Appl. Phys. A 69, 3–12 (1999) / Digital Object Identifier (DOI) 10.
1007/s003399900087
Invited paper
The excitation mechanism of rare-earth ions in silicon nanocrystals
G. Franzò1 , V. Vinciguerra2 , F. Priolo2
1 CNR-IMETEM, Stradale Primosole 50, I-95121 Catania, Italy
(Fax: 39-095/713-9154, E-mail: franzo@imetem.ct.cnr.it)
2 INFM and Dipartimento di Fisica dell’Università, Corso Italia 57, I-95129 Catania, Italy
(Fax: 39-095/383-023, E-mail: priolo@ct.infn.it)
Received: 9 April 1999/Accepted: 10 April 1999/Published online: 2 June 1999
Abstract. A detailed investigation on the excitation mechan-
isms of rare-earth (RE) ions introduced in Si nanocrystals (nc)
is reported. Silicon nanocrystals were produced by high-dose
80-keV Si implantation in thermally grown SiO2 followed by
1100 ◦ C annealing for 1 h. Subsequently some of the samples
were implanted by 300-keV Er, Yb, Nd, or Tm at doses in
the range 2 × 1012 –3 × 1015 /cm2 . The energy was chosen in
such a way to locate the RE ions at the same depth where
nanocrystals are. Finally an annealing at 900 ◦ C for 5 min
was performed in order to eliminate the implantation dam-
age. These samples show intense room-temperature lumines-
cence due to internal 4 f shell transitions within the RE ions.
For instance, luminescence at 1.54 µm and 0.98 µm is ob-
served in Er-doped nc, at 0.98 µm in Yb-doped nc, at 0.92 µm
in Nd-doped nc and two lines at 0.78 µm and 1.65 µm in
Tm-doped nc. Furthermore, these signals are much more
intense than those observed when RE ions are introduced
in pure SiO2 in the absence of nanocrystals, demonstrating
the important role of nanocrystals in efficiently exciting the
REs. It is shown that the intense nc-related luminescence at
around 0.85 µm decreases with increasing RE concentration
and the energy is preferentially transferred from excitons in
the nc to the RE ions which, subsequently, emit radiatively.
The exact mechanism of energy transfer has been studied
in detail by excitation spectroscopy measurements and time-
resolved photoluminescence. On the basis of the obtained
results a plausible phenomenological model for the energy
transfer mechanism emerges. The pumping laser generates
excitons within the Si nanocrystals. Excitons confined in the
nc can either give their energy to an intrinsic luminescent cen-
ter emitting at around 0.85 µm nor pass this energy to the RE
4 f shell, thus exciting the ion. The shape of the luminescence
spectra suggests that excited rare-earth ions are not incorpo-
rated within the nanocrystals and the energy is transferred
at a distance while they are embedded within SiO2 . Rare-
earth excitation can quantitatively be described by an effect-
ive cross section σeff taking into account all the intermediate
steps leading to excitation. We have directly measured σeff for
Er in Si nc obtaining a value of ≈ 2 × 10−17 cm2 . This value is
much higher than the cross section for excitation through dir-
ect photon absorption (8 × 10−21 cm2 ) demonstrating that this
Applied Physics A
Materials
Science & Processing
 Springer-Verlag 1999
process is extremely efficient. Furthermore, the non-radiative
decay processes typically limiting rare-earth luminescence in
Si (namely back-transfer and Auger) are demonstrated to be
absent in Si nc further improving the overall efficiency of
the process. These data are reported and their implications
discussed.
PACS: 76.30.Kg; 7.55.-m; 61.72.Tt
Silicon, the leading semiconductor in the microelectronics in-
dustry, has for a long time been considered unsuitable for
optoelectronic applications which remained the domain of
III-V semiconductors and glass fibers. This is mainly due to
the silicon indirect band gap, which makes it a poor emitter,
and to the absence of linear electro-optic effects. The enor-
mous progress in communication technologies in recent years
resulted in an increased demand for optoelectronic functions
integrated with electronic circuits. This would allow us to
couple the information processing capabilities of microelec-
tronics with the efficient interconnection properties of op-
toelectronics. In principle, silicon would be the material of
choice, due to its mature processing technology and to its
unrivaled domain in microelectronics, the main limiting step
being the absence of efficient Si-based light sources.
Recently a strong effort has hence been devoted to study
all of those processes able to circumvent the physical inability
of silicon to emit light [1]. Since the discovery of light emis-
sion from porous silicon made in 1990 by Canham [2] a lot of
work has been performed in studying silicon nanostructures.
These comprise not only porous silicon but also nanocrystals
produced by several techniques [3–10], as well as silicon-
insulator multilayers [11, 12]. The initial problems related to
the instability of the luminescence yield have finally been
solved and today reliable, stable structures, compatible with
the silicon technology have been fabricated. In particular, the
group at Rochester University has now produced silicon-rich
silicon dioxide electroluminescent devices integrated with sil-
icon microelectronic circuitry [13]. Alternative approaches
comprise the doping of silicon with rare earths [14–22]. In
this case the luminescence is due to an internal 4 f shell
4
transition of the rare-earth ion excited through electron–hole
recombinations within the silicon matrix. Among rare earths
Er ions have been most widely studied since they emit light
at 1.54 µm, a wavelength that is strategic in the telecommuni-
cation technology matching the window of maximum trans-
mission for the optical fibers. The initial problems related
to erbium incorporation and luminescence quenching have
been now understood. In particular, it has been shown that
Er excitation occurs very efficiently in Si (with a cross sec-
tion of 3 × 10−15 cm2 , to be compared with the cross section
for direct photon absorption of 8 × 10−21 cm2 ) demonstrating
that, in principle, Er luminescence in Si can be very effi-
cient [17]. The main limiting step has been recognized in the
non-radiative decay channels, back-transfer (with the energy
transferred back from excited Er to electron–hole couples)
and Auger (with the energy released to free carriers) [16, 17].
