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Universidade de So Paulo

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2014-02

Advances in rare earth spectroscopy and


applications
Journal of Nanoscience and Nanotechnology, Valencia : American Scientific Publishers - ASP, v. 14,
n. 2, p. 1578-1596, Feb. 2014
http://www.producao.usp.br/handle/BDPI/50917
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Review
Journal of
Nanoscience and Nanotechnology

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Vol. 14, 15781596, 2014


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Advances in Rare Earth Spectroscopy and Applications


Y. Dwivedi and S. C. Zilio
Instituto de Fsica de So Carlos, Universidade de So Paulo, CP 369, 13560-970 So Carlos, SP, Brasil
Rare earth (RE) elements are prime constituents in a large amount of innovative materials and
several technological advances would not be possible without their contribution. In this review, recent
progress in the eld of rare earth spectroscopy is highlighted, with a special emphasis on clean
energy, sensors and telecommunications, providing a broad view on past and recent developments.

Keywords: Rare Earth, Spectroscopy, Lanthanides, Solar Cell, Telecommunication, Clean


Energy, Light Emitting Diode.

CONTENTS

clean energy through their applications in nuclear reactors,

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1578
solar cells, wind turbines, light emitting diodes (LEDs)
2. Uniqueness of RE Spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . 1579
and others. RE ions exhibit the ability of converting
3. Clean Energy Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1580
long-wavelength near infrared radiation to shorter visi3.1. Solar Cells . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1581
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wavelengths, through
process known
as frequency
3.2. Light Emitting Diodes . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1584
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upconversion
(UC).10:50:43
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RE elements were invented, such as APTE
4.2. Ion, pH and Hydrocarbon Sensors . . . . . . . . . . . . . . . . . . . 1587
[Addition de Photon par Transfert dEnergie], cooperative
4.3. Magnetic Field Sensor . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1589
emission, multi-photon absorption, photon avalanche, and
5. Telecommunications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1590
so on. With the advent of nanotechnology, it is worth it
6. Concluding Remarks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1592
Acknowledgment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1593
to re-investigate these processes for RE ions conned in
References and Notes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1593
nano-structures. Despite the countless potential applica-

1. INTRODUCTION
The study of f -shell electrons is of paramount importance due to their unique optical and magnetic properties,
often related to potential applications in a variety of elds.
Spectroscopy of lanthanide (Ln) elements is a hot topic
of research as they not only cover vast commercial applications but also help to understand basic mechanisms of
several peculiar emission dynamics. Ln elements present
several interesting luminescent properties such as sharp
emission lines, meta-stable states and high quantum efciency (QE) which make them suitable for the manufacture
of numerous optical devices.1 Their use permits technological applications of a number of materials like superconductors, miniaturized magnets, catalysts, lamp, display
devices, lasers, biomedical, memory devices, sensors, optical ampliers, and so on. In particular, regarding the issue
of energy generation and its related harmful environmental impact, RE doped materials are alternative sources of

Author to whom correspondence should be addressed.

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tions of RE doped materials, several puzzling problems are


yet to be solved, suggesting the need of further research
effort. Some of the technological challenges in RE spectroscopy is to understand opto-magnetic interactions, optimizing black body radiation (heat generation) and nding
single phase multifunctional luminescent material compatible with biomedical purposes.
It is interesting to note that even though these elements
are quite important for the development of new technological products, this area is under threat after the announcement made by the largest supplier, China, to limit exports to
40% (especially, of heavy Ln ions) from 2010 to 2015. This
announcement immediately impacted the global market and
the prices of a few elements faced unexpected increase.
The economical aspect raised questions on future
research using RE materials and encouraged the governments to formulate regulation policies to assure sustainable
production of these metals. Another issue of growing interest is the ecological and biological impacts of Ln, as their
true toxicity level is not well known, especially when used
as dopants in nano-dimension structures. It is interesting
1533-4880/2014/14/1578/019

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Dwivedi and Zilio

Advances in Rare Earth Spectroscopy and Applications

Figure 1. High intake and/or chronic exposure of these elements lead to bioaccumulation, a supposed threat to the
neural system and liver, in addition to damage to cell membranes of aquatic animal species with negative effects on
the reproduction and the nervous system.5
The present article reviews one of the most discussed
elds of spectroscopy, namely rare earth spectroscopy, and
some of its applications in frontline research. It is appropriate to consider RE spectroscopy as a different branch
of spectroscopy, as experimentations, optical processes
and analysis are different from conventional spectroscopy.
Since it is practically impossible to cover all the aspects
of RE spectroscopy in a brief review, here we emphasize
three technological frontiers of RE spectroscopy, namely,
clean energy, sensors and telecommunications, by giving a
brief account on the current status of each subject.

2. UNIQUENESS OF RE SPECTROSCOPY
The discovery of rare earth elements probably occurred
in the summer of 1787, at the island of Roslaga, near
Stockholm, when an exceptionally heavy piece of black
rock, found in the dumps of the Ytterby quarry, called the
to note that the worldwide annual consumption of RE
attention of Lieutenant Carl Axel Arrhenius (17571824).
elements in 2010 was about 136 million tons,2 in prime
Further analysis of the stone revealed a new element, later
sectors like electric vehicles, wind turbines, rechargeable
named Yttrium (atomic number 39). Thereafter, a whole
batteries, night vision, weapons guidance systems, securange of elements was discovered, which are now known
rity inks, polishing,
lens
making,
Ni
battery
coating,
magDelivered by Publishing Technology to: UNIVERSIDADE SAO PAULO IF
as 03
Ln Feb
elements,
atomic numbers ranging from 57
nets, petroleum products, catalytic
applications,
cell
phone
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2014with
10:50:43
to 71. Though
Ln and Yttrium elements occupy differpower sources, at screen TVs, solid
state lasers,
LEDs, Scientific
Copyright:
American
Publishers
ent positions in the periodic table, they are collectively
optical telecommunications, biological imaging,3 radiation
referred to as rare earths because of their similar chemisensors, lighting and displays, lasers, homeland security,
cal properties. Occasionally, Scandium (Sc) and Thorium
agricultural fertilizer4 and many other products. Some of
the prime sectors of RE consumption are highlighted in
(Th) are also referred as rare earths elements. As a matter
Figure 1.

Some of the prime RE consumption sectors.

Y. Dwivedi received his Ph.D. degree from the Banaras Hindu University, India, in the
eld of Rare Earth doped materials and was FAPESP postdoctoral fellow at Institute of Physics of So Carlos, University of Sao Paulo, Brazil. At Present he is Assistant
Professor of Physics at NIT Kurukshetra, India. He has been awarded the four young
scientist/best poster presentation awards. His research focuses on linear and nonlinear
spectroscopic investigations of lanthanide doped materials.

S. C. Zilio received his Ph.D. in physics from the University of So Paulo, at So Carlos,
in 1983. He is currently a full professor at the Institute of Physics of So Carlos, University
of Sao Paulo. His research interests include nonlinear optics and optical instrumentation.

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This mechanism becomes dominant when the ions occupy


