1804 J. Opt. Soc. Am. B / Vol. 21, No. 10 / October 2004 Zhang et al.

Enhanced luminescence and size effects of

Y2 O3 :Eu3⫹ nanoparticles and ceramics revealed
by x rays and Raman scattering

Kai Zhang, A. K. Pradhan,* and George B. Loutts

Center for Materials Research, Norfolk State University, 700 Park Avenue, Norfolk, Virginia 23504

Utpal N. Roy, Yunlong Cui, and Arnold Burger

Department of Physics, Fisk University, 1000 Seventeenth Avenue North, Nashville, Tennessee 37208-3051

Received March 8, 2004; revised manuscript received May 12, 2004; accepted May 21, 2004
Europium-doped yttrium oxide (Y2 O3 :Eu3⫹) nanophosphors were synthesized by wet chemical routes with
both combustion and coprecipitation techniques. We explicitly illustrate the dynamics of Y2 O3 :Eu3⫹ nano-
phosphors with a particle size that is influenced by extrinsic stress and revealed by x rays and Raman scat-
tering. The influence of Eu3⫹ activation on Raman spectra is illustrated. We demonstrate the significant
enhancement of emission characteristics of ceramics synthesized from nanoparticles by using the combustion
technique and by controlling the vacuum-sintering conditions. © 2004 Optical Society of America
OCIS codes: 160.0160, 160.2540, 160.5690.

1. INTRODUCTION tion without any detrimental effects.10,11 Among all

Luminescent light-emitting materials based on lan-
thanide phosphors are emerging rapidly and are revolu-
tionizing the display and lighting industries. It is antici-
pated that oxide phosphors have the potential of
replacing conventional displays. However, significantly
improved performance of displays demands high-quality
phosphors having sufficient brightness and long-term sta-
bility. Lanthanide-activated rare-earth oxides1,2 remain
as promising materials for next-generation display tech-
nology because of several important superior properties,
such as luminescent characteristics, stability in vacuum,
and corrosion-free gas emission under electron bombard-
ment compared with traditional cathode ray tube red
phosphors used in current field emission displays.3,4 On
the other hand, a unique combination of the optical and
thermal properties makes rare-earth oxides attractive for
several applications, such as damage-resistant and high-
reflection material in light-emitting diodes, high-power
pulsed ultraviolet lasers, and as infrared and high-
temperature windows under stringent environment.
Hence, extensive research is currently pursued to develop
rare-earth-based oxide phosphors for superior perfor-
mance.
Among rare-earth oxide-based phosphors there has
been significant research interest in the development of
Y2 O3 :Eu3⫹ composite material as one of the most prom-
ising red phosphor systems.5–9 Because of 5 D 0 → 7 F 2
transitions within europium, Y2 O3 :Eu3⫹ shows lumines-
cent properties and emits red light at a wavelength of 611
nm and can be used as the red phosphor for trichromatic
fluorescent lamps.1 The Y2 O3 :Eu3⫹ has a lumen equiva-
lent brightness of 70% relative to 611-nm light and radi-
ant efficiency of approximately 8.7% with better satura-
rare-earth-based phosphors, Y2 O3 :Eu3⫹ is inexpensive
and practical for mass production. To optimize the syn-
thesis procedure for significant enhancement in lumines-
cent properties, several novel techniques have been con-
templated. Although there are several advantages in the
use of thin-film-based Y2 O3 :Eu3⫹ phosphors, the applica-
tions are limited because of poor brightness.7–9 On the
other hand, there has been some success in synthesizing
nanocrystalline phosphors by use of several chemical
means.6,12–14 However, the particle size dependence of
optical and spectroscopic properties, which is important
for these materials,5,15 remains unexplored. Here we
demonstrate the emission characteristics of nanoparticles
and ceramics that are significantly influenced by particle
size and sintering conditions. We explicitly show the dy-
namics of Y2 O3 :Eu3⫹ nanophosphors and ceramics with
increasing particle size, revealed by x rays and Raman
scattering.
2. EXPERIMENTS
The nanocrystalline Y2 O3 :Eu3⫹ powders were synthe-
sized with both modified combustion12 (CM) and copre-
cipitation (CP) techniques16 from their respective nitrate
solutions. Eu doping was kept as low as 5 at. % for all
the samples. For the CM technique, the precursor mix-
ture with urea (1:3 ⫽ Y2 O3 :urea) was dehydrated com-
pletely before combustion at a temperature of 600 °C, at
which precursor powders comprised of nanoparticles were
obtained. The CM technique provides several ways to
obtain high-quality nanopowders as reported in Ref. 12.
For CP, the well-stirred nitrate solution was mixed with
an aqueous solution of drops of NH4 HCO3 to form the pre-

