Supporting Information:

Competition between Disentanglement Effect and Interfacial

Effect Determines the Chain Relaxation Dynamics of Entangled
Ultrathin Polystyrene Films

Fengliang Wang,1 Sijia Li,2 Hongkai Guo,1 Jiaxiang Li,3,4 Jianquan Xu,1 Tongfei Shi,5
and Xinping Wang1*

1
School of Chemistry and Chemical Engineering, Key Laboratory of Surface &

Interface Science of Polymer Materials of Zhejiang Province, Zhejiang Sci-Tech

University, Hangzhou 310018, P. R. China

2
School of Intelligence Policing, China People’s Police University, Langfang 065000,

P. R. China

3
State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of

Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, P. R. China

4
School of Applied Chemistry and Engineering, University of Science and Technology

of China, Hefei 230026, P. R. China

5
School of Chemical Engineering and Light Industry, Guangdong University of

Technology, Guangzhou 510006, P. R. China

Corresponding Author

Xinping Wang-School of Chemistry and Chemical Engineering, Key Laboratory of

Surface & Interface Science of Polymer Materials of Zhejiang Province, Zhejiang Sci-

S1
Tech University, Hangzhou 310018, P. R. China; ORCID: 0000-0002-9269-3275;

Email: wxinping@zstu.edu.cn

1. Characterization of the phenyl-modified substrates.

Surface content of phenyl groups is calculated based on the Cassie equation1, 2:

cos   f OH cos  OH  f  phenyl cos   phenyl f  OH  f  phenyl  1 (S1)

where θ, θ-OH, and θ-phenyl are the water contact angle of the phenyl-modified substrate,

silicon surface covered completely by-OH (i.e. 7°)3 and the substrate fully covered by

phenyl groups (i.e. 91°)4, respectively; and f-OH and f-phenyl are the fraction of hydroxyl

and phenyl group on substrate surface, respectively.

The surface free energy of polymer film and substrates were calculated according

to the Owens-Wendt method (Eq. S2-S4)5 on the basis of contact angle values of water

and diiodomethane on polymer and substrate surface:

 s   sD   sp (S2)

 d  cos  d  1   p
/  wp  w  cos  w  1
 
D 0.5

d
(S3)
  
s
2   
D
d d
p D
w / p
w

 w  cos  w  1   D
/  dD  d  cos  d  1
 p 0.5

w
(S4)
  wp   wD  dp /  dD  
s
2

where  s and  s are the dispersive component and polar component of surface free
D p

energy of the polymer film and substrates, respectively;  d ,  d , and  d are the
D p

overall, dispersive and polar component of surface energy of diiodomethane,

respectively;  w ,  w , and  w are the overall, dispersive and polar component of

D p

surface energy of water, respectively;  d is the contact angle of diiodomethane and

S2
 w is the contact angle of water. The total surface tension of water is 72.8 mJ m−2 with

a polar component of 51 mJ m−2 and a dispersive component of 21.8 mJ m−2.6-8 The

surface tension of diiodomethane are as follows: polar component is 2.4 mJ m−2 and

dispersive component is 48.6 mJ m−2.6 The interfacial energy for PS/substrate (γs–p) is

deduced by the harmonic mean equation9:

 sub
D
 poly
D
 sub
p
 poly
p

 s  p   poly   sub  4  4 (S5)

 sub
D
  poly
D
 sub
p
  poly
p

where γpoly and γsub are the surface free energy of PS and substrates, respectively.

The contact angle values on polymer and substrates were measured using the

sessile droplet method at a Drop Shape Analysis (DSA10-Mk2, Kruss, Germany) using

ultrapure water and diiodomethane as probe liquids, at room temperature and a relative

humidity of 45%. In the experiments, a 3 μL water or 2 μL diiodomethane was gently

deposited on the sample surface, and the contact angle was determined on the basis of

the droplet profile by a tangent-leaning method.10 The contact angle for each sample

was the average of results of ten measurements. X-ray photoelectron spectroscopy

(XPS) was performed using a PHI5000C ESCA system with an Mg Kα X-ray source

(1253.6 eV). The X-ray gun was operated at a power of 250 W, and the high voltage

was maintained at 140 kV. The emission angle of the photoelectron to the surface plane

was selected to be 30°. Sum frequency generation (SFG) vibration spectroscopy was

performed using an EKSPLA system (EKSPLA Co., Lithuania) as previously

described.11, 12
The incident angles of visible and IR beams were 60° and 53°,

respectively. The visible beam with a wavelength of 532 nm was generated by

frequency doubling of the fundamental output pulses from a Nd: YAG laser (PL2241).
S3
The IR beam was generated from an optical system, which included a parametric

generation/amplification/difference frequency generation (OPG/OPA/DFG) system,

based on LBO and AgGaS2 crystals, which produced a tunable range between 1000 and

