Thin Sohd Ftlm~, 89 (1982) 249-262

ELECTRONICS AND OPTICS 249

O P T I C A L P R O P E R T I E S O F T H I N FILMS*

D E. ASPNES
Bell Laboratortes, Murray Htll, NJ07974 [ U S A )
(Received September 15.1981, accepted September 22. 1981 )

In this paper we discuss the connection between the microstructure of a

heterogeneous thin film and its macroscopic dielectric response e Effective medium
theory is developed from a solution of the Clausms-Mossottl problem from basic
principles. The solution zs generahzed to obtain the Lorentz-Lorenz, Maxwell
Garnett and Bruggeman expressions. The connection between microstructure and
absolute hmits to the allowed values of the dielectric response of two-phase
composites is reviewed. The form of these hmits for two-phase composites of known
composition and two- or three-dimensional lsotropy can be used to derive simple
expressions for e and also for the average fields within each phase. These results are
used to analyze d~electric function spectra of semiconductor films for information
about density, polycrystallinity and surface roughness. Examples illustrating the
detection of unwanted overlayers and the real-time determination of nucleation
growth are also given.

I, INTRODUCTION

It ts well known that grain boundames, voids, disordered regions and other
inhomogeneitles on the mlcrostructural length scale of I0-10000 ~ significantly
affect the vislble-near-UV optical properties of thin films, even if the films are
macroscoplcally uniform 1. First, the intrinsic dielectmc response of an individual
homogeneous region or grain depends on its composition and (if the grain is large
enough) on the presence or absence of long-range order. Secondly, screening charge
develops at the boundaries between grams, which causes d~fferences between the
local field and the macroscopic applied field. Because the effectiveness of screening
depends on the shape and relative s~ze of a gram, its contribution to the macroscopic
dielectric response will also depend on these parameters. Thirdly, the definition of
the dielectric function as the dipole moment per umt volume suggests that the
magnitude of the dielectric response of a polycrystalline or amorphous film with
respect to a standard spectrum can provide a simple, convenient and contactless

* Paper presented at the Fifth International Thin Films Congress, Herzha-on-Sea, Israel, September
21-25, 1981

0040-6090/82/0000-0000/$02 75 ~1 Elsevier Sequola/Prmted in The Netherlands

250 D. E ASPNES

means of measuring the density of the film The macroscopic dielectric response of a
thin film IS therefore connected in an intimate way with the compositional and
microstructural parameters that determine ItS other physical properties
Can the procedure be reversed, with quantitative microstructural information
being deduced from measured optical properties? The answer is yes, within limits
that at least can be estimated if certain conditions are met 2 The first condition is that
accurate dielectric function spectra must be available over a reasonably wide energy
range for the composite sample and for each possible constituent The Vlslble-near-
UV is a practical minimum range that is easily covered with existing ellipsometric
and polarlmetric instrumentation 3 and contains, for semiconductors and metals, a
substantial and characteristic--fraction of the oscillator strength of the bonding
electrons The second condition is that the individual dielectric responses of the
constituents must be combined in an effective medium model to reproduce the
measured dielectric response of the composite in terms of a few wavelength-
Independent parameters such as thicknesses or volume and void fractions Some
insight, such as a knowledge of the presence or absence of a surface oxide, may be
necessary to construct the model. Thirdly, the values of these parameters that give
the best least-squares fit of the calculated spectra to the measured spectra must be
obtained objectively with linear regression analysis (LRA) The correlation and
confidence-limit data that are a byproduct of LRA are extremely useful in
estabhshlng whether the model contains inappropriate parameters or too many
parameters, or even whether the data are determining the parameters at all. Finally,
the recent limits derived by Bergman '~ and Milton 5 for two-phase composites should
be applied to estimate the intrinsic uncertainties in the model parameters that result
from our Inability to specify the actual mlcrostructure exactly.
In this paper, we shall emphasize the quantitative description of the macro-
scopIc dielectric function ~ of a heterogeneous material in terms of its composition
and mlcrostructure, with particular emphasis on the limits to e that exist even if the
composition and mlcrostructure are completely unknown The characteristic
changes in s caused by specific lnhomogeneltles in thin films have already been
reviewed by Hunderl (' We shall show how the macroscopic dielectric function is
related to mlcrostructural parameters by calculating ~: for a simple cubic micro-
structure for which the local fields and polarizations can be obtained exactly. We
shall then show how special mlcrostructures can be used to establish absolute limits
(the Wiener bounds ~) to c for a composite material even if nothing is known about
the volume fractions or mlcrostructure of Its constituents. We next review how these
hmlts become more restrictive if information is available about macroscopic
attributes such as the volume fractions of constituents (the Hashln-Shtrikman
hmlts ~) or the presence or absence of two- or three-dimensional lsotropy (the
Bergman-Mllton limits ~' 5) We use the fact that all bounds are circular arcs m the
complex c plane to give a representation of ~:for two-phase composxtes in which the
compositional and screening parameters are clearly identified and the Bergman-
Milton limits are expressed through a host dielectric function whose range is
also restricted to lie within the Wiener bounds.
We shall assume throughout that the samples are macroscoplcally homo-
geneous, ~.e that their internal structure cannot be resolved with an optical
microscope. In discussing effective medium theories we shall use the quash-static
OPTICAL PROPERTIES OF THIN FILMS 251

