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The consistent application of Maxwell–Garnett effective medium theory to

anisotropic composites

Article  in  Applied Physics Letters · May 1997

DOI: 10.1063/1.118821 · Source: IEEE Xplore

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The consistent application of Maxwell–Garnett effective medium theory
to anisotropic composites
I. L. Skryabin, A. V. Radchik, P. Moses, and G. B. Smitha)
Department of Applied Physics, University of Technology, Sydney, Broadway, N.S.W. 2007, Australia
~Received 27 December 1996; accepted for publication 24 February 1997!
The Maxwell–Garnett class of effective medium model applies if a representative cell can be found
whose polarization vanishes upon insertion in the effective medium. For an anisotropic composite
with randomly distributed ellipsoidal particles aligned along the principal axis, this leads to
electrostatic restraints on the shape of such cells. It is shown that the cell boundary must have
different depolarization factors to the inclusion within the cell. Practice is to equate them. A new
physically correct ellipsometric modeling routine still with only two fitting parameters is
demonstrated. © 1997 American Institute of Physics. @S0003-6951~97!00517-2#

This article seeks to refine fundamental ideas used in lish a broad principle which dictates the link between the
electrostatics and some optical problems which involve ar- particle shape and the additional ‘‘shape parameters’’ in
rays of polarizable inclusions. The simplest models use ei- simple Maxwell–Garnett type models. ‘‘Envelopes’’ in such
ther the classical Lorentz cavity approach or the related con- theories may be either representative cells containing one
cept of a representative cell containing one inclusion which particle1,2 or a Lorentz cavity containing many inclusions.
when embedded in the medium produces no additional po- Our second aim is to refine the practical application of an-
larization ~or scattering!. For random arrays, the term ran- isotropic Maxwell–Garnett models, in ellipsometric model-
dom unit cell ~RUC! was introduced for the latter ing routines.
approach.1,2 The issue of how to handle such problems when We consider an anisotropic composite as a dielectric ma-
either the particles or the array are anisotropic has not been trix ~the host! with embedded ellipsoidal particles ~the guest!
rigorously addressed, although these systems are often mod- aligned along the optical axis ~Fig. 1!. Two extreme limits of
eled using various simple but unjustified assumptions.3–5 these ellipsoids are either spheres or cylinders so this
We seek to correct a common practice in effective me- approach covers all possible degrees of anisotropy, which
dium models for ellipsoidal inclusions. Composites contain- are described by the set of guest depolarization factors
ing inclusions which are nonspherical, will display either L gj ( j5x,y, or z!. The extended Maxwell–Garnett effective
uniaxial or biaxial optical response. The complex refractive medium theory1 is usually expressed as
index N5n2ik will be a 333 tensor in these materials, if e MG
j 2eh e g2 e h
the effective medium approach is applicable. The composite 5f , ~1!
behaves like a single component anisotropic material in its e h 1L j ~ e j 2 e h !
h MG
e h 1L gj ~ e g 2 e h !
optical response. where e MG
j is an effective dielectric constant; f is a volume
It is possible, in principle, to extract the components of
N using spectroscopic ellipsometry. However, in practice,
a multiparameter model ~either polynomial or oscillator type!
for each principle component of N introduces many fitting
parameters. Nevertheless inversion or modeling of ellipso-
metric or spectrophotometric data to obtain
N5(N x ,N y ,N z ! has been attempted.5–7 Examples of impor-
tant materials where such responses occur include columnar
thin films,8 metal/insulator composites used for glare and en-
ergy control, micropolarizing materials,9 and nanostructures.
Some of these exhibit strong absorption anisotropy leading
to asymmetric transmittance for light incident in the same
plane but opposite sides of the normal.8 If reliable and sim-
ply implemented effective medium models and some struc-
tural information is available the number of arbitrary fitting
parameters in the models is reduced and they have a physical
basis. Various simple effective medium models for aniso-
tropic composites exist and are widely used in practice.
Some of these formulations, however, neglect underlying
physical restraints. Unfortunately, it is these that seem to
have been more widely used to invert ellipsometric data.6,7
Our purpose in this article is two-fold. One is to estab- FIG. 1. An anisotropic composite with ellipsoidal inclusions and two pos-
sible basic cells for use in deriving the MG model. Cell with surface geo-
metrically similar to its inclusion is on the left and one in which it is
a!
Electronic mail: G.Smith@uts.edu.au confocal is on the right.

