3+

Luminescence properties of Sm doped YPO4: Effect of solvent, heat-treatment,

2+ 6+
Ca /W -co-doping and its hyperthermia application
Dimple P. Dutta, R. S. Ningthoujam, and A. K. Tyagi

Citation: AIP Advances 2, 042184 (2012); doi: 10.1063/1.4773443

View online: https://doi.org/10.1063/1.4773443
View Table of Contents: http://aip.scitation.org/toc/adv/2/4
Published by the American Institute of Physics

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 AIP ADVANCES 2, 042184 (2012)

Luminescence properties of Sm3+ doped YPO4 : Effect

of solvent, heat-treatment, Ca2+ /W6+ -co-doping and its
hyperthermia application
Dimple P. Dutta, R. S. Ningthoujam,a and A. K. Tyagi
Chemistry Division, Bhabha Atomic Research Centre, Mumbai 400085, India
(Received 22 September 2012; accepted 12 December 2012; published online 18 December
2012)

Sm3+ doped YPO4 spherical nanoparticles are prepared by wet chemical route. Pure
YPO4 shows the tetragonal phase, which is stable up to 900 ◦ C, whereas pure SmPO4
shows the phase transition from hexagonal to monoclinic when heated above 800 ◦ C.
The (2-10 at.%) Sm3+ doped YPO4 shows the mixture of phases of tetragonal and
hexagonal, which transform to the tetragonal phase above 800 ◦ C. Infra-red study
could distinguish confined water in the pore of hexagonal phase from water present on
the surface of particles. Luminescence intensities of Sm3+ at 564, 601 and 645 nm are
weak in case of as-prepared samples because of high non-radiative rate arising from
the H2 O molecules present in pores of hexagonal lattice. The intensities increase for
samples heated up to 900 ◦ C because of increase of extent of radiative rate. Lumines-
cence lifetime increases with increase of heat-treatment up to 900 ◦ C. When solvent
of as-prepared sample was changed from the H2 O to D2 O, 5 times enhancement in
luminescence intensity is observed, which can be ascribed to the lower vibration en-
ergy of D-O over H-O, which is near to Sm3+ . When Y3+ and P5+ ions are substituted
by Ca3+ and W3+ up to 3 at.%, there is an enhancement of luminescence. In order
to use them as bio-labeling in drug delivery for hyperthermia applications, hybrid
of Fe3 O4 @YPO4 :7Sm is prepared and heating up to 45 ◦ C is observed under AC
magnetic field. Copyright 2012 Author(s). This article is distributed under a Creative
Commons Attribution 3.0 Unported License. [http://dx.doi.org/10.1063/1.4773443]

I. INTRODUCTION
Recently, nanomaterials are developed in the form of nanofilms, nanoparticles and nanopores.1–3
Lanthanide phosphates as a material find extensive application as laser, ceramic, sensor, phosphor,
heat-resistant materials, field-effect transistors and also in optoelectronics, medical and biological
labels, solar cells and light sources.4–11 Lanthanide phosphate-based compositions are used as host
matrices in fluorescent lamps and color TV monitors due to their strong vacuum ultra-violet (VUV)
absorption which is attributed to their (PO4 ) tetrahedral.12–14 Among the different kinds of rare-earth
orthophosphates, yttrium orthophosphate has been shown to be an efficient host lattice for rare earth
activator ions, which have become a research focus because of their important role in the field of
light display systems, lasers, and optoelectronic devices.15 The origin of luminescent properties is
from the intra 4f and 4f–5d transitions of different kinds of rare earth ions, especially the intra 4f
transitions which are less influenced by the surrounding ligands owing to the shielding of the 4f
orbital by the outer 5s and 5p orbitals. Though there has been a few reports on Eu3+ , Nd3+ , Pr3+ ,
Er3+ , Ce3+ , Tm3+ doped YPO4 , studies on Sm3+ doped YPO4 are relatively scarce.16–24 The lowest
excited level of Sm3+ is 4 G5/2 and it has three main emitting levels 6 Hj (j = 5/2, 7/2 and 9/2) located
at 564, 601 and 645 nm, respectively, which gives reddish-orange emission.23, 24 However, when wet

a Author to whom correspondence should be addressed. Electronic mail: rsn@barc.gov.in

