pubs.acs.

org/Langmuir Article

Chain Movements at the Topmost Surface of Poly(methyl

methacrylate) and Polystyrene Films Directly Evaluated by In Situ
High-Temperature Atomic Force Microscopy
Kouki Koike and Jiro Kumaki*
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ABSTRACT: The surfaces of polymeric materials are thermody-

namically unstable, and the glass-transition temperature (Tg) is
Downloaded via BOGAZICI UNIV on October 14, 2023 at 15:29:26 (UTC).

significantly lower than that in the bulk material. However, the

mobility of the chains at the top of the surface has never been
directly evaluated. In this study, the movements of the topmost
chains of poly(methyl methacrylate) (PMMA) and polystyrene
(PS) bulk films were observed in situ at high temperatures with
atomic force microscopy in tapping mode. PMMA and PS chains
started moving at ∼97 and ∼50 °C, respectively, which were slightly
and significantly below the values of their bulk Tg (PMMA, 108 °C;
PS, 104 °C), respectively. The activation energies of the apparent
diffusion constants of PMMA and PS, derived by particle image
velocimetry analysis, were 193 and 151 kJ mol−1, respectively, and
reasonable for the glass transition. Movements of isolated PMMA chains deposited on a PMMA film by the Langmuir−Blodgett
technique were also observed and confirmed to be essentially the same as those on the PMMA film surface.

1. INTRODUCTION molecular level. This is because (1) chains are closely

Since the invention of scanning probe microscopy, such as condensed with separations much smaller than the resolution
atomic force microscopy (AFM), polymer structures have been of usual AFM instruments; (2) unlike crystalline structures, it
is difficult to use AFM to recognize irregular amorphous
observed at the molecular level, and extensive studies have
structures; and (3) the surfaces of bulk films are too rough to
been reported.1−10 Currently, AFM is one of the most
be observed at high magnification. In this article, we report that
important research tools for studying polymer structures at
the information on chain movements of polymer surfaces was
the molecular level. We have been observing polymer
obtained by the direct in situ observation of bulk PS and
structures mainly using two-dimensional (2D) films, especially
PMMA films at high temperatures using conventional tapping-
Langmuir−Blodgett (LB) monolayers, which are suitable for
mode AFM (Figure 1).
observation by AFM at maximum resolution.5,9 We found that
Polymer surfaces are thermodynamically unstable, and the
resolution close to or slightly less than 1 nm could be attained
values of their glass-transition temperature (Tg) (surface Tg)
by conventional tapping-mode AFM and reported various
are believed to be significantly lower than those of the
molecular images: isolated chains,11 folded-chain crystal
bulk.21−26 In 1994, Keddie and co-workers studied the
structures with tight and loose tie chains,12 in situ folded-
temperature dependence of the thickness of a PS ultrathin
chain crystallization,13 chain packing in amorphous mono- film on a silicone substrate by ellipsometry and found that the
layers,14 synthetic helical polymers,5,15 and a poly(methyl Tg was significantly reduced from the bulk value.27 Since then,
methacrylate) (PMMA) stereocomplex.16 Resolution higher extensive studies have been reported.21−26 Today, we believe
than subnanometer was attained for the observation of that a thin film on a substrate has a three-layer structure: (1) a
poly(ethylene) crystals by torsional tapping mode17 and topmost layer at the air interface having a Tg several tens of
bimodal tapping mode18 by Hobbs et al. and Proksch et al.,
respectively. More recently, Korolkov et al. attained resolution
close to the atomic level by the low-amplitude excitation of Received: July 8, 2022
higher eigenmodes of a cantilever,19 and Heath et al. applied Revised: August 28, 2022
localization image reconstruction algorithms to peak positions Published: November 1, 2022
in tapping-mode AFM images.20 However, to the best of our
knowledge, the surfaces of conventional polymer films, such as
polystyrene (PS) and PMMA, have never been observed at the
© 2022 The Authors. Published by
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and was rather small, approximately 10 °C, for PMMA but

∼54 °C for PS. Furthermore, we showed that the movements
of the PMMA surface were essentially equivalent to those of
isolated PMMA chains deposited on the PMMA film by the LB
technique. AFM observations of the PMMA and PS film
surfaces were used successfully to evaluate the movements of
the topmost chains at the film surfaces.

