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Langmuir 2000, 16, 2281-2284

2281

Thickness of Spin-Cast Polymer Thin Films Determined by


Angle-Resolved XPS and AFM Tip-Scratch Methods
C. Ton-That, A. G. Shard, and R. H. Bradley*
Materials Surfaces and Interfaces Group, School of Applied Sciences, The Robert Gordon
University, St. Andrew Street, Aberdeen AB25 1HG, U.K.
Received May 18, 1999. In Final Form: November 5, 1999
Polystyrene (PS) and poly(methyl methacrylate) (PMMA) thin films (<100 nm thickness) have been
spin-cast from chloroform solution onto cleaved mica surfaces (roughness within 0.2 nm). An algorithm
for calculating the film thicknesses based on the relative intensities of the C 1s peak of the films and the
Si 2s peak of the mica from angle-resolved X-ray photoelectron spectroscopy (XPS) is presented. The film
thickness changes as a function of casting conditions. Data from this approach are comparable with thickness
measured by an atomic force microscopy (AFM) tip-scratch method in the range 1.5-5.5 nm. Thicknesses
of the films are shown to increase linearly with concentration of cast solutions.

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.

tips. By controlling the loading force of the AFM tip on


film surfaces, it is possible to scratch through the film
without damaging the substrates. Film thickness is then
simply measured by passive AFM imaging of the scratch.
The atomic-scale wear properties of mica have been studied
previously by AFM,8,9 and it was found that mica wear
depended on loading force, number of scans, and tip shape.
In this work, scratch experiments were carried out on
polymer films with the loading force below the mica
damage threshold. Thicknesses measured from the angleresolved XPS and AFM scratch methods are compared for
various polymer films cast from different PS or PMMA
concentrations in chloroform.
2. Experimental Section
The polystyrene (PS) and poly(methyl methacrylate) (PMMA)
used in this work have weight-average molecular weights of 280K
and 350K, respectively. Films have been spin-cast at 293 K from
solutions prepared by dissolving a known weight of each polymer
in a fixed volume of chloroform (g/mL % concentration). All films
were cast from 60 L aliquots of the polymer solutions onto freshly
cleaved mica substrates of about 1 cm 1 cm area, which were
rotated at 3000 rpm for 2 min. The cleaved mica surface, whose
roughness was measured within 0.2 nm, was atomically flat.
Film thickness was varied by controlling the concentrations of
polymer in solution. The chloroform solvent was completely
evaporated from the films as no chlorine signal was detected by
XPS.
The XPS spectra were acquired using a Kratos Axis HSi
5-channel electron spectrometer using monochromated Al KR
(1486.6 eV) X-rays. The main chamber of XPS instrument was
maintained at 10-9 Torr. Survey spectra (0-1100 eV binding
energy) were collected using a pass energy of 80 eV, and the
X-ray gun was operated at 150 W. An electron flood gun was
used to offset charge accumulation on the samples. The XPS
survey spectra were taken at five takeoff angles (relative to the
surface normal) of 0, 30, 50, 60, and 70. The relative photoelectron
intensities of C 1s and Si 2s peaks were evaluated from peak
areas after subtraction of a linear background.
Atomic force microscopy was performed with a Digital Instruments (DI) Multimode SPM IIIa system in contact mode using
square pyramid Si3N4 probes. Short (nominal length 100 m,
nominal tip radius 20-60 nm10) Si3N4 triangular cantilevers with
wide legs were used for scratching the films while longer
(8) Miyake, S. Appl. Phys. Lett. 1994, 65, 980.
(9) Hu, J.; Xiao, X. D.; Ogletree, D. F.; Salmeron, M. Surf. Sci. 1995,
327, 358-370.
(10) Digital Instruments, Santa Barbara, CA.

10.1021/la990605c CCC: $19.00 2000 American Chemical Society


Published on Web 01/29/2000

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Langmuir, Vol. 16, No. 5, 2000

Ton-That et al.

For an incoherent scattering model of a uniform thin


film of thickness d on a substrate, eq 1 can be written for
the film and substrate photoelectrons using the depthconcentration profile (z ) 0 to d, Xs ) 0; z ) d to , Xf )
0).
For the film:

If )

Ifo
f

z
dz
0dXf exp(-f cos
)

(2)

And for the substrate:

Iso
Is )
s

Figure 1. Effect of takeoff angle on sampling depth.


cantilevers (less stiff) were used for imaging the resulting
scratches. Scratches were formed on the polymer films by
scanning the tip repeatedly back and forth over the same line
with high loading forces. Several different scratches were
measured for each film to allow statistical analysis of data. The
normal spring constants of the cantilevers were calculated using
their measured unloaded resonant frequencies.11,12 Individually
measured spring constants of each cantilever were used in the
estimation of loading forces and the calibration of the instrument.
The calibrated values for the short cantilevers were in the range
from 0.46 to 0.76 N/m. A loading force of approximately 260 nN
(inclusive of the capillary force due to adsorbed water layer),
which was evaluated from the calibrated values of spring
constants, was used for scratching of all the films. The same
force was used to scratch the PS and PMMA films because the
two polymers have similar physical properties and surface
stiffness. Scratch tests on bare mica substrates using the same
cantilevers and force have shown no damage on mica surfaces.
It was also found by subsequent imaging in tapping mode, which
has been demonstrated to be less intrusive,13 that contact mode
imaging in the low loading force regime (<10 nN) does not
significantly damage the polymer films and scratches. The
average depth of the scratch below the mean surface plane,
corresponding to the film thickness, was measured using the
cross-section analysis software. All images of scratched films
were acquired in air and were stable and reproducible.