2158-3226/2012/2(4)/042184/17 2, 042184-1 
C Author(s) 2012
042184-2 Dutta, Ningthoujam, and Tyagi AIP Advances 2, 042184 (2012)

chemistry synthesis technique is used for preparation of inorganic luminescent materials, quenchers
like OH− adsorbed on the material surface can get coordinated with the rare earth ions.25, 26 This
can lead to a decrease in emission intensity from the rare earth ion. Control of water molecules
associated with any phase structure is also difficult using wet chemistry synthesis. What will be the
effect of wet chemistry synthesis on the luminescence properties of Sm3+ doped YPO4 ? The role
of solvent in the luminescence and phase transformation of YPO4:Sm3+ has not been studied yet.
There are also not any reports regarding the luminescence recovery of these materials which, has
been quenched by the presence of a luminescence quencher such as OH− ions.
In this study, we have prepared Sm3+ (2, 5, 7, 10 and 20 mol%) doped YPO4 , in aque-
ous condition using a co-precipitation technique. The correlation among phase transformation,
content of water molecules, and luminescence intensity of Sm3+ has been studied using X-ray
diffraction (XRD), infrared spectroscopy (IR), thermo gravimetry (TG), transmission electron mi-
croscopy (TEM), and luminescence techniques. Core shell nanoparticles like CaWO4 @YPO4 :Sm3+
and Fe3 O4 @YPO4 :Sm3+ have also been synthesized. Some important results have been found:
(i) undoped YPO4 is purely tetragonal, Sm3+ doped YPO4 samples have mixture of both tetrago-
nal and hexagonal phases whereas undoped SmPO4 is purely hexagonal, (ii) on annealing above
900 ◦ C, there are no structural phase transition in pure YPO4 , phase transition from hexagonal to
monoclinic in pure SmPO4 whereas low concentration Sm3+ doped YPO4 samples are monophasic
with tetragonal structure, (iii) luminescence intensity of Sm3+ doped YPO4 increases with increasing
heat-treatment indicating decrease of non-radiative rate from surface of particles or water present on
the particles and (iv) enhancement of luminescence from Sm3+ doped YPO4 when co-doped with
Ca2+ and WO4 2− .
We also report the luminescence measurements of Sm3+ doped YPO4 samples with a change
of solvent from H2 O to D2 O. Significant enhancement in luminescence is observed indicating the
effect of OH− quenchers on these samples synthesized using wet chemistry technique.
It has been established that ceramic microspheres of YPO4 using radioactive yttrium (90 Y)
or phosphorus (32 P) elements are useful for in situ radiotherapy of deep-seated cancer since they
can be activated to become β-emitters by neutron bombardment.27, 28 Fe3 O4 @YPO4 :Re (Re = Tb,
Eu) hybrid spheres have been used for bio-labeling of human cervical carcinoma Hela cells.29 The
Fe3 O4 @YPO4 :Sm3+ (7 at.%) nanoparticles synthesized by us, achieve the hyperthermia temperature
for cancer therapy.

II. EXPERIMENTAL SECTION

A. Preparation of Sm3+ doped YPO4 nanoparticles
All reagents used were of analytical grade (AR) grade. Sm3+ doped YPO4 (Sm3+ = 2, 5, 7, 10,
and 20 at.%) was prepared by the co-precipitation method in aqueous medium at 150 ◦ C. For the
preparation of 7 atom% Sm3+ , Y2 (CO3 )3 (894 mg, 99.99%, Aldrich) was dissolved in 1 ml of dilute
HNO3 to get a clear solution. The excess amount of HNO3 acid was removed by evaporation and 50 ml
of distilled water was added to it. This was followed by addition of Sm(NO3 )3 .6H2 O (145 mg,
99.99%, Aldrich) and the resultant solution was heated at 80◦ C for 30 min. An aqueous solution of
(NH4 )H2 PO4 (536 mg, 99.99%, Aldrich) was added to it and heated for 2 h at 150 ◦ C. The white
precipitates that appeared were separated by centrifugation, washed twice with methanol and dried
under ambient conditions. Sm3+ doped YPO4 samples are written as YPO4 :nSm (n = 2, 5, 7, 10,
and 20 at.%).

B. Preparation of SmPO4 nanoparticles

For the synthesis of undoped SmPO4 , Sm(NO3 )3 .6H2 O (667 mg, 99.99%, Aldrich) was dis-
solved in 50 ml of distilled water and heated at 80◦ C for 30 min. An aqueous solution of (NH4 )H2 PO4
(500 mg, 99.99%, Aldrich) was added to it and heated for 2 h at 150 ◦ C. The white precipitates that
appeared were separated by centrifugation, washed twice with methanol and dried under ambient
conditions.
042184-3 Dutta, Ningthoujam, and Tyagi AIP Advances 2, 042184 (2012)

C. Preparation of Ca2+ and W6+ co-doped YPO4 :7Sm nanoparticles

Ca2+ and W6+ ions (3 at.% each) are co-doped in YPO4 :7Sm. Initially, stoichiometric amounts
of precursors CaCO3 (13.5 mg, 99.99%, Aldrich) and Y2 (CO3 )3 (834 mg; 99.99%, Aldrich) were
dissolved in 1 ml of dilute HNO3 to get a clear solution. The excess amount of HNO3 acid was
removed by evaporation and 50 ml of distilled water was added to it. This was followed by addition
of Sm(NO3 )3 .6H2 O (140 mg, 99.99%, Aldrich) and the resultant solution was heated at 80◦ C for
30 min. An aqueous solution of (NH4 )H2 PO4 (502 mg, 99.99%, Aldrich) and Na2 WO4 .2H2 O
(44 mg, 99.99%, Aldrich) was added to it and heated for 2 h at 150 ◦ C. The white precipitates that
appeared were separated by centrifugation, washed twice with methanol and dried under ambient
conditions.