0740-3224/2004/101804-05$15.00 © 2004 Optical Society of America

Zhang et al. Vol. 21, No. 10 / October 2004 / J. Opt. Soc. Am. B 1805

cipitate. The precipitate was filtered and ultrasonically

washed with water and methanol several times followed
by final drying at approximately 100–120 °C. Then the
powders were calcined in the 800–1500 °C temperature
range for 2–5 h to vary the particle size. For ceramic
processing, the precursor powders calcined at 1100 °C
were mixed with a binder and solvent, and ball milled.
We palletized the milled powders into a circular disk by
using uniaxial pressure followed by calcination at 600 °C
to remove the organic components. Finally, the pellets
were vacuum sintered at 1700–1800 °C in a W-mesh
heater-assembled vacuum chamber with a vacuum better
than 2 ⫻ 10⫺6 Torr for 4–6 h depending on the size of the
sample.
Phase identification was performed with the x-ray pow-
der diffraction (XRD) method on a Rigaku x-ray diffracto-
meter with CuK␣ radiation. The crystallite size of the
powder was calculated from the line broadening (the full
width at half-maximum, FWHM or ⌫). Powder and sin-
tered ceramic surface morphology and microstructures
were observed by scanning electron microscopy (SEM).
The Raman spectra were recorded with a LabRam micro-
Raman spectrometer with He–Ne laser excitation
(632.8-nm wavelength).
Fig. 1. Crystallite size dependence of the XRD patterns of
Y2 O3 :Eu3⫹ powders: solid curves, combustion; dotted curves,
3. RESULTS AND DISCUSSION coprecipitation (coppt.) techniques. The inset shows the particle
Figure 1 shows the XRD patterns of an as-synthesized size versus calcination temperature.
Y2 O3 :Eu3⫹ precursor and nanocrystalline powders cal-
cined at various temperatures (700–1500 °C). The XRD
results for all the samples are consistent with the cubic
phase of Y2 O3 . By analyzing the diffraction peaks of dif-
ferent orders, (211), (222), (400), and (440), we deter-
mined the crystallite size D s by using the Scherrer equa-
tion shown in the Fig. 1 inset. The grain size grows
rapidly above a calcination temperature of 1200 °C.
However, the weighted volume crystallite size D w (⬃4/3
⫻ D s ) and the crystalline distortion that is due to strain
⑀ are also responsible for the XRD line broadening.17
Therefore, we have followed a method described
recently,17 ⌫ cos ␪ ⫽ (K␭/Dw) ⫹ 4⑀ sin ␪, where K is the
Scherrer constant of 0.9, to calculate the strain whose
broadening is proportional to tan ␪ for spherical particles.
The strain decreases from 0.1 to 0.06% with an increase
in particle size from 30 to 60 nm, illustrating that the lo-
cal strain decreases rapidly with increasing particle size. Fig. 2. Scanning electron micrographs of Y2 O3 :Eu3⫹ powders
Furthermore, a slight, systematic shift of the x-ray lines calcined at (a) combustion, 1100 °C, (b) coprecipitation, 1100 °C,
(c) ceramic (combustion) 1750 °C, (d) ceramic (coprecipitation)
to a higher angle with increased, particle size is a mani- 1750 °C.
festation of the decrease of the interatomic distances in-
duced by the reduced local surface strain of the nanopar-
ticles. the trend as shown in the Fig. 1 inset. The SEM micro-
Figures 2(a)–2(d) show the SEM morphologies of the structures of CM samples vacuum sintered at 1750 °C for
powders and ceramics synthesized by use of both tech- 4 h show grains of ⬃2–5 ␮m. On the other hand, the CP
niques. The micrographs presented in Figs. 2(a) and 2(b) samples prepared under similar sintering conditions
clearly indicate the nanostructured network of the showed similar grains with large surface irregularities.
Y2 O3 :Eu3⫹ precursors calcined at 1100 °C. The particles Figure 3 shows the evolution of the Raman spectra of
are less than 50 and 60 nm for both CM and CP powders, Y2 O3 :Eu3⫹ powders with varying particle sizes and a
respectively, which was confirmed by transmission elec- ceramic-sintered sample, mainly from the CM technique
tron microscopy in which particle sizes ranging from 20 to with a particle size of 60 nm for comparison, illustrating
50 nm were observed. The particle sizes increase gradu- the increase of Raman intensity with increasing particle
ally in powders calcined up to 1400 °C, and increase size. The Y2 O3 crystallizes in the cubic system space
sharply beyond this calcination temperature similar to group Ia3 (T h7 ), and the structure is body centered, the
1806 J. Opt. Soc. Am. B / Vol. 21, No. 10 / October 2004 Zhang et al.

