Shape effects in plasmon resonance of individual colloidal silver

nanoparticles
J. J. Mock, M. Barbic, D. R. Smith, D. A. Schultz, and S. Schultz

Citation: J. Chem. Phys. 116, 6755 (2002); doi: 10.1063/1.1462610

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 JOURNAL OF CHEMICAL PHYSICS VOLUME 116, NUMBER 15 15 APRIL 2002

Shape effects in plasmon resonance of individual

colloidal silver nanoparticles
J. J. Mock, M. Barbic,a) D. R. Smith, D. A. Schultz, and S. Schultzb)
Department of Physics, University of California, San Diego, La Jolla, California 92093-0319
共Received 13 November 2001; accepted 29 January 2002兲
We present a systematic study of the effect of size and shape on the spectral response of individual
silver nanoparticles. An experimental method has been developed that begins with the detection and
characterization of isolated nanoparticles in the optical far field. The plasmon resonance optical
spectrum of many individual nanoparticles are then correlated to their size and shape using
high-resolution transmission electron microscopy. We find that specific geometrical shapes give
distinct spectral responses. In addition, inducing subtle changes in the particles’ morphology by
heating causes a shift in the individual particle spectrum and provides a simple means of tuning the
spectral response to a desired optical wavelength. Improved colloidal preparation methods could
potentially lead to homogeneous populations of identical particle shapes and colors. These
multicolor colloids could be used as biological labels, surface enhanced Raman scattering
substrates, or near field optical microscopy sources covering the full range of wavelengths in the
visible spectrum. © 2002 American Institute of Physics. 关DOI: 10.1063/1.1462610兴

Metal colloidal nanoparticles are becoming increasingly
important in a variety of scientific fields. In molecular spec-
troscopy applications, the interest stems from the significant
improvement in the detection of the Raman signal from mol-
ecules adsorbed on roughened metal surfaces. In the field of
surface-enhanced Raman scattering 共SERS兲,1 the spectral
signature from single molecules has recently been
observed.2,3 This effect is believed to be due, in part, to the
significant electromagnetic field enhancement at the metal
particle surface that strongly interacts with the internal en-
ergy levels of the adsorbed molecule.4 The plasmon reso-
nance 共unique colors兲 and the large effective scattering cross
section of individual silver nanoparticles, as well as their
nonbleaching properties have significant potential for single
molecule labeling based biological assays.5,6 Metal nanopar-
ticles are also used in various near field optical microscopy
applications7,8 where they provide increased signal output
due to their efficient scattering properties.
Although the effect of shape is often stated as significant
for the spectral properties of colloidal nanoparticles,9 the re-
lationship between the geometrical shape of an individual
particle and its plasmon resonant spectral response has not
been experimentally investigated. While visual observation
of individual silver colloids was reported by Zsigmondy in
1914,10 it has only recently been realized that modern optical
microscopy techniques can be tailored for the electronic
characterization of individual silver colloids.5,7,11,12 In this
report, we combine the use of an optimized optical detection
technique with high-resolution transmission electron micros-
copy 共TEM兲 analysis for the systematic investigation of the
effects of shape on the surface plasmon resonance of indi-
vidual silver colloidal nanoparticles. Nanoparticles of vari-
a兲
The author’s name changed from Todorovic to Barbic in 1999.
b兲
Electronic mail: sschultz@ucsd.edu
ous shapes and sizes, from approximately 40 to 120 nm,
having colors ranging from violet 共400 nm兲 to red 共700 nm兲,
were characterized. This study forms a basis for further de-
velopment of carefully engineered colloidal metal particles,
and provides experimental information that can complement
and guide the theoretical efforts of modeling complex metal
particle shapes,13 that have recently been advanced by new
methods in numerical solutions of the electromagnetic
equations,14,15 and the experimental TEM studies of shapes
of nanometric sized particles.16
The silver colloids in solution were prepared by nucle-
ating silver salts 共silver enhancement kit, BBI International兲
on 5 nm gold nuclei 共BBI International兲. A typical protocol is
as follows: approximately 2 mg of Knox brand geletin 共for
coating and stabilizing the colloids兲 is added to 20 ml of
double-distilled water (DDH2O) in a small vial with a mag-
netic stir bar. The solution is brought to a boil and then
cooled to room temperature, at which time 20 ␮l of 5 nm
gold nuclei, 150 ␮l initiator, and 80 ␮l enhancer from the kit
is added. The silver colloid growth takes approximately 1
min to reach completion. The average size of the silver col-
loid can be controlled by varying the amount of enhancer
added to the solution. The colloidal nanoparticles are immo-
bilized on formvar coated TEM grids 共Ted Pella兲, at low
density, by placing a drop of the colloidal solution on the
grid, followed by a rinse in DDH2O and ethanol. The geletin
coating firmly immobilizes the silver nanoparticles to the
surface, and no other adhesive reagent is necessary.
We used several experimental techniques to precisely
correlate the optical spectrum of individual silver nanopar-
ticles to their geometrical shapes. The sample is first exam-
ined by an optical microscope system modified for single
particle spectroscopy.5 All optical imaging is performed with
a Nikon Optiphot microscope with CF Plan BD 100X, 0.8
numerical-aperture objective lens. To obtain a plasmon reso-