Nevertheless Er:Si devices operating at room temperature,
with efficiencies of 0.1% and modulation speed of 10 MHz,
have been fabricated [18–22].
In these last years an increasing interest has been dedi-
cated to rare-earth-doped nanocrystals [23–26]. Si nanocrys-
tals embedded within Si dioxide emit light in the visible due
to the recombination of confined excitons within the nanos-
tructure [3–10]. When rare-earth ions are also introduced in
the matrix by a co-sputtering technique an interaction can
occur between the nanocrystal and the rare earth with the
energy preferentially transferred from the nanocrystal to the
rare earth, which subsequently de-excites radiatively [23–
26]. Many points appear of extreme interest in this process.
First of all the nanocrystals seem to act as efficient sensitiz-
ers for the rare earth which is excited much more efficiently
than in pure silicon dioxide. Indeed, room-temperature lumi-
nescence yields two orders of magnitude higher are observed
for Er-doped SiO2 in the presence of nanocrystals than in
pure SiO2 [23]. Moreover, since Er is now embedded within
a larger gap matrix the non-radiative decay channels typic-
ally limiting Er luminescence in Si, back-transfer and Auger
de-excitations, might be absent in this case. This further im-
proves the luminescence yield. This system holds high poten-
tial since it is possible to think of applications where an am-
plifier is made by waveguides containing Er-doped nanocrys-
tals with an Er excitation enhanced with respect to typical
waveguides. Indeed, amplification properties have recently
been verified [26]. A lot of interest exists also from a funda-
mental point of view since little is known on the nanocrystal–
rare-earth interaction and on the mechanisms leading to the
energy exchange.
In this paper we study in some detail the interaction be-
tween nanocrystals and rare earths co-introduced in a SiO2
matrix by ion implantation. Several different cases are ex-
plored both in terms of concentration and atomic species
(namely Er, Yb, Tm, and Nd). It is shown that intense, sharp,
room-temperature luminescence, whose wavelength can be
properly tuned by changing the rare-earth ion, can be ob-
tained in all cases. The non-radiative de-excitation processes
are demonstrated to be absent, while the energy transfer
mechanisms are investigated. Though the interaction depends
on the particular rare earth, many general features are present.
On the basis of the experimental data a plausible phenomeno-
logical model on the energy exchange between rare earths and
nanocrystals is proposed. The impact of these results will be
eventually discussed.
1 Experimental
Silicon nanocrystals were formed by 80-keV Si implantation
to a dose of 1 × 1017 /cm2 into a 400-nm-thick Si dioxide
layer thermally grown onto crystalline Si. This implantation
energy locates the Si atoms at around 110 nm from the sample
surface. Nanocrystal formation was induced by precipitation
of the Si atoms during an 1100 ◦ C annealing for 1 h under ni-
trogen atmosphere. Nanocrystals were subsequently observed
by high-resolution transmission electron microscopy showing
that their maximum size was ≈ 3 nm. Some of the samples
were also implanted by 300-keV Er, Yb, Nd, or Tm at dif-
ferent doses in the range 2 × 1012 –3 × 1015 /cm2 . The energy
of these implants was chosen in such a way to have a pro-
jected range of ≈ 110 nm, in order to locate the rare earths at
the same depth where the nanocrystals are. Finally samples
were further annealed at high temperature to remove the dam-
age of these latter implants. Several treatments were used but
900 ◦ C/5 min in nitrogen flux showed to be the one giving the
best luminescence performances.
Photoluminescence (PL) measurements were performed
by pumping with the 488-nm line of an Ar-ion laser. The
pump power was varied between 0.5 and 500 mW over a cir-
cular area of ≈ 1 mm in diameter and the laser beam was
mechanically chopped at a frequency of 10 Hz. The lumines-
cence signal was collected with two lenses focusing it on the
entrance slit of a single-grating monochromator and it was de-
tected either by a photomultiplier tube or by a liquid-nitrogen-
cooled Ge detector. Spectra were recorded with a lock-in
amplifier with the chopper frequency as a reference. All spec-
tra have been corrected for the detector response. Lumines-
cence lifetime measurements were performed by monitoring
the decay of the PL signal after pumping to steady state and
mechanically switching off the laser beam. The overall time
resolution of our system is 30 µs. Low-temperature meas-
urements were performed by using a closed-cycle liquid He
cooler system with the samples kept in vacuum.
2 Results and discussion
2.1 Photoluminescence
Figure 1 shows the room-temperature PL spectra of Er-
implanted Si nanocrystals at different Er doses and at a pump
power of 50 mW. In the absence of Er a well-known signal at
around 0.85 µm is observed coming from the Si nanocrystals
(dashed line) as a result of confined exciton recombination, in
agreement with literature data [3–10]. As soon as Er is intro-
duced, also at doses as small as 2 × 1012 /cm2 , the signal from
Si nanocrystals at 0.85 µm is seen to decrease, while a new
peak at around 1.54 µm, coming from the 4I13/2 → 4I15/2 intra
4 f shell Er transition, appears. With increasing Er dose this
phenomenon becomes particularly evident with a quench-
ing of the visible nanocrystal luminescence corresponding to
a simultaneous enhancement in the Er-related luminescence.
