This article was downloaded by: [informa internal users]

On: 20 October 2010

Access details: Access Details: [subscription number 755239602]
Publisher Taylor & Francis
Informa Ltd Registered in England and Wales Registered Number: 1072954 Registered office: Mortimer House, 37-
41 Mortimer Street, London W1T 3JH, UK

Philosophical Magazine
Publication details, including instructions for authors and subscription information:
http://www.informaworld.com/smpp/title~content=t713695589

Synthesis, characterization and photoluminescence properties of CaSiO3 :

Dy3+ nanophosphors
H. Nagabhushanaa; B. M. Nagabhushanab; Madesh Kumarc; H. B. Premkumara; C. Shivakumarad; R. P.
S. Chakradhare
a
Department of PG Studies in Physics & Research, University Science College, Tumkur University,
Tumkur-572 103, India b Department of Chemistry, M.S. Ramaiah Institute of Technology, Bangalore-
560 054, India c Department of Physics, Cambridge Institute of Technology, Bangalore-560 078, India d
Solid State and Structural Chemistry Unit, Indian Institute of Science, Bangalore-560 012, India e Glass
Technology Laboratory, Central Glass and Ceramic Research Institute (CSIR), Kolkata-700 032, India

Online publication date: 12 July 2010

To cite this Article Nagabhushana, H. , Nagabhushana, B. M. , Kumar, Madesh , Premkumar, H. B. , Shivakumara, C. and
Chakradhar, R. P. S.(2010) 'Synthesis, characterization and photoluminescence properties of CaSiO3 : Dy3+
nanophosphors', Philosophical Magazine, 90: 26, 3567 — 3579
To link to this Article: DOI: 10.1080/14786435.2010.491810
URL: http://dx.doi.org/10.1080/14786435.2010.491810

PLEASE SCROLL DOWN FOR ARTICLE

Full terms and conditions of use: http://www.informaworld.com/terms-and-conditions-of-access.pdf

This article may be used for research, teaching and private study purposes. Any substantial or
systematic reproduction, re-distribution, re-selling, loan or sub-licensing, systematic supply or
distribution in any form to anyone is expressly forbidden.

The publisher does not give any warranty express or implied or make any representation that the contents
will be complete or accurate or up to date. The accuracy of any instructions, formulae and drug doses
should be independently verified with primary sources. The publisher shall not be liable for any loss,
actions, claims, proceedings, demand or costs or damages whatsoever or howsoever caused arising directly
or indirectly in connection with or arising out of the use of this material.
 Philosophical Magazine
Vol. 90, No. 26, 14 September 2010, 3567–3579

Synthesis, characterization and photoluminescence properties

of CaSiO3 : Dy3Y nanophosphors
H. Nagabhushanaa*, B.M. Nagabhushanab, Madesh Kumarc,
H.B. Premkumara, C. Shivakumarad and R.P.S. Chakradhare*y
a
Department of PG Studies in Physics & Research, University Science College, Tumkur
University, Tumkur-572 103, India; bDepartment of Chemistry, M.S. Ramaiah Institute
of Technology, Bangalore-560 054, India; cDepartment of Physics, Cambridge Institute
of Technology, Bangalore-560 078, India; dSolid State and Structural Chemistry Unit,
Indian Institute of Science, Bangalore-560 012, India; eGlass Technology Laboratory,
Downloaded By: [informa internal users] At: 13:11 20 October 2010

Central Glass and Ceramic Research Institute (CSIR), Kolkata-700 032, India
(Received 7 January 2010; final version received 4 May 2010)