2. EXPERIMENTAL SECTION
2.1. Materials. PMMA with a number-average molecular weight
(Mn) of 1.81 × 105 and a molecular weight distribution (Mw/Mn) of
1.84 and PS with a Mn of 1.40 × 105 and a Mw/Mn of 2.24 were
purchased from Sigma−Aldrich. The molecular weight was measured
by size exclusion chromatography (SEC) in tetrahydrofuran using
PMMA and PS standards (Shodex, Tokyo, Japan) for calibration. The
Figure 1. Schematic representation of the evaluation of chain bulk Tg of PMMA and PS was measured with a Q-2000 differential
movement on the surfaces of PMMA and PS bulk films by AFM at scanning calorimetry (DSC) system (TA Instruments, New Castle,
high temperature. DE, USA) at a heating rate of 10 °C/min under a nitrogen
atmosphere after the removal of the thermal history by heating to 150
degrees lower than that of the bulk; (2) beneath the topmost °C (10 °C/min), and the samples were held at this temperature for 5
layer, a layer with a Tg comparable to the bulk value; and (3) a min and then cooled to 20 °C (10 °C/min) in advance of the
layer at the substrate interface with a Tg higher or lower than measurements. The bulk Tg of PMMA and PS was 108 and 104 °C,
that of the bulk value, depending on the interaction with the respectively. A PS-b-PMMA diblock copolymer with a PS block Mn of
1.40 × 105, a PMMA block Mn of 6.56 × 105, and a Mw/Mn of 1.32
substrate. The Tg values of ultrathin films have been studied by was purchased from Polymer Source, Inc. (Montreal, Canada). Mica
various methods, including the temperature dependence of was purchased from Okensyoji Co. (Tokyo, Japan). Highly purified
film thickness measured by ellipsometry27 and X-ray and benzene (Infinity Pure, Fujifilm Wako Pure Chemical Corp., Osaka,
neutron reflectometry,28 the evaluation of molecular mobility Japan) was used as the solvent for the spreading solutions in the
using fluorescent probes,29,30 the temperature dependence of preparation of LB films. Water was purified using a Milli-Q system
surface friction using lateral force microscopy,31 the near-edge and used as the subphase for LB preparation.
X-ray adsorption fine structure analysis of a rubbed surface,32 2.2. Dip-Coated Film Preparation. Glass slides with a thickness
the dielectric spectroscopy of thin films,33 and others. AFM has of ∼1 mm were immersed in a PMMA or PS chloroform solution at a
also been used to evaluate the decrease in Tg of thin film concentration of ∼4.4 wt % and withdrawn from the solution at a rate
of 0.5 mm/s using a computer-controlled dipping machine (YN2-
surfaces in a somewhat macroscopic manner by evaluating the TKB, SAKIGAKE-Semiconductor Co., Ltd., Kyoto, Japan). The films
penetration rate of gold nanoparticles deposited on a thin were dried at room temperature in air for 24 h and then annealed at
film34 and the fusion rate of nanoholes prepared by the 150 °C for an additional 24 h in vacuo. The thickness of the dip-
deposition and removal of nanoparticles on a thin film.35 coated film was measured with an ellipsometer and was 430 nm for
If the mobility of the topmost chains at the surfaces could be PMMA and 350 nm for PS. The interaction at the substrate/film
directly evaluated by AFM, then more direct information about interface is reported to propagate through the film and affect the
the topmost surface Tg could be obtained. However, as dynamics at the topmost air surface by a long-range interaction; the
mentioned above, due to the limited resolution of AFM, direct effect extends as far as 180 nm39 or 250 nm.40 The PS and PMMA
evaluation of the mobility of the topmost chains is difficult and films are sufficiently thick that the effect of the film/substrate interface
on the surface Tg is negligible.
has never been reported. In previous studies, to overcome this 2.3. Langmuir−Blodgett (LB) Film Deposition. A PS-b-PMMA
difficulty, we prepared a molecularly flat substrate by thermally benzene solution (2.0 × 10−5 g/mL) was spread on a water surface at
imprinting a PMMA plate with an atomically stepped sapphire 23 °C in a commercial LB trough (3-22YG3, USI, Fukuoka, Japan).
substrate or mica mold and deposited isolated PMMA chains The surface pressure−area (π−A) isotherms were measured at a
by the Langmuir−Blodgett (LB) technique.36−38 The isolated constant compression rate with a moving barrier speed of 0.5 mm/s
chains deposited on the molecularly flat substrates were clearly (Figure S1 in the Supporting Information). The PS-b-PMMA
observed by AFM, and the isolated chains and nanostructure at monolayer was deposited on a dip-coated PMMA film and mica for
the flat substrate surface started moving at a temperature close comparison by pulling them out of the water at a rate of 4.2 mm/min
to the bulk Tg.38 During the course of those studies, we (the vertical dipping method). The monolayer was deposited at 0
mN/m over an area wider than the onset of the π−A isotherm with
considered possible ways to evaluate the movements of the the moving barrier stopped to deposit individual PS-b-PMMA
topmost chains of films by using bulk PMMA films without molecules prior to compression to form a condensed film. The
nanoimprinting and the deposition of isolated PMMA chains. details were shown in a previous report.38
In this article, we report that thin films of PMMA and PS 2.4. AFM Observation and Image Analysis. The samples were
were prepared by dip coating, and the movements of the observed with a commercial AFM (NanoScope IIIa and IIId/
topmost chains were directly evaluated by in situ real-time multimode AFM unit, Bruker, Santa Barbara, CA, USA) at room
AFM observation of the surface at high temperatures (Figure temperature or by high-temperature AFM (Agilent 5500) with a
1). In addition to PMMA, we selected PS as an additional temperature-controlled sample plate enclosed in an environmental
research sample because both of them are the most extensively chamber for stable temperature control (Agilent Technologies, Inc.,
Santa Clara, CA, USA) at high temperatures with supersharp silicon
studied polymers for the reduction of the surface Tg.26 We cantilevers (model, SSS-NCH; nominal spring constant, 42 N/m;
quantitatively analyzed the surface movements by image nominal tip radius, 4 nm; NanoWorld AG, Neuchâtel, Switzerland) in
analysis and showed that the activation energies were air in tapping mode. Preliminary experiments indicated that similar
reasonable for the glass transitions. The decrease in surface results were also obtained with standard silicon cantilevers (model,
Tg from the bulk value depended on the polymer composition NCH; nominal spring constant, 40 N/m; nominal tip radius, 8 nm;