(infinite-wavelength) approximation, which is valid if the grain sizes do not exceed

about 0.12, where 2 is the wavelength of light 9' lo. We shall indicate how the quasi-
static approximation breaks down ff the grain s~zes exceed this limit Although
effective medium models of varying degrees of complexity are legion, we shall avoid
discussing them not only because they have been reviewed elsewhere lI 12 but also
because they are unnecessarily detailed for the analysis of macroscoplcally averaged
data without additional information. In any case, their predictions all fall within the
limits mentioned above. We shall also avoid discussing laminar systems (one-
dimensional inhomogeneities), whose description can be found elsewhere (see for
example ref. 13) Examples to illustrate representative applications to semicon-
ductors are also given

2 DIELECTRIC PROPERTIES OF HETEROGENEOUS MEDIA

2.1. Oi,eri'tew
The dielectric response of a heterogeneous material and the limits to the
amount of microstructural information that can be drawn from it are easily
understood if we recall that electrodynamlcs deals--as does thermodynamics--with
macroscopic observables that are basically averages of their microscopic counter-
parts. The solution to the dielectric response problem therefore involves two distinct
steps, first, the electrostatic problem is solved exactly for a given microstructure to
obtain the local electric field e(r) and dipole m o m e n t p(r) per unit volume at every
point in space: secondly, these microscopic solutions are averaged to obtain their
macroscopic counterparts E and P 14. The macroscopic dielectric function Itself is
calculated from the definition

D = eE = E + 4 ~ P (1)

The problem, of course, is that the first step cannot be done, even in principle,
for an actual heterogeneous sample with r a n d o m domains because the micro-
structure is not known exactly. In fact, however, such a solution would contain far
too much information and consequently would be virtually useless. For example,
the average properties of a gas, such as the pressure and the temperature, are far
more useful than a detailed description of the motion of each molecule. Similarly, the
dielectric response function is more useful than a knowledge of the microscopic
fields The effective medium problem is essentially one of defining suitable average
variables in some way and then establishing limits on e in terms of all possible
compositions and microstructures.