D. Preparation of Fe3 O4 @ YPO4 :7Sm core-shell nanoparticles

100 mg of YPO4 :7Sm and 25 mg of Fe3 O4 were dispersed in 10 ml of EG (ethylene glycol)
under ultra-sonication separately. The preparation method for Fe3 O4 nanoparticles was used from our
published work.30 The dispersed Fe3 O4 particles are added to YPO4 :7Sm drop wise under constant
stirring for 1 h. Then it is centrifuged and dried in air atmosphere. Dried particles are dispersible in
water.

E. Characterization
X– ray diffraction (XRD) measurements were carried out using a Panalytical powder X– ray
diffractometer with Ni filtered Cukα radiation. The tube voltage was fixed at ∼40 kV and current at
∼30 mA. XRD patterns recorded in the angular range 10 ≤ 2θ /deg ≤ 70 with a step size of 2θ
= 0.02◦ . The average crystallite size (D) was calculated from Scherrer relation.

0.89λ
D= , (1)
βhkl Cosθ

where λ is the wavelength of X-rays and B is the full width at half maximum. The lattice parameters
were calculated from the least square fitting of the diffraction peaks. The X-ray data was analyzed
using Fullprof software.31
The Fourier Transform Infrared (FTIR) spectrum of GdPO4 sample was recorded using Bomem
(MB102-Series) Infrared spectrometer. For all studies, fitting to data was analyzed using Origin6.1
software.
Transmission electron microscopy (TEM) images were recorded using 200 keV JEOL 2010
(HRTEM) microscope. For the TEM measurement, the samples were ground and mixed together
with EG and dispersed under ultrasonication for 30 min. A drop of dispersed sample was put over
carbon coated copper grid and evaporated to dryness under a lamp.
Thermal analyses of as prepared powder sample were carried out using a Thermogravimetic-
differential thermal analysis (TG-DTA) instrument (SETARAM 92-16.18). The samples under ex-
amination were heated at a rate of 5 ◦ C min−1 in Ar atmosphere.
The excitation and emission spectra at room temperature were measured with a Hitachi F-4500
fluorescence spectrometer having a 150 W Xe lamp as the excitation source. Lifetime measurement
for Sm3+ transitions was carried out using μs flash lamp attached to Edinburgh Instruments – (model
F920). Powder samples (5 mg) were mixed with methanol (1 ml), spread over a quartz plate, dried
at ambient atmosphere and mounted inside the sample chamber.
Induction heating of samples (5, 10 and 15 mg each dispersed in 1 ml of water) was carried out
using instrument (Easy Heat 8310, Ambrell, UK) with 6 cm diameter (4 turns) coil. To keep system
at room temperature (25-28 ◦ C), water circulation was provided in the coils. Current and frequency
measured are 400 A (i.e., 335 Oe or 26 kA m−1 ) and 265 kHz (i.e., radiofrequency), respectively.
042184-4 Dutta, Ningthoujam, and Tyagi AIP Advances 2, 042184 (2012)

FIG. 1. (a) XRD patterns of as-prepared samples of YPO4 , YPO4 doped with different concentrations of Sm3+ (2, 5, 7, 10,
20 at.%) and SmPO4 . (b) Variation in peak positions of (200) plane with Sm3+ in YPO4 .

