9928 Langmuir 2000, 16, 9928-9935

Core-Shell (Ag)Au Bimetallic Nanoparticles: Analysis of

Transmission Electron Microscopy Images
Ivana Srnová-Šloufová,*,†,‡ František Lednický,‡ Antonı́n Gemperle,§ and
Juliana Gemperlová§
Department of Physical and Macromolecular Chemistry, Charles University, Hlavova 2030,
128 40 Prague 2, Czech Republic, Institute of Macromolecular Chemistry, Academy of Sciences
of the Czech Republic, Heyrovsky Sq. 2, 162 06 Prague 6, Czech Republic, and Institute of
Physics, Academy of Sciences of the Czech Republic, Na Slovance 2,
182 21 Prague 8, Czech Republic

Received July 6, 2000. In Final Form: September 18, 2000

Layered core-shell bimetallic silver-gold colloids in the size range of 10-16 nm have been prepared
by the seed-growth method. Silver nuclei were covered by gold shells of various thicknesses without any
stabilization agent. Interfacial (Ag)Au colloid-2,2′-bipyridine films were prepared from these bimetallic
colloids and used for the purpose of analysis of transmission electron microscopy (TEM) images and electron
diffraction. Both observed and calculated TEM images were used to characterize the prepared nanoparticles.
On the basis of the analysis of TEM images, the calculated TEM image contrast, and results obtained by
electron diffraction, energy-dispersive X-ray analysis, and other experiments, the core-shell structure of
the prepared (Ag)Au nanoparticles was revealed. Particles were found to consist of a silver core and a gold
shell enriched with silver.

Introduction of Pd and Pt, bimetallic colloids of gold and silver in

Bimetallic colloids, in which two kinds of metals are
contained in one particle, have unique catalytic, electronic,
and optical properties1-11 distinct from those of the
corresponding monometallic particles. Two main groups
of bimetallic colloids exist, alloys and layered (core-shell)
colloids. Bimetallic colloids can be prepared7 by simul-
taneous co-reduction of two kinds of metal ions with or
without the protective agent (usually a polymer or a
surfactant) or by successive reduction of one metal over
the nuclei of another. Preparations of bimetallic colloids
containing gold or silver in combination with other noble
metals have been published in numerous papers. They
are perspective substrates for surface-enhanced Raman
spectroscopy (SERS).12-15 Because of high catalytic activity
* To whom correspondence should be addressed. Fax: +4202
367 981. Tel: +4202 20403 310. E-mail: srnova@imc.cas.cz
† Charles University.
‡ Institute of Macromolecular Chemistry.
§ Institute of Physics.
(1) Chen, Y. H.; Nickel, U. J. Chem. Soc., Faraday Trans. 1993, 89,
2479.
(2) Toshima, N.; Harada, M.; Yamazaki, Y.; Asakura, K. J. Phys.
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R. M. J. Phys. Chem. 1995, 99, 6096.
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Chem.sEur. J. 1996, 2, 1099.
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(8) Aihara, N.; Torigoe, K.; Esumi, K. Langmuir 1998, 14, 4945.
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Natan, M. J. J. Phys. Chem. 1996, 100, 718.
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Bastl, Z. Manuscript in preparation.
combination with Pd and Pt have been studied in great
detail: Au-Pd2-5,16-21, Au-Pt17,22-24, Ag-Pd10,25-27, and
Ag-Pt.22,28
Ag-Au alloys were prepared by Esumi et al. in laponite
suspensions8 and in ethanol solution containing poly(N-
vinyl-2-pyrrolidone)9 (PVP). Teo et al.11 studied Au18Ag20
alloy clusters. Ag-Au colloids immobilized on imogolite
fibers were prepared by Liz-Marzan and Philipse.22 Shi
et al.29 synthesized Ag-Au alloys by putting Au and Ag
particles in monolithic mesoporous silica by a soaking and
annealing method. Hostetler et al.30 prepared alkanethi-
olate-protected Ag-Au alloy clusters that can be isolated
in solvent-free forms and redissolved. Simultaneous co-
reduction of AgNO3 and HAuCl4 with sodium citrate was
used for synthesis of Ag-Au alloys by Link et al.31 Han
et al.32 studied dodecanethiol-derivatized Ag-Au alloy
(16) Turkevich, J.; Kim, G. Science 1970, 873.
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Int. Ed. Engl. 1991, 30, 874.
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R.; Nagata, Y. J. Phys. Chem. B 1997, 101, 7033.