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Figure 2. AFM height images of a PMMA film at various surface temperatures. A movie constructed from sequential AFM images (14 images for
40 min) is available in Movie S1 in the Supporting Information. To observe the surface movements, we recommend viewing the movie in repeated
replay mode in the viewing software. There appears to be no surface movement below 92 °C, and movement begins above 96 °C.

Bruker). For high-temperature observations, the samples were first image. Then the plug-in repeats this procedure three times while
observed at a prescribed temperature and then heated stepwise to the reducing the interrogation and searching windows with the PIV
next temperature at a heating rate of 5 °C/min. The temperature was information from the previous round as guidance for determining the
allowed to stabilize until the drift became negligible for 30 min, at correlation peak. The typical interrogation/searching window sets
which point the AFM observation started and the sequence was were 128/256, 64/128, and 32/64 pixels using cropped images from
repeated. The surface temperature of a dip-coated film on the heating the original 750 pixel × 750 pixel (1 μm × 1 μm) AFM images, except
plate was measured by a thermocouple sandwiched with a piece of where otherwise specified. The modification of the interrogation/
mica, and the thermal loss due to the slide glass and the dip-coated searching window sizes and the magnification of the original AFM
film was corrected. The obtained AFM images are presented in this images slightly affected the absolute value of the displacement vectors;
article without any image processing except flattening. Movies were however, the effect on the temperature dependence of the
constructed from sequences of AFM images by manually canceling displacement was negligible.
the drifts of the images by ImageJ (public domain software from the
National Institutes of Health) and further registered using the 3. RESULTS AND DISCUSSION
StackReg plug-in of ImageJ developed by Philippe Thévenaz to 3.1. Chain Movements of a PMMA Film Surface.
eliminate the small residual drift effect. The displacement of the
Figure 2 shows AFM height images of a PMMA film dip-
surface structure was evaluated using the iterative particle image
velocimetry (PIV) plug-in of ImageJ developed by Tseng Qingzong
coated on a slide glass observed at various surface temper-
using two odd or even sequential images with the same slow scan atures. The root-mean-square (RMS) roughness was 0.28 nm
direction to minimize the effect of deformation due to drift. The PIV at 25 °C and almost constant up to 119 °C. As shown in Figure
plug-in was used in the template matching method by a normalized 2, no meaningful structure or structure difference at various
correlation coefficient algorithm. The plug-in searches identifying temperatures was found in this static AFM observation.
features that are present in the interrogation window in the first image However, in dynamic observations, we could recognize
and searches for them in the larger searching window for the next significant movements at higher temperatures. The sample
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Figure 3. (a) Composite of the third and fifth AFM images of Movie S1 at 25, 101, 115, and 119 °C. Magnified images of the areas indicated by the
yellow squares are also shown. The third and fifth images are colored yellow and magenta, respectively. When there is no movement at 25 °C, the
composite image is black and white; with an increase in the surface movements, the yellow and magenta areas are separately observed. As shown in
the magnified images, string-like structures with a width of ca. 4 nm are present. (b) Magnified AFM height image of a PMMA film at 110 °C with a
height profile along the yellow line.

