314 Thin Solid Films.

206 (1991) 314- 380

Real time spectroscopic ellipsometry for characterization of thin

film optical properties and microstructural evolution

R. W. Collins, Ilsin An, H. V. Nguyen and T. Gu

Materials Reseurclz Laboratory and Department of Physics, The Pennsylvaniu State University, University Park, PA 16802 (U.S.A.)

Abstract

A rotating polarizer multichannel ellipsometer was applied in spectroscopic (1.3-4.2 eV) investigations of thin films during
deposition. In this review, two examples are selected which demonstrate real time spectroscopic ellipsometry. In the first, we
compare results for amorphous silicon and germanium sputtered to approximately 50 A on native oxide-covered c-Si. For these
films, the evolution of the effective optical properties with thickness is dominated by changes in void volume fraction and surface
roughness which accompany nucleation and growth. Abrupt transitions from cluster to bulk film growth occur at total
thicknesses of 10P 15 A for materials deposited under optimum conditions of microstructural uniformity. In the second example,
corresponding results for aluminum evaporated to opacity onto thermally oxidized c-Si are discussed. In this case, the evolution
of the effective optical properties with thickness is strongly influenced by changes in the intrinsic aluminum dielectric function.
In particular, we find that the relaxation time for the (200) parallel-band transition increases abruptly with thickness over the
55560 A range. The enhanced scattering of electrons in the films less than 60 A thick may originate from a disordered or
fine-grained film structure, and for thicknesses less than 55 8, the (200) parallel-band feature in the aluminum dielectric function
at 1.5 eV disappears.

1. Introduction ture. The resulting unbiased estimator of the mean

square deviation CJ us. time allows us to assess the
The optical functions of thin films from initial nucle- quality of the LRA best fit over various growth regimes
ation to 100 A in thickness are of fundamental and and thus the validity of the chosen model [6].
practical interest. In the nucleation stage, optical We describe results of two studies representing ex-
functions provide information on the electronic struc- tremes with respect to the evolution of the optical
ture of the material as a function of the electron functions. We have investigated the growth of amor-
confinement volume. They also provide information on phous silicon [7] and germanium films by sputtering
microstructure through changes in void volume which and aluminum films by evaporation. In this work, the
accompany cluster growth and coalescence. A difficult substrate, deposition method, and conditions were opti-
problem in this early stage involves separating the mized for bulk-film microstructural uniformity. Because
intrinsic effects of size from the extrinsic effects of the above-gap optical functions of amorphous semicon-
microstructure, as interpreted by effective medium ductors are only sensitive to the short-range order, size
theories [l-3]. effects are estimated to be small. In contrast, the optical
Real time ellipsometry is a technique that can address functions of aluminum are influenced by electron scat-
this problem because it provides continuous optical tering at grain boundaries and surfaces, and this alters
data us. accumulated film thickness [4]. Until recently, the Drude and interband components of (E, , Ed).
measurements were performed at a selectable photon
energy. From such data it is difficult, however, to
extract the contributions of intrinsic size effects from 2. Experimental details
microstructural effects.
Recently, a multichannel ellipsometer has been devel- The real time spectroscopic ellipsometer has been
oped that acquires 128-point ($, d) spectra with a time described elsewhere [.5]. Briefly, it consists of the follow-
resolution similar to that of fixed photon energy instru- ing: xenon lamp, collimator, polarizer rotating at angu-
ments [.5]. The advantage is that if dielectric functions lar frequency w, sample, fixed analyzer, prism
(F,, E*) of the bulk-deposited film are obtained, linear spectrometer, and silicon photodiode array detector.
regression analysis (LRA) [6] can be applied to the The array integrates the incident irradiance, and its
spectra to deduce the time evolution of photon energy- exposure time is set by the duration between successive
independent parameters which characterize the optical pulses generated every 45” of rotation by an optical
functions of the material and/or its microstruc- encoder attached to the polarizer. From the four