CaSiO3 : Dy3þ (1–5 mol. %) nanophosphors were synthesized by a simple

low-temperature solution combustion method. Powder X-ray diffraction
patterns revealed that the phosphors are crystalline and can be indexed to a
monoclinic phase. Scanning electron micrographs exhibited faceted plates
and angular crystals of different sizes with a porous nature.
Photoluminescence properties of the Dy3þ-doped CaSiO3 phosphors were
observed and analyzed. Emission peaks at 483, 573 and 610 nm
corresponding to Dy3þ were assigned as 4F9/2 ! 6H15/2, 4F9/2 ! 6H13/2
and 4F9/2 ! 6H11/2 transitions, respectively, and dominated by the
Dy3þ 4F9/2 ! 6H13/2 hyperfine transition. Experimental results revealed
that the luminescence intensity was affected by both heat treatment and the
concentration of Dy3þ (1–5 mol. %) in the CaSiO3 host. Optimal
luminescence conditions were achieved when the concentration of Dy3þ
was 2 mol. %. UV–visible absorption features an intense band at 240 nm,
which corresponds to an O–Si ligand-to-metal charge transfer band in the
SiO2
3 group. The optical energy band gap for the undoped sample was
found to be 5.45 eV, whereas in Dy3þ-doped phosphors it varies in the
range 5.49–5.65 eV. The optical energy gap widens with increase of Dy3þ
ion dopant.
Keywords: phosphor; X-ray diffraction; scanning electron microscopy;
FTIR spectra; optical absorption; photoluminescence

1. Introduction
In recent years, extensive research has been carried out on the synthesis and
characterization of nanophosphors, especially those with three-dimensional (3D)
microfabrications, owing to their novel luminescent properties [1–3]. Among these,

*Corresponding author. Emails: [email protected]; [email protected]

y
Present address: Scientist, CSIR-NAL, Bangalore-560 017, India

ISSN 1478–6435 print/ISSN 1478–6443 online

ß 2010 Taylor & Francis
DOI: 10.1080/14786435.2010.491810
http://www.informaworld.com
 3568 H. Nagabhushana et al.

of particular interest is the synthesis and characterization of rare earth (RE)-doped

nanophosphors with emphasis on luminescence properties and how these change
with reduced dimensionality. RE ions are prominently effective as luminescent
centers in host lattices due to their marked improvement in lumen output, color
rendering index, energy efficiency and greater radiation stability [4–7]. Dy3þ is one
of the most investigated ions and has been studied extensively because it provides
two typical emission bands in the blue (480 nm) and yellow (570 nm) regions, which
are necessary for full color displays [8–10]. In addition, the emission probability of
electric-dipole transitions is greatly affected by the crystal field and radial integral
of the 4f and 5d electrons. Thus, it is interesting to study the luminescence properties
of Dy3þ in different host lattices.
Silicates are considered one of the best host materials for luminescent centers due
to their excellent chemical and thermal stability. When mixed with RE ions
or transition metal ions, silicates become phosphor powders that produce excellent
luminescence in the blue, green and red regions of the spectrum. Furthermore,
Downloaded By: [informa internal users] At: 13:11 20 October 2010

considerable attention has been paid to silicate hosts because of their stable crystal
structure, high physical and chemical stability, good formability, long persistence
time, relatively easy preparation, multicolor phosphorescence and resistance to acid,
alkali and oxygen [11,12].
Generally, phosphors are prepared by traditional solid-state reaction methods.
Owing to insufficient mixing and low reactivity of the raw materials, several impurity
phases can easily coexist in the product. In addition, phosphor particles prepared by
solid-state reaction are large in size, generally in the micrometer range [13].
Combustion synthesis provides an interesting alternative over other elaborate
techniques because it offers several attractive advantages, such as simplicity of the
experimental set-up, a surprisingly short time between the preparation of reactants
and the availability of the final product, and low cost coupled with energy saving.
A study of the literature reveals that Dy3þ-activated CaSiO3 nanophosphors
prepared by the solution combustion route have not been reported previously. In
this paper, the luminescence properties are reported for different CaSiO3 :Dy3þ
nanophosphors of different compositions prepared by the combustion process.

