2532 Macromolecules 2004, 37, 2532-2537

Glass Transition Temperature Determination of Poly(ethylene

terephthalate) Thin Films Using Reflection-Absorption FTIR

Ying Zhang, Jianming Zhang, Yonglai Lu, Yongxin Duan, Shouke Yan,* and
Deyan Shen*
State Key Laboratory of Polymer Physics & Chemistry, Joint Laboratory of Polymer Science &
Material, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100080,
People’s Republic of China

Received November 12, 2003; Revised Manuscript Received February 5, 2004

ABSTRACT: By using the in-situ reflection-absorption infrared technique, the glass transition temper-
atures of poly(ethylene terephthalate) thin films were determined by detecting the abrupt change in the
absorbance ratio of two comparable bands at 1340 cm-1 (trans conformation) and 1370 cm-1 (gauche
conformation) during heating. It was found that the Tg of thin PET films reduces with respect to that of
bulk sample and has a great dependence on the film thickness. The conformational energy difference
(∆E) between trans and gauche states of each film was also calculated. The results indicate that the
thickness dependence of calculated ∆E is nearly consistent with that of Tg measured. Furthermore, the
relaxation behavior of the PET chains in thin films prepared by spin-coating and the influence of annealing
on the Tg measured were also investigated.

Introduction Grohens et al.17 deduced the Tg of PMMA thin films with

different stereoregularities from the infrared spectra
Nowadays much focus is given to the anomalous subtraction. Both of these works using FTIR put em-
physical property of polymers in confined geometry such phasis on studying the effect of stereoregularity on Tg
as thin films due to its importance in science and of PMMA; the investigation of thickness dependence of
technology.1,2 The confinement effect on the glass tran- Tg for thin films, however, has not been involved.
sition dynamics has been observed in a large number
of polymer thin film systems.3-17 Conventional methods Poly(ethylene terephthalate) (PET) is a semicrystal-
used to measure the glass transition temperature (Tg) line polymer of considerable commercial importance. It
of bulk polymers including differential scanning calo- has been used to make a variety of products such as
rimetry (DSC) and dynamic mechanical analysis (DMA) films, fibers, and bottles. Even though the property of
are not well suited to the Tg characterization of polymer PET has been extensively studied, the glass transition
thin films. Therefore, lots of methods such as ellip- of its thin films has not been reported so far. In this
sometry,3-9 X-ray reflectivity,10,11 local thermal analy- study, the Tg of PET films was determined by temper-
sis,11,12 positron lifetime spectroscopy,13 and Brillouin ature-dependent reflection-absorption infrared (RAIR)
light scattering14,15 have been developed to investigate spectra. Different from the earlier works, a method was
the Tg of polymer thin films. suggested in our present study by choosing two bands
that are sensitive to the conformational changes in the
Fourier transform infrared (FTIR) spectroscopy is an RAIR spectra. The Tg of polymer thin films was deter-
important technique for characterizing the glass transi- mined from the abrupt change of the plot for the
tion of polymers. The utility of FTIR stems from the absorbance ratio of the two bands vs the temperature.
specificity of the IR probe to different submolecular and The conformational energies of the thin films were also
segmental constituents of polymeric systems, which calculated to verify the results. Moreover, the relaxation
gives this method a unique capacity to elucidate the behavior of the PET chains in thin films prepared by
molecular origin of transition phenomena.16 However, spin-coating and the influence of annealing on the Tg
because of the limitation of sensitivity and signal-to- measured were also investigated.
noise ratio, its application in characterizing the Tg of
polymer thin films was relatively rare, and the studies
usually concentrated on some specific polymers such as Experimental Section
poly(methyl methacrylate) (PMMA).16,17 Among these
Sample Preparation. PET pellets (Mw ∼ 36 000-41 000
studies, Shin et al.16 measured temperature-dependent g/mol, Mw /Mn ∼ 1.8-2.05) were produced by Changzheng
FTIR spectra of PMMA thin films. From these spectra, Chemical Industries, Beijing. The PET pellets were dissolved
two-dimensional (2D) maps of the first derivative of the in chloroform-trifluoroacetic acid (volume ratio 9:1). Thin
absorbance with respect to temperature over the space films of different thickness were prepared by spin-coating PET
of wavenumber and temperature were constructed. solutions of various concentrations at a speed of 2000 rpm
These maps were used to determine the Tg and to about 60 s onto the gold-coated glass wafers. All glass wafers
investigate the subtle temperature dependence of the were cleaned in fresh piranha solution (30% H2O2 mixed in
population of trans and gauche conformers in three 1:5 ratio with concentrated H2SO4) prior to spin-coating. Then
PMMA thin films with different stereoregularities. the thin films were kept under vacuum at ambient tempera-
ture for 2 days to remove the residual solvent. Before mea-
surement, all samples were annealed at about 85 °C for 4 h
* Corresponding authors. E-mail: dyshen@pplas.icas.ac.cn; and then slowly cooled to room temperature. The films after
skyan@iccas.ac.cn. annealing at 85 °C for 4 h were amorphous as the fraction of