0040-6090/9 I /S3.50 :(‘~I1991 Elsevier Sequoia, Lausanne

 R. W. Collins et cd. I Red time speclroscopic ellipsome~r~ 375

exposures over one optical cycle ( 180”) the normalized dielectric functions for c-Si [lo] and vitreous silica [ 1 l]
20~ Fourier coefficients of the irradiance can be de- were used as input, and the native oxide thickness was
duced. Error correction procedures are discussed in an determined. The oxide could then be analytically re-
accompanying article [ 81. moved from substrate spectra obtained at T, just prior
The ellipsometry spectra j$(hv). d(hv)f, can be to film growth to obtain the required c-Si dielectric
obtained after calibrations that relate detector pixels function. Here, we neglected the temperature depen-
to photon energy and that determine the phase of dence of the oxide dielectric function.
the irradiance waveform. For our system, with The dielectric functions of a-Si and a-Ge can be
o/2n = 12.5 Hz, 128-point spectra can be collected in a obtained directly from {$(hv), d(hv)) only if the films
40 ms optical cycle. For amorphous semiconductor de- are opaque and their surfaces are atomically clean and
position, 80 cycles were averaged for sub-monolayer smooth. Early studies of a-Si have shown that the
precision with a time resolution of 3.2 s. The repetition optical effect of surface roughness can be simulated
period was approximately 14 s; in this interval data with a two-component overlayer of bulk material and
reduction, graphical output, and correction for the am- voids with a dielectric function determined by the
bient plasma glow were performed. The time-averaged Bruggeman effective medium approximation (EMA)
deposition rates for a-Si and a-Ge were 1.83 A min ’ [ 121. For thin roughness layers (less than 20 A), it is
and 4.75 A min-‘. For aluminum with its higher depo- customary to fix the roughness volume fractions at
sition rate of 280 A min-‘, 20 optical cycles were aver- 0.50/0.50. In the following paragraphs, we describe two
aged for a resolution and repetition rate of 0.8 s and different approaches to determine both roughness and
1.25 s respectively. In this case continuous ambient light bulk thicknesses for a-Si and a-Ge in order to deduce
correction was unnecessary. the dielectric function analytically from ($(A v), d(h v) )
Two different vacuum chambers (base pressures spectra by inversion.
5 x lo-‘Torr) were used for thermal evaporation and In the approach for a-Si, the accurate 25 “C reference
sputtering. For sputtering, the operating argon pressure dielectric function of a low pressure chemical vapor
was chosen at the minimum value for a stable plasma. deposition (LPCVD) a-Si film was employed [ 131. First,
This insured that the incident atoms were unthermal- we used real time spectroscopic ellipsometry to monitor
ized and impacted the surface with sufficient energy for the sputter deposition of relatively thick a-Si onto
uniform films, i.e. minimum void volume fraction and oxide-c-Si under standard optimum conditions. Next,
surface roughness. For a-Si and a-Ge, substrate temper- the film was cooled under vacuum from T, = 300 “C to
atures T, of 300 ‘C and 25 “C were also selected for 25 “C and remeasured. If we assume that the difference
uniformity. Substrates used for sputter deposition were between the dielectric functions of this bulk film and the
c-Si with a 23 A thick layer of native oxide. LPCVD reference can be described by one parameter,
For aluminum deposition by sputtering, we were the relative void volume fraction, then the { +(hv), d(h v)}
unsuccessful in achieving a low bulk-film void fraction spectra at 25 “C can be interpreted by LRA. In this way,
whatever the conditions of T, and pressure. For thermal we obtain the bulk and surface roughness thicknesses
evaporation, we found a void-free microstructure and (330 A and 20 A), and the bulk void volume fraction
smooth surface for films deposited at 25 “C onto c-Si relative to the reference ( -0.03). (The negative void
with a 71 A thick layer of thermal oxide. For thin native fraction implies that the sputtered a-Si is denser than the
oxides the bulk aluminum void fraction was enhanced; LPCVD a-Si.) The thicknesses were used to determine
for thick thermal oxides, the roughness layer was en- the bulk dielectric function of our material at
hanced. Because our deposition occurred at a pressure: T, = 300 C by numerical inversion of the real time
rate ratio of approximately lo-” Torr min A-‘, previous {t+b(hv),d(hv)) obtained just prior to cooling.
experience indicates that contamination is negligible for For a-Ge, however, a suitably accurate reference
optical purposes [ 93. dielectric function is unavailable. Thus, we generate our
own by the Co-minimization technique [ 141. First, a
relatively thick a-Ge film is sputtered onto oxide-c-Si
3. Results and discussion under standard optimum conditions, and {$(hv), d(hv) )
are collected during growth. For the last spectra, ac-
3.1. Amorphous semiconductors quired just after terminating growth, we guess the thick-
In order to interpret real time {$(hv), d(hv)} for a-Si ness of the bulk and roughness layers, allowing us to
and a-Ge in terms of microstructural development, bulk perform inversion to obtain a trial dielectric function.
dielectric functions for the substrate and two film mat- Then the numerous real time spectra are fit by LRA
erials are needed at the appropriate T, values. For the using the trial dielectric function as input. The sum of all
native-oxide-covered c-Si substrate, we obtained unbiased estimators (X0) provides a measure of the
{$(hv), d(hv)} at 25 “C and applied LRA. Literature global quality of the fit. The correct guesses for the bulk
 376 R. W. Collins et ul. I Red time spectroscopic eilipsometry

