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Electronic properties of small silver particles: the optical constants and their temperature

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1974 J. Phys. F: Met. Phys. 4 999

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J. Phys. F: Metal Phys, Vol. 4, July, 1974. Printed in Great Britain. @ 1974.

Electronic properties of small silver particles :


the optical constants and their temperature dependence

U Kreibig
Fachrichtung 1 1.2 Experimentalphysik, Universitaet des Saarlandes, 66 Saarbruecken,
Germany

Received 25 July 1973, in final form 27 December 1973

Abstract. Specimen size dependences of the dielectric constant and of its variations with
temperature have been investigated by measuring the optical plasma resonance absorption
of small silver particles embedded in glass. The following relations hold at the wavelength
+
405nm: cz (imaginary part at 300K) = 023 2,64/R, and (300K) - c2 ( 1 3 K) 5 0.07
- O.OS/R where R is the particle radius in nm.
Agreement has been found with the free path effect but not with the quantum size effect
theories of Kawabata and Kubo and of Glauberman and Adamyan. The behaviour of the
temperature dependence can partly be explained by thermal lattice contraction. The ratio
of electron density to the optical effective mass shows no distinct changes as R varies from
10.5nm to 1.1 nm. It may hence be concluded that normal metallic properties are present
in silver particles embedded in glass which contain more than about 400 atoms.

1. Introduction

In the condensation of metal atoms to a solid the first stages are characterized more by
molecule-like properties than by metallic properties. The one electron energy levels,
the number of which is of the order of the number of atoms in the cluster, have not yet
formed energy bands, but are discrete (Frohlich 1937, Sex1 1960). Hence the valence
electrons cannot be continuously accelerated by an external electric field but are able
to change their energy only through transitions between the quantized eigenstates.
Changes of the electronic properties of particles caused by the discreteness of the energy
levels are known as quantum si= effects. In particles of arbitrary shape, the mean spacing
of energy levels is of the order
AE - EJZ (14
where E , = Fermi energy, Z = number of atoms in the particle. In nearly cubic or
spherical particles, symmetry degeneracy causes AE to increase, and
AE - E,/Z2'3 (1b)
(Kubo 1969). A particle consisting of lo3 atoms with E , = 5 eV has AE 5 x
or 3 x
eV
eV, from equations (la) and (lb), respectively. Assuming the particle to be
-
spherical with a lattice constant of 0.3 nm, its diameter would be about 3 nm.
Kubo (1969)has pointed out that these discrete electron eigenstates will be broadened
by lifetime limitation. This broadening may possibly increase with decreasing particle

999
F-F7
1000 U Kreibig

size. Quantum size effects should vanish in particles where the energy level broadening
6E exceeds the mean spacing AE between the levels. Since AE depends on the particle
size d, a critical diameter d, can be defined with
d < d, 6 E < AE (quantum size region)
(2)
d > d, 6 E > AE (quasicontinuous energy bands).

The critical diameter will be a function of temperature and will depend on the method
of preparation of the particle because both AE and 6E may be influenced by the form and
the crystalline structure of the particles, by impurities, and, also, by the nature of the
embedding matrix.
If d > d,, the conduction band is quasicontinuous as in the bulk metal, and a mean
free path or a collision frequency may be used for calculating the conductivity. The free
path becomes size dependent in small particles by enhanced surface scattering (Euler
1954,v Fragstein and Roemer 1958, Doyle 1958).Thus the electronic properties depend on
particle size differently in the quantum size region than in the free path effect (FPE)
region.
It should be possible experimentally to decide whether a discrete eigenstates or a
conduction band model is appropriate for a given sample of metallic particles. In the
present paper, this has been done by investigating the optical plasma resonance absorption
of spherical silver particles at different temperatures (300 K and 1.5 K) and evaluating
the dielectric constant of the particle material.
In such particles, special modes of surface plasmons (eg Crowell and Ritchie 1968,
Fujimoto and Komaki 1968, Kreibig and Zacharias 1970) appear. Their excitation by
light is described by the dielectric theory of Mie (1908).Clanget (1972)has shown recently
that only small deviations from Mies results occur when the Sauter-Forstmann bound-
ary condition is taken into account.
Kawabata and Kubo (1966) predicted as a quantum size effect that the first plasmon
mode should be broadened, because energy is transferred from the plasmon to single
electron excitations between the quantized levels. This effect is expressed by a size
dependent contribution to the dielectric constant (Kawabata-Kubo effect, KKE).
Another calculation of the absorption of silver particles in the quantum size region
has been given by Glauberman and Adamyan (1969). They predicted that when the
particle diameter is increased from 1 to 10nm, the position of the absorption peak should
shift through the whole visible spectrum.
To our knowledge, no calculation has been made of a quantum size effect, predicted
by Kubo (1969) for the temperature dependence of the dielectric constant. The electron-
phonon scattering, which is the prime cause of this temperature dependence in silver in
the investigated spectral region, may be suppressed in small particles, since it is difficult
to conserve both energy and quasimomentum if the eigenstates of the electrons, and in
free particles also of the phonons, are discrete. No electron-phonon interaction will be
possible in particles where AE exceeds the maximum phonon energy, which is 2 x 10- eV
in silver. If equality signs are inserted in equations (la) and (lb), Z < 4000 and Z < 250
is found for such particles, with and without symmetry degeneracy, respectively, and their
diameters are 2R < 4.8 nm and 2R < 1.9nm, respectively. According to Maksimov and
Motulevich (1972), the electron-phonon relaxation is related to the electron-phonon
coupling constant, which may thus be changed in small particles.
On the other hand, in the quasicontinuous energy band region (d > d,) the FPE
should be valid, which predicts size dependences of the dielectric constant and of the
Electronic properties of small silver particles 1001

