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Rare-Earth-Activated Glasses for Solar Energy Conversion

Guillaume Alombert Goget 1,6, Davor Ristic 1,5, Belto Dieudonn2, Enrico Moser 3, Stefano Varas1,
Simone Berneschi 4,7, Mile Ivanda5, Andre Monteil6, Claire Arfuso Duverger2,
Giancarlo C. Righini 7, Brigitte Boulard2, Maurizio Ferrari1
1 - CNR-IFN, CSMFO Lab., Via alla Cascata 56/c, Povo, 38123 Trento, Italy
Tel: (39) 0461 314918, Fax: (39) 0461 314875, e-mail: mferrari@science.unitn.it
2 - LdOF Lab., UMR CNRS 6010, Universit du Maine, Av. O. Messiaen, 72085 Le Mans, cedex 09 France
3 - Dipartimento di Fisica, Universit di Trento, via Sommarive 14, Povo, 38123 Trento, Italy
4 - Museo Storico della Fisica e Centro di Studi e Ricerche Enrico Fermi,
Piazza del Viminale 2, 00184 Roma, Italy
5 - Ruder Bokovic Institute, P.O.Box 180, 10002 Zagreb, Croatia
6 - Laboratoire de Photonique d'Angers, Universit d'Angers, 2, bd Lavoisier 49045 Angers cedex 01France
7 - CNR-IFAC, MDF Lab, "Nello Carrara" Institute of Applied Physics,
Via Madonna del Piano 10, 50019, Sesto Fiorentino, Firenze, Italy
ABSTRACT
The solar cells efficiency may be improved by better exploitation of the solar spectrum, making use of the downconversion mechanism, where one high energy photon is cut into two low energy photons. The choice of the
matrix is a crucial point to obtain an efficient down-conversion process with rare-earth ions. When energy
transfer between rare earth ions is used to activate this process, high emission and absorption cross sections as
well as low cut-off phonon energy are mandatory. In this paper we present some results concerning 70SiO230HfO2 glass ceramic planar waveguides co-activated by Tb3+/Yb3+ ions, fabricated by sol gel route using a topdown approach, and a bulk fluoride glass of molar composition 70ZrF4 23.5LaF3 0.5AlF3 6GaF3 co-activated by
Pr3+/Yb3+ ion. Attention is focused on the assessment of the energy transfer efficiency between the two couples
of rare earth ions in the different hosts.
Keywords: Quantum cutting; Rare earth; Glass-ceramic waveguides; Silica-Hafnia, Fluoride glass; Energy
transfer.
1. INTRODUCTION
A main limitation of a photovoltaic device is related to the mismatch between the incident solar spectrum and the
spectral absorption properties of the material of the cell [1]. Several routes were proposed in the past decades to
modify the incident spectrum and improve the conversion efficiency of a semiconductor solar cell [1,2]. Among
these, the down conversion, also called quantum cutting, permits to generate more than one low energy photon
exploiting the energy of one incident high energy photon [1]. The most used solar cells are based on crystalline
Si (c-Si). In this context, the down-conversion would be beneficial if a photon with a wavelength shorter than
approximately 500 nm (around twice the energy of the silicon band gap) could be converted in two photons with
wavelengths around 1000 nm (with a energy just above the band gap of c-Si) [2]. Several approaches have been
considered at the aim to develop suitable down-converters using rare earth activated powders, glasses, crystals,
and glass-ceramics. Rare earth ions, where absorption and emission take place via a number of energy levels,
allow down-conversion processes. Initial work on down conversion materials was aimed at the conversion of one
UV photon in two visible photons. So, most of the works on the quantum cutting concerned the photon cascade
emission (sequential emission) or energy transfer by steps, from the 1S0 level of Pr3+ or from the 6GJ levels of the
Gd3+. Recently for application on the solar cell, down conversion mechanisms using Yb3+ emission at 980 nm
were studied. Table 1 presents a short list of systems recently reported in the literature. The effective quantum
efficiency that depends on the transfer efficiency between the donor and acceptor ions is also reported.
Table 1. Some systems employed as down-converters. The couple of rare earth ions and the estimated effective
quantum efficiency of the conversion mechanism are reported.
Rare earth molar
Effective quantum
Reference
Host matrix
content
efficiency
3+
3+
45SiO2-12Na2O-23Al2O3-20LaF3
0.5Tm /8 Yb
162%
[3]
50SiO220Al2O320LiF10GdF3
0.5Tm3+/30 Yb3+
187%
[4]
La0.45AlGe2O7
5Tm3+/0Yb3+
160%
[5]
32SiO29AlO1.531.5CdF28.5PbF25.5ZnF2
3.5Er3+/1Yb3+
199%
[6]
GdBO3
1Tb3+/75Yb3+
198%
[7]
KY3F10
0.5Pr3+/20Yb3+
194%
[8]
50GeO210B2O320ZnO20LaF3
0.5Pr3+/30Yb3+
184%
[9]

