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 ECS Transactions, 16 (30) 23-31 (2009)
10.1149/1.3106668 © The Electrochemical Society

Fluorescence Properties of Nd3+-Doped KNbO3 Nano-Phosphors

R. Balakrishnaiaha,b, Dong Woo Kima, Soung Soo Yia,*, Kwang Duk Kimc, Sung Hoon
Kimc, Kiwan Jangb, Ho Sueb Leeband Jung Hyun Jeongd
a
Department of Electronic Materials Engineering, Silla University, Busan 617-736,
Republic of Korea
b
Department of Physics, Changwon National University, Changwon 641- 773, Republic
of Korea
c
Department of Engineering in Energy and Applied Chemistry, Silla University, Busan
617-736, Republic of Korea
d
Department of Physics, Pukyong National University, Busan 608-737, Republic of
Korea

Nd3+-doped potassium niobate (K(1-x)NbO3:Nd3+x (x = 0.01, 0.03, 0.05 and

0.07)) polycrystalline powder nano-phosphors were prepared by the
conventional solid state reaction method and were characterized by X-ray
diffraction (XRD), scanning electron microscopy (SEM) and
photoluminescence measurements. The XRD data has shown single phase
orthorhombic structure for x = 0.01 and 0.03 moles of Nd3+ ion
concentrations while an additional NdNbO4 phase is observed at higher
concentrations of Nd3+ ions. The photoluminescence spectrum has shown
an intense emission at 1061 nm along with two low intense emission bands
at 883 and 1343 nm when the samples were excited with 514.5 nm
radiation of an Ar+ ion laser. No drastic changes of intensity of emissions
are observed with concentration variation, except changes in crystal-fields
peak intensities.

Introduction

Research interest on lanthanide (Ln)-doped materials is rapidly growing in the

coming generation due to their potential applications as non-linear optical materials.
These materials found wide useful in the development of plasma display panels (PDP),
field emission displays (FED) and electro-luminescent panels. Many researchers reported
various phosphor host matrices with suitable luminescent Ln ions that found applications
in optical devices like fluorescent lamps, cathode ray tubes and X-ray intensifying
screens (1-5). Potassium niobate (KNbO3) is recognized to be one of the best host matrix
for Ln ions as it is a useful candidate for ferroelectric materials with excellent electro-
optic and nonlinear optical coefficients which have attracted a great amount of interest
for applications in optical waveguides, frequency doublers and holographic storage
systems (6, 7). Among Ln ions, Nd3+ ion is one of the most extensively studied ions for
solid state lasers due to its laser emission at a very useful wavelength, 1064 nm, in
addition to the possibility of lasing at other wavelengths such as 1800 nm, 1350 nm and
880 nm at room temperature (RT). Also, its absorption in the UV–VIS–NIR regions
allow efficient pumping either with broad band sources (Xenon lamp) or with sources of
selected wavelength using diode lasers (8, 9).

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 ECS Transactions, 16 (30) 23-31 (2009)

In our present work, K(1-x)NbO3:Ndx3+ nano-phosphors have been prepared by

solid state reaction method for x = 0.01, 0.03, 0.05 and 0.07 concentrations of Nd3+ ions
and the dependence of various optical and morphological properties of the prepared
materials on Nd3+ ion concentration has been discussed.

Experimental details

The KNbO3:Nd powder nano-phosphor samples under present investigation were

synthesized by the conventional solid state reaction method by using the raw materials of
high purity chemicals: K2CO3, Nb2O5 and Nd2O3. These powders with correct
proportional amounts of materials were finely grinded in an agate mortar with piston on
adding a little amount of acetone. Then the mixture is taken in an alumina crucible,
heated in an electric tubular furnace at 120 ℃ for one hour, 750 ℃ for four hours,
1050 ℃ for four hours and finally annealed at 400 ℃ for ten hours in air atmosphere.
The concentration of the Nd3+ ions doped in the K(1-x)NbO3+δ: Nd3+x phosphors is taken as
x = 0.01, 0.03, 0.05 and 0.07. Here afterwards, for simplicity, these samples have been
labeled as KNN01, KNN03, KNN05 and KNN07 for x = 0.01, 0.03, 0.05 and 0.07
concentrations of Nd3+ ions, respectively. The crystal structures of the prepared samples
were examined by XRD analysis using a high-resolution x-ray diffraction system with
CuKα1 radiation (λ = 1.542 Å). The surface morphologies of the samples were
investigated by a field emission gun scanning electron microscope (Quanta 200 FEG)
operated at 15 kV. The emission spectra were measured using the 514.5 nm excitation
wavelength of an Ar+ ion laser.

