VOLUME 88, NUMBER 3 PHYSICAL REVIEW LETTERS 21 JANUARY 2002

Incoherent Neutron Scattering and the Dynamics of Confined Polycarbonate Films

C. L. Soles, J. F. Douglas, and W.-l. Wu
NIST Polymers Division, Gaithersburg, Maryland 20899-8541

R. M. Dimeo
NIST Center for Neutron Research, Gaithersburg, Maryland 20899-8562
(Received 6 March 2001; published 2 January 2002)
Incoherent elastic neutron scattering measurements are performed on thin (75 to 1015 Å) polycarbon-
ate films supported on Si wafers. We find that the mean-square atomic displacement 具u2 典 is diminished
by thin film confinement. For film thicknesses comparable to the unperturbed dimensions of the macro-
molecule, we observe two characteristic crossover temperatures in 具u2 典 as a function of temperature T ,
one above and the other below the bulk Tg . Furthermore, the harmonic force constant k, defined by
the low temperature dependence of 具u2 典 (i.e., k 艐 kB T 兾具u2 典), increases as the film thickness decreases.
These observations suggest that the atoms are more strongly localized in the thin supported films.

DOI: 10.1103/PhysRevLett.88.037401 PACS numbers: 78.66.Qn, 28.20.Cz, 64.70.Pf, 78.70.Nx

A sharp rise in the scale of atomic thermal fluctuations, 13 to 15 wafers for each film thickness were broken into
relative to the scale of the interatomic separation, is a gen- 艐共20 3 50兲 mm2 strips and placed in a cylindrical, thin-
eral feature of the onset of fluidity in both crystalline and walled aluminum cell. This resulted in only 0.6 to 7.1 mg
glassy materials. It is reasonable to expect that this ubiq- of PC in the sample cell in comparison to 52 to 58 g of
uitous material “softening” process is affected by thin film Si. The cell was mounted on the high flux backscattering
confinement. Changes in the softening temperature with spectrometer (HFBS) on the NG2 beam line at the NIST
film thickness can have particularly serious ramifications in Center for Neutron Research [7] and cooled to 40 K
polymer thin film applications. For example, an increased under vacuum. The spectrometer operated in the fixed
viscosity for an exceedingly thin lubrication film, such as window mode (stationary Doppler drive) with the elastic
those used in hard disk lubricants, could lead to device fail- intensities recorded over a Q range of 0.25 to 2.0 Å21 .
ure. Likewise, enhanced mobility in a thin chemically am- The sample temperature (T) was ramped at 0.5 K兾min
plified photoresist film could lead to excessive photoacid (1014 Å films) to 0.1 K兾min (75 Å films) to 525 K with
diffusion and blurring of the latent lithographic image. It the elastic intensities summed over intervals of 1 to 3 K.
is then crucial to develop fundamental methods to under- The HFBS energy resolution of 0.8 meV (FWHM) implies
stand finite-size effects on molecular mobility in thin poly- that dynamics on a time scale of 200 MHz (approximately
mer films. a nanosecond) or slower are considered static.
In this Letter, we present the first incoherent elastic The neutron scattering in polymers is typically domi-
neutron scattering measurements to directly probe the dy- nated by H which has a total scattering cross section ap-
namics of molecularly thin supported polymer films. The proximately 20 times greater than either C or O, and nearly
elastic scattering intensity of a harmonic solid reflects the 40 times larger than the Si substrate. Given there is nearly
amplitude of the thermal motions in a manner described 100 times more Si than PC in each sample cell, it might
by the Debye-Waller approximation: seem unreasonable to extract dynamical information from
2
具u2 典 the polymer. However, with a neutron wavelength of
Iinc 共Q兲 ~ e 2共1兾3兲Q , (1)
6.271 Å, the accessible Q range of the HFBS spectrometer
where Q is the scattering vector and 具u2 典 is the mean- is just below the first Bragg peak of Si (Q 艐 2.67 Å21 ).
square atomic displacement. Within this framework, 具u2 典 This ensures that the dynamics of Si are transparent to the
is defined by the slope of ln关Iinc共Q兲兴 vs Q 2 . While most spectrometer.
atomic motions in soft condensed matter are character- The nonlinear thermal decrease in the elastic scattering
istically nonharmonic, this approximation has proven intensity in Fig. 1 demonstrates our sensitivity to polymer
extremely useful in synthetic [1 –3] and biological macro- films as thin as 75 Å. The transmission coefficients are
molecules alike [4,5]. approximately 0.99 for all of the thin films, indicating that
Thin polycarbonate (PC) (GE Lexan ML-4235 [6]; multiple scattering is not an issue. At each temperature,
Mr,w 苷 36.3 kg兾mol) films were spin cast from cyclo- the ln共Ielastic 兲 versus Q 2 slope yields the mean-square dis-
hexanone solutions onto silicon wafers (Silicon Inc., placement 具u2 典. These linear fits are shown in Fig. 2 for
75 mm diam, N具100典, thickness 艐0.3 mm) with freshly the 75 Å film in the region Q 2 , 1.0 Å22 . At each Q,
prepared oxide surfaces. Four sets of films with thickness the elastic intensities are normalized by their 40 K val-
values of 75, 128, 298, and 1015 Å, as determined by ues, thereby setting 具u2 典 equal to 0 at 40 K. At higher Q,
specular x-ray reflectivity, were studied. Approximately there is a peak, for both bulk PC and the thin films, that