2.2 Microstructure and dtelectrtc response the C l a u s m s - M o s s o t t l expression

The solve-average approach can be illustrated and the theory of heterogeneous
dielectrics introduced with an exactly solvable configuration, that of a simple cubic
lattice of points with lattice constant a and polarizability ~ (the Clausius-Mossotti
model). This is the prototypical lnhomogeneous material, being a mixture of
polarizable points and empty space. If a uniform field E, IS apphed, the points
polarize as p = ~Elo~, where Eio~ = e(R,) is the local field at a lattice site R,. The
microscopic field e(r) is the superposition of E, and the dipole fields from p and can
252 D E ASPNES

be written d o w n by inspection
e(r) = E, + ~ Ed,p(r-- R,) (2a)
Rn
where
3(p'r)r - pr a
Ed,p(r ) -- rS (2b)

Because &poles occur only on lattice sites we have also by inspection

p(r) = ~ :¢e(O)8(r- R,t [3)

R.

since all e(R,) are equal. If eqns. (2) are valid everywhere they are certainly valid at
r = O, whence

e(0)---E,+ ~ Ed,p(RnJ {4)

R.~O

E q u a h o n (3) is a self-consistency relation between e(0) = Eloc and E. F o r full cubic

s y m m e t r y the sum over R~ vanishes and we have simply E, = E~o¢. However, this is
not generally true For systems of lower symmetry, such as molecules adsorbed on a
surface ~s, ~6
We n o w have an exact microscopic solution and can proceed to the second step.
Averaging eqn (3) is trivial because of the 8 Function

P = NaElo
[,T c= n0CElo c (5)

where V is the volume of the sample and n = a - 3 is the volume density of points The
volume average of e(r) IS slightly more complicated because the volume integral of a
dipole field is not zero, but -4rip~3. Using this result, we find from eqn (2a) the
average or macroscopic field to be
4n
E = E, oc~ - ~ , l C ¢ ) (6)

Therefore the uniform microscopic field E, = E~oc that was actually applied is larger
than the uniform macroscopic field E that was apparently applied because the
induced dipoles oppose on the average the applied field. After some algebra, all fields
can be eliminated from eqns. (1), (5) and (6) and we obtain the Clausius-Mossottl
result
~,- 1 4n
-- na {7)
a+2 3

that IS usually derived in a more intuitive m a n n e r with the aid of a fictmous cavity
(see for example ref. 17).
The model is simple, but It shows the connections a m o n g m~crostructure and
microscopic and macroscopic fields and polarizations. It is also intended to
demonstrate that there is nothing mysterious a b o u t the dielectric response of an
m h o m o g e n e o u s medium.
OPTICAL PROPERTIES OF THIN FILMS 253

23. Heterogeneous media, effective dielectric functions

The simplest heterogeneous m e d i u m is one in which the points of the preceding
example are r a n d o m l y assigned two different polarizabihties ~a and ~b. By repeating
the derivation we find
e- 1 4n
- ( n , ~ + nb~b) (8)
e+2 3
where e ~s now the effective dielectric function of the composite. The form is a w k w a r d
because it revolves microstructural parameters that are not measured directly, but if
the dielectric functions e, and 8b of phases a and b in thmr pure forms are available,
we can use eqn. (7) to rewrite eqn (8) as
e- 1 ea - 1 eb - 1
- f a ~ +fb725 (9)
e+2 e,+2 Oh--
where f~,b = na,b/(na+ rib) are the volume fractions of the phases a and b. This is the
L o r e n t z - L o r e n z effective medium expression18,19
Let us suppose next that the separate phases a and b are not m~xed on an atomic
scale but rather consist of regions large e n o u g h to possess their own dielectric
identity. Then the assumption of v a c u u m (e = 1) as the host medium in which to
embed points is not good. If we suppose that the host dielectric function is eh, then
eqn. (9) becomes

g - - gh Ea - - F'h gb - - gh
(1 O)

Specifically, if b represents the ddute phase then we should choose eh = ~a, in which
case

e+2e~
- - Ea
--Jb~ gb - - ~a
(11)

E q u a t i o n (11} and the alternative e q u a t m n obtained with eh = eb are the Maxwell

G a r n e t t effecttve medium expressions 2°.
In cases w h e r e £ a n d f b are comparable, ~t m a y not be clear whether a or b is the
host medium. O n e alternative is simply to m a k e the self-consistent choice 8h = e, in
which case eqn. (10) reduces to

0 = f"e~ +f"~-b+ 2e (12}

This is the Bruggeman expressmn, c o m m o n l y called the effective m e d m m approxi-

m a t i o n (EMA} z~. Although they are related, eqn. (11) actually describes a cermet or
coated-sphere mlcrostructure where a is completely surrounded by b while eqn. (12)
refers to the aggregate or r a n d o m - m i x t u r e mlcrostructure where a and b are inserted
into the effective m e d i u m itself.