III. RESULTS AND DISCUSSION

A. XRD study
XRD patterns of as-prepared Sm3+ doped YPO4 samples prepared in water medium are shown
in Fig. 1(a). Tetragonal phase is observed for pure YPO4 sample (JCPDF 11-0254). When 2 at.%
Sm3+ is co-doped in YPO4 , additional peaks related to hexagonal phase appear, but their intensities
are very weak. On increasing Sm3+ concentration, peak intensities related to hexagonal phase in-
crease, whereas peak intensities corresponding to the tetragonal phase decrease. Pure SmPO4 shows
the hexagonal phase (JCPDS 27-0583), but peaks are broad as compared to pure YPO4 or Sm3+
doped YPO4 . The reported lattice parameters of pure SmPO4 (hexagonal) were a = 6.78, c = 6.34 Å
and unit cell volume V = 252.39 Å3 (JCPDF 27-0583). Reflection peak of (200) plane of tetragonal
structure shifts to the lower 2 theta upto 7 at.% Sm3+ doping indicating substitution of Sm3+ into Y3+
site of YPO4 (Fig. 1(b)). Ionic sizes of Sm3+ and Y3+ are 1.09 and 1.01 Å, respectively based on 8
co-ordination numbers.32 Unit cell volume of the tetragonal phase increases with Sm3+ . The lattice
parameters of the pure YPO4 and SmPO4 synthesized by us are a = 6.902(1), c = 6.036(1) Å
(unit cell volume V = 287.57 Å3 ) and a = 6.927(1), c = 6.447(1) Å (unit cell volume V
= 267.97 Å3 ), respectively. Crystallite sizes calculated using Scherrer’s relation are found to be
21 and 15 nm for pure YPO4 and SmPO4 , respectively.
In case of 900 ◦ C heated samples (Fig. 2(a)), pure YPO4 sample shows the tetragonal phase,
which is same as the as-prepared sample, whereas pure SmPO4 exhibits the monoclinic phase
(JCPDF 46-1239) which is different from as-prepared sample (hexagonal phase). The reported
lattice parameters of pure SmPO4 (monoclinic) are a = 6.686, b = 6.891, c = 6.368 Å and unit cell
volume V = 284.90 Å3 (JCPDF 27-0583). The lattice parameters of pure YPO4 are a = 6.876(1),
c = 6.018(1) Å (unit cell volume V = 284.50 Å3 ), which is less than those of as-prepared sample
because in as-prepared sample, positions of XRD peaks could not be determined distinctly. The
lattice parameters of pure SmPO4 are a = 6.686(1), b = 6.872(1), c = 6.350 Å (unit cell volume V
= 283.47 Å3 ) and α = γ = 90◦ , β = 104◦ . The peak corresponding to (200) plane of tetragonal
structure shifts to the lower 2theta on Sm3+ doping and is more prominent as compared to as-prepared
sample (Fig. 2(b)). Variation of unit cell volume with Sm3+ is shown in Fig. 2(c) and unit cell volume
increases with Sm3+ . Crystallite sizes calculated using Scherrer’s relation are found to be 30 and
25 nm for pure YPO4 and SmPO4 , respectively. Up to 10 at.% Sm3+ doping, only tetragonal phase
042184-5 Dutta, Ningthoujam, and Tyagi AIP Advances 2, 042184 (2012)

FIG. 2. (a) XRD patterns of 900 ◦ C heated samples of YPO4 , YPO4 doped with different concentrations of Sm3+ (5, 7, 10,
20 at.%) and SmPO4 , (b) variation in peak positions of (200) plane with Sm3+ in YPO4 and (c) variation in unit cell volume
with Sm3+ in YPO4 .

is obtained; however, 20 at.% Sm3+ doped sample gives the tetragonal phase along with a very small
contribution from monoclinic phase.
Variation in crystal structure after doping of Sm3+ in Y3+ sites of YPO4 is related to ionic sizes.
Usually, when it goes from lower to higher ionic size of RE3+ , co-ordination number (CN) of RE3+
can be increased up to 11-12 in any compound containing RE (rare-earth ion).22, 33 Since Y3+ has the
relative lower ionic size, it prefers lower co-ordination, whereas Sm3+ with relatively higher ionic
size prefers to have higher co-ordination. Thus Y3+ in YPO4 prefers to have 8 CN and 8CN of Y3+
in YPO4 can have tetragonal structure. Sm3+ in REPO4 (RE = rare earth atom) prefers 9-10 CN
and thus monoclinic or hexagonal structure is exhibited. Mix phases of tetragonal and hexagonal
observed in Sm3+ doped samples are due to the preparation of sample in aqueous phase because
hexagonal phase is stable when water co-ordinated in pores of structure along c-axis is present.
Usually, such water molecules are so stable up to 600-800 ◦ C at ambient pressure, thus hexagonal
phase is stable. Once water molecules are removed, phase transition to tetragonal or monoclinic
phase occurs.
Rietveld plot to XRD data of 900 ◦ C heated sample of 5 at.% Sm3+ doped YPO4 sample is
shown in Fig. 3(a). The atomic positions of Y3+ /Sm3+ , P5+ and O2− are (0, 0.750, 0.125), (0,
0.250, 0.375) and (0, 0.065, 0.216), respectively. The lattice parameters are a = 6.887, b = 6.887,
042184-6 Dutta, Ningthoujam, and Tyagi AIP Advances 2, 042184 (2012)

FIG. 3. (a) Rietveld plot to the XRD data of 900 ◦ C heated sample of 5 at.% Sm3+ doped YPO4 and (b) polyhedral
representation of YPO4 structure.

c = 6.028 Å. Y is surrounded by 8O with two different bond lengths (4(Y-O1 = 2.3026 Å) and
4(Y-O2 = 2.3671 Å) to form YPO8 dodecahedron. Sm3+ ions occupy Y3+ sites randomly, but SmO8
polyhedra is highly asymmetric, which is expected that the electric dipole transition will dominant
over magnetic dipole transition of Sm3+ in luminescence spectra (discussed later). P is surrounded
by 4O with equal bond length (P-O = 1.5504 Å) to form tetrahedron. PO4 has S4 symmetry whereas
Y/SmO8 has D2d symmetry. Bragg R-factor = 6.12 and Rf -factor = 7.45 are obtained after fitting.
The crystal structure is shown in Fig. 3(b). The 2O are corner-sharing between YO8 and PO4 units.
Figure 4 shows the XRD patterns of as-prepared and intermediated heated 7 at.% Sm doped
YPO4 samples up to 900 ◦ C. The mixture of tetragonal and hexagonal phases is found up to 700 ◦ C.
Only when annealed at or above 800 ◦ C, the tetragonal phase is found.