of fact, the name of this unique family is misleading as
these materials are quite abundant in the Earth curst. Tm
sites with inversion symmetry, as the crystal eld confor example, which is estimated to be less abundant among
tribution vanishes in this case. Since the electric dipole
the Ln, has an profusion in the Earth curst comparable to
transitions are weakly allowed, they present low absorpSilver and Cadmium (Cd), while Ce is more common than
tion coefcients and relatively long lifetimes (up to several
Tin. However, as most of the rare earths are found in ores,
milliseconds). 4f electrons do not take part in the bond
ultrapure Lns are still difcult to obtain.
making with the host and are well shielded by the s and p
Ln elements possess electronic conguration [Xe] 4f n
shells, resulting in narrow line transitions in absorption and
6s 2 or [Xe] 4f n1 5d 6s 2 , where [Xe] stands for the Xenon
emission spectra. Though the shielding of the 4f electrons
electronic structure. When Ln elements are dispersed in a
makes them almost insensitive to the near eld, a few tranhost matrix, they may attain either + 2, + 3 or + 4 oxidasitions exaggerate the small changes in the lattice coordition states, with + 3 oxidation state being the most comnation sphere. These transitions are termed hypersensitive
mon. When a trivalent ion is formed, the atom gives up its
transitions. Their intensity is signicantly enhanced as the
outermost 6s electron, besides losing its 5d electron, if it
symmetry of the Ln complex lowers or the polarizability
has one. If it doesnt, it loses one of the 4f electrons, leavof the ligands increases. Jrgenson and Judd9 noted that
ing a partially lled 4f shell, shielded by the outer 5s and
hypersensitive transitions obey the selection rules J 2,
5p shells. In appropriate conditions, Ln ions also show + 2
L 2, and S 0. In contrast to electric dipole, magand + 4 oxidation states, such as Sm2+ , Eu2+ , Yb2+ (stanetic dipole transitions do not violate the parity selection
bility order Eu2+  Yb2+  Sm2+ , and Ce4+ , Pr4+ and
rule once they can occur between states of the same parTb4+ . Similar to Ln ions, Y also shows a + 3 ionic state
ity. However, the strengths of these transitions are much
but it has no optical transitions. Among Ln ions, La3+ and
weaker than the allowed electric dipole transitions. MagLu3+ have a completely empty and a completely lled 4f
netic dipole contributes to the intra-4f electronic transishell, respectively, and therefore they have no optical trantions of Ln ions such as Er3+ , Eu3+ and Tb3+ . A detailed
sitions. Ce3+ has one electron and a single 4f level just
discussion on RE spectroscopy, including energy level calabove the ground state. Due to the small energy difference
culation, strength and other spectroscopic characterizations
between the inner 4f levels and the outer or valence electechniques, can be found in Refs. [1015].
trons, it takes only a minimal amount of energy to change
As 4f 4f transition
Delivered by Publishing Technology to: UNIVERSIDADE
SAOprobabilities
PAULO IF are very weak to
the relative occupancy of theIP:
electronic
levels.
Hence,
Ce
yield
efcient
light,
an
option
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On: Mon, 03 Feb 2014 10:50:43 to improve emission is to
possesses dual valence states: Ce4+ (ceric)
(4f 0  American
and Ce3+ Scientific
enhance the
electric eld by means of metal nanopartiCopyright:
Publishers
(cerous) (4f 1 .6 Ce4+ ion has a higher stability as a concles (NPs), coreshell structures, sensitization via host,
sequence of the unlled orbital. For this reason, it is reaorganic, or RE ions.1620 Ln ions belong to the hard acid
sonable to assume that the Ce3+ ion has a lower ionization
class21 and so, they have the tendency of binding with hard
potential and would be a good hole trap. The tetravalent
bases, primarily those that contain oxygen and nitrogen as
oxidation state of cerium ions does not contain any elecdonor atoms, resulting in RE tri-cations of a hydrophilic
tron in the 4f orbital and so, no emission from Ce4+ ions
nature. Dense energy levels and splitting produce sevis observed. Trivalent Yb ion also possesses one excited
eral exclusive optical phenomena in Ln ions, such as
state in the 4f conguration, at 10,000 cm1 . Another
excited state absorption (ESA), APTE, cooperative emisLn ion, Pm, is a non-natural occurring radioactive material
sion, multiphoton absorption, photon avalanche and crossand exists only as a temporary intermediate product in the
relaxation. These processes produce photons of higher
ongoing radioactive decay of other elements.
energy upon excitation with lower energy photons, a pheThe 4f orbital in the RE3+ ion is shielded by 5s 2 and
nomenon that is known as upconversion.2225 It may also
5p6 orbitals and thus, their spectroscopic and magnetic
occur through energy transfer via host, hetero RE ions,
properties are nearly unaffected by the host. In Ln ions,
organics, etc., phonon assisted energy transfer and cooperdifferent types of transitions may take place, namely 4f
ative processes.2629 UC processes can be induced by a low
4f , 4f 5d 4f , and charge transfer band 4f sub-shell.
power (1103 W cm2 ) continuous wave laser. In contrast
Among them, the intrashell 4f 4f transition is parity
to a costly high-intensity (106 109 W cm2  pulsed laser
forbidden due to Laportes rule which states that elecsource for the generation of a two-photon process.
tric dipole transitions can only occur between levels of
opposite parity. These transitions appear as low intensity
3. CLEAN ENERGY APPLICATIONS
lines because odd-order terms in the crystal Stark eld
The growing global concerns on the predicted reduction
mixes the 4f N states to higher lying opposite parity states,
in fossil energy and environmental pollution foster great
such as 4f N l 5d, partially relaxing the Laportes selecenthusiasm for clean energy alternatives. In addition, the
tion rule,7 8 besides providing a split of the energy levels
ever increasing demand for electricity aggravates the sitby removing the 2J + 1 degeneracy. A weaker mechauation. Usually, two approaches are considered to handle
nism that can also contribute to the mixing of states is
the interaction of electronic states with lattice vibrations.
this situation. First, to search alternative clean (low carbon)
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Advances in Rare Earth Spectroscopy and Applications

or renewable energy sources for individual purposes and


Wind turbines use Ln-ecked supermagnets inside the
turbines, such as NeodymiumIronBoron and Samarium
second, to improve the efciency of existing equipment
Cobalt magnets, which are powerful, lightweight, strong
in order to reduce energy consumption. In recent years,
and relatively cheap. The world production of Neodymium
at least three different technologies, namely wind turis about 7,000 tons per year and Nd magnets are used
bines, nuclear reactors and solar cells, boosted up the
in a variety of other products like cars, engines and head
clean energy sector, suggesting that they may be the future
phone sets. Ln improves the efciency of iron alloys, espeenergy sources. According to the report of the Nuclear
cially through the use of terbium and dysprosium elements.
Energy Institute, the contribution of nuclear energy in 2012
These blends expand and contract efciently in the preswas 64%, solar/wind 13.5% and hydro energy 22.6%.30
ence of a magnetic eld, helping sensors, actuators and
Energy sources that release carbon intensities lower
injectors to perform better. Car batteries used in electricthan 0.82 metric tons per megawatt-hour are considered
powered vehicles also rely heavily on RE elements. As
clean energy sources.31 Existing natural renewable energy
this work relates only to spectroscopy, we will not dissources based on water, wind, biomass and sunlight are
cuss other applications of Ln such as magnets and neutron
considered clean energy sources. Nuclear energy is also
absorbing rods. Details on the use of Lns in these two
an alternative, despite the debate whether it may be consectors can be found in Ref. [33].
sidered renewable or clean sources since its byproducts
Important applications still seeking some breakthrough
may bring serious threat to the environment. Moreover,
from Ln elements are solar cells and LEDs. Similar to
the security of large nuclear plants is a concern of local
wind energy, solar energy is also a clean and renewhabitants as any leak may contaminate the water and soil,
able energy as it directly converts sunlight into electrical
and may worsen their life. Nuclear power plants do not
energy, while the use of efcient LEDs could reduce the
emit toxic gases like CO2 or SO2 . Despite the various conworldwide electricity consumptions up to 20%.
cerns about nuclear energy production, it is regarded as
a clean energy source and is being used by almost every
major country around the world. By May 2013, 30 coun3.1. Solar Cells
tries worldwide were operating 436 nuclear reactors for
A solar or photovoltaic cell is a device that converts energy
electricity generation and 70 new nuclear plants are under
radiated from the sun into heat or electricity. When a phoUNIVERSIDADE
IF pair is created
construction in 14Delivered
countries.30by
It Publishing
is also noted Technology
that nuclear to:ton
hits a photovoltaic SAO
cell anPAULO
electronhole
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power plants provided 12.3% IP:
of the
worlds electricity On:
pro- Mon,
and03
if collected
properly,
these carriers lead to an electric
Copyright: American Scientific
Publishers
duction in 2011.
current. The
process of converting solar power to electricThe major contribution of Ln elements for clean energy
ity is called photovoltaics (PV). The PV process includes
production is multifaceted. It includes preparing neutron
light absorption followed by the generation of electron
absorbers for nuclear reactors, high efciency magnets for
hole pairs or excitons, the separation of charge carriers of
wind turbines, quantum cutting and IR absorbing materiopposite types and the extraction of those carriers to an
als for solar cell application, coating materials for LEDs,
external circuit. Though the theoretical efciency limit of
phosphor for lamps, and others. The use of Ln in a nuclear
a solar cell (ratio of the electrical output to the incident
reactor, especially Samarium, Gadolinium, and Europium,
energy in the form of sunlight) is estimated to be 33.7%
is to control the fusion, as the Lns have large neutron
(in single pn junctions of crystalline silicon),34 the maxcross-sections and are highly efcient for capturing neuimum efciency so far reported in practice is 24% at
trons. One of the Samarium isotopes, Sm,149 is frequently
the cell level and 20% at the module level, as reported by
used in nuclear control rods.
SunPower company35 http://us.sunpowercorp.com/, while
In addition to nuclear energy, another widely used
a recent report from the University of New South Wales
source takes advantage of the kinetic energy of the wind
indicates an efciency achievement of 25%. Details on
to produce mechanical energy. The mechanical power can
efciency comparisons can be found in Ref. [36]. The efbe used for specic tasks (such as grains grinding or water
ciency of solar cells further increase up to 40.7% and
pumping) or a generator can convert it to electricity. Wind
42.8% in multiple-junctions solar cell with dies assemenergy can be transform to electrical energy through giant
bled into a hybrid package.37 The efciency of a solar
wind turbines which essentially need high performance Ln
cell is a function of several factors that include reectance
supermagnets. Wind turbines can produce energies in the
efciency, thermodynamic efciency, charge carrier seprange from a few kilowatts to several megawatts. Single
aration efciency and conductive efciency. The overall
small turbines, below 100 kilowatts, are used for homes,
efciency is the product of these individual efcientelecommunications dishes or water pumping. China has
cies. The efciency of solar cells largely depends on the
the largest wind resources in the world and researchers
deposition of nanomaterials on a conductive electrode.
from Harvard University and Tsinghua University have
Various techniques of extremely thin semiconductor quanfound that the China could meet all of its electricity
tum dots deposition has been discuss in a review by Yin
demands from wind power by 2030.32
et al.38 Solution-based electrochemical deposition of ZnO
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Advances in Rare Earth Spectroscopy and Applications

nanowire arrays for large area deposition, and large scale


production were discussed by Zeng et al.39 Singh et al.40
reviewed various techniques to synthesize TiO2 and CuO
nanotubes and nanowires.
The sun is regarded as a black-body radiator, with a temperature around 6000 K, and the solar spectrum covers a
broad spectral region ranging from 300 to 2200 nm, with a
peak around 500 nm (2.4 eV). However, silicon can absorb
only a part of this spectrum, as shown in Figure 2(D). The
main hurdle to improve efciency in semiconductors is
that low energy photon (sub-bandgap energy) cannot excite
the electrons from the valence to the conduction band and
simply pass through the cell. In contrast, high energy photons (above-bandgap energy) produce a pair of e-hole but
lose their energy as heat, limiting the cell performance.
Approximately, 47% of the solar energy is converted into
heat and 18% of the photons pass through the solar
cell.
Due to the Si-based solar cell limited absorption, UV
and IR radiations are considered as unwanted. Ln elements
can help to absorb these unwanted wavelengths and convert
them into photons that can absorbed by silicon, improving the overall efciency. They do it by the processes of
downconversion (DC), especially quantum cutting, where
the UV photon is absorbed to produce two IR photons,41