plasmon peak position, which differ markedly from the quantum size effect predictions.
The experimental results given below will thus allow one to decide whether d < d ,
or d > d , for the investigated samples of silver particles.
Results of the temperature variation measurements are also given and discussed
below.

2. Theory

2.1. Plasma resonance absorption of silver particles


As is known from numerical computations (Kreibig 1970), the conduction electron
absorption in silver particles is restricted mainly to the excitation of the first spherical
surface plasmon mode, if RIAmax< 5 x (where R is the particle radius, A,, is the
wavelength of the plasmon peak). The absorption constant K of a system of particles
can be calculated using Mies theory, which gives the following simple expression for
particles, embedded with a volume concentration C in a medium of dielectric constant
eo, if R/Amax5 1.8 x
l8xC~;~~
K=
A((El + 2E0)2 + 2, (3)

The assumptions are made that C is low and the particles possess uniform sizes and
spherical shapes. The dielectric constant E = el + iez = (n + ik) (where n is the
refractive index, k is the absorption coefficient),defined for bulk material, is assumed to
describe suitably the particle material properties, irrespective of the particle size.
In equation (3) K does not depend explicitly on R, and thus any experimentally
observed size dependence of K may be related to size dependences of cl and/or eZ.
A Kramers-Kronig analysis method, described elsewhere (Kreibig 1970), permits
evaluation of the spectra of and e2 from measured K spectra, for particles where
equation ( 3 ) is valid.
Three other methods for evaluating E and changes of E, which may occur by varia-
tions of size or temperature, follow from equation (3). They yield E only for the wavelength
of the plasmon peak, however.
Method (i): If, as is the case of silver, e2 does not depend markedly on 1near A,,
the peak position is given by the minimum of the denominator of equation (3), that is
El(Amax) = -EO* (4)
The peak is shifted, if is changed, and for small changes we have

A = i,,,,.

d,/dA is nearly the same in the particles as in bulk silver (Kreibig 1970).
Method (ii): Combining equation (4) with equation (3) gives

Small changes AK,,, are thus related to changes Ac2 by


1002 U Kreibig

Method (iii): The halfwidth of the plasmon peak of equation (3) is determined both
by e2 and by de,/dA. Numerical computations have shown that for silver r depends
linearly on the refractive index n:
(,ax) = A (8)
A = 0.813 eV- for a particular choice of optical constants of bulk silver (Kreibig and
v Fragstein 1969).
Since n and e2 depend weakly on A near A,, in silver, the values resulting from methods
(ii) and (iii) can be attributed to a fmed wavelength; that chosen is the mean peak wave-
length. 405 nm.