was observed multiple times at each temperature, and a movie with a fast scan in a single horizontal direction but a slow scan
was constructed from 14 sequential images. Each image took in the vertical direction, alternatively changing the direction
2.84 min, and the total movie took ∼40 min, as shown in the between downward and upward. Therefore, if a constant linear
Supporting Information (Movie S1). The number of images in thermal drift was present during the observation, then the
the movie was limited, and we recommend that readers view resultant images alternatively expanded and compressed mainly
the movie in repeated replay mode in the viewer software. As in the vertical direction with a minor distortion in the
shown in Movie S1, the surface structures were fixed at 25 °C, horizontal direction. Therefore, the alternative elongation and
but vigorous movements of nanostructures less than a few tens compression of entire images, except nanoscale movements,
of nanometers in size started at approximately 101 °C and are not true movements but artifacts. Thus, the structure was
became more significant with increasing temperature. Some fixed at 25−84 °C. If we assume that the thermal drift was
alternating expansion and compression of images in the vertical linear at a constant rate and use sequential odd or even images
direction were typically seen at 75−92 °C; these were with the same slow scan direction, then AFM always scans the
distortions of images due to residual thermal drift that could same parallelogram shape. As a result, no alternative elongation
not be removed by image processing. AFM evaluates a sample or expansion of images is seen. Movie S2 was constructed from
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Figure 4. Vector plot of the displacement between the third and fifth images of Movie S1 obtained by PIV analysis. The vector is enlarged by a
factor of 5 for clarity.

the third and fifth images of Movie S1, which were scanned in Figure 3b shows a magnified AFM height image of the PMMA
the same slow scan direction. Since most of the alternative film at 110 °C with a height profile along the yellow line. As
expansion and compression of images were removed, we indicated, the height of the chain-like structures was 0.16−0.42
recognized more clearly that the movements at the nanoscale nm, which was comparable to the height of PMMA chains on
started at approximately 96 °C (shown in Movie S2 in mica (∼0.3 nm in Figure 8b). The width was ca. 4 to 5 nm,
repeating replay mode in the viewer software). In our typical which should be broadened to a similar extent due to the tip
observations, the thermal drift during the recording of each radius (nominal diameter, 4 nm). Due to the broadening by
image was ca. 1% of the image size on average, and the error in the AFM tip, we could not precisely conclude, but we note that
the evaluation of a displacement described below was it could be a single chain or a bundle composed of a small
negligibly small. Figure 3a shows summed images of the number of PMMA chains. Figure 4 shows a vector plot for the
third and fifth images in Movie S1, which were colored yellow displacement between the third and fifth images of Movie S1
and magenta, respectively. The time lapse between the two obtained by PIV analysis. The displacement between two
images was 5.67 min. Yellow and magenta are complementary images is indicated by vectors. The size of the vector was
color pairs. At 25 °C, no movements were observed, and as a
enlarged by a factor of 5 for clarity. As shown, the surface
result, the summation was a black and white image. With
structures apparently started moving at approximately 101 °C.
increasing movement between the two images, yellow and
The mean displacement at each temperature is plotted in
magenta areas were separately observed with increases in the
Figure 5a as a blue filled triangle. The displacement started
size and area (101−119 °C). The structure of the moving units
is not clear in the low-magnification movies. Movie S3 is a increasing at approximately 97 °C, which was only slightly
magnified version of Movie S1. The moving structures in lower than the bulk Tg (108 °C) of PMMA. No significant Tg
condensed regions are not clear; however, in the dilute regions decrease at the surface of the PMMA film occurred. The
indicated by the arrows, chain-like structures 4 to 5 nm in displacement obtained here was up to several nm/5.67 min.
width are clearly observed, which appeared to be moving, and We derived the apparent diffusion constant by assuming that
the movements became more vigorous at high temperatures. the surface movement obeyed the two-dimensional (2D)
The size of the structure moving in the condensed regions is diffusion equation
quite similar, so it is reasonable to assume that the condensed 2
regions are also composed of similar chain-like structures. = 4Dt (1)

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where λ is the displacement, D is the apparent diffusion