3. Results and Discussion


3.1. Angle Resolved XPS. The purpose of the following
calculation is to determine the thickness of any uniform
thin film on a substrate. The thickness measurements
are based on the relative peak intensities of the film and
substrate at different takeoff angles.
By assuming that the X-ray intensity does not diminish
within the XPS sampling depth, the relation between
intensity Ii and concentration Xi of an element i can be
described as a function of the electron escape depth i:14

Ii )

Iio
i

0Xi(z) exp(-zi) dz

(1)

where Iio is the intensity for an elemental bulk standard


and Xi(z) is the local concentration in mole fraction at
depth z. The effective escape depth i is simply (cos ),
where is the takeoff angle from the surface normal
(Figure 1). The sampled vertical depth, where 95% of the
XPS signal intensity originates from, is 3(cos ).
(11) Cleveland, J. P.; Manne, S.; Bocek, D.; Hansma, P. K. Rev. Sci.
Instrum. 1993, 64, 403-405.
(12) Hazel, J. L.; Tsukruk, V. V. J. Tribology-Trans. ASME 1998,
120, 814-819.
(13) Zhong, Q.; Inniss, D.; Kjoller, K.; Elings, V. B. Surf. Sci. 1993,
290, L 688-L 692.

dXs exp(-scosz ) dz

(3)

Integration of eqs 2 and 3 gives

)]

d
If ) IfoXf 1 - exp f cos

(4)

and

d
Is ) IsoXs exp s cos

(5)

Taking the ratio of the peak intensities of the film and


substrate from the above two equations

[ (

)]

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)

The normalization factor, K ) (Ifo/Iso)(Xf/Xs), can be


calculated from the atomic sensitivity factor (ASF) of the
film and substrate elements or experimentally determined
from the bulk standards. The film thickness can be
evaluated using eq 7 by measuring the If/Is ratio if the
attenuation lengths of the film and substrate photoelectrons are known.
To simplify eq 7 one could choose the film and substrate
XPS peaks for analysis such that f = s, the second
exponential term in brackets becomes approximately one.
Rearranging eq 7, we have

ln

If 1
d
+ 1 ) sec
Is K

(8)

which shows that if XPS intensities of the film and


substrate are measured for several takeoff angles, a plot
of ln((IC 1s/ISi 2S)(1/K + 1)) vs sec should give a straight
line through the origin provided that the film thickness
is homogeneous on the substrate. The slope of this line
equals the thickness of the film in units of the attenuation
length.
One photoelectron peak from the film and one from the
substrate are chosen so that there is no contribution of
substrate elements to the film peak intensity and vice
versa. For a thin PMMA film (t < 3) on a mica substrate,
the C 1s and Si 2s peaks are used to calculate the ratio
(14) Briggs, D.; Seah, M. P. Practical Surface Analysis, Vol 1sAuger
and X-ray Photoelectron Spectroscopy; John Wiley & Son: Chichester,
England, 1995.

Thickness of Spin-Cast Polymer Thin Films

Figure 2. Plot of ln((IC 1s/ISi 2s)(1/3.69) + 1) vs sec for PMMA


film cast from 0.02% w/v solution. The dashed line is a simple
linear regression of the data, which has a slope of 0.47.

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 )

IC 1sXC 0.25 5/7


)
) 3.69
ISi 2sXSi 0.23 4/
19

Figure 2 shows a plot of eq 8 for the PMMA film cast from


0.02% w/v solution using the calculated K value above.
The linear regression line of the data has a slope of 0.47.
The film thickness of the PMMA film d ) 0.47 ) 0.47
3.0 nm ) 1.41 nm (taking the attenuation length of C 1s
and Si 2s photoelectrons in PMMA as 3.0 nm16). The
linearity of the graph is an indication of uniformity in the
film thickness. Imaging with AFM of the spun-cast PMMA
and PS films also reveals flat and uniform surfaces with
RMS roughness measured on 5 m 5 m area less than
0.3 nm.
The same algorithm is applied to the thin PS films on
mica substrate with a KC 1s/Si 2s value of 5.16 and ) 3.1
nm for C 1s photoelectrons in PS.16 Figure 3 shows a plot
of eq 8 and the line of linear regression for the PS film cast
from 0.02% w/v, which have a slope of 0.43. The thickness
of the PS film is d ) 0.43 ) 1.33 nm. Results of measured
d/ values from the slope of the plots of eq 8 and film
thicknesses for the PS and PMMA films spun-cast from
different solution concentrations are shown in Table 1.
3.2. AFM Tip-Scratch Method. For this method to
give an accurate measure of film thickness, three main
criteria must be fulfilled. First, only the film must be
scratched by the AFM tip with no damage being caused
to the substrate. A force of 260 nN was found to scratch
(15) Seah, M. P.; Dench, W. A. Surf. Interface Anal. 1979, 1, 1-11.
(16) Lukas, J.; Jezek, B. Collect. Czech. Chem. Commun. 1983, 48,
2909.

