no change of parity can occur. The odd-order terms of a
noncentral crystalline field can force a coupling between odd and even states, resulting in
mixed parity states that mitigates Laporte’s rule.

It would take another 25 years after Van Vleck's paper before the appearance of the
papers by Judd and Ofelt. What is the reason for the quarter century gap? The main reason is
that the techniques of group theory were not applied to lanthanides until 1949 and, even then,
it took some years for these ideas to be absorbed, incorporated and accepted. The seminal
papers by Guilio Racah in the 1940’s would revolutionize the entire subject of complex
spectra. In a series of papers , culminating in his 1949 paper regarding 4ƒ electrons, he
created a powerful set of tools that made possible many complex spectroscopic calculations.
The work of Condon and Shortly in “The Theory of Atomic Spectra” published in 1935 is a
classic and seminal work in itself, but the tools are much more cumbersome than the newer
group theory. The ideas of Racah took some time to root and proved to be a key ingredient in
the solution to a problem regarding the calculation of forced electric dipole transitions. The
concept of representing operators as irreducible tensors and their subsequent manipulation
would play a pivotal role in the solution of the problem. Another reason for the delay
between Van Vleck’s paper and those of Judd and Ofelt concerns the dawn of computers. The
computer made possible the tabulation of all angular momentum coupling coefficients .This
did not occur until 1959, but by then the stage was set for a revolution in understanding the
complex spectra of lanthanide ions. The decade of the 1960’s can be viewed as a revolution

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in spectroscopic research on rare earth ions. This decade saw the invention of the laser go
from a device in search of an application to applications in search of laser devices. The theory
of Judd and Ofelt remains in history at the forefront of this revolution.

Praseodymium (Pr) is a rare-earth element with atomic number 59 and symbol Pr. It
belongs to the lanthanide series of the periodic table. It is a soft, silvery metal that tarnishes in
air and is widely used in a variety of applications. It is used in alloys for making magnets,
especially in combination with neodymium to create high-strength magnets. These magnets
are used in various technologies including electric vehicles, wind turbines, and audio
speakers. Praseodymium compounds are also used as catalysts in organic synthesis and in the
production of specialized glasses and ceramics. The ions are known for their luminescent
properties and are often used as dopants in materials such as glasses and crystals to create
materials with specific optical properties.

These materials find applications in lasers, optical fibers, and phosphors for lighting
and displays.It does not have any known biological role and is not essential for living
organisms. In fact, it can be toxic in certain forms if ingested.It is relatively abundant in the
Earth's crust, but it is not found in its pure form due to its high reactivity. It is mainly
obtained from monazite and bastnasite ores, which are rich in rare-earth elements.It was
discovered in 1885 by Carl Auer von Welsbach, an Austrian chemist. He separated it from
other rare-earth elements by fractional crystallization of double ammonium nitrates. The
name "praseodymium" comes from the Greek words "prasios" and "didymos," meaning
"green twin," referring to the green color of its salts and its close association with
neodymium.

RESULT AND DISCUSSION

Absorption spectra

Typical absorption spectrum of the prepared Pr3+ doped sol-gel silica glass annealed
to 100°C is shown in Fig. 1. Absorption peaks were observed at 449 nm, 473 nm, 484 nm and
589 nm corresponding to the transitions from the ground state 3H4 to the excited states 3P2,
3
P1, 3P0 and 1D2 respectively. These absorptions are in the violet-blue and yellow-orange
regions without prominent green absorption causing the samples to appear pale green. The

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strong 3H4→1D2 absorption peaking at 589 nm implies that efficient photo-excitation is
possible by 450 nm source. The other absorption peaks were observed with relatively less
intensity than the 3H4→1D2 transition.

Fig.1. Absorption spectrum of Pr3+ doped sol-gel silica glass.

PL spectra

The PL spectra of the prepared sample annealed at 1000°C at varying concentration of

Pr3+ are shown in Fig. 2. The 450 nm source excites the Pr3+ ions to the 3P2 state which is
short lived due to the very small energy gap below and so the excited ions quickly relax non-
radiatively to the lower energy states. Multiple emission peaks mainly due to radiative
transitions from 3P0 and 1D2 states are observed in the visible and NIR region. The strong
peaks at 497 nm, 614 nm and 649 nm are due to 3P0 → 3H4, 1D2 → 3H4 and 3P0 → 3F2
transitions respectively. Relatively weak 3P1 → 3H5 transition around 542nm is also observed
as the 3P1 level lies very close to 3P0 metastable state and can be thermally populated at room
temperature. The strong 1D2 → 3H4 emission peaking at 614 nm implies that efficient photo-
excitation is possible by 450 nm source. The other emission peaks were observed with
relatively less intensity than the 1D2 → 3H4. The intensity of the PL spectra were observed to

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be increasing at higher concentration of Pr3+ . The energy diagram of the transitions occurring
in the prepared Pr3+ sample is also shown in fig.3

Fig2. PL spectra of Pr3+ doped sol-gel silica glass with varying Al3+ co-doping

(λexc = 450 nm)

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 Fig3. Energy diagram of Pr3+ showing cross relaxation and energy transfer

CONCLUSIONS

Pr3+ doped sol-gel silica glass with varying concentrations of Al3+ codopant were prepared
and the optical properties were studied. Judd-Ofelt parameters were calculated and used to
estimate the line strength of the transitions responsible for the various cross-relaxation
mechanisms affecting the 3P0 and 1D2 states. The values of the line strengths suggest higher
probability of cross-relaxation quenching for the 1D2 state which was evident from the
relatively weak emission from this state in absence of Al3+. Co-doping with Al3+ dramatically
enhance the luminescence which is attributed to reduction in cross-relaxation. The 1D2
emission was particularly improved with Al3+ co-doping and the strong orange-red
luminescence due to the 614 nm peak (1D2→ 3H4) can be seen with naked eye under 450 nm
excitation. The findings of this work are strong evidence that co-doping with Al minimizes
cross-relaxation between RE ions. The 1D2/3 P0 emission intensity ratio may also serve as a
probe for the extent of cross-relaxation in RE doped systems. Slow annealing to 1000 °C is

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also suggested for RE doped sol-gel silica glass as it reduces hydroxyl quenching and
prevents further reabsorption of atmospheric moisture by densifying and closing the pores.

REFERENCE

1. Luminescence enhancement of Pr3+ doped sol-gel silica glass as a result of Al3+ co-
doping – A.L.Fanai, U.Khan, S.Rai.
2. Linear and nonlinear and optical properties of Sm3+ co-doped alimino-silicate glass
prepared by sol-gel method – KMS Dawngliana,S.Rai
3. S. Hazarika , S.Rai (2004), Structural , optical and non-linear investigation of Eu3+
ions in sol-gel silicate glass, Optical Materials,27(2), 173-179.
4. Dawngliana K.M.S.,Fanai, A.L., & Rai,S.(2023). Structural and Spectroscopic
Properties of Eu3+ ions in Alumino-Silicate Glass. Indian Journal of Pure & Applied
Physics (IJPAP), 61(3), 182-189.

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