0021-9606/2002/116(15)/6755/5/$19.00 6755 © 2002 American Institute of Physics

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 6756 J. Chem. Phys., Vol. 116, No. 15, 15 April 2002 Mock et al.

nance spectrum from individual silver nanoparticles, un-

polarized light from a 75 W Xe source is incident on the
particle using dark field illumination. The light scattered
from the nanoparticle is directed to an image plane aperture
共0.2 mm diameter兲 to reduce scattered light from other re-
gions of the sample getting to the detector. An ocular focused
on the aperture is used to position a selected nanoparticle
into the center of the aperture, and the transmitted light is
directed into a SPEX 270M grating spectrometer using a
mirror and focusing lenses. A Princeton Instruments CCD
camera is mounted at the exit slit of the spectrometer. The
spectrum is first collected from a particle, and then from a
dark region of the formvar grid close to the particle’s loca-
tion, but positioned so that there are no particles inside the
aperture selected area. This latter data constitutes the sub-
strate background spectrum and is subtracted from each par-
ticle spectrum. The wavelength dependence of the source,
optics, and CCD is removed by normalizing the measured
spectrum to that obtained from a broad-band light-scattering
target 共Labsphere, New Hampshire兲.
In order to have a spatial map of the relative locations of
the particles, a wide-field optical image containing approxi-
mately 100 particles is recorded. This image is subsequently
used as a pattern recognition template during the TEM analy-
sis to locate and correlate the spectral response of the particle
to its shape and size. Following the optical investigation of
the particle, the sample is imaged and analyzed by high reso-
lution TEM using a 100 keV JEOL 1200 microscope in the
standard bright-field mode. Recognizable features of the
sample found in the wide field optical microscope CCD im- FIG. 1. 共Color兲 共Top兲 An electronic camera 共Nikon Coolpix 950兲 color-
image of a typical sample of silver nanoparticles as viewed under the dark-
age can be directly correlated to the same features seen on field microscope. The brightness of the particles increases from blue to red
the electron microscope fluorescent screen by visual inspec- due to both the intrinsic optical scattering cross section and the spectral
tion during the TEM examination. output of the light source. As a result, the red particle is overexposed. This
Our particle mapping method is illustrated by comparing image is subsequently used as a pattern recognition template during the
TEM analysis. 共Bottom兲 A bright field TEM image of the same collection of
the optical image of Fig. 1共a兲 to a TEM image of the same silver nanoparticles.
collection of silver nanoparticles shown in Fig. 1共b兲. Figure
1共a兲 shows a color image of a typical sample of individual
colloidal silver nanoparticles as viewed under the Nikon particle by measuring its spectrum prior to performing the
dark-field microscope. The color population is approxi- TEM analysis. We assign a size to each particle from the
mately: 85% of the particles are blue, 5% of the particles are TEM images, taken with the e-beam normal to the sample,
green, 5% of the particles are red, and 5% of the particles by comparing a characteristic dimension to the TEM calibra-
have a broad or double peaked spectral signature that indi- tion bar. The characteristic dimension for a spherical particle
cates clustering or other complex shapes not characterized in 共with a circular image兲 is a diameter, for a pentagon it is the
this study. Although 40–120 nm in size, the plasmon reso- length between opposite corners, and for a triangle it is the
nant effect in silver nanoparticles makes them easily detect- length of a side.
able in the visible spectrum using standard far-field optics.5 In order to investigate the relationship between the size,
Based on the experimental results obtained from high- shape, and color of silver nanoparticles in more detail, we
resolution TEM images at normal beam incidence, we con- made particles of various sizes by preparing several colloidal
clude that most of the particles that image as a triangle ap- solutions, which differed in the amount of silver enhancer
pear red, particles that image as a pentagon appear green, and added in the sample preparation method. We find that with
particles that image as a circle 共roughly spherical particles, increase in particle size the corresponding spectra are red-
verified by TEM sample tilt feature兲 appear blue. The data shifted, and the dependence of color on shape, as shown in
supporting this principal conclusion is illustrated in Fig. 2, Fig. 2, is maintained. Figure 3 shows a plot illustrating the
where the spectrum of an individual red, green, and blue relationship between the size 共as determined from TEM im-
particle is presented on the same graph, and the high- age measurement兲 and the spectral peak wavelength for a
resolution TEM images of the corresponding particles are diverse collection of individual silver nanoparticles. Repre-
shown above their respective spectrum. Because there is a sentative high-resolution TEM images for three different size
correlation between the color of a particular particle and its particles, for each geometrical shape, are also shown. A sig-
geometrical shape, we can generally predict the shape of a nificant scatter in the data for the shapes of the triangular