This effect is a demonstration of an energy transfer from the
excitons confined in the nanocrystals to the erbium ions.
In order to properly tune the luminescence wavelength
and understand the exact mechanism of energy transfer we
have also analyzed the effect of several other rare earths on
nanocrystal luminescence, namely Nd, Tm, and Yb. First of

Fig. 1. Room-temperature PL spectra of Er-implanted Si nanocrystals at
different Er doses. The pump power of the laser beam was 50 mW
all, the decrease in the visible nanocrystal luminescence with
increasing rare earth dose (shown in Fig. 1 for Er), appears
to be a general feature and is present in all cases. Moreover,
rare-earth-related luminescence peaks are observed to emerge
in all the luminescence spectra. Figure 2 shows the room-
temperature PL spectra of Si nanocrystals doped at a dose of
3 × 1015 /cm2 with Er (a), Nd (b), Tm (c), and Yb (d). At
this higher Er dose (Fig. 2a) the nanocrystal-related lumines-
cence has been almost completely quenched. Together with
the 1.54-µm peak, however, a luminescence peak at around
0.98 µm due to the transition 4I11/2 → 4I15/2 emerges. Note
that in pure SiO2 the luminescence intensity at 1.54 µm is two
orders of magnitude smaller, whereas the peak at 0.98 µm is
totally absent. This further demonstrates the efficiency of Er
luminescence in the presence of Si nanocrystals. In the case
of Nd (Fig. 2b) two clear Nd-related peaks, due to transitions
Fig. 2a–d. Room-temperature PL spectra of Er (a), Nd (b), Tm (c), and
Yb (d) implanted Si nanocrystals. In all cases the rare-earth dose was
3 × 1015 /cm2 . Spectra were taken at a pump power of 200 mW. The rare
earths internal 4 f shell transitions leading to the observed luminescence
peaks are also reported
5
between the Stark-split 4F3/2 and 4I9/2 4 f shell multiplets,
appear at around 0.92 µm. These peaks can also be observed
in Nd-doped pure SiO2 , however in that case the intensity is
more than a factor of 5 less. Moreover, in SiO2 no signal is
observed by pumping with the 488 nm line and, with an Ar-
ion pumping laser, a signal can be observed only with the
514.5 nm line, which is in resonance with the direct absorp-
tion of the Nd3+ 4 f shell. In contrast, in Nd-doped nanocrys-
tals only a weak dependence on the excitation wavelength
is observed, demonstrating, once more, that excitation is not
a direct photon absorption process (as in insulator hosts) but
is mediated by excitons in the nanocrystals. In the case of
Tm (Fig. 2c) two different peaks at 0.78-µm ( 3F4 → 3H6) and
1.65-µm ( 3H4→ 3H6) appear, and finally for Yb (Fig. 2d)
a typical peak (coming from the 2F5/2 → 2F7/2 transition)
emerges at 0.98 µm.
The temperature dependence of all of these rare-earth-
related peaks (excluding those Tm-related) is very weak
(Fig. 3). In fact, the PL intensity decreases by less than a fac-
tor of three in the temperature range 17 K – 300 K in all cases,
excluding Yb where a slightly stronger quenching (a factor
of 8) is observed. This behavior is very different from what
occurs in a Si host (in which strong temperature quenching
occurs) and suggests that non-radiative decay processes play
a minor role in the present case. Totally different is the case
of Tm. The temperature dependence of the two Tm-related
peaks is reported in Fig. 4 and shows quite interesting fea-
tures. Whereas the 0.78-µm signal intensity increases with
decreasing temperature, the peak at 1.65 µm has an opposite
temperature dependence: it has its highest value at 300 K, de-
creases with decreasing temperature, and it disappears below
100 K. These data are plotted against the temperature in Fig. 5
where it is clear that the PL intensities of the two lines have
just opposite dependencies. Whereas a decrease in PL inten-
sity with increasing temperature is a typical result, the oppo-
site behavior of the 1.65-µm line is quite surprising and might
be due to one of three different processes: (i) a reflection of
a peculiar temperature dependence of Tm excitation, with Tm
excited preferentially at higher temperatures, (ii) a reverse
temperature dependence of the non-radiative de-excitation
processes, with higher rates of non-radiative processes at
lower temperatures, (iii) a temperature-dependent internal
Fig. 3. PL intensity vs. reciprocal temperature for Er-doped (at λ = 1.54 µm
and λ = 0.98 µm), Yb-doped (at λ = 0.98 µm), and Nd-doped (at λ =
0.92 µm) nanocrystals. Data are normalized to their value at 17 K
6
Fig. 4a,b. Tm-related luminescence spectra in Si nanocrystals at around
0.78 µm (a) and 1.65 µm (b) at different temperatures. The Tm dose was
3 × 1015 /cm2 and the laser pump power 200 mW
Fig. 5. Temperature dependence of the Tm-related luminescence peaks in
Tm-doped Si nanocrystals
balance between different competitive radiative decay routes
within the Tm 4 f shell. Process (i) can be excluded since
a temperature-dependent excitation should have had a simi-
lar effect also on the 3F4 → 3H6 decay leading to the 0.78 µm
line. Process (ii) can be experimentally tested by measuring
the temperature dependence of the decay time of the 1.65 µm
luminescence. We have performed these measurements and
obtained a value of 300 µs, independent of temperature in
the range 180–300 K. Since in this range the luminescence
intensity varies, these results prove that such variations are
not associated with the presence of non-radiative processes.