978-1-4577-0882-4/11/$26.00 2011 IEEE

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In the following we present two systems that can be suitable as down converters, namely, a) sol-gel derived
Tb3+7Yb3+-activated SiO2-HfO2 glass ceramic planar waveguides, b) Pr3+/Yb3+ -activated bulk fluoride glasses.
Figure 1 and Figure 2 show the schematic diagram for the Pr3+ Yb3+ and Tb3+ Yb3+ energy transfer process,
respectively,

Figure 1. Upon excitation of Pr3+ into the 3PJ (J = 0, 1, 2) levels, depopulation of the 3P0 excited state can occur
through two sequential resonant energy transfer steps between Pr3+ and Yb3+ with 1G4 acting as the intermediate
level: Pr3+(3P0 1G4)Yb3+(2F7/2 2F5/2) followed by Pr3+(1G4 3H4)Yb3+(2F7/2 2F5/2); this results in two
excited Yb3+ ions and the emission of two NIR photons. Therefore two NIR photons are emitted by Yb3+ ions after
the absorption of a single photon by a Pr3+ ion.

Figure 2. The Tb3+: 5D4 energy level corresponds at about twice the energy of the Yb3+: 2F5/2 energy level.
The Yb3+ ions dont present an energy level above the 2F5/2 level up to the UV region. The cooperative energy
transfer between a Tb3+ ion and two Yb3+ions can be the main relaxation route to achieve the NIR luminescence
of the Yb3+. Therefore two NIR photons are emitted by Yb3+ ions after the absorption of a single photon by a Tb3+
ion.
2. ASSESMENT of the ENERGY TRANSFER EFFICIENCY
The energy transfer efficiency RE-Yb, where RE=(Pr, Tb) indicates the donor ion, can be obtained experimentally
by dividing the integrated intensity of the decay curves of the RE3+-Yb3+ co-doped glass ceramics by the
integrated intensity of the RE3+ single doped curve [11]:

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RE Yb = 1

I
I

RE Yb
RE

dt

(1)

dt

In some papers, effective quantum efficiency is employed. It is defined by the ratio between the number of
emitted photons and the number of photons absorbed by the material. In our case, a perfect down-conversion
system would have an effective quantum efficiency value of 200%, corresponding to the emission of two
photons for one absorbed. The relation between the transfer efficiency and the effective quantum efficiency is
linear [10] and is defined as:
EQE = RE-r(1 RE-Yb) + 2RE-Yb
where the quantum efficiency for the donor ion , RE-r, is set equal to 1.

(2)

3. RESULTS AND DISCUSSION

3.1 Frequency converter layers based on terbium and ytterbium activated HfO2 glass-ceramics
70SiO2 30HfO2 glass ceramic waveguides activated by different molar percentages of terbium and ytterbium
ions were prepared by solgel route using the dip-coating technique as detailed reported in [10]. The decay
curves of the Tb3+ 5D4 state were measured upon 355 nm excitation for the different samples. Nearly single
exponential luminescence decay is observed for the sample without Yb3+ co-doping. For the co-doped samples
a fast and not single exponential luminescence decay was observed, attributed to the energy transfer from the
Tb3+: 5D4 to the Yb3+: 2F5/2 [11]. The not exponential behavior of the decay is due to different distributions of
Yb3+ ions around the Tb3+ ions, which lead to different energy transfer rates for the different Tb3+ ions [12]. The
transfer efficiency is then obtained using Eqs. (1) and (2). The obtained results are reported in Tables 2 and 3.