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 J. Chem. Phys., Vol. 116, No. 15, 15 April 2002
FIG. 2. Typical optical spectroscopy measurements of individual silver
nanoparticles. The figure shows the spectrum of an individual red, green,
and blue particle, and the high-resolution TEM images of the corresponding
particle are shown above their respective spectrum. This example is a rep-
resentative of the principle conclusion that the triangular shaped particles
appear mostly red, particles that form a pentagon appear green, and the blue
particles are spherical.
particles is evident in the figure, and we attribute this to
variation of the vertical 共out of the imaging plane兲 morphol-
ogy of the triangular particles as discussed following.
In an effort to understand the reason for the scatter in the
size of the triangular particles having the same spectral peak
wavelength in Fig. 3, we have attempted to quantify the
three-dimensional 共3-D兲 morphology using the sample rota-
tion and tilt capabilities of the TEM. One side of a triangle as
observed at normal incidence was first aligned parallel with
the tilt axis of the TEM specimen rod. After taking the image
of the triangle at this zero degrees position, the sample was
tilted by the maximum allowed tilt angle of ⫹60 degrees and
a new image was recorded. The sample was then tilted in the
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Shape effects on plasmon resonance of Ag particles 6757
opposite direction, to ⫺60 degrees, and the image was again
recorded. There was a significant difference among the trian-
gular particles in the image features taken at ⫾60 degrees,
although they were all equilateral triangles when imaged at
zero degrees. We attribute this to the differences of the trian-
gular particle morphology in their vertical direction. To fur-
ther understand the two-dimensional 共2-D兲 TEM projection
image representation of the 3-D triangular features, we cre-
ated model Styrofoam structures of possible 3-D particle
shapes. These included flat platelets, complete tetrahedrons,
as well as tetrahedrons with their tops rounded or cut off.
The models were placed on a light plate, and imaged using
the CCD camera at the same angles 共0, ⫹60, ⫺60兲 as the
nanoparticles in the TEM investigation. These images were
compared with the TEM micrographs of the nanoparticles,
and such analysis allowed us to characterize the 3-D shape of
a variety of triangles.
Figure 4 shows an example of such an investigation. The
top of Fig. 4共a兲 shows an isometric shaded drawing of the
3-D structure of what we term a flat-topped tetrahedron with
the arrow representing the tilt axis of the TEM specimen rod.
Figure 4共b兲 shows the normal incidence 共0 degrees兲 2-D
CCD camera image of the constructed Styrofoam model with
one side selected parallel to the rotation axis. Figures 4共c兲
and 4共d兲 show the 2-D CCD camera image of the same struc-
ture at ⫹60 and ⫺60 degrees. Figures 4共e兲– 4共g兲 show the
TEM micrographs of one of the triangular silver particles
corresponding to the same three angles. As can be seen, there
is an excellent correlation between the Styrofoam model and
the triangular silver nanoparticle sequence of TEM images.
Figure 5 shows an example of a flat triangular platelet
particle. The sequence of Figs. 5共b兲–5共d兲 show the 2-D CCD
image representation of the Styrofoam model structure at 0,
⫹60, and ⫺60 degree orientation, while Figs. 5共e兲–5共g兲
show a sequence of TEM images of the selected triangular
nanoparticles at the same three imaging angles. Again there
is excellent correlation between the images of the Styrofoam
model and the silver particle. Although the images of Figs.
4共b兲 and 5共b兲 appear essentially the same, they are notably
different when taken at ⫹60 and ⫺60 degrees imaging
FIG. 3. Plot of the TEM lateral size vs the spectral peak
wavelength for a diverse collection of individual silver
nanoparticles. We assign a size to each particle using
the TEM image taken with the e-beam normal to the
sample and by comparing a characteristic dimension to
the TEM calibration bar. The characteristic dimension
for a spherical particle 共circular image兲 is the diameter,
for a pentagon it is the length between opposite corners
and for a triangle it is the length of a side. Typical
colloidal sample color population is approximately:
85% of the particles are blue, 5% of the particles are
green, 5% of the particles are red, and 5% of the par-