The last remaining possibility is process (iii). Since this pro-
cess is related to the internal configuration of the Tm 4 f
shell it should be almost independent of the host material. We
have therefore studied Tm luminescence in a different host.
Since no Tm signal can be obtained in either Si and SiO2 ,
we have analyzed the Tm signal directly from Tm2 O3 pow-
der. Indeed, also in this case, the 0.78-µm line decreases with
increasing temperature whereas the 1.65-µm line has just the
opposite behavior. The anomalous temperature dependence
of Tm is therefore an effect of an internal redistribution within
the Tm 4 f shell which favours the 3F4 → 3H6 transition (at
0.78 µm) at low temperatures and the 3H4→ 3H6 transition
(at 1.65 µm) at high temperatures.
A few general observation need to be done. First of all it
should be noted that the 0.98-µm peak of Er, the 0.92-µm
peak of Nd, the 0.98-µm peak of Yb, and the 0.78-µm peak
Fig. 6. Dependence of the PL intensity on the pumping laser excitation
wavelength. Data are shown for undoped Si nanocrystals (at λ = 0.85 µm),
and for Er-doped (at λ = 1.54 µm and λ = 0.98 µm), Yb-doped (at λ =
0.98 µm), Nd-doped (at λ = 0.92 µm), and Tm-doped (at λ = 0.78 µm and
λ = 1.6 µm) Si nanocrystals. All data are taken at room temperature and at
a pump power of 50 mW. The different sets of data are normalized among
themselves in order to compare the trends. The continuous line is a guide
to the eye
of Tm cannot be observed in crystalline Si since their en-
ergy is greater than the Si band gap and therefore they cannot
be excited. The observation we have just reported here is an
effect of the band gap enlargement due to quantum confine-
ment. Most of these signals can also be observed in pure SiO2
without nanocrystals (excluding the 0.98-µm peak of Er and
those of Tm that are observed only in presence of nanocrys-
tals), but their intensities are much smaller (a factor of 50 less
in the case of the 1.54-µm line of Er, a factor of 5 for Nd, and
a factor of 4 for Yb). This demonstrates that the nanocrystal
mediated excitation is in all cases much more efficient than
pure photon absorption. Indeed, the dependence on excita-
tion wavelength is quite instructive. In Fig. 6 we show on the
same plot the variation of excitation wavelength of several
PL intensities measured on different samples. All intensities
are taken at room temperature, at a pump power of 50 mW,
and are normalized among the different samples in order to
compare the trends. Data for pure Si nanocrystals (at λ =
0.85 µm), for Er-doped nanocrystals (at λ = 1.54 µm and λ =
0.98 µm), for Yb-doped nanocrystals (at λ = 0.98 µm), for
Nd-doped nanocrystals (at λ = 0.92 µm), and for Tm-doped
nanocrystals (at both λ = 0.78 µm and λ = 1.65 µm) are re-
ported. It is extremely interesting to note that the general
trend is similar in all cases and resemble the excitation wave-
length dependence of the nanocrystal signal. This is a clear
evidence that in all cases excitation is mediated by excitons in
the nanocrystals. The increase in PL intensity with decreasing
excitation wavelength is the result of the fact that at shorter
wavelengths also smaller nanocrystals (with larger gap) can
be excited and therefore the number of centers able to transfer
energy to the rare earths increases.
2.2 Energy transfer mechanism
A few questions arise on the basis of the results reported
above. First of all it is interesting to understand where the
rare earths are located. The shape of the rare-earth-related
PL spectra is very similar to that observed in Si dioxide and

clearly differs from the shape in Si (for Er which is the only
one showing PL in Si). Since this shape depends on the Stark
splitting which, in turn, reflects the crystal field around Er
and hence its chemical surrounding, these data suggest that
the emitting rare earths are indeed within SiO2 . As a mat-
ter of fact, the excited rare earths do not need to be within
the nanocrystals since they can be excited also if they are
close to the nanocrystals. We have estimated that the average
distance between nanocrystals is ≈ 1–2 nm. Hence, the dis-
tance between a rare earth and a nanocrystal is, in any case,
smaller. It is well known that in rare earths energy can be
transferred from one another at a distance. For instance, in
Er-doped SiO2 , Er ions transfer their energy between them-
selves at concentrations above 3 × 1020 /cm3 [27], corres-
ponding to a mutual Er–Er distance of ≈ 1.5 nm. A similar
energy transfer among different nanocrystals has also been
proposed [28]. It is therefore plausible to think that an exci-
ton in a nanocrystal recombines giving its energy to a rare
earth close by (embedded in silicon dioxide or at the Si/SiO2
interface).
A second issue concerns the actual mechanism of energy
transfer. Indeed, in Fig. 1 the nanocrystal luminescence at
around 0.85 µm decreases as the Er concentration increases.
This behavior suggests that the two processes are in competi-
tion: in the absence of Er the exciton recombines radiatively,
in the presence of Er the energy transfer to the Er 4 f shell
takes over. If this picture is correct one might expect that,
as the Er concentration increases, not only the nanocrystal
PL signal decreases, but also its decay time. In fact, if the
energy is preferentially transferred to Er, the energy trans-
fer process should be faster than the radiative recombination
of the exciton. The exciton lifetime then decreases. The de-
cay time of the signal at 0.85 µm should reflect the exciton
lifetime and one can expect its decrease with increasing Er
content. In this way, in principle, one should be also able to
measure the average time of energy transfer to the rare earth.