and surface layer thicknesses (410 A and 4 A) minimize

X:0.
Armed with the bulk dielectric functions for a-Si and
a-Ge at T,, the microstructural evolution in the early
stages of film growth can be determined. Such results
were obtained from separate depositions of ultrathin
films. In Fig. 1, we show the unbiased estimator vs. time
obtained from LRAs of the spectra for the thin a-Si
and a-Ge depositions, assuming one- and two-layer
models for the film structure. The two-layer (rough-
ness/bulk) model makes contact with the dielectric 0 2 4 6 8 10 12 14
THICKNESS (A)
function analyses that were performed on the thicker
films. For times less than 5.5 min for a-Si and less than Fig. 2. Void volume fraction (relative to our sputtered reference
1.3 min for a-Ge, the two models give overlapping B material) US.film thickness, derived from an LRA of spectroscopic data
values. This implies that the two-layer model is an for the initial nucleation of a-Si ( 0) and a-Ge (0) using a one-layer
model. The lines were calculated from a model assuming that hemi-
overinterpretation of the data in these regimes and that
spherical nuclei form at the vertices of a square grid and increase in
the one-layer model should be selected. radius uniformly until contact. The values denote the grid size.
In Fig. 2, we show the two free parameters of the
one-layer model, the void volume fraction vs. thickness,
deduced over the regime of validity of the model. The Figure 3 shows results for the surface and bulk layer
two data sets follow the same gradually decreasing thicknesses vs. time derived from the two-layer model
trend with a steeper slope for a-Ge. The solid curves for a-Si and a-Ge. This model is only strictly valid for
would be expected if hemispherical clusters were to times greater than the vertical lines, but for shorter
form on a square grid, increase in radius, and make times the two-layer model returns bulk thicknesses near
contact (at 0.48 void fraction). It is clear from these zero. The open circles in Fig. 3 are obtained from the
results that the substrate coverages in the first mono- one-layer models of Fig. 2. Thus, the surface film in the
layer for a-Si and a-Ge are approximately 30X-40%. two-layer model simulates the cluster film in the one-
Thus, the first deposited atoms do not form hemi- layer model. In the LRA, the surface layer void fraction
spheres, but rather two-dimensional discs, presumably was varied, but the bulk layer value was fixed at that
centered at statistically distributed nucleation sites. It is obtained from the final spectra.
possible, however, that the discs evolve into hemispher- Both data sets in Fig. 3 show fascinating behavior.
ical clusters in the multilayer regime, with a spacing For a-Si, a discontinuous transition in the surface layer
that may actually increase with film thickness owing to growth rate occurs at 5.5 min, corresponding to the
a process of statistical aggregation. This may explain transition in a(t) in Fig. l(a). From this time onward,
the fact that the data still cut across the calculated the arriving silicon atoms accumulate predominantly in
nucleation curves just prior to cluster contact. the bulk layer. Thus, this transition demarcates cluster