4300 cm-1. The beams were pumped by the second harmonic and the fundamental

output of the laser, with a repetition rate of 50 Hz and a pulse width of ∼30 ps. SFG

spectra with a ssp polarization combination (i.e., an s-polarized sum frequency output,

an s-polarized visible input, and a p-polarized infrared input) were collected. Atomic

force microscopy (AFM, MultiMode-8, Bruker Co., USA) was adopted to observe the

surface morphology of the phenyl-modified substrates. A standard tapping mode was

used with a cantilever with a spring constant of 40 N/m and a tip with a curvature radius

of 10 nm.

Table S1. Surface and Interface Properties of the PS and Substrates

Contact angle (°) Surface free energy (mJ m−2) a

Samples
CH2I2 γD γP

PS 35 ± 1 41.4 1.0

SiOx/Si 32 ± 1 27.7 45.1

S-1 41 ± 1 26.4 33.1

S-2 44 ± 1 28.4 18.6

S-3 46 ± 1 29.7 11.3

S-4 48 ± 1 32.5 3.3

a
Surface energies calculated by the Owens-Wendt theory.5

The phenyl-functionalized substrates were characterized by XPS, SFG, and AFM.

XPS analysis shows that the intensity of the characteristic peak corresponding to the C

1s binding energy of the PTS at approximately 285 eV increases with increasing

S4
reaction time between the PTS solution and the SiOx/Si substrate, as shown in Figure

S1(a). Meanwhile, SFG spectroscopy showed a characteristic peak at 3060 cm-1, which

is attributed to the v2 vibration of the phenyl group of PTS molecules, and the intensity

of the peak increases with increasing reaction time, see Figure S1(b). The AFM results

showed that the roughness of the substrate surface increased slightly with the increase

of phenyl groups content, but the roughness was less than 0.5 nm in all cases (Figure

S2), suggesting that the PTS was not hydrolysed.4

(a) (b)

Figure S1. (a) XPS and (b) SFG spectra of bare SiOx/Si and phenyl-modified substrates.

SiOx/Si S-1

RMS=0.281 nm RMS=0.302 nm

S-2 S-3 S-4

RMS=0.313 nm RMS=0.334 nm RMS=0.363 nm

Figure S2. AFM morphology of bare SiOx/Si and phenyl-modified substrates.

2. Detailed experimental procedures for the extraction of wetting ridge height.

S5
 A high precision constant temperature heating stage with an accuracy of ±1 K was

used to heat the sample. A supported film is transferred to the heating stage after the

temperature reaches the experimental temperature. The film is first kept on the heating

stage for 5 min to preheat, to keep the sample and the heating stage at the same

temperature. Subsequently, a 2 μL droplet of [EIM]BF4 was gently put onto the film

surface and left for a given time. Then, the sample was quickly transferred onto a copper

plate that was kept at 273 K, resulting in the shape of the wetting ridge being well

preserved. The ionic liquid droplet was then suck using a filter paper, and the film was

rinsed with a large amount of distilled water to remove the residual ionic liquid and

dried under a nitrogen stream. The wetting ridge formed on the PS surface was observed

using atomic force microscopy (AFM, Multimode-8; Bruker; USA) by the tapping

mode at 298 K. The probes were silicon, with a spring constant of approximately 9 N/m

and a resonant frequency of 115 kHz. The parameters used for image acquisition were

1.0 Hz scan frequency, 20 μm × 20 μm scan size, and 512 × 512 image resolution.

3. Detailed description of bond fluctuation model (S-BFM).

S-BFM can simply switch “on” or “off” the chain crossing, which makes it

possible to obtain equilibrium conformation for noncrossing chains (or real chains)

within a relatively short period by starting from equilibrated crossing chains.13 First, we

run 106−107 MCs to equilibrate the systems. During this process, the chain crossing is

allowed, and only the excluded volume interaction is considered between all monomers

and particles. Then, the polymer-wall interactions are turned on, and 106-107 MCs are

run to gradually remove those chain crossings. Finally, the equilibrium configurations

S6
are obtained, and the 107-108 MCs are run to collect data.