Langmuir, Vol. 16, No. 5, 2000 2283

Figure 3. Plot of ln((IC 1s/ISi 2s)(1/5.16) + 1) vs sec for PS film


cast from 0.02% w/v solution. The dashed line is a simple linear
regression of the data, which has a slope of 0.43.
Table 1. Thickness of the Polymer Films Measured by
Angle-Resolved XPS and AFM Tip-Scratch Methods
(Standard Deviations Also Shown for the Latter)

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

the polymer film but to cause no damage to the mica


surface (that could be detected by AFM in either tapping
mode or in contact mode with a low loading force (<10
nN)). Second, to check that the AFM tip reached the mica
substrate, the films were scratched for various time
durations and the resulting scratch depths measured by
passive AFM imaging (tapping or low force). The scratch
depths were found to increase with scratching time up to
a limiting value which was reached after a few hundred
seconds. Depth values were found to increase with the
concentration of the polymer in the casting solutions as
expected. Finally, back-filling of scratches due to film
relaxation was examined by imaging the scratches at 90
s intervals after scratching finished. This resulted in an
exponential change in depth with time allowing an overall
relaxation constant for the system to be calculated. By
using this method it was found that the relaxation time
(approximately 30 min) is much larger than the acquisition
time for one AFM image (45 s). We are confident that we
have scratched to the substrate, but no further and that
no depth decrease occurs due to film relaxation before
secondary AFM imaging. Consequently, use of the limiting
depth so measured corrected using the mean surface plane,
to avoid inclusion of scratch-edge debris, leads to an
accurate measure of film thickness.
Figure 4 shows a typical image of the scratch on the PS
film, which is cast from 0.06% w/v solution. The ridges
formed along the lips of the scratch, which are proud of
the sample surface, are due to PS which is displaced during
scratching. Local depth in one scratch relative to the mean
surface plane varies within 8%. To improve accuracy in
thickness measurements, the average depth of each
scratch is measured (Figure 5). Recorded film thicknesses
and their standard deviations, shown in Table 1, are
averages of at least three scratches at different locations
on the films.
Comparison of the thicknesses evaluated by XPS
algorithm and AFM scratch method is shown in Table 1.

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Langmuir, Vol. 16, No. 5, 2000

Ton-That et al.

Figure 6. Variation of thickness of the PS films with


concentration of cast solutions. The film thickness increases
almost linearly with concentration. The dashed line is a simple
linear regression of the data.

Figure 4. AFM image of the scratch on the PS film cast from


0.06% w/v solution. The scratch was formed by AFM tip at the
force of 260 nN.

Figure 5. Image of the scratch and its average cross section


of the PS film cast from 0.5% w/v solution. The average depth
of the scratch relative to the mean surface plane is 30.9 nm.

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

than 45, the range of angle resolved measurable signals


is reduced. For the films cast from solutions with
concentration of 0.2% w/v (thickness 15 nm) or greater
the mica signals are absent in the normal ( ) 0) spectra,
making the algorithm unusable.
Correlation to within 15% between the XPS algorithm
and AFM scratch method is observed for the thicknesses
in the range from 1.4 to 5.5 nm. The differences in the film
thicknesses measured by the two techniques can be
partially attributed to thickness variations at different
locations on the cast films. AFM measurements show a
slight decrease (within 10%) in film thickness moving away
from the center of the spun samples (this is probably due
to the centrifugal effect of the spinning). Difference in
sampling areas of the two techniques (submicron scale
for AFM and tens of microns for XPS) can also result in
discrepancies if the film thickness is inhomogeneous. As
also seen in Table 1, the PS and PMMA films, which are
cast from the same conditions, produce comparable film
thicknesses. The variation of thickness of PS films with
concentration of cast solutions is shown in Figure 6. Film
thickness increases almost linearly with the concentration
in the range 1.5-65 nm. The dashed line is a linear
regression of the data, which gives a relation d [nm] )
63.5C, where C is the concentration (% w/v) of polymer
solutions. The proportionality factor in the thicknessconcentration relation is expected to vary when changing
the spin rate of film casting.
4. Conclusion
The algorithm based on angle-resolved XPS has been
used for calculation of film thickness up to a value of 2.
For Al KR X-rays and polymer samples, this value is
approximately 6 nm. Data have been compared to thickness measurements made using an alternative AFM tipscratch technique. Correlation to within 15% between the
two methods is observed. Measured thicknesses of spincast films were shown to increase linearly with the
concentration of cast solutions.
LA990605C