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D. M.; Valetsky, P. M.; Hartmann, J.; Wenz, E.; Antonietti, M. Chem.
Mater. 1997, 9, 923.
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91, 4111.
(22) Liz-Marzan, L. M.; Philipse, A. P. J. Phys. Chem. 1995, 99, 15120.
(23) Yonezawa, T.; Toshima, N. J. Mol. Catal. 1993, 83, 167.
(24) Schmid, G.; West, H.; Mehles, H.; Lehnert, A. Inorg. Chem. 1997,
36, 891.
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109, 55.
(26) Silvert, P.-Y.; Vijayakrishnan, V.; Vibert, P.; Herrera-Urbina,
R.; Elhsissen, K. T. Nanostruct. Mater. 1996, 7, 611.
(27) Torigoe, K.; Esumi, K. Langmuir 1993, 9, 1664.
(28) Torigoe, K.; Nakajima, Y.; Esumi, K. J. Phys. Chem. 1993, 97,
8304.
(29) Shi, H. Z.; Zhang, L. D.; Cai, W. P. J. Appl. Phys. 2000, 87, 1572.
(30) Hostetler, M. J.; Zhong, C. J.; Yen, B. K. H.; Anderegg, J.; Gross,
S. M.; Evans, N. D.; Porter, M.; Murray, R. W. J. Am. Chem. Soc. 1998,
120, 9396.
(31) Link, S.; Wang, Z. L.; El-Sayed, M. A. J. Phys. Chem. B 1999,
103, 3529.

10.1021/la0009588 CCC: $19.00 © 2000 American Chemical Society

Published on Web 11/10/2000
Core-Shell (Ag)Au Bimetallic Nanoparticles
Table 1. Characterization of (Ag)Au Colloids Including the EDX Analysisa
(Ag)Au-0.8
x mL of HAuCl4 and NH2OH‚HCl in preparation
the molar fraction of Au
mean particle diameter [nm] measured
calculated
mean diameter of bright centers [nm] measured
Au/Ag ratio (atomic) EDX
calculated
a The mean particle diameter of Ag nuclei is 9 ( 2 nm.
particles. Papavassiliou33 prepared Ag-Au alloy nano-
particles in 2-butanol by evaporation and condensation of
the alloys.
Layered Ag-Au (core-shell) colloids have been de-
scribed in fewer studies than Ag-Au alloys. In most of
these systems, segregation occurs during reduction so that
the more noble of the metals constitutes the core and the
less noble metal forms the shell of a cluster.34 Freeman
et al.12 prepared bimetallic colloids with a gold core and
silver shell by consecutive reduction of HAuCl4 and AgNO3
by sodium citrate. Morriss and Collins35 synthesized this
colloid of the same composition by reduction of slightly
alkaline HAuCl4 solution with pure phosphorus and
successive reduction of Ag2O with NH2OH‚HCl. Reversed
colloids, in which the less noble metal, silver, forms the
core and the more noble metal, gold, forms the shell, have
been reported as well. Mulvaney et al.6 deposited gold
onto radiolytically prepared silver sol by reirradiation of
KAu(CN)2 solution, and Treguer et al.34 prepared a layered
colloid by radiolysis of a mixed AuIII/AgI solution. A silver
colloid with gold reduced in the surface layer was prepared
by Chen and Nickel,1 who mixed a solution of HAuCl4
with a Ag colloid and then added a reducing agent (p-
phenylenediamine).
In this work, we used for the preparation of Ag-Au
colloids (silver core, gold shell) the modified seed-growth
method of Turkevich and Kim,16 who used this method for
preparation of gold-plated palladium colloids. NH2OH‚
HCl, the reducing agent used in this study, is known to
be very efficient for deposition of a second metal layer
over nuclei (parent colloid), because no new particle
nucleation occurs in solution in this step.5,16,36
Bimetallic colloids have often been studied by high-
resolution transmission electron microscopy (HRTEM).5-7,31
This method enables one to distinguish core/shell structure
on the basis of observing different lattice spacing. On the
other hand, transmission electron microscopy (TEM)
emphasizes the intensity contrast. Such contrast of TEM
images of Ag-Au colloids has so far been observed in only
two studies, published by Chen and Nickel1 and Morriss
and Collins.35 No attempts to explain these TEM observa-
tions have been made. We tried to characterize core-
shell Ag-Au colloids. Applications of these in SERS
spectroscopy will be given elsewhere.15 The prepared Ag-
Au colloids are used for preparation of the two-dimensional
metal colloid-adsorbate films37-40 suitable for TEM
imaging.