We have therefore performed lifetime measurements of the
0.85-µm nanocrystal signal in the absence of Er and with in-
creasing Er concentration. The results are reported in Fig. 7.
In the absence of Er the lifetime is around 130 µs. Surpris-
ingly, with increasing Er content, in spite of the decrease of
the luminescence at 0.85 µm (see Fig. 1), no change in life-
Fig. 7. Time decay curves of the nanocrystal-related luminescence at
0.85 µm in the absence of Er and for different Er contents. The system
response is also reported. Data were taken by pumping to steady state at
50 mW and mechanically switching off the laser beam at t = 0
7
Fig. 8. Plausible scenario for the energy transfer process. An exciton within
a Si nanocrystal can transfer its energy either to an intrinsic luminescent
center or to the rare earth. The two processes are in competition with one
another
time is observed (see Fig. 7). This result has been confirmed
by measuring the nanocrystal luminescence lifetime also in
the presence of other rare earths and it therefore demonstrates
that the energy transfer has general characteristics. The be-
havior is however very different from what is expected.
Recently several authors have proposed [9, 10] that
nanocrystal luminescence is not due to direct exciton recom-
bination. According to their model the laser energy is ab-
sorbed by electron–hole pairs confined within the nanocrys-
tal, this energy is subsequently transferred to a luminescent
center that they proposed being located at the interface be-
tween the nanocrystal and SiO2 . Therefore, although the
absorption depends on pumping wavelength (the shorter the
wavelength the more nanocrystals can be excited), the radia-
tive emission occurs at smaller energy with respect to the
theoretically predicted nanocrystal band gap and is due to
an intrinsic luminescent center. This picture clearly explains
the decay time data of Fig. 7. In fact, the process depicted in
Fig. 8 emerges as a plausible mechanism. Confined excitons
within the nanocrystals are excited by the pumping laser. Ex-
citons can transfer their energy to the intrinsic luminescent
centers. The presence of rare-earths provides an alternative
route for the energy transfer and, as the rare-earth concentra-
tion increases, it becomes the main transfer route. This is the
reason for the decrease of the 0.85-µm nanocrystal lumines-
cence (intrinsic center-related). However, there is no need for
a change in lifetime: in fact, fewer luminescent centers are ex-
cited, but those being excited can decay with an unchanged
decay time, in agreement with the experimental data.
2.3 Quantitative description
Based on the experimental data we have just presented we can
propose a quantitative phenomenological model of the exci-
tation processes leading to nanocrystal and rare-earth (RE)
excitations. According to this model the overall process can
be described by the following three rate equations:
dNexc Nexc
= σφN − , (1)
dt τ
dNc∗ Nexc N ∗
= c − cc , (2)
dt τtr τd
8
∗ ∗
dNRE NRE
= R∗ − RE . (3)
dt τd
Equation (1) describes the formation of excitons (Nexc ) within
the nanocrystals. Here the first term is the generation rate
proportional to a generation cross section σ, to the pumping
laser photon flux φ and to the nanocrystal concentration N.
The second term represents the exciton recombination with
a characteristic recombination time τ whose dependencies
will be discussed later on. Equation 2 describes the excitation
of the luminescent center (Nc∗ ) leading to the nanocrystal-
related luminescence at around 0.85 µm. The first term rep-
resents the excitation of the center (depicted in Fig. 8) pro-
portional to the exciton concentration through a character-
istic energy transfer time τtrc , whereas the second term de-
scribes its de-excitation with a typical time τdc (taking into
account both radiative and non-radiative de-excitation pro-
cesses). Finally, (3) describes the RE excitation through ex-
citon recombination and the de-excitation processes of the
∗ Clearly the steady-state exciton concentration decreases
excited RE ions. Here NRE represents the excited RE con-
∗
centration, R is the effective increase of the excited rare-
earth population through energy transfer from an exciton to
the appropriate excited state of the RE 4 f shell (for in-
stance, in the case of the 1.54-µm line of Er the first ex-
cited state 4I13/2 ) and τdRE is the decay time of excited RE
taking into account both radiative and non-radiative pro-
cesses. The luminescence intensity from the luminescent cen-
ters at 0.85 µm and from the RE will be given repectively
by:
Nc∗
Ic ∝ c , (4)
τrad
∗
NRE
IRE ∝ RE , (5)
τrad
τrad
c
and τrad
RE
being the radiative decay time of the center
and of the excited RE, respectively. The determination of
the luminescence intensities, therefore, consists in the deter-
mination of the concentration of excited centers (Nc∗ ) and
excited RE ions (NRE ∗
) through the resolution of the rate (1)–
(3).