constant, and t is the time. Figure S2a in the Supporting
Information shows the λ2 plot as a function of time for the
PMMA film at 101, 110, 115, and 119 °C. λ2 increased linearly
with time, indicating that the movements of the nanostructure
at the PMMA film surface obeyed the 2D diffusion equation in
this time and temperature range. Figure 5b shows an Arrhenius
plot of the apparent D estimated by eq 1 (blue filled circles).
The activation energy obtained for the apparent D at
temperatures higher than 96 °C was 193 kJ mol−1. The
activation energies reported for the glass transition of PMMA
in the literature are summarized in Figure 5c. The reported
activation energies are scattered and include 400 kJ mol−1 by
McCrum et al.,41 274 kJ mol−1 by Jud et al.,42 109 kJ mol−1 by
Van Alsten et al.,43 and 371 kJ mol−1 by Shearmur et al.44 Our
value is in the range of values reported for the glass transition
and is at the somewhat lower end of that range. Some of the D
values reported in the literature for PMMA systems with
molecular weights similar to those in our study are shown in
Figure 5b as blue open symbols. Liu et al. measured the
interdiffusion of PMMA bilayers utilizing gold nanoparticles at
the interface by X-ray reflectometry.45 In other studies,
interdiffusion at the interface of deuterated and protonated
PMMA was measured by neutron reflectometry (Lin et al.46),
attenuated total reflectance infrared spectroscopy (ATR-IR)
(Van Alsten et al.43), and nuclear reaction analysis (Shearmur
et al.44). The D values reported by Van Alsten et al. were large
and appeared to be consistent with our values, but most of the
D values were shifted to higher temperatures and smaller than
our values if compared at the same temperature. This is
reasonable because high-molecular-weight polymer chains
should diffuse in the entangled 3D melt by reptating, whereas
at the surface, as shown in the movies, chains can move
laterally and D should be larger. Although the D values in this
study were generally larger than those in the 3D melt, the
movement observed here had an activation energy that was
reasonable for the glass transition. We concluded that the
movements observed here were closely related to the glass
transition.
3.2. Chain Movements of a PS Film Surface. Figure 6
shows AFM height images of a PS film dip-coated on a slide
glass observed at various surface temperatures. The RMS was
0.23 nm at 25 °C and almost constant up to 101 °C. Similar to
the PMMA film, no meaningful structure or structural
differences at various temperatures were observed in this static
AFM observation. However, in dynamic observations, we
could recognize significant movements at higher temperatures.
A movie constructed from eight sequential images (total time:
22.7 min) is available in the Supporting Information (Movie
Figure 5. (a) Mean displacements of PMMA and PS films obtained S4). As shown in Movie S4, movements started at
by PIV analysis as functions of the surface temperature. The PMMA approximately 60 °C, which was much lower than that of the
and PS surfaces started moving at approximately 97 and 50 °C, PMMA film and significantly lower than the Tg of bulk PS (104
respectively. The PMMA and PS bulk Tg values are also indicated. (b) °C), and they became more significant with increasing
Arrhenius plot of apparent diffusion constants calculated from the temperature. In the movie, chain-like structures several
mean displacement of a PMMA film (filled blue circles) and a PS film nanometers in width (indicated by the arrows in a magnified
(filled red circles). The activation energy was approximately 193 kJ image of Figure 6b) appear to be moving, which was similar to
mol−1 for the PMMA film and 151 kJ mol−1 for the PS film. Diffusion the surface of the PMMA films (zoom in on Movie S4 to see
constants reported in the literature are shown by blue open symbols
the chain-like structures). Figure 7 shows a vector plot of the
for PMMA and red open symbols for PS. (c) The activation energy
reported for the glass transition of PMMA and PS is summarized in displacement between the fifth and seventh images with the
comparison with the values obtained in this work. Molecular weights same slow scan direction by PIV analysis. A movie constructed
are indicated in parentheses. d- and h- indicate the molecular weights from the fifth and seventh images of Movie S4 is available in
of the deuterated and hydrogenated polymers, respectively, used for Movie S5 in the Supporting Information (we recommend
interdiffusion measurements. using repeated replay mode). As shown in Figure 7, the
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Figure 6. (a) AFM height images of a PS film at various surface temperatures. A movie constructed from sequential AFM images (eight images for
22.7 min) is available in Movie S4 in the Supporting Information. To view the surface movements, we recommend viewing the movie in repeated
replay mode in the viewer software. It appears that there was no surface movement below 50 °C, and movement started above 60 °C. (b)
Magnified AFM height image at 25 °C. Some string-like structures are indicated by yellow arrows. The significant movements of string-like
structures are visible at higher temperatures in Movie S4.

movements started at approximately 60 °C, and the displace- mass spectrometry (SIMS),50 and Green et al. used Rutherford
ment increased with increasing temperature. The mean backscattering spectrometry to study the displacement of the
displacement at each temperature is plotted as red filled interface marked by gold particles.51 The D values in 3D melts
triangles in Figure 5a. The movements started at approximately appeared to be shifted to higher temperatures. The D values in
50 °C, which was 54 °C lower than the PS bulk Tg (104 °C). A our study were roughly shifted by ∼30 °C below the literature
significant decrease in Tg at the surface was observed for PS. value in 3D melts. The shift of the D value is smaller than the
The apparent D was estimated from the displacement using eq decrease of the surface Tg evaluated by the onset of the
1. A plot of λ2 as a function of time for the PS film at 84, 96, movements (∼54 °C). It is probably not appropriate to
and 101 °C is shown in Figure S2b; λ2 increased linearly with compare D values in this study with those obtained by different
time. The movements of the chain-like structure at the PS film methods. We note that the apparent D value can be evaluated
surface obeyed the 2D diffusion equation in the observed time from AFM observations and that the activation energy was
and temperature ranges. The estimated D values are plotted as
reasonable relative to those expected for glass transitions.
red filled circles in Figure 5b. The values were somewhat
As described above, the significant movements of chain-like
scattered, but the activation energy derived from D values at
structures several nanometers in width were observed at the
temperatures higher than 50 °C was ∼151 kJ mol−1. The
activation energies reported for the glass transition of PS in the surfaces of PMMA and PS films at high temperatures, and the
literature are summarized in Figure 5c; they include 269 kJ activation energies of the movements were consistent with
mol−1 by Whitlow et al.,47 264 kJ mol−1 by Kim et al.,48 and those expected for the glass transition. The movements
176 kJ mol−1 by Antonietti et al.49 The activation energy observed here should be similar to the chain movements;
observed in our study was comparable to or slightly lower than however, the chain-like structures were several nanometers in
the reported values. Some of the D values reported for PS width and observed to be broadened due to the tip diameter of
systems with a molecular weight similar to that used in our the cantilever. We could not conclude that the chain
experiment are shown as red open symbols in Figure 5b. movements were directly evaluated. If we could deposit
Antonietti et al. studied the diffusion of fluorescein-labeled PS isolated polymer chains on the same polymer film and compare
chains in a matrix,49 Whitlow et al. studied interdiffusion at the the movements of the deposited isolated chains on the surface
interface of deuterated and protonated PS by secondary ion with the chain-like movements of the films observed here, then
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Figure 7. Vector plot of the displacement between the fifth and seventh images of Movie S4 obtained by PIV analysis. The vector is enlarged by a
factor of 3 for clarity.