(32) Han, W. S.; Kim, Y.; Kim, K. J. Colloid Interface Sci. 1998, 208,
272.
(33) Papavassiliou, G. C. J. Phys. F: Met. Phys. 1976, 6, L103.
(34) Treguer, M.; de Cointet, C.; Remita, H.; Khatouri, J.; Mostafavi,
M.; Amblard, J.; Belloni, J. J. Phys. Chem. B 1998, 102, 4310.
(35) Morriss, R. H.; Collins, L. F. J. Chem. Phys. 1964, 41, 3357.
(36) Brown, K. R.; Natan, M. J. Langmuir 1998, 14, 726.
(37) Vlčková, B.; Barnett, S. M.; Kanigan, T.; Butler, I. S. Langmuir
1993, 9, 3234.
(38) Solecká-Čermáková, K.; Vlčková, B.; Lednický, F. J. Phys. Chem.
1996, 100, 4954.
(39) Srnová, I.; Procházka, M.; Vlčková, B.; Štěpánek, J.; Maly, P.
Langmuir 1998, 14, 4666.
Langmuir, Vol. 16, No. 25, 2000 9929
(Ag)Au-0.6 (Ag)Au-0.4 (Ag)Au-0.3 (Ag)Au-0.2
25 10 5 3.5 2
0.80 0.61 0.44 0.35 0.24
16 ( 2 12 ( 2 11 ( 2 10 ( 2 10 ( 2
15.3 12.3 10.9 10.4 9.8
6(1 5(1 6(1
3.82 1.62 0.85 0.51 0.29
3.93 1.57 0.79 0.55 0.31
Experimental Section
Materials. Deionized distilled water and analytical grade
chemicals were used for all sample preparations.
Preparation Procedure. Ag Colloid. The Ag colloid was
prepared according to the preparation procedure (II) in ref 41.
(Ag)Au Bimetallic Colloids. A sample of the Ag colloid (mean
particle size 9 ( 2 nm) prepared as mentioned above was employed
as a source of particle cores for preparation of a series of (Ag)Au
bimetallic colloids with the expected core-shell structure and
varying thicknesses of Au shells. A variation of the seed-growth
procedure described in ref 16 and based on the reduction of
HAuCl4 with NH2OH‚HCl was used to grow the Au shell. To 12.5
mL of Ag colloid diluted with 30 mL of deionized distilled water,
x mL of 6.52 × 10-3 M NH2OH‚HCl and x mL 4.65 × 10-4 M
HAuCl4 were added dropwise (ca. 4 mL/min) with two separate
pipets upon vigorous stirring. The values of x in relation to the
notation of the prepared colloid and mole fractions of Au are
listed in Table 1.
Preparation and Deposition of (Ag)Au Colloid-2,2′-Bipyridine
(bpy) Films. Parent (multilayer) interfacial films consisting of
adsorbate-covered metal nanoparticles were prepared according
to the procedure described in ref 37 for Ag colloid-bpy films.
Transfer and deposition of a monolayer metal colloid-adsorbate
film was accomplished by further improvements of the method
described in ref 40 for Ag colloid-bpy films: a metal colloid-
adsorbate film was collected from the dichloromethane-water
interface together with small portions of both solvents with a 1
mL micropipet. During these steps, the film was redispersed in
the water phase in the pipet as an almost homogeneous phase.
The volume of the mixture was reduced to ca. 1/3 by ejection of
the corresponding solvent volume, and the adsorbate-modified
metal nanoparticles together with the residual solvent (water)
were transferred onto a substrate (glass slides in subsequent
TEM sample preparation or carbon disks in energy-dispersive
X-ray analysis (EDX)). Adsorbate-covered metal nanoparticles
reassembled on the surface of a water drop into a film. In the
case of samples prepared for EDX analysis, the film was deposited
by removal of the liquid with a piece of filter paper. Another
procedure was used with samples for TEM and electron diffraction
(ED). A drop covered by a reassembled film was formed on a
microscopic glass. A carbon-coated Cu grid was held with
tweezers, and the film was firmly touched by the coated side of
the grid. In the end, the grid was placed on a filter paper to dry.
Another possibility of deposition of the film onto a carbon-coated
Cu grid was to transfer the colloid-adsorbate interfacial film
onto a water surface instead of the microscopic glass and to touch
it. This new deposition technique is suitable not only for the
substrates mentioned above but also for many others.15,40
Instrumentation. A JEOL-JEM 200 CX transmission elec-
tron microscope was employed for imaging (Ag)Au colloid-2,2′-
bipyridine films and (Ag)Au colloids deposited on carbon-coated
Cu grids. Samples of (Ag)Au colloid-bpy films were prepared as
described in the Experimental Section, and samples of (Ag)Au
colloids were prepared by drying a drop of colloid on a carbon-
coated Cu grid.
