Please cite this article in press as: D. Timmerman, T. Gregorkiewicz, Mater. Sci. Eng. B (2009), doi:10.1016/j.mseb.2009.02.010
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Materials Science and Engineering B xxx (2009) xxx–xxx
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Materials Science and Engineering B
journal homepage: www.elsevier.com/locate/mseb
Space-separated quantum cutting in differently prepared solid-state dispersions
of Si nanocrystals and Er
3+
ions in SiO
2
D. Timmerman
*
, T. Gregorkiewicz
Van der Waals-Zeeman Institute, University of Amsterdam, Valckenierstraat 65, NL-1018 XE Amsterdam, The Netherlands
article info
Article history:
Received 2 May 2008
Received in revised form 11 February 2009
Accepted 13 February 2009
Keywords:
Silicon
Erbium
Excitation
Quantum structures
Photoluminescence
Quantum cutting
Optical properties
abstract
We investigate the efficiency of Si nanocrystal-mediated photoluminescence of Er
3+
ions in SiO
2
as a
function of quantum energy of incoming photons. We demonstrate that for identical nanocrystals the
threshold energy of the recently reported space-separated quantum cutting effect does not change with
the nanocrystal-to-Er distance. In contrast, the enhancement of excitation efficiency observed above the
threshold, in the high-energy photon regime, diminishes at larger separations, thus exhibiting a clear
nanocrystal-to-Er distance dependence.
© 2009 Elsevier B.V. All rights reserved.
1. Introduction
One way of improving the optical properties of indirect semi-
conductors is by reducing their dimensionality, e.g. by forming
nanocrystals (NCs). When the size of a structure becomes compara-
ble to the size of the Bohr radius of an exciton in the used material,
quantum confinement effects will set in and alter the electronic
structure [1]. Following Heisenberg’s uncertainty principle, spatial
localization of carriers will decrease the momentum determina-
tion. As a result, k is not a good quantum number anymore. In this
way, the k-conservation rule, which severely inhibits rate of radia-
tive transitions in indirect bandgap semiconductors like silicon, will
relax and the probability for them to take place will increase. In this
way, nanostructuring opens the way for silicon-based photonics.
For Si-NCs it is generally accepted that the emission of photons
is due to band-to-band recombinations of quantum confined e–h
pairs [2]. It is possible to create an e–h pair in a NC by absorption
of a photon. Since the absorption cross-section of silicon grows
for shorter wavelengths, it is frequently inferred that short exci-
tation wavelengths are necessary for efficient photoluminescence
(PL) from Si-NCs.
When the Si-NCs are incorporated in SiO
2
together with Er
3+
ions, they can act as sensitizers of erbium-related luminescence
[3–5]. In this case the NCs, which have been excited by a photon,
*
Corresponding author.
E-mail address: d.timmerman@uva.nl (D. Timmerman).
can transfer their energy to neighboring Er
3+
ions and bring them
in an excited state. Because the excitation of the Er
3+
ions pro-
ceeds via the Si-NCs, it is expected that the generation efficiency of
erbium-related luminescence will also grow for shorter excitation
wavelengths.
2. Space-separated quantum cutting
In order to study the energy transfer process between Si-NCs
and Er
3+
ions, we performed PL excitation measurements on solid
dispersions of small Si-NCs (average diameter 3.1 nm) embedded in
a SiO
2
matrix. Some of the dispersions were doped with Er
3+
ions
(details of the fabrication procedure can be found in Ref. [6]). In
the experiments, we followed the efficiency of the luminescence
for different excitation wavelengths of either exciton-related PL, in
the samples containing only Si-NCs, or the erbium-related PL in co-
doped samples. Subsequently, these measurements were compared
with separately measured absorbance to determine the relative
quantum efficiency with which absorbed photons are contribut-
ing to the luminescence. From these investigations, we concluded
on the occurrence of a process of space-separated quantum cutting
(SSQC) [7] in which absorption of the single high-energy photon
might result in formation of two excitons in two neighboring, NCs,
or induce excitation of two Er
3+
ions:
1. NC-PL: When the quantum energy of the incoming photon
exceeds two times the nanocrystal bandgap two excitons per
one absorbed photon might be generated. Moreover, in contrast
0921-5107/$ – see front matter © 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.mseb.2009.02.010