2.2. The Kawabata-Kubo ejfect


If there are quantized one electron eigenstates in a particle, energy may be transferred
from the plasma modes to one electron excitations by dipolar transitions between these
levels. This energy transfer broadens the plasmon peak. In the theory of Kawabata
and Kubo (1966) the particle surface is not thought to scatter the electrons, but, rather,
to determine their discrete eigenstates. The quantum size broadening of the plasmon
peak is described by an additional term in c2, to be inserted into equation (3):
EZ(W9 R, = 2 , bulk(o) + 2, s(O, (9)
where e2,buk is the imaginary part of the dielectric constant of the bulk metal.
e2 is given by (R Kawabata, private communication)

32 e2 g(v) v=-
ho
62,,(W, R) =
n3hw R E,
where w is the angular frequency and E , is the Fermi energy.
1
g(v) = V- dx[x3(x + v)]~ v,=l-v V<l

vo = 0 v > 1. (1 1)
Since the energy of the first spherical plasmon mode in silver is about 3eV, whereas
E , = 5.5 eV, v < 1 holds for our investigations and we get:
g(V) = [(l + v ) ~ - (1 - v ) ~ ~ ] / ( ~-v ~[(2
) + v)(l + v ) ~- (2 - v ) ( l - v ) ~ ] / ( ~ v ~ )
+ In ([2 + v + (1 + v)I2]/[2 -v + (1 - ~ ) ~ ] ) / 1 6 . (12)
E, is taken as independent of R, and is consequently proportional to R-, No pre-
dictions about a size dependence of are made by the KKE.

23. The free path ejfect


The FPE is based upon the Drude-Sommerfeld theory and gives an expression for a
size dependent collision frequency w,,. The particle surface is regarded as a scatterer of
conduction electrons. Assuming this scattering process to be diffuse, the appropriate
mean free path LspheRof an electron, disregarding its coupling to the Fermi liquid,
can easily be calculated for spherical particles:
Electronic properties of small silver particles 1003

L(8) is the free path of an electron leaving an infinitesimal surface element dfat an angle
8 to its normal, after a scattering event.
If the number of scattering events per unit time, dw, is
dw = constant x dfdQ (14)
where d!2 is the solid angle, then:
'sphere R= (15 )
(Euler 1954, v Fragstein and Roemer 1958, Doyle 1958).
Equation (14) means that the scattering of each electron is isotropic. If, however,
a Lambert cosine law is assumed to guarantee an isotropic density of the scattered
electrons :
dw = constant x df'cos 8 dl2 (16)
we obtain
'sphere = :R* (17)
Provided that all scattering mechanisms of the conduction electrons in a spherical
particle are independent of one another, the effective collision frequency oDis given by
wD = wD, bulk + 'FILspherc. (18)
The numerical values for silver, used in the following, are: wD,bulk = 2.7 x 1013s-':
Fermi velocity vF = 1.4 x 106ms-'.
o,of equation (18) is assumed to be isotropic. It may be a rough approximation that
all scattering mechanisms, except the surface scattering, are taken as independent of the
particle size in equation (18). o, is now inserted into the Drude part of the dielectric
constant :

where Z is the interband contribution while opis the Drude plasma frequency. A possible
size dependence of E is disregarded, as it is assumed to be substantially smaller than that
of the Drude terms (Doremus 1964). Since o2 9 w; holds in silver near Amax, we obtain
from equations (18), (19) and (15):

or

In this approximation cl becomes independent of R, and according to equation ( 5 )


the same holds for Amax. The size dependent E~ of equation (20b) resembles equation (9)
'.
of the KKE, both containing an additional surface term proportional to R- Yet, their
numerical factors differ from each other, as will be shown later.
1004 U Kreibig

3. Experimental details

3.1. Sample preparation and sample properties


Measurable values of K can be obtained only with samples containing a large number of
particles (about 10" if R = 1.5nm). Conclusions about the behaviour of the single
particle can therefore be drawn only from absorption spectra of such samples, if most
of the particles have closely similar sizes and shapes and do not influence one another.
These conditions are approximately fulfilled for noble metal particles produced in
photosensitive glasses (Stookey 1949).Silver particles, developed in this glass, were thus
used in the present investigation.
The glass samples had the following composition: 70-75 wt% SO,, 25% Na,O,
04% A1,0,, 0-1 % ZnO, 0 . 3 4 4 % Sb,O,, 0 4 . 2 % CeO,, 0.02406%Ag,O.
The glasses were melted at 1450C for several hours, then pulverized, melted again,
and finally cooled down rapidly. The samples were colourless and free from schlieren
patterns and bubbles, yet, birefringence patterns could be observed when they were
placed between crossed polarizers. The dielectric constant eo is 2.25.
For particle nucleation the samples were irradiated for various times by a Hg
pressure lamp or by x rays. The particles grew from these nuclei when the samples were
tempered at 550C. The tempering process was interrupted repeatedly to record the
absorption spectra.
Plasma resonance spectra could be taken only for 1 2 340nm, since both the base
glass and the cerium ions absorb at shorter wavelengths. A greenish fluorescence has
been observed at about 280 nm.