and by upconversion (UC), where infrared radiation is converted into visible wavelengths.42 Through the processes of
DC and UC, 32% (149 W m2  and 35% (164 W m2 
of the sunlight intensity can be respectively accessed,43
improving signicantly the solar cell efciency. In a typical DC/UC-Si bifacial solar cell, a DC or UC layer is
coated on the back side of the cell (Fig. 2(A)) and a
reector returns all emitted photons back into the solar
cell.
A theoretical study on realistically modeled UCs reveals
that the cell efciency can be enhanced up to 44%.44 Older
studies show that the upper limit of the PV conversion
efciency of a single junction solar cell coupled to an
ideal UC device is 47.6%, when the sun is modeled as a
6000 K blackbody, and 50.7% under the standard air-mass
(AM1.5) terrestrial spectrum.42 45 Briggs et al.46 investigated the effect of narrow-band UC on the efciency of
a solar cell and determined that the addition of an ideal
upconverter with absorption bandwidth between 0.1 eV
and 0.5 eV should boost the efciency of a 1.7 eV bandgap
cell from 28.2% to between 33.5% and 43.6%.
Among Ln elements, Er and Yb ions are promising
candidates for UC solar cells. However, other elements
like Tm, Ce and Ho were also reported to be suitable
for solar cell applications.47 Er3+ is a favorable ion to

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Copyright: American Scientific Publishers

Figure 2. (A) Schematic layer arrangement for UC or DC phosphor solar cell, (B) green and red upconversion emission in Er:Yb doped Y8 V2 O17
nanophosphor under 976 nm excitation, (C) red downconversion emission in Eu(DBM)3 Phen upon excitation with LED (395 nm), (D) solar and
Silicon absorption spectra. Reprinted with permission from [41], B. S. Richards, Sol. Energy Mater. Sol. Cells 90, 2329 (2006). 2006, Elsevier.

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study the UC process with NIR and IR lasers (796, 976


enhancement in a broad range of sub-bandgap wavelengths
and 1550 nm) as it has metastable levels (4 I9/2 , 4 I11/2 and
throughout the entire upconverting core and nanocrescent,
4
I13/2 near 12,000, 10,000 and 6450 cm1 and so,
enabling a 100-fold increase in the above-bandgap power
it offers interesting possibilities of excited-state absorption
emission.
and cross-relaxation processes. One inherent problem of
In contrast to the UC process, where successive absorpLns is the weak absorption, which can be solved by using
tion of infrared photons results in UV-Vis photons, the
a sensitizer (with broad emission) or through plasmonic
DC process converts a UV-blue photon to lower energy
coupling.48 The absorption cross-section of trivalent erbium
photons (down shift) or in two photons by the quantum
ion at 980 nm is of the order of 1021 ,49 while for the
cutting (QC) process.58 The latter is a very important pro2
2
F5/2 F7/2 transition of Yb is roughly 10 times higher,
cess as emission of two visible photons from a single UV
suggesting that it can act as an effective sensitizer for Er
photon increases the efciency of light-emitting devices
ions and improve absorption at 980. However, the addition
up to 200%. The mechanism for QC or cascaded emisof Yb may induce a possible loss mechanism as Si and
sion includes mainly two different processes: simultaneous
Yb both absorb around 1000 nm. Several efforts have been
energy transfer from a donor to two acceptors that equally
made to improve the efciency by using a more efcient
shares the energy and sequential emission of two photons
UC material, namely NaYF4 doped with Er and Yb ions.
after the absorption of a UV photon as in the Ln ion.59
Shalav et al.50 showed UC under lower excitation density
Examples of the rst type of QC are Tb:Yb, Bi:Yb, Ce:Yb,
of 2.4 W/cm2 , reaching a QE of 3.4% at 1523 nm in a
Eu2+ :Yb, VO43 group:Yb3+ ,60 while for the second type
3+
crystalline silicon solar cell with NaYF4 doped with Er .
of QC is YF3 :Pr3+ .61 Another type of QC that includes a
51
Henke et al. reported improvement in the external
two-step energy transfer process was reported in the Gd:Eu
quantum efciency by using Er:Yb codoped ZBLAN
system.62 In this case, a 202 nm photon is absorbed in 6 GJ
52
glasses subjected to 1540 nm excitation. de Wild et al.
levels of Gd ion and the energy is transferred to Eu ions
investigated -NaYF4 :Yb3+ (18%), Er3+ (2%) coated solar
in two steps, resulting in a bright visible emission. Low
cell excited with 980 nm diode (28 mW) and observed
energy photons can also be obtained through the process of
a maximum current enhancement of 6.2 A, which corphonon-assisted energy transfer, as reported for the Eu:Yb
responds to a solar cell external quantum efciency of
codoped system.63
0.03%. It was also veried that broad-band excitation
For Pr ions, the QC occurs from the 1 S0
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SAO PAULO IF
1
may be more effective because
different
wavelengths
can
(
47,000
 10:50:43
state only when it does not overlap
IP: 143.107.180.158 On: Mon, 03
Febcm
2014
be simultaneously absorbed and converted.
The American
response Scientific
with the 4f
5d band. The excited Pr ion relaxes to the
Copyright:
Publishers
of the solar cell due to the upconverted emission of
ground-state through a two-step process: (1) 1 S0 1 I6 ,
3
Gd2 O2 S:Er:Yb under broad-band excitation was compared
PJ ( 400 nm) and (2) 3 P0 3 FJ , 3 HJ (480700 nm).
to that of a monochromatic laser light and the responses
The QC process is observed in various Pr doped uwere about the same, despite the fact that the power denoride hosts YF3 (excitation at 185 nm),59 oxide hosts
53
SrAl12 O19 ,64 LaMgB5 O10 ,65 LaB3 O6 .66 Kuck et al.67 invessity of the laser was three times higher.
3+
3+
tigated different Pr-doped uoride hosts YF3 , LuF3 , PrF3 ,
Similar to the Er ion, Ho ion also yields benecial Vis-NIR emission on excitation with infrared ( 1
BaMgF4 , LiCaAlF6 , LiSrAlF6 and KMgF3 which exhibit
m) radiation,54 Lin et al.55 observed the enhancement
QC under vacuum ultraviolet synchrotron excitation at
200 nm, with a theoretical internal QE higher than one.
of NIR emission of Ho:Yb combination in a BaGdF5
However, the application of these materials for lamps
host, mainly through second- and rst-order energy transis inadequate because the emission occurs at 405 nm,
fer (ET) processes: Ho(5 F3  2Yb(2 F5/2 +h, Ho(5 S2 +
where the human eye is not sensitive.
Yb(2 F7/2  Ho (5 I6  + Yb (2 F5/2  + h and the correIkeda et al.68 investigated the QC in SrAl12 O19 :Pr for
sponding QE were calculated to be 192%.
56
Pillai et al. carried out an investigation on the effect
172 nm excitation and observed two visible photons,
one at 401.8 nm and the other at either 486.3, 526.3,
of silver nanoparticles on the absorption character of Si
623.7 or 644.6 nm via 1 S0 state. Photoluminescence meaand reported that surface plasmons can increase the spectral response of thin-lm cells over almost the entire solar
surements showed that the relative QE of SrAl12 O19 :Pr
spectrum. At wavelengths close to the Si band gap, a sigto BaMgAl10 O17 :Eu2+ is 38.4%. Lee et al.69 observed
nicant enhancement of the absorption was observed for
Pr-sensitized QC in K2 GdF5 :Eu3+ :Pr3+ phosphor through
both thin-lm and wafer-based structures. A seven-fold
cross-relaxation and direct energy transfer process. It was
enhancement was reported for wafer-based cells at  =
suggested that due to the increased absorption in the UV
1200 nm and up to 16-fold enhancement at  = 1050 nm
and VUV spectral regions, the theoretical QE of K2 GdF5 :
for 1.25 m thin silicon-on-insulator cells, and the results
Eu3+ , Pr3+ increases to 138%. Loef et al.70 discussed a
were compared with a theoretical dipole-waveguide model.
case of visible QC in LiGdF4 :Er and Tb. Upon VUV exciAn effort to harvest solar radiation using an upconvertertation to the 4f 10 5d levels of Er, part of the excitation
doped plasmonic nanocrescent was made by Atre et al.57
energy can be transferred to Gd by cross-relaxation, resulting in both Er and Gd in excited-states. This is followed
Numerical calculations revealed a > 10-fold absorption
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clean energy production. One is to use efcient renewable