A JEOL-1200EX transmission electron microscope operating
at 120 kV was used for observation of selected-area electron
diffraction (SAED) patterns of a (Ag)Au-0.8 colloid-bpy film
deposited on a carbon-coated Cu grid.
(40) Srnová, I.; Vlčková, B.; Němec, I.; Šlouf, M.; Štěpánek, J. J. Mol.
Struct. 1999, 483, 213.
(41) Vlčková, B.; Matějka, P.; Šimonová, J.; Čermáková, K.; Pančoška,
P.; Baumruk, V. J. Phys. Chem. 1993, 97, 9719.
9930 Langmuir, Vol. 16, No. 25, 2000
Figure 1. TEM images and particle size distributions of (Ag)Au colloid-bpy films: (a) (Ag)Au-0.8, (b) (Ag)Au-0.6, (c) (Ag)Au-0.4,
(d) (Ag)Au-0.3, and (e) (Ag)Au-0.2.
A JEOL Superprobe 733 scanning electron microscope equipped
with a JXA 733 X-ray analyzer and a Kevex ∆ EDX spectrometer
were used for chemical analysis. The MR line of Au and the LR
line of Ag were selected. Samples for EDX analysis were prepared
as described in the Experimental Section. The error of the analysis
was less than 20%.
Particle size distributions and bright centers of colloid particles
were measured using LUCIA version 4.00 (Laboratory Imaging)
software. Particle size distributions were calculated from the
binary image by a standard procedure using the EqDiameter
(equivalent diameter) feature. The equivalent diameter is a size
feature derived from the area of the object. It determines the
diameter of a circle having the same area as the corresponding
object.
Srnová-Šloufová et al.
TEM contrast simulations were carried out using Gatan Digital
Micrograph software.
Results and Discussion
Particle Size Distributions. Transmission electron
micrographs of (Ag)Au colloid-bpy interfacial films and
the size distributions of bimetallic particles prepared by
adding various amounts of HAuCl4 to the same amount
of parent silver colloid are shown in Figure 1. The shape
of the particles deviates from spherical, which is especially
remarkable for higher amounts of gold. The higher the
Au/Ag ratio, the better developed are the shapes of colloidal
Core-Shell (Ag)Au Bimetallic Nanoparticles Langmuir, Vol. 16, No. 25, 2000 9931

particles (hexagonal, triangular, and truncated triangu-

lar). There is a very good agreement between the
theoretically predicted size of bimetallic particles calcu-
lated from the colloid preparation and the mean particle
diameter measured in TEM images of (Ag)Au colloid-
bpy films (Table 1). The accuracy of the particle size
measurement was estimated to be 0.5 nm. The difference
between the predicted and observed values of particle size
was within 5%.
EDX Analysis. The total average composition of
prepared (Ag)Au particles was determined using the EDX
analysis of (Ag)Au colloid-bpy films deposited on carbon
disks. Table 1 contains the values of the Au/Ag ratios
obtained by EDX analysis in comparison with the ratios
calculated from the colloid preparation. A good agreement
between measured and predicted values indicates that
almost no metal (within the experimental error of EDX
analysis) was dissolved in solution.
Experiments dealing with the composition of the surface
layer of prepared colloids will be discussed elsewhere.15
Here, we are trying to summarize some experimental
evidence concerning the shapes and the TEM image
contrast of the particles.
TEM Image Contrast and Electron Diffraction.
TEM images of prepared (Ag)Au particles starting from
the colloid (Ag)Au-0.4 (Table 1) display an unusual ”core-
shell” contrast; most of the particles (for the (Ag)Au-0.4
colloid and higher Au amounts) have a bright central part
and a dark outer part, or there is a dark line between the
central (core) and the outer (shell) parts. The mean
diameters of the bright central spots determined from the
TEM images (Figure 1) are given in Table 1. We have Figure 2. (a and b) Selected-area electron diffraction pattern
tried to reveal whether the bright central part corresponds of (Ag)Au-0.8 colloid-bpy film. (c) Calculated electron diffraction
to the expected Ag core and the dark outer part to the Au pattern of gold.
shell. To find proof of this statement, we carried out some the satellites in the SAED ring diffraction pattern.