2. Experimental details
2.1. Synthesis of CaSiO3 : Dy3Y nanophosphors
The stoichiometric composition of the redox mixture used for the combustion
process was calculated using the total oxidizing (O) and reducing valencies of the
ingredients, which serve as numerical coefficients for the stoichiometric balance so
that the equivalence ratio (’e) is unity (O/F ¼ 1) and the energy released by the
combustion is a maximum [14]. According to the concepts used in propellant
chemistry, the valence of C ¼ þ4, H ¼ þ1, of divalent metal ions ¼ þ2, and
of trivalent metal ions ¼ þ3 and O ¼ –2. The valence of nitrogen is considered to
be zero. Based on these considerations, calcium nitrate has an oxidizing valence of
10 and diformylhydrazine (C2H4N2O2; DFH) a reducing valence of þ8. The total
valence of SiO2 is zero. In the present study, DFH was used as fuel for combustion
synthesis; its preparation procedure given elsewhere [15]. For the preparation
 Philosophical Magazine 3569

of CaSiO3 : Dy3þ the required mole ratio of Ca(NO3)2
6H2O : SiO2 : DFH
was 1 : 1 : 1.25.
Analytical grade calcium nitrate (Ca(NO3)2
6H2O; Merck), fumed silica
(SiO2, 99.9%, surface area 200 m2/g), dysprosium oxide (Dy2O3; Sigma Aldrich)
and DFH were used as the starting materials. During the synthesis, dysprosium oxide
was converted into dysprosium nitrate. Then calcium nitrate and DFH were dissolved
in a minimal quantity of water in a cylindrical petri dish of 300 ml capacity. To this
fumed silica was added and dispersed well using a magnetic stirrer for 5–10 min. The
heterogeneous reaction mixture was rapidly heated in a preheated muffle furnace
maintained at 500 C. The redox mixture boils, froths and thermally dehydrates
forming foam, which ruptures with a flame and glows to incandescence. During
incandescence the foam further swells to the capacity of the container. The entire
combustion process was complete within 5 min. Figure 1 shows a flow chart for the
synthesis of CaSiO3 : Dy3þ phosphors by this solution combustion method.
The chemical equation assuming complete combustion of the redox mixture used
Downloaded By: [informa internal users] At: 13:11 20 October 2010

for the synthesis may be written as

4CaðNO3 Þ2 ðaqÞ þ 4SiO2 ðaqÞ þ 5C2 H4 N2 O2 ðaqÞ

! 4CaSiO3 ðsÞ þ 9N2 ðgÞ þ 10H2 OðgÞ þ 10CO2 ðgÞ: ð1Þ

Flow chart

Calcium nitrate +
Dysprosium nitrate +
Diformyl hydrazine +
silica fumes

Preheated muffle
furnace

Combustion

Final product
CaSiO3 : Dy3+

Figure 1. Flow chart for synthesis of CaSiO3 : Dy3þ phosphors.

 3570 H. Nagabhushana et al.

50 CaSiO3 : Dy 5 mol%

0
75 4 mol%
Intensity (a.u.)

0
75 3 mol%
0
75 2 mol%
0
100 1 mol%
0
20 30 40 50 60 70
2 (deg)
Downloaded By: [informa internal users] At: 13:11 20 October 2010

Figure 2. PXRD patterns of CaSiO3 : Dy3þ (1–5 mol. %) phosphors.

2.2. Instrumentation
An X-ray powder diffractometer (Philips PW 1050/70) using Cu K radiation with
a Ni filter was used to confirm the crystallinity of the phosphor. Scanning electron
microscopy (SEM) was performed with a JEOL (JSM-840A) instrument. A JEM
2000 Ex instrument (JEOL, Tokyo, Japan) was used for transmission electron
microscopy (TEM) studies. Fourier transform infrared (FTIR) spectroscopy was
carried out on a Perkin Elmer spectrometer (Spectrum 1000). The excitation and
emission spectra were measured at room temperature on a Shimadzu spectro-
fluorometer RF-5301 PC equipped with a xenon discharge lamp as an excitation
source. The optical band gaps of the undoped and Dy-doped phosphors were
determined using a ELICO SL 159 UV–visible spectrophotometer.

