Académique Documents
Professionnel Documents
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2014-02
Review
Journal of
Nanoscience and Nanotechnology
CONTENTS
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
03 Feb 2014
upconversion
(UC).10:50:43
Several exclusive optical UC phenom4. Sensors . . . . . . . . . . . . . . . . . . . IP:
. . . .143.107.180.158
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1586 Mon,
4.1. Gas Sensor . . . . . . . . . . . . . . . . . . . .Copyright:
. . . . . . . . . . . . American
. . . . . 1586 Scientific
ena usingPublishers
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
1578
doi:10.1166/jnn.2014.9104
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
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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.
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.
1579
1581
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
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.
1582
1583
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
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band at IF
490 nm and a red
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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
J. Nanosci. Nanotechnol. 14, 15781596, 2014
1585
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
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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
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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
1587
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
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
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
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
Technology
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
Copyright:
Publishers
( 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
16251675
Ho
1591
1593
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