TEM image simulations. In the beginning, we needed some Particles B in Figure 3 show stripes only over the “central”
evidence of the crystalline or noncrystalline character of (core) part. In distinction to the previous one, these stripes
the prepared particles. The crystalline character was are equidistant. The most probable reason for observation
proved by electron diffraction and by analysis of TEM of these stripes is the Moiré pattern. Generally, three types
images of selected particles. As colloids with low Au mole of Moiré patterns are observable:44 parallel, rotation, and
fractions (up to the colloid (Ag)Au-0.3, Figure 1) are quite mixed. The distance of the dark stripes (about 1 nm) and
inhomogeneous, all the results below were obtained from the difference between the interplanar distances of the
the (Ag)Au-0.8 bimetallic colloid with the highest Au/Ag Ag and Au (8 × 10-4 nm for {100} planes) are too small
ratio. This colloid yields the best-developed crystal shapes to correspond to the parallel Moiré pattern. In the case
and the most distinct core-shell contrast. of the rotation Moiré pattern, identical spacings d are
The selected-area diffraction pattern taken from the supposed,44 which is not true in our case. Therefore, the
(Ag)Au-0.8 colloid-bpy film (Figure 2a,b) exhibits the mixed Moiré pattern (appearing because of overlapping
Debye-Scherrer rings corresponding to the fcc structure. gratings with different spacings and a small relative twist)
The lattice constant calculated from these rings without is the most probable. Interpretations of different fringes,
calibration differs from those of Au and Ag by less than observed over the colloidal particles as microtwins or a
1%. Au and Ag lattices are irresolvable because of the Moiré pattern, convince us that the particles are single
close lattice constants (4.0862 and 4.0783 Å for Ag and crystals.
Au, respectively42). The first, unindexed satellite ring and TEM Image Simulations. Crystal shapes of (Ag)Au-
the satellite associated with the 220 ring in Figure 2a,b 0.8 particles were studied to elucidate the origin of the
(marked with arrows) are the consequence of microtwins bright centers in the TEM images. Several model systems
on {111} planes.43 The consistence of relative intensities described below were proposed for this purpose. Two
of the Debye-Sherrer rings in Figure 2a,b and the groups of geometrical shapes of particles were consid-
calculated powder SAED pattern (see Appendix) of gold ered: (i) three-dimensional (3-D) crystals with a core-
(Figure 2c) allow us to assume that no preferential shell structure and (ii) nanocrystals with one crystal plane
orientation of the (Ag)Au-0.8 particles with respect to the preferentially developed with a core part composed of a
electron beam exists in the sample. material different from the outer one. The dimensions of
Particles A in Figure 3 show dark fringes over the whole the particles of these model systems were comparable with
particle (over both its central and outer parts). These those in Table 1.
fringes are not equidistant and are caused by microtwins As the diffraction contrast is the dominating mechanism
present in silver and/or gold particles, as evidenced by of imaging of the metal crystalline 16 nm (mean particle

(42) Wyckoff, R. W. G. Crystal Structures; Interscience, J. Wiley: (44) Hirsch, P. B.; Howie, A.; Nicholson, R. B.; Pashley, D. W.; Whelan,
New York, 1965; Vol. 1. M. J. Electron Microscopy of Thin Crystals; Butterworths: London,
(43) Pashley, D. W.; Stowell, M. J. Philos. Mag. 1963, 8, 1605. 1965.
9932 Langmuir, Vol. 16, No. 25, 2000
Figure 3. Selected TEM images of the (Ag)Au-0.8 colloid: (A)
particles with fringes over the whole crystal, (B) particles with
fringes over only the central part, (C) particles with visible
crystal planes, (D) particles with grain boundaries in the central
part, and (E) particles with a hexagonal central part.
size of the (Ag)Au-0.8 colloid) objects,44 theoretical TEM
images were calculated on the basis of contrast from
inclusions.45
In the following, all the considered crystal shapes
together with the possible origin of the core-shell contrast
observed in the TEM images of the (Ag)Au colloid will be
discussed.
Disk Particles with a Hole in the Center. Alloyed disk
particles with a hole in the center were selected as the
first model system. Even if this model is highly improbable
(45) Ashby, M. F.; Brown, L. M. Philos. Mag. 1963, 8, 1649.