Appl. Phys. Lett. 70 (17), 28 April 1997 0003-6951/97/70(17)/2221/3/$10.00 © 1997 American Institute of Physics 2221
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fraction of the guest particles; superscripts g and h denote
guest and host matrix, respectively. In all examples, we have
seen to date the practical realization of Maxwell–Garnett
theory ~1! in ellipsometric procedures is simplified by the
assumption6,7,10 L g 5L h . For an ellipsoid of rotation ~Fig. 1!
with semi axes a,b5c, the depolarization factors of this el-
lipsoid are given by11 L z 5(1/3) 2 F 1 (1,1,5/2,12 x 2 ), L x,y
51/2(12L z !, where x 5a/b ~anisotropic ratio! and 2 F 1 is a
hypergeometric function.12 For an ellipsoid with all three
semi-axes, different ~aÞbÞc! more complex expressions
for L j apply but conclusions are the same. L g 5L h means
x g 5 x h . This assumption of geometrical similarity in shapes
is demonstrated in Fig. 1 lower left ~particle in its cell!. Al-
though intuitive structurally, it is not correct.
To derive the Maxwell–Garnett Eq. ~1! for ellipsoidal
inclusions, the Laplace’s equation for a coated ellipse is
solved1 with the following necessary assumption: the coating
or cell surface is confocal with the ellipsoidal particle as seen
in Fig. 1, lower right. Therefore geometrical similarity be-
tween the particle and shell, would explicitly lead to a dif-
ferent effective medium model than that of Maxwell–
Garnett. The choice L g 5L h in ~1!, though adopted widely,
contradicts the following simple electrostatic arguments. A
metallic ellipsoid within a confocal dielectric is placed in an
external uniform electrostatic field. The shell yielding a
Maxwell–Garnett approximation represents the surface of a
shell whose dimensions depend on the fill factor f of guest
material. Now let us vary f ~i.e., shrink or expand the inner
ellipsoid! in two different ways.
~1! The shrunken ellipsoid remains confocal with the outer
shell. As both surfaces are still equipotentials, the
shrinking of the inner ellipsoid would not perturb the
internal field and therefore the polarization of the outer
shell stays the same. In other words, the shrinking pro-
cess will be reflected in ~1! only by the change of the fill
factor. The surfaces of the inner and outer ellipsoid are
coordinate surfaces in the same frame and can be con-
sidered as electrostatically similar.
~2! Geometrically similar shrinking has the shrunken inner
ellipsoid semiaxes proportionally smaller in relation to
the outer ones. The decrease in size shifts the focal po-
sitions, so the inner and the outer ellipsoids are not equi-
potentials of the same coordinate frame. The field lines
are distorted by this shrinking so the polarization of the
outer shell changes. It is obvious that this change in po-
larization cannot be represented simply by varying the
fill factor in ~1! so a Maxwell–Garnett effective medium
model is invalid.
To summarize, for a general Maxwell–Garnett type of
effective medium theory, the cell can be constructed only to
be electrostatically similar with the inclusion surface. The
shape of this electrostatic unit cell ~EUC! must also produce
a uniform electric field within the cell. Only a sphere, ellip-
soid, and a ‘‘flat capacitor’’13 are known to satisfy this cri-
teria. To construct an EUC to be confocal with the ellipsoidal
guest particle, we proceed as follows.1,14 The surface
of the cell is given by the equation of an ellipsoid
@(x 2 1y 2 )/(b h ) 2 ]1 @ z 2 /(a h ) 2 # 51 with semi axes:
2222 Appl. Phys. Lett., Vol. 70, No. 17, 28 April 1997
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FIG. 2. Ellipsometric parameters calculated for the same material using
existing practice ~dashed lines! and the suggested model ~solid lines!.
b h 5 Ak1 ~ b g ! 2
a h 5 Ak1 ~ a g ! 2 .
k is dependent on the fill-factor f 5 @ a g (b g ) 2 /a h (b h ) 2 # and
could be found as a real positive root of the cubic equation:
~ a g ! 2~ b g ! 4
@ k1 ~ a g ! 2 #@ k1 ~ b g ! 2 # 2 5 . ~3!
f2
The depolarization factors of the cell boundary are thus
functions of fill factor. For small fill factors, where the
Maxwell–Garnett model usually applies all cell depolariza-
tion factors approach L h 51/3, which is significantly different
from the inclusion. The spherical surface is the limiting equi-
potential of any ellipsoidal coordinate frame. If the compos-
ite is dense and the Maxwell–Garnett approach is still valid,
the cell surface must closely resemble the surface shape of a
particle. The depolarization factors of particle and the shell
are thus then close in magnitude and approach L gz ,1/3 or
L gx .1/3, which can be very different for elongated particles.
Thus from the degenerate value L51/3 at f 50, the cell de-
polarization factors rise or fall smoothly with f until they
equal those of the inclusion at f 51. Calculations using ~2!
and ~3! shows smooth change with most variation between
f 50 and 0.4.
Ellipsometric modeling subject to the constraints ~2! and
~3! can now be implemented. The fitting parameters are the
fill-factor f and the degree of anisotropy of the inclusion
x g . Other parameters in ~1! are then determined via the con-
straints. We now compare predicted measurable ellipsomet-
ric parameters C and D when L h 5L g with those from the
correct confocal model. The host material is Al2O3 with sil-
ver inclusions. Dielectric constants are from Palik,15 guest
ellipsoids are aligned perpendicular to the sample surface,
f 50.2 and the particle shape is given by the ratio x g 51.5. C
and D calculated assuming geometric similarity are com-
pared with those using electrostatic similarity in Fig. 2. The
difference between the two models is much larger than typi-
cal experimental uncertainty.
Figure 3 shows excellent agreement between thin film
experimental data obtained on a Jobin–Yvon Variable Angle
Spectroscopic Ellipsometer and curves obtained with our fit-
ting procedure, for an angle of incidence of 40°. Angles of
incidence data from 30° to 80° in 10° steps were used simul-
taneously to fit the data. The model structure consists of bulk
Skryabin et al.
 ites. A new ellipsometric fitting procedure results using an-
isotropic ratio x and fill factor f as independent fitting
parameters.
The authors would like to express our gratitude to S.
Dligatch for the assistance with providing suitable experi-
mental ellipsometric results.

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In conclusion, there are two electrostatic constraints on 12
A. P. Prudnikov, Y. A. Brychkov, and O. I. Marichev, Integrals And
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Appl. Phys. Lett., Vol. 70, No. 17, 28 April 1997 Skryabin et al. 2223
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