Mat. Res. Soc. Symp. Vol.
629 © 2000 Materials Research Society
Tacticity and surface chemistry effects on the glass transition temperature of thin
supported PMMA films.
Y.Grohens , L.Hamon, P.Carriere, Y.Holl, J.Schultz
Institut de Chimie des Surfaces et Interfaces-CNRS
15, rue J.Starcky, BP 2488
68057 Mulhouse Cedex, France
ABSTRACT
The glass transition temperature (Tg) of thin supported films of stereoregular poly(methyl
methacrylate) on silicon has been investigated by ellipsometry in temperature. The Tg of the
spin coated layers of isotactic PMMA increases for thickness lower than 100 nm whereas a
depression of the Tg is observed for the syndiotactic PMMA. This opposite trend in the Tg
variation in thin layer between the two isomers evidenced a fascinating effect of the chain
organization at an interacting interface. Hydrofluric acid surface etching of the silicon wafer
was shown to decrease the threshold thickness at which the change in Tg occurs for both
PMMA isomers. The influence of the interfacial interactions along with the tacticity
dependent characteristics of the polymer will be discussed.
INTRODUCTION
The properties of macromolecules in an interfacial region is of technological importance in
many industrial fields. It is known that the conformation [1,2] and the mobility [3,4] of the
polymer chains will be strongly influenced by a surface. The glass transition temperature of
thin layers of polymers has been investigated by many groups in the last years [5-8]. One of
the main conclusion that can be drawn from these works is that Tg of thin films decreases for
free standing films and for weekly interacting systems. Polymers at free surfaces or in contact
with repulsive surfaces are dominated by entropic effects such as disentanglements,
confinement effects or chain end segregation which lead to a Tg depression [9-10]. In
contrast, the increase of Tg for polymer thin layers in strong interaction with a substrate is
often ascribed to particular chain organization (conformation, orientation) or chain packing
(local density fluctuation) [8,12]. In the present study, the thermal expansion of thin supported
layers of stereoregular PMMA was investigated by ellipsometry. Hydrofluoric acid, UV-
ozone and H2O plasma surface treatments were done to vary the chemistry of the Si wafer
substrate. The interfacial interactions were studied by FT-IR in ATR mode. The importance of
the static and dynamic stiffness of the polymer chain in the structuration of the interfacial
zone was discussed.
EXPERIMENTAL DETAILS
The PMMA used here were purchased from Polymer Source Inc. Their characteristics are
given in table 1.
PMMA Tacticity (%) Mn Mw/Mn Tg (°C)
i:h:s (10-3g/mol)
FF1.7.1
i-PMMA 97:03:0 37 1,21 61
s-PMMA 0:20:80 33 1,05 131
Table 1 : Characteristics of the PMMA used. i, h and s represents the isotactic, heterotactic
and syndiotactic triads, respectively.
They were synthesized by anionic polymerization to ensure well defined tacticity,
polydispersity and molecular weight. These polymers were spin cast from chloroform
solutions on (111) silicon surfaces. The substrates were treated by hydrofluoric acid, UV-
Ozone or H2O plasma prior to polymer deposition. The spin coated samples were studied after
annealing, above the Tg of the bulk polymer, for at least 3 hours and cooled down at constant
rate.
Attenuated total reflectance (ATR) infrared was carried out by using a Bruker IFS 66
spectrometer equipped with a Specac ATR heating device. Si crystals were used after plasma
or hydrofluoric acid surface treatment. Grams software used for the curve-fitting of the
carbonyl peak allowed the determination of the absorbance due to the bonded carbonyls and
the absorbance due to the free carbonyls.
Spectroscopic ellipsometry experiments were performed by using a Sopra ES4M apparatus
working in a range of wavelength from 0.4 to 0.8 µm. It was equipped with a heating rate
programmable hot-stage. The ellipsometric angles were recorded at stabilized temperatures
increased by 10° increments. The fit of tan φ and cos ∆ in this range of frequencies allows the
calculation of thickness and refractive index of the layers. The so-called kinetic ellipsometric
scans were performed by focusing on only one wavelength (0.75 micrometers) and with a
heating rate of 2 °/mn.
