Permittivity and transmission of metals

Davíð Örn Þorsteinsson (1), Guðjón Henning Hilmarsson (2) and Saga Huld Helgadóttir (3)
1) [email protected] 2) [email protected] and 3) [email protected]

Abstract: Transmission measurements for both with wavelength. The relation between r and  is
nanosphere solutions and various metal films on
glass are performed. The results are then com-  = r 0 (2)
pared to theoretically calculated values. Also, the
electron permittivity of the metal films is compared where r is the relative permittivity of the material
to the Drude model. and 0 is the vacuum permittivity. The relative
permittivity can be compared to the Drude model
Introduction
Thin films of silver and gold, with thickness ωp2
smaller than the wavelength of light, are put on D (ω) = 1 − (3)
ω(ω + iγ)
glass. When light strikes the surface of a film it is
either transmitted or reflected. Transmission and where ωp is the bulk plasma frequency and γ is the
reflection of the films can be calculated if the re- intraband damping term (inverse of the relaxation
fractive index of the material is known. The refrac- time τ ). Experimentally determined values from
tive index here is a complex number, commonly M. G. Blaber et al[2] used in the Drude model can
denoted as n̂ = n + ik, where the imaginary part be seen in table 1.
gives absorbtion of the material and the real part
gives the phase speed. From this refractive index Table 1: Experimental determined values used in
the electron permittivity can be determined. the Drude model.
Nanoparticles, or ultrafine particles, have a diam-
eter between 1 and 100 nm. Nanoparticle research Element ωp [eV ] γ[eV ]
is currently a very interesting area because of a Ag 9.6 0.0228
wide variety of potential applications in biomedi- Au 8.55 0.0184
cal, optical and electronic fields. They are a bridge
between bulk materials and atomic or molecular A Fabry-Pérot etalon is usually a transparent plate
structures. A bulk material should have constant with two reflecting surfaces. Its transmission spec-
physical properties regardless of its size. But at trum as a function of wavelength shows peaks of
the nanoscale, properties dependent of size are of- large transmission corresponding to resonance of
ten observed. That is the properties of materials the etalon. Interference between the multiple re-
change when their size approaches the nanoscale flections of light between the two reflecting sur-
and the percentage of atoms at the surface of a faces is the reason for the varying transmission
material becomes significant. Nanoparticles are function of the etalon. If the transmitted beams
small enough to confine their electrons and pro- are in phase a constructive interference occurs
duce quantum effects and therefore often possess which corresponds to a high transmission peak of
unexpected optical properties. Gold nanoparticles the etalon. If the transmitted beams are not in
appear deep red to black in a solution, they melt phase, destructive interference occurs. This cor-
at much lower temperatures than gold slabs and responds to a transmission minimum. The wave-
the smaller the particles are the greater the solar length of the light, the angle it travels at through
absorption is. the etalon, the thickness of the etalon and the re-
fractive index of the material between the reflect-
Theory
ing surfaces determines whether the multiple re-
The electron permittivity, r , is the material’s abil-
flected beams are in phase or not. A high finesse
ity to transmit, or permit, an electric field. The
etalon shows sharper peaks and lower transmission
electron permittivity for silver and gold can be cal-
minima than a low finesse etalon.
culated from
To complicate things the symmetry of etalon is
r = (n + ik)2 (1) broken with an addition of a thin film. Reflection
and transmission of the film is typically followed
where the real part, n, is the refractive index and with a change in phase while a simple junction,
the imaginary part, k, indicates the amount of loss like etalon, gives a change in sign at most.
due to absorption when the electromagnetic wave In this experiment one to three layers on a glass
propagates through the material. For gold both are observed.
parts vary with wavelength, nAu decreases and kAu When a particle’s diameter d is much smaller
has an overall increase. For silver the refractive than the wavelength of light in the surrounding
index is a constant, nAg =0.045, and kAg increases medium, d  λ, the interaction of the particle
with the electromagnetic field can be analyzed us- A Matlab program was provided in order to calcu-
ing the simple quasi-static approximation. The late theoretical transmission of the metal films.
phase of the harmonically oscillating electromag-
Calculations
netic field is practically constant over the particle
In figs. 2 and 3 the relative electron permittivity
volume, so the spatial field distribution can be cal-
for silver and gold is determined with eqs. (1) and
culated by assuming a particle in an electrostatic
(2) and compared to the Drude model, eq. (3).
field. The harmonic time dependence can then be
added to the solution once the field distributions
are known. This is the lowest-order approximation
of the full scattering problem and describes the op-
tical properties of nanoparticles of dimensions be-
low 100 nm for many purposes. The polarizability
of a small sphere of sub-wavelength diameter in
the electrostatic approximation is
 − m
α = 4πa3 (4)
 + 2m
where a is the particle’s radius, m the dielectric
constant of the isotropic and non-absorbing sur-
rounding medium and  the simple complex num-
ber taken for the dielectric function (ω) which de- Fig. 2: =() for both measurements and the
scribes the dielectric response of the sphere. Res- Drude model.
onance frequency (wavelength) is when α reaches
its maximum value.
Experimental
In the setup an EQ-99 LDLS (Energetiq-99 Laser-
Driven Light Sources) was used as a light source.
The light source emits white light because it has
a very high brightness across the visible spectrum.
In front of the lamp is a filter to decrease the light
intensity towards the sample. Behind the sample
is another filter to focus the light to the spectrom-
eter. This setup can be seen in fig. 1.
Transmission as a function of wavelength is mea-
sured for thin metal films. First a background
measurement is made along with the spectrum
from the light source. The setup and surround- Fig. 3: <() for both measurements and the
ings are kept unchanged while transmission mea- Drude model.
surements for various thin silver and gold films
are made. The films measured were 15 nm and Transmission for the three types of silver films on
30 nm thick silver films, two 15 nm silver films the glass is shown in fig. 4. The Matlab program
with a 670 nm thick plastic in between and 6 nm was used to find the best match to the measured
and 15 nm gold films. Because of irregular trans- curves. A loss factor of k=0.027 for all wavelengths
mission activity for the 6 nm gold film, compari- was added to the PMMA plastic in the calculations
son measurements are made for gold nanospheres for a better coherence with measurements.
with diameters of 50 nm and 100 nm. Before this The transmission for the 6 nm and 15 nm gold
was done, new background measurements with a films can be seen on fig. 5, along with the the-
water-jacketed absorbtion cell were made. Then oretical transmission calculated with the Matlab
the particle solutions are added to the cell. program.
Transmission for the 50 nm and 100 nm gold par-
ticles is shown in fig. 6 along with accurately cal-
culated values for 20, 40 and 80 nm gold particles
acquired from P. K. Jain et al[1] . The resonance
wavelength for the particles are shown in table 2.
Eq. (4) with the electron permittivity from eq. (1)
Fig. 1: Schematic experimental setup. a) Light is used to calculate the resonance wavelength for
source; b) filters; c) mounted sample; d) spectrom- a small gold particle, a  λ, in various mediums.
eter. The results can be seen in table 3.
 Table 2: Resonance wavelenght for the gold par-
ticles.

