Professional Documents
Culture Documents
2281
1. Introduction
Accurate determination of surface film or overlayer
thickness is an important aspect in many areas of surface
and materials science. Several authors have proposed
methods for measurements of thickness of thin films using
ellipsometry1,2 or reflectometry.3,4 These optical techniques
are often used for the film thicknesses in the range from
tens to hundreds of nanometers. In contrast, angleresolved XPS is widely used to study very thin layers, i.e.,
a few nanometers thick. For a thin overlayer on a substrate
which both contain a common element, XPS-based algorithms exist which relate the ratios of chemically shifted
peaks to thickness, e.g., SiO2 on Si5,6 or Al2O3 on Al.7
Recently, we have been studying the physicochemical
properties of polymer blends and, in one aspect of this
work, have been attempting to relate spin-cast film
thickness and property with casting parameters. As part
of this work we have developed an algorithm which allows
thickness calculation for any uniform film of thickness (t
< 3) on a substrate using the relative peak intensities
of two peaks (one of which is characteristic of the substrate
and the other is characteristic of the film) measured at
different photoelectron take off angles. is the attenuation
length of emitted photoelectrons. In this paper, this method
is demonstrated for PS and PMMA films cast from
chloroform solution using the C 1s peak of the film and
the Si 2s peak of the mica. Atomically flat mica surfaces
are used as substrates in this work in order to eliminate
the effect(s) of substrate roughness on thin films.
For thin films which are relatively soft compared to
substrates, e.g., polymer films on mica or silicon, thickness
can also be determined by scratching the films with AFM
* Corresponding author. Telephone: (44.1224) 262800. Fax:
(44.1224) 262828. E-mail: r.bradley@rgu.ac.uk.
(1) Gesang, T.; Fanter, D.; Hoper, R.; Possart, W.; Hennemann, O.
D. Surf. Interface Anal. 1995, 23, 797-808.
(2) Henck, S. A. J. Vac. Sci. Technol.sVac. Surf. Films 1992, 10,
934-938.
(3) Shelley, P. H.; Booksh, K. S.; Burgess, L. W.; Kowalski, B. R.
Appl. Spectrosc. 1996, 50, 119-125.
(4) Hirvi, K.; Makela, T.; Pekola, J.; Paalanen, M. Rev. Sci. Instrum.
1994, 65, 2735-2736.
(5) Hill, J. M.; Royce, D. G.; Fadley, C. S.; Wagner, L. F.; G. F. J.,
Chem. Phys. Lett. 1976, 44, 225.
(6) Fulghum, J. E. Surf. Interface Anal. 1993, 20, 161.
(7) Zemek, J.; Hucek, S.; Jablonski, A.; Tilinin, I. S. Surf. Interface
Anal. 1998, 26, 182.
2282
Ton-That et al.
If )
Ifo
f
z
dz
0dXf exp(-f cos
)
(2)
Iso
Is )
s
Ii )
Iio
i
0Xi(z) exp(-zi) dz
(1)
dXs exp(-scosz ) dz
(3)
)]
d
If ) IfoXf 1 - exp f cos
(4)
and
d
Is ) IsoXs exp s cos
(5)
[ (
)]
df - ds
If Ifo Xf
d
)
exp
- exp
Is I oXs
s cos
sf cos
s
(6)
or
[ (
)]
If
df - ds
d
) K exp
- exp
Is
s cos
sf cos
(7)
ln
If 1
d
+ 1 ) sec
Is K
(8)
of the photoelectron intensities from the film and substrate, respectively. Atomic sensitivity factors of 0.25 (C
1s) and 0.23 (Si 2s) from the Kratos Vision software,
version 1.4.0, which take into account the transmission
function of the Kratos instrument have been used in the
work presented here. The use of alternative ASFs e.g.
from ref 14 resulted in differences in K values of less than
3% and consequently differences in film depth well within
experimental error. The Si 2s peak was used instead of
the main peak Si 2p because the Si 2s photoelectrons have
their binding energy closer to that of C 1s photoelectrons.
The attenuation length of C 1s and Si 2s photoelectrons
is effectively the same because of their similar kinetic
energies (if using the E1/2 law, i.e., E1/2 where E is the
electron energy in eV,15 the difference in attenuation
lengths of C 1s and Si 2s photoelectrons is less than 5%).
Ignoring all hydrogen atoms which are not detectable
by XPS, stoichiometric molar fraction of carbon in PMMA
and silicon in mica (KAl2Si4O12H) is 5/7 and 4/19, respectively. The K value for C 1s/Si 2s intensity ratio is
calculated by
KC 1s/Si 2s )
casting
solution (% w/v)
measured
d/
thickness
measured by
angle-resolved
XPS, nm
PMMA 0.02
PS 0.02
PMMA 0.04
PS 0.04
PMMA 0.06
PS 0.06
PS 0.1
PMMA 0.2
PS 0.2
PS 0.5
PS 1
0.47
0.43
1.18
1.04
1.74
1.76
1.41
1.33
3.54
3.11
5.22
5.46
thickness
measured
by AFM
tip-scratch, nm
1.6 ( 0.2
1.4 ( 0.3
3.0 ( 0.2
2.8 ( 0.4
5.9 ( 0.6
5.2 ( 0.3
6.3 ( 0.5
15.0 ( 1.2
13.7 ( 2.1
30.9 ( 2.8
64.3 ( 5.1
2284
Ton-That et al.
The XPS method can only be used for very thin films (d
< 6 nm), which give measurable photoelectron intensities
from the substrate. Indeed, the error of the intensity ratio
If/Is gets larger and the plot of ln((If/Is)(1/K) + 1) vs sec
becomes less linear for the thicker films because of the
weak substrate signals. Consequently, for measurement
of the thickness of the films cast from solutions of between
0.06% and 0.1% w/v, where the mica signals are weak at
) 0 and completely disappear at takeoff angles greater