by the emission of two visible photons: one from Er and
the other from Tb, after the energy transfer from Gd to
energy sources and the other is to make devices more efTb. Yim et al.71 introduced green emitting Y2 SiO5 :Tb3+
cient, especially for illumination purposes, where around
nanophosphors into a TiO2 based dye sensitized solar cell
20% of the electricity consumed worldwide is used. The
and monitored its performance. Y2 SiO5 :Tb3+ absorbs UV
global electricity consumption has increased faster than the
light from 220 to 300 nm which is then downconverted
overall energy consumption because of the versatile nature
into visible-light at 545 nm. Recently, Chen et al.72
of its production. The worldwide electricity consumption
reported QC in Pr/Yb:YF3 nanocrystals under excitation
in 2006 was 16378 TWh, which was 11.8% of the total
with 482 nm, which yielded 976 nm through an efprimary energy consumption. According to the 2009 Intercient cooperative energy transfer from Pr to Yb. The optinational Energy Outlook, the worlds total net electricity
mal QE was found to be around 200%. Dwivedi et al.73
production in 2030 is expected to increase by 77% comobserved bright red emission following 266 nm excitation
pared to the 2006 level.86
in Pr:Y2 O3 nanocrystals with QE greater than 80%.
Another concern is the bulky, expensive and less efRecently, Han et al.74 observed QC in Na3 Gd0 9x
cient conventional illumination sources (lamp, bulb, tube
Yx Si3 O9 :0.1Tb3+ phosphor for 274 nm excitation. QC in
light, etc.) that is also one of the primary domestic polNd:Yb system was also observed by Sun et al.75 and
lutant sources as it contains or emits toxic materials like
Meijer et al.76 in CaWO4 , and YF3 hosts, respectively.
mercury (Hg), sulphur, carbon dioxide (CO2  and uraWegh et al. studied the visible QC in LiGdF4 :Eu62 and
nium. The need for efcient, economical and eco-friendly
LiGdF4 :Er,Tb,77 whose QC efciency has found to be
sources brought a surge of research works and the most
190% and 130%, respectively, when the absorption from
suitable replacement suggested for conventional illumiother centers than Gd or Er is neglected. Liu et al.78
nation sources is the light emitting diode (LED), which
reported a two-step energy transfer QC in BaF2 :Gd,Eu
is supposed to reduce the consumption up to 7080%
with visible QE up to 194%. QC process in TmYb doped
when compared to conventional lamps. According to the
LaF3 nanocrystals were observed with 468 nm excitaresearchers of Strategies Unlimited LED Lighting, sales
tion in Tm 1 G4 energy level which results in emission
increased from $2.7 billion in 2008 to $9.4 billion last year
between 950 and 1100 nm from Yb ions. The maximum
and the growth is expected to be at a breathtaking annual
QE reported was 162% in 0.5Tm8Yb composition. Deng
rate of 20% through 2016. The research group noted that
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et al.79 demonstrated QC in NaYF4 :Ho,Yb synthesized by
more
LED 2014
lighting
products are becoming mainstream
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03 Feb
10:50:43
the hydrothermal method. With 359Copyright:
nm excitation,
nearin
various
markets.
Frost
and Sullivan, a market trends
American Scientific Publishers
infrared QC could occur through cross-relaxation in a tworesearch group, anticipates revenues in the efcient lightstep resonance energy transfer from Ho to Yb, with a
ing market in Europe to hit just under $2bn by 2018, doumaximum QE of 155.2%. Yu et al.80 observed QC in
ble the last years gure, driven largely by the legislation
hexagonal beta-NaYF4 doped with Ho:Yb by exciting with
of the European Commission to rule out various traditional
300550 nm, yielding two NIR photons. It was found that
light bulbs.87
NIR-QC can occur via two energy transfer mechanisms:
The concept of a LED88 for general illumination is
through the simultaneous excitation of two Yb ions via
attractive due to the reliability of solid-state devices, the
cooperative energy transfer and via resonant energy transpotential for delivering very high luminous efciency
fer followed by a sequential 5 I6 5 I8 transition in Ho ion.
compared to conventional incandescent and uorescent
Zhou et al.81 observed a three-photon cutting in CaAl2 O4
sources, long lifetime, vivid color emission, possibility of
phosphor doped with Yb ions via the energy transfer from
variable and multihued devices, its compact, environment
Yb2+ to Yb3+ ions. Chen et al.82 reported two-photon
friendly (mercury free) and designable features. LEDs
QC in Ce3+ /Yb3+ co-doped borate glasses on 330 nm
are subcategorized in three types, inorganic, organic and
excitation via energy transfer from Ce3+ :5d to Yb3+ :2 F5/2
hybrid LEDs. Recently, Reineke et al.89 reported excelions. The maximum ET and the corresponding DC eflent white organic LED, more efcient than uorescent
ciencies were estimated to be 74% and 174%, respectube light. However, the performance of organic LEDs
tively. Near infrared ( 1000 nm) QC was observed in
is deleteriously affected at high temperature and addiYb:NaY(WO4 2 phosphor by Deng et al.83 through cooptionally the materials in an organic LED are sensitive
erative energy transfer in high Yb concentrations (up to
to air and moisture, which leads to their degradation
40%). QC in chalcohalide glasses was also reported, occuras well as to the quenching of excited-states within the
ring from Eu2+ to Yb3+ .84 Detailed information on various
molecule.90 As most of the highly uorescent materiupconversion and downconversion materials that can be
als yields poor electroluminescence compared to optical
used for solar cell can be found in Ref. [85].
excitation, a concept of hybrid LED coated with yellow organic/inorganic phosphor materials are also mostly
3.2. Light Emitting Diodes
acceptable.91
Electroluminescent (EL) devices based on Ln-complex
As stated earlier, there may be several possible ways
to tackle the interconnected problems of pollution and
thin layers, schematically shown in Figure 3, are of
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Advances in Rare Earth Spectroscopy and Applications

eye.94 However, the concept of yellow and blue mixing may not be so good because it has a few disadvantages, such as poor color rendering index (CRI) property,
blue/yellow color separation and lacking of red component in the spectrum of this kind of LED. This problem can be solved to some extent by co-doping with Gd
ion along with Ce, which causes a shift in yelloworange
range.95
Divalent Eu ion96 usually yields blue emission but it
can also be tuned in a wide range of green, yellow
and red regions, as well. Park et al.97 reported bright
Figure 3. Schematics of layers conguration of an EL cell.
green emission in (Ba1 2 Ca0 8x Eux SiO4 phosphor. Xiea
et al.98 found a bright yellow emission in Eu doped
great interest because of their possible applications as
oxynitride phosphor a-SiAlON. Due to the formation of
low voltage operating large-area light-emitting displays.
Eu2+ ions, light is efciently absorbed in the UV-visible
In general, a thin layer of Ln-complex (amorphous or crysspectral region and results in a single intense broadtalline) is sandwiched between a hole transport layer and
band emission at 583603 nm, which is used to create
electron transport layer. When an electric eld is apply, the
white light with 450 nm LED excitation. Kuo et al.99
generation of light results from the recombination of holes
reported a red phosphor, CaZnOS:Eu2+ , which has a broad
and electrons injected from the electrodes. Such recomabsorption band in the 450550 nm region and emits
bination in the emitter layer excites the emitter material.
600700 nm. This phosphor was combined with green
The efciency can be further improved by blocking elec((Ba,Sr)2 SiO4 :Eu2+  and yellow (YAG:Ce) emitting phostrons and holes from moving into the electrode without
phors to produce white light. Similarly, broad red emission
recombination.
was also observed in Sr2 Si5 N8 :Eu2+ ,100 CaAlSiN3 :Eu2+ ,101
The problems related to organic LEDs could be overwhile white light emission was reported for single cryscome up to some extent by using Ln-doped inorganic
talline Ca9 Gd(PO4 7 :Eu2+ , Mn2+ phosphor, which exhibits
by Publishing
Technology
SAO PAULO
phosphors, which Delivered
provide narrower
and efcient
emission. to:a UNIVERSIDADE
broad bluegreen emission
band at IF
490 nm and a red
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2014
For single color LEDs, Eu3+IP:
(red),
Eu2+ (blue, yellow),
emission
at 10:50:43
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Tb (green), Tm (blue), Dy (yellow),
and Ce (blue,
yel- Scientific
ions, respectively.102 When Sr3 SiO5 :Ce3+ ,Li+
and Mn2+Publishers
low) ions complexes are used. Organic molecules that
and high quality TOP/TOPO/HDA-capped CdSe quancan act as sensitizer for Ln ions are beta-diketone functum dots (QDs) were coated on a blue LED chip, white
tional groups such as acetylacetone, dibenzoylmethane
LEDs with an excellent color rendering property were
(DBM), 2-thenoyltriuoroacetone, carboxylic groups such
obtained. The white LEDs exhibited a luminous efas o-benzoyl benzoic acid, salicylic acid, o-phthalic acid,
ciency of 14.0 l mW1 , Ra 90 1, and Tc 8864 K,
organic compounds which have ketone or aldehyde groups
which is acceptable for general lighting, indicating that
adjacent to hydroxy groups, such as salicylaldehyde,
the combination of phosphor and QDs in LEDs can
o-hydroxyacetonephenone or o-hydroxybenzophenone,
be a good solution to provide white light sources with
oxine analogues such as 8-hydroxyquinoline or 5,7high color rendering properties.103 Kim et al.104 fabri
dibromo oxine; pyridine analogues such as 2,2 -dipyridine,
cated a GaN-LED using a mixture of Ba3 MgSi2 O8 :Eu2+
2,2 2 -tripyridine, 1,10-phenanthroline and cryptates and
and Sr2 SiO4 :Eu2+ phosphors which yielded a broadband
crown ethers.92 These ligands can also be combined, using
spectrum, higher color rendering index and higher color
more than one ligand in the same device. Additionally, varstability against forward bias currents than Y3 Al5 O12 :Ce3+ ious semiconductor hosts and inorganic nanophosphors are
based white LEDs. Li et al.105 synthesized a new material,
also considered for LED applications. Recently, gallium
MSi2 O2x N2+2/3x :Eu2+ (M = Ca, Sr, Ba), which yielded
nitride based devices, co-doped with Eu and Mg, showed
bluegreen emission at 490500 nm for BaSi2 O2 N2 :Eu2+ ,
luminescence efciency as high as 77%. Mg doping selecyellow emission at 560 nm for CaSi2 O2x N2+2/3x :Eu2+
tively enhances a specic emission site and increases emis(x 0) and a green-yellow emission peaking from 530 to
sion intensity at least by one order, suggesting that Eu and
570 nm for SrSi2 O2x N2+2/3x :Eu2+ (x 1), being the maxMg doped GaN may be used for new devices.93 However,
imum dependent on the exact value of x. BaSi2 O2 N2 :Eu2+
for general household lighting purposes mostly white light
is the most promising conversion phosphor for white-light
is desired.
LEDs due to its high conversion efciency for blue light
In practice, a blue emitting GaInN LED chip was
from InGaN-based LEDs related to its very small Stokes
coated with Yttrium Aluminum Garnet (YAG) doped with
shift. White light was also reported from the combination
Cerium, absorbing blue emission from the LED and yieldof complementary colors in Dy doped SrSiO3 long-lasting
ing yellow emission, which apparently looks white to the
phosphor which yielded two emissions at 480 nm and
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etc.) and (2) unsaturated ligands (Beta-Diketonate complex,