3. Results and discussion

Figure 2 shows the powder X-ray diffraction (PXRD) profiles of Dy3þ-doped CaSiO3
(1–5 mol. %) phosphors, calcined at 950 C for 3 h. The PXRD patterns of 1–4 mol. %
Dy-doped samples were readily indexed to the -CaSiO3 phase. The peak positions are
in good agreement with literature values [16,17]. However, the sample doped with
5 mol. % Dy exhibited mixed -CaSiO3 phase (JCPDF-310297) along with small
traces of the orthorhombic CaSiO3 phase. All the diffraction peaks match very well the
standard values from the Joint Committee on Powder Diffraction Standards (JCPDF)
(data card No. 84-0655), which were readily indexed to the monoclinic phase [16,17].
The average particle size (D) of the CaSiO3 : Dy3þ phosphors was estimated from the
full width at half maximum (FWHM) of the diffraction peak of the powders, using
Scherrer’s formula [18]

D ¼ K=FWHM cos , ð2Þ

 Philosophical Magazine 3571

where  is the wavelength of X-rays used,  the Bragg angle and K is a constant that
depends on the grain shape (0.89 Å for circular grains). It was observed that
the average particle size of the Dy-doped CaSiO3 is in the range 120–187 nm.
For the combustion method, it is well known that the morphological characteristics
of the prepared powder are strongly dependent on the amount of heat and the gases
generated during the complex decomposition. Large amounts of gases are suitable
for preparation of fine particles, whereas the heat released is an important factor for
crystalline growth.
Figure 3 shows SEM micrographs of as-formed and Dy3þ (1–5 mol. %)-doped
CaSiO3. In the micrograph of the as-formed phosphor faceted plates and angular
crystals of different sizes can be seen. The powders also exhibit a porous structure.
The redox reaction with nitrate salts is strongly exothermic and makes the system
undergo violent combustion. Owing to the uncontrolled dynamics of the process, the
pores formed are sparse and irregular. But this porous structure is distributed
non-uniformly in the matrix and, in some regions, the porous structure is absent.
Downloaded By: [informa internal users] At: 13:11 20 October 2010

This non-uniformity of shape is believed to be related to the non-uniform

distribution of temperature and mass flow in the combustion flame. The phosphors
obtained from the combustion process contain small particles and pores and these
are inherent features of the process [19]. With an increase of Dy dopant, the
phosphor becomes more porous in nature (Figures 3b–3f).
Figure 4 shows the TEM image of 2 mol. % Dy3þ-doped CaSiO3 heat treated at

950 C for 3 h. It can be seen that the particles are irregular in shape and size, which
was further confirmed from SEM micrographs. The mean particle size is observed to
be 200 nm. The mean particle size calculated using Scherrer’s formula is almost equal
to that observed in TEM. The corresponding SAED pattern showed in the inset
displays bright spots, which indicates the single crystal nature and high degree of
crystallanity of the synthesized product.
The FTIR spectra of the CaSiO3 : Dy3þ phosphors were recorded to provide
information on their structures (Figure 5). The spectroscopic analysis confirmed that
the IR peaks at 465, 504, 691 and 964 cm-1 are due to -CaSiO3 [20,21]. The peak at
1460 cm1 is due to the existence of CaO in the structure. The absorption band
occurring at 750 cm1 arises from O–Si–O vibrations and the absorption at
415–600 cm1 from Si–O vibrations.
The UV–visible absorption of the Dy3þ-doped (1–5 mol. %) CaSiO3 phosphor
was measured using diffuse reflection spectroscopy (Figure 6). The spectra were
deconvoluted and absorption bands observed at 230–280 nm, which corresponds to
O–Si ligand-to-metal charge-transfer (LMCT) in the SiO2 3 group. The broad band
at 300–324 nm is attributed to the intraconfigurational 4f–4f transitions from the
ground 7F0 level, which corresponds to the excitation spectra. These results are
in good agreement with those reported in the literature [22].
The optical energy gaps, Eg, of undoped and Dy3þ-doped (1–5 mol. %) CaSiO3
were estimated using the Tauc relation [23,24]

ðhÞ  ðh  Eg Þ1=n , ð3Þ

where h is the photon energy and  is the optical absorption coefficient near
the fundamental absorption edge. The absorption coefficients were calculated from
 3572 H. Nagabhushana et al.