Srnová-Šloufová et al.
with respect to the crystal growth, the striking resem-
blance of “macrophotographs” of such a system with the
particles in Figure 1 is evident. To eliminate such a
possibility, two experiments were carried out. First, we
calculated the theoretical TEM image contrast (Figure
4a) for an ideal Ag-Au alloy with a Au/Ag ratio of 3.93:1
corresponding to the metal ratio in the (Ag)Au-0.8 colloid
(Table 1). The extinction distance of this alloy, ξAuAg, was
calculated as
ξAuAg ) xAuξAu,(111) + xAgξAg,(111)
where xAu and xAg are the mole fractions of the metals and
ξAu,(111) and ξAg,(111) are the extinction distances at the exact
Bragg angle for the {111} plane for Au and Ag, respectively:
-22.4 nm for Ag and 15.9 nm for Au.44 The extinction
distance of the alloy, ξAuAg, is then 17.2 nm. The model
consisted of a disk, 16 nm in diameter and 12 nm in height
with a hole 6 nm in diameter in the center. The height of
the disk was calculated under the following assumptions:
(i) no new nucleation occurred 5,16,36during the addition of
HAuCl4 and NH2OH‚HCl to the system and (ii) all particles
are 16 nm in diameter (mean particle size of the (Ag)-
Au-0.8 colloid is 16 nm, Table 1). As expected, a bright
core and a dark shell are observable in this model. If we
carried out the simulation of TEM images using longer
extinction distances,44 we would obtain a dark ring with
a bright center as well. To fully eliminate interpretation
of our TEM images using this model, further experiment
was necessary. We have recorded TEM micrographs of
the same particles of the (Ag)Au-0.8 colloid under at least
two independent orientations; the sample was tilted 0°
and 40° from its position (Figure 5). If a hole (6 nm in
diameter) were in the center of such a disk particle, a
rather complicated image with a line of no contrast in the
center, perpendicular to the tilt axis, would result after
tilting the sample about 40°. No such effect was observed.
The bright spots remain preserved in their original shape
in the tilted TEM images as well (Figure 5). Moreover,
the electron diffraction pattern obtained from the (Ag)-
Au-0.8 colloid-bpy film (Figure 2) shows that no orienta-
tion of colloidal particles is preferred, and there are visible
crystal faces of particles C in Figure 3. Similar images
would be observed for disk crystals with a central part
composed of material different from that forming the shell.
Equiaxed 3-D Particles with a Hole or a Disordered
(Amorphous) Phase in the Center. This was the next model
system to be examined. From the point of view of the TEM
diffraction contrast image, a hole and a disordered phase
behave in the same way. The possibility of the existence
of a disordered phase in the center of the particle was
taken into consideration because of the possible formation
of the AgCl compound during the colloid preparation.15
This model could theoretically yield images similar to those
described in the previous paragraph (particles C in Figure
3, Figure 5). On the other hand, this model seems
improbable because of the lattice parameter of AgCl (5.546
Å) in comparison with the Ag or Au lattice parameters
(4.086 and 4.078 Å, respectively). We have selected a 16
nm alloy sphere (Au/Ag ratio of 3.93, Table 1) with a 6 nm
spherical hole in the center as a model system. Calculated
TEM images for particles with planes {111}, {311}, {511},
and {531} in reflection positions are shown in Figure 4b.
Images corresponding to the {111} and {200} (not shown
here, but almost the same as for {111}) reflection positions
exhibit a dark center with bright circles around the center
and dark outer parts. Starting from the {220} reflection
(not shown here), bright centers appear with a dark line
between the center and the dark outer part (see the {311},-
Core-Shell (Ag)Au Bimetallic Nanoparticles
Figure 4. Simulation of TEM intensity contrasts of model systems: (a) disk particles with a hole in the center, (b) equiaxed 3-D
particles with a hole or a disordered (amorphous) phase in the center, and (c) equiaxed 3-D particles with a Ag core and a Au shell
for {111}, {311}, {511}, and {531} reflection positions.
Figure 5. TEM images of the (Ag)Au-0.8 colloid tilted by 0°
and 40°.
{511}, and {531} reflections in Figure 4b), which could
correspond to the TEM images of the (Ag)Au-0.8 colloidal
particles (Figure 1). No particles of the real system with
a TEM contrast similar to that obtained for {111} and
{200} were observed. Nevertheless, other observations
exclude this model: (i) The core of particles D in Figure
3 does not exhibit uniform contrast and is divided into
two parts, grains. Twinning of the crystalline central part
of the particle can probably explain the observation of
such divided cores. (ii) The Moiré pattern observed for
particles B in Figure 3. (iii) A detailed examination of the
Langmuir, Vol. 16, No. 25, 2000 9933
shape of the bright centers reveals that most of them are
of hexagonal shape, which corresponds to a crystalline
phase in the core (particles E in Figure 3).