10.1021/ma035709f CCC: $27.50 © 2004 American Chemical Society

Published on Web 03/12/2004
Macromolecules, Vol. 37, No. 7, 2004 Poly(ethylene terephthalate) Thin Films 2533

trans conformer is nearly 10%18-22 (see the section “Relaxation the temperature region of glass transition, the con-
Behavior of Spin-Cast Thin PET Films during Annealing”). former transition from gauche (1370 cm-1) to trans
Thickness Determination. Thickness measurement of (1340 cm-1) will take place. Abrupt changes that marks
thin films was performed with a NanoScope A MultiMode Tg in the absorbance ratio of 1340 and 1370 cm-1 bands
atomic force microscope (AFM) (Digital Instrument) in tapping have been found during glass transition for bulk PET.18,34
mode. The film thickness was determined by AFM height Considering that FTIR provides us the information
profile after partially removing the thin film from the glass
about different submolecular and segmental constitu-
wafers. The thicknesses of gold film and PET-gold film were
measured. They were defined as the distance between the glass ents of polymeric systems, it is reasonable for applying
surface and the average of all height values taken in a line A1340/A1370 to determine the Tg of thin PET films. In this
scan across the sample surface.23 To minimize the experimen- work, we make an effort to determine the glass transi-
tal errors, several height profiles taken from different locations tion temperature of PET thin films using the above-
of one sample were averaged. Then the thickness of PET thin mentioned method. Before the Tg measurements, an
film was acquired by subtracting the gold film thickness from investigation on the relaxation process of the spin-cast
that of PET-gold film. Considering the absorbance of RAIR films by RAIR was carried out, in which the bands 1340
spectra increase almost linearly with thickness for thin films and 1370 cm-1 were also used. This will be discussed
having thickness less than about 400 nm,24 most of the film
in the following section.
thicknesses were deduced by comparing their intensities of the
1410 cm-1 band in IR spectra, which is related to thickness Relaxation Behavior of Spin-Cast Thin PET
variations,25 with that of several AFM-measured thicknesses Films during Annealing. For glassy thin polymer
of the films. films, a possible cause for the anomalous behavior may
Reflection-Absorption FTIR Measurement. Reflec- originate from sample preparation. The widely used
tion-absorption FTIR spectra in the region of 400-4000 cm-1 process of spin-coating can potentially produce samples
were collected with a Bruker EQUINOX 55 FT-IR spectrom- that are far from equilibrium. Although in most studies
eter equipped with a MCT detector. The measurements were the used thin films have been annealed above the bulk
obtained by an average of 32 scans and a resolution of 4 cm-1. glass transition to remove residual solvent and relax
The incidence angle is fixed at 83° for getting the best signal
internal stresses, it is not clear whether this represents
recording. The polarization of the incoming beam was parallel
to the plane of incidence (p-polarized). A homemade heating sufficient annealing. Therefore, in this work, in-situ
stage was used to assist obtaining the in-situ FTIR spectra in RAIR measurement during annealing of thin PET films
the temperature range from ambient temperature to100 °C. with different thickness prepared by spin-coating was
Accuracy of temperature was controlled to be (0.3 °C. carried out, from which a thorough understanding on
the relaxation behavior of the thin films during anneal-
ing and its dependence on film thickness may be
Results and Discussion
obtained. Since the glass transition temperature of PET
is 74.5 °C (DSC, 20 K/min)35 and PET tends to crystal-
The polymer transition in different temperature
lize at temperature above 100 °C, we chose 85 °C as
reflects a certain type of segmental motion. This motion
can result in the changes of partial molecular conforma- the annealing temperature.
tion and relevant intramolecular and intermolecular Figure 1a shows the FTIR spectra of 1340 and 1370
interactions (e.g., dipole-dipole effect, hydrogen bond cm-1 bands for a PET film of about 71 nm in thickness
effect). FTIR has a great advantage on characterizing at different times during annealing at 85 °C. It can be
the conformation in polymer and molecular interactions. clearly seen that as the annealing time increases, the
This method offers an opportunity for understanding absorbance of 1340 cm-1 band grows apparently, while
the structure basis of the transitions in polymers since, the absorbance change of 1370 cm-1 band can hardly
in general, the structural origins of bands in the infrared be observed. The absorbance change of the 1340 cm-1
spectra of most polymers are known or can be deter- band can be clearly identified even if the sample was
mined. As it reaches the transition temperature of a cooled to ambient temperature after annealing, as
polymer, anomalous changes of the absorbance or loca- shown in Figure 1b. The intensity of 1340 cm-1 band is
tion in some infrared bands representing a certain kind evidently higher than that of the unannealed sample.
of conformation and interaction may occur.26-29 Since The absorbance changes of the two bands in Figure 1
the Tg represents actually a type of structural relax- indicate the occurrence of deorientation (or in other
ation, the aforementioned changes usually occur in the words, relaxation) of the PET chains during annealing.
vicinity of the Tg of a polymer. The Tg is a temperature It is believed that the spin-coating method can cause
at which there is an onset of motion of chain segments orientation of the PET films. As a result, the molecular
in the amorphous region of a polymer, and the polymer chains of PET are prone to be stretched and parallel to
goes from a hard, glassy state to a soft, rubbery one. In the surface of the film plane. Since the 1340 cm-1 band
molecular chain structure of PET, the -O-CH2-CH2- is parallel polarization,32 its transition moment will take
O- moiety shows gauche and trans conformers through a direction parallel to the main chain and thus parallel
the internal rotation of the C-C bond. In crystalline to the film plane after spin-coating. For the p-RAIR, it
regions the -O-CH2-CH2-O- moiety adopts a trans selects only the polarization of the incident electric field
conformation, while in amorphous regions it is mainly perpendicular to the metal surface. If molecules are
in the gauche conformation with some small contribu- adsorbed onto the substrate with a preferred orienta-
tion of trans conformation. A number of studies have tion, vibration modes having transition moments per-
appeared for the infrared spectroscopic characterization pendicular to the surface will appear greater in intensity
of contributing conformers of the PET chains.22,30-33 In than modes having transition moments parallel to the
the infrared spectrum of PET, the 1340 and 1370 cm-1 surface.36 For this reason, the absorbance of 1340 cm-1
bands have been assigned to the CH2 wagging mode in band is low in RAIR spectra before annealing. When
trans and gauche conformers, respectively.31 The inten- the films were annealed at temperature above Tg, the
sities of these two bands are comparable in the spectrum relaxation of molecular chain occurred and more transi-
of amorphous PET. When the PET is heated through tion moments of the 1340 cm-1 band tended to deviate
2534 Zhang et al. Macromolecules, Vol. 37, No. 7, 2004

