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Broadband spectral conversion of visible light to near-infrared

emission via energy transfer from Ce3+ to Nd3+/Yb3+ in YAG


Jiajia Zhou and Yu Teng
State Key Laboratory of Silicon Materials, Zhejiang University, Hangzhou 310027, China

Xiaofeng Liu
State Key Laboratory of High Field Laser Physics, Shanghai Institute of Optics and Fine Mechanics, Chinese
Academy of Sciences, Shanghai 201800, China

Zhijun Ma
State Key Laboratory of Silicon Materials, Zhejiang University, Hangzhou 310027, China

Jianrong Qiua)
State Key Laboratory of Silicon Materials, Zhejiang University, Hangzhou 310027, China; and Institute of Optical
Communication Materials, South China University of Technology, Guangzhou 510640, China
(Received 27 April 2010; accepted 19 November 2010)

Broadband spectral conversion from visible light to near-infrared radiation in Ce3+Nd3+/Yb3+


codoped yttrium aluminum garnet is reported. Excitation, emission spectra, and decay curves have
been measured to prove the energy transfer from Ce3+ to Nd3+ or Yb3+. The energy transfer
efciencies have been estimated, and the mechanisms of the energy transfer between Ce3+ and
Nd3+/Yb3+ have been proposed. Ce3+Nd3+ codoped YAG can obtain more effective emission in the
desired near-infrared region (around 1100 nm) through broadband conversion, showing potential
application to improve the conversion efciency of Si solar cells.

I. INTRODUCTION

Photoelectric transformation efciency of solar cells


can be improved by spectral modication, which reduces
the energy losses that limit the efciency related to
spectral mismatch.1 There are two ways to adapt the solar
spectrum before it is absorbed by the solar cells. One is
known as upconversion (UC), whereby two lower-energy
photons are absorbed to give out one higher-energy
photon. It is a nonlinear process depending on the incident
power and is especially useful for solar cells with a large
band gap where transmission losses dominate. The other is
to cut one higher-energy photon into two lower-energy
photons, known as downconversion (DC). This is a linear
process and is most benecial for solar cells with a smaller
band gap where thermalization losses are the major loss
factor. Using nonconcentrated sunlight as light source, DC
has the capability to get high conversion efciency.
For DC spectral modication method by rare earth
(RE) doping, a RE ion pair is usually needed. One ion
acts as a sensitizer to absorb higher-energy photons and
the other as luminescence center to output lower-energy
photons. To consider the practical application on solar
cells, Ce3+ is chosen as sensitizer, which shows broadband
absorption due to the fd transition in high-energy region.
For c-Si solar cell, the spectral response is gradually
a)

Address all correspondence to this author.


e-mail: qjr@zju.edu.cn
DOI: 10.1557/jmr.2010.84
J. Mater. Res., Vol. 26, No. 5, Mar 14, 2011

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increased from the ultraviolet (UV) region to the nearinfrared (NIR) region with the maximum value at around
1100 nm, which is in agreement with the band gap of Si
(1.1 eV). Many investigations have been carried out on
DC of UV or visible photons to NIR photons choosing
Yb3+ as the luminescence
center226 because the energy
3+ 2
level difference of Yb : F5/2 and F7/2 is a little larger than
the band gap of Si. Making the couple of Ce3+ and Yb3+ as
an ion pair has been reported before; however, the practical quantum efciency is much lower than the theoretical
quantum efciency.7 In this paper, we investigate whether
we can get more efcient NIR emission with Ce3+Nd3+
couple compared with Ce3+Yb3+ couple in YAG. Since
Nd3+ energy level transitions have a NIR emission similar
to Yb3+ for application in Si solar cell and the rst-order
energy transfer (ET) with an intermediate level (ET
between Ce3+ and Nd3+), they may be more efcient than
the second-order cooperative energy transfer process (ET
between Ce3+ and Yb3+).
II. EXPERIMENTAL

YAG powder samples with different doping concentrations of Ce3+ and Nd3+/Yb3+ [Y3 x yCex(Nd/Yb)y
Al5O12] (x 5 0, 0.12; y 5 0, 0.024, 0.06, 0.12, 0.24,
0.36) were prepared with a sol-gel route using citric acid
and ethylene glycol (EG) as the chelating agents.8 The
obtained powders comprise single-phase YAG (JCPDS
No. 33-0040), which was identied with x-ray diffraction
Materials Research Society 2011

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J. Zhou et al.: Broadband spectral conversion of visible light to near-infrared emission via energy transfer from Ce3+ to Nd3+/Yb3+ in YAG

(XRD). Excitation, emission spectra, and decay curves


were recorded with a FLS920 uorescence spectrophotometer under ambient atmosphere. All the measurements
were carried out at room temperature.
III. RESULTS AND DISCUSSION