Equiaxed 3-D Particles with a Ag Core and a Au Shell.
This was the last and the most probable model. Figure 4c
shows a theoretical TEM image pattern of a bimetallic
sphere, 16 nm in diameter with a Ag core 6 nm in diameter
and a 5 nm Au shell, for selected reflections: {111}, {311},
{511}, and {531}. Moreover, theoretical images were
calculated for all reflections from {111} up to {600}. Images
for reflections {111} (Figure 4c) and {200} yield particles
with high contrast between the shell and the core, without
a dark fringe around the bright part. Images of reflections
{311} (Figure 4c) and {222} yield particles without a bright
center and without any bright fringe around the core as
described for 3-D particles with a hole or disordered
(amorphous) phase in the center (Figure 4b). From
reflections {222} up to {600} (the last calculated), all
particles have a brighter center and a darker shell with
a dark line on the core-shell boundary, with only the
contrast differing. Particles corresponding to all of these
images are abundant in the TEM image of the (Ag)Au-0.8
colloid-bpy film (Figure 1). In addition, the interpretation
of the observed TEM images of (Ag)Au-0.8 colloidal
particles as 3-D bimetallic particles with a Ag core and
a Au shell is in agreement with all observed experimental
facts, as described in the following paragraphs.
(i) The mean particle diameter grows with an increase
in the Au/Ag ratio. The amount of Ag colloid used in the
preparation is the same in the whole series of (Ag)Au
colloids; only the addition of HAuCl4 and NH2OH‚HCl
differs. The dimension of the bright centers is preserved
from the (Ag)Au-0.4 to the (Ag)Au-0.8 colloid and is 6 (
1 nm (Table 1). The experimental accuracy of the
measurement of the object diameter was estimated to be
1 nm. Therefore, the growth of the (Ag)Au colloid is caused
by enlargement of its Au shell. We assume that the bright
center corresponds to the Ag particle and the dark shell
to the gold deposited over it. A reduction in the dimension
of the bright centers (6 ( 1 nm) in comparison with the
9934 Langmuir, Vol. 16, No. 25, 2000
mean particle size of the parent Ag colloid (9 ( 2 nm)
occurs during the deposition of the Au shell. The dissolved
silver enriches the gold shell.
We have taken into account two additional models
concerning the localization of the missing silver phase.
Both models are formed by spheres 16 nm in diameter
consisting of a Ag core 6 nm in diameter. In the first model,
a 5-nm-thick shell of alloy composition (Au/Ag 5.57:1) is
present, the shell being enriched with the silver missing
in the core. In the second model, the 4.6-nm-thick Au shell
is covered with a 0.4 nm Ag surface layer; that is, the
missing Ag is concentrated on the surface of the particle.
Both these models yield virtually the same theoretical
TEM images, as shown in Figure 4c and described above.
Finally, the localization of silver in the Au shell on the
basis of surface-enhanced Raman spectroscopy, X-ray
photoemission spectroscopy, and UV-vis measurements
is discussed in detail in ref 15.
(ii) Another fact supporting the 3-D Ag/Au core-shell
model involves the well-developed crystal shapes. Both
metals, Ag and Au, crystallize in the Fm3m space group,
and their lattice parameters,42 4.086 Å for Ag and 4.078
Å for Au, differ very little, allowing the epitaxial crystal-
lization. Silver nanocrystals usually have hexagonal or
pentagonal projections,46 which correspond to the shape
of the observed core.
(iii) The observation of dark fringes across the center
of a particle (Moiré pattern) and across the whole particle
(perturbation in stacking of the layers in a face-centered
cubic cell) and the electron diffraction pattern show that
the particles are single crystals with a lattice constant
very close to that of gold and/or silver.
(iv) Differing core-shell intensity contrast within the
whole (Ag)Au colloidal particle set (Figure 1) is readily
explained when no preferential orientation is assumed
(proved by electron diffraction, Figure 2) and extinction
distances for various diffraction positions are taken into
account. The deviation of the particle orientation from
the exact Bragg angle could be another reason for
observation of the different core-shell intensity contrasts.
In this case, it is necessary to consider the effective
extinction distance44 ξw g in the TEM image simulation,
which is smaller than the extinction distance ξg for the
exact Bragg angle. However, this effect is smaller than
that resulting from consideration of different diffraction
positions.