25 -

20

z
0.006 z 15

(T
9
0.004 x ‘0
0 f
= 5
d
f
0.000 0 I
0 5 IO 15 0 2 4 6 8 10 5 10 15 0 2 4 6 6

TIME (min) TIME (min) TIME (min) TIME (min)

Fig. 1. The unbiased estimator of the mean square deviation ob-
tained in LRA fits to real time ellipsometry spectra for the sputter-de-
position of (a) a-Si at 300 “C, and (b) a-Ge at 25 “C onto oxide-c-Si.
The open and solid circles are for one- and two-layer microstructural
models of film growth respectively. Vertical lines denote the transition
from a one- to two-layer model.
Fig. 3. Surface layer thicknesses ( 0) and bulk layer thicknesses ( V)
US.time, derived from a linear regression analysis of spectroscopic data
for the growth of (a) a-Si and (b) a-Ge using a two-layer model. The
open circles are results obtained for the one-layer model of Fig. 2, valid
only until the vertical lines. In this regime the nucleating film in the
one-layer model simulates the surface film in the two-layer model.
 377

from bulk film growth and occurs when the bulk film is
one monolayer or approximately 2.5 8, thick, and the
total film is approximately 15.5 A thick. It is clear from
Fig. 3(a) that the transition to bulk film growth occurs
over a single monolayer in accumulated thickness. The
surface roughness induced in the nucleation process,
13 A just prior to bulk film growth, is enhanced with
time, eventually reaching 20 A after a total film thick-
' 0.2 - Spectroscopic
ness of 350 A. 0
For a-Ge, a similar transition to bulk film growth is 9
- t 1
- 0.0 1 I
observed at the respective monolayer and total film 2 4 THI&NESBS 10 12

thicknesses of 2.5 A and 1 I.5 A, but in contrast to a-Si, (A)

a-Ge becomes slightly smoother upon bulk jilm jbrma- Fig. 4. Void volume fraction vs. film thickness for the initial nucle-
tion. Consequently, we conclude that the surface diffu- ation of a-Ge. derived from the time evolution of (I/I. A) at two
sion length for germanium adatoms at 25 “C is greater selected photon energies. The deposition is the same as that in Fig. 2.
Results deduced from the full spectroscopic analysis (Fig. 2) are also
than the a-Ge in-plane roughness scale [ 151. Con-
included (solid line). The error bars denote 90% confidence limits in
versely, for the a-Si surface to roughen, the surface the spectroscopic analysis.
diffusion length for silicon adatoms at 300 “C must be
less than the corresponding a-Si roughness scale. If we
propose that the aSi and a-Ge clusters are nearly dielectric function is small, unless the effect can in fact
hemispherical just prior to bulk film growth, then the be mimicked by a void fraction change. It is clear that
in-plane roughness scale for the two materials is 26 A experimental accuracy and precision need improvement
and 18 A respectivley, being controlled by the initial for further study of this effect.
nucleation density. In summary, the differences in be-
havior appear to be related ultimately to the higher 3.2. Aluminum
nucleation density for a-Ge and/or greater germanium In order to model real time {$(hv), d(hv)) for alu-