tripode complex, porphyrinate complex, oligopyridinepolycarboxylate complex, dendrimer complex etc). The
saturated sensitizer ligand provides an additional advantage for shielding Ln ions from ambient hydroxylic-like
solvent molecules that would otherwise quench the Ln
luminescence and are used for the labeling of biological proteins and DNA molecules. However, for sensing
purposes, the ligand should be sufciently nearby to the
emissive site to permit efcient energy transfer, besides
containing vacant sites for the guest ion. The complexes
of Eu3+ and Tb3+ exhibit red and green luminescence,
while Nd3+ and Yb3+ complexes provide NIR emission.
They are highly luminescent and desirable for in vitro and
in vivo analyses. The long-lived energy levels of Ln also
offer an advantage over shorter lived background emission (auto-uorescence) and light scattering from biological environments.112
Ln ions probe some of the toxic gases as soman, which
was reported to be used in wars.113 It should be noted
that one of the serious threats of chemical warfare is the
use of nerve agents that causes rapid and severe effects
Figure 4. Luminescence spectra of (A) Er:Pr:Yb, (B) Er:Yb (C)
on humans. Basically, these nerve agents are made of
Pr:Yb co-doped tellurite glasses. Reprinted with permission from [109],
organophosphate that stops the function of the acetylY. Dwivedi, et al., J. Appl Phys. 104, 043509 (2008). 2008, American
cholinesterase enzyme, leading to various organ failures.
Institute of Physics.
Ln has the property of linking to organophosphate and
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to:
UNIVERSIDADE
SAO PAULO
helps
to detect the nerve
agent.114 IF
Detection of nerve
572 nm.106 White light was also
simulated
by
RGB
color
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On:
Mon,
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2014 on
10:50:43
agents
are based
variations of the uorescence inten107
108
109
TmHoYb, Copyright:
PrErYb (Fig.
4).
mixing in TmErYb,
American
Scientific
sity uponPublishers
complexation to Ln (Eu and Tb) ions (Fig. 5).
However, the suitability of these materials still needs to be
Comparing the uorescence intensity of free ligand and
tested in real devices.
complex, the chemical agent can be detected. By tailoring
the nature of the metal-ligand interactions, it is possible to
4. SENSORS
enhance the sensitivity of such systems and improve their
selectivity towards different analytes. Another advantage
It has been previously recognized that since Ln complexes
of Ln sensors is its exceptional selectivity to other chemiexhibit characteristically narrow excitation and emission
cal compounds like ester, ketones, etc.
bands, intense uorescence and long excited-state lifeKnapton et al. 116 reported Mebip-functionalized ethynytimes, they are suitable to be used as chemical sensors.110
Ln exhibits intra-conguration optical transitions and just
lene derivatives for the detection of organophosphate and
a few of them, known as hypersensitive, are susceptible
demonstrated the ability of readily controlling the extent
enough for environment sensing. However, in addition to
to which the uorescence of the Mebip ligands changes
them, paramagnetic Ln elements have a large number of
upon metal binding. It was observed that upon binding
degenerate energy levels and are sensitive to a variety of
with La3+ , the emission spectrum of the ligand experiences
metal ions, anions, humidity, hydrogen peroxide, magnetic
a signicant bathochromic shift (max = 73 nm, emission
eld, pH and various gases like NH3 and O2 . Readers are
color change from blue to green and the uorescence
referred to Ref. [111] for more detailed information.
intensity is signicantly decreased).
Tremblay et al.117 proposed a general strategy for the
4.1. Gas Sensor
rational design of ratiometric, luminescent probes based on
a heterometallic bislanthanide (Eu3+ and Tb3+ (or Dy3+ 
As mentioned earlier, Ln elements possess a small absorpplatform. The relative emission intensities can be tuned
tion cross-section and to improve their sensitivities, senby adjusting the stoichiometry and since the luminescence
sitizer ligand molecules are usually employed. It is
is sensitized by a single antenna, changes in its elecinteresting to note that the coordination number of Ln is
tronic structure can manifest themselves as changes in the
> 6, providing enough sites to accommodate both the senrelative ratio of luminescence from each metal. Jenkins
sitizer ligand and the analyte in their inner coordination
et al.118 reported a uorescence based ber optic probe for
sphere. Two types of coordination ligand are in practices
organophosphates, using a supramolecular complex up to
(1) saturated (Caged complex, cyclen complex, helicate
1586

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Advances in Rare Earth Spectroscopy and Applications

Figure 5. Proposed displacement mechanism for the Ln supramolecular sensor. Reprinted with permission from [115], M. Burnworth, et al., Chem.
Eur. J. 129, 7828 (2007). 2007, John Wiley & Sons.

sensing of hydrogen peroxide in a broad linear concentrathe detection limit of 660 ppq. They used a molecularly
tion range.
imprinted polymer sensor of [Eu-(dvmb)3 (pmp)(NO3 2 ],
Tsang and Bulpitt123 reported superior performance of
a Eu3+ complex with three different ligands. Although the
rare earth oxides over tin oxide-based ethanol sensors.
response of this sensor is limited by analyte diffusion, the
They proposed that adsorbed oxygen of strong basicity
sensitivity is high enough for precise detection even in
can facilitate the oxidative dehydrogenation of ethanol,
the presence of chemically similar organophosphates.
with the intermediate acetaldehyde giving a high molecuEu complex coated tiny silica particle shows instantalar response. They further investigated a different sensing
neous and signicant color change, from pink to blue, on
mechanism in the case of Pr oxide-based sensor, where
exposure to liquid and vapor (for 2 h at 60 C) triethyl
their labile lattice oxygen is active for ethanol oxidation
phosphate. Another approach for detection is by using an
even at low temperatures ( 150 C). The electron hopenzyme as the binding motif in presence of Au-NPs. This
ping sites associated to the mixed valence cations are
concept is based on the variation of the uorescence intenDelivered by Publishing Technology to:partially
UNIVERSIDADE
SAO PAULO IF
destroyed in a stream of ethanol vapor, causing
sity of Ln ions with the relative distance to the metal NPs
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an increase
in the electrical resistance. Upon removal of
owing to changes of the eld nearCopyright:
the Ln ion.American
Detach- Scientific
Publishers
ethanol, molecular oxygen in air replenishes the vacant
ment of NPs from Ln complex occurs in the presence of
oxygen sites, reverting sensor to its initial resistance
a weakly bound phosphate derivative, uorophore, to the
value. The lattice oxygen can be tuned to react only
enzyme which is, by its turn, covalently attached to gold
with ethanol but not with n-butane at or below 300 C,
nanoparticles. Separation of the metal NP from the comachieving 100% selectivity. This mechanism can selecplex reduces the emission intensity of the Ln complex.
tively transduce the ethanol concentration into an electriThis displacement occurs through the competitive binding
cal signal. Niu et al.124 reported nanometer materials of
with an analyte that has a higher binding afnity to the
119
REFeO3 (RE = Eu, Gd) which were sensitive to C2 H5 OH,
enzyme than the phosphate derivative. Simonian et al.
H2 S, gasoline and H2 . The studies of gas-sensing charreported organophosphorus hydrolase as the receptor for
acteristics show the sensitivities of EuFeO3 (20 nm) and
organophophorus analytes.
GdFeO3 (21 nm) nanometer materials to gasoline are 39
Koshizaki and Oyama120 investigated the selective
and 45 ppm at 340 C, respectively, and both have the
enhancement of NO2 against NO sensing by rare earth eleappropriate
selectivity. Aono et al.125 accounted for NO2
ment doping. Er-doped ZnO lm exhibited good sensitivity
sensing
using
SmFeO3 and REFeO3 (Re = La, Nd, Sm, Gd,
in the sub-ppm concentration range, good selectivity and
and Dy) materials.
fast response time to NO above 200 C.
An amount of H2 S gas over > 250 ppm is known to be a
4.2. Ion, pH and Hydrocarbon Sensors
potentially hazardous gas for the health. Hence, it is necessary to determine H2 S quantitatively, especially at the coal
Ln based sensors were studied for the detection of
oil or natural gas manufacturing site or laboratories. Zhong
metal cations, organic and inorganic anions, small neuet al.121 reported a novel Ln (Eu, Gd, Ho):In2 O3 -based H2 S
tral molecules in solution and various volatile organic
gas sensor and found that 5 wt.% Ho3+ In2 O3 sensor
chemicals detection. The use of encapsulated Ln as
exhibited the highest response value, excellent selectivsensitized photoactive centers capable of analyte bindity and quick responsive for H2 S gas in the range from
ing has emerged as a compelling strategy for lumines1100 ppm. Li et al.122 studied a simple and effective
cent supramolecular sensor development.126 They utilize
solvent swelling method to prepare PMMA/Eu complex
the large absorption cross-sections of selected organic
hybrid nano-spheres (100200 nm). These luminescent
molecules and the long lifetime and sharp emission characteristics of Ln ions to generate very efcient molecular
nano-spheres show high sensitivity in the luminescence
J. Nanosci. Nanotechnol. 14, 15781596, 2014