RESULTS AND DISCUSSION
0 .5 2 5
0 .5 2
i- P M M A la y e r
0 .5 1 5
0 .5 1
Cos Delta
0 .5 0 5
0 .5
0 .4 9 5
0 .4 9
0 .4 8 5 T g = 9 0°C
0 .4 8
0 50 100 150 200
T e m p e r a tu r e (°C )
Figure 1: Raw plot of the kinetic ellipsometric scan (only cos delta) of a 40 nm i-PMMA thin
film on a silicon wafer.
FF1.7.2
The Tg of the stereoregular PMMA was determined by variable temperature ellipsometry as
shown in figure 1. The ellipsometric angles recorded as a function of temperature are related
to the thickness and refractive index of the layer. The discontinuity that occurs in the thermal
expansion at Tg allows its determination with a reproducibility of ± 5° C. The evolution of the
Tg with the film thickness is plotted in figure 2.
140
130
120
110 iPMMA
100 sPMMA
Tg (°C)
90
80
70
60
50
40
0 50 100 150 200 250 300
Thick ness (nm )
Figure 2. Glass transition temperature of thin supported PMMA films as a function of the
thickness. The surface treatment is H2O plasma or UV-ozone. ◆ represents isotactic PMMA
and ▲ represents syndiotactic PMMA
The Tg of the layers of isotactic PMMA increases significantly for thickness lower than 100
nm whereas a decrease of the Tg is observed for the syndiotactic PMMA. This threshold
value of the thickness corresponds to 10 Rg for the polymers under investigation. The Tg of
the thinner layers seems to tend to the same value of 100°C independently of the PMMA
tacticity.
The specific interactions taking place between the polymer and the silicon can be studied by
infrared spectroscopy in ATR mode by spin coating directly the silicon crystal by the tactic
PMMA under investigation. The region of the infrared spectra assigned to carbonyl peak
(1700-1800 cm-1) exhibit a splitting of the υ(C=O) vibration due to H-bonding as shown in
figure 3.
FF1.7.3
140°C
130°C
120°C
110°C
100°C
90°C
80°C
70°C
55°C
1850 1800 1750 1700 1650 1600
Wavenumber (cm-1)
Figure 3 : Atr spectra of a 25 nm layer of i-PMMA recorded at different temperatures. The
spectral region corresponds to the υ(C=O) absorption frequency.
The peak at 1735 cm-1 and 1705 cm-1 are assigned to free carbonyls and bonded carbonyls,
respectively. An evolution with the temperature in the relative intensity of these two
absorption bands can be observed. The calculation of the fraction of bonded carbonyls p has
been described elsewhere [15]. This fraction p of chains units stuck at the surface increases
with temperature whatever the thickness of the layer and the tacticity of the PMMA as shown
in figure 4. The polymer/silicon interface is assumed to reconstruct via conformational
changes of segments and diffusion of chains, to produce interfacial configurations having
lower interfacial free energy at a given temperature. This reconstruction is reversible with
temperature and no hysteresis is detected. It turns out that segmental mobility can be achieved
at temperatures below the Tg of the bulk i- and s-PMMA. For the later mobility appears at
Tgbulk-100°C. Moreover, the slope of the curves δp/δT are independent of the stereoregularity
for a given thickness. This brings us to the question of whether the bulk Tg is a meaningful
parameter for describing the mobility of chain segments at the surface. Tuning the PMMA
tacticity provide evidence that the migration of chain units near a surface is independent of
the bulk Tg and obeys to other laws. The attractive surface is assume to drive a specific
molecular structuration of the layer which is much different from what it is in the bulk. The
resulting free volume is supposed to become independent of the PMMA stereoregularity.
Unfortunately, the packing efficiency at the surface cannot be directly estimated by the
infrared measurements
FF1.7.4
0.6
0.5
0.4
0.3
P
0.2
0.1
0
20 40 60 80 100 120 140 160
Temperature (°C)
Figure 4 : Evolution of the fraction of bonded carbonyls as a function of temperature for a 25
nm film of i- and s-PMMA. ◆ represents s-PMMA and ■ represents i-PMMA.