I I I I I 1

200 300 4 00 500


A h )
Figure I. Measured absorption spectra of the Ag and Ce free base glass due to uv radiation,
after various times of tempering at 550 "C(K is the absorption constant, d the sample thickness).
J. Phys. F: Metal Phys., Vol. 4, July 1974 @ 1974. U Kreibig

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Electronic properties of small silver particles 1005

Figure 1 shows that the irradiation produces additional absorption in the Ag and
Ce free base glass, which, however, vanishes rapidly when the sample is tempered. This
renders the investigation of extremely small particles more difficult.
Because the number of particles is determined by the irradiation (Maurer 1958,
Doremus 1965),it is constant during each tempering cycle. The increase of the absorption
due to prolonged tempering time can therefore be attributed directly to the growth of the
single particle. The integral plasmon absorption is proportional to K,,,T, and also to
the concentration C. The growth of each particle between the nth and the ( n + 1)th
interruption of the tempering process is therefore given by

Once one value of R is known, all other particle radii of a tempering cycle are given by
equation (21). Larger particles have been investigated with the electron microscope
for this purpose (Kreibig and v Fragstein 1969). The accuracy of the method is estimated
to be about AR/R N & 15 %. Dupree and Smithard (1972) determined the sizes of very
small particles directly with an electron microscope and found reasonable agreement
with our results. For a particular sample, the two methods yielded particle diameters of
5.5 and 4 nm, respectively.
In the present investigation, the samples for electron microscopy were prepared by
pulverizing the glass and suspending it in water. Because of the solubility of the glass,
some of the embedded particles were thus dissolved from the matrix and could be
deposited on to carbon films. A typical electron micrograph is shown in figure 2 (plate).
The particles have evidently coagulated after having been dissolved from the glass.
Their qhapes are almost spherical. The size distribution histogram of a particular sample

r--
I l / l I / I I l l l I 1
03 I1 1.9 23
1 R,
Figure 3. Size distribution hlstogrdm of a sample of Ag particles in gldss with mean particle
diameter 2R = 11.5 nm.
1006 U Kreibig

is given in figure 3. The distribution curve is fairly narrow, 74% of the particles having
radii Ri between 0.7 < R J R < 1.3 ( R is the mean radius). The distribution of the particle
sizes is perhaps even narrower in the glass since the described method of preparation
is rather crude.
The high growth temperature and the extremely slow growth velocity (eg about
1 atoms s-') may favour spherical particle shapes. Migration of edge and corner
atoms along the surface causes a rounding of the particles (Mayer 1955). Further, re-
arrangements of inner atoms may keep the lattice imperfection density low.

3.2. Apparatus
The absorption spectra at room temperature were recorded with a commercial Zeiss
Double Prism Spectrophotometer in the region 340 < I < 605nm. Reflection losses
due to the glass surfaces could be eliminated by irradiating only one half of the samples
and using the colourless part as a reference sample. Particles with 2.2 < 2R < 21 nm
were investigated at room temperature.
A special apparatus was used for the low temperature measurements. The samples
were put into liquid 4He, the vapour pressure of which was lowered to about 5 mm Hg.
The true sample temperature was thus about 1.5 K.
Samples with mean diameters of 3.2, 3.4, 4.3, 5.4, 11.5 and 21 nm were investigated.
Each low temperature measurement was preceded and followed by a measurement at
room temperature. Since the changes of the absorption spectra due to the cooling
down were only small, special care had to be taken to prevent the optical equipment
becoming unadjusted during the cooling down or warming up. We therefore renounced
conventional optics, and used, instead, a combination of rigid and flexible quartz light
guides (made by Schott, Mainz, Germany).