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devices. One of the major constituents of our environmental system, Nitrogen, is generally not considered
toxic for living bodies though its metabolites may be
carcinogens.127 However, the use in large scale of nitrogenand phosphorus-based fertilizers in the agriculture sector
may pollute the soil, wastewater and ultimately food, via
plants. The detection of excess amounts of nitrates generally is based on the ion exchange principle. It is known
that counter ions can coordinate to Ln ions in unsaturated ligands to fulll the coordination requirements for
Ln ions. Generally, there are two ways of modulating the
emission property of Ln complexes by anions. First, water
molecules bound to the Ln center should be displace by
anions, leading to an enhanced luminescent intensity and
second is the displacement of ligands by anions resulting
in the increase or decrease of the luminescent intensity.128
Ln based anions detection can be possible by the careful design of antenna ligands that leave some coordinate
vacancy for anion binding to Ln. In general three design
strategies are considered to sense anions
(1) supramolecular recognition, such as hydrogen bonding
interactions,
(2) Lewis acidbase interactions, and
(3) anion ion-induced chemical reactions.129 130

the emission intensity variation of Eu ions as a function of halide ions (Cl, Br, I) in aqueous solution of Euoctadentate monoamindetriphosphinate or chiral tetraamide
complex, which was attributed to the competition between
the excited-state quenching rate of the chromophore and the
rate of intersystem crossing from triplet state of the chromophore to the 4f level of Eu ion. Faulkner et al.136 showed
the selective stabilization of a more luminescent bound
form to give an intense near-infrared Yb3+ luminescence
on addition of SCN ion in a dendrimer complex. Wang
et al.137 found that the phenanthroline-based imidazole Euor Tb-complexes can efciently detect different anions
(F , CH3 COO , and HSO
4  through hydrogen bonding
interaction. Parker138 reported on heptadentate cyclen ligands for Ln ions that selectively bind bidentates such as
HCO3 and carboxylate anions and found greater dynamic
displacement of the coordinated water molecules by the
guest anions than octadentate cyclen complexes. Distinc
tive anion-selective (NO
3 and Cl  luminescence enhancement was demonstrated by Kataoka et al.139 in different
Eu-tripodes complexs bearing quinoline chromophores.
Ln ions, Eu:Tb ions dispersed in a polymer hybrid and
doped with a proton-sensitive amide-type beta-diketonated
photosensitizer, N -(2-pyridinyl)benzoylacetamide was
129
shown to be highly luminescence sensitive to OH conYang et al.
reported an efcient long uorescence
centrations, thus representing a new paradigm for full
lifetime polymer-based sensor based on Eu(TTA)2 vinylcolor displays.140
Phen complex [TTA

=
thiophentriuoroacetone);
Phen
=
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sensors were developed for selective
phenanthroline] as chromophore
for the specic detection
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detection
of
alkali
and
DMSO solution.
On Scientific Publishers alkaline earth metals (Li, Na, K, Zn,
of F , CH3 COO , and H2 PO4 inCopyright:
American
Ca, Mg) that are necessary to monitor and regulate a numbinding to F , CH3 COO , and H2 PO
uorescence
of
4
ber of cellular functions and heavy metal cations (Pb, Cu,
Eu-polymer quenched by an approximately 95% due to
Hg) for biomedical purposes. It is interesting to know that
strong hydrogen bonding interaction and deprotonation

bound Cu2+ plays a vital role in many enzymatic processes,


interaction at high concentration for F , due to which Euwhile free Cu2+ can disrupt and damage various biologpolymer sensor selectively sense F even in the presence

ical processes, causing several conditions such as Wilson


of CH3 COO , and H2 PO4 .
and Menkes diseases.141 Similarly, Hg2+ is toxic to humans
Douce et al.131 synthesized the Eu complex of bisand can accumulate in the blood-brain barrier, resulting in
bipyridinephenylphosphine oxide and reported an increase
severe neurological disorders.142 Lead is also a cumulative
in luminescence yield and lifetime due to the anion bindpoison, with fetuses, infants, and pregnant women being
ing. The authors concluded that this new system is applithe most susceptible to adverse health effects, especially in
cable to other molecules because it allows detection of
the central nervous system. Evident signs of acute intoxitraces of halides and nitrates by luminescence monitoring
cation include dullness, restlessness, irritability, poor attenof the Eu center, whose long excited-state lifetime allows
tion, headaches, muscle tremor, hallucinations and loss of
the enhancement of the signal-to-noise ratio with the use
memory.143 In addition, there are several other environmenof time-resolved spectroscopy. Santos et al. [132] investital concerns regarding cations. The emission intensity of
gated interesting anion-sensing with cyclen Ln complexes
Eu ions is enhanced after the addition of alkali metal ions
which recognize CH3 COO and H2 PO
through
hydro4
(Na+ , K+  by at least one order of magnitude in Ln ion
gen bonding interactions and potential metal ion coordina3+
133
aza crown molecular complex144 due to the suppression of
tion to Tb ion. Zhang et al. synthesis Eu(DBM)3 DPPZ
electron transfer from the nitrogen atom of aza crown to
(DBM = dibenzoylmethane, DPPZ = dipyrido [3,2-x2 ,3 excited Eu ion. Nevertheless, this result was analogous to
c]phenazine), which was found to be efcient to recogthe case of Tb-complex, which is thought to be due to the
nize AcO ions over other anions due to the replacement
existence of additional relaxation nonradiative pathways
of DPPZ by AcO . The output of a sharp characterisfor 5 D4 :Tb ion.
tic Eu3+ emission is read as 0 only in the absence of

A Tb3+ -cyclen-based sensor was proposed for the pH


AcO ion under oxygen atmosphere. Optical sensing of

3
independent, selective detection of Cu2+ and Hg2+ ions in
Cl and NO anions were reported in Eu and Tb complexes with tetradentate tripodes.134 Parker et al.135 reported
water. The changes in the Tb3+ emission were monitored
1588

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Dwivedi and Zilio

Advances in Rare Earth Spectroscopy and Applications

by carrying out metal titrations which quenches Tb emisphenyl) naphthalene-1-sulfonamide, DR1 = N 1 -(4-(dision by ca. 65% (Cu) and 40% (Hg).145 Plush and
methylamino)-benzylidene)N 2 -(rhodamine-6G) lacta146
designed and synthesized a novel staGunnlaugsson
methylene-diamine).
These
pH-sensitive
emitter
ble dinuclear Eu conjugate by tethering a mono-aza-18components have pKa values of 5.0 and 7.2 respectively.
crown-6-ether moiety to a cyclen macrocyle. The analysis
Eu(TTA)3 -DR1 was able to detect pH values at both near
of this conjugate showed that anions such as acetate and
neutral pH and acidic pH ranges, and was also able to
L-aspartate give rise to quenching of the Eu3+ emission,
detect pH in both cultured cells and in vivo.
while malonate give rise to large luminescent enhanceLn ions are also used for protein labeling, specically
ments, where the largest changes were seen in the hypermetalloproteins which are reported to form stable Ln comsensitive transition.
plexes. Two of the natural occurring proteins, transferrin
Hanaoka et al.147 reported the design and synthesis of
and lactoferrin, contain a Fe3+ metal center. It is intera novel Ln sensor molecule, using the quinolyl ligand, to
esting to note that two bound Fe3+ cations are released
detect Zn2+ ions. Upon the addition of Zn2+ to a solufrom lactoferrin at pH 2.54.0 while transferrin loses Fe3+
tion of Eu complex, the luminescence of Eu3+ is strongly
cations at pH 4.06.0, which are substituted by Ln ions,
enhanced, with high selectivity for Zn2+ over other biologthus forming an emissive complex.156 Another protein,
ically relevant metal cations. One of the important advanapoferritin, is reported to form complex with Tb ions157
tages of this complex is that it can be excited with longer
and make the Tb luminescence longer. Kataoka et al.158
excitation wavelengths ( 340 nm) as compared with prereported pH-dependent Tb luminescence in proteins apoviously reported Zn2+ -sensitive luminescent Ln sensors,
lactoferrin and apotransferrin.
whose excitation wavelength is at too high an energy level
Since hydrocarbons do not coordinate to Ln ions,
for biological applications. This complex was claimed as
a
rather different technique is needed to detect them.
the rst Zn2+ sensitive Ln chemosensor that can be used
In
this case, two different ligands are used, one for the
for studies of the biological functions of Zn2+ and the
Ln ion (aza crown) and the other for the hydrocarbon
design strategy should yield a range of long-lived Ln
(functionalized cyclodextrin).159 Mortekkari et al.160 introprobes for sensing Zn2+ or, after appropriate modication
duced a tri-anionic diethylenetriaminepentaacetate to the
of the acceptor moiety, other molecules of interest in bioTb-cyclodextrin complex to improve the strength of arological applications.
matic
hydrocarbon binding
reported
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ity of such complex towards hydrocarbon. The detection of
complex luminescence lifetime (combining
a hard
donor Scientific Publishers
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protease inhibitors is very important due to its application
with two soft pyridine donors) upon the addition of ATP,
in curing different diseases (cancer, AIDS, inammatory
whereas ADP and AMP did not induce signicant changes.
disorders, etc.). Karvinen et al.161 162 reported a protease
Ln ions in liquid chromatography149 can also serve the
assay based on a complicated time-resolved uorescence
purpose of detection of single stranded nucleic acids,150
resonance energy transfer (TR-FRET). Mizukami et al.163
151
152
153
hormones, amino compounds and labeled thiols.
developed a novel luminogenic Tb probe for detecting proDetermining the uorescence pH probe molecules
tease activities.
for imaging purposes in living cells is one of the very
important aspects as minor variations of intracellular pH
4.3. Magnetic Field Sensor
may induce cellular dysfunction, desirable pH uoresMagnetic eld sensing is one of the requirements in the
cent probes should be able to respond sensitively to a
elds of navigation, vehicle detection, current sensing,
minor change of pH, and to avoid interference from native
and spatial and geophysical research. Optical magnetic
cellular species. Liu et al.154 discuss time-resolved lumield sensors are desirable because of their immunity
nescence bioassay technique using highly stable Europium