2.4. Microstructure. screenmg and hmits

W h a t happens if the microstructure is not point like (spherically symmetric) as
assumed previously? Let us suppose that all internal boundaries are parallel to the
applied field, as in a laminar sample with the field applied parallel to the layers. The
254 D, E. ASPNES

boundary condition on tangential E shows that the field is uniform everywhere. The
polarization is then s~mply proportional to e, or eb, according to whether r is located
m a or b. Averaging everything leads to
= Jaea +fbeb (13)
a simple volume average eqmvalent to capacitors connected in parallel. If E is
apphed perpendicular to the layers, then D is uniform throughout and averaging
now leads to
- 1 = ]'aB a 1 q_fbSb 1 (14)
equivalent to capacitors connected m series.
Equations (13) and (14) are the Wiener absolute bounds to e 7. They are
absolute because no matter what the microstructure there can never be less
screening than no screening (all boundaries parallel to the field, eqn. (13)) nor more
screening than m a x i m u m screening (all boundaries perpendicular to the field, eqn.
(14)) For any composition and microstructure, e must he on or within the region in
the complex e plane enclosed by eqns. (13) and (14) as long as the microstructural
dimensions remain small compared with the wavelength of hght. The Wiener
bounds are easy to construct since eqn. (13) is a strmght hne between e, and ~b wh]le
eqn. (14) is a circle passing through ea, ~b and 0. An example is shown in Fig. 1.

Im(,~ ) 4

E0

TM

TE j
~b

-2 -1 0 1
Re (,E)

Fig 1 Limits on the allowed range of~ for a composite with ea - - 2 + 1 3 and ~b = 1 +11 The Wiener
absolute bounds for arbitrary composition and microstructure are the line and are enclosing the largest
region The Hashtn-Shtnkman hmlts for fixed composition (here fa = 0 6) define the smaller shaded
region The smallest region Ls defined by the Bergman-Mllton hmlts for fa = 0 6 and three-dimensional
macroscopic lsotropy (after ref 5) The three trajectories show values of~ for TE, TM and TEM modes in
a laminar sample for J. = 0 6 and d/z increasing by increments of 0 1 (after ref 10)

The existence of more stringent hmits based on general macroscopic attributes

has also been proven 4" s, 8 Hashin and Shtrikman 8 used a variational principle to
OPTICAL PROPERTIES OF THIN FILMS 255

show that the two Maxwell Garnett expressions (eqn. (10) with eh = ~:a and eh = E:b )
provide absolute limits to e for a two-phase composite if the macroscopic
composition fa ---- 1 --fb is known. Their work for real e. and eb was generahzed to
complex values by Bergman 4 and by Mdton 5. An analytic representatmn of
derived initmlly by Bergman 2z was used by Bergman 4 and by Milton 5 to derive
additional limits for two-phase composites macroscopically isotropic in two or
three dimensions.
All the above limits take the form of circular arcs in the complex e plane,
meaning that the effective dielectric function of a two-phase composite can be
expressed quite simply, yet generally, as a bilinear transformation in suitably defined
real variables:

(15a)
5 + (L% + A~.)
where

(1 --q)eh (15b)
q

Here q is a screening parameter of range 0-1 and eh ~S the host dielectric function.
The Wiener absolute bounds are given by q = 0 and q = 1 for 0 ~<fa ~< 1. The
Hashin-Shtrikman bounds for a known composition f~ are gwen by the Maxwell
Garnett lines eh = e, and e~ = eb for 0 ~< q ~< 1. The Bergman-Milton limits for a
known composition and two-dimensional (q = 1/2) or three-dimensional (q = 1/3)
macroscopic isotropy are given by the hnes eh = xe, +(1 --X)eb and eh- 1 = Xea- 1 _[_
+ (1 -- x)eb 1 for 0 ~< x ~< 1 This is equivalent to imposing the Wiener bounds on eh
Examples of these regions are given in Fig. 1.
These limit theorems are remarkably s~mple, and they are particularly
important because they establish previously unavailable intrinsic confidence limits
on the values of parameters obtained from effective medium theories. In general they
show that, ff ea and eb are similar, then e is determined almost entirely by the
composition and is essentmlly independent of mlcrostructure, If ~a and % are
substantially different, then microstructure is the dominant varmble 2. Since the
relative magnitudes of ea and eb often change with wavelength, spectral measure-
ments offer the possibility of obtaining both parameters.
The above results can also be used to estabhsh limits to the average value of the
local field within each constituent of a composite materml. For the two-component
mixture described above, the field-enhancement factors 7a = Ea/E and ~'b ~--- Eb/E are
given by

eb q- ~:
7, = (16a)
+ (Leb + fb~.)

~+ea (16b)
7b = ~ _~. (faE b _~_fb/3a)

The previously discussed limits on e now lead to hmits on ~'a and 7b which are also
circular arcs in the complex 7 plane These can be useful m estimating uncertainties
256 D E. A S P N E S

in composmons deduced from inelastic Raman scattering, fluorescence or m-

tegrated intensities under 1R absorpuon hnes, all of which are sensmve to the
average magnitude of the local fields 23 24

2.5 Finite-wavelength effects

The above quasi-static hmlts are derived by assuming that the wavelength is
infinite At fimte frequencies e can be defined In terms of an average forward
propagation vector K: as 8
e : C2kz2/¢02 (17)
Within each phase of a composite, the wavevectors must satisfy the wave equations
C2ka 2/(02 ----- ~'a
2 "~ ~ (18)
C kb-/(O- ~ eb

while the z components on the average must saUsfy k,z = kb: = / ~ Clearly, these two
condmons can only be satisfied simultaneously if k~ and k b have components k~l
and kbl perpendicular to the z direction. We find from eqns. (17) and (18) that
~, = e, -- C2kal2,"(,~ z (19a)

-~- ~'h - - c Z k b l 2 / ( t ) 2 (19b)

Because e is itself constrained to lie somewhere "between" e~ and eb, xt follows that
propagation will be evanescent m the less dense phase and that the wave energy will
tend to focus in the phase, say a, with the larger value of Re(c}. This wavegmding or
focusing mechanism skews e at finite frequencies toward G (fiber optics works)).
Figure 1 shows the evolution of ~,with values of d/2 increasing in 0.1 increments
for TE, TM and TEM modes for a laminar model with the parameters of the
preceding limits calculation l°. Approximate calculations have also been performed
for spherical inclusions by expanding the Mle theory z5 in powers of d~2 9 The first
non-vanishing corrections are quadratic in this ratio, a consequence of eqns. (18) and
(19). The laminar model calculations show that finite-wavelength effects are
neghglble if d/2 <~0 1, while the Mie results are somewhat less restrictive, allowing
d/2 < 0.3. Thus the quasi-static expressions and limits summarized in SecUons
2.2-2.4 are vahd for most thin film systems,
The above discussion shows why effective medium models also describe
microscopic roughness. If the characteristic d~menslons of the mlcrostructure are
small compared with 2, the corresponding distortions of the wavefront required to
saUsfy the boundary condlUons will not be important. Then the material can be
described as a composite medium This has been shown to be a good approximation
for rough silicon films over a wide spectral range 2~