unit cell contains the primitive cell twice, having eight

formula units. The irreducible representations for the
optical Raman active modes18 are ⌫ op ⫽ 4A g ⫹ 4E g
⫹ 14F g . The observed Raman lines shown in Fig. 3(a)
are consistent with the prediction. The extra lines
marked by asterisks are due to Eu3⫹ doping. It has been
shown18 that the calculated and the observed 21 Raman
lines are found between 120 and 600 cm⫺1 for Y2 O3 .
Therefore, the Raman bands shown in Fig. 3(b) are due
entirely to Eu3⫹ doping and can be used as a powerful tool
to optimize the material quality.
To analyze the Raman data, we adopted the framework
of the gradient model,19 in which two parameters are con-
sidered, such as the maximum strain at surface ⑀ 0 of the
nanoparticle, a weighted particle size D w , and FWHM d s
for a suitable strain function of a Lorentian type. This
study reveals the influence of crystallite-size effects on
both physical and optical properties, and thereby size and
size distribution, and large extrinsic stress that is detri-
mental to the intrinsic property of the nanoparticles, can
be avoided. Within the framework of the first approxi-
mation of the quasi-harmonic Grüneisen relation and the
local Raman frequency ␻(␹) caused by a gradient in the
force constant ␥, defined by d␻ ( ␹ )/d␻ ⫽ 3 ␥⑀ ( ␹ ), the
mean frequency of particles ␻ (D) can be defined in the
following way:

␻ 共 D 兲 ⫽ ␻ 0 关 1 ⫺ 3 ␥⑀ 共 ␹ 兲共 2d s /D 兲 arctan共 D/2d s 兲兴 . (1)

Fig. 4. Emission spectra of (a) Y2 O3 :Eu3⫹ nanopowders and ce-

ramics sintered at 1700 and 1750 °C for 4 h and (b) Y2 O3 :Eu3⫹
ceramics sintered at 1750 °C for 16 h with an intermediate heat-
ing of 2 h at 1100 °C in vacuum. The inset in (b) shows the scan-
ning rate dependence of the emission spectra.

