Plasmon enhanced luminescence of Tb
3+
doped Li
2
O-LaF
3
-Al
2
O
3
-SiO
2
glass containing Ag nanoparticles
P. Piasecki, A. Piasecki, Z. Pan*, A. Ueda, R. Aga Jr, R. Mu, and S. H. Morgan
Department of Physics, Fisk University, Nashville, TN, USA 37208
ABSTRACT
Tb
3+
and Ag co-doped glass nano-composites are synthesized in a glass matrix Li
2
O-LaF
3
-Al
2
O
3
-SiO
2
(LLAS) by a melt-
quench technique. The nucleation and growth of Ag nanoparticles (NPs) were controlled by a thermal annealing process.
A broad absorption band peaking at about 420 nm was observed due to surface plasmon resonance (SPR) of Ag NPs.
Annealing of glass samples results in the growth of Ag NPs. Photoluminescence (PL) emission and excitation spectra
were measured from glass samples with different Ag concentrations and different annealing times. Plasmon enhanced
Tb
3+
luminescence was observed at certain excitation wavelength regions. Luminescence quenching was observed for
samples with high Ag concentration and longer annealing time. Our luminescence results suggest that there are two
competitive effects, enhancement and quenching, acting on Tb
3+
luminescence in the presence of Ag NPs. The
enhancement of Tb
3+
luminescence is mainly attributed to local field effects: the SPR of Ag NPs causes an intensified
electromagnetic field around the NPs, resulting in enhanced optical transitions of Tb
3+
ions in the vicinity. The
quenching effect in the presence of Ag NPs suggests an energy transfer from Tb
3+
ions to Ag NPs. The competition
between the plasmonic enhancement and the quenching effect is discussed for samples with different Ag concentrations
and annealing times.
Keywords: Ag, nanoparticle, SPR, Tb
3+
, luminescence
1. INTRODUCTION
Rare-earth doped glasses are important for applications in optical devices such as scintillators, optical fiber amplifiers,
lasers, optical converters of infrared radiation to visible regions, etc
1- 4
. In addition to the common advantages of low-
cost, large-volume production possibility and easy shaping of elements of glasses, oxide glasses generally possess good
mechanical strength, chemical durability, and thermal stability. Tb-doped Li
2
O-LaF
3
-Al
2
O
3
-SiO
2
(LLAS) glass was
previously reported to have good photoluminescence (PL) and β-induced luminescence light-yield for scintillator
application
1
.
The incorporation of metallic nanoparticles (NPs) in rare-earth doped glasses may enhance or quench the luminescence
of rare-earth ions
5-8
. The enhancement has been attributed to local field enhancement effects on excitation and emission
of rare-earth ions and energy transfer from metallic NPs to rare earth ions due to the excitation of SPR of metallic NPs
9
.
The quenching effect is due to energy transfer from ions to the metallic NPs
5, 6
. Rare-earth doped glasses containing
metallic NPs have recently attracted great interest
7 - 11
. However, in spite of the large amount of work published on this
topic, the mechanism of energy transfer from metallic NPs to rare earth ions has not been clarified
5, 6
.
In order to further understand the interaction between metallic NPs and rare earth ions in glass, we have studied Tb-
doped LLAS glass containing Ag NPs. In present work, we report optical absorption, photoluminescence emission and
excitation of Ag co-doped LLAS:Tb glass with different Ag concentrations and annealing times, and discuss the possible
mechanisms for plasmonic enhancement and quenching effects on Tb
3+
luminescence.
2. EXPERIMENT
Reagent grade anhydrous oxide powders of Li
2
CO
3
, LaF
3
, Al
2
O
3
, SiO
2
, TbF
3
, and AgNO
3
were used to prepare glasses.
The compositions of lithium-lanthanum-aluminosilicate glass were 28Li
2
O-11LaF
2
-6Al
2
O
3
-55SiO
2
(LLAS). Four
* zpan@fisk.edu
Plasmonics: Metallic Nanostructures and Their Optical Properties VIII, edited by Mark I. Stockman,
Proc. of SPIE Vol. 7757, 77572M · © 2010 SPIE · CCC code: 0277-786X/10/$18 · doi: 10.1117/12.863061
Proc. of SPIE Vol. 7757 77572M-1