DOI: 10.1002/adma.200600118
The Microemulsion Synthesis of Hydrophobic
and Hydrophilic Silicon Nanocrystals**
By Richard D. Tilley* and Kenji Yamamoto
1. Introduction
Research in the field of semiconductor nanocrystals synthe-
sized in the liquid phase has been intense since the formation
of CdSe quantum dots by Murray et al. in 1993.
[1]
Like CdSe
quantum dots, silicon particles have intense visible lumines-
cence because of quantum confinement, as first reported in
porous silicon by Canham.
[2]
The most promising applications
include biological imaging agents,
[3–8]
optoelectronic devices,
and photovoltaic devices.
[9–13]
The main difference between
quantum dots made in solution and those made in the vapor
phase is that those in solution are capped or coated by surface
molecules. Thus, applications best suiting solution-phase
quantum dots are those where the presence of a coating of
surface molecules is an advantage rather than a hindrance.
For example, particles capped with hydrophobic groups misci-
ble with conducting polymers could be used in the manufac-
ture of optoelectronic devices.
Quantum dots are becoming popular as replacements for
fluorescent dyes in biological fluorescence imaging because of
their superior resistance to photobleaching. To date, consider-
able emphasis has been placed on using CdSe quantum dots
with a ZnS shell as biological chromophores, since they emit
light that can be tuned throughout the visible spectrum.
[1]
However, concerns have been raised about the toxicological
issue of quantum dots in living systems. Quantum dot toxicity
can stem from two sources: i) the quantum dot core, and
ii) the capping molecule. A recent study by Derfus et al.
showed that quantum dots with a CdSe core and without a
ZnS shell, after exposure to UV light, were toxic to liver
cells.
[14]
The potential biocompatibility of silicon makes
photoluminescent silicon-core quantum dots an ideal candi-
date for biological fluorescence imaging and should eliminate
any potential toxicology problems of quantum dots that might
arise from having a CdSe core.
[15]
For quantum dots to be used
as fluorescence imaging agents in biological systems, surface
capping is of critical importance to produce particles that are
hydrophilic and biologically compatible.
The solution-phase synthesis of silicon nanocrystals has
been previously reported by Kauzlarich and co-workers using
a variety of reducing agents,
[16,17]
by Korgel and co-workers at
high temperatures
[18,19]
and pressures, and by Wilcoxon et al.
RESEARCH NEWS
Silicon nanocrystals, also called quantum dots, have unique optical
properties when in the quantum-confinement regime. These optical
properties make silicon nanocrystals promising materials for a wide
variety of applications ranging from optoelectronic devices to fluoro-
phores in biological imaging. A liquid-phase synthetic approach is re-
ported using surfactant molecules to control particle growth, producing
highly monodisperse silicon particles. The surface of the nanocrystals
are capped by functional organic molecules that passivate and protect
the silicon particles from oxidation, enabling the particles to be used in hydrophobic and hydro-
philic applications. The use of hydrophilic silicon quantum dots as optical probes is illustrated
by the imaging of Vero cells.
–
[*] Dr. R. D. Tilley
School of Chemical and Physical Sciences
MacDiarmid Institute of Advanced Materials and Nanotechnology
Victoria University of Wellington
P.O. Box 600, Wellington (New Zealand)
E-mail: Richard.tilley@vuw.ac.nz
Prof. K. Yamamoto
Department of Medical Ecology and Informatics, Research Institute
International Medical Center of Japan
Toyama 1-21-1, Shinjuku, Tokyo 162-8655 (Japan)
[**] The authors thank Jamie Warner, Akiyoshi Hoshino, and Amane
Shiohara for contributing to this research. R. D. T. thanks the Mac-
Diarmid Institute of Advanced Materials and Nanotechnology for
funding.
Adv. Mater. 2006, 18, 2053–2056 © 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim 2053