(a) (b)

(c) (d)
Downloaded By: [informa internal users] At: 13:11 20 October 2010

(e) (f)

Figure 3. SEM micrographs of (a) as-formed and (b–f) 1–5 mol. % Dy3þ-doped CaSiO3
phosphors.

these optical absorption spectra. The values of the optical band gaps of the undoped
and Dy3þ-doped CaSiO3 were obtained by plotting (h)n versus h in the
high-absorption range followed by extrapolating the linear region of the plots
to (h)n ¼ 0 (Figure 7a). The analysis of the present data showed that the plots give
linear relationships, which can, for the most part, be fitted with the above equation
with n ¼ 2 for both the undoped and Dy-doped samples. This indicates that allowed
 Philosophical Magazine 3573

Figure 4. TEM image of 2 mol. % Dy3þ-doped CaSiO3 phosphor (inset: SAED pattern).
Downloaded By: [informa internal users] At: 13:11 20 October 2010

Dy3+: CaSiO3 950°C for 3hrs

(e)

(d)
%T

(c)

(b)

(a)

500 1000 1500 2000

Wavenumber (cm–1)

Figure 5. FTIR spectra of CaSiO3 : Dy3þ : (a) 1 mol. %; (b) 2 mol. %; (c) 3 mol. %;
(d) 4 mol. %; (e) 5 mol. %.

direct transitions are responsible for the interband transitions in the undoped and the
doped samples. The optical energy band gap for the undoped sample was found
to be 5.45 eV, and for the Dy3þ-doped (1–5 mol. %) phosphors it varies between 5.49
and 5.65 eV. These values are well matched to those reported in the literature [25].
It is noted that the optical band gap is found to be lower in the undoped sample when
compared to the Dy-doped CaSiO3.
Figure 8 shows the excitation spectrum (within the range 200–400 nm) of
the 2 mol. % CaSiO3 : Dy3þnanophosphor, measured with the emission wavelength
fixed at 577 nm corresponding to the electronic transition 4F9/2 ! 6H13/2.
 3574 H. Nagabhushana et al.

(a) (b)

(c) (d)

Primary UV–Vis spectrum

-0-0-0- Guassian fit
Guassian fit for different peaks
Downloaded By: [informa internal users] At: 13:11 20 October 2010

Intensity (a.u)

250 300 350 400

(e)

200 250 300 350 400

Wavelength (nm)

Figure 6. UV–visible absorption spectra of Dy3þ-doped (1–5 mol. %) CaSiO3 phosphors.

The spectrum consists of sharp and broad excitation bands at 258 nm, which are
assigned to the host absorption band (HAB), along with broad excitation bands in
the 270–380 nm region. Clearly, the latter arise from f–f transitions of Dy3þ within its
4f 9 configuration, which are assigned to the electronic transitions (6H15/2 ! 5P3/2) at
320 nm, (6H15/2 ! 5P7/2) at 351 nm, (6H15/2 ! 5P5/2) at 366 nm, and (6H15/2 ! 4I13/2)
at 378 nm.
The concentration effect (1–5 mol. %) on the emission of CaSiO3 : Dy3þ
nanophosphors excited at 351 nm is shown in Figure 9. The photoluminescence
(PL) spectra consist of three main groups of lines in the blue (460–500 nm) and
yellow (555–610 nm) regions, in addition to some weak lines observed in the red
(677 nm) region. These blue, yellow and red emissions were assigned to the electronic
 Philosophical Magazine 3575