037401-1 0031-9007兾02兾88(3)兾037401(4)$20.00 037401-1

VOLUME 88, NUMBER 3 PHYSICAL REVIEW LETTERS 21 JANUARY 2002

1 qualitative result is insensitive to both the details of the

fits in Fig. 2 and the Debye-Waller approximation as the
Ielastic
.9 75 Å same conclusion can be drawn from Fig. 1; the extent of in-
elastic scattering is diminished with decreasing film thick-
.8 1015 Å ness. The Debye-Waller analysis provides a framework for
.7 -1
quantifying relative changes in 具u2 典 as a function of film
Q = 0.36 Å bulk PC thickness.
.6 In Fig. 3 we observe a strong increase in the slope of
100 200 300 400 500 具u2 典 versus T in bulk PC near the calorimetric glass tran-
T (K)
sition, Tg 苷 423 K. This apparent softening temperature
FIG. 1. The decrease in the elastic scattering intensity as a shifts to higher T as the films become increasingly thin.
function of temperature at Q 苷 0.36 Å21 for the 75 Å film, Breaks in 具u2 典 versus T are often observed near Tg in
1015 Å film, and bulk PC. The standard uncertainty from the a wide range of glasses, as discussed in several reviews
counting statistics is less than the size of the data points.
[1,2,4]. In this respect the shift of the break in 具u2 典 to
higher T might be interpreted as an increase of Tg as the
disrupts the linear relation between ln共Ielastic 兲 and Q 2 (see film becomes molecularly thin (65 Å radius of gyration).
the Fig. 2 inset for the bulk data). The peak coincides with However, it is prudent to confirm this result with a tech-
the position of the amorphous halo for PC (Q 2 艐 1.5 Å22 ) nique more widely accepted as a method to measure Tg in
leading us to believe that there is a significant amount of thin polymer films.
coherent scattering. Thus, we limit the fitting of our data Specular x-ray reflectivity as a function of T is com-
to the low Q region (Q 2 , 1.0 Å22 ), which effectively monly used to estimate the apparent Tg of thin polymer
emphasizes the larger amplitude motions. Preliminary un- films. The Fig. 3 inset compares the thermal expansion in
published data indicate that these high Q features are not terms of a percent change in D normal to the surface for
present in similar measurements on poly(methyl methacry- both a 720 Å and a 75 Å PC film on identical substrates.
late), while similar trends are found for the dependence of The break in the expansion is close to the calorimetric Tg
具u2 典 on film thickness. for the thicker film but shifted to lower T in the thinnest
While the x 2 values for the linear fits are significant in film. This seems to contradict the apparent increase in
Fig. 2, the average slope increases with T which leads to Tg implied from the 具u2 典 data. However, Fig. 4 expands
an increase in 具u2 典, as seen in Fig. 3. It is evident that the the vertical axis of Fig. 3 for the 75 Å film and reveals a
relative values of 具u2 典 are diminished as the film thickness steplike feature in 具u2 典 between 250 and 350 K. Interest-
decreases, indicating that confinement reduces the ampli- ingly, this steplike feature, which does not occur in films
tude of the atomic thermal fluctuations. This important thicker than 128 Å, appears to “plateau” close to the ap-
parently reduced Tg estimate of 艐380 K from x-ray reflec-
tivity. Whether these two features are related remains to
be established.
0.0 40 K
100 K
-0.2 200 K
300 K 720 Å bulk
1
∆D ( % )