4. The discussion of the influence of free surface and disentanglement effects on

the chain relaxation dynamics of polymer films.

Green et al. investigated the effect of a free surface on the chain relaxation

dynamics of a confined PS film.14 The effective viscosity of the PS film on SiOx/Si

decreased monotonically with the decrease in h. This trend aligns with the observed

decrease in the Tg of the SiOx/Si-based PS film with a decreasing h.15 An empirical

formula (Eq. S6) describing the relationship between Tg and film thickness is used to

elucidate the thickness-dependent behavior of chain relaxation time in the PS film.14

 rep  h 
 1 k  A / h

(S6)
 rep  bulk 

where A and δ are identical to the parameters used for fitting the Tg data, while k

represents a constant.

Winey et al. investigated the chain relaxation dynamics of polymer films under

thin film confinement via MD simulation and proposed that the average number of

entanglements per chain (Z) determines the relaxation dynamics of polymer films and

satisfies the relation expressed as Eq. S7.16

 rep  h  Z  h
 (S7)
 rep  bulk  Z  bulk 

In this model, ρe far from the substrate is simplified to a step function, and ρe is zero in

the range of hd from the substrate.16 The value of Z is derived using Eq. S8.

Z  h h  2hd
 (S8)
Z  bulk  h

where hd represents the thickness at which ρe is zero.

S7
 Table S2. Simulation details for polymer melts

12
M Lx=Ly H=Lz H Rg2,b

115 76 6 0.74
120 60 10 1.24
116 50 14 1.74
116 44 18 2.23
117 40 22 2.73
138 40 26 3.23
160 40 30 3.72
181 40 34 4.22
202 40 38 4.72
224 40 42 5.21
245 40 46 5.71
266 40 50 6.21
330 40 62 7.70
M represents the number of polymer chains in the simulation box, Lx=Ly is the lateral length of the
12
simulation box, H=Lz denotes the film thickness, and H Rg2,b represents the normalized film

thickness.

Figure S3. Thickness dependence of Tg(h) for PS films with different molecular weight on substrate

with different interfacial energy. The dash line indicates the Tg,bulk of the PS bulk and the solid lines

indicate the best fit for all data using empirical equations.15, 17

S8
 inner

microgroove

Figure S4. Height profile of a wetting ridge on the PS film with time. Film thickness: 89 nm; T=393

K. S-1 was used as a substrate, test liquid: [EIm]BF4.

Table S3. The values of the fitting parameters were obtained by fitting the thickness dependence of

whole chain relaxation time of PS films with different molecular weights supported on PTS

substrates using Eq. 5.

PS-168k PS-222k PS-482k

System γs-p (mJ m-2)
hs ζs/ζ0 hd hs ζs/ζ0 hd hs ζs/ζ0 hd

S-1 33.5 18.6 2.87 1.26 20.0 2.97 1.34 23.0 3.05 1.58

S-2 18.2 21.6 2.99 1.55 24.0 3.08 2.01 27.4 3.22 2.50

S-3 10.6 23.8 3.06 1.86 26.1 3.21 2.40 30.2 3.35 3.40

S-4 2.3 27.2 3.18 2.20 30.4 3.38 3.20 36.6 3.55 4.81

S9
 hc

Figure S5. τ*(h) as a function of film thickness for PS-222k films on substrate with different

interfacial energies (T = Tg+20 K). The solid line is a best fit to the data using Eq. 5 and the fitting

parameters are listed in Table S3.

hc

Figure S6. τ*(h) as a function of the thickness of PS-482k on substrates with different γs–p values (T

= Tg + 20 K). The solid line represents the optimal fit to the experimental data achieved using Eq. 5

with the corresponding fitting parameters detailed in Table S3.

S10
Figure S7. (a) ζs/ζ0 of PS segments and the bottom substrate interface with different γs–p versus

molecular weights. (b) hs for all phenyl-modified interfaces with different γs–p versus molecular

weights.

Figure S8. Average number of near-neighboring particles of each monomer ( n ij ) as a function of

film thickness (H) for attractive polymer-wall interactions.

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