(a)
5.45 eV (un-doped)
5.49 eV (1 mol %)
5.52 eV (2 mol %)
5.56 eV (3 mol %)
5.60 eV (5 mol %)

(a hn )2 (eV2m–2)
5.65 eV (4 mol %)

3 4 5 6
Energy (eV)
(b) 5.70
Downloaded By: [informa internal users] At: 13:11 20 October 2010

5.65
Energy gap (eV)

5.60

5.55

5.50

5.45

0 1 2 3 4 5
Dy3+ concentration (mol %)

Figure 7. (a) A plot of (h)2 vs. energy for CaSiO3 : Dy3þ phosphors. (b) Variation of optical
band gap energy with Dy content.

transitions 4F9/2 ! 6H15/2, 4F9/2 ! 6H13/2 and 4F9/2 ! 6H11/2, respectively. The blue
(4F9/2 ! 6H15/2) emission corresponds to the magnetic dipole transition and the
yellow (4F9/2 ! 6H13/2) emission belongs to the hypersensitive (forced electric dipole)
transition with the selection rule DJ ¼ 2 [26–28]. The assignment of all the transitions
in the excitation and emission spectra are based on the earlier results of Carnall et al.
[29]. The crystal-field splitting components of Dy3þ can be observed and are well
correlated with the Kramer’s doublets, (2 J þ 1)/2, where J is the angular momentum
of the electrons. It indicates that the Dy3þ ions are well substituted on to Ca3þ sites,
because the ionic radius of the Dy3þ (0.103 nm) is smaller than Ca3þ (0.106 nm).
In these CaSiO3 : Dy3þ nanophosphors, the intensity of the yellow emission is greater
than that of the blue emission, which can be explained as follows. It is well known
that the hypersensitive (forced electric dipole) transition is strongly influenced by
the surrounding environment and the magnetic dipole transition is insensitive
 3576 H. Nagabhushana et al.

320
274
258
Relative excitation intensity (a.u.)

340
HAB

351
366
6 4
H15/2 P13/2
6 6
H15/2 P3/2

378
6 5
H15/2 P6/2

= 574nm
emi
Downloaded By: [informa internal users] At: 13:11 20 October 2010

220 240 260 280 300 320 340 360 380 400
Wavelength (nm)

Figure 8. Excitation spectrum of the 2 mol. % Dy3þ-doped CaSiO3 phosphor.

to the crystal-field strength around the Dy3þ ions. When Dy3þ is located at
a low-symmetry local site (without inversion symmetry), the yellow emission is often
dominant in the emission spectrum, whereas when Dy3þ is at a high-symmetry local
site (with inversion symmetry) the blue emission is stronger than the yellow emission
and is dominant in the emission spectrum [28]. It is observed that the PL intensity
increases up to 2 mol. % of Dy and thereafter the emission intensity decreases with
further increase of the Dy3þ dopant concentration; this can be attributed
to concentration quenching. The concentration quenching might be enhanced by
the following two factors: (i) the excitation migration due to resonance
between the activators is enhanced when the doping concentration is increased,
and thus the excitation energy reaches quenching centers, and (ii) the activators
are paired or coagulated and are changed to quenching centers [30]. Furthermore,
the yellow to blue (Y/B) ratio is found to depend on the concentration of Dy3þ.
When the concentration increases to 2 mol. %, the Y/B ratio increases and when the
concentration increases above 2 mol. % the Y/B ratio decreases. This can be
understood if one considers that the DJ ¼ 2 transition probability changes with
polarity of the neighboring ions.
The emission intensity of Dy3þ with respect to annealing temperature was studied
and is shown in Figure 10. As the temperature increased from 850 to 1050 C,
the intensity of the yellow emission became stronger; this can be attributed
to the improved crystallization of the products, thus reducing the defect concentration
and producing a more uniform distribution of Dy3þ in the host lattices.
Figure 11 shows the energy level scheme used to explain the mechanisms involved
in the emission processes in CaSiO3 : Dy3þ nanophosphors [29,30].
 Philosophical Magazine 3577