4 Experimental results

Two plots of measured plasma resonance absorption spectra of silver particles in glass
are given in figures 4(a) and 4(b) and they show clearly two main features :
First, the plasmon peak is markedly broadened when the particle size is decreased.
This confirms results of Doremus (1965), Kreibig and v Fragstein (1969) and Smithard
(1973).
Secondly, the changes of the peak due to variations of temperature are smaller in
minute than in big particles. This has earlier been observed at high temperatures by
Doremus (1965).
The peak position I,,, is only slightly shifted by variations of sample temperature
and of particle size in the investigated size region 2R < 21 nm. The size dependence is in
accordance with our previous results (1969),but is somewhat lower than that reported by
Smithard (1973).This contradicts the quantum size theory of Glauberman and Adamyan
(1969),which predicts a shift of I,,, through the whole visible spectrum in the investigated
size region.
The size dependence of the bandwidth r is shown in figure 5 and is compared with
experimental data of Doremus (1965) and Smithard (1973). Our own previous results
(1969) are added.
In his paper, Doremus plotted l / r as a function of (Kmaxr)li3. To estimate roughly
the appropriate sizes he assumed the diameter dshifFabove which the peak was found
Electronic properties of small silver particles I007

/ / l l / I 1 I 1
i60 380 400 420 4%

hgure 4. Measured absorption spectra of Ag particles in glass at 300 K and 1.5 K. Mean
particle diameters: (a) 2R = 11.5nm and (b) 2R = 3.4nm ( K is the absorption constant,
d is the sample thickness).

to shift to longer wavelengths, to be 10 nm. Our computations have shown this diameter
to lie between 15 and 20nm, the shifts being distinct above 20nm (1969 figure 7). We
therefore chose a diameter (IIhift of 1 7 . 5 to
~ compute the particle sizes plotted in
figure 5 for his data of l/r.
The spectra of c1 and c2, derived by Kramers-Kronig analysis from the measured
absorption spectra, are shown in figures 6(a) and 6(b).They are in good accordance with
our earlier results (1970). The marked increase of c2 with decreasing particle size, which
is shown once more for the wavelength 405 nm in figure 7 clearly reflects the increase of r.
The particle size 2R = 21 nm exceeds the limit of validity of equation (3), which is
used in the analysis, and the c2 spectra had thus to be slightly corrected by an iteration
method.
As figure 4(a) shows, the plasma peak is sharpened by cooling the samples, and c2
is accordingly lowered. This change equals the bulk value in larger particles and is
diminished as the particles become smaller (figures 6(b) and 8). The temperature depen-
dence in figure 6(b) should, however, only be regarded as qualitative confirmation, since
the accuracy of the Kramers-Kronig analysis is considered to be of the order of the
changes in c2, due to temperature variations. Systematic errors are included in the
analysis, because the interband absorption spectra of the particles (A < 340nm) could
not be measured but had to be computed from the optical constants of bulk silver
(Daniels 1969), and thus possible changes of the interband absorption with size and
with temperature are disregarded.
The spectra of cl, examples of which are given in figure 6(a), show slight dependence
on size and on temperature.
1008 U Kreibig

E
a +

c
i
A A 6 e
** +
20 .
+
I I 1 , ,
I , , , , I , 1 , , I ,
5.0 100 IM 20.0
2R(nm)
Figure 5. Reciprocal of the halfwidth of the plasma absorption band, against particle
diameter 2R. 0 Own experimental results: Acomputed from experimental results of Doremus
+
(1965) wing a diameter d,bil, of 17.5 nm: experimental results of Smithard (1973).

The methods, described in 52.1, for evaluating the optical constants at A = 405 nm
are more accurate than the Kramers-Kronig analysis, being limited only by the experi-
mental accuracy. The following discussion will therefore be restricted to their results,
which are listed below :
Method (i): The absorption peak is slightly shifted to shorter wavelengths by cooling.
This shift appears to be weakly size dependent, but this is of the order of the experimental
error, which is somewhat higher in very small particles because of the broadness of the
peak.

follows AE, = -0.045, or AE,/E, = (1.0 k 0.3)%.Since E,


wavelength region, we have Ak = 0-01.
-
The mean shift for all particle sizes is M,, = (0.6 f 0.2)nm, and from equation (5)
-k2 in the investigated

Method (ii): Equations (4), (7) and (8) can be combined giving N -2(2~,)"~
x Al?AKmaX/Kmax. The values of resulting from this relation are plotted in figure 8
against the reciprocal of the particle radius. The points are averages from several
measurements, the bars give the error of each measurement.
Method (iii): Equation (8) allows one to evaluate changes of n. To obtain Ac2, the
changes of k resulting from method (i) must be included:

Ac2 = 2kAn + 2nAk = ~ ( ~ E , ) ' / ~ A+A 2Al?BAAmaX


T B=*l
I=d,,,

The average values of Ae2 for each particle size are plotted in figure 8.
The results of both method (ii) and (iii) indicate a distinct decrease of the temperature
dependence of c2 with decreasing particle size.
Equation (3) shows that Amax and l? depend markedly on E,. The temperature de-
pendence of E,, has, however, only negligible influence, as has been proved by numerical
computations, using E, (300 K) - E, (1.5 K) = 1.5 x (Landolt-Bomstein).
Electronic properties of small silver particles 1009

A
Bulk
B
-0
380 400 420 440
A h )
Figure 6. Spectra of (a) c1 and ( b )c2 of Agparticles of various diameters, evaluated by Kramers-
Kronig analysis from measured absorption spectra at 300 K (curves A) and 1.5 K (curves B).
The spectra are from Leis (1970).

5. Discussion

5.1. Size dependence ofel at 300 K


The slight size dependence of el, shown in figure 6(a),is explained quantitatively by the
FPE as due to the increasing importance of wD in the Drude term of equation (19), and
no variations of wp, which mainly determines the Drude part of el, are indicated. We
hence conclude that, for particles containing down to about lo3 atoms, the quantity
N / m where N is the conduction electron density and m is the optical effective mass equals
that of bulk silver within the limits of experimental error. The value of copwill be given in
$5.2. Only in the most minute particles ( R N 1.1 nm) does the peak position indicate a
slight increase of Nlm, yet the determination of A,, is difficult there because of the
broadness of the peak.

5.2. Size dependence of e2 at 300 K


In figure 7, c2 is plotted against 1/R for I = 405nm. Although the Kramers-Kronig
values differ slightly from the values evaluated from the halfwidth r, the linearity is
obvious. The dependence is given by
~ ~ ( 4 nm,
0 5 R ) = 0.23 + 2*64/R R in nm. (22)
1010 U Kreibig

The extrapolated value for 1/R + 0 agrees well with the bulk value, c2.buk (410nm)
= 0.224, measured by Leis (1970).
The linear dependence is predicted by the KKE and the FPE. Both are plotted in
figure 7. The KKE gives a slope of 1.11nm, which is less than half of the experimental
value. The slope due to the FPE agrees with the experimental result, being 2*64nm, if
Lsphere= R is used. It is 2.0nm for Lsphere= $R.
The experiments thus clearly support the FPE, which is based on the assumption of
metallic conductivity in the particles. The KKE predicts correctly a linear dependence,
but quantitative agreement is not found. We hence conclude that the condition d d, of =-
equation (2) is fulfilled down to mean diameters of 2.2 nm (about 400 atoms per particle)

1 I I I

- /:
,

I 1 1 I 1 I
02 04 0.6 08
/?-I (nm-1)
Figure 7. E&,? = 405nm) of Ag particles, against 1/R. Experimental: 0 from absorption
halfwidth, 0 from Kramers-Kronig analysis. Curves F P E ~and FPE2: free path effect with
Llphcrc= R and Laphere
= 4R. Curve KK: Kawabata-Kubo effect.

in the system of silver particles in glass and still smaller particles are needed to study
quantum size effects. Figure 1 shows why it is difficult to investigate them in this system.
In addition to the lifetime effects, lattice imperfections or irregular shapes of the
particles influence the energy levels. More important for the smearing out of the energy
bands are possibly the interactions with neighbouring matrix ions, which increase with
decreasing particle size (ie with increasing ratio of surface to volume atoms).
According to Smithard (1973) the FPE should even hold for particles with 2R 1 nm,
ie for particles consisting of approximately 40 atoms.
-
In 45.1 it was stated that wp does not depend on R. Its value can now be computed
from the slope of the experimental curve in figure 7. Assuming the free path of equation
(15), it follows from equation (20) that de,/d(l/R) = w,Zv,/o3, and we obtain w, = 1.38
x 1016s-'.
In the free path effect, it is assumed that the surface scattering is the sole size depen-
dent scattering mechanism; but there may also be other size dependent processes.
Electron micrographs of noble metal particles, grown by evaporation (eg Ino 1966) or by
chemical reduction (eg Kreibig and Zacharias 1970), show that these particles generally
Electronic properties of small silver particles 1011

consist of several grains, regardless of their sizes. If the density of grain boundaries
depends on the particle size, the grain boundary scattering (eg Hasse 1958, Andrews
1965, Bispinck 1970, Zacharias 1970, Hunderi 1973) will also display a size dependence.
The reasonable accordance of the experimental results of figure 7 with the FPE and the
bulk values of Leis shows that this mechanism is unimportant in the silver particles of
our system. Presumably the high growth temperature and low growth velocity favour
the development of particles with low lattice imperfection density.