Let’s first find the steady-state solutions for these equa-
tions. As far as (1) is concerned the solution is simply:
Nexc = σφNτ. (6)
Therefore the steady-state exciton population is propor-
tional to the concentration of nanograins, to the generation
cross section, to the photon flux, and to the recombination
time τ. A question arises on what are the processes affecting
the value of τ. Following our description reported in Fig. 7
we assume that an exciton can recombine either by giving
its energy to the luminescent center (associated with each
nanograin) with the characteristic transfer time τtrc or by ex-
citing a RE ion. These two processes are in competition one
another. Of course the transfer of energy to a RE ion depends
on the availability of such an ion close to the exciton in the
nanograin. We can describe this transfer through an effective
interaction time τtreff equal to:
τtrRE
τtreff = . (7)
NRE Λ
In this formula NRE is the total RE concentration and we
describe the exciton rare-earth interaction through an interac-
tion volume Λ. Only those RE ions being inside the volume
Λ can absorb energy from the exciton with a transfer time
per ion of τtrRE . Hence NRE Λ represents the average number
of RE ions contained within the volume Λ. Note that all the
rare-earth ions can be excited and those that are already in
an excited state can be further excited to a higher state. The
exciton recombination time τ will then be given by:
1 1 1
= eff + c . (8)
τ τtr τtr
The steady-state exciton concentration of (6) can hence be
written as:
τtreff τtrc
Nexc = σφN . (9)
τtreff + τtrc
as τtreff decreases, i.e. as the RE concentration increases, as
a result of a new possible recombination route. This effect,
in turn, affects the steady-state population of excited lumines-
cent centers Nc∗ . In fact, the steady-state solution to (2) is:
τdc τtreff τdc
Nc∗ = Nexc c = σφN eff , (10)
τtr τtr + τtrc
where we have used the results of (9). From the data shown
in Fig. 1 we know that as the RE concentration increases the
transfer of energy from the exciton to the RE ions (in a time
τtreff ) becomes the dominant mechanism with respect to the
transfer from the exciton to the luminescent center at 0.85 µm
(with a time τtrc ). Therefore, as NRE increases, τtreff becomes
much smaller than τtrc . In this regime the luminescence inten-
sity of the centers at steady steady is described by:
Nc∗ 1 τtreff τdc
Ic ∝ = σφN (11)
τrad
c
τrad
c
τtreff + τtrc
τ c τ eff τc τ RE
≈ σφN dc tr c = σφN c d c tr ,
τrad τtr τrad τtr NRE Λ
where we have used (4), (7), and (10). It is interesting to note
that the nanocrystal luminescence intensity decreases with
increasing RE concentration in agreement with the experi-
mental data.
Let’s now analyze the RE luminescence intensity. In order
to do that, according to (5), we should first solve the rate (3)
and find a solution for the RE population in the appropriate
excited state from which luminescence occurs (NRE ∗
; for in-
4
stance in the case of the 1.54-µm line of Er the I13/2 state).
In order to solve (3) a plausible hypothesis should be made
for R∗ . This term represents the effective number of RE ex-
citations into the appropriate excited state (for example an Er
ion on the first excited state) per unit volume and time. It dif-
fers from Nexc /τtreff in that this latter rate takes into account all
excitations bringing the RE ion to one of the several excited
states. Of course, if a RE ion is excited into a highly excited
state it can subsequently decay to the appropriate excited state
(the first excited state in the case of Er). This process has how-
ever a certain probability to occur and not all of the excited
ions will do so. Moreover, we can also have that some of the
 9

excitons will excite to a higher state a RE ion that is already in We have now calculated the main features of the present
∗
the appropriate level thus decreasing the population NRE . We description. In the following section we will make a direct
can then assume that the effective excitation rate R∗ has the comparison with the experimental data.
following expression:
∗ ∗
Nexc (NRE − NRE )Λη Nexc NRE Λ 2.4 Comparison with the experiment
R∗ = − (1 − η) (12)
τtr
RE
τtr
RE
∗ We have measured the room-temperature pump power depen-
Nexc (ηNRE − NRE )Λ
= . dence of the 1.54-µm luminescence in Er-doped Si nanocrys-
τtr
RE
tals and the data, normalized to the maximum intensity, are
reported in Fig. 9. These data can be fitted by means of (15)
The first term in this expression represents the filling rate
using, as a unique fitting parameter, the product σeff τdRE . The
of the appropriate excited state. This will clearly be propor-
fit is also reported in the figure as a continuous line yielding
tional to the exciton population Nexc , to the concentration
∗ a value σeff τdRE = 5 × 10−20 cm2 s. An independent measure
of RE ions that are not already in that level (NRE − NRE ),
of the decay time of the Er luminescence in Si nanocrystals
to the volume of interaction Λ, divided by the transfer time
(τdRE ) would allow us to obtain σeff . We have indeed meas-
τtrRE , and multiplied by the probability η that, once excited,
ured this decay time by pumping the system to steady state
the RE will then decay populating the appropriate level. Note
and mechanically shutting the pump laser. The results are
that not all of the RE ions within the volume Λ can be
shown in Fig. 10 for both 17 K and 300 K and show a de-
excited to the appropriate state but only those that are not
∗ cay time of ≈ 3 ms. It is interesting to note that this decay
already in that state (i.e. (NRE − NRE )). Moreover, only a frac-
time of the luminescence at 1.54 µm is almost temperature
tion η (with η ≤ 1) of the excited ions will then decay to
the metastable appropriate excited state hence increasing the
∗
excited population NRE . The second term in (12) describes
∗
a decrease of NRE due to the fact that also a RE ion in
the appropriate level can be excited to a higher state, thus
depopulating that level. Of course a fraction η of these ex-
citations will then return to the initial metastable level thus
producing no net change in the rate, while a fraction (1 − η)
will be lost forever thus decreasing the effective excitation
rate.