Using the Grüneisen parameter ␥ ⫽ 0.7, which is a

Fig. 3. Experimental size dependence of the Raman shifts of
Y2 O3 :Eu3⫹ powders and ceramics. The inset shows the shift of
the mean Raman frequency as a function of inverse particle di-
ameter. The solid curve represents the theoretical line from the
gradient model.
reasonable value for optical phonons, and introducing the
shared parameters,19 such as d s ⬃ 2 nm, and ⑀ 0 ⫽ 1.2%
( ⑀ 0 and d s exist over a narrow surface range), we deter-
mined the inverse crystallite sizes 1/D w from Eq. (1), and
they are plotted in the Fig. 3 inset. This is found to be
fairly consistent with the theoretical curve (shown as a
solid curve) evaluated from Eq. (1) and also with the XRD
data that show the finite-size effect. The Raman line
shift to higher frequencies and the decrease of the lattice
constant with increasing crystallite size is a manifesta-
tion of the structural gradient of the interatomic dis-
tances induced by the local surface strain of nanopar-
ticles.
Figure 4(a) shows the emission spectra of some select
samples starting from the CM nanocrystalline Y2 O3 :Eu3⫹
precursor powders and sintered ceramic samples to illus-
trate luminescence behavior. The luminescence behavior
of a ceramic sample synthesized by the CP route is also
shown for comparison. Note that the emission intensity
at 610 nm for the ceramic sample by CM is approximately
an order of magnitude larger than that of the CP tech-
nique. This remarkable enhancement in intensity is re-
lated to the surface morphology described above. We
Zhang et al.
also note that the emission intensity increases with in-
creasing particle size that is consistent with Raman data.
All the emission spectra illustrate that the Eu3⫹ ions are
in cubic symmetry and exhibit the characteristics of red-
luminescent Y2 O3 :Eu3⫹, in which the 5 D 0 → 7 F 2 transi-
tion at ⬃610 nm is prominent, and the relatively weak
emissions at the shorter wavelengths are due to the 5 D 0
→ 7 F 1 transitions. The cubic structure provides two
sites, C 2 and S 6 , from two different crystalline sites, in
which the 5 D 0 → 7 F 2 transition originates from the C 2
site of the electric dipole moment of Eu3⫹ ions that
scarcely arises for the S 6 site because of the strict inver-
sion symmetry. This suggests that the emission emerges
mainly from the C 2 site in the cubic structure. In view of
the above, the increased volume for the photon–solid in-
teraction at the surface as well as improved crystallinity
of the Y2 O3 :Eu3⫹ powders with increasing particle size
(finite-size effect) is clearly responsible for the enhanced
emission intensity. The most profound emission for the
sintered ceramics compared with their nanocrystalline
powder is attributed to the increase of the crystallites,
which make up the ceramics and reduce the surface-to-
volume ratio, which diminishes the negative processes re-
lated to the surface effects. Most importantly, both lat-
tice imperfections and strains associated with the
nanoparticles that are deleterious for carrier-mediated
energy transfer are almost absent in sintered ceramics.
To illustrate the emission property of a highly translu-
cent Y2 O3 :Eu3⫹ ceramic through which letters can be
clearly read, we show the excitation dependence of the
emission spectra in Fig. 4(b). The ceramic body was syn-
thesized from the CM nanopowders and sintered in
vacuum in two steps, 2 h at 1100 °C and then 16 h at
1750 °C. The remarkable enhancement in emission in-
tensity was observed for all excitation wavelengths, al-
though the maximum intensity was recorded for the
254-nm excitation wavelength. The enhancement of lu-
minescent property can be attributed to the efficient en-
ergy transfer rate from the luminescence centers caused
by reduced interfaces in the processed ceramics and cor-
rection of the oxygen defects.20 The Fig. 4(b) inset shows
that the emission line at 611 nm does not depend on the
scanning rates used in the current experiments. Al-
though the superior performance of the ceramics depends
on the nanopowder precursor, the vacuum-sintering time
and temperature remain important in this class of mate-
rials to obtain optical quality ceramics for various appli-
cations. The wet chemical routes have several merits, in-
cluding mass production of nanopowders over other
techniques, such as nanoparticles produced by laser
vaporization.21,22
4. CONCLUSION
In conclusion, we have demonstrated a significant en-
hancement of the emission characteristics of the ceramics
synthesized from nanoparticles by use of the combustion
technique. We have illustrated the dynamics of
Y2 O3 :Eu3⫹ nanophosphors with increasing particle size,
revealed by x rays and Raman scattering. Our results
suggest that the structural parameters are strongly influ-