adatom surface diffusion length. minum evaporation in terms of the evolution of mi-
The assumptions in the analyses that led to Figs. 2-3 crostructure or optical functions, the bulk dielectric
are (1) that the microstructure of the continuous film function of our aluminum is required. Thus, the lust
can be described in terms of a simple two-layer model pair of real time spectra for the opaque film was
and (2) that the thick film bulk dielectric function can interpreted by LRA using a three-medium model (am-
be used in the EMA at the cluster level. The fact that bient/roughness/bulk) and the aluminum reference
a(t) in Fig. 1 for the two-layer models remains below dielectric function of Smith et al. [9]. The following
0.01 throughout the growth process supports both as- three best-fit (CT= 0.012) parameters were obtained: a
sumptions. roughness thickness of 10.5 f 0.6 A, and surface and
As noted earlier, we attempted to ensure the validity bulk layer void fractions of 0.51 + 0.02 and
of assumption (1) by depositing under conditions of 0.001 f 0.005 respectively. The roughness layer is ana-
optimum microstructure using unthermalized flux. In lytically removed from the last spectra to obtain the
contrast, an analysis of results for a-Si obtained at high required aluminum dielectric function for subsequent
argon pressure, and hence thermalized flux, showed analysis. The close agreement between the void frac-
that o(t) for the two-layer model increases significantly. tions of our optimized material and the reference sug-
This suggests that the model is an oversimplification, gests that both films exhibit single-crystal density.
and such films exhibit a graded void density from the The first pair of spectra obtained prior to film growth
substrate interface, typical of columnar structure. was also interpreted by LRA using a three-medium
We explored the validity of assumption (2) with model (ambient/oxide/substrate). Thus, we find a ther-
independent analyses of data at different photon ener- mal oxide thickness of 71 A, and this layer is analyti-
gies. When the one-layer model is valid, the void frac- cally removed from the first spectra to obtain the bulk
tion and thickness can be deduced from ($, d) at a dielectric function of the c-Si substrate. The literature
single photon energy directly by inversion rather than dielectric function for SiO, is used throughout the
by an LRA of the full spectra. Figure 4 shows the void analysis [ 111.
fraction us. thickness for the a-Ge film of Fig. 1, An analytical form for the aluminum dielectric func-
deduced from i+(t), d(t)} for hv 0.4eV above and tion in terms of parameters independent of photon
below the Ed peak at 2.9 eV, along with the results of the energy is needed to study size effects vs. thickness using
full spectroscopic LRA from Fig. 2. The close agree- an LRA approach. We apply the ‘well known Aschroft-
ment suggests that any effect of cluster size on the Sturm form [ 161 including (1) parallel-band transitions
318 R. W. Collins et (11.I Red time spectroscopic ellipsometry