The steady-state solution of (3), under the conditions de-
scribed in (12), and using the result of (6), will be:

∗ σeff τdRE φ
NRE = ηNRE , (13)
σeff τdRE φ + 1

where we have defined:

ΛNτ Fig. 9. PL intensity at 1.54 µm as a function of the pumping laser pho-
σeff = σ. (14) ton flux. Data are taken at room temperature in Er-doped Si nanocrystals
τtrRE implanted with 3 × 1015 Er/cm2 . Data are normalized to the maximum PL
intensity. Also shown, as a continuous line, a fit to the data with the model
σeff is the effective cross section for the excitation to the ap- described in the text
propriate level (the 4I13/2 level for erbium). It is the product
of several parameters since excitation of RE requires sev-
eral steps and represents the cross section for the overall
∗
process. The shape of the excited RE population (NRE ) as ob-
tained from (13) is quite interesting since it demonstrates that
the excited RE concentration increases with increasing pump
power φ. For small values of φ the increase is linear whereas
for high values of φ the excited concentration tends to satu-
rate towards the total amount of RE ions NRE multiplied by
the factor η
A similar behavior should be observed for the lumines-
cence intensity versus pump power (through (5)). In fact, the
luminescence intensity should behave according to the fol-
lowing expression:

IRE σeff τdRE φ

= , (15)
MAX
IRE σeff τdRE φ + 1
Fig. 10. Time decay of the PL intensity at 1.54 µm in Er-doped Si nanocrys-
MAX tals. Data are shown for both room temperature and 17 K
IRE being the saturation value.
10

independent. This demonstrates once more that non-radiative

processes, typically limiting Er luminescence in Si, are al-
most absent in the present case. Moreover, the small decrease
in PL intensity reported in the Fig. 3 (a factor of 3 between
17 K and 300 K) cannot be ascribed to non-radiative pro-
cesses and is hence a result of a small reduction in excita-
tion efficiency. Finally, by using the measured lifetime it is
therefore possible to obtain an independent estimate for σeff
of ≈ 1.7 × 10−17 cm2 . This is an extremely important value.
In spite of the fact that excitation requires several differ-
ent sequential steps (photon absorption from the nanocrystals
with exciton formation and transfer of the energy to the Er
4 f shell), the overall cross section for this process is three
orders of magnitude higher than the cross section for excita-
tion through direct photon absorption typically occurring for
Er in insulating hosts (8 × 10−21 cm2 [29]). This clearly ex-
Fig. 11. Time-resolved PL intensity at 1.54 µm when switching on the
plains why this process is so efficient. As a consequence of pumping laser at t = 0. Data are taken at room temperature and at different
this efficiency, saturation of the luminescence intensity is ob- pump powers. The sample is the same as in Fig. 8. Data are normalized to
served in Fig. 9 even at room temperature, demonstrating that the maximum intensity
most of the Er ions can indeed be excited thus achieving pop-
ulation inversion. It should be noted also that Er in Si has
a high excitation cross section (3 × 10−15 cm2 [17]); in that
case, however, this efficient excitation is counterbalanced by
the strong non-radiative processes absent in the present case.
Another interesting point to be addressed is the transient
behavior of the excited Er population. In particular, it is inter-
esting to verify the increase of the excited population as the
pumping laser is switched on. In order to calculate this it is
necessary to solve the rate (3). Though the general solution
can be obtained, we can gain important information by mak-
ing the further assumption that the exciton population reaches
its steady state much before the excited Er population. This
assumption is quite plausible. Under these conditions (3) can
be easily solved by inserting for Nexc its steady state value.
We hence obtain:
Fig. 12. Reciprocal of the τon time as obtained from the data in Fig. 9 as
∗ σeff τdRE φ a function of the pump laser photon flux. The slope gives the effective cross
NRE (t) = ηNRE (16) section for Er excitation
σeff τdRE φ + 1
    
1
× 1 − exp − σeff φ + RE × t . to the vertical axis should correspond to the reciprocal of the
τd
lifetime and indeed yields a value for τdRE of 2.7 ms, in agree-
The excited Er population (and hence the luminescence ment with the data of Fig. 10. It is noteworthy that we have
intensity through (5)) should increase with a characteristic measured very similar σeff values with totally independent
time τon given by: methods. These results give confidence on the applied pro-
cedure and demonstrate the high efficiency of Er excitation
1 1 through energy transfer by Si nanocrystals.
= σeff φ + RE . (17)
τon τd We would like to make a few more comments. The cross
section we have just determined is the probability of Er ex-
Therefore the increase in PL intensity should become citation mediated by Si nanocrystals and hence it represents
faster and faster as the pump power is increased. Moreover, a lower limit for the cross section of the nanocrystal ex-
from such a measurement we can obtain an independent esti- citation itself. Though this last cross section is not known
mate of the effective cross section of excitation. one can make a very rough estimate. In fact, for a spher-
We have therefore measured the time-resolved increase of ical nanograin of diameter d = 3 nm, the area exposed to
the 1.54-µm PL intensity at different pump powers. These the photon beam is A = π(d/2)2. Within a single nanograin
signals, normalized to the steady state population at each a photon will travel for a depth d, hence if α is the absorption
pump power, are reported in Fig. 11. The τon time decreases coefficient, the cross section for a photon to be absorbed gen-
with increasing pump power in agreement with the predic- erating an exciton will simply be σ ≈ A × [1 − exp(−αd)].
tions of (17). From these data we have measured the τon We have no hint on the value of α in a Si nanograin but,
time at each pump power and reported its reciprocal value as as a first approximation, we can use the absorption coeffi-
a function of the pumping photon flux φ. These data are re- cient of bulk crystalline silicon at the pump wavelength of
ported in Fig. 12. The slope gives a value for the effective 488 nm. Doing so we obtain σ ≈ 4 × 10−16 cm2 . At an Er
cross section σeff of ≈ 2 × 10−17 cm2 . Moreover the intercept dose of 3 × 1015 /cm2 (corresponding to that used in the ex-

periments of Figs. 9–12) we have estimated that there are
≈ 20 Er ions per nanocrystal. The effective cross section for
Er excitation through nanocrystal absorption should there-
fore be, at maximum, 20 times less than the nanocrystal
excitation cross section, i.e. 2 × 10−17 cm2 . It is quite inter-
esting and instructive to note that this number, in spite of
the rough estimates made, is similar to that experimentally
determined.