we could clarify how the chain-like movements relate to true observed Tg may not have been apparently reduced from the
chain movements at the surface. bulk value.
Next, we compared the movements of isolated PMMA In this study, we attempted to observe and evaluate the
chains deposited on a PMMA film with the chain-like movements of isolated PMMA chains deposited on a dip-
movements of the PMMA film surface observed here. coated PMMA film without the effects of any additives or
3.3. Deposition of Isolated PMMA Chains on a PMMA thermal press process. Is it possible to observe isolated PMMA
Film and AFM Observation of the Chain Movements. chains deposited on the rough surface of a dip-coated film and
To use AFM to observe isolated polymer chains deposited on a use AFM to evaluate their movements?
substrate, we believe that the substrate should be sufficiently To deposit PMMA as isolated chains by the LB method, a
flat and the roughness should be smaller than the height of the PMMA monolayer should be deposited in a dilute state at 0
isolated polymer chains. Thus, atomically flat substrates, such mN/m before being compressed to form a condensed film.
as mica and highly ordered pyrolytic graphite (HOPG), are Since PMMA is deposited imhomogeneously on a substrate in
used as substrates for the observation of deposits of isolated the dilute state and it is expected to be difficult to find
chains. We previously reported the preparation of molecularly deposited PMMA chains, especially on the rough dip-coated
film surface, we used a PS-b-PMMA block copolymer instead
flat PMMA substrates (RMA ≈ 0.20 and 0.15 nm) by heat
of a PMMA homopolymer. As shown in Figure 8a, PS without
pressing a commercial PMMA plate (2 mm thick, RMS ≈ 0.42
hydrophilic groups did not spread on the surface of water but
nm) with an atomically stepped sapphire substrate or a mica
formed particles, much thicker than monolayers, that were
mold, using the LB technique to deposit isolated PMMA used as probes to find the PMMA chains emanating from
chains on the molecularly flat PMMA substrates, and using them.11,36−38 Figure 8b shows an AFM height image of PS-b-
AFM to observe the isolated PMMA chains.34−36 Furthermore, PMMA deposited on mica in a dilute state. PS particles with a
we reported, but only qualitatively, that the deposited isolated thickness of ∼3.1 nm surrounded by a condensed PMMA
PMMA chains and the nanostructures observed at the surface monolayer with a thickness of ∼0.3 nm were observed. On the
of the molecularly flat PMMA substrate started to move close PMMA film, isolated PMMA chains emanating from PS
to the Tg of bulk PMMA, and no significant decrease in Tg was particles were also clearly observed but extended in the dip
observed.38 However, in this case, (1) the surface Tg of the direction. The observed structures were clearly different from
PMMA plate may have increased by the thermal press process those of the PMMA film surface without the deposition of PS-
and (2) the PMMA plate was a commercially available cast b-PMMA chains (Figure 2) and were PS-b-PMMA deposited
plate obtained by the thermal polymerization of MMA and on the PMMA film. Why were the PMMA chains deposited on
contained a small amount of release agent, which may have the PMMA film elongated? Hydrophilic mica strongly
prevented the decrease in the surface Tg. As a result, the adsorbed the PMMA monolayer, and a condensed PMMA
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Figure 8. (a) Schematic representation of PS-b-PMMA on a water surface. AFM height images of PS-b-PMMA chains deposited on (b) mica and
(c) a PMMA film from a water surface in a dilute state at 0 mN/m. The deposition direction was vertical. (d) AFM height images of PS-b-PMMA
chains deposited on a PMMA film observed in situ at various surface temperatures. A movie constructed from sequential AFM images (12 images
for 34 min) is available in Movie S6 in the Supporting Information. To observe the chain movements, we recommend viewing the movie in
repeated replay mode in the viewer software. It appears that there was no movement of the PMMA chains of PS-b-PMMA below 101 °C, but the
chains started moving above the bulk Tg at 106 °C. (b) Reproduced with permission from ref 36. Copyright 2019 American Chemical Society.