3. APPLICATIONS AND EXAMPLES

3.1. Long-range order, denm O"and microscopic roughness

Figure 2 shows measured (ez) = I m ( e ) spectra for a smooth crystalhne silicon
(c-S1) sample, a smooth amorphous slhcon (a-Si) film and a c-Sl wafer that had been
thermally etched in ultrahigh vacuum to generate a microscopically rough but
OPTICAL PROPERTIES OF THIN FILMS 257

atomically clean surface 2v. The pseudodlelectnc function ( e ) is that of the

hypothetical uniform isotropic material with a clean mathematically sharp surface
boundary that gives the same ellipsometric data as the actual sample. This ideal
configuration is approximated by the smooth c-Si and a-Si samples but not by the
thermally etched wafer. Therefore (e2) ~s a good representation of the intrinsic bulk
e,2 response only for the smooth samples

40

SMOOTH
ROUGH~

£ 20 o-S~ ~ ,
/

/11I I/ r~
0 Z--~-----T--"~I t I ~ I i
2 3 4 5
E(eV)
Fig 2 Measured ( ~ ' 2 ) spectra for a smooth c-S1 wafer ( - - , upper), a microscopically rough c-Sl wafer
( - - , lower) and a smooth a-Sl film (. . . . . ) (after ref 27)

The (a2) spectra of the three samples are qmte different, even though all of them
consist of sihcon atoms tetrahedrally bonded to other sdicon atoms. The intrinsic e 2
response of the S~--S1 bond, represented by the a-Si spectrum, has a single broad
peak at 3.6 eV. When long-range order IS present, Bragg scattering off the crystal
lattice concentrates the electronic polarizability into two peaks E 1 and E 2 at 3 4 eV
and 4.2 eV respectively, seen in the (e2) spectrum for the smooth c-Si wafer. These
peaks are the signature by which the onset of polycrystallinity m nominally
amorphous films, defined approximately by the presence of crystalline order over at
least 20 ~, can be ~dentified. The size estimate is taken from the refractive index data
of Schwidefsky zs, which reached essentially bulk values when reflection electron
diffraction measurements indicated the presence of coherent regions of about this
size.
Microscopic roughness is a form of density deficit that lowers the value of e2, as
expected from ~ts defimtlon m terms of dipole moment per unit volume. This is seen
in Fig. 2 above 3.4 eV, where the penetration depth of light is of the order of the
roughness scale and (e2) therefore approximates the intrinsic response of density-
deficient bulk material. However, the apparent Increase in ( e 2 ) below this energy is
purely an ellipsometric effect. The less dense surface material shifts the relative
phases of the s- and p-polarized components of the reflected beam, causing the
observed distortion in the (e2) spectrum. An LRA using the two-dimensional
258 O E. ASPNES

Bruggeman E M A in a one-layer representation shows the effective thickness dov and

the density deficit fv (void fraction) of the overlayer to be 43 +_2 A and 0.40 + 0.02
respectively. The calculated spectrum is not shown since it essentially coincides with
the measured spectrum on the scale of Fig. 2. This type of roughness ts below the
resolution level of a scanning electron microscope and has only a small effect on light
scattering, so it would be very difficult to detect by other means.
Another example of density and long-range order effects is given in Fig 3,
which shows (F,2) ~ e 2 spectra of smooth sihcon films prepared by low pressure
chemical vapor deposition (LPCVD) 2°. Both the film deposited at 525 ~C and that
rapidly deposited at 625 :C are clearly amorphous. Because a simple scahng factor
takes one spectrum into the other we can conclude that they differ only in the denstty
of SI--S1 bonds per unit volume. Assuming two-dimensional lsotropy, the
Bergman-Milton theory places limits of 0.03 < J~ < 0.07 on the 525 °C sample if the
rapidly deposited 625 °C film is taken as the reference If the deposition rate is slowed
to 60/~ rain i the atoms have more time to reach thermodynamically preferred
lattice positions The structure in the ( % ) spectrum shows that this film is
polycrystalhne. By varying the deposition rate and temperature, it was found
possible to produce L P C V D a-Si films that contained less than 0.l°o H but still
could be substitutlonally doped, indicating a high degree of connectivity and a low
intrinsic defect density 3°