B. Microstructure study
Figure 5(a) shows the TEM image of the as-prepared YPO4 :Sm (7 at.%) sample. The particles
are spherical in shape and quite monodispersed. Its particle size distribution is shown in Fig. 5(b).
The data are fitted with Gaussian distribution. The mean value is found to be 4.6 nm (± 2.3 nm).
Its HRTEM image is shown in Fig. 5(c). The d-spacing value is found to be 3.45 Å, which is close
to (200) plane of the hexagonal phase. Figure 6(a) shows the TEM image of the 900◦ C annealed
042184-7 Dutta, Ningthoujam, and Tyagi AIP Advances 2, 042184 (2012)

FIG. 4. XRD patterns of 7 at.% doped YPO4 : as-prepared and intermediate heated samples up to 900 ◦ C.

YPO4 :Sm (7 at.%). The particles are found to be agglomerated which can be explained on the basis
of high temperature heating. The mean size is found to be 35 nm (± 5 nm). The corresponding
HRTEM image is shown in Fig. 6(b). The d-spacing value is found to be 3.40 Å, which is close
to plane (200) of hexagonal. Its selected area electron diffraction (SAED) is shown in Fig. 5(c). It
suggests the formation of well crystalline sample.

C. TGA and DTA studies

Figure 7 shows the TGA and DTA curves of SmPO4 prepared in aqueous medium. In TGA
curve, there are two steps of wt.% loss: one below 211 ◦ C and another below 500 ◦ C. The former
loss is related to the surface water and the later one to bound water. There is a weak peak in DTA
curve at ∼800 ◦ C, which is related to the phase transition from hexagonal to monoclinic.

D. FTIR study
Figure 8(a) shows FTIR spectra of as-prepared, 500 and 900 ◦ C annealed samples. In as-prepared
sample, the peaks at 535, 622 cm−1 (due to PO4 3− , ν 3 ), broad peaks in 969-1109 cm−1 (due to PO4 3− ,
ν 4 ), peak at 1616 cm−1 (due to the bending vibration of H2 O), and broad peak in 3330-3500 cm−1
due to the stretching vibration of H2 O are observed.33 500 and 900 ◦ C annealed samples show the
similar peaks of as-prepared sample. However, on careful analysis of spectra between 1500-1800
and 3300-4000 cm−1 (Fig. 8(c)), as-prepared shows the maximum peaks at 1616 and 3500 cm−1 ,
whereas 500 or 900 ◦ C annealed sample shows the maximum peak at 1640 and 3436 cm−1 , which
are related to the surface water present on the particles. It is to be noted that as-prepared sample
has the pores along c-axis of hexagonal structure. Such change from the vibrations of the surface
water is related to influence of confined H2 O present in the pore of hexagonal structure. The similar
observations were reported in GdPO4 :Eu3+ .33
042184-8 Dutta, Ningthoujam, and Tyagi AIP Advances 2, 042184 (2012)

FIG. 5. (a) TEM image of as-prepared sample of 7 at.% Sm3+ doped YPO4 . Its (b) particle size distribution and (c) HRTEM
image.

When as-prepared sample is prepared in D2 O medium, additional peaks for D2 O at 1439 (sharp)
and 2453-2647 cm−1 (broad) are observed in addition to others observed for as-prepared sample in
H2 O medium (Fig. 8(b)).33 Intensity of O-H stretching vibration is less than that of D-O stretching
vibration.

E. Luminescence study
Figure 9(a) shows the excitation spectra of as-prepared samples of Sm3+ doped YPO4 . The
peaks at 311, 324, 338 (6 H5/2 →6 H9/2 ), 351, 369 (6 H5/2 →4 D3/2 ), 382, 397 (6 H5/2 →6 P3/2 ), 409
(6 H5/2 →4 L13/2 ), 423, 446 (6 H5/2 →4 F5/2 ), 471, 483 (6 H5/2 →4 M12/2 ) and 504 (6 H5/2 →4 G7/2 ) nm
are observed and these are from Sm3+ .34–36 The highest intensity excitation peak is observed at
409 nm. After excitation at 409 nm, the emission peaks are observed at 564 (4 G5/2 →6 H5/2 ), 601
(4 G5/2 →6 H7/2 ) and 645 (4 G5/2 →6 H9/2 ) nm, which are assigned to Sm3+ (Fig. 9(b)). Luminescence
intensity increases with Sm3+ up to 5 at.% and decreases with further increase of Sm3+ . Figure 10
shows the excitation and emission spectra of 500 ◦ C heated samples of Sm3+ doped YPO4 . Distinct
peaks could be observed as compared to those of as-prepared sample. Luminescence intensity
increases with Sm3+ up to 7 at.% and decreases with further increase of Sm3+ . 900 ◦ C heated
042184-9 Dutta, Ningthoujam, and Tyagi AIP Advances 2, 042184 (2012)