(v) In addition, TEM images obtained for our (Ag)Au
bimetallic particles discussed above are in good agreement
with the TEM image published by Morriss and Collins.35
They prepared a three-layered gold-silver-gold hydrosol
with an average particle diameter of about 40 nm.
Preparation of the colloid started with gold nuclei ap-
proximately 10 nm in diameter, and then a layer of silver
and a second layer of gold were added. The TEM
micrographs of the gold-silver-gold colloid contain
irregular particles with dark-bright-dark image con-
trast. Chen and Nickel1 prepared silver-gold particles by
mixing a solution of HAuCl4 with a silver colloid without
or with a reducing agent (p-phenylenediamine). Bright
centers and darker surrounding layers are again visible
in their TEM micrographs.
Conclusion
The structure of bimetallic colloidal particles, suitable
for using in surface-enhanced Raman spectroscopy, was
(46) Wales, D. J.; Kirkland, A. I.; Jefferson, D. A. J. Chem. Phys.
1989, 91, 603.
Srnová-Šloufová et al.
studied by transmission electron microscopy, energy-
dispersive X-ray analysis, and electron diffraction. Re-
duction of HAuCl4 with NH2OH‚HCl over a Ag colloid
leads to a bimetallic silver-gold colloid with well-
developed single-crystal shapes. The core-shell structure
of colloidal particles was revealed by both the analysis of
the observed TEM images and the simulation of image
contrast of the model systems. Particles were found to
consist of a silver core and a gold shell enriched with silver.
TEM image analysis showed that the mean particle size
increases from 10 nm for (Ag)Au-0.2 to 16 nm for (Ag)-
Au-0.8, which is in good agreement with predicted
theoretical values. The produced (Ag)Au colloid was
successfully used for preparation of (Ag)Au colloid-2,2′-
bipyridine interfacial films. Electron diffraction of a (Ag)-
Au-0.8 colloid-2,2′-bipyridine film proved that no orien-
tation of particles is preferred after deposition on a
supporting surface.
Acknowledgment. Financial support of this work by
the 1830/2000 Grant awarded by the Grant Agency of the
Board of Universities (FRVŠ) is gratefully acknowledged.
We thank Dr. J. Jurek for performing EDX analysis and
J. Hromádková for help with TEM imaging.
Appendix: Intensity of Ring Patterns
In materials with randomly oriented crystalline objects,
for example, grains in polycrystalline foils or spheroidal
particles in films, the diffraction spots form ring patterns.
The intensity of a ring can be obtained by averaging the
expressions for kinematical or dynamical intensity44 over
all deviations s from the exact reflecting position and over
the angles φ between the beam direction and the normal
of the foil or film.
From the kinematical theory of electron diffraction, it
follows that the intensity of diffracted waves is given by
π sin2 πts
Ikin ≈ (1)
ξg2 (πs)2
where t is the thickness of the sample, ξg ) (πVc cos θ)/
(λFg) is the extinction distance, Vc is the volume of the
unit cell, λ is the wavelength of the incident beam, Fg is
the structure factor for the reflection g, and θ is the Bragg
angle. The vector g is perpendicular to the family of lattice
planes with Miller indices (hkl). For a perfect crystal, the
diffracted intensity calculated on the basis of two-beam
dynamical theory is given by expression 1 where s is
replaced by seff ) [s2 + 1/ξg2]1/2.
2
π sin πtseff
Idyn ≈ (2)
ξg2 (πseff)2
For large deviations from reflecting positions, seff reduces
to s.
As the intensity averaged over φ does not differ too
much from the original one,47 it is sufficient to average
only over s. The integrated intensity per ring unit length
is equal to averaged expressions 1 or 2 divided by 2πr,
where r is its distance from the center; rdhkl ) Lλ, where
dhkl is the interplanar spacing of crystal plane hkl and L
is the camera length. In the kinematical case, it is given
(47) Blackman, M. Proc. R. Soc. London, Ser. A 1939, 173, 68.
Core-Shell (Ag)Au Bimetallic Nanoparticles Langmuir, Vol. 16, No. 25, 2000 9935

by Fg
Idyn ≈ λ2| |d p (4)
Vc hkl hkl
Fg
Ikin ≈ λ2| |2dhklphklt (3)
Vc
corresponds better to the measured one.
where phkl is the multiplicity of diffracting planes. Diffraction on particles 16 nm in size corresponds better
When the dimensions of individual objects are compa-
to the kinematical expression 3.
rable with the extinction distance πt . ξg or if the lattice
parameters are g1 nm, the dynamical intensity LA0009588