30 I i i , i

625C S ~ PCVD
60
262
A/ram
~Imm
~
- -

2O

525C - -

/
I0

O I I I t | I
2 3 4 5 6
E(eV)
Fig 3 Measured (~2) spectra for slhcon films prepared by LPCVD - - (lower), 262 ~ m m - 1 at
525 ~C,-- (upper), 2 6 2 / ~ m m - l a t 625 "C, - - , 60 A m m - 1 at 6 2 5 C (after ref 29)

The effect of incorporating hydrogen into the slhcon lattice results first m a
density decrease, but increasing amounts of hydrogen have been observed to shift
the 3.6eV peak to higher energies 31. This indicates that S t - - H bonds are also
removing oscillator strength from remaining S1--Si bonds and shifting it to higher
energies.

3.2. Cleanmg, growth and the tdentificatton oJ thin films

The spectrum m Fig 2 for the thermally roughened wafer clearly shows the
importance of smooth, clean samples for obtaining ~:data that accurately represent
OPTICAL PROPERTIES OF THIN FILMS 259

the true bulk values. The connection between ( e ) and e for a material with an
overlayer is given by 32
4~idna ~s(es-eo)(eo-ea)/e . \1/2
(~> = e~4 2 ~o(~,- ~a) L~ -s'nz~b ) (20a)
4~1d 3/2
e~+--~-e~ (20b)

where eo and d are the (effective) dielectric function and the thickness of the overlayer
respectively, and e~ and ~ pertain to the substrate and ambient respectively. The
overlayer may be a graded region, although eqn. (20a) changes form slightly in this
case 33. Equation (20b) follows if led >> r~ol ~> ea = 1, a condition not hard to achieve
in semiconductors where the ellipsometer can be tuned to the E 2 peak in e2 (see Fig.
1) Remarkably, eo has dropped out ofeqn. (20b) completely, which means that films
can be detected and removed without having to be identified 34. In fact, some
informanon about film identity can be obtained from spectral measurements and
also from chemical reactivity, since measurements are made in real time in an
atmospheric environment. The latter diagnostic approach is not possible In
ultrahigh vacuum.
For example, we show in Fig. 4 the removal of a film developed during a 2
year exposure of a Syton-polished c-Si(111) wafer to New Jersey air 34. The scale
shows that the film thickness is about 27 ~ initially and that about 12 ~ of this film
are removed with methanol and water. This layer is clearly not S i O 2 but consists of
organic and Inorganic contamination. The removal of 12 ~ more with H F shows
this to be the true limiting oxide th]ckness for this material. The final 3-4 ~ are
removed only by chemical polishing and preferential etching, indicating micro-
scoplc roughness or subsurface damage resulting from the initial polishing
operation. Therefore less than half the original interface region was actually SiO2.
Comparisons between chemically cleaned samples and those prepared in ultrahigh
vacuum by Ar ÷ bombardment and annealing show by the "biggest is best" criterion

.50 ! I I [

"%~-~--- BRM
/ ~ B H F
45 OXlDES---~ /

s.o~L.N~,,
E NgO.
,&
40 MeOH,H20 /El//
ORGANICS- - - ~ / /
/ (CP-4)
35 /)~ 0
~/rI ~:.R~
....
L J I I l
-15 -10 -5 0
<'1 >
Fig 4 Variation in (/~> at 4 25 eV with chemical processing for an air-exposed SI(1 l l ) wafer to permit
identificationof the differentlayers(afterref 34) Incrementsof 5 •, referredto SiO2,are shown
260 D E. ASPNES

that more abrupt dielectric d l s c o n t m u m e s can be achieved with chemical etching 27.
It is also possible to make analogous Inferences during film deposition. Figure 5
shows elhpsometncally measured (t~,A) values at )~ = 5461 ,~ for an a-Si film
deposited onto an S13N 4 substrate at 580 °C 35. The data deviate strongly at the
beginning from the pred;ctlon of a model calculation that assumes that film growth
is uniform over the surface. However, if the a-Sl is assumed to accrete as hemispheres
a b o u t nucleation centers, an effective m e d i u m calculaUon reproduces the initial
growth phase very accurately The c o m p a r i s o n of the experimental and calculated
results shows that the hemtspheres coalesce at a b o u t 90/~ to form a continuous but
microscopically rough film which s m o o t h s out as the thickness increases. Thus the
spacing between nucleation centers, as well as the growth mechanism, is estabhshed
The remarkable feature about these data ~s that the sensitivity ts sufficient to follow
the growth and to identify the growth mechanism m real time at a thickness of less
than 2/~, far below the detection limits of electron microscopy.

