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Journal of Luminescence
journal homepage: www.elsevier.com/locate/jlumin
Instituto de Fsica, Universidade Federal do Rio Grande do Sul, Av. Bento Gonc- alves 9500, 91501-970, Porto Alegre-RS, Brazil
Instituto Federal Sul-rio-grandense, Campus Pelotas, Prac- a 20 de Setembro 455, 96015-360, Pelotas-RS, Brazil
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 28 May 2012
Received in revised form
2 October 2012
Accepted 5 October 2012
Available online 16 October 2012
The present work deals with the photoluminescence (PL) emitted from Eu and Tb ions implanted at
room temperature (RT) up to 350 1C in a SiO2 matrix, followed by a further anneal process. The ions were
implanted with energy of 100 keV and a uence of 3 1015 ions/cm2. Further anneals were performed in
atmospheres of N2 or O2 with temperatures ranging from 500 up to 800 1C. PL measurements were
performed at RT and structural measurements were done via transmission electron microscopy (TEM).
In addition, the Rutherford backscattering technique (RBS) was used to investigate the corresponding ion
depth proles. For Tb, the optimal implantation temperature was 200 1C, and the anneal one was of
500 1C. Under these conditions, the PL yield of the sharp band centered at 550 nm was signicatively
higher than the one obtained with RT implants. The PL spectra corresponding to the Eu ions show two
bands, one narrow centered around 650 nm and a second broad one in the bluegreen region.
The implantation temperature plays a small inuence on the PL shape and yield. However, the annealing
atmosphere has a strong inuence on it. Samples annealed in N2 present a broad PL band, ranging from
370 up to 840 nm. On the other hand, the O2 anneal conserves the original as-implanted spectrum, that
is: a broad PL band in the bluegreen region together with sharp PL band in the red one. For both ions,
Tb and Eu, the TEM analyses indicate the formation of nanoclusters in the hot as-implanted samples.
& 2012 Elsevier B.V. All rights reserved.
Keywords:
Earth-rare photoluminescence
Ion implantation
Eu nanoparticles
Tb nanoparticles
1. Introduction
Silicon has been the material of choice for several decades in the
microelectronics industry due to its excellent electrical, chemical
and mechanical properties. With the increasing miniaturization of
the integrated circuits, according to the Moores Law [1], several
difculties are currently hampering their evolution in terms of
processing and transmission speed. Those difculties arise due to
numerous physical factors that become more relevant as the scale
of such circuits becomes closer to atomic dimensions [2]. One
promising alternative is to replace the way that the signals are
transmitted and processed inside the integrated circuits, namely,
the use of photons instead of electrons. However, silicon being an
indirect band gap semiconductor also makes it a poor photoemitter
due to the low probability of radiative recombination.
In the search for the luminescence of silicon-compatible materials,
novel elements were used in order to obtain a more intense emission
with a wider range of wavelengths. Regarding rare earths (RE)
embedded in SiO2 matrixes; the rst successful result related with
PL emission was reported in 1983 by Ennen et al. [3]. In this case,
it was observed that a 1.54 mm emission from Er3 ions was
0022-2313/$ - see front matter & 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jlumin.2012.10.010
2. Experimental details
A 100 nm thick SiO2 layer was thermally grown over a o1 0 04
Si substrate. The implantations were performed with a uence of
3 1015 ions/cm2, at an energy of 100 keV (Rp 45 nm, DRp 9 nm),
resulting in peak concentrations of approximately 1 at%. During the
implantations, the samples were kept at a constant temperature,
ranging from RT to 350 1C. Afterwards, the samples were annealed
for 1 h in N2 or O2 atmosphere, with temperatures ranging from 500
to 800 1C.
For the PL measurements, the samples were excited with a
266 nm (4.66 eV) solid state laser, with 7 mW of excitation
power. The samples emission was dispersed by a 30 cm monochromator and then detected by a CCD camera. All the spectra
were corrected taking into account the systems response.
In order to verify the PL emission reproducibility of the
samples and, in particular, to compare the PL behavior of samples
prepared with different parameters we have prepared at least six
independent samples by starting with the same substrate. The
results have shown that statistically the PL shapes and corresponding yields differ in less than 5%.
Rutherford backscattering technique (RBS) and transmission
electron microscopy (TEM) were used in the samples characterization. In the rst case we have used the 1.2 MeV He beam
provided by a 3 MV Tandetron accelerator and for the second one
a 200 kV Jeol transmission electron microscope was used.
3. Results
3.1. Terbium
3.1.1. PL measurements
In Fig. 1(a), a typical PL spectrum of a Tb implanted sample is
displayed. The spectrum presents several emission lines which
correspond to radiative electronic transitions of the Tb ions, as
reported in the literature [16,17]. The shape of the measured Tb
spectra does not change with the implantation or annealing temperatures, neither with the anneal atmosphere, only its intensity is
233
modied. Further, the emission lines maintain their relative intensities. In what follows, we will refer the obtained results only related
to the doublet at 542 nm, which is the most intense PL line.