ticle population has a broad or double peaked spectral
signature that indicates clustering or other complex
shapes. Representative high-resolution TEM images for
three different size particles, of each geometrical shape,
are also shown.
 6758 J. Chem. Phys., Vol. 116, No. 15, 15 April 2002
FIG. 4. A 3-D comparative shape analysis based on images taken at various
tilt angles. 共a兲 Shows an isometric shaded drawing of the 3-D structure of a
flat-topped tetrahedron. The arrow indicates the orientation of the tilt axis.
共b兲 shows the 2-D CCD camera image of a constructed 3-D Styrofoam
model at normal light incidence 共0 degrees兲. 共c兲 and 共d兲 show the 2-D CCD
camera image of the same model at ⫹60 and ⫺60 degrees. 共e兲–共g兲 show the
TEM micrographs of a triangular silver particle at the same three tilt angles.
The correlation in the sequences of images between the Styrofoam model
and the triangular silver particle is evident.
angles. Using this comparative analysis, we found that the
morphology of the triangles varied widely from thin platelets
to flat topped tetrahedrons, and to even more complicated
3-D structures. Therefore, the scatter in the 2-D characteriza-
tion of plasmon resonance of the Fig. 3 triangles may likely
be attributed to the variance of the morphology in the third
dimension of the tetrahedron shaped silver particles. Another
method of identifying a thin platelet of any geometry is that
the nucleating Au colloid can be recognized within the Ag
particles’ TEM image taken at 0 degrees. The triangular
TEM particle image in Fig. 2 is such an example.
Additional insight into the shape dependence of the op-
tical spectra was obtained from controlled heating experi-
ments on silver particles. We observed morphological and
spectral changes of individual triangular particles as a func-
tion of heat treatments. In this study, the particles were im-
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Mock et al.
FIG. 5. 3-D analysis of a triangular platelet particle. The illustration is of the
same technique described in Fig. 4. The correlation between the optical
images of the Styrofoam model 关共b兲–共d兲兴 and the TEM image of the silver
particle 关共e兲–共g兲兴 are evident. We note an important difference between Figs.
4 and 5. Although the images of both particles are essentially the same at
normal incidence, they are notably different when taken at ⫹60 and ⫺60
degrees.
mobilized on more robust, 20 nm thick, silicon nitride TEM
membranes 共Structure Probe Inc.兲. These membranes sur-
vived being subjected to several cycles of heating the sample
to 200 °C for a period of 20–30 min on a hotplate, and then
cooling to room temperature. Figure 6 shows an example of
the effects observed. The initial triangular nanoparticle had a
spectral peak centered at 625 nm. After heating for 30 min at
200 °C the particle shape changes and the triangular corners
are more rounded. The spectral peak has shifted to 585 nm,
and the particle appeared orange. An additional heating cycle
for 20 min resulted in further rounding of the particle cor-
ners, and the particle appeared yellow/green with the spectral
peak now centered at 555 nm. The TEM images presented in
Fig. 6 suggest a strong dependence of the particle spectral
response on the specific corner features of the colloidal nano-
particle. A complete understanding of the effects of the heat-
 J. Chem. Phys., Vol. 116, No. 15, 15 April 2002 Shape effects on plasmon resonance of Ag particles 6759

Jin et al.17 where similar shape effects on the optical proper-

ties of silver colloids are observed. In their work, the authors
report intentionally inducing shape transformation on a col-
loidal suspension of silver nanospheres to nanoprisms, and
observing a spectral shift from blue to red. They further theo-
retically predict the strong dependence of the spectral re-
sponse on the corner features of the nanoprism. Here, we
confirm analogous shape effects by investigating the as-
prepared and annealed individual silver nanoparticles, and
our data match well with the results of their work.

ACKNOWLEDGMENTS
The authors thank James Bower and Professor Mark
Ellisman of the UCSD National Center for Microscopy and
Imaging Research, and Andy Pommer of the UCSD Physics
Machine shop for valuable technical help. This work was
supported by grants from NSF: DMR 9724535 and DBI-98-
16651, the NIH: PHS HG01959-02, the Richard Lounsbury
Foundation, and NSF: DMR0100962.
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