200 AsTING

ILANE ON

180 i "-~ ~,. CALC

•~ . _ 50 A "",-
"ID ~,~EXP "IL...,.,...,.
<3
160 IO 0 A ~ ~ ~

,., j ,i,
140 200

1 J I J I i 1 i 1
11 13 15 17 19
,//(deg)
Fig 5 Real-time experimental (~,, A) trajectory ( - - ) for an a-Sl film deposxted on Sl3N4, - - - ,
theoretical locus assuming a uniform film, , theoretical loci assuming nucleation and
hemispherical accretion about centers spaced as md;cated (after ref 35)

3.3. Three-phaae systems

We have discussed m detail only two-phase systems. However, eqns. (10) and
(12) are easily generalized to three or more constituents, even t h o u g h corresponding
B e r g m a n - M i l t o n limits to estimate intrinsic uncertainties are not yet available.
Consequently, only relative parameter values should be considered as having
meaning.
Figures 6 and 7 show a spectra for a polycrystalhne silicon (p-S0 film as
deposited at 6 5 0 - C and after heat treatment in a PBr3 atmosphere for 0 5 h at
OPTICAL PROPERTIES OF THIN FILMS 261

950 °C 3 6 . A qualitative comparison of these data with those of Fig. 2 shows three
consUtuents to be present: c-Si, as indicated by the structures at 3.4 and 4.2 eV, a-Sl,
as indicated by the broad background centered about 3.6 eV, and a density-deficient
consUtuent, indicated by the relatively small values of el and %.

I I [ I [ I

20 EXP
{0 25 vOID +
- - - - - - ,~014 c-S,+

-10 i I 1 t I I
3 4 5 6
E (eV)
Fig 6 Measured and model (L> spectra for an as-deposited p-SI film(after ref 36)

I ' I T 1 I

~ EXP
20 / ~ roosvo,D+
~ ------<0 57c-SI +

A IO
V

3 4 5
E~e~)
Fig 7 As Fig 6, but after heat treatment (after ref 36)

The data were analyzed in a three-parameter model consisting o f a Bruggeman

E M A calculation for the substrate to determine the crystalline and void fracUons
and the thickness of a density-deficient surface region. The computed spectra are
seen to be in excellent agreement w~th the data over the entire spectral range,
showing that the model indeed accurately describes the sample. The parameters
obtained by linear regression analysis werefv = 0.25 _+0.06,Jc = 0.14_+ 0.02 (leavmg
fa = 0 6 1 + 0 . 0 8 ) and dov = 1 2 _ 3 4 for the as-deposited material and fv = 0 . 0 8
_+0.01, fc = 0.57+0.04 (leaving fa = 0.35+0.05) and dov = 3 8 + 3 / ~ for the heat-
treated sample. The film densities and crystalhnity increase upon heat treating, in
agreement with expectations.
262 D E. A S P N E S

4. S U M M A R I Z I N G REMARKS

Although effective medium models have been known for many years, the recent
work of Bergman 4 and Milton 5 provides the key to establishing intrinsic hmits on
model parameters for systems where the d~electric functmns are complex. These
hmtts define our capablhtles for determining microstructural parameters from the
optical properties of thm films. The work needs to be extended to n-phase
composites. Further investigations are also needed to understand how the changing
d~electnc response with wavelength for real systems can be used to advantage to
narrow these hmits. The importance of spectral data, and of the need for effective
medium models to analyze these data, should be apparent from the examples gwen.
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