Figure 1 shows the excitation and emission spectra of


Y3 x yCexNdyAl5O12 (x 5 0, 0.12; y 5 0, 0.024, 0.06,
0.12, 0.24, 0.36). From the excitation spectrum of
Y2.82Ce0.12Nd0.06Al5O12 monitored at 1062 nm, the hybridized peaks in long
wavelength
from 450
to 2900 nm
are
4
4
4
2
3+ 4
ascribed
to
Nd
:
I
/
G
,
G
,
G
,
G
,
G
9/2
11/2
3/2
9/2
9/2
7/2,
4
4
4
4
2
4
4
G5/2, F9/2, S3/2, F7/2, H3/2, F5/2, F3/2 transitions, which
could also be identied from the excitation spectrum of
Y2.64Nd0.36Al5O12. Also, the broad bands (325360 and
400520 nm) of Y2.82Ce0.12Nd0.06Al5O12 in excitation
spectrum monitored
at2 1062 nm, which are ascribed to
2
Ce3+:4f / 5d ( B1g, A1g) transition, are in good accordance with that of Y2.88Ce0.12Al5O12 excitation spectrum
monitored at 540 nm. This can be an evidence of the energy
transfer from Ce3+ to Nd3+. In Fig. 1(b), the emission
intensity changes with various Nd3+ concentration (y 5 0,
0.024, 0.06, 0.12, 0.24, 0.36) and a xed Ce3+ concentration
(x 5 0.12) in visible and near-infrared region under
excitation at 467 nm. The intensity of broad emission bands
of Ce3+:5d / 4f transition (500750 nm) decreases
monotonously with increasing y from 0 to 0.36. Also the
concaves in the luminescence curves at 588 nm
are ascribed
4
4
to the uorescence reabsorption of Nd3+: I9/2 / G5/2
transition. Meanwhile, the NIR luminescence intensities
of Nd3+ show a maximum when y is equal to 0.06. Also, the
remarkable decrease of the NIR luminescence intensity is
due to concentration quenching, when y further increases.

Figure 2 shows the excitation and emission spectra of


Y3 x yCexYbyAl5O12 (x 5 0, 0.12; y 5 0, 0.024, 0.06,
0.12, 0.24, 0.36) as that of Y3 x yCexNdyAl5O12 (x 5 0,
0.12; y 5 0, 0.024, 0.06, 0.12, 0.24, 0.36) shown in Fig. 1.
The energy transfer from Ce3+ to Yb3+ is also proved
through the excitation spectra, and the strongest nearinfrared emission at 1028 nm is observed when x and y are
equal to 0.12. The inset is the enlarged view of the
excitation spectrum of Y2.64Yb0.36Al5O12 from 200 to
500 nm, which is monitored at 1028 nm. There are four
peaks located at 275, 340, 405, and 470 nm, which
correspond to the transitions from stark split 2F7/2 level
of the Yb3+ ion in the garnet to the charge transfer state.9
The decay curves of Ce3+:5d / 4f transition of
Y3 x yCex(Nd/Yb)yAl5O12 (x 5 0.12; y 5 0, 0.024,
0.06, 0.12, 0.24, 0.36), are depicted in Fig. 3. The decay
time decreases when y increases from 0 to 0.36 both
in Y2.88-yCe0.12NdyAl5O12 and Y2.88-yCe0.12YbyAl5O12,
implying the introduction of extra decay path, i.e.,
energy transfer from Ce3+ to Nd3+/Yb3+. From these decay
curves, the energy transfer efciency (gET) of Y2.88-y
Ce0.12NdyAl5O12 and Y2.88-yCe0.12YbyAl5O12 could be
estimated by:10
R
Iy dt
gET;y 5 1 R
;
Iy 5 0 dt
where I stands forthe decay intensity. The obtained results
plotted in Fig. 3 indicate that both gET of Y2.88-y
Ce0.12NdyAl5O12 and Y2.88-yCe0.12YbyAl5O12 exhibit
a monotonous increase with doping concentration of
Nd3+/Yb3+ (y). Also, every gET of Y2.88-yCe0.12NdyAl5O12
is larger than that of Y2.88-yCe0.12YbyAl5O12, when they
have the same y value. However, the maximum effective

FIG. 1. Excitation and emission spectra of Y3 x yCexNdyAl5O12 (x 5 0, 0.12; y 5 0, 0.024, 0.06, 0.12, 0.24, 0.36). (a) Excitation spectra of Nd3+
emission monitored at 1062 nm and Ce3+ emission spectra excited at 540 nm. (b) Emission intensity changes with Nd3+ concentrations in visible and nearinfrared region under excitation at 467 nm.
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J. Zhou et al.: Broadband spectral conversion of visible light to near-infrared emission via energy transfer from Ce3+ to Nd3+/Yb3+ in YAG

FIG. 2. Excitation and emission spectra of Y3 x yCexYbyAl5O12 (x 5 0, 0.12; y 5 0, 0.024, 0.06, 0.12, 0.24, 0.36). (a) Excitation spectra of Ce3+
emission monitored at 540 nm and Yb3+ emission monitored at 1028 nm. Inset is the enlarged view of the excitation spectrum of Y2.64Yb0.36Al5O12 from
200 to 500 nm. (b) Emission intensity changes with Yb3+ concentrations in visible and near-infrared region under excitation at 467 nm.

gET (the strongest NIR luminescence is obtained before


concentration quenching) of Y2.88-yCe0.12NdyAl5O12 (44%,
when y 5 0.06) is smaller than that of Y2.88-yCe0.12
YbyAl5O12 (57%, when y 5 0.12).
Figure 4 compares the NIR emission intensities of
Y2.82Ce0.12Nd0.06Al5O12 and Y2.76Ce0.12Yb0.12Al5O12
under the same measure condition. The integrated intensity of Y2.82Ce0.12Nd0.06Al5O12 is 8 times larger than
that of Y2.76Ce0.12Yb0.12Al5O12 in the region from 860 to
1150 nm, while gET of them is equal to 44% and 57%,
respectively. This may be due to the different energy
transfer mechanism from Ce3+ to Nd3+ and Ce3+ to Yb3+.
The inset shows the energy levels of Ce3+ and Nd3+ with
transitions that may be involved in the energy transfer
process. Here the nonradiative energy transfer and the
radiative energy transfer are involved.11 And from Fig. 3,
we can see that the decay time of Ce3+: 5d / 4f transition
changes apparently after Nd3+ codoping. So it is notable
that the nonradiative energy transfer contributes to the
whole energy transfer process. In the nonradiative energy
transfer process, after excitation of the Ce3+ 5d state the
electrons can either relax radiatively to the 4f ground state,
producing broadband4 luminescence in the visible range,
or
4
transfer to the Nd3 + G9/2 level. Also, the electrons at G9/2
level further relaxed through
nonradiative decays to
4
the
intermediate
level
(
F
),
since
the emission due to
3/2
4
4
G9/2 / F3/2 transition is not observed. Then4 the NIR
emits
are observed
by the radiative decays from F3/2 level
4
4
to I11/2 or I9/22 level. However, Yb3+ only has simple
energy levels of F5/2,7/2, and the energy transfer from Ce3+
to Yb3+ is due to the second-order cooperative energy
transfer process.7,12,13 Also, second-order cooperative
energy transfer process has a lower efciency, making it
only efcient at very high Yb3+ concentrations where the

FIG. 3. Decay curves of Ce3+:5d / 4f transition and the calculated


energy transfer efciency (gET) with different Nd3+/Yb3+ concentration
in Y3 x yCex(Nd/Yb)yAl5O12 (x 5 0.12; y 5 0, 0.024, 0.06, 0.12, 0.24,
0.36).

Yb3+ emission is largely quenched through concentration


quenching. In addition, it has been reported that the
emissions of Ce3+ and Yb3+ are quenched by the process
of charge transfer state (Ce4+Yb2+) in Ce3+Yb3+
codoped YAG.7 So Ce3+Nd3+ codoped YAG is more
efcient than Ce3+Yb3+ codoped YAG for the similar

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691
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J. Zhou et al.: Broadband spectral conversion of visible light to near-infrared emission via energy transfer from Ce3+ to Nd3+/Yb3+ in YAG

ACKNOWLEDGMENTS

This work was nancially supported by the National


Natural Science Foundation of China (Grant No.
50872123 and 50802083), National Basic Research Program of China (Grant No. 2006CB8060007), and the
Program for Changjiang Scholars and Innovative Research Team in University (Grant No. IRT0651).
REFERENCES

FIG. 4. Spectral response of c-Si solar cell and near-infrared emission


spectra of Y2.82Ce0.12Nd0.06Al5O12 and Y2.76Ce0.12Yb0.12Al5O12 under
excitation at 467 nm. Inset is the energy levels of Ce3+ and Nd3+
with transitions that may be involved in the energy transfer process.

spectral response of c-Si at 1062 and 1028 nm, as we


observed from the large difference between the NIR
emission intensities.
IV. CONCLUSION

In summary, we have synthesized pure-phase Ce3+ and


Nd3+/Yb3+ codoped YAG by sol-gel method. When
excited by visible light, efcient NIR emission at 1064
and 1028 nm were observed and the energy transfer from
Ce3+ to Nd3+/Yb3+ were proved. The optimum composition of Ce3+ and Nd3+/Yb3+ codoped YAG were
Y2.82Ce0.12Nd0.06Al5O12 and Y2.76Ce0.12Yb0.12Al5O12,
and the corresponding energy transfer efciencies were
calculated to be 44% and 57%. The mechanisms of the ET
processes between Ce3+ and Nd3+/Yb3+ were compared.
The results show that it is inappropriate to codope the ion
pairs that are composed of one ion that tends to be oxidized
and another one that tends to be reduced through the
charge transfer state, such as the ion pair of Ce3+Yb3+.
Ce3+Nd3+ codoped YAG can obtain more effective
emission in the desired near-infrared region through
broadband absorption and rst-order energy transfer. It
shows potential application to improve the conversion
efciency of Si solar cells by realization of efcient
spectral modication of solar spectrum.

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