Diameter [nm] Wavelength [nm]

20 521
40 528
50 534
80 549
100 569

Table 3: Resonance wavelengths for gold

nanoparticles in various mediums.

Fig. 4: Measured and calculated transmission as Medium Refr. index n Res. wavelength [nm]
a function of wavelength for the silver films. Air 1.0 536
Water 1.333 551
Glass 1.5 564

than expected. The PMMA thickness controls at

what wavelenghts the transmission peaks are, so a
730 nm thick PMMA is more likely than the ex-
pected 670 nm. Also, the plastic might have a
curved surface, making the middle thicker than
the edges, which might be the reason for this dif-
ference.
For the gold and silver films, figs. 4 and 5, the
measured transmission is somewhat smaller than
theoretically calculated. This can be caused by
Fig. 5: Measured and calculated transmission as losses from the rugged surface of the glass and from
a function of wavelength for the two gold films. the glass to air junction. These losses were not
included in the calculations.
The 6 nm gold film from fig. 5 has an unexpected
behaviour. The cause of this is because it is so
thin that it starts behaving like individual particles
instead of a solid film. The unexpected drop in
transmission around 500 nm can to some extent
be related to the transmission drop of the gold
nanospheres from fig. 6.
The measurements of the gold nanoparticles fit in
with values taken from P. K. Jain et al[1] for 20,
40 and 80 nm particles.
References
[1] Prashant K. Jain et al. Calculated absorption
and scattering properties of gold nanoparticles
Fig. 6: Transmission as a function of wavelength of different size, shape and composition: Appli-
for the gold nanoparticles. The dotted lines show cations in biological imaging and biomedicine.
the resonance freq. for nanospheres with different The journal of physical chemistry, 2006.
diameters from table 2. [2] Martin G. Blaber et al. Search for the ideal
plasmonic nanoshell: The effects of surface
scattering and alternatives to gold and silver.
The journal of physical chemistry, 2009.
Conclusion
[3] http://www.raunvis.hi.is/~ario/fr-lj/
As can be seen in figs. 2 and 3, the Drude model
FabryPerot07.pdf
is relatively consistent with measured permittivity
of silver and gold, except for =() of gold, where [4] http://en.wikipedia.org/wiki/Fabry-Perot_
interferometer
the Drude model is by no means comparable to
[5] http://en.wikipedia.org/wiki/Nanoparticle
the measured value.
Transmission measurements of silver, seen in fig.
4, show that the PMMA plastic is probably thicker