associated with planes parallel to the (200) and ( 111) parameters deduced for this model are consistent with a
Brillouin zone faces and (2) the Drude contribution. nucleation-growth sequence. We will not discuss
We neglect normal-band contributions. Because the the detailed results because the CJ values (as well as
(200) parallel-band feature overlaps our spectral range, an inspection of the fits) show that the fits are unac-
the analyses are most sensitive to the associated ceptable in the first 8 s. Improvements in CJ cannot
parameters. The following were fixed in all analyses: (1) be obtained by using instead the simple Maxwell-
Fermi wavevector, k, = 1.749 A-‘; (2) plasma energy, Garnett (MG) or Lorentz-Lorenz effective medium
hv, = 12.5 eV; (3) Fourier coefficient of the crystal po- theories [ 31.
tential, 1U,, ,I = 0.25 eV; (4) Drude optical mass, As an alternative to the approach with only mi-
m, = 1.55m, (m, is the electron mass) [9]. crostructural free parameters, we allowed the parame-
After having eliminated overlayers from consider- ters that describe the aluminum dielectric function to
ation, we attempted to fit our bulk aluminum dielectric vary with film thickness. IU,,,I was fixed at the bulk
function by LRA using four free parameters, 1U,,,, 1and value of 0.733 eV, in the expectation that size effects are
the relaxation times r for the (200) and ( 111) parallel- related to electron relaxation and not to intrinsic band
band and Drude contributions [ 161. The 1.3 eV lower structure. Thus, we first used a model with three
limit of our spectral range, however, precluded determi- parameters: film thickness, r,,, and rPg. We assumed
nation of the latter two r values. Thus, we equated the that the (200) and ( 111) r values were equal, but found
parallel-band t values and fixed the Drude r at the that solutions for z,, and zPs were highly correlated. To
literature bulk value (z,, = 10.6 x lo- I5 s) [9]. A good avoid this problem, the relationship
fit (CJ= 0.025) was then obtained for ]U,,,I = 0.733 eV
r -1 _- ~,u,k-’ + v,lR (1)
and for the parallel-band r, zpr, = 4.1 x 10P” s, in close
agreement with literature results [ 171. To compare a(t) was applied. Here, r and T,,“,~ are the size-modified and
for the microstructural and size effect models on an bulk relaxation times, R is an effective-particle radius,
equal footing, an analytically generated aluminum and vr is the Fermi velocity [ 181. Equation ( 1) simulates
dielectric function was used in all LRAs. effects of increased scattering in the early growth stage
The unbiased estimators for the best-fit microstruc- arising from surfaces and voids, disorder and defects, or
tural model are plotted us. time in Fig. 5 (open circles) undeveloped crystallites. This approach has been ap-
for the first 30 s (approximately 150 A) of growth. plied successfully by Niklasson et al. [ 191. Through eqn.
Fixed bulk parameters for the analytically generated (l), R is used as a free parameter in the LRA, from
aluminum dielectric function are used throughout this which z,, and zPs can be calculated from rbulk.
LRA (see previous paragraph). In the first 10 s (50 A), Figure 5 shows that this model which includes only a
the data could only support a one-layer model for the size effect provides a major improvement in the fits
film with two free parameters, the thickness and void compared with the model which includes only mi-
fraction. The Bruggeman EMA was used in these calcu- crostructure, in some cases by more than a factor of
lations 131. After 10 s, a two-layer (surface/bulk) model two. With the exception of the third and fourth spectra
could be justified. The evolution of the microstructural (t = 2.5, 3.75 s), CJis as low as can be expected given the
quality of the analytical fit to the aluminum dielectric
function in the bulk regime. For t 3 5 s, incorporation
of the void fraction as a parameter in the size effect
model leads to values less than 0.10 and thus has a
minor influence on the fit; for t < 5 s correlations pre-
vent such an analysis. As will be shown, further inter-
pretation is required in the latter regime in any event.
Figure 6 shows rPg and R plotted vs. the deduced film
thickness d. The 90% confidence limits in the LRA are
included as the error bars. These reflect a typical corre-
lation coefficient between rPR and d of 0.65. (Vertical
0.000 1 b I bars on R are omitted for clarity.) The results show a
0 5 10 15 20 25 30
remarkable effect: tpg increases by a factor of 5 (from
TIME (sac)
0.4 x lo-‘5 to 2 x lo-l5 s) for 55 cd <6OA. This
Fig. 5. The unbiased estimator obtained in an LRA of real time arises from an increase in R from 10 A to 100 A. Above
ellipsometry spectra for aluminum evaporation on a thermally oxi-
the transition the effective-particle radius increases ac-
dized c-Si substrate at 25 “C. The open circles and solid triangles
cording to R z 2d. If we assume that grain boundary
represent the best microstructural and size effect models respectively.
For the former, one- and two-layer models for film growth are scattering predominates above the transition and that
employed. For the latter, the electron relaxation times are varied. the grain radius equals d, then this relationship implies
 R. W. Collins et al. / Real time spectroscopic ellipsometry 379