Results and discussion

The XRD patterns of the prepared samples were shown in Fig. 1. As can be seen
from Fig. 1, the diffraction peaks appeared at the diffraction angle 2θ of around 22.05
(110), 22.30 (001), 31.55 (111), 44.95 (220), 45.60 (002, 50.75 (221), 51.20 (112), 56.00
(311), 56.40 (022) and 65.95 (222) were found consistent with the theoretical values of
KNbO3 (JCPDS No. 32-0822) indicating the well formation of KNbO3. Most of the
diffraction peaks are found on the higher angle side when compared with JCPDS data
indicating the lattice contraction with incorporation of Nd3+ ions into the KNbO3 lattice.
The lattice contraction with incorporation of Nd3+ ions may be attributed to substitution
of Nd3+ ions into the K+ sites that are having relatively larger ionic radius. All the samples
are found orthorhombic in structure because of the split of the diffraction peaks, (220)
and (002) (10). According to earlier literature, KNbO3 phosphor undergoes phase
transitions from rhombohedral to orthorhombic at -10 ℃, orthorhombic to tetragonal at
225 ℃ and finally tetragonal to cubic at 435 ℃ temperatures (11-14). The observed
orthorhombic phase of the present KNbO3 samples at room temperature is in agreement
with these results. As can be seen from Fig. 1, KNN01 and KNN03 samples are found
single orthorhombic phase while an additional NdNbO4 phase (JCPDS No. 22-1175) is
appeared at the diffraction angle 2θ of 27.80 and 29.45, (represented by ‘*’ mark) at

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 ECS Transactions, 16 (30) 23-31 (2009)

higher concentrations. Similar type of EuNbO4 phase formation in Eu3+-doped KNbO3

phosphors was also noticed by Fang and his coworkers (11) for Eu3+ ion concentrations
beyond 5 mol %. The (111) peak is found the most intense with a full width at half
maximum (β(2θ)) of 0.27 to 0.33 degrees. The crystallite size (D) in (111) direction was
calculated from the Debye-Scherrer formula (15),

0 .9 λ
D = (1)
β ( 2θ ) Cos θ

and was found 25 nm for KNN01 and KNN03 samples, 30.6 nm for KNN05 and 25.8 nm
for KNN07 samples. The crystallinity of the samples is found not much varied with the
concentration of Nd3+ ions, except the formation of additional phase. The SEM images of
the samples are shown in Fig. 2 which represent the surface microstructures of the
KNbO3:Nd3+ phosphors under present investigation. Agglomeration of particles can be
clearly noticed from the SEM images.

A typical partial energy level diagram of Nd3+ ions in KNbO3 nano-phosphor is

shown in Fig. 3. As can be seen from Fig. 3, when the Nd3+-doped KNbO3 nano-
phosphor is excited with 514.5 nm radiation of an Ar+ laser, the Nd3+ ions in the ground
state absorb this energy and get excited to the 4G9/2 level of Nd3+ ions. Then due to
smaller energy gaps between adjacent levels, non-radiative multiphonon relaxation (NR)
will take place down to 4F3/2 level. Then due to sufficiently large energy gap between
4
F3/2 level to its lower lying 4I15/2 level (approximately 5,600 cm-1), radiative emission (R)
will predominate from this level which gives the NIR emissions at 880, 1061, 1343 and
1800 nm. The emission spectrum for different concentrations of Nd3+ ions-doped KNbO3
phosphors measured under 514.5 nm excitation of an Ar+ laser is shown in Fig. 5. As can
be seen from Fig. 5, the spectrum consists of three emission bands near 880 nm, 1061 nm
and 1343 nm in the NIR region. These bands are assigned to the 4F3/2 → 4I9/2, 4I11/2 and
4
I13/2 transitions of Nd3+ ions, respectively. The 4F3/2 → 4I15/2 emission at 1800 nm is not
measured due to lack of experimental facility in that region. The emission peak at 1061
nm is found to be the most intense peak. The experimental branching ratios of the
observed emission transitions are found to be 21.99 % (880 nm), 71.43 % (1061 nm) and
6.59 % (1343 nm) for KNN01 sample. The intensity of the emissions increased from
KNN01 to KNN03 and then decreased for higher concentrations. However, on an outlook,
the intensities of KNN1, KNN05 and KNN07 are found almost similar. The only change
is in the intensities of crystal-field (CF) peaks those corresponding to the 4F3/2 → 4I11/2
transition. The crystal-field peaks corresponding to 4F3/2 → 4I11/2 transition are presented
in Fig. 4. As can be seen from Fig. 4, the crystal-field levels are found at 1060.6, 1065.4,
1068.5 and 1077.6 nm for KNN01 sample. The maximum intense CF peaks are found to
be 1060.6 nm (KNN01), 1060.9 nm (KNN03), 1067.9 nm (KNN05) and 1067.9 nm
(KNN07) samples. The red shifting of maximum intensity of the transition with increase
of Nd3+ ion concentration may be attributed to the increase of covalence bond of Nd3+
ions with their nearest neighboring atoms. The peak position corresponding to the 4F3/2 →
4
I11/2 transition at 1061 nm in the present KNbO3:Nd3+ phosphor is found on the higher
energy side when compared to that 1080 nm in case of LiNbO3:Nd3+ channel waveguides
(16), but on the lower energy side when compared to that in case of Nd3+-doped
phosphate glasses (1054 nm) (17).