-0.4 4 0 75 Å 1014 Å
ln ( I elastic )

0
∆< u >40K ( Å )

-1
2

-1 400 K 3
-0.6 -2 Tg bulk
-2 -3 298 Å
-3 2 350 400 450
-0.8 fit 128 Å
2

-4 T(K)
500 K 1
0 1 2 3 75 Å
-1.0
Tg bulk
0.2 0.4 0.6 0.8 1.0 0
2 -2
Q (Å ) 100 200 300 400 500
T(K)
FIG. 2. The elastic intensity, normalized by its 40 K value,
as a function of Q 2 for the low angle detectors in the 75 Å FIG. 3. 具u2 典 as a function of temperature for both bulk PC and
films. 具u2 典 is proportional to the slope at each temperature. The the confined films (standard uncertainties are less than the size
inset reveals a maximum near Q 2 艐 1.5 Å22 for bulk PC. The of the data points). There is a clear suppression of 具u2 典 with
linear fit indicates the range below this maximum used to extract decreasing film thickness. The inset displays the correspond-
具u2 典 from the low Q data. The standard uncertainties from the ing thermal expansion, from x-ray reflectivity, for both a thick
counting statistics are significantly less than the point to point (720 Å) and thin (75 Å) PC film. While 具u2 典 suggests an in-
variations. crease of the thin film Tg , the expansion data predict a decrease.

037401-2 037401-2
VOLUME 88, NUMBER 3 PHYSICAL REVIEW LETTERS 21 JANUARY 2002

1.4 this anharmonic regime, the values of 具u2 典 are qualitative

κ ( N/m )
6 at best. However, between 50 and 200 K it is safe to as-
∆< u >40K ( Å ) 1.2 4 sume that the atoms are confined to local minima in the po-
1.0 tential energy landscape and it is reasonable to model their
2

2
motions in these wells by a three-dimensional harmonic
0.8 0 500 1000 oscillator. This results in a linear increase of 具u2 典 with T
0.6 h(Å) (i.e., k 艐 kB T 兾具u2 典), with k defining a vibrational force
2