5.3. Size dependence of'de.,/rlT


The temperature dependence of E of bulk silver is mainly caused by the electron-phonon
relaxation in the investigated wavelength region. At 1.5 K the major part of it is frozen
out (Holstein 1954). In the bulk metal, a distinct temperature dependence is observed in
e2, but only a slight one in el. In the particles, the change of e2 due to temperature
variation proved to depend on their sizes. Ae2 is lowered by about 65% in the investigated
size interval. A dependence roughly proportional to R-' can be recognized in figure 8:
e2 (405 nm, 300 K) - e2 (405 nm, 1.5 K) = Ae2 (405 nm)
N 0.07 - 0.08/R R in nm. (23)
The extrapolated value for 1/R -,0 corresponds well with the bulk value (Leis 1970) of
Ae2 (410nm) = 0.066.
An essential part of this size dependence is caused by the thermal contraction of the
particle during the cooling down. Both the bulk and the surface terms, in equations (10)
and (20a), respectively, are changed by lattice contraction. The surface terms increase in
small particles, and this renders Ae2 size dependent.

c -1
-Bulk - -- - I

005

4-

0
0011

02 04 06
A'(nm-')
Figure 8. A<?(; = 405nm) = e2 (300K) - et (l.SK), against 1/R. Experimental: 0 with
equation (7), 0 with equation (8), A from Kramers-Kronig analysis. Calculated: curve FPE,
free path effect with thermal contraction; curve KK, Kawabata-Kubo effect with thermal
contraction. Ac2, measured by Leis (1970).
1012 U Kreibig

The surface term E;,? of the FPE in equation (20), including N and uF, contains R as
R-5.Accordingly, a variation AR due to a temperature change yields A E ~ = , - e l , ,5AR/R
in a particle of radius R. This gives a negative sign to d e i $dT. Since the sign of de2,bulk/dT
is positive, the changes in e2, and partly cancel out. Hence, the overall temperature
dependence of e2 is quenched in small particles, and even changes sign in extremely
minute particles. The temperature dependence of E ~ of, the ~ KKE cannot be estimated
in such a simple way, but numerical computations have shown the functional dependence
to be similar to that of the FPE,if one considers the Fermi energy in equation (10) to be
proportional to N2I3.A quantitative evaluation is difficult since the thermal expansion
properties of a single component in a composite material, such as the photosensitive
glass, are exceedingly complicated. We wish to estimate the resulting thermal particle
contraction with a simple model: as is known from investigations of the internal stress
of silver films evaporated on to glass substrates (eg Kinosita 1968),the adhesion between
silver and glass is very high. The adhesion at the glass-metal interface of the embedded
silver particle will consequently cause its linear thermal expansion coefficient, a,,,, to
differ from the coefficient of bulk silver, aAg.The coefficient of the host matrix, clglass, is
smaller than aAg,and thus, without adhesion, the particles would shrink to a greater
extent on cooling than the cavity in the matrix.
If we assume that the particles adhere closely to the matrix, elastic deformations both
of the matrix and the particles will occur, according to the elastic compression moduli
K~~~ and K ~ The ~ thermal
. volume contraction is given by dVeff/V2: 3aeff d T (V is the
particle volume). The corresponding values of the free particles and of the empty cavity
in the matrix are dVAg/V and dVghsJV. Since dVAg> dVghss,elastic deformations
appear in the particle and the surrounding glass: (dVAg- dVe,,)/V = - p A g / ~ A gand
(dVglass- dV,,,)/V = -pglas$~glasswhere p is the strain normal to the interface. The
equilibrium condition pAg+ pglass= 0 yields:
dT
- - - 3(aAg(T) 'Ag
'e''' + aglass(T) 'glass)
V 'Ag -k 'glass

and, hence, the thermal contraction of our particles is given by

The following values were used for numerical evaluation of equation (26):
icAg = 10.8 x 10"dyncm-2; K~~~~ = 5 x 10"dyncm-2 (Landolt-Bomstein)
1.5 K
aAg(T)dT= -4.25 x (Waterhouse and Yates 1968)
6 0 0 K

s,,
1.5K
aghss(T)dT= -1.5 x (Landolt-Bornstein 1962).