Figure 1. Reflection-absorption FTIR spectra of a 71 nm PET film with different thermal histories. (a) Films at different times
during annealing at 85 °C. (b) Annealed (at 85 °C for 240 min) and unannealed films at ambient temperature.

Figure 3. FTIR spectra of a 43 nm film for every 10 °C from

30 to 80 °C.

Figure 2. Changes of A1340/A1370 as a function of annealing amorphous, the fraction of trans conformer (T) of the
time. films annealed is calculated by the following equa-
tion:18,19

off the film plane. Thus, the absorbance of this band A1340
increased. For the band of 1370 cm-1, its orientation is T) (1)
A1340 + 6.6A1370
much weaker than that of the 1340 cm-1 band or even
no orientation,32,37 which contributed to the unapparent where A1340 and A1370 are integral absorbance of 1340
absorbance changes. and 1370 cm-1, respectively. The calculated T for all of
Plotting the absorbance ratio of the 1340 and 1370 the samples annealed for 4 h goes near to 10%, so it
cm-1 bands vs times assesses the relaxation processes can be concluded that these films are nearly amor-
of thin PET films with different thickness during phous.18-22
annealing more quantitatively. This is shown in Figure Tg Determination of Thin PET Films. In-situ
2. We choose the absorbance ratio of 1340 and 1370 cm-1 measurement of RAIR spectra were performed during
bands for the aim to eliminate the effect of film thick- heating the annealed PET samples at a rate of 1 °C/
ness changes during annealing. From Figure 2, it can min from ambient temperature to 85 °C for determining
be seen that the relaxation behavior depends strongly the Tgs of thin PET films. The FTIR spectra of a 43 nm
on the film thickness. As film thickness increases, it film for every 10 °C from 30 to 80 °C are displayed in
becomes easier to relax. This is probably because that Figure 3. It can be found that the absorbance of 1340
for thinner films higher orientation is generated during cm-1 nearly keep stable in the temperature region of
film preparation, which can be deduced from the initial 30-60 °C, while abrupt increase can be found in the
value of A1340/A1370 for each film in Figure 2. As a result, spectra for 70 and 80 °C. The absorbance decrease of
it will take longer time to relax than the thicker ones. 1370 cm-1 in 70 and 80 °C is relatively unapparent
In addition, we found that all of the samples reach compared with that of 1340 cm-1. This attributes to the
relaxation equilibrium state in the time scale measured. less absorption coefficient in the 1370 cm-1 band.18,19
So we selected 4 h as the annealing time to relax the To get more quantitative description about this confor-
samples. To make sure whether the films annealed are mational transition process, plots that give the temper-
Macromolecules, Vol. 37, No. 7, 2004 Poly(ethylene terephthalate) Thin Films 2535

Figure 5. Measured glass transition temperature (Tg) vs film

thickness for thin PET films. The solid line represents the best
fit of eq 2 using Tg∞ ) 73.3 °C.

reported that a number of different factors may render

the free surface region of a polymer with added
mobility38-45 such as segregation of chain ends,38-41
density gradient in polymer surface,42 reduction in
polymer entanglement,43 and so on. Of course, there are
Figure 4. Changes of A1340/A1370 as a function of temperature also studies that argue against this high-mobility
for different film thickness. model.15,46-48 In the present case, we applied our data
to eq 2, and the results showed a good fit (smooth line
in Figure 5). The best fit has been achieved by choosing
ature dependence of A1340/A1370 for every 2 °C increase Tg∞ ) 73.3 °C, ê0 ) 2.9 nm, and the exponent ν ) 1.4,
of thin PET films with different thickness are made and among which the Tg∞ is in good agreement with the bulk