0.4 slope ∝ 1/κ constant. We find k 苷 1.9 6 0.3 N兾m, 2.0 6 0.3 N兾m,
3.9 6 1.7 N兾m, and 5.8 6 1.0 N兾m in the 1015, 298,
0.2 75 Å films 128, and 75 Å films, respectively, shown graphically in the
0.0 Fig. 4 inset. The thickest films are consistent with bulk PC,
100 200 300 400 500 k 苷 1.9 6 0.1 N兾m, while the analogous value for pure
T(K) Si is k 苷 78.5 N兾m [13]. The PC k’s appear reasonable
given that the coefficient of thermal expansion in Si is typi-
FIG. 4. The 具u2 典 data for the thinnest (75 Å) film in Fig. 3 cally 1 to 2 orders of magnitude less than most polymers;
is shown with an expanded vertical scale, revealing a steplike
feature between 250 and 350 K. Below 200 K, the 具u2 典 versus differences in the thermal expansion coefficients should
T slope defines a harmonic force constant k. The inset shows track differences in elastic constants. The bulk PC force
how k stiffens with decreasing film thickness. constant is also consistent with analogous measurements
on proteins below 200 K [5]. Qualitatively, the increase
It is not clear how the disparate estimates of crossover in k in the thin films suggests that the atoms are trapped
temperatures in neutron and x-ray data influence the des- in deeper potential energy minima in comparison with the
ignation of the true thin film Tg . Which characteristic tem- bulk, or more strongly caged by their environment. This
perature is most appropriate to identify with Tg ? However, intuitive picture is sometimes used to describe a decrease
there is precedent for observing multiple characteristic in the fluid fragility in glass-forming liquids [2,4,9]. A de-
T ’s, even in bulk glass-forming liquids. Note that the crease in the fluid fragility with confinement has also been
high T break in the thermal dependence of 具u2 典 occurs at suggested in other recent investigations [14,15].
T 艐 1.2Tg,bulk for the 75 Å films. A variety of evidence In the presence of strongly anharmonic motions (i.e.,
[2,8,9] indicates that changes in the dynamics of super- above 200 K), we have discussed how the values of 具u2 典
cooled liquids occur at T 艐 1.2Tg . These changes include are approximations at best. Frick and Fetters [16] demon-
deviations in the Stokes-Einstein and Debye-Einstein rela- strate that nonvibrational motions, such as methyl group
tions, a bifurcation of the a and b relaxation processes, rotations, can dominate the Debye-Waller analysis in the
and the breaking of ergodicity as predicted by mode cou- low Q region analyzed here. In principle, details of the
pling theory. It seems interesting that the break in 具u2 典 molecular motions can be extracted from the full inelastic
for highly confined PC films also occurs near 1.2Tg,bulk . neutron scattering spectra, as eloquently shown for bulk
Similarly, a sub-Tg,bulk characteristic temperature is found PC [17]. Unfortunately, the limited scattering signal from
by fitting viscosity or relaxation data to the Vogel-Fulcher the thin PC films precludes a similar analysis here; the in-
equation (e.g., h 艐 h` exp关DT0 兾共T 2 T0 兲兴). Experimen- elastic scattering intensity is several orders of magnitude
tal evidence [2] and theoretical arguments by Adam and weaker than the elastic. To obtain better insight into the
Gibbs [10] suggest that the configurational entropy stops meaning of 具u2 典 in this anharmonic regime, it is instruc-
varying well below (艐50 K below) Tg,bulk near T0 . The tive to examine a more generalized (and thus complicated)
lower temperature crossovers in both 具u2 典 and reflectivity representation [18]:
µ ∂
data also occur close to a broad range of estimates (340 , 3h̄ Z vm 1 h̄v
T0 , 375 K) for the Vogel-Fulcher T0 for PC [11]. 具u 典 苷
2
coth g共v兲 dv , (2)
The ramifications of these observations need to be es- 2M 0 v 2kB T
tablished by extending the measurements to a broad range where v is the frequency and g共v兲 is the density of states.
of confined glasses. However, our observations raise sev- In the high T limit, the quantity inside the integral is pro-
eral interesting questions. Specifically, it is not clear why portional to g共v兲兾v 2 , indicating that low frequency mo-
the two characteristic temperatures become pronounced in tions significantly dominate 具u2 典. This is analogous to
the thin film geometry. The thickness dependence of these x-ray crystallography where it is well known that the long
characteristic temperatures seems to indicate that confine- range acoustic modes, not the high frequency optic modes,
ment broadens the glass transition over a wider temperature dominate the Debye-Waller factor. In short, the increase
range. Similar reports of a broadened glass transition have in 具u2 典 above 200 K is dominated by the lowest frequency
recently appeared in the polymer thin film literature [12]. motions that are still within the energy resolution of the
In Figs. 3 and 4, the 具u2 典 versus T curves deviate from HFBS spectrometer (faster than 200 MHz).
linearity beyond 200 K, thereby invalidating the harmonic By their nature, low frequency, long range motions
approximation implicit in the Debye-Waller analysis. In are collective across several atoms or particles. If the