enced by the size effect of the nanoparticles that are due
Vol. 21, No. 10 / October 2004 / J. Opt. Soc. Am. B 1807
mainly to local surface strain. The results are useful for
the optimization of phosphor nanoparticles, for which the
size and local strain significantly influence the structural
and spectroscopic properties of the phosphors. We have
demonstrated the superior emission performance of pro-
cessed ceramics by controlling the vacuum-sintering tem-
perature and time.
ACKNOWLEDGMENTS
This research is supported by the National Aeronautics
and Space Administration (NASA) and University Re-
search Center (URC) cooperative agreement NCC-3-1035
and National Science Foundation (NSF) for Center for Re-
search Excellence in Science and Technology (CREST)
grant HRD-9805059.
*Address all correspondence to apradhan@nsu.edu.
REFERENCES
1. K. C. Mishra, J. K. Berkowitz, K. H. Johnson, and P. C.
Schmidt, ‘‘Electronic structure and optical properties of
europium-activated yttrium oxide phosphor,’’ Phys. Rev. B
45, 10902–10906 (1992).
2. R. C. Ropp, The Chemistry of Artificial Lighting Devices:
Lamps, Phosphors, and Cathode Ray Tubes (Elsevier, New
York, 1993).
3. S. Itoh, T. Kimizuka, and T. Tonegawa, ‘‘Degradation
mechanism for low-voltage cathodoluminescence of sulfide
phosphors,’’ J. Electrochem. Soc. 136, 1819–1823 (1989).
4. H. C. Swart, J. S. Sebastian, T. A. Trottier, S. L. Jones, and
P. H. Holloway, ‘‘Degradation of zinc sulfide phosphors un-
der electron bombardment,’’ J. Vac. Sci. Technol. A 14,
1697–1703 (1996).
5. T. Ye, Z. Guiwen, Z. Weiping, and X. Shangda, ‘‘Combustion
synthesis and photoluminescence of nanocrystalline
Y2 O3 :Eu phosphors,’’ Mater. Res. Bull. 32, 501–506 (1997).
6. B. Allieri, L. E. Depero, A. Marino, L. Sangaletti, L. Ca-
paraso, A. Speghini, and M. Bettinelli, ‘‘Growth and micro-
structural analysis of nanosized Y2 O3 doped with rare
earths,’’ Mater. Chem. Phys. 66, 164–171 (2000).
7. S. L. Jones, D. Kumar, R. K. Singh, and P. H. Holloway, ‘‘Lu-
minescence of pulsed laser deposited Eu doped yttrium ox-
ide films,’’ Appl. Phys. Lett. 71, 404–406 (1997).
8. J. S. Bae, J. H. Jeong, S.-S. Yi, and J.-C. Park, ‘‘Improved
photoluminescence of pulsed-laser-ablated Y2 O3 :Eu3⫹ thin-
film phosphors by Gd substitution,’’ Appl. Phys. Lett. 82,
3629–3631 (2003).
9. K. G. Cho, D. Kumar, D. G. Lee, S. L. Jones, P. H. Holloway,
and R. K. Singh, ‘‘Improved luminescence properties of
pulsed laser deposited Eu:Y2 O3 thin films on diamond
coated silicon substrates,’’ Appl. Phys. Lett. 71, 3335–3337
(1997).
10. G. Blasse and B. C. Grabmaier, Luminescent Materials
(Springer-Verlag, Berlin, 1994).
11. T. Hase, T. Kano, E. Nakazawa, and H. Yamamoto, ‘‘Phos-
phor materials for cathode-ray tubes,’’ Adv. Electron. Elec-
tron Phys. 79, 271–373 (1990).
12. E. Zych, ‘‘On the reasons for low luminescence efficiency in
combustion-made Lu2 O3 :Tb,’’ Opt. Mater. 16, 445–452
(2001).
13. C.-H. Lu and R. Jagannathan, ‘‘Ceriumion-doped yttrium
aluminum garnet nanophosphors prepared through sol-gel
pyrolysis for luminescent lighting,’’ Appl. Phys. Lett. 80,
3608–3610 (2002).
14. G. Tessari, M. Bettinelli, A. Speghini, D. Ajo, G. Pozza, L. E.
Depero, B. Allieri, and L. Sangaletti, ‘‘Synthesis and optical
1808 J. Opt. Soc. Am. B / Vol. 21, No. 10 / October 2004
properties of nanosized powders: lanthanide-doped Y2 O3 ,’’
Appl. Surf. Sci. 144–145, 686–689 (1999).
15. E. T. Goldburt, B. Kulkarni, R. N. Bhargava, J. Taylor, and
M. Libera, ‘‘Size dependent efficiency in Tb-doped Y2 O3
nanocrystalline phosphor,’’ J. Lumin. 72–74, 190–192
(1997).
16. A. K. Pradhan, K. Zhang, and G. B. Loutts, ‘‘Synthesis of
neodymium-doped yttrium aluminum garnet (YAG) nano-
crystalline powders leading to transparent ceramics,’’
Mater. Res. Bull. 39, 1291–1298 (2004).
17. H. Natter, M. Schmelzer, M.-S. Löffler, C. E. Krill, A. Fitch,
and R. Hempelmann, ‘‘Grain-growth kinetics of nanocrys-
talline iron studied in situ by synchrotron real-time x-ray
diffraction,’’ J. Phys. Chem. B 104, 2467–2476 (2000).
18. Y. Repelin, C. Proust, E. Husson, and J. M. Beny, ‘‘Vibra-
Zhang et al.
tional spectroscopy of the C-form of yttrium sesquioxide,’’ J.
Solid State Chem. 118, 163–169 (1995).
19. Ch. Beck, K. H. Ehses, R. Hempelmann, and Ch. Bruch,
‘‘Gradients in structure and dynamics of Y2 O3 nanopar-
ticles as revealed by x-ray and Raman scattering,’’ Scr.
Mater. 44, 2127–2131 (2001).
20. E. Zych, D. Hreniak, and W. Strek, ‘‘Spectroscopy of Eu-
doped Lu2 O3 -based x-ray phosphor,’’ J. Alloys Compd. 341,
385–390 (2002).
21. H. Eilers and B. M. Tissue, ‘‘Laser spectroscopy of nano-
crystalline Eu2 O3 and Eu3⫹:Y2 O3 ,’’ Chem. Phys. Lett. 251,
74–78 (1996).
22. B. M. Tissue, ‘‘Synthesis and luminescence of lanthanide
ions in nanoscale insulating hosts,’’ Chem. Mater. 10, 2837–
2845 (1998).