FIG. 6. (a) TEM image of 900 ◦ C heated sample of 7 at.% Sm3+ doped YPO4 . Its (b) HRTEM image and (c) SAED pattern.

samples (Fig. 11) show the enhanced luminescence intensity as compared to lower heated samples.
This is related to extent of increase of radiative rate with increasing heat-treatment. During heating
to higher temperature, non-radiative rate contribution from surface dangling bonds, water amount
present in pore of hexagonal phase and on the surface of particle decreases. Decrease of luminescence
intensity for Sm3+ concentration above 5-7 at.% is related to the concentration quenching effect.
When we see J = 1 in transition, this is magnetic allowed transition, whereas when J
= 2 or more, this is the forced electric dipole transition, which is sensitive to asymmetry nature of
SmO9 . Here, the highest intensity is found at 601 nm (4 G5/2 →6 H7/2 ) with J = 1 (magnetic dipole
transition). On other hand, asymmetric behavior of SmO9 is observed on basis of XRD crystal
structure. Thus, this is not pure magnetic dipole transition, but this is a mixture of electric and
magnetic dipole transitions. This was supported by other reports.34–36
Figure 12(a)–12(c) show the decay curves for 4 G5/2 level of Sm3+ in Sm3+ doped YPO4 as-
prepared samples and those annealed at 500 and 900 ◦ C, respectively. Excitation at 409 nm and
emission at 601 nm are monitored. For mono-exponential decay, it can be expressed as:

I = I0 ex p(−t/τ ), (2)

Where I0 and I are intensities at zero time and at time t, respectively and τ is the lifetime for
transition. By taking logarithm, equation (3) can be written as:

ln(I ) = ln(I0 ) − t/τ (3)

042184-10 Dutta, Ningthoujam, and Tyagi AIP Advances 2, 042184 (2012)

FIG. 7. TGA (left) and DTA (right) sides of curves for SmPO4 . Arrow indicates the phase transition from hexagonal to
monoclinic.

FIG. 8. FTIR spectra of 7 at.% Sm3+ doped YPO4 : as-prepared, 500 and 900 ◦ C heated samples (a) and as-prepared sample
in D2 O (b). (c) Variations of peaks for bending and stretching vibrations of O-H.
042184-11 Dutta, Ningthoujam, and Tyagi AIP Advances 2, 042184 (2012)

FIG. 9. Excitation (a) and emission (b) spectra of as-prepared Sm3+ doped YPO4 samples. Emission and excitation wave-
lengths are monitored at 600 and 409 nm, respectively.

FIG. 10. Excitation (a) and emission (b) spectra of 500 ◦ C heated Sm3+ doped YPO4 samples. Emission and excitation
wavelengths are monitored at 600 and 409 nm, respectively.

Plot of ln(I) vs. t for as-prepared 2 at.% Sm3+ doped YPO4 is shown in Fig. 13. It is not fitted
well. Further, the emission decay curves were fitted with bi-exponential decay equation:

I = I1 exp(−t/τ1 ) + I2 exp(−t/τ2 ), (4)

Where I1 and I2 are intensities at two different interval times and corresponding decay lifetimes are
τ 1 and τ 2 . τ 1 and τ 2 values are found to be 293 μs (29%) and 1051 μs (71%), respectively for
as-prepared 2 at.% Sm3+ doped YPO4 sample, which can be attributed to surface and core Sm3+ . The
parameters obtained after bi-exponential fit to decay data are given in Table I. In a particular sample
(say 2 Sm3+ doped), decay for 4 G5/2 level of Sm3+ becomes faster when it goes from centre/core
to surface of particle. At surface, non-radiative rate is high as compared to that at core. Usually,
quenching is assumed to take place via a dipole – dipole interaction mechanism and it has a distance
dependence of r−6 , where r is the distance between the quenching moiety and the excited lanthanide
ion (Ln3+ ).37
Average lifetime (τ av ) is calculated on the basis of equal distribution of Sm3+ ions inside
particle. Since shape of particle is spherical, sphere can be divided in to two equal volumes: inside
(core) and surface. Then, τ av is defined as:37
 
τav = I1 τ12 + I2 τ22 /(I1 τ1 + I2 τ2 ) (5)
042184-12 Dutta, Ningthoujam, and Tyagi AIP Advances 2, 042184 (2012)

FIG. 11. Emission spectra of 900 ◦ C heated Sm3+ doped YPO4 samples after excitation at 409 nm.