monolayer formed on the water surface was transferred, distributed, but the width of the thinnest part was ∼4 to 5
maintaining its condensed structure. However, the hydro- nm, the nominal tip radius of the cantilever was 4 nm, and the
phobic PMMA film weakly adsorbed the PMMA monolayer, PMMA chain should be observed to be broadened by the tip
and PMMA chains were stretched in the dip direction during to a similar extent. The thinnest parts of the PMMA chains
LB deposition.36−38 The widths of PMMA chains were were similar to a single chain. The height of the thinnest part
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was ∼0.6 nm, which was slightly higher than that on mica (0.3 surface would be expected in the translational motion of the
nm), probably due to the deposition of the chains on the rough chains over a long period of time.
surface of the dip-coated PMMA film. Since the motion of the PMMA chains deposited on the film
Figure 8d shows the AFM height images observed at various surface by the LB method and that of the surface of the PMMA
temperatures. A movie constructed from 12 sequential images film were almost the same, we concluded that the motion of
for 34 min observed at 25, 97, 101, 106, 110, 115, and 119 °C the dip-coated film observed by in situ AFM was closely
is available in the Supporting Information (Movie S6). A correlated to the chain motion of the film surface.
movie of the fifth and seventh images (Movie S7) and the We note that there is no significant difference between the
vector diagram of the displacement evaluated by PIV analysis surface Tg of the dip-coated pure PMMA film without the
(Figure S3) are also available in the Supporting Information. thermal press process and the surface Tg of the molecularly flat
Figure 9 shows the average displacement at each temperature PMMA surface prepared with the thermal press process in a
previous study,38 indicating that the thermal press process and
additives such as the release agent did not significantly affect
the surface Tg of PMMA and the decrease in the surface Tg of
PMMA was limited.
The decrease in the surface Tg of the PMMA film was
limited, but for the PS system, a significant decrease in Tg of as
high as 54 °C was observed, indicating that the decrease in
surface Tg was greatly influenced by the polymer composition.
A considerable number of studies related to the surface Tg of
PS and PMMA thin films have been reported. A number of
studies are summarized in a recent comprehensive review, as
shown in Table 2 for PS, Table 4 for PMMA, and Table 5 for a
comparison between PS and PMMA in ref 26. A larger Tg
decrease at the surface of PS compared to that of PMMA,
similar to our study, was reported as follows. Torkelson and co-
workers studied the surface Tg of PS and PMMA by a localized
fluorescence method and found that the Tg of the topmost 12−
14 nm layer of thick films (>250 nm) decreased 32 K for PS29
but decreased only 7 K for PMMA.52 The Tg of free-standing
Figure 9. Mean displacement of PS-b-PMMA chains on a PMMA film PS and PMMA films measured by ellipsometry indicated that
in comparison with that of a PMMA film obtained by PIV analysis as the Tg at a thickness of 40 nm decreased 52 K for PS53 but
a function of surface temperature. PS-b-PMMA undergoes slightly only 15 K for PMMA54 for samples of similar molecular weight
higher movement at 25−101 °C but quite similar movements at
(∼7.7 × 105−7.9 × 105 g/mol). Paeng et al. evaluated the
higher temperatures, indicating the quite similar movements by chains
at the surface of the PMMA film and PMMA chains deposited on the thickness of the surface mobile layer by measuring the
film. No significant difference was observed. reorientation of diluted fluorescent probes by the photo-
bleaching technique and found that the thickness of the mobile
layer was 7 nm for PS but 4 nm for PMMA at the bulk Tg.55,56
in comparison with that of the PMMA film surface. The Inoue and co-workers studied the Tg distributions in PS and
contrast of the images comes mostly from the deposited PMMA multilayer films composed of deuterated and hydro-
PMMA chains, indicating that the motion of the deposited genated polymers by neutron reflectivity and found that the Tg
PMMA isolated chains was mainly evaluated in the PIV of the topmost surface (∼4 nm thick) decreased 20 K from the
analysis. At low temperatures, the deposited PMMA chains had bulk value for PS, but no decrease was observed for PMMA.
slightly higher mobility than the PMMA film surface, and the They interpreted these results to mean that the surface Tg was
temperature at which the movements become significant was affected by the substrate interface due to the small total
∼106 °C, which was slightly higher than the temperature of the thickness of the multilayered film (∼90 nm).28,57 However,
PMMA film surface (∼97 °C). However, in the high- this may also indicate a small decrease in the surface Tg of
temperature region above 100 °C, the movements of the PMMA.
deposited PMMA chain and the surface of the PMMA film
were almost the same, indicating that the movements observed 4. CONCLUSIONS
for the PMMA film surface were similar to the movements of The motion of PMMA and PS dip-coated film surfaces was
the PMMA chain deposited on the substrate. The chains at the observed in situ by high-temperature AFM. Vigorous move-
surface of the PMMA film were expected to be partially ments of chain-like structures several nanometers in width
exposed outside the surface, while the residual parts were were observed at higher temperatures. PIV analysis of the
embedded inside the film. However, the motion of the PMMA movements indicated that the movements started at ∼97 °C
chains exposed outside the surface was essentially the same as for PMMA, slightly below the bulk Tg (108 °C), but at ∼50
that of the chains deposited two-dimensionally on the surface °C, significantly below the bulk Tg (104 °C), for PS. The
of the film. The motion we observed here is a significantly apparent diffusion coefficient was derived from the displace-
localized motion of the polymer chain, less than several ment of the movements, and the activation energy of the
nanometers, and the motion of chains exposed outside of the diffusion coefficient was 193 kJ mol−1 for PMMA and 151 kJ
surface may not be affected by the chain part embedded inside mol−1 for PS, which was reasonable relative to the activation
the film. However, a large difference in dynamics between the energy of the glass transition reported in the literature. The
surface chains of the film and the chains deposited on the movements of isolated PMMA chains deposited on a PMMA
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film by the LB technique were evaluated and found to be π−A isotherm of PS-b-PMMA; mean squared displace-
essentially the same as the movements of the PMMA film ments of PMMA and PS films as functions of time;
surface. Thus, the chain-like movements observed at the film vector plot of the displacement of PMMA-b-PS
surface by AFM were similar to the chain movements of the deposited on the PMMA film; and a list of the
film surface. supporting movies (PDF)
Previously, AFM was used to evaluate the surface Tg of film Movie constructed from sequential AFM height images
surfaces in somewhat macroscopic observations, such as the of a PMMA film observed at various surface temper-
sedimentation of gold nanoparticles deposited on a film atures (14 images for 40 min) (Movie S1) (AVI)
surface34 and the welding of nanoholes formed by nano- Movie constructed from the third and fifth images of
particles on a film surface.35 The present results show that the Movie S1 (Movie S2) (AVI)
chain movements of a film surface can be directly evaluated by
dynamic AFM observations of the film surface. Magnified version of Movie S1 (Movie S3) (AVI)
Researchers generally believe that it is not possible to use Movie constructed from sequential AFM height images
AFM to obtain meaningful images of individual chains at film of a PS film observed at various surface temperatures (8
surfaces because the chains are condensed with an interchain images for 22.7 min) (Movie S4) (AVI)
separation much smaller than the resolution of AFM (usually Movie constructed from the fifth and seventh images of
∼1 nm for tapping-mode AFM). Why is it possible to use AFM Movie S4 (Movie S5) (AVI)
to evaluate surface motion similar to chain movements? As Movie constructed from sequential AFM height images
schematically shown in Figure 10, if the chains (gray chains) of PS-b-PMMA chains deposited on a PMMA film
observed at various surface temperatures (12 images for
34 min) (Movie S6) (AVI)
Movie constructed from the fifth and seventh images of
Movie S6 (Movie S7) (AVI)