In Fig. 1(b) the 542 nm PL yield as a function of both the
implantation and annealing temperatures is displayed. An inspection of the gure shows the following features: The implantation
temperature strongly inuences the PL yield. With increasing
implantation temperatures, there is an increase of the PL emission,
being the minimum for the RT and maximum for 350 1C. Concerning the annealing temperature, the maximum is observed at
500 1C regardless of the implantation temperature. However, the
maximum PL yield is observed at a combination of a hot implant
at 200 1C and anneal at 500 1C. Finally, it should be stated that for
temperatures higher than 500 1C, all the samples show a decrease
in the PL yield, independent of the implantation temperature.
Fig. 1. (a) Typical spectrum of a Tb implanted sample, showing the radiative electronic transitions of the Tb ions. (b) PL intensity of the 542 nm line as function of the
annealing temperature for samples implanted at RT, 200 and 350 1C.
234
3.2.1. PL results
In Fig. 4 the PL spectra of Eu implanted samples at different
temperatures, without further annealing are illustrated. As can be
observed, the bluegreen region of the spectra (400550 nm)
presents a broad PL emission band. On the other hand, in the red
region of the spectra (550800 nm), some emission lines are
resolved being the most intense one situated at around 645 nm.
Fig. 2. RBS spectra from Tb implanted samples at RT and 350 1C, before and after
an 800 1C, 1 h anneal in a N2 atmosphere.
3.2. Europium
Fig. 3. TEM images for Tb implanted samples: (a) as-implanted at 350 1C, (b) Implanted at RT and further annealed at 800 1C and (c) implanted at 350 1C and subsequently
annealed at 800 1C. Corresponding histograms are shown in gures (d), (e) and (f).
and 200 1C, the intensities are practically the same. On the other
hand, the samples implanted at 350 1C present a 20% increase in
the PL intensity of the lines that are in the red region of the
spectrum, and 45% for the bluegreen PL band, as compared with
the ones implanted at RT.
235
Fig. 6. PL spectra of Eu implanted samples at RT and 350 1C: (a) as-implanted, (b) annealed for 1 h in a O2 atmosphere at 500 1C, (c) at 600 1C and (d) at 800 1C.
236
Fig. 7. PL spectra of samples successively annealed in two distinct atmospheres, at (a) 700 1C for 1 h N2 and subsequently with O2 and (b) rst with O2 and then with N2.
4. Discussion
In the present work, the inuence of the implantation and
annealing temperatures as well the annealing atmosphere on Tb
and Eu implanted samples were investigated.
The PL emission intensity from the samples studied in the
present work as a function of implantation and annealing temperature depend essentially on two conicting factors. On one
hand, the post-implantation anneal favors the nucleation and
growth of the nanoparticles, which is not only unnecessary but
also unwanted. This is because the PL emission from rare earth
oxides is due to electronic transitions of atomic levels of such
ions. On the other hand, non-radiative defects present mainly in
the as-implanted samples, compete in the capture of excitation
photons and even of the emitted photons from the RE luminescent centers, hampering the PL emission. A way to maximize the
PL emission of such systems consists in the passivation of the
non-radiative defects generated by the implantation process and,
at the same time, trying to avoid the growth of the precipitates.
The hot implantation partially eliminates the non-radiative
Fig. 9. RBS spectra from Eu implanted samples at RT and 350 1C before and after
an 800 1C, 1 h in a N2 atmosphere.
237
Fig. 10. TEM images for Eu implanted samples (a) implanted at 350 1C, and (b) after the 800 1C anneal in N2. The respective histograms are shown in gures (c) and (d).
238
5. Summary
In the present work we have investigated the inuence of the
implantation temperature, temperature and atmosphere of
annealing on the PL emission of Tb and Eu implanted into a
SiO2 matrix. The microstructural characterization was done with
TEM images and the resulting histograms. The concentration
depth proles of the implanted ions were obtained at each step
of the experiments by using the RBS technique.
In the case of Tb as-implanted samples, it was observed that
the hot implantation gives the highest PL intensity as compared
with the ones implanted at RT. The hot implantation technique
induces concurrently, the nucleation of nanoparticles and the
passivation of defects inside the oxide matrix. It was also shown
that after the hot implants, nanostructures are already present in
the SiO2 lm. The thermal treatment at 500 1C gives the highest
PL intensity for both implanted ions, regardless of the implantation temperature. TEM images show that the mean size distribution of the nanoparticles increases with increasing annealing
temperatures. On the other hand, the annealing atmosphere does
not have any inuence on the Tb PL results.
For the Eu-implanted samples, we also have observed that the
implantation temperature increases the PL yield as compared
with the RT implants. However, the PL enhancement is smaller in
comparison with the Tb implanted samples. At variance with
what was observed for Tb, the annealing atmosphere plays a
major role in the Eu PL results. In fact samples annealed in N2
presented a broad PL band, ranging from 370 up to 840 nm. On
the other hand, the O2 anneal conserves the original shape of the
as-implanted spectra, that is: a broad PL band in the bluegreen
region together with sharp PL band in the red region. This feature
is due to the strong passivation effect of the oxygen atmosphere
together with its inuence in favoring the Eu3 state.
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