τ av decreases with increase of Sm3+ concentrations due to concentration quenching effect. On the
other hand, τ av increases on annealing at higher temperature due to increase of radiative rate. During
annealing, crystallinity improves and also the particle size increases. Number of Sm3+ ions at the
surface decreases on annealing, which can be observed from Table I where τ 1 (surface) amount
decreases and τ 2 (core) amount increases on annealing up to 900 ◦ C.

F. Effect of D2 O
In order to study solvent effect on luminescence spectra of sample, we have prepared 7 at.%
Sm3+ doped YPO4 in H2 O and D2 O mediums. Luminescence intensity is improved by 5 times
for sample prepared in D2 O as-compared to that for sample in H2 O (Fig. 14). Improvement in
luminescence is related to reduction of phonon contribution. Stretching vibrations of O-H and O-D
are 3450 and 2500 cm−1 , respectively.
In water medium prepared sample, H2 O molecules occupy the pores of hexagonal structure in
addition to surface water on the particles. H2 O molecules in the pores of hexagonal structure is main
source of non-radiative rate on exciting sample and thus, loss of excited energy/photons or rate of
non-radiative rate follows exponential relation:22

R0 = ae[−(E−2hvmax )b] , (6)

where, a and b are constants. E is the difference in energy between the excited and ground states of
Sm3+ ion (10000-15000 cm−1 ). ν max is the highest available vibrational modes of the surroundings
of the rare earth ion (i.e., H2 O can have 3450 cm−1 ). The third overtone of stretching vibration of
the OH group can match E. When E ≈ 2ν max , R0 value becomes large. In such situation, most
042184-13 Dutta, Ningthoujam, and Tyagi AIP Advances 2, 042184 (2012)

FIG. 12. Decay curves of 4 G5/2 level of Sm3+ in Sm3+ doped YPO4 samples: (a) as-prepared, (b) 500 and (c) 900 ◦ C heated
samples. Excitation and emission wavelengths are fixed at 409 and 601 nm, respectively.

excited photons will be used for excitation of nearby phonons particularly H2 O molecules. The
process is known as multiphonon relaxation.
In case of D2 O medium prepared sample, even third overtone of D2 O could not bridge E.
Thus, its luminescence intensity is higher than that of H2 O medium prepared sample (Fig. 14).

G. Effect of Ca and W in YPO4 :Sm in luminescence

Figure 15 shows the luminescence spectra of 7 at.% Sm3+ doped YPO4 with and without 3
at.% (Ca and W each) as co-dopant. Excitation wavelength is fixed at 409 nm. Ca2+ and W6+ ions
substitute Y3+ and P5+ sites up to 3 at.% simultaneously because of similar ionic sizes.32 After
doping, the tetragonal structure is obtained. Solubility limit is up to 3 at.% Ca2+ or W6+ and above
this, mixture phase is obtained. Solubility limit of RE3+ at the Ca3+ sites up to 3 at.% in CaMoO4
was reported.38 Here, 2 mg of sample was dispersed over glass slide (3 × 4 cm2 ). Experiments are
repeated twice. There is an enhancement in luminescence intensity after co-doping of Ca and W.
Such enhancement of luminescence is related to the increase of optical transition probability and
change in optical dielectric constant after doping of Ca and W.

H. Application to hyperthermia
Figure 16 shows the temperature achieved by YPO4 :7Sm-Fe3 O4 sample (4:1) at the current of
400 A and frequency of 265 kHz. The sample was prepared by mixing YPO4 :7Sm and Fe3 O4 in
4:1 wt. ratio. The crystallite size of Fe3 O4 is 10 nm and detail synthesis procedure was published
in our recent study.30 Amount of 5, 10 and 15 mg each is dispersed in 1 ml of water. Temperatures
042184-14 Dutta, Ningthoujam, and Tyagi AIP Advances 2, 042184 (2012)

FIG. 13. ln(I) vs. time curve for 2 at.% Sm3+ doped YPO4 (as-prepared). The solid line is the linear fit to data.

TABLE I. Parameters obtained after bi-exponential fitting to luminescence data. Excitation and emission wavelengths are
monitored at 409 and 601 nm, respectively.