A last observation: in the process we are describing a pa-
rameter that matters of course is the ratio between Er ions
and nanocrystals. At low Er doses there are more nanocrys-
tals than Er ions and, within each interaction volume Λ,
there is, at most, only one Er ion. In this regime the lu-
minescence intensity is limited by the Er concentration.
More complicated is the regime in which several rare-earth
ions need to be excited by the same nanocrystal. In this
regime, once the nanocrystal is excited, it can transfer the
energy only to one Er ion. However, if the photon flux is
high enough, the nanocrystal can be excited again while
the first Er is still in the excited state and hence a sec-
ond ion can be excited. In principle, if the photon flux is
sufficiently high, all of the ions within Λ can be brought
to the excited state by the same nanocrystal. The time be-
tween two different exciton formation in the same nanocrystal
will be 1/σφ. Using, as a first approximation, the esti-
mated value for σ we have that 1/σφ equals the Er lifetime
(≈ 3 ms) at a flux of ≈ 8 × 1017 photons/cm2s (corresponding
to ≈ 10 mW). Therefore, at pump powers below this pho-
ton flux one nanocrystal can have only one excited Er ion
at a time within its interaction volume. In this regime lumi-
nescence is limited by the concentration of the nanocrystals.
However, with increasing photon flux, the situation changes
and, eventually, several ions can be excited by the same
nanocrystal.
These observations support the idea that nanocrystals are
extremely efficient in acting as sensitizers in rare-earth lumi-
nescence since many rare-earth ions can indeed be excited by
a single excitation centre.
3 Summary
In conclusion, we have reported a detailed investigation on
the rare-earth luminescence in Si nanocrystals. We have
shown that rare-earth ions are excited very efficiently through
an energy transfer process from excitons confined within the
nanocrystals. Several general features can be recognized:
(i) the rare-earth luminescence in Si nanocrystals is much
more intense than that observed in pure SiO2 as a result
of a very efficient excitation process;
(ii) the rare-earth luminescence in Si nanocrystals is much
more intense than that observed in bulk crystalline Si
as a result of the absence of non-radiative de-excitation
processes;
(iii) the shape of the luminescence spectra suggests that the
excited rare-earth ions are not incorporated within the
nanocrystals and the energy is transferred at a distance
while they are embedded within SiO2 ;
(iv) wavelengths below 1 µm (for example 0.98 µm for Er,
0.98 µm for Yb, 0.92 µm for Nd, 0.78 µm for Tm) can
be excited in Si nanocrystals as a result of the widening
11
of the band gap due to confinement. These lines cannot
be observed in crystalline Si;
(v) the rare-earth-related luminescence temperature depen-
dence is generally weak as a result of reduced non-
radiative de-excitations. The only different case is Tm
in which, as result of an internal redistribution, the
1.65-µm line is seen to increase in intensity with in-
creasing temperature, whereas the 0.78-µm line has just
the opposite behavior;
(vi) the temperature dependence of the rare-earth-related lu-
minescence lifetime is very weak confirming the ab-
sence of non-radiative de-excitations;
(vii) with increasing rare-earth concentration the nanocrystal-
related luminescence at 0.85 µm decreases while the
rare-earth-related luminescence increases demonstrat-
ing the presence of an energy transfer. The decrease in
the 0.85-µm luminescence, however, is not associated
with a decrease in its decay time;
(viii) the excitation wavelength dependence of rare-earth-
related luminescence peaks follows exactly the de-
pendence of the nanocrystals related luminescence at
0.85 µm demonstrating, once more, that the energy is
transferred from the nanocrystals to the 4 f shell.
On the basis of these results a phenomenological model
on the excitation mechanisms has been proposed. The pump-
ing laser generates excitons within the Si nanocrystals. These
excitons can transfer their energy either to an intrinsic lumi-
nescent center emitting at around 0.85 µm or to a rare earth
close by, the two processes being in competition one another.
With increasing rare-earth concentration the 0.85-µm lumi-
nescence is hence quenched. The process leading to rare-earth
excitation needs several intermediate steps, it can however
be described by an effective cross section σeff taking into
account all of the different effects. Through time-resolved
measurements we have experimentally determined σeff in the
case of Er obtaining a value of ≈ 2 × 10−17 cm2 . This value
is much higher than the cross section for excitation through
direct photon absorption (8 × 10−21 cm2 ) typically present in
insulating hosts. This demonstrates that indeed nanocrystals
act as very efficient sensitizers for rare-earth ions embed-
ded within silicon dioxide. Moreover, since Auger and back-
transfer non-radiative de-excitations are absent, the overall
process is also much more efficient than rare-earth lumines-
cence within bulk crystalline silicon. These data demonstrate
that applications such as light amplification in waveguides
simultaneously containing nanocrystals and rare earths hold
great potentialities.
Acknowledgements. This work has been supported in part by the Project
LUNA by INFM, by the Project MADESS II by CNR and by the ESPRIT
Project SCOOP financed by the European Community.
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