  

to electromagnetic interference, low weight, small size
and terbium (4 -hydroxy-2,2 :6 ,2 -terpyridine-6,6 -diyl)
and long-distance signal transmission for remote operbis(methylenenitrilo) tetrakis(acetic acid) (HTTA) comation. The well-known Faraday effect rotates the plane
plexes as luminescent probes/sensors. It was reported
of polarization of an optical wave in the presence of
that the HTTAEu3+ is strongly dependent on the pH
Ka
an external magnetic eld and hence it can be used
values in weakly acidic to neutral media (p = 5 8, pH
for magnetic sensing.164 Optical current/magnetic-eld
4.87.5), while that of HTTATb3+ is pH-independent.
3+
sensors based on the Faraday effect offer the advanUsing the intensity ratio of Tb emission at 540 nm to its
tages of simplicity and high electrical insulation. Optical
Eu3+ emission at 610 nm in HTTAEu3+ /Tb3+ mixture the
magnetic-eld sensors based on rare earth iron garnets,
UV absorption spectrum changes at different pHs (pH 4.0
such as Y3 Fe5 O12 and Gd2 BiFe3 O12 , have an extremely
7.0) also display a ratiometric response to the pH changes
large Verdet constant, which characterizes the Faraday
with the ratio of absorbance at 290 nm to that at 325 nm.
effect, yielding higher sensitivity, frequency response,
Zhag et al.155 synthesized new complexes Eu(TTA)2 DSQ
temperature characteristics and domain effects than senand Eu(TTA)3 -DR1 (HDSQ = 5-(dimethylamino)-N -(4-(2sors based on diamagnetic and paramagnetic materials.165
((8-hydroxyquinolin-2-yl) methylene)hydrazinecarbonyl )
J. Nanosci. Nanotechnol. 14, 15781596, 2014

1589

Dwivedi and Zilio

Advances in Rare Earth Spectroscopy and Applications

The Faraday effect of rare-earth-containing oxide, uorelies on transmitting signals over a larger bandwidth, with
minimum attenuation. Optical bers work in the condiride and oxyuoride glasses has been well discussed.166
tion of total internal reection, where the electromagnetic
It is known that trivalent Ce, Pr, Tb, Dy and divalent
wave is reected when passing from a higher index mateEu result in large Verdet constants in the visible range.
rials to a lower refractive index material above the critTanaka et al.167 measured the Faraday effect and optiical angle. Fibers can be made of glasses or polymers
cal absorption of Pr-containing lithium borate glasses and
(PMMA, polystyrene, etc.), but for long distance data
reported large magneto-optical gures of merit in the vistransmission, silica bers are used because they are more
ible range. In particular, 25Pr2 O3 75B2 O3 and 20Pr2 O3
transparent in the NIR region. The signal amplitude at
5Li2 O75B2 O3 glasses exhibit gures of merit larger than
the receiver depends on several factors, but the two most
250 /m at 400 nm under an external magnetic eld of
important factors are attenuation and dispersion. The sig15 kOe. Therefore, these glasses are promising materials
nal attenuation is due to absorption and scattering. Optifor use as an optical isolator for the (Ga,In)N laser diode
cal ber for communications typically operates in several
with the emission wavelength of 400 nm. Itoh et al.168
electromagnetic spectral windows, as given in Table I. Evideveloped a 5 mm wide optical magnetic-eld sensor
dently, the transparency at long wavelengths is limited by
based on the novel Bi0 98 Gd0 92 La0 03 Y1 07 Fe4 72 Ga0 28 O12
the infrared vibrational or multiphonon absorption edge,
garnet, that demonstrated high accuracy with 1.0%
which is determined by the frequency of the fundamental
error and shows high temperature stability for sensitivlattice vibration, as shown in Figure 6.
ity of less than 2.0% from-20 to + 80 C. Potter and
The dispersion, which produces a pulse spreading,
Sinclair169 review two inorganic materials classes used
accounts for the fact that different wavelengths travel with
for optical sensors: photosensitive glasses and rare-earth
different speeds in a dispersive medium, being inversely
doped materials. The discussion on rare-earth doped optiproportional to the bandwidth. Several bers were studied
cal sensor materials emphasizes the important contribuwith this respect: polymer bers, quantum dot dispersed
tion of the host material to the observed optical behavior
ber and micro-structured bers.174 175
of rare-earth ions. The use of rare-earth doped mateAmong oxide glasses, silica offers the advantages of
rials in applications ranging from temperature sensing
the smallest amount of absorption at 1550 nm (losses
to ber-optic gyroscopes is also described. Sun et al.170
dB/km) and highest
and as a result, it
accounted for a 2Delivered
cm long ofby56Publishing
wt% terbium
doped sil- to:0.2
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UNIVERSIDADE
SAObandwidth
PAULO IF
is
the
choice
for
long
distance
communications
purpose,
icate ber as a Faraday rotator,
with
a
Verdet
constant
of
IP: 143.107.180.158 On: Mon, 03 Feb 2014 10:50:43
while still,
polymer bers can be used for short distance
24.5 rad/(Tm) at 1053 nm. The sensor
had aAmerican
sensitiv- Scientific
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( 500 m) applications.176 To improve the signal quality at
ity of 0.49 rad/T and can measure magnetic elds from
the receiver, repeaters can be used to convert the optical
0.02 to 3.2 T. The highest Faraday rotation in the visiinto electronic signal, amplify it and re-transmit in the form
ble spectral regimes was obtained in the composite lm
of an optical signal at higher intensity. However, the use of
(BiDy)3 (FeGa)5 O12 :Bi2 O3 with values 10 /m, 2.6 /m,

repeaters decreases the transmission rate and is expensive.
and 1.9 /m for wavelengths 532, 635 and 670 nm,
respectively. In this composite lm, it was demonstrated
Table I. List of telecommunication windows and Ln elements used for
that as the wavelength of the incident light increases, the
OPAMs.
171
Similarly, at the telecomFaraday rotation decreases.
Window
Range (nm) Transmission
Ln element
munication wavelength of 1.55 m, the Faraday rotation measured in CeYIG,Co-doped CeO2 lms, CeFeO3
Tm, Er
First window
800900
Due to high
lms, YbIG, Sc doped EuIG, scandium substituted EuIG
losses use for
short distance
lms were found to be 0.44, 0.60, 0.60 0.0420, 0.0450
communication
and 0.0500 deg/m, respectively.172 Sekhar et al.173
only.
measured the Faraday rotation in Bix Ce3x Fe5 O12 lms
Original (O)
12601360 Region of almost Pr, Nd, Dy
prepared by pulsed laser deposition and found 1.6 and
band
zero dispersion.
50 times larger than that of CeYIG and YIG, respectively.
Extended (E)
13601460

5. TELECOMMUNICATIONS
Nowadays, probably the most important commercial products are television, internet and communication systems.
In these systems, the signal transmission is carried out
through an optical ber. Long-distance data transport was
a challenge and witnessed a series of developments starting from optical ber transmission at low attenuation to
the now fourth generation data transmission of 14 tera
bit per second at 160 km. The future of ber optics
1590

band
Short (S) band

Conventional
(C) band
Longer (L)
band
Ultra (U ) band

14601530

Lower silica
absorption,
some
dispersion, long
range
communication

Tm

15301565

Er

15651625

Pr, Pr:Er, Er:Yb

16251675

Ho

J. Nanosci. Nanotechnol. 14, 15781596, 2014

Dwivedi and Zilio

Advances in Rare Earth Spectroscopy and Applications

Figure 7. Energy levels and some of the telecommunication interest


transitions in Nd, Pr, Dy and Er ions (energy levels are not to scale).
Figure 6. (A) Communication windows in absorption spectrum of silica
ber and (B) schematic diagram of optical ber containing core, cladding
and protecting coating.