Plasma and UV-ozone treatments provide reactive Si-OH surfaces. Identical Tg values are
found for PMMA thin films for both treatments as shown in figure 2. In contrast, hydrofluoric
acid etching leads to a smooth hydrogen passivated hydrophobic surface. The evolution of the
Tg on this Si-H surface is somewhat different than on a SiO2 recovered surface. Indeed, the
Tg of the layer remains equal to the bulk Tg up to thickness of 30 nm. Deviations from the
bulk Tg are observed for ultra-thin films (h<30nm) for which the Tg of i-PMMA increases to
80°C whereas the Tg of s-PMMA decreases to 90°C. Experimental evidence that no specific
interactions are present between PMMA and the Si-H surface has been provided by ATR
infrared spectroscopy for film thickness higher than 100 nm. Since the experiments are
carried out in air, some oxidation of the surface occurs during heating, through the polymer
ultra-thin film, allowing the development of specific interactions. Unfortunately, no
experiments were carried out under vacuum. From these experiments is can be assumed that
strong interactions are necessary to deeply modify the Tg of thin layers of PMMA. However,
if the isotactic isomer exhibit the expected increase of Tg, things are more surprising for the s-
PMMA. Indeed, favorable interactions can hardly be the driving force for mobility
enhancement at an interface.
Several workers [5, 8,16] stated that thin polymer layers can exhibit changes in Tg according
to nature of the interfacial interactions. Thus, for PMMA Tg depressions were observed on a
gold substrate where no specific interactions are expected while this polymer on a silicon
oxide substrate showed small increase in the Tg. Since that time many other contributions
have showed the same trends: the Tg of thin films increases for systems in strong interaction
whereas unfavorable interactions with the air or a substrate leads to a Tg depression. In
stereoregular PMMA the opposite variation of Tg in thin layers between the two isomers
evidences a fascinating effect of the chain organization at an interacting interface. Indeed,
since the ‘chemistry of the system’ is kept constant by tuning only the tacticity of the
polymer, the nature of the interfacial interactions with the silicon substrate is identical.
Therefore, other characteristic factors of the polymer intrinsically related to the PMMA
microstructure have to be addressed. Static and dynamic characteristics of the stereoregular
PMMA have been listed in table 2 for the sake of comparison .
FF1.7.5
i-PMMA s-PMMA
Local conformations (Ftrans)(1) 0.72 0.89
Static properties Characteristic ratio (C∞)(1) 10.2 7.2
Dynamic properties Activation energy of relaxation Ea 23 kJ/mol 32 kJ/mol
(T1) in the bulk (2)
Activation energy of relaxation Ea of 42 kJ/mol 67 kJ/mol
adsorbed species (3)
Table 2 : Static and dynamic characteristics of stereoregular PMMA. (1) values calculated
from molecular simulation: Vacatello et al. [17], (2) values calculated from α-methyl NMR
relaxation studies: Tanaka et al. [18], (3) values calculated from molecular simulation of
tactic PMMA adsorbed on aluminum: Shaffer et al. [19].
The influence of the chain stiffness in the adsorption of a polymer chain has already been
pointed out [20]. It is worth mentioning that the i-PMMA chain, as shown by the higher
characteristic ratio, exhibit a higher static stiffness than the s-PMMA. Therefore, stereoregular
dependent behavior of the polymer at the interface is expected. Indeed, our group has proven
that the stiffer isotactic sequences are preferentially adsorbed at the chloroform/silica interface
[21]. Moreover, we believe that the higher dynamic flexibility of the isotactic sequences,
indicated by the lower activation energy of relaxation of both bulk or adsorbed chains, allows
local conformational adjustments of the chains segments. These favored conformational
rearrangements are required for the first adsorbed chains to fit the surface interacting sites but
also for the later diffusing chains to access to the remaining silanol groups. Therefore, the
static stiffness of the isotactic chains along with their dynamic flexibility are likely to allow a
denser chain packing at the interface than in the bulk. The free volume resulting from this
packing at the interface is assumed to be decreased as compared to the bulk for the isotactic
isomer whereas it may increase for the syndiotactic isomer. The packing density induced by
the interacting surface is assumed to cause a modification of the Tg of both isomers which
tends towards a unique Tg as shown in figure 2. In other words, the memory of the packing
density of bulk stereoregular PMMA is likely to be lost in the vicinity of a reactive surface.
CONCLUSION
This study shows that thin films of PMMA exhibit a stereospecific evolution of the glass
transition temperature with the thickness. Modification of the chain packing in the confined
state is assumed to be responsible for this behavior. The role of the static and dynamic
stiffness of the chain on the adsorption process has been envisaged to explain the tacticity
dependent properties of the layers.
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FF1.7.7