037401-3 037401-3
VOLUME 88, NUMBER 3 PHYSICAL REVIEW LETTERS 21 JANUARY 2002

mean-square displacement is dominated by the low fre- [2] C. A. Angell, K. L. Ngai, G. B. McKenna, P. F. McMillan,
quency modes, the diminution of 具u2 典 with confinement and S. W. Martin, J. Appl. Phys. 88, 3113 (2000).
primarily reflects a suppression of these collective mo- [3] J. Colmenero and A. Arbe, Phys. Rev. B 57, 13 508
tions. Suppressed collectivity was observed in molecular (1998).
dynamics simulations on confined supercooled soft-sphere [4] C. A. Angell, Science 267, 1924 (1995).
[5] G. Zaccai, Science 288, 1604 (2000).
liquids [15]. Furthermore, Zorn et al. [19] confirm that
[6] Certain commercial equipment and materials are identified
confinement primarily affects the low frequency motions in this Letter in order to specify adequately the experimen-
with inelastic neutron scattering experiments on salol in tal procedure. This does not constitute a recommendation
controlled pore glasses. The notion of decreased collec- by the National Institute of Standards and Technology nor
tivity in molecular motion is consistent with the low T does it imply that the material or equipment identified is
observation that the particles in the thin films are strongly necessarily the best available for this purpose.
trapped in deep potential energy minima. Roughly speak- [7] P. M. Gehring and D. A. Neumann, Physica (Amsterdam)
ing, the atoms become strongly “caged” by their environ- 241B– 243B, 64 (1998).
ment in thin films. It is more difficult for the motion of [8] E. Rossler, Phys. Rev. Lett. 65, 1595 (1990).
one of these strongly caged particles in the thin films to be [9] C. A. Angell, J. Phys. Condens. Matter 12, 6463 (2000).
influenced in a cooperative manner by one of its neighbors. [10] G. Adam and J. W. Gibbs, J. Chem. Phys. 43, 139
(1965).
In closing, we note that our results are qualitatively con-
[11] K. L. Ngai and D. J. Plazek, in Physical Properties of Poly-
sistent with surface forces apparatus measurements [20] mers Handbook, edited by J. E. Mark (American Institute
on liquid films (polymer and small molecule fluids) which of Physics, Woodbury, NY, 1996), p. 349.
show a dramatic increase in viscosity h when the thick- [12] S. Kawana and R. A. L. Jones, Phys. Rev. E 63, 021501
ness falls below 艐10 molecular diameters. Furthermore, (2001).
Buchenau and Zorn [21] note an exponential dependence [13] C. Flensburg and R. F. Stewart, Phys. Rev. B 60, 284
of h on 1兾具u2 典 liquid and glassy Se, which points to an (1999).
increase in stiffness for our thinnest PC films. Similarly, [14] K. L. Ngai, A. K. Risos, and D. J. Plazek, J. Non-Cryst.
increased elastic moduli [22,23] have been observed in liq- Solids 235– 237, 435 (1998).
uid films which is an expected consequence of the increase [15] K. Kim and R. Yamamoto, Phys. Rev. E 61, R41 (2000).
in the harmonic force constants deep in the glassy regime. [16] B. Frick and L. J. Fetters, Macromolecules 27, 974
(1994).
In total, these observations provide indirect evidence of
[17] G. Floudas, J. S. Higgins, G. Meier, F. Kremer, and E. W.
stronger caging of the atoms in thin polymer films. We also Fischer, Macromolecules 26, 1676 (1993).
emphasize that our disparate estimates of the crossover [18] G. L. Squires, Introduction to the Theory of Thermal Neu-
temperatures suggest that confinement effects on the glass tron Scattering (Cambridge University Press, Cambridge,
transition in thin polymer films should be interpreted 1978).
cautiously. [19] R. Zorn, D. Richter, L. Hartmann, F. Kremer, and B. Frick,
C. L. S. is grateful for support by the NIST NRC Post- J. Phys. IV (France) 10, 83 (2000).
doctoral Program and the critical discussions with Dan [20] S. Granick, Science 253, 1374 (1991).
Neumann. [21] U. Buchenau and R. Zorn, Europhys. Lett. 18, 523
(1992).
[22] H. W. Hu and S. Granick, Science 258, 1339 (1992).
[23] A. L. Demirel and S. Granick, Phys. Rev. Lett. 77, 2261
[1] B. Frick and D. Richter, Science 267, 1939 (1995). (1996).

037401-4 037401-4