4 6
F9/2 H13/2

Relative PL intensity (a.u)

=351 nm
ex i
1mol% Dy
2mol% Dy
3mol% Dy
4mol% Dy
5mol% Dy
4 6 4 6
F9/2 H15/2 F9/2 H11/2

(e)

)
%
(d)

ol
(m
(c)

n
io
(b)

at
tr
(a)

en
Downloaded By: [informa internal users] At: 13:11 20 October 2010

nc
450 500 550 600 650 700 750

co
Dy
Wavelength (nm)

Figure 9. PL emission spectra of CaSiO3 : Dy3þ: (a) 1 mol. %; (b) 2 mol. %; (c) 3 mol. %;
(d) 4 mol. %; (e) 5 mol. %.

= 351 nm
950 °C

Relative intensity (a.u)

exi

4
1050 °C
6
F9/2 H13/2
1150 °C

4 6
F9/2 H11/2
4 6
F9/2 H15/2

(c)
)
C
°

(b)
(
e
ur
at

(a)
r
pe
m
Te

500 600 700

Wavelength (nm)

Figure 10. PL emission spectra of heat-treated (850, 950 and 1050 C for 3 h) CaSiO3:Dy3þ
(2 mol. %) phosphor.

4. Conclusions
In summary, a solution combustion method using DFH as fuel has been successfully
used to synthesize Dy3þ-doped CaSiO3 phosphors. Features such as easy
preparation, low processing cost, energy efficiency and high production rate,
nanosize crystals and high purity are among the benefits of the technique.
 3578 H. Nagabhushana et al.

37 HAB
5
P3/2
5
P7/2
4
I13/2

Energy (x 103 cm–1)

4
F9/2

258 nm
320 nm
351 nm
378 nm

677 nm
482 nm

577 nm
6
H11/2
6
H13/2

6
0 H15/2

Figure 11. The energy level scheme of the CaSiO3 : Dy3þ phosphors.
Downloaded By: [informa internal users] At: 13:11 20 October 2010

The PL of the Dy3þ-doped CaSiO3 phosphor has been observed and analyzed.
The emission peaks at 483, 573 and 610 nm correspond to emissions of Dy3þ and can
be assigned to be transitions 4F9/2 ! 6H15/2, 4F9/2 ! 6H13/2 and 4F9/2 ! 6H11/2,
respectively, and dominated by the Dy3þ 4F9/2 ! 6H13/2 hyperfine transition.
The emission mechanism has been explained in terms of an energy level scheme.
Experimental results revealed that the luminescence intensity may be affected
by both heat treatment and the concentration of Dy3þ in the CaSiO3 host. Optimum
luminescence conditions could be achieved when the concentration of Dy3þ was
2 mol. %. The optical energy band gap of the undoped phosphor is found to be lower
than that of the Dy3þ-doped phosphors.

Acknowledgements
One of the authors (H.N.) thanks UGC for awarding a minor research project and Dr S.C.
Sharma, Vice-Chancellor, Tumkur University, for constant support and encouragement.
Dr R.P.S. Chakradhar thanks Dr H.S. Maiti, Director, CGCRI, and Dr Ranjan Sen, Head,
GTL Lab, CGCRI for their constant support and encouragement.

References

[1] T. Igarashi, M. Ihara, T. Kusunoki, K. Ohno, T. Isobe and M. Senna, Appl. Phys. Lett. 76
(2000) p.1549.
[2] H. Peng, H. Song, B. Chen, S. Lu and S. Huang, Chem. Phys. Lett. 370 (2003) p.485.
[3] H.X. Mai, Y.W. Zhang, R. Si, Z.G. Yan, L.D. Sun, L.P. You and C.H. Yan, J. Am. Chem.
Soc. 128 (2006) p.6426.
[4] C. Feldmann, T. Justel, C.R. Ronda and P.J. Schmidt, Adv. Funct. Mater. 13 (2003) p.511.
[5] M. Yu, J. Lin, Z. Wang, J. Fu, S. Wang, H.J. Zhang and Y.C. Han, Chem. Mater. 14
(2002) p.2224.
[6] W.M. Yen and M.J. Weber (Eds.), Inorganic Phosphors: Composites, Preparation and
Optical Properties, Vol. 20, CRC Press, 2004.
 Philosophical Magazine 3579