shown in Figure 4. In Figure 4, the point at which two Tg measured by DSC. For the parameters ν and ê0,
straight-line segments intersect can be detected for each Keddie supposed that ν is a constant for amorphous
of the PET films. As mentioned above, this may repre- materials but ê0 is material dependent.3 This is sup-
sent the abrupt change point of the conformational ported by comparing our data with the results of PMMA
transition from gauche to trans with increasing tem- for ν ) 1.9 ( 0.6 and ê0 ) 7.2 ( 3.6 nm if experimental
perature and thus can be taken as Tg of each films. As errors are considered.3
indicated in Figure 4, the determined Tg depends
As mentioned above, the relaxation behavior of thin
remarkably on film thickness. The film thickness de-
PET films depends strongly on the film thickness. Films
pendence in our present study is found to be similar to
with different thickness take different times to relax.
that of other works.3-9 This will be discussed in a later
Now a question may be raised about whether there is
section. We also found that it is more difficult to
influence of the annealing time on the measured Tg. To
measure Tg in thinner films since the abrupt change in
make this question clear, the Tgs of PET films annealed
A1340/A1370 at Tg is less obvious because of the high noise
for different times, e.g. 30 min and 10 h, were measured.
level in RAIR spectra. Such difficulties lead to an
Also, four different thicknesses, i.e., 23, 45, 60, and 118
effective lower limit of sensitivity for RAIR technique
nm, were adopted. The corresponding result is shown
to Tg measurement in extremely thin films.
in Figure 6. We found that all the measured Tgs of those
Figure 5 displays the plot of measured Tg vs film
annealed for 10 h are nearly unchanged compared with
thickness for PET films. The data exhibit a monotonic
those annealed for 4 h. However, if the films were
reduction in Tg with decreasing film thickness. When
annealed only for 30 min, it becomes more difficult to
the films are thinner than about 65 nm, substantial
detect the abrupt changes in the plot with decreasing
reduction in Tg can be identified. The lowest Tg is about
film thickness though the thicker films (60, 118 nm)
25 °C lower than the value of 74.5 °C for bulk samples
remain the same Tg as 4 h annealed films. From Figure
measured by DSC. A number of models have been
2, it can be concluded that 30 min annealing is not
proposed to explain this kind of behavior. Among them,
enough for the used films to relax entirely. Moreover,
Keddie et al.3 proposed the existence of a high-mobility
the thinner films should have the higher degree of
region. It suggests that a high-mobility region exists
residual orientation than the thicker ones after anneal-
below the bulk Tg, which expands as temperature, T,
ing. During the heating process for the Tg measurement,
increases. The Tg is reached when the high-mobility
the relaxation will continue simultaneously with the
region covers the entire film. By assuming that the
conformation transition induced by increasing temper-
thickness of the high-mobility region, êT, expands ac-
ature, and both of them will contribute to the increase
cording to ê0(1 - T/Tg∞)-1/ν, a model for the thickness
of A1340/A1370. For this reason, the abrupt change in glass
dependence of Tg was thus obtained:
transition for thinner films may be masked. For the case
of 10 h annealing, the Tg of the films remains the same
Tg(t) ) Tg∞[1 - (ê0/t)ν] (2) as that of 4 h, and a nearly amorphous state is
confirmed by eq 1. However, the possibility of crystal-
where Tg∞ is the bulk Tg and ν is a constant. It was lization is nonnegligible for further annealing.
2536 Zhang et al. Macromolecules, Vol. 37, No. 7, 2004