a given frequency signal matches the energy of an excited


level, the ions get depopulated by emitting an additional
photon of same phase, direction and frequency of the
The preferable solution to this problem is to use an optical
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UNIVERSIDADE
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IF ber is strongly
In this way, the
signal
in the
amplier (OPAM) that is much faster as it directly ampliIP: 143.107.180.158 On: Mon,
03
Feb
2014
10:50:43
amplied in the propagation direction. Other options of
es the signal via stimulated emission.
Up to now,
several Scientific
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American
Publishers
amplifying media are disperse Ln ions encapsulated by
optical ampliers are used, including Raman, semiconducsensitizer ligands (in a polymer matrix) and quantum
tor, optical parametric, Ln based ampliers and so on.
dots of Ln elements in bers.174 177 The use of sensitizer
The performance of optical ampliers is affected by many
ligands presents three important advantages that include
factors such as optical amplifying gain and noise gure,
the increased solubility of Ln ions (to avoid aggregation)
that are related to the gain medium parameters (geometry,
in polymer matrix, the sensitization for Ln ions and the
compositions of gain materials, etc.), working conditions,
shielding from vibrations of the host matrix.178
pumping method wavelength and power of the input sigSeveral Ln ions are considered as potential candidates
nal. In general, Ln:OPAM possesses some advantages over
for optical amplier, but just a few are in use. Curother OPAM because it is transparent to bit rates and transrently, OPAM are mainly based on Er3+ ( 1550 nm)
mission formats, and allows simultaneous amplication of
and Pr3+ ( 1330 nm). There is, however, great intera large number of channel wavelengths. The gain of RE
est in developing efcient OPAMs with other Ln ions in
doped ber ampliers is insensitive to polarization because
order to achieve amplication in all windows. An inherent
the active dipoles are randomly oriented in the glass matrix
problem with Ln:OPAM is the concentration quenchand are stable over a 100 C temperature range due to
ing (> 5 ppm) occurring because of clustering that delethe homogeneous line broadening. Owing to the relatively
teriously affects the gain. To circumvent this problem,
long upper level lifetime, the gain is nearly immune to the
Ln:OPAM bers are usually made longer and with lower
interference between light channels and noise gures close
concentrations. Other drawbacks are the noise induced by
to the theoretical limit of 3 dB can be achieved. Ln ber
the amplied spontaneous emission (ASE) and gain satuampliers are compatible with transmission bers and other
ration. Readers are suggested to read Ref. [179] for more
ber components and when compared to Raman ampliers
details.
it requires less laser power. In Ln, optical amplication is
The rst communication window (800900 nm) is used
achieved by the process of stimulated emission after a high
for short distance signal distribution and local area netpower pump excites the Ln ion to an excited energy level.
work. Among the Lns, only Er3+ and Tm3+ ions proEnergy levels of different telecommunication important Ln
vide efcient amplication in this band through their 4 S3/2
ions are given in Figure 7.
to 4 I13/2 and 3 F4 to 3 H6 transitions, respectively. HowThe excited ions are distributed in diverse levels posever, only a few reports are available for this band. Tm3+
sessing long and different lifetimes. When the energy of
J. Nanosci. Nanotechnol. 14, 15781596, 2014

1591

Advances in Rare Earth Spectroscopy and Applications

Dwivedi and Zilio

ion not only provides amplication at 800 nm but also


a lower frequency phonon energy glass host like InF3
based uoride glass gain coefcients up to 0.36 dB/mW
at 1470 and 1900 nm.180 Dye et al.181 reported the rst
can be obtained. To circumvent the deleterious effect of
engineered 800 nm Tm:OPAM using two pump lasers of
oxide hosts, efforts were directed to sulphide and uoride
a single wavelength (780 nm), which was further modihosts. The lifetime of the 1 G4 level is reported to increase
ed by Akasaka et al.182 They demonstrated a Tm-doped
from 110 microsecond in ZBLAN191 to 250, 295, 337 and
optical amplier with 30 dB gain at the 850 nm window
360 microsecond in AsS,192 GaLaS,193 GeAsS194 and
using a special ber subjected to excitation with 690 and
183
glasses, respectively. So far, Pr: OPAM with
in GeS196
1400 nm. Watekar et al. reported a simulation model
x
concentration
5001000 ppm, were reported to provide
and the experimental realization of a novel single-mode
a
gain
of
1020
dB when pumping with 100500 mW.
Tm-doped silica glass optical ber amplier optimized for
The rst breakthrough in Ln based OPAM was the Erthe 800 nm window and a gain of about 11 dB at 840 nm
doped ber amplier (EDFA),196 which plays an important
was obtained upon pumping with a 1064 nm Nd-YAG laser
184
role by providing efcient broad band optical signal amplisource. Whitley et al. demonstrated an Er-doped uocation in the C-Band (15301560 nm). It was rst fabrirozirconate ber amplier providing over 20 dB of small
cated by Mears in 1986 using a diode laser ( 1480 nm)
signal gain at 850 nm by pumping with 801 nm. Gonzalez
to excite the 4 I13/2 level of the Er ion.197 In principle, the
et al.185 reported optical gains of 1.33 cm1 (5.7 dB/cm)
transition 4 I13/2 to 4 I15/2 is parity forbidden and hence, the
and 0.63 cm1 (2.73 dB/cm) for the 0.25 and 0.5 mol%
ion
remains in the 4 I13/2 level for a time greater than 3 ms.
Er-doped uoroindate glass samples at 840 nm.
In
a
situation where the pumping rate is fast enough to
The second and third windows (O and E band) lie in
overcome the spontaneous decay rate, population inverrange from 1260 to 1460 nm, where at least three Ln
sion occurs. In this condition, when a travelling signal at
ions, Nd, Dy and Pr, can be used. The Nd-doped OPAM
1550 nm propagates along the ber, the stimulated emiswas rst discussed by Koestner and Snitzer.186 It works
sion generates an additional replica photon. Most of the
over the range 13101360 nm and 13601400 nm in
research on Ln doped OPAMs was focused on EDFA
ZBLAN and silica glass, respectively, on excitation with
due to its high gain. EDFA can be excited at 980 and
795 and 810 nm radiations.187 Nevertheless, the quan1480 nm (1480 nm is more efcient) though different
tum efciency is very low, leading to a small gain that
(forward,SAO
backward
and IF
bidirectional). High
by Publishing
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makes Nd:OPAMDelivered
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The low to:mechanisms
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(3050
dB),
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(
90
nm), high output
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On: Mon, 03 Feb 2014 10:50:43
efciency of Nd:OPAM is due
losses by excited-state
power
(1030
dBm)
and
low
noise
gure
(35 dB) can
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absorption and amplied spontaneous emission that reduce
be achieved at 1.55 m in silica glass bers.198 In telluritethe overall gain. ASE arises due to the low branching ratio
based EDFA,199 a signal gain of 20 dB or more was
of the 1.3 m transition, with two competing transitions,
obtained in a bandwidth of 80 nm (noise gure < 5 dB).
at 0.9 m and 1.06 m, both having much higher branchThe high gain in the C band can be extended to the L
ing ratios. Similar to Nd ions, the Dy ion also suffers from
band (15651625 nm) by codoping with Yb and Er ions.
nonradiative decay processes and hence, the quantum efIt is interesting to note that the bands are used mostly
ciency at the 1300 nm transition (6 H9/2 + 6 F11/2 to 6 H15/2 
for
amplication (C and L) and provide only < 25% of
188
189
varies from 1.5% in oxide to 19% in sulphide and
the
usable communication window and it is also neces190
90% in selenide glass.
sary
to investigate other bands. Till now, various ampliPr is the preferred dopant choice as it provides efcient
ers
were proposed, like the ber Raman amplier, that
amplication at 1300 nm due to the radiative transition
uses
stimulated
Raman scattering,200 the S-band EDFA201
from the metastable 1 G4 to the 3 H5 state. However, the gain
and the Tm:ber.202 Among these options, Tm:OPAMs are
in Pr:OPAM is deleteriously affected by the small energy
more suitable in terms of power conversion efciency. The
separation ( 3000 cm1  between 1 G4 and3 F4 levels. This
Tm ion is a potential candidate for the S band because
promotes a non-radiative relaxation that leads to the reducits transition 3 H4 to 3 F4 covers the spectral range 1440
3
tion of the radiative lifetime of the H5 state, ultimately
1520 nm. Several single pumping schemes were sugaffecting both gain and efciency of the OPAM. In the
gested at 1047,203 1050204 and 1064 nm,205 together with
presence of high frequency vibrational groups in the host,
a dual-wavelength pumping at 800 + 1050 nm and 800 +
such as BO ( 1400 cm1 , PO ( 1200 cm1 ), SiO
1410 nm.206 Furthermore, codoping the OPAM with Tm
1
1
1
( 1100 cm , OH ( 3600 cm , CO ( 1100 cm ,
and Yb ions allows excitation with a cheap diode laser
CH ( 3000 cm1  and NH ( 3300 cm1 , the proba( 980 nm).207
bility of nonradiative relaxation increases due to the emission of phonons and thus, efforts were made to select
6. CONCLUDING REMARKS
lower phonon vibration hosts. This is the big hurdle in the
development of OPAMs for O and E band. In silica glass
Rare earth (or Ln) elements have unique optical and
(1200 cm1 , the QE at 1300 nm is < 1% while in uochemical properties which make them most appropriate
rozirconate ZBLAN glass (580 cm1  it is 4%. Using
non-isotopic alternative to organics. The exploitation of
1592

J. Nanosci. Nanotechnol. 14, 15781596, 2014

Dwivedi and Zilio

Advances in Rare Earth Spectroscopy and Applications

their multifunctional properties brings new energy efcient


devices. In this review article we tried to give insights
of Ln spectroscopy applications in at least three frontline
research topics, namely clean energy, sensors and telecommunications. These elds are supposed to be frontline topics as they not only cover huge commercial aspect but also
make human life easier and comfortable. We have tried
to give a glimpse of these developments in the context of
optical techniques.

20. X. Chen, L. Liu, and G. Liu, J. Nanosci. Nanotechnol. 8, 1126


(2008).
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Weng, Sci. Adv. Mat. 4, 1 (2012).
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dao de Amparo Pesquisa do Estado de So Paulo
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Cientco e Tecnolgico (CNPq), Brazil, for nancial sup32. http://www.energy.senate.gov/public/index.cfm/les/serve? File_id=
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Received: 16 August 2013. Accepted: 9 November 2013.

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