■ AUTHOR INFORMATION
Corresponding Author
Jiro Kumaki − Department of Organic Materials Science,
Graduate School of Organic Materials Science, Yamagata
University, Yonezawa, Yamagata 992-8510, Japan;
orcid.org/0000-0001-9552-3303; Email: kumaki@
yz.yamagata-u.ac.jp
Author
Kouki Koike − Department of Organic Materials Science,
Graduate School of Organic Materials Science, Yamagata
Figure 10. Schematic representation of a film surface. If the film University, Yonezawa, Yamagata 992-8510, Japan
surface is flat and polymer chains are condensed with a chain−chain
distance of less than the AFM resolution (gray chains), then it is not Complete contact information is available at:
possible to observe movements close to single chains. However, the https://pubs.acs.org/10.1021/acs.langmuir.2c01788
film surface is rough. If a part of the chain is exposed out of the
surface and deposited on the surface discretely, as shown by the Notes
yellow chains, then movements close to single chains could be The authors declare no competing financial interest.
observed by AFM.

are uniformly condensed with an interchain separation smaller

■ ACKNOWLEDGMENTS
We thank associate professor Daisuke Yokoyama, Yamagata
than the AFM resolution (typically ∼1 nm in tapping-mode University, for the thickness measurements made with
AFM), then the single chains cannot be resolved with AFM. ellipsometry. We thank Daichi Ikejima, Yamagata University,
However, in reality, the surface of the film is rough. If a part of for the Tg measurements made with DSC. This work was
the chains exposed from the surface are deposited on the supported by JSPS KAKENHI grant numbers JP20H05201,
surface with a separation larger than the AFM resolution, then JP21H01993, and JP21K18993.
AFM could observe movements similar to single-chain
movements. Researchers sometimes assume that the film
surface is uniform, but in reality, it is not. If chains are
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