Figure 6. Changes of A1340/A1370 as a function of temperature for different annealing time and film thickness.

Conformational Energies Calculation of Thin

PET Films. Conformational energy, which is directly
affected by the chain rearrangement, has an intimate
relation with Tg of polymers. Through studying the
stereoregular PMMA,49 Gibbs and DiMarzio proposed
that conformational energy is a primary factor in
determining the glass transition temperature of a
polymer. O’Reilly et al.50,51 reported that the Tg of a bulk
polymer could be determined from the conformational
energy calculated using FTIR spectroscopy. The confor-
mational energy obtained from FTIR spectroscopy was
claimed to be consistent with that predicted by the
rotational isomeric state calculation. The conformational
energy calculation has also been applied to study
polymer thin films. Grohens et al.17 studied the inter-
facial conformational energy of stereoregular PMMA on
aluminum substrate using RAIR spectroscopy. Their Figure 7. Van’t Hoff plot of ln (A1340/A1370) vs reciprocal
results showed a large increase in conformational temperature for PET film of 43 nm in thickness (in temper-
energy of thin film samples as compared to that of the ature range 66-85 °C).
bulks. Furthermore, the glass transition temperature
deduced from the spectral subtraction also exhibits a and gauche conformational states. The Van’t Hoff equa-
large increase for i-PMMA. They interpreted these tion is as follows:
results in terms of interfacial gauche to trans confor-
mational changes and restrictions in molecular motions A1340 ∆E
due to strong specific interactions between PMMA and
ln ) ln K - (3)
A1370 RT
aluminum.
The calculation of conformational energy was em- where K is constant and R refers to the gas constant.
ployed in this study to verify our results of the measured By plotting ln(A1340/A1370) vs reciprocal temperature, the
Tg. At temperature below Tg, as the long-range molec- ∆E of thin PET films can be acquired from the slope of
ular motions of PET chains are restricted, the confor- the resulting line, as shown in Figure 7.
mational energy calculated at those temperatures may Table 1 lists the calculated ∆E and the corresponding
only refer to side-chain conformational changes. So a Tg value in the temperature range of Tg - 85 °C for the
temperature range from Tg to 85 °C was chosen for the PET films of varying thickness. The result indicates that
measurement of energy difference between trans and the calculated ∆E exhibits similar thickness dependence
gauche conformational states. In this temperature as the measured Tg. The ∆E decreases with the film
region, the Van’t Hoff equation can be used to calculate thickness and Tg. The ∆E change is more clearly with
the conformational energy difference ∆E between trans films thinner than 65 nm, while it is not obvious with
Macromolecules, Vol. 37, No. 7, 2004 Poly(ethylene terephthalate) Thin Films 2537

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