τ 1 (%) τ 1 (%) τ av
Samples (μs) (μs) (μs) χ2

As-prepared 2 293 (29) 1051 (71) 973 0.936

5 263 (23) 927 (67) 868 0.928
7 254 (30) 956 (70) 884 0.956
10 328 (58) 1147 (42) 915 0.701
500 ◦ C 2 526 (13) 2000 (87) 1944 1.076
5 495 (24) 1561 (76) 1463 1.019
7 523 (22) 1689 (78) 1595 1.048
10 657 (54) 1748 (46) 1409 0.676
900 ◦ C 2 96 (1) 2251 (99) 2250 1.325
5 117 (2) 1692 (98) 1689 1.787
7 483 (12) 1800 (88) 1753 2.301
10 241 (7) 1077 (93) 1063 0.877

achieved by 5, 10 and 15 mg of samples are 35.4, 39.5 and 44.6 ◦ C, respectively. Only 15 mg of
sample can achieve the hyperthermia temperature for cancer therapy. The specific heat absorption
(SAR) is calculated from the following formula:
T 1
S AR = c (7)
t m magn
042184-15 Dutta, Ningthoujam, and Tyagi AIP Advances 2, 042184 (2012)

FIG. 14. Emission spectra of 7 at.% Sm3+ doped YPO4 prepared in H2 O and D2 O.

FIG. 15. Luminescence spectra of 7 at.% Sm3+ doped YPO4 with and without 3 at.% of each Ca2+ and W6+ as co-dopants.
042184-16 Dutta, Ningthoujam, and Tyagi AIP Advances 2, 042184 (2012)

FIG. 16. Temperature achieved by YPO4 :7Sm@Fe3 O4 samples under 400 A and 265 kHz (induction heater).

where C is the sample-specific heat capacity which was calculated as a mass weighed mean value of
sample and water.30 Amount of sample is much less than amount of water and thus C value of water
(4.18 J/gK) was used. Change in T/t is high up to 5-7 minutes and thus this range was used.
The heat-generation is mainly coming from Fe3 O4 magnetite present in YPO4 :7Sm-Fe3 O4 sample
(4:1). The mmagn value is considered as amount of Fe3 O4 or Fe per total amount of magnetite or Fe
and water. The SAR values per Fe3 O4 of 5, 10 and 15 mg samples are 38.3, 48.8 and 46.7 Wg−1 ,
respectively. Here SAR value of pure Fe3 O4 is 38.4 Wg−1 .30
The heat-generation from dispersed particles in induction coil come from (i) hysteresis loop,
(ii) eddy current, (iii) spin relaxation (known as Néel’s spin relaxation) and Brownian relaxation.
Details are discussed in our earlier work.30 Since Fe3 O4 is superparamagnetic,30 the heat-generation
from hysteresis loop is negligible. Also, Fe3 O4 is semi-metal or semiconductor, eddy current is
negligible. Thus, the main heat-generation is come from Néel’s spin and Brownian relaxations.

IV. CONCLUSIONS
Sm3+ doped YPO4 nanoparticles are prepared by wet chemical method at 150 ◦ C. As-prepared
pure YPO4 shows the tetragonal phase, which does not change even heated up to 900 ◦ C. As-prepared
pure SmPO4 shows the hexagonal phase, which changes to monoclinic phase when heated above
800 ◦ C. In case of (2-10 at.%) Sm3+ doped YPO4 , as-prepared sample shows a mixture of tetragonal
and hexagonal phases, which changes to a tetragonal phase above 800 ◦ C. As-prepared YPO4 :Sm
(7 at.%) sample exhibits spherical particles (∼5 nm), which are quite monodispersed and its 900 ◦ C
heated sample exhibits agglomerated particles (∼35 nm). As-prepared sample shows the maximum
peaks at 1616 and 3500 cm−1 , which are related to confined water present in the pores of hexagonal
phase; whereas 500 or 900 ◦ C annealed sample shows the maximum peak at 1640 and 3436 cm−1 ,
which are related to the surface water present on the particle. Luminescence emission peaks are
042184-17 Dutta, Ningthoujam, and Tyagi AIP Advances 2, 042184 (2012)

observed at 564 (4 G5/2 →6 H5/2 ), 601 (4 G5/2 →6 H7/2 ) and 645 (4 G5/2 →6 H9/2 ) nm, which are assigned
to Sm3+ . Luminescence intensity increases with heat-treatment up to 900 ◦ C, which is related to
extent of increase of radiative rate. When solvent is changed from H2 O to D2 O, 5 fold enhancements
in luminescence intensity is observed. Ca and W co-doping improves luminescence intensity. Hybrid
of YPO4 :7Sm@Fe3 O4 under 400 A and 265 kHz frequency shows the heating up to 45 ◦ C, which
is necessary for hyperthermia application. SAR values of 38-49 W/g of Fe3 O4 are observed.

ACKNOWLEDGMENTS
Authors thank Dr. D. Das, Dr. R. K. Vatsa, A. I. Prasad, Dr. R. Mishra and R. Shukla, Chemistry
Division, BARC, Mumbai for their assistance and encouragement during this study, Ashutosh Rath,
R. R. Julurid and Dr. P. V. Satyam, Institute of Physics, Sachivalaya Marg, Bhubaneswar for providing
TEM images and is also grateful to Smt. Annie Thomas, Heavy water Board, DAE, Mumbai for
supplying D2 O.

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