From equation.(26) we obtain AV,,,/V = - 1.01 x which is to be compared with


AVAg/V = - 1.28 x of bulk silver and AVgh&' = -0.45 x of the glass.
The influence of T on K has been disregarded. The same holds for a size dependence of
I C ~which
~ , may occur because the ratio of surface to volume atoms increases in small
particles. Considering now spherical particles we put AV,,,/V 1: 3ARIR. The influence
of the thermal contraction on Ae2 can then be computed from equations (9) and (20) for
the KKE and the FPE,respectively. The results are plotted in figure 8. For the com-
putation the bulk value of AeZwas taken from Leis (1970).
Electronic properties of small silver particles 1013

Distinct size dependences are obvious. The plots against 1/Rshow linear dependences
and the slope for the FPE case is about twice that for the KKE case.
The measured quenching of dc,/dT in small particles somewhat exceeds the predic-
tion of the FPE. It differs, however, markedly from the KKE curve. If the KKE were
assumed to be valid, this difference could be attributed to the suppression of the electron-
phonon interaction in particles with quantized eigenstates, mentioned in 1. This inter-
pretation may be questioned, however, since the difference may merely be a consequence
of the failure of the KKE to describe the measured size dependence of E, at a fixed tem-
perature.
Changes of the phonon spectrum of small particles due to surface phonons (eg
Dickey and Paskin 1968, Genzel and Martin 1972) and phonons of the host matrix
possibly cause an additional size dependence in the electron-phonon relaxation, which
may affect dc,/dT.

5.4. Size dependence of' dc,ldT


dc,/dT does not depend on particle size within the limits of experimental accuracy.
At 2=405 nm the relativechangedue tocooling from 300 to 1.5KisAc1/c1 =(1.0+0.3)%.
This value agrees with the change of cl, AEJE, = 1.15%, which is calculated by con-
sidering the thermal lattice contraction in the Drude term of e , of equation (19).

6. Conclusions

The size dependences, observed in the optical plasma resonance absorption and in its
variation due to temperature changes, of small silver particles in photosensitive glass
have been expressed by a size dependent dielectric constant of the particle material.
If we accept that the Kawabata Kubo effect and the free path effect describe correctly
the size dependences of c2 in the particle size regions d < d, and d > d, of equation (2),
respectively, we can conclude from the accordance of the experimental results with the
FPE predictions that silver particles in photosensitive glasses behave down to diameters
of 2.2 nm (or, to approximately 400 atoms per particle) like metals with a common
conduction band. In the most minute particles more than half of the atoms form the
particle surface.
The agreement with the free path of equation (15), Lsphere = R, is quantitative and
implies that the scattering of the conduction electrons at the particle surface is completely
diffuse. The predictions of the KKE differ from the experimental results by a factor of
about two.
No marked changes are observed in E,, and this indicates that N / m , the ratio of
electron density to optical effective mass, is independent of R within the limits of experi-
mental accuracy. The value of cop is wp = 1.38 x 10l6s-'.
It can therefore be concluded that normal metallic properties are present when about
400 atoms have condensed in a cluster.
The observed size dependence of dc,/dT, being roughly proportional to R - ' , does
not allow a definite interpretation. If we assume the FPE to be valid, the main part of the
size effect can be explained by the influence of thermal lattice contraction, although there
is no quantitative agreement.
Lattice contraction also causes the observed dc,/dT, which proved to be independent
of size within the limits of accuracy.
1014 U Kreibig
On the other hand, thermal contraction explains only 30% of the measured size
dependence of e2, if the Kawabata-Kubo effect is taken as valid. The difference might
then be explained through the suppression of the electron-phonon scattering due to the
energy level spacing in minute particles.This interpretation, however, may be questioned,
since the Kawabata-Kubo theory fails to describe the size dependence of e2 itself in the
size region investigated. None of the other relaxation mechanisms which contribute to
the Drude relaxation frequency of silver, nor the interband part of the dielectric constant
of equation (19) seems to develop a dependence on particle size which exceeds the limits of
experimental accuracy.
The experiments have not verified the marked size dependence of the absorption band
position, predicted by the quantum size theory of Glauberman and Adamyan.
In the search for quantum size effects in the-system of silver particles in photosensitive
glass, particles are thus required which consist of less than 400 atoms, and the measure-
ments of Smithard indicate that they should be substantially smaller.

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