[7] H.S. Nalwa, L.S. Rohwer (Eds.), Handbook of Luminescence, Display Materials and
Devices, Vol. 2, American Scientific, 2003.
[8] R.-P. Wei, Z.-H. Ju, J.-X. Ma, D. Zhang, Z.-P. Zang and W.-S. Liu, J. Alloy Comp. 486
(2009) p.L17.
[9] Y. Chen, X. Cheng, M. Liu, Z. Qi and C. Shi, J. Lumin. 129 (2009) p.531.
[10] B. Liu, L. Kong and C. Shi, J. Lumin. 122–123 (2007) p.121.
[11] T. Matsuzawa, Y. Aoki, N. Takeuchi and Y. Marayama, J. Electrochem. Soc. 143
(1996) p.2670.
[12] P. Dorenbos, J. Electrochem. Soc. 152 (2005) p.H107.
[13] D. Jia, Y. Wang, X. Guo, K. Li, Y.K. Zou and W. Jia, J. Electrochem. Soc. 154
(2007) p.J1.
[14] J.J. Kingsley and K.C. Patil, Mater. Lett. 6 (1988) p.427.
[15] C. Ainsworth and R. Jones, J. Am. Chem. Soc. 77 (1995) p.621.
[16] A.M. Pires, M.R. Davolos and O.L. Malta, J. Lumin. 244 (1997) p.72.
[17] Y.H. Yun, S.D. Yun, H.R. Park, Y.K. Lee and Y.N. Youn, J. Mater. Synth. Process. 10
(2002) p.205.
Downloaded By: [informa internal users] At: 13:11 20 October 2010

[18] B.D. Cullity, Elements of X-ray Diffraction, 2nd ed., Addison-Wesley, Reading, MA,
2003.
[19] V. Singh, R.P.S. Chakradhar, J.L. Rao and D.-K. Kim, Solid State Sci. 10 (2008) p.1525.
[20] F. Branda, R. Fresa, A. Costantini and A. Buri, Biomaterials 17 (1996) p.2247.
[21] S.J. Dhoble, N.S. Dhoble and R.B. Pode, Bull. Mater. Sci. 26 (2003) p.377.
[22] L. Hou and B. Yan, J. Phys. Chem. Solid 69 (2008) p.2877.
[23] J. Tauc, in Optical Properties of Solids, F. Abeles, ed., North-Holland, Amsterdam, 1970.
[24] J. Manam, V. Chatterjee, S. Das, A. Choubey and S.L. Sharma, J. Lumin. 130 (2010)
p.292.
[25] J.M. Henriques, E.W.S. Caetano, V.N. Freire, J.A.P. Da Costa and E.L. Albuquerque,
Chem. Phys. Lett. 427 (2006) p.113.
[26] B. Vengala Rao and S. Buddhudu, Spectrochim. Acta Mol. Biomol. Spectros. 71
(2008) p.951.
[27] J. Wang, Y. Xu, M. Hojamberdiev, Y. Cui, H. Liu and G. Zhu, J. Alloy Comp. 479 (2009)
p.772.
[28] G. Seetarama Raju, J.Y. Park, H.C. Jung, B.K. Moon, J.H. Jeong and J.H. Kim, Curr.
Appl. Phys. 9 (2009) p.e92.
[29] W.T. Carnall, P.R. Fields and K. Rajnak, J. Chem. Phys. 49 (1968) p.4424.
[30] G. Blasse, in Handbook on the Physics and Chemistry of Rare Earths, Vol. 4,
K.A. Gschneider, Jr. and L. Eyring, eds., North Holland, Amsterdam, 1979.