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 ECS Transactions, 16 (30) 23-31 (2009)

Conclusions

Various concentrations of Nd3+ ions-doped KNbO3 nano-phosphors have been

synthesized by solid state reaction method and were characterized by X-ray diffraction
(XRD), scanning electron microscopy (SEM) and photoluminescence measurements. The
XRD data has shown single orthorhombic phase for 1 and 3 mol % Nd3+ ion
concentrations while an additional NdNbO4 is observed at higher concentrations. The
fluorescence spectra have shown three emission bands in the IR region of the spectrum at
881, 1061 and 1343 nm. The intensity of the 3 mol % Nd3+-doped sample is found higher
than that of the other samples. No much variations are observed in luminescence nature
of the samples except variation of intensities of CF levels related to the 4F3/2 → 4I11/2
transition. The red shifting of transition with increasing of Nd3+ ion concentration might
be attributed to the increase of covalence bonding of Nd3+ ions with their the neighboring
ligands.

Acknowledgements

This work was supported by Korea Research Foundation grant funded by the Korean
Government (KRF-J00902).

References

1. H. C. Yang, C. Y. Li, H. He, Y. Tao, J. H. Xu and Q. Su, J. Lumin. 118, 61 (2006).

2. Y. Zhang, Y. Li and Y. Yin, J. Alloys Compd. 400, 222 (2005).
3. H. W. Song, J. W. Wang, B. J. Chen, H. S. Peng and S. Z. Lu, Chem. Phys. Lett.
376, 1 (2003).
4. B. Vengala Rao, U. Rambabu and S. Buddhudu, Mater. Lett. 61, 2868 (2007).
5. C. S. Park, M. Kwak, S. S. Choi, Y. S. Song, S. J. Hong, J. I. Han and D. Y. Lee, J.
Lumin. 118, 199 (2006).
6. P. Gunter, Phys. Rep. 93, 199 (1982).
7. M. K. Chun, L. Goldberg and J. F. Weller, Appl. Phys. Lett. 53, 1170 (1988).
8. J. H. Campbell and T. I. Suratwala, J. Non-Cryst. Solids 263&264, 318 (2000).
9. M. Ajroud, M. Haouari, H. Ben Ouada, H. Maaref, A. Brenier and C. Garapon, J.
Phys.: Condens. Matter 12, 3181 (2000).
10. C-H. Lu, S-Y. Lo and H-C. Lin, Mater. Lett. 34, 172 (1998).
11. T-H. Fang, Y-J. Hsiao, Y-S. Chang and Y-H. Chang, Mater. Chem. Phys. 100, 418
(2006).
12. C-H. Wen, S-Y. Chu, S-L. Tyan and Y-D. Juang, J. Cryst. Growth 262, 225 (2004).
13. C-H. Wen, S-Y. Chu, Y-D. Juang and C-K. Wen, J. Cryst. Growth 280, 179
(2005).
14. C-H. Wen, S-Y. Chu and C-K. Wen, J. Cryst. Growth 269, 479 (2004).
15. B. E. Warren, X-ray Diffraction, p. 253, Dover, New York, 1990.
16. E. Cantelar, G. Lifante, F. Cusso, M. Domenech, A. Busacca, A. Cino and S. R.
Sanseverino, Opt. Mater. 30, 1039 (2008).
17. R. Balakrishnaiah, P. Babu, C. K. Jayasankar, A. S. Josi, A. S. Speghini and M.
Bettinelli, J. Phys. Condens. Matter 18, 165 (2006).

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 ECS Transactions, 16 (30) 23-31 (2009)

Figures and Figure Captions

Fig. 1. XRD patterns of various concentrations of Nd3+-doped KNbO3 nano-phosphors.

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 ECS Transactions, 16 (30) 23-31 (2009)

Fig. 2. Scanning electron micrographs of Nd3+-doped KNbO3 nano-phosphors under

investigation.

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 ECS Transactions, 16 (30) 23-31 (2009)

Fig. 3. Partial energy level diagram of Nd3+ ions-doped KNbO3 nano-phosphors

representing the emission mechanism.

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 ECS Transactions, 16 (30) 23-31 (2009)

Fig. 4. Emission spectra of Nd3+ ions-doped KNbO3 nano-phosphors under 514.5 nm

excitation.

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 ECS Transactions, 16 (30) 23-31 (2009)

Fig. 5. Crystal-field levels corresponding to the 4F3/2 → 4I11/2 transition of Nd3+ ions in
KNbO3 nano-phosphors.

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