optical functions are similar to those of thick aluminum

quenched from the vapor at 25 K [22]. It is possible that
the 55 A transition arises from the crystallization of
small- diameter, closely packed clusters, or disordered
clusters, which lack the (200) translational symmetry of
bulk aluminum.
To conclude, we return to the early spectra (t < 4 s) for
which ITrises abruptly from zero for the substrate to 0.03.
This poor fit reveals a problem with applying the
i
. . .. Ashcroft-Sturm form for the aluminum dielectric func-
0
0 50 100 150 200 250 300 tion in the earliest stage of growth. Specifically, the
THICKNESS (A) effective-particle radius from eqn. ( 1) exhibits unphysical
Fig. 6. Electron relaxation time associated with parallel-band absorp- dimensions here. A representative aluminum dielectric
tion and effective particle radius from eon. (I) as a function of function in this stage (Fig. 7, broken line) fits a single
thickness deduced from an LRA of spectroscopic elhpsometry data Lorentz oscillator centered at 3.7 eV with a full width of
obtained in real time during the evaporation of aluminum. 3.3 eV. Optical absorption bands have long been ob-
served for small metal particles [2] and have been modeled
for aluminum using a modified MG effective medium
a grain boundary reflection coefficient of 0.25, in ap- theory along with a size effect (eqn. ( 1)) [23, 241. Thus, it
proximate agreement with a value of 0.15 determined is likely in our case that the 23 A thick film is composed of
electrically [ 201. separated aluminum clusters. The transition between the
To clarify the origin of the abrupt change in optical Lorentz oscillator and free electron behavior occurs near
structure, inversions of (J/(hv), d(hv)) for the alu- 40 8, and presumably represents a regime of cluster
minum dielectric functions were undertaken. In this contact. This thickness lies within the range of earlier
approach a single-layer model was used, and the thick- estimates of 20-25 A and 70 A for the percolation
nesses were chosen to eliminate c-Si substrate-related threshold for evaporated aluminum films [25,26].
artifacts near 3.3 eV in the aluminum dielectric function Because of the similarity of the dielectric function of
[21]. The thicknesses required to eliminate the artifacts the 23 A aluminum to low density a-Si, it was important
matched those in Fig. 6 within 10 A. The fact that the to explore possible interfacial reaction between SiO,
artifacts could be eliminated justifies the use of a single- and aluminum to form a-Si and A&O,. Thus, the final
layer model. Spectra just below and well above the opaque film was immersed in 5% HCl in H,O to remove
transition are shown in Fig. 7. Interestingly, the (200) the aluminum, and the bare substrate was then remea-
parallel-band feature is absent for the 53 A film, sured by spectroscopic ellipsometry upon removal from
whereas it is readily apparent for the 103 A film. the solution. The final SiO, thickness was identical
The optical functions below the 55 A transition clearly ( f0.5 A) with that obtained on the substrate prior to
indicate metallic behavior. The results for the 53 A thick aluminum deposition. Thus, we conclude that an interfa-
film cannot be fit to a single Drude contribution as cial reaction even at the monolayer level can be ruled out
would be expected if it were in the liquid state. Thus, the at 25 “C.

20 , 40

- 35

30

- 25

- 20
5
- 15

- 10

-5

I I $1 1 I I I1 I I 81 I I
.O 1.5 2.0 2.5 3.0 3.5 4.0 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5”

PHOTON ENERGY (d) PHOTON ENERGY (eV)

Fig. 7. Dielectric functions for thin aluminum films, deduced by inversion of real time {$(hv). d(hv)) assuming a one-layer model, in the three
regimes of the evolution of the optical properties.
380 R. W. Collins et al. I Real time spectroscopic ellipsometry

4. Summary the evolution of the complete optical functions of ultra-

thin aluminum and demonstrate the power of spectro-
Real time spectroscopic ellipsometry was applied to scopic ellipsometry in fundamental investigations of the
probe the evolution of microstructure and optical prop- effects of size on the electronic structure of thin films.
erties in the early stages of thin film growth. We have
reviewed two cases, thin film amorphous semiconduc-
tors and thin film aluminum, which require different Acknowledgments
modeling approaches.
For a-Si and a-Ge sputter-deposited onto oxide-cov- We would like to thank H. S. Witham, K. Vedam
ered c-Si, the influence of microstructure on the effec- and R. Messier for contributions to the development of
tive optical properties, as calculated with the EMA, the ellipsometry facility. Financial support from the
appears to be large in comparison with the influence of National Science Foundation under Grants DMR-
microstructural size on the intrinsic optical functions. 890103 1 and DMR-8957159, and DuPont Corporation
As a result, unprecedented sensitivity to the microstruc- is acknowledged.
tural evolution of the film has been obtained. For aSi
on native oxide-covered c-Si at 300 “C, we find that the
first monolayer coverage is 40%. Compact initial
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silicon. This abrupt transition is only observed when D. E. Aspnes, Thin Solid Films, 89 (1982) 249.
the growth conditions lead to enhanced adatom surface R. W. Collins, Reo. Sci. Instrum., 61 (1990) 2029.
Y.-T. Kim, R. W. Collins and K. Vedam, Surf. Sci., 233 ( 1990) 341,
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25 “C. Initial coverage is 30% clusters make contact Thin Solid Films, 206 (1991) 300.
9 D. Y. Smith, E. Shiles and M. Inokuti, in E. D. Palik (ed.),
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