Table 2. Transfer efficiency and effective quantum efficiency as a function of Yb3+ molar concentration for
70SiO2 30HfO2 glass ceramic waveguides where Tb3+ content is fixed at 0.5 mol%.
Composition (Yb concentration in mol%)

1%

2%

3%

Transfer efficiency

14%

24%

25%

Effective quantum efficiency

114%

124%

125%

Table 3. Transfer efficiency and effective quantum efficiency as function of (Yb3++Tb3+) molar
concentration for 70SiO2 30HfO2 glass ceramic waveguides with constant molar ratio Yb/Tb=4
Composition (Tb+Yb concentration in mol %)

1%

3%

5%

Transfer efficiency

1%

18%

38%

Effective quantum efficiency

101%

118%

138%

The results on these samples indicate an increase of the transfer efficiency with the increase of the
ytterbium/terbium molar ratio. For a given concentration of donors (Tb3+), increasing the number of acceptors
(Yb3+) located near to the Tb3+ ion, also the Tb-Yb transfer probability increases. The Tb-Yb energy transfer
efficiency increases with the increase of the total amount of rare earth ions, too. The sample with the highest
concentration of rare earths (5%), presents an energy transfer efficiency of 38%.
3.2 Down-converter based on rare earth doped fluoride glass
A series of fluoride ZLAG glasses 70ZrF4 (23-x)LaF3 0.5PrF3 xYbF3 0.5AlF3 6GaF3 in mol% (x = 0,1,2,3 and 5
%) were prepared by standard method (melting at 850C for 15 min in covered platinum crucible casting of
the melt rapidly heated at 900C in a brass mould at 180C). The decay curves of the Pr3+: 3P0 state were
measured upon excitation at 440 nm as a function of the Yb3+ content. Also in the case of fluoride glasses an
early single exponential luminescence decay was observed for the sample without Yb3+. The decay curves of the
co-doped samples showed a progressive quenching of the 3P0 luminescence with the increase in Yb3+
concentration. The fast luminescence decay observed for the co-doped samples is clearly due to the energy
transfer from the Pr3+ to the Yb3+ [11]. The non exponential behavior of the decay can be explained by different
distributions of Yb3+ ions around the Pr3+ ions, which lead to different energy transfer rates for the different Pr3+
ions [8, 12]. The transfer efficiencies, obtained using Eqs. (1) and (2), are reported in Table 4 for the investigated
fluoride glasses.

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Table 4. Evaluated energy transfer efficiency as a function of Yb3+ molar concentration for
the 70ZrF4 (23-x)LaF3 0.5PrF3 xYbF3 0.5AlF3 6GaF3 ZLAG glasses.
YbF3 (mol%)

Transfer efficiency %

10 (*)

38

55

70

82

92

Effective quantum efficiency %

138 155 170 182
192
3+
(*) A mixed composition ZLAG/ZBLA=9/1 allowed to achieve 10% mol Yb doping
(ZBLA=57ZrF4 34BaF2 4LaF3 5AlF3)
In the case of 10 mol% Yb3+ we obtained a energy transfer efficiency practically equal to the one measured in
K3YF10 crystal with 20 mol% Yb3+ (cfr Table 1 and ref. [8]).
4. CONCLUSIONS
In summary, efficient down-converter Tb3+: Yb3+ co-doped 70 SiO2 - 30 HfO2 glass ceramic waveguide and Pr3+:
Yb3+ fluoride glasses have been developed. The fluoride glass co-doped by 0.5 mol% Pr3+and 10 mol% Yb3+
exhibits an energy transfer efficiency of 92%, similar to the best results obtained in fluoride crystals with
a double amount of Yb3+. In the case of glass-ceramic waveguide a Tb3+/Yb3+ transfer efficiency of 38 % is
measured. The waveguide configuration, because the possibility to obtain high radiation confinement, opens new
possibilities for integration of down-converters and light concentrators.
ACKNOWLEDGEMENTS
This research was performed in the framework of the following research projects: Oxi-Solar, High Concentration
Solar Cell HCSC, EU COST Action MP0702, and NSMBO research project (2010-2013).
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