Journal of Luminescence 87}89 (2000) 469}471

Photobrightening of CuBr nanocrystals in PMMA

M. Oda*, M.Y. Shen, M. Saito, T. Goto
Department of Physics, Graduate School of Science, Tohoku University, Aramaki, Aoba, Sendai 980-8578, Japan

Abstract

The photoluminescence (PL) intensity and its decay time of CuBr nanocrystals (NCs) embedded in poly methyl
methacrylate increase with increasing the exposure time of the excitation light at 77 K. The PL intensity becomes smaller
with increasing applied electric "eld, and returns to the initial one as soon as the electric "eld is cut. From these results, we
propose a mechanism that an electron and a hole are generated inside the NC by light, and then, either of them goes out
of the NC to neutralize a charged center outside the NC. On the other hand, the photodarkening e!ect by an applied
electric "eld may be caused by the neutralization of the ionized centers inside the NC.  2000 Elsevier Science B.V. All
rights reserved.

Keywords: Nanocrystal; Photoluminescence; Photobrightening; Electric "eld

The dynamics of excitons in nanocrystals (NCs) is
closely related to the surface states because the ratio of
the number of surface atoms to that of all the atoms in
the NCs is signi"cantly large. In many kinds of NCs, the
photodarkening e!ect of photoluminescence (PL) was
observed, and is explained as due to the carrier move-
ment around the NC surface [1]. Recently, in CuI and
CuCl NCs [2,3], the photobrightening e!ect of PL was
observed. Namely, the PL intensity increases with in-
creasing irradiation time of UV light. In CuI NCs, the
luminescence is associated with bound or localized ex-
citons. In CuCl NCs, the luminescence is associated with
free excitons, but the photobrightening may originate
from chemical change of surface atoms of the NCs. How-
ever, to our knowledge the photobrightening e!ect dir-
ectly relating to the dynamics of free excitons has not
been reported. Here, this kind of photobrightening e!ect
has been studied in CuBr NCs embedded in poly methyl
methacrylate (PMMA).
The CuBr NCs embedded in PMMA were prepared by
Yao's technique [4]. The weight concentration of the
NCs in PMMA was about 0.18%, and the thickness of
the PMMA "lm was about 0.24 mm. For PL measure-
* Corresponding author. Fax: #81-22-217-6498.
E-mail address: masaru@mail.cc.tohoku.ac.jp (M. Oda)
0022-2313/00/$ - see front matter  2000 Elsevier Science B.V. All rights reserved.
PII: S 0 0 2 2 - 2 3 1 3 ( 9 9 ) 0 0 4 9 6 - 2
ments, the samples were excited by a 325 nm light from
a He}Cd laser with an intensity of 10 mW/cm on the
sample surface. The absorption and PL spectra were
measured with an Acton Spectra Pro-500 single mono-
chromator and a Hamamatsu C4196 silicon photodiode
array.
The spectral resolution of all the measurements was
less than 3 meV. The excitation light for the temporal
decay of the PL was the second harmonic of light from
a mode-locked Ti-Sapphire laser pumped by an Ar>
laser which has the wavelength 378 nm, the pulse width
1 ps, the repetition rate 76 MHz, and the average power
on the sample surface 5 mW/cm. The time pro"le of the
PL intensity was measured by a double monochromator
and a streak camera. The integrated time of the measure-
ment was 20 s, and hence, the change of the PL intensity
was negligible in this integration time. For the applica-
tion of electric "eld up to 6 kV, the PMMA "lm was
sandwiched between an indium-tin oxide (ITO) glass
and a Cu-electrode. For all the optical measurements,
the sample was immersed in liquid nitrogen to be kept
at 77 K.
In Fig. 1, an absorption spectrum of a PMMA "lm
containing CuBr NCs is shown by a broken line. The
absorption spectrum consists of two intense bands. The
lower and higher energy bands are associated with
the Z and Z excitons, respectively [5]. The absorp-
 
tion peak energies of the Z and Z excitons in the bulk
 
470 M. Oda et al. / Journal of Luminescence 87}89 (2000) 469}471
Fig. 1. The absorption and PL spectra of CuBr NCs with an
average radius of 4.0 nm. A broken line shows the absorption
spectrum. The dotted and solid lines show the PL spectra before
and after the 325 nm light irradiation for 430 min, respectively.
The peak positions of the Z and Z exciton absorption bands
 
in bulk CuBr are shown by vertical arrows.
CuBr crystal are indicated by vertical arrows at the upper
edge of the "gure. Due to the size quantization of the
exciton translational motion [6], the Z and Z peaks
 
of the NCs are shifted to the higher energy side in
comparison with those of the bulk crystal. The average
radius of the CuBr NCs is estimated to be about 4 nm
from the peak energy of the Z exciton absorption

band. The band broadness may be due to the in-
homogeneity of the NC size. PL spectra before and after
the excitation light irradiation are shown by a dotted line
and a solid line, respectively. The irradiation time is
430 min. A Stokes shift from the Z absorption band is

found to be 24 meV in this "gure, and it becomes larger
as the size of the NC decreases. At 4.2 K, another sharp
PL peak appears together with the PL peak in Fig. 1, and
its peak energy is lower than the PL peak energy in
Fig. 1, which however is not shown here. This sharp PL
peak that appears at 4.2 K is assigned as due to an
I bound exciton on the analogy of that in the bulk CuBr
 
crystal, because its peak energy hardly depends on the
size of the NCs. On the contrary, the PL peak in Fig. 1
moves to the higher energy side as the size of the NC
becomes smaller, which is interpreted by the quantum-
size con"nement e!ect. Thus, the PL peak observed at
77 K is concluded to be associated with the free exciton
annihilation. On the analogy of the bulk CuBr crystal,
the absorption peaks are associated with dipole allowed
Z and Z exciton states and the PL peak with the
 
dipole forbidden Z exciton state that is the lowest energy

state of the Z exciton [7]. Thus, the "nite Stokes shift

is explained.
The PL intensity after the light irradiation for 430 min
reaches 15 times that of the initial one. The PL peak
shows either blue shift or red shift after the light irradia-
tion, but the energy shift is less than 5 meV. On the
Fig. 2. The exposure time dependences of the PL intensity (open
circles) and its decay time (closed circles). An inset shows decay
curves of the Z exciton luminescence before (open circles) and

after (closed circles) the light irradiation.
contrary, the absorption spectrum hardly changes after
the light irradiation. After the light irradiation at 77 K,
we raise the sample temperature to room temperature
and maintain it for several hours at room temperature,
and then cool it to 77 K. Such a thermal treatment makes
the PL intensity to decrease and to revert to the initial
intensity. After the sample is cooled down to 77 K, the
photobrightening e!ect can be again observed.
In the inset of Fig. 2, the temporal behavior of the PL
intensity is shown. Open and closed circles show the PL
time decay before and after the light irradiation, respec-
tively. The PL intensity and the decay time calculated
from the "tting to a single exponential decay curve are
shown by open and closed circles, respectively, in Fig. 2.
Both the PL intensity and the decay time become larger
with increasing exposure time of the excitation light. This
is in contrast to the photodarkening phenomenon that
both the PL intensity and its decay time decrease with
increasing exposure time of the excitation light [8].
The external electric "eld dependences of the PL inten-
sity in the Z free exciton and of its decay time are
shown by closed and open circles, respectively, in Fig. 3.
Before the measurement of the electric "eld dependence,
the sample was su$ciently irradiated by the excitation
light. The change in the PL decay time is hardly observed
in this experiment, while the PL intensity becomes small-
er with increasing applied electric "eld. The PL intensity
immediately returns to the initial one as soon as the
applied electric "eld is removed.
We suggest that there exists charged centers inside and
outside the NCs before the light irradiation. This can be
imagined from a mechanism proposed in order to inter-
pret phenomena of photodarkening [1] and spectral dif-
fusion [9]. For example, an ionized acceptor and an
ionized donor are located inside and outside the NC,
respectively. In such a NC, the photo-generated carriers
may be trapped at the ionized centers inside and outside
 M. Oda et al. / Journal of Luminescence 87}89 (2000) 469}471
Fig. 3. The electric "eld dependences of the PL intensity (closed
circles) and its decay time (open circles).
the NC, or the wavefunction of the light generated
exciton may be shrunk by the ionized center. The former
decreases the PL e$ciency and the latter decreases the
decay time of the PL intensity. After the light is irradiated
on the sample, the photo-generated electron and hole
may be trapped at these charged centers, resulting in the
disappearance of the above two e!ects due to the charged
centers.
When there exist an ionized donor and acceptor inside
the NC, the photo-generated electron and hole may be
accelerated to be easily trapped at these ionized centers
under the applied electric "eld, and then they recombine.
If the exciton is not generated in such a NC, the PL
intensity may decrease but the decay time may not be
changed. When there exists a neutralized center inside
471
and outside the NC, the photo-generated carriers recom-
bine to an exciton and then annihilates radiatively. In
this case, both the PL intensity and its decay time may
not change in the applied electric "eld. Therefore, the
total PL intensity may become smaller, while the PL
decay time may not change.
In conclusion, the PL intensity and its decay time of
CuBr NCs embedded in PMMA increase with increasing
exposure time of the excitation light. The photobrighten-
ing phenomenon is considered to be caused by the photo-
neutralization of local charged centers inside and outside
the NC. On the other hand, the photodarkening e!ect
under the applied electric "eld may